optoelectronic device

专利摘要:
optoelectronic device. the invention provides an optoelectronic device comprising a photoactive region, which photoactive region comprises: an n-type region comprising at least one n-type layer; a p-type region comprising at least one p-type layer; and, disposed between the n-type region and the p-type region: a layer of a perovskite semiconductor without open porosity. the perovskite semiconductor is generally light absorbing. in some embodiments, disposed between the n-type region and the p-type region is (i) a first layer comprising a support material, which is typically porous, and a perovskite semiconductor, which is typically disposed in the pores of the support material. ; and (ii) a buffer layer disposed in the first layer, which buffer layer is said layer of a perovskite semiconductor without open porosity, wherein the perovskite semiconductor in the buffer layer is in contact with the perovskite semiconductor in the first layer. layer. the non-open porosity perovskite semiconductor layer (which may be said buffer layer) typically forms a flat heterojunction with the n-type region or p-type region. the invention also provides processes for producing such optoelectronic devices which typically involve solution deposition or vapor deposition of perovskite. in one embodiment, the process is a low temperature process; for example, the entire process can be carried out at a temperature or temperatures not exceeding 150°C.
公开号:BR112015005926B1
申请号:R112015005926-0
申请日:2013-09-17
公开日:2022-01-25
发明作者:Henry James Snaith；Edward James William Crossland；Andrew Hey；James Ball；Michael Lee；Pablo Docampo
申请人:Oxford University Innovation Limited；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[0001] The invention relates to an optoelectronic device, and in particular to a flat junction optoelectronic device. The invention also relates to a process for producing such an optoelectronic device. BACKGROUND OF THE INVENTION
[0002] Thin-film photovoltaics are a promising alternative to their monocrystalline counterparts due to their high efficiency, comparable stability, and potentially lower production cost. The most widely studied thin-film materials currently under investigation for photovoltaic applications include the CdTe compound semiconductors [X. Wu, Solar Energy, vol. 77, p.803, 2004], CuIn1-xGaxSe2 (CIGS) [Chirila et al., Nature Materials, vol. 10, p. 857, 2011], Cu2ZnSnS4 (CZTS) [D. Barkhouse and others, Progress in Photovoltaics, vol. 20, p. 6, 2012]; dye-sensitized solar cells [A. Yalla et al., Science, vol. 334, p. 629, 2011]; and organic semiconductor solar cells [Y. Liang et al., Advanced Energy Materials, vol. 22, p. E135, 2010]. Inorganic semiconductor compounds comprising high-efficiency solar cells are typically manufactured employing expensive vacuum-based deposition although recent routines focused on CIGS and CZTS solution processing have presented high-efficiency devices [M. Graetzel and others, Nature, vol. 488, p. 304, 2012]. Organic and dye-sensitized solar cells with lower recording efficiencies are typically manufactured with solution-based deposition procedures, but suffer from poor long-term stability. Furthermore, the relatively low production capacity of tellurium and indium makes CdTe and CIGS potentially commercially unattractive.
[0003] The perovskites [D. Mitzi et al., Science, vol. 267, p. 1473, 1995] are an alternative family of semiconductor materials that have been investigated for device applications [D. Mitzi et al, IBM Journal of Research and Development, vol. 45, p. 29, 2001]. For photovoltaics, perovskites have been used as the sensitizer in liquid electrolyte photoelectrochemical cells [J.-H. Im and the others, Nanoscale, vol. 3, p. 4088, 2011; A. Kojima et al., Journal of the American Chemical Society, vol. 131, p. 6050, 2009], although in this previously reported electrolyte system, perovskite absorbers decay rapidly and solar cells drop in performance after only 10 minutes. Perovskites have also been used in solid-state photoelectrochemical cells [H.-S. Kim et al., Scientific Reports, doi: 10.1038/srep00591; A. Kojima and others, ECS Meeting Abstracts, vol. MA2007-02, p. 352, 2007] and as the hole carrier in solid-state dye-sensitized solar cells [I. Chung, Nature, vol. 485, p. 486, 2012]. The main operating principle of sensitized solar cells is that the role of light absorption and charge transport are separated in the different materials in the solar cell. This allows light-absorbing materials, which would inefficiently generate charge if light shined on a solid film of the material, to operate very efficiently in a sensitized solar cell. As a result, since there are examples of perovskites employed as sensitizers in mesostructured solar cells, or as hole carriers in dye-sensitized solar cells, but no reports of perovskite solid films functioning efficiently in solar cells, it would be reasonable to assume that perovskites are not a family of materials to be used as solid thin films in thin film photovoltaics. SUMMARY OF THE INVENTION
[0004] The invention provides optoelectronic devices having a final film of a light-emitting or light-absorbing perovskite arranged between n-type (electron conduction) and p-type (hole conduction) layers. The inventors have unexpectedly found that good device efficiencies can be obtained by using a compact thin film of the photoactive perovskite, as opposed to the requirement for a mesoporous composite. Although an open porous perovskite structure can typically be infiltrated with a p- or n-type material to form a bulky heterojunction with that material, the dense layer of perovskite employed in the present invention will generally form a flat heterojunction with that material. pe/type layer or n-type layer.
[0005] The perovskites employed in the optoelectronic devices of the invention are attractive for optoelectronic device applications because they can be formed from abundant elements on earth for both solution and vacuum processing, have tunable range structures (and therefore of electronic and optical), and can be stable under atmospheric conditions. The inventors have shown that photoactive perovskite film can be grown on a thin support or seed layer, or in the absence of such support, by solution deposition. Devices incorporating the thin layer of seed can be fully processed at temperatures not exceeding 150°C, which is important for reducing the cost of production, and for allowing processing on plastic substrates to provide flexible devices, and also for allowing the processing on top of the other layers to allow the production of serial and multi-junction devices. The perovskite thin film can also be usefully formed by means of evaporation from a filler powder or by means of co-evaporation of the perovskite precursor compounds.
[0006] Thus, the invention provides an optoelectronic device comprising a photoactive region, characterized in that the photoactive region comprises:
[0007] an n-type region comprising at least one n-type layer;
[0008] a p-type region comprising at least one p-type layer; and, arranged between the n-type region and the p-type region:
[0009] a layer of a perovskite semiconductor without open porosity.
[0010] Typically, the optoelectronic device is a photovoltaic device.
[0011] Alternatively, the optoelectronic device may be different from a photovoltaic device. The optoelectronic device may, for example, be a light-emitting device.
[0012] In some modalities, the photoactive region comprises:
[0013] said n-type region;
[0014] said p-type region; and, arranged between the n-type region and the p-type region:
[0015] (i) a first layer comprising a support material and a perovskite semiconductor; and
[0016] (ii) a buffer layer disposed on said first layer, which buffer layer is said layer of a perovskite semiconductor without open porosity,
[0017] where the perovskite semiconductor in the buffer layer is in contact with the perovskite semiconductor in the first layer.
[0018] In another aspect, the invention provides a process for producing an optoelectronic device comprising a photoactive region, characterized in that the photoactive region comprises:
[0019] an n-type region comprising at least one n-type layer;
[0020] a p-type region comprising at least one p-type layer; and, arranged between the n-type region and the p-type region:
[0021] a layer of a perovskite semiconductor without open porosity,
[0022] whose process comprises:
[0023] (a) provide a first region;
[0024] (b) arranging a second region in the first region, which second region comprises a layer of a perovskite semiconductor without open porosity; and
[0025] (c) arrange a third region in the second region,
[0026] where:
[0027] the first region is an n-type region comprising at least one n-type layer and the third region is a p-type region comprising at least one p-type layer; or
[0028] the first region is a p-type region comprising at least one p-type layer and the third region is an n-type region comprising at least one n-type layer.
[0029] Typically, the process of the invention is for producing a photovoltaic device comprising said photoactive region.
[0030] Alternatively, the process can be employed to produce an optoelectronic device other than a photovoltaic device, whose optoelectronic device comprises said photoactive region. The process can, for example, be employed to produce a light-emitting device comprising said photoactive region.
[0031] In some embodiments of the process of the invention the photoactive region comprises: said n-type region; said p-type region; and, arranged between the n-type region and the p-type region:
[0032] (i) a first layer comprising a support material and a perovskite semiconductor; and
[0033] (ii) a buffer layer disposed on said first layer, which buffer layer is said layer of a perovskite semiconductor without open porosity, wherein the perovskite semiconductor in the buffer layer is in contact with the semiconductor of perovskite in the first layer.
[0034] In such embodiments, the process of the invention comprises:
[0035] (a) provide said first region;
[0036] (b) arranging said second region in the first region, wherein the second region comprises:
[0037] (i) a first layer comprising a support material and a perovskite semiconductor; and
[0038] (ii) a buffer layer in said first layer, which buffer layer is said layer of a perovskite semiconductor without open porosity, wherein the perovskite semiconductor in the buffer layer is in contact with the perovskite semiconductor in the first layer; and
[0039] (c) arranging said third region in the second region.
[0040] The invention also provides an optoelectronic device which is obtainable by the process of the invention for producing an optoelectronic device.
[0041] Typically, the optoelectronic device is a photovoltaic device.
[0042] Alternatively, the optoelectronic device may be different from a photovoltaic device. The optoelectronic device may, for example, be a light-emitting device. BRIEF DESCRIPTION OF THE FIGURES
[0043] Figure 1 provides schematic illustrations of: (a) the generic structure of an embodiment of the optoelectronic device of the present invention; and (b) the photovoltaic cells exemplified here (variations in which the thin layer of Al2O3 or TiO2 is omitted are also investigated). At least one of the metallic electrodes is semi-transparent across the visible to near infrared region of the solar spectrum. Semi-transparent is typically 80% transparency, and ranging from 40 to 90%.
[0044] Figure 2 shows (a) XRD spectra of films of perovskite grown in each of the sublayer ranges investigated in the Examples below; and (b) an XRD spectrum of the perovskite formed by evaporation.
[0045] Figure 3 shows the normalized UV-vis spectra of perovskite films grown in each of the sublayer ranges investigated in the Examples below.
[0046] Figure 4 shows representative JV characteristics of the devices with the following variations: (a) HT B-AI2O3, (b) HT B-TiO2, (c) HT Al2O3, (d) HT TiO2, (e) HT C, (f) LT Al2O3, (g) LT TiO2, (h) LT C, and (i) Evaporates.
[0047] Figure 5 shows SEM micrographs of the solar cell cross-sections with the following variations: (a) HT B-AI2O3, (b) HT B-Ti02, (c) HT A1203, (d) HT Ti02, ( e) HT C, and (f) LT C.
[0048] Figure 6 shows the top view of SEM plane micrographs of substrate treatments with the following variations: (a) HT B-AI2O3, (b) HT B-TiO2, (c) HT AI2O3, (d) HT TiO2, (e) HT C, and (f) LT C.
[0049] Figure 7 shows the SEM plane micrographs of the substrate treatments with the following variations: (a) LT Al2O3, and (b) LT TiO2.
[0050] Figure 8 shows a schematic device for inverted p-i-n thin film solar cells.
[0051] Figure 9 shows the steady-state photoluminescence spectra for the bilayers of a perovskite absorber in a) p-type layers and b) n-type layers. The emission is centered on the photoluminescence peak of the CH3NH3Pbl3-xClx perovskite absorber.
[0052] Figure 10 shows a) SEM cross-sectional image of the optimized inverted device configuration. Scale bar represents 250 nm. The different layers were colored with the schematic device drawing color scheme shown in b).
[0053] Figure 11 shows an SEM top view of the substrates after the PEDOT:PSS deposition followed by the perovskite layer for the substrates containing a) and c) PEDOT:PSS annealed at 150 °C for 20 minutes and b) and d) PEDOT :PSS crosslinked with a 0.25 M aqueous solution of FeCb. The scale bars in a) and c) correspond to 25 μm and in b) and d) to 2.5 μm.
[0054] Figure 12 shows a) the JV curves and b) absorption spectrum for typical devices consisting of both crosslinked (circles) and annealed (squares) PEDOT:PSS layers. The in-between shows the short circuit current density (Jsc, mAcm-2), energy conversion efficiency (Eff, %), open circuit voltage (Voc, V) and fill factor (FF) for typical devices of both types. architectures.
[0055] Figure 13 shows a top view SEM image of the substrates after deposition of a) and c) NiO, and b) and d) V2O5 with the layer formed from perovskite on top. The scale bars in a) and b) correspond to 25 μm and in c) and d) to 2.5 μm.
[0056] Figure 14 shows the JV curves of devices containing a vanadium oxide (squares) and a p-type NiO contact (circles).
[0057] Figure 15 shows a) temporal evolution of the JV curves of the same device with lighting time. Sweeps are performed every minute with the first smallest sweep down and the last highest sweep up b) JV curves for fine regular configuration devices (triangles) and our inverts (circles). The in-between shows the short circuit current density (Jsc, mAcm-2), energy conversion efficiency (Eff, %), open circuit voltage (Voc, V) and fill factor (FF) for both device architectures .
[0058] Figure 16 shows a schematic illustration of a hybrid solar cell architecture in series, at this point a c-Si HIT (Intrinsic Thin Layer Heterojunction) cell is employed as the back cell in the series junction, where i = intrinsic, a = amorphous, c = crystalline, TCO = transparent conductive oxide. Sunlight is incident from above.
[0059] Figure 17 shows a schematic illustration of a hybrid solar cell architecture in series, at which point a perovskite solar cell is employed as the top cell, with a conventional thin film solar cell as the back cell at the series junction. , where TCO = transparent conductive oxide. Notably for the current generation of thin film technologies (eg solar cells from GIGS) there is a need to realize "inverted" perovskite solar cells for monolithic two-device terminals in series. Sunlight is incident from above.
[0060] Figure 18 shows a photograph of an evaporation chamber for dual source vapor deposition of a perovskite.
[0061] Figure 19 shows a schematic diagram of a dual source evaporation chamber.
[0062] Figure 20 shows a) completed dual source evaporated perovskite solar cell; b) illustration of the cross-sectional image; c) SEM cross-sectional image of the complete device.
[0063] Figure 21 shows a) the sample processed in the FTO coated glass with a compact layer of TiO2 and perovskite coated by centrifugation only; b, c) SEM image of the spin coated perovskite surface; d) the sample with FTO coated glass and compact TiO2 layer and evaporated perovskite only; and, f) SEM image of the surface of the evaporated perovskite.
[0064] Figure 22 shows the J-V curve measured under simulated AMI.5. 100m Wcm-2 sunshine from the best dual source evaporated perovskite solar cell. The in-between gives the solar cell performance parameters derived from this J-V curve.
[0065] Figure 23 shows XRD measurement of evaporated perovskite compared to centrifuge coated perovskite (named K330), methyl ammonium iodide (MAI) lead iodide (PM2) and TiO2 coated FTO glass.
[0066] Figure 24 shows a comparison of the absorbance of 200 nm thin films of spin-coated and evaporated perovskite.
[0067] Figure 25 shows a comparison between the annealed and non-annealed layers of perovskite deposited by vapor deposition from two sources: left: surface of non-annealed evaporated perovskite (when evaporated); right: annealed evaporated perovskite surface (after annealing at 100 degrees Celsius for 45 minutes in a nitrogen glove box).
[0068] Figure 26 shows a comparison of surface coverage by means of vapor deposition from two sources and by means of solution deposition: left: evaporated and annealed perovskite films; right: spin coated and glass coated annealed perovskite / FTO / TiO2 film.
[0069] Figure 27 shows a comparison between SEM cross-sections: left: two-count flat junction evaporated device, right: centrifuge coated flat junction device.
[0070] Figure 28 shows an XRD comparison between a perovskite layer formed by means of vapor deposition from two sources and a perovskite layer formed by centrifuge coating with a perovskite precursor solution. For both films the starting precursors were MAI and PbCl2.
[0071] Figure 29 shows the cross-section of the scanning electron microscopy of the devices showing (from bottom to top) the glass substrate, FTO, TiO2 electron selective layer, photoactive layer, spiro-OMeTAD. The photoactive layers are (a) PbCl2 and (b) CH3NH3Pbl3-xClx after dip coating a PbCl2 film and a CH3NH3I propan-2-ol solution.
[0072] Figure 30 shows the cross-section of the scanning electron microscopy of the devices showing, from the bottom to the top, the glass substrates, FTO, TiO2 electron selective layer, photoactive layer, spiro-OMeTAD. The photoactive layers are (a) Pbl2 and (b) CH3NH3Pbl3 after dip coating a film of Pbl2 in a propan-2-ol solution of CH3NH3I.
[0073] Figure 31 shows X-ray diffraction spectra of thin films of (a) PbCl2, (b) CH3NH3Pbl3-xClx, (c) Pbl2 and (d) CH3NH3Pbl3. After dip coating, the films of both precursors show a decrease in the relative intensity of the peaks corresponding to the precursor lattice and a relative increase in the perovskite lattice (absent in the precursor XRD spectra) indicating predominant conversion of the precursor films to the perovskite.
[0074] Figure 32 shows the voltage and current density characteristics of a device made employing Pbl2 as the active layer (dashed line) and a device in which the evaporated Pbl2 was converted to CH3NH3Pbl3 (solid line) by coating by immersion in a solution of methylammonium iodide in propan-2-ol. The performance parameters for Pbl2 are Jsc = 1.6 mA/cm2, PCE = 0.80%, Voc = 0.97 V, FF = 0.57. The performance parameters for CH3NH3PbI3 are Jsc = 5.3 mA/cm2, PCE = 2.4%, Voc = 0.82 V, FF = 0.61.
[0075] Figure 33 shows the voltage and current density characteristics of a device made employing PbCl2 as the active layer (dashed line) and a device in which evaporated PbCl2 was converted to CH3NH3PbI3-xClx (solid line) by coating by immersion in a solution of methylammonium iodide in propan-2-ol. The performance parameters for PbCl2 are Jsc = 0.081 mA/cm2, PCE = 0.006%, Voc = 0.29 V, FF = 0.27. The performance parameters for CH3NH3PbI3-xClx are Jsc = 19.0 mA/cm2, PCE = 7.0 %, Voc = 0.80 V, FF = 0.49.
[0076] Figure 34 shows the photoluminescence measurements and fits a model for a CH3H3Pbl3-xClx mixed organolead triiodide perovskite film and a CH3NH3Pbl3 triiodide perovskite film, in the presence of p- or n-type extinguishers . Time-resolved PL measurements taken at the emission peak wavelength of halide perovskite mixed with an electron quenching layer (PCBM; triangles) or hole (Spiro-OMeTAD; circles), along with exponential adjustments stretched to the films coated with PMMA data insulator (black squares) and fitted to interrupted samples using the diffusion model described in the text. A pulsed excitation source (from 0.3 to 10 MHz) at 507 nm with a fluence of 30 nJ/cm2 found on the glass substrate side. In between in Figure 34: Comparison of PL decays of the two perovskites (with PMMA coating) on a longer time scale, with lifetimes x and quoted as time taken to reach 1/e of initial intensity.
[0077] Figure 35 shows the photoluminescence measurements and fits a model of a CH3NH3PbI organolead triiodide perovskite film, in the presence of p- or n-type extinguishers. Time-resolved PL measurements taken at the emission peak wavelength of halide perovskite mixed with an electron quenching layer (PCBM; triangles) or hole (Spiro-OMeTAD; circles), along with stretched exponential adjustments for the PMMA data insulator coated films (black squares) and fits to interrupted samples employing the diffusion model described in the text. A pulsed excitation source (from 0.3 to 10 MHz) at 507 nm with a fluence of 30 nJ/cm2 found on the glass substrate side.
[0078] Figure 36 shows a cross-sectional SEM image of a thick 270 nm mixed halide absorption layer with an upper hole quenching layer of Spiro-OMeTAD.
[0079] Figure 37 shows the photoluminescence disintegration for a CH3NH3Pbl3-xClx mixed organolead triiodide perovskite film (black squares) and a CH3NH3PbI3 organolead triiodide perovskite film (gray squares), coated with PMMA. Lifetimes ye quoted as the time taken to reach 1/e of the initial intensity. DETAILED DESCRIPTION OF THE INVENTION
[0080] The invention provides an optoelectronic device comprising a photoactive region. The photoactive region comprises: an n-type region comprising at least one n-type layer; a p-type region comprising at least one p-type layer; and, disposed between the n-type region and the p-type region: a layer of a perovskite semiconductor without open porosity.
[0081] The term "photoactive region", as used herein, refers to a region in the optoelectronic device that (i) absorbs light, which can then generate free charge carriers; or (ii) accept charge, from both electrons and holes, which can subsequently recombine and emit light.
[0082] The term "semiconductor" as used herein refers to a material with electrical conductivity intermediate in magnitude between that of a conductor and a dielectric. A semiconductor can be an n-type semiconductor, a p-type semiconductor, or an intrinsic semiconductor.
[0083] As used here, the term "n-type region" refers to a region of one or more electron-carrying materials (ie, n-type). Similarly, the term "n-type layer" refers to a layer of a material carrying the electron (ie, an n-type). An electron-carrying material (ie, an n-type) can be a single electron-carrying compound or elementary material, or a mixture of two or more electron-carrying compounds or elementary materials. An electron transporting compound or elemental material may be doped or undoped with one or more doping elements.
[0084] As used herein, the term "p-type region" refers to a region of one or more hole-carrying materials (ie, p-type). Similarly, the term "p-type layer" refers to a layer of a hole-carrying material (i.e., a p-type). A hole-carrying material (i.e., a p-type) can be a single hole-carrying compound or elemental material, or a mixture of two or more hole-carrying compounds or elemental materials. A hole-carrying compound or elemental material may be doped or undoped with one or more doping elements.
[0085] The term "perovskite", as used herein, refers to a material with a three-dimensional crystal structure related to that of CaTiO3 or a material comprising a layer of material, wherein the layer has a structure related to that of CaTiO3. The structure of CaTiO3 can be represented by the formula ABX3, where A and B are cations of different sizes and X is an anion. In the unit cell, the A cations are at (0,0,0), the B cations are at (1/2, 1/2, 1/2), and the X anions are at (1/2, 1/2, 0). The A cation is generally larger than the B cation. The skilled person will observe that when A, B and X are varied, the different ion sizes can cause the perovskite material structure to distort away from the structure adopted by CaTiO3 to the distorted structure. of low symmetry. Symmetry should also be less if the material comprises a layer that has a structure related to that of CaTiO3. Materials comprising a layer of the perovskite material are well known. For example, the structure of materials adopting K2NiF4 type structure which comprises a layer of perovskite material. The skilled person will observe that a perovskite material can be represented by the formula [A][B][X]3, where [A] is at least one cation, [B] is at least one cation, and [X] is at least an anion. When the perovskite comprises more than one A cation, the different A cations can be distributed in the A sites in an ordered or a disordered manner. When the perovskite comprises more than one B cation, the different B cations can be distributed in the B sites in an ordered or a disordered manner. When the perovskite comprises more than one X anion, the different X anions can be distributed at the X sites in an ordered or a disordered manner. The symmetry of a perovskite comprising more than one A cation, more than one B cation, or more than one X cation must be lower than that of CaTiO3.
[0086] As mentioned in the previous paragraph, the term "perovskite", as used herein, refers to (a) a material with a three-dimensional crystal structure related to that of CaTiO3 or (b) a material comprising a layer of material, in that the layer has a structure related to that of CaTiO3. Although both categories of perovskite can be employed in the devices according to the invention, it is preferable in some circumstances to use a perovskite of the first category, (a), i.e. a perovskite having a three-dimensional (3D) crystal structure. Such perovskites typically comprise a 3D network of perovskite unit cells without any separation between the layers. Perovskites of the second category, (b), on the other hand, include perovskites having a two-dimensional (2D) layered structure. Perovskites having a 2D layer structure may comprise perovskite unit cell layers which are separated by (interleaved) molecules; an example of such a 2D layer perovskite is [2-(1-cyclohexenyl)ethylammonium]2PbBr4. 2D-layer perovskites tend to have high exciton binding energies, which favors the generation of bound electron-hole pairs (exxons), rather than free charge carriers, under photoexcitation. Bonded electron-hole pairs may not be mobile enough to reach p-type or n-type contact where they can then transfer (ionize) and generate free charge. Consequently, in order to generate free charge, the exciton binding energy has to be exceeded, which represents an energy cost for the charge generation process and results in a lower voltage on a photovoltaic cell and a lower efficiency. In contrast, perovskites having a 3D crystal structure tend to have much lower exciton binding energies (on the order of thermal energy) and can therefore generate free carriers directly following photoexcitation. Thus, the perovskite semiconductor employed in the devices and processes of the invention is preferably a perovskite of the first category, (a), that is, a perovskite having a three-dimensional crystal structure. This is particularly preferable when the optoelectronic device is a photovoltaic device.
[0087] The perovskite semiconductor employed in the present invention, in said layer of a perovskite semiconductor without open porosity, is typically one that is capable of (i) absorbing light, and thereby generating free charge carriers; and/or (ii) emission of light, through the acceptance of charge, from both electrons and holes, which subsequently recombine and emit light. Thus, the perovskite employed is typically a light-emitting and/or light-absorbing perovskite.
[0088] As the skilled person will observe, the perovskite semiconductor employed in the present invention, in said layer of a perovskite semiconductor without open porosity, may be a perovskite that acts as an electron-carrying semiconductor, of type n when photo-doped. Alternatively, it may be a perovskite that acts as a p-type hole-carrying semiconductor when photo-doped. Thus, the perovskite may be n-type or p-type, or it may be an intrinsic semiconductor. In preferred embodiments, the perovskite employed is one that acts as an electron-carrying semiconductor, of the n-type when photo-doped.
[0089] Typically, the perovskite semiconductor employed in the present invention is a photosensitizing material, that is, a material that is capable of performing both photogeneration and charge (electron or hole) transport.
[0090] As used herein, the term "porous" refers to a material within which pores are arranged. Thus, for example, in a porous support material, the pores are the volumes within the support in which there is no support material. Individual pores can be the same or different sizes. Pore size is defined as the “pore size”. The limiting pore size, for most phenomena in which porous solids are involved, is that of its smallest dimension, which, in the absence of any other precision, is referred to as the pore width (i.e., the width of a pore). slit-shaped pore, the diameter of a spherical or cylindrical pore, etc.). To avoid an illusory shift in scale when comparing slit-shaped and cylindrical pores, one should use the diameter of a cylindrical pore (rather than its radius) as its "pore width" (J. Rouquerol and others, " Recommendations for the Characterization of Porous Solids", Pure & Appl. Chem., Vol. 66, No. 8, pp.1739-1758, 1994). The following definitions and distinctions were adopted in earlier IUPAC documents (KSW Sing, et al., Pure and Appl. Chem., vol .57, n04, pp 603-919, 1985; and IUPAC "Manual on Catalyst Characterization" , J. Haber, Pure and Appl Chem., vol.63, pp. 1227-1246, 1991):
[0091] -- Micropores have widths (ie pore sizes) smaller than 2 nm.
[0092] -- Mesopores have widths (ie pore sizes) from 2 nm to 50 nm.
[0093] -- Macropores have widths (ie pore sizes) of more than 50 nm.
[0094] The pores in one can include "closed" pores as well as open pores. A closed pore is a pore in a material that is an unbound cavity, that is, a pore that is isolated within the material and not bound by any other and which cannot, for that reason, be accessed by means of a fluid ( e.g. a liquid such as a solution) in which the material is exposed. An "open pore" on the other hand would be accessible by such a fluid. The concepts of open and closed porosity are discussed in detail in J. Rouquerol et al., "Recommendations for the Characterization of Porous Solids", Pure & Appl. Chem., Vol. 66, No. 8, pp.1739-1758, 1994.
[0095] Open porosity, for this reason, refers to the fraction of the total volume of porous material in which the fluid flows can effectively occur. For this reason, it excludes closed pores. The term "open porosity" is interchangeable with the terms "bonded porosity" and "effective porosity", and in the art is generally reduced simply to "porosity". (The perovskite semiconductor present in the "layer of a perovskite semiconductor without open porosity", in the optoelectronic device of the invention, cannot therefore be said to be a "porous perovskite".)
[0096] The term "no open porosity", as used here, therefore refers to a material with no effective porosity.
[0097] The optoelectronic device of the present invention comprises a layer of a perovskite semiconductor without open porosity. This layer, and the perovskite semiconductor within it, are without open porosity. The perovskite semiconductor in the layer is therefore not infiltrated by, or any of the n-type material(s) in the n-type region, and likewise is not infiltrated by, or any of the n-type material(s). p in the p-type region. Preferably, the perovskite semiconductor in that layer typically forms a flat heterojunction with either the p-type or n-type region, or in some cases forms the flat heterojunctions with both the n-type region and the p-type region.
[0098] Likewise, when the perovskite semiconductor layer without open porosity is a "buffering layer", which is arranged in a first layer comprising a support material and a perovskite semiconductor, the buffer layer is not infiltrated by the supporting material otherwise, because the buffer layer and the perovskite semiconductor inside the buffer layer are without open porosity. The perovskite in the first layer, on the other hand (which is generally the same perovskite compound as the perovskite compound in the buffer layer), is typically disposed in the pores of the supporting material and can therefore be the referred to being "infiltrated" by the support material.
[0099] In some embodiments of the optoelectronic device of the present invention, the perovskite semiconductor layer without open porosity is non-porous. The term "non-porous" as used herein refers to a material without any porosity, that is, without open porosity and also without closed porosity.
[0100] Generally speaking, the perovskite semiconductor layer without open porosity consists essentially of the perovskite semiconductor. A perovskite is a crystalline compound. Thus, the perovskite semiconductor layer without open porosity typically consists essentially of perovskite crystallites. In some embodiments, the perovskite semiconductor layer without open porosity consists of the perovskite semiconductor. Thus, typically the perovskite semiconductor layer without open porosity consists of perovskite crystallites.
[0101] The perovskite semiconductor layer without open porosity is, in general, in contact with at least one of the n-type region or the p-type region.
[0102] The perovskite semiconductor layer without open porosity typically forms a flat heterojunction with the n-type region or the p-type region. Either the n-type region or the p-type region can be arranged in the perovskite semiconductor layer without open porosity, but as explained above, since the perovskite semiconductor layer is without open porosity in the n-type or p-type infiltrates the perovskite semiconductor to form a bulky heterojunction; preferably it generally forms a flat heterojunction with the perovskite semiconductor. Typically, the perovskite semiconductor layer without open porosity forms a flat heterojunction with the n-type region.
[0103] In some embodiments, the perovskite semiconductor layer without open porosity is in contact with both the n-type region and the p-type region. In such embodiments, there must also be another layer (such as a "first layer" comprising a support material and a perovskite semiconductor) separating the non-open porosity perovskite semiconductor layer from the n-type region or the non-open porosity region. type p. As explained above, since the perovskite semiconductor layer is without open porosity, in such embodiments neither p-type nor n-type region material infiltrates the perovskite semiconductor to form a bulky heterojunction; preferably, it generally forms a flat heterojunction with the perovskite semiconductor. In this way, the perovskite semiconductor layer without open porosity can form plane heterojunctions with both p-type and n-type regions on either side of the layer. Thus, in some embodiments of the optoelectronic device of the invention, the perovskite semiconductor layer forms a first flat heterojunction with the n-type region and a second flat heterojunction with the p-type region.
[0104] The optoelectronic device of the invention is typically a thin film device.
[0105] Generally, the layer thickness of perovskite semiconductor without open porosity is from 10 nm to 100 μm. More typically, the thickness of the perovskite semiconductor layer without open porosity is 10 nm to 10 μm. Preferably, the layer thickness of the perovskite semiconductor without open porosity is from 50 nm to 1000 nm, for example from 100 nm to 700 nm. The thickness of the perovskite semiconductor layer is many times greater than 100 nm. The thickness can, for example, be from 100 nm to 100 µm, or for example from 100 nm to 700 nm.
[0106] In order to provide highly efficient photovoltaic devices, the absorption of the absorber/photoactive region should ideally be maximized in order to generate an optimal amount of current. Consequently, when employing a perovskite as the absorber in a solar cell, the thickness of the perovskite layer should ideally be on the order of from 300 to 600 nm in order to absorb most of the sunlight across the visible spectrum. In particular, in a solar cell the perovskite layer must generally be thicker than the absorption depth (which is defined as the thickness of the film required to absorb 90% of incident light of a given wavelength, which for the perovskite materials of interest is typically above 100 nm if significant light absorption is required over the entire visible spectrum (from 400 to 800 nm)), when using a photoactive layer in photovoltaic devices with a thickness of less than 100 nm can be detrimental to device performance.
[0107] In contrast, electroluminescent (light emitting) devices do not need to absorb light and are therefore not forced by the depth of absorption. Furthermore, in practice the p-type and n-type contacts of electroluminescent devices are typically chosen so that, once an electron or hole is injected into one side of the device, it will not flow out of the other (i.e., they are selected in order to only inject or collect a single carrier), regardless of the photoactive layer thickness. In essence, the charge carriers are prevented from transferring outside the photoactive region and will thus be available to recombine and generate the photons, and can therefore make use of a photoactive region that is significantly thinner.
[0108] Typically, for this reason, when the optoelectronic device is a photovoltaic device, the thickness of the perovskite semiconductor layer is greater than 100 nm. The thickness of the perovskite semiconductor layer in the photovoltaic device can, for example, be from 100 nm to 100 μm, or, for example, from 100 nm to 700 nm. The thickness of the perovskite semiconductor layer in the photovoltaic device can, for example, be from 200 nm to 100 μm, or, for example, from 200 nm to 700 nm.
[0109] As used herein, the term "thickness" refers to the average thickness of a component of an optoelectronic device.
[0110] The inventors have shown that a thin support can be employed to seed the growth of the photoactive perovskite layer where most of the photoactivity (eg light absorption) occurs in a buffer layer that forms the above support. This buffer layer is the above-mentioned layer of perovskite semiconductor without open porosity, and, in these embodiments, a "first layer" separates that buffer layer from either the n-type region or the p-type region.
[0111] Thus, in some embodiments, said photoactive region of the device comprises:
[0112] said n-type region;
[0113] said p-type region; and, arranged between the n-type region and the p-type region:
[0114] (i) a first layer comprising a support material and a perovskite semiconductor; and
[0115] (ii) a buffer layer disposed on said first layer, which buffer layer is said layer of a perovskite semiconductor without open porosity.
[0116] The perovskite semiconductor in the buffer layer is in contact with the perovskite semiconductor in the first layer.
[0117] Since the perovskite in the first layer and the perovskite in the buffer layer are often deposited together in the same step, typically by the same vapor deposition or solution deposition step, the perovskite semiconductor in the buffer layer It is generally produced from the same perovskite compound as the perovskite semiconductor in the first layer.
[0118] Unlike the first layer, which comprises both the support material and the perovskite semiconductor, the buffer layer does not comprise the support material. As explained above, the buffer layer, which is said layer of a perovskite semiconductor without open porosity, typically consists essentially of, or consists of crystallites of the perovskite semiconductor. The buffer layer generally, for this reason, consists essentially of the perovskite semiconductor. In some embodiments, the buffer layer consists of the perovskite semiconductor.
[0119] The first layer comprises said support material and said perovskite semiconductor arranged on the surface of the support material. The term "support material" as used herein refers to a material whose function(s) include acting as a physical support for another material. In the present case, the support material acts as the support for the perovskite semiconductor present in the first layer. The perovskite semiconductor is disposed, or supported on, the surface of the supporting material. The support material is generally porous, meaning it typically has an open porous structure. Thus, the "surface" of the support material at this point typically refers to the pore surfaces in the support material. In this way, the perovskite semiconductor in the first layer is typically disposed on the pore surfaces in the support material.
[0120] In some embodiments, the support material is porous and the perovskite semiconductor in the first layer is arranged in the pores of the support material. The effective porosity of said supporting material is generally at least 50%. For example, an effective porosity can be around 70%. In one embodiment, the effective porosity is at least 60%, for example at least 70%.
[0121] The support material is generally mesoporous. The term "mesoporous", as used herein, means that the average pore size of the pores in the material is from 2 nm to 50 nm. The individual pores can be of different sizes and can be any shape.
[0122] Alternatively, the support material can be macroporous. The term "macroporous", as used herein, means that the average pore size of the pores in the material is greater than 2 nm. In some embodiments, the pore size in the support material, when it is macroporous, is greater than 2 nm and equal to or less than 1 μm, or, for example, greater than 2 nm and equal to or less than than 500 nm, more preferably greater than 2 nm and equal to or less than 200 nm.
[0123] The support material may be a charge-carrying support material (eg, an electron-carrying material such as titania, or alternatively a hole-carrying material) or a dielectric material such as alumina. The term "dielectric material", as used herein, refers to material that is an electrical insulator or a very poor conductor of electrical current. The term dielectric therefore excludes semiconductor materials such as titania. The term dielectric, as used herein, typically refers to materials having a band gap of equal to or greater than 4.0 eV. (The band gap of titania is about 3.2 eV.) The skilled person is naturally able to measure the band gap of a semiconductor, employing well-known procedures and requiring no undue experimentation. For example, the semiconductor bandwidth can be estimated by building a photovoltaic diode or solar cell from the semiconductor and determining the spectrum of photovoltaic action. The monochromatic photon energy, at which the photocurrent starts to be generated by the diode, can be taken as the semiconductor band gap; one such method was employed by Barkhouse and others, Prog. Photovolt: Res. App. 2012; 20:611. References herein to semiconductor band gap means the band gap as measured by this method, i.e. the band gap as determined by recording the spectrum of photovoltaic action of a photovoltaic diode or solar cell made from the semiconductor and observing the monochromatic photon energy at which the significant photocurrent begins to be generated.
[0124] Generally, the perovskite semiconductor in the first layer (whose layer also comprises the support material) contacts one of the ne-type p-type regions, and the perovskite semiconductor in the buffer layer contacts the other of the ne-type regions of type p. Typically, the perovskite semiconductor in the buffer layer forms a flat heterojunction with the region it is in contact with, that is, with the p-type region or the n-type region.
[0125] In a preferred embodiment, the perovskite semiconductor in the buffering layer contacts the p-type region, and the perovskite semiconductor in the first layer contacts the n-type region. Generally, in this embodiment, the supporting material is either an electron-carrying supporting material or a dielectric supporting material. Typically, the perovskite semiconductor in the buffer layer forms a flat heterojunction with the p-type region.
[0126] In another embodiment, however, the perovskite semiconductor in the buffering layer contacts the n-type region, and the perovskite semiconductor in the first layer contacts the p-type region. Typically, in this embodiment, the support material is a hole-carrying support material or a dielectric support material. Typically, the perovskite semiconductor in the buffer layer forms a flat heterojunction with the n-type region.
[0127] The thickness of the buffer layer is generally greater than the thickness of the first layer. Most of the photoactivity (eg light absorption) for this reason usually occurs in a buffer layer.
[0128] The thickness of the buffer layer is typically from 10 nm to 100 μm. More typically, the thickness of the buffer layer is from 10 nm to 10 μm. Preferably, the thickness of the buffer layer is from 50 nm to 1000 nm, or, for example, from 100 nm to 700 nm.
[0129] The thickness of the buffer layer can, for example, be from 100 nm to 100 μm, or, for example, from 100 nm to 700 nm. A buffer layer having a thickness of at least 100 nm is generally preferred.
[0130] The thickness of the first layer, on the other hand, is often from 5 nm to 1000 nm. More typically, it is from 5 nm to 500 nm, or, for example, from 30 nm to 200 nm.
[0131] The perovskite semiconductor employed in the present invention, in said layer of a perovskite semiconductor without open porosity, and, when present, in said first layer, is typically one that is capable of (i) absorbing light, and hence mode, generating free charge carriers; and/or (ii) emission of light, through the acceptance of charge, from both electrons and holes, which subsequently recombine and emit light.
[0132] Thus, the perovskite employed is typically a light-emitting and/or light-absorbing perovskite.
[0133] Generally, perovskite is a light absorbing material. Typically, a perovskite is employed that is capable of absorbing light having a wavelength from 300 to 2000 nm (i.e. a perovskite that is capable of absorbing light having a wavelength that decreases anywhere within this range ). More typically, the perovskite employed is one that is capable of absorbing light having a wavelength in the range from 300 to 1200 nm, or, for example, capable of absorbing light having a wavelength from 300 to 1000 nm. . More typically, the perovskite employed is one that is capable of absorbing light having a wavelength anywhere in the range from 300 to 800 nm.
[0134] The perovskite semiconductor employed in the optoelectronic device of the invention preferably has a band gap that is narrow enough to allow excitation of electrons by incident light. A band gap of 3.0 eV or less is particularly preferred, especially when the optoelectronic device is a photovoltaic device, because such a band gap is small enough for sunlight to excite electrons through it. Certain perovskites, including some oxide perovskites and the 2D layer perovskites, have swath openings that are wider than 3.0 eV, and are therefore less preferred for use in photovoltaic devices than perovskites that have a range opening of 3.0 eV or less. Such perovskites include CaTiO3, SrTiO3 and CaSrTiO3:Pr3+, which have band openings of about 3.7 eV, 3.5 eV and 3.5 eV respectively.
[0135] Thus, the perovskite semiconductor employed in the optoelectronic device of the invention typically has a band gap of equal to or less than 3.0 eV. In some embodiments, the perovskite band gap is less than or equal to 2.8 eV, for example, equal to or less than 2.5 eV. The band gap may, for example, be less than or equal to 2.3 eV, or, for example, less than or equal to 2.0 eV.
[0136] Generally, the range opening is at least 0.5 eV. Thus, the perovskite band gap can be from 0.5 eV to 2.8 eV. In some embodiments it is from 0.5 eV to 2.5 eV, or, for example, from 0.5 eV to 2.3 eV. The perovskite band gap can, for example, be from 0.5 eV to 2.0 eV. In other embodiments, the perovskite band gap may be from 1.0 eV to 3.0 eV, or, for example, from 1.0 eV to 2.8 eV. In some embodiments it is from 1.0 eV to 2.5 eV, or, for example, from 1.0 eV to 2.3 eV. The range gap of the perovskite semiconductor can, for example, be from 1.0 eV to 2.0 eV.
[0137] Perovskite band gap is more typically 1.2 eV to 1.8 eV. The range openings of organometal halide perovskite semiconductors, for example, are typically in this range and may, for example, be about 1.5 eV or about 1.6 eV. Thus, in one embodiment, the perovskite band gap is from 1.3 eV to 1.7 eV.
[0138] The perovskite semiconductor employed in the optoelectronic device of the invention typically comprises at least one anion selected from halide anions and chalcogenide anions.
[0139] The term "halide" refers to an anion of a group of 7 elements, that is, of a halogen.
[0140] Typically, halide refers to a fluoride anion, a chloride anion, a bromide anion, an iodide anion, or an astatide anion. The term "chalcogenide anion" as used herein refers to an anion of a group of 6 elements, that is, of a chalcogen. Typically, chalcogenide refers to an oxide anion, a sulfide anion, a selenide anion, or a telluride anion.
[0141] In the optoelectronic device of the invention, the perovskite often comprises a first cation, a second cation, and said at least one anion.
[0142] As the skilled person will observe, perovskite may comprise other cations or other anions. For example, perovskite may comprise two, three or four different first cations; two, three or four different second cations; or two, three of four different anions.
[0143] Typically, in the optoelectronic device of the invention, the second cation in the perovskite is a metal cation. The metal may be selected from tin, lead or copper, and is preferably selected from tin and lead.
[0144] More typically, the second cation is a divalent metal cation. For example, the second cation can be selected from d C 2+ Sr2+ Cd2+ C 2+ Ni2+ Mn2+ F 2+ C 2+ Pd2+ G 2+ Sn2+ Pb2+ Sn2+ of Ca , Sr , Cd , Cu , Ni , Mn , Fe , Co, Pd, Ge, Sn, Pb, Sn, Yb2+ and Eu2+. The second cation can be selected from Sn2+, Pb2+ and Cu2+. Generally, the second cation is selected from Sn2+ and Pb2+.
[0145] In the optoelectronic device of the invention, the first cation in the perovskite is usually an organic cation.
[0146] The term "organic cation" refers to a cation comprising carbon. The cation may comprise other elements, for example the cation may comprise hydrogen, nitrogen or oxygen.
[0147] Generally, in the optoelectronic device of the invention, the organic cation has the formula (R1R2R3R4N)+, where:
[0148] R1 is hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl;
[0149] R2 is hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl;
[0150] R3 is hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl; and
[0151] R4 is hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl.
[0152] Alternatively, the organic cation may have the formula (R5NH3)+, where: R5 is hydrogen, or substituted or unsubstituted C1-C20 alkyl. For example, R5 can be methyl or ethyl. Typically, R5 is methyl.
[0153] In some embodiments, the organic cation has the formula (R5R6N = CH - NR7R8)+, wherein: R5 is hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl; R6 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl; R7 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl; and R8 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl.
[0154] Typically, R5 in the cation (R5R6N = CH - NR7R8)+, is hydrogen, methyl or ethyl, R7 is hydrogen, methyl or ethyl, and R8 is hydrogen, methyl or ethyl. For example, R5 can be hydrogen or methyl, R6 can be hydrogen or methyl, R7 can be hydrogen or methyl, and R8 can be hydrogen or methyl.
[0155] The organic cation can, for example, have the formula (H2N=CH-NH2)+.
[0156] As used herein, an alkyl group can be a substituted or unsubstituted branched or straight chain saturated radical, it is often a substituted or an unsubstituted straight chain saturated radical, more often a saturated chain radical unsubstituted linear. A C1-C20 alkyl group is a substituted or unsubstituted branched or straight chain saturated hydrocarbon radical. Typically C1-C10 alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, or C1-C6 alkyl, for example methyl, ethyl, propyl, butyl, pentyl or hexyl , or C1-C4 alkyl, for example methyl, ethyl, i-propyl, n-propyl, t-butyl, s-butyl or n-butyl.
[0157] When an alkyl group is substituted it typically bears one or more substituents selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted aryl (as defined herein), cyano, amino, C1-C10 alkylamino, di (C1-C10)alkylamino, arylamino, diarylamino, arylalkylamino, amido, acylamido, hydroxy, oxo, halo, carboxy, ester, acyl, acyloxy, C1-C20 alkoxy, aryloxy, haloalkyl, sulfonic acid, sulfhydryl (i.e. thiol, -SH), C1-C10 alkylthio, arylthio, sulfonyl, phosphoric acid, phosphate ester, phosphonic acid and phosphonate ester. Examples of substituted alkyl groups include haloalkyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl and alkaryl groups. The term alkaryl, as used herein, refers to a C1-C20 alkyl group in which at least one hydrogen atom has been replaced with an aryl group. Examples of such groups include, but are not limited to, benzyl (phenylmethyl, PhCH2-), benzhydryl (Ph2CH-), trityl (triphenylmethyl, Ph3C-), phenethyl (phenylethyl, Ph-CH2CH2-), styryl (Ph-CH =CH-), cinnamyl (Ph-CH=CH-CH2-).
[0158] Typically a substituted alkyl group carries 1, 2 or 3 substituents, for example 1 or 2.
[0159] An aryl group is a substituted or unsubstituted monocyclic or bicyclic aromatic group that typically contains from 6 to 14 carbon atoms, preferably from 6 to 10 carbon atoms in the ring portion. Examples include phenyl, naphthyl, indenyl and indanyl groups. An aryl group is either substituted or unsubstituted. When an aryl group as defined above is substituted typically bears one or more substituents selected from C1-C6 alkyl which is unsubstituted (to form an aralkyl group), aryl which is unsubstituted, cyano, amino, C1- C10, di(C1-C10)alkylamino, arylamino, diarylamino, arylalkylamino, amido, acylamido, hydroxy, halo, carboxy, ester, acyl, acyloxy, C1-C20 alkoxy, aryloxy, haloalkyl, sulfhydryl (i.e. thiol, -SH ), C1-10 alkylthio, arylthio, sulfonic acid, phosphoric acid, phosphate ester, phosphonic acid and sulfonyl phosphonate ester. Typically carries 0, 1, 2 or 3 substituents. A substituted aryl group may be substituted at both positions with a single C1-C6 alkylene group, or with a bidentate group represented by the formula -X-(C1-C6)alkylene, or -X-(C1-C6)alkylene -X-, wherein X is selected from O, S and NR, and wherein R is H, aryl or C1-C6 alkyl. Thus a substituted aryl group can be an aryl group fused to a cycloalkyl group or to a heterocyclyl group. The ring atoms of an aryl group may include one or more heteroatoms (as in a heteroaryl group). Such an aryl group (a heteroaryl group) is a substituted or unsubstituted mono- or bicyclic heteroaromatic group that typically contains from 6 to 10 atoms in the ring portion including one or more heteroatoms. It is generally a 5- or 6-membered ring, containing at least one heteroatom selected from O, S, N, P, Se and Si. It may contain, for example, 1, 2 or 3 heteroatoms. Examples of heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, pyrazolidinyl, pyrrolyl, oxazolyl, oxadiazolyl, isoxazolyl, thiadiazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, quinolyl and isoquinolyl. A heteroaryl group may be substituted or unsubstituted, for example, as specified above for aryl. Typically carries 0, 1, 2 or 3 substituents.
[0160] Mainly, in the optoelectronic device of the invention, R1 in the organic cation is hydrogen, methyl or ethyl, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, methyl or ethyl, and R4 is hydrogen, methyl or ethyl. For example, R1 can be hydrogen or methyl, R2 can be hydrogen or methyl, R3 can be hydrogen or methyl, and R4 can be hydrogen or methyl.
[0161] Alternatively, the organic cation may have the formula (R5NH3)+, where: R5 is hydrogen, or substituted or unsubstituted C1-C20 alkyl. For example, R5 can be methyl or ethyl. Typically, R5 is methyl.
[0162] In one embodiment, the perovskite is a mixed anion perovskite comprising two or more different anions selected from halide anions and chalcogenide anions. Generally, said two or more different anions are two or more different halide anions.
[0163] Thus, the perovskite employed may be a mixed anion perovskite comprising a first cation, a second cation, and two or more different anions selected from halide anions and chalcogenide anions. For example, mixed anion perovskite may comprise two different anions and, for example, the anions may be a halide anion and a chalcogenide anion, two different halide anions or two different chalcogenide anions. The first and second cations may be as defined above. Thus, the first cation may be an organic cation, which may also be defined here. For example, it can be a cation of the formula (R1R2R3R4N)+, or of the formula (R5NH3)+, as defined above. Alternatively, the organic cation may be a cation of the formula [RsR6 = CH - R7R8]+ as defined above. The second cation can be a divalent metal cation For example, the second cation can be selected from Ca2+, Sr2+, Cd2+, Cu2+, Ni2+, Mn2+, Fe2+, Co2+, Pd2+, Ge2+, Sn2+, Pb2+, Yb2+ and Eu2+. Generally, the second cation is selected from Sn2+ and Pb2+.
[0164] In the optoelectronic device of the invention, the perovskite is generally a mixed halide perovskite, wherein the two or more different anions are two or more different halide anions. Typically these are two or three halide anions, more typically two different halide anions. Generally halide anions are selected from fluoride, chloride, bromide and iodide, for example chloride, bromide and iodide.
[0165] Often, in the optoelectronic device of the invention, perovskite is a perovskite compound of formula (I):
[0166] [A][B][X]3 (I)
[0167] in which:
[0168] [A] is at least one organic cation;
[0169] [B] is at least one metal cation; and
[0170] [X] is the said at least one anion.
[0171] The perovskite of formula (I) may comprise one, two, three or four different metal cations, typically one or two different metal cations. Likewise, the perovskite of formula (I) may, for example, comprise one, two, three or four different organic cations, typically one or two different organic cations. Likewise, the perovskite of formula (I) may comprise one, two, three or four different anions, typically two or three different anions.
[0172] The metal or organic cations in the perovskite compound of formula (I) may be as defined above. In this way, organic cations can be selected from cations of formula (R1R2R3R4N)+ and cations of formula (R5NH3)+ as defined above. Metal cations can be selected from divalent metal cations. For example, metal cations can be selected from d C 2+ Sr2+ Cd2+ C 2+ Ni2+ Mn2+ F 2+ C 2+ Pd2+ G 2+ Sn2+ Pb2+ Yb2+ from Ca , Sr , Cd , Cu , Ni , Mn , Fe , Co , Pd , Ge , Sn , Pb , Yb and Eu2+. Generally, the metal cation is Sn2+ or Pb2+.
[0173] The organic cation can, for example, be selected from cations of the formula (R5R6N = CH - NR7R8)+, and cations of the formula (H2N = CH - NH2)+, as defined above. Metal cations can be selected from divalent metal cations. For example, metal cations can be selected from Ca2+, Sr2+, Cd2+, Cu2+, Ni2+, Mn2+, Fe2+, Co2+, Pd2+, Ge2+, Sn2+, Pb2+, Yb2+ and Eu2+. Generally, the metal cation is Sn2+ or Pb2+.
[0174] Typically, [X] in formula (I) is two or more different anions selected from halide anions and chalcogenide anions. More typically, [X] is two or more different halide anions.
[0175] In one embodiment, the perovskite is a perovskite compound of formula (IA):
[0176] AB[X]3 (IA)
[0177] in which:
[0178] A is an organic cation;
[0179] B is a metal cation; and
[0180] [X] is two or more different halide anions.
[0181] Typically, [X] in formula (IA) is two or more different anions selected from halide anions and chalcogenide anions. Generally, [X] is two or more different halide anions. Preferably, [X] is two or three different halide anions. More preferably, [X] is two different halide anions. In another embodiment [X] is three different halide anions.
[0182] The metal or organic cations in the perovskite compound of formula (IA) may be as defined above. Thus, the organic cation can be selected from cations of the formula (R1R2R3R4N)+ and cations of the formula (R5NH3)+ as defined above. The metal cation may be a divalent metal cation. For example, the metal cation can be selected from Ca2+, Sr2+, Cd2+, Cu2+, Ni2+, Mn2+, Fe2+, Co2+, Pd2+, Ge2+, Sn2+, Pb2+, Yb2+ and Eu2+. Generally, the metal cation is Sn2+ or Pb2+.
[0183] The organic cation can, for example, be selected from cations of the formula (R5R6N = CH - NR7R8)+, and cations of the formula (H2N = CH - NH2)+, as defined above. The metal cation may be a divalent metal cation. For example, the metal cation can be selected from Ca2+, Sr2+, Cd2+, Cu2+, Ni2+, Mn2+, Fe2+, Co2+, Pd2+, Ge2+, Sn2+, Pb2+, Yb2+ and Eu2+. Generally, the metal cation is Sn2+ or Pb2+.
[0184] Typically, in the optoelectronic device of the invention, perovskite is a perovskite compound of formula (II):
[0185] ABX3-yX'y (II)
[0186] in which:
[0187] A is an organic cation;
[0188] B is a metal cation;
[0189] X is a first halide anion;
[0190] X' is a second halide anion that is different from the first halide anion; and
[0191] y is from 0.05 to 2.95.
[0192] Generally, y is from 0.5 to 2.5, for example from 0.75 to 2.25. Typically, y is from 1 to 2.
[0193] Again, in formula (II), the metal or organic cations may be as defined above. Thus the organic cation can be a cation of the formula (R1R2R3N)+ or, more typically, a cation of the formula (R5NH3)+, as defined above. The metal cation may be a divalent metal cation. For example, the metal cation can be selected from Ca2+, Sr2+, Cd2+, Cu2+, Ni2+, Mn2+, Fe2+, Co2+, Pd2+, Ge2+, Sn2+, Pb2+, Yb2+ and Eu2+. Generally, the metal cation is Sn2+ or Pb2+.
[0194] In some embodiments, the perovskite is a perovskite compound of formula (IIa):
[0195] ABX3ZX'3(1-Z) (IIa)
[0196] in which:
[0197] A is an organic cation of the formula (R5R6N = CH-NR7R8)+, wherein: R5 is hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl; R6 is hydrogen, not substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl; R7 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl; and R8 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl;
[0198] B is a metal cation;
[0199] X is a first halide anion;
[0200] X' is a second halide anion which is different from the first halide anion; and z is greater than 0 and less than 1.
[0201] Generally, z is from 0.05 to 0.95.
[0202] Generally, z is from 0.1 to 0.9. Z can, for example, be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, or z can be a range a from any of these values to any other of these values (for example, from 0.2 to 0.7, or from 0.1 to 0.8).
[0203] B, X and X' may be as defined above. The organic cation may, for example, be (R5R6 = CH - NR7R8)+, wherein: R5, R6, R7 and R8 are independently selected from hydrogen and substituted or unsubstituted C1-C6 alkyl. For example, the organic cation can be (H2N = CH - NH2)+.
[0204] Often, the optoelectronic device of the invention, the perovskite is a compound of selected perovskite from CH3NH3PbI3, CH3NH3PbBr3, CH3NH3PbCl3, CH3NH3PbF3, CH3NH3PbBrI2, CH3NH3PbBrCl2, CH3NH3PbIBr2, CH3NH3PbICl2, CH3NH3PbClBr2, CH3NH3PbI2Cl, CH3NH3SnBrI2, CH3NH3SnBrCl2, CH3NH3SnF2Br, CH3NH3SnIBr2 , CH3NH3SnICl2, CH3NH3SnF2I, CH3NH3SnClBr2, CH3NH3SnI2Cl and CH3NH3SnF2Cl.
[0205] For example, the optoelectronic device of the invention, the perovskite can be selected from CH3NH3PbBrI2, CH3NH3PbBrCl2, CH3NH3PbIBr2, CH3NH3PbICl2, CH3NH3PbClBr2, CH3NH3PbI2Cl, CH3NH3SnBrI2, CH3NH3SnBrCl2, CH3NH3SnF2Br, CH3NH3SnIBr2, CH3NH3SnICl2, CH3NH3SnF2I, CH3NH3SnClBr2, CH3NH3SnI2Cl and CH3NH3SnF2Cl.
[0206] Typically, perovskite is selected from CH3NH3PbBrI2, CH3NH3PbBrCl2, CH3NH3PbIBr2, CH3NH3PbICl2, CH3NH3PbClBr2, CH3NH3PbI2Cl, CH3NH3SnF2Br, CH3NH3SnICl2, CH3NH3SnF2I, CH3NH3SnI2SCl and CH3NH3Cl.
[0207] More typically, perovskite is selected from CH3NH3PbBrI2, CH3NH3PbBrCl2, CH3NH3PbIBr2, CH3NH3PbICl2, CH3NH3PbClBr2, CH3NH3PbI2Cl, CH3NH3SnF2Br, CH3NH3SnF2I and CH3NH3SnF2Cl.
[0208] Generally, perovskite is selected from CH3NH3PbBrI2, CH3NH3PbBrCl2, CH3NH3PbIBr2, CH3NH3PbICl2, CH3NH3SnF2Br, and CH3NH3SnF2I.
[0209] Often the perovskite employed is CH3NH3PbCl2I.
[0210] In some embodiments, the perovskite may be a perovskite of the formula (H2N = CH - NH2)Pbl3zBr3(1-z), where z is greater than 0 or less than 1. Z may be as defined. Upper.
[0211] The perovskite semiconductor employed in the optoelectronic device of the invention may comprise said mixed anion perovskite and a single anion perovskite, for example in a mixture, wherein said single anion perovskite comprises a first cation, a second cation and an anion selected from halide anions and chalcogenide anions; wherein the first and second cations are as defined herein for said mixed anion perovskite. For example, the optoelectronic device may comprise: CH3NH3PbICl2 and CH3NH3PbI3; CH3NH3PbICl2 and CH3NH3PbBr3; CH3NH3PbBrCl2 and CH3NH3PbI; or CH3NH3PbBrCl2 and CH3NH3PbBr3.
[0212] The optoelectronic device may comprise a perovskite of the formula (H2N = CH - NH2)Pbl3zBr3(1-z), where z is as defined here, and a single anion perovskite, such as, (H2N = CH - NH2 )PbI3 or (H2N = CH - NH2)PbBr3.
[0213] Alternatively, the perovskite semiconductor employed in the optoelectronic device of the invention may comprise more than one perovskite, wherein each perovskite is a mixed anion perovskite, and wherein said mixed anion perovskite is as defined herein. For example, the optoelectronic device may comprise two or three said perovskites. The optoelectronic device of the invention may, for example, comprise two perovskites wherein both perovskites are mixed anion perovskites. For example, the optoelectronic device may comprise: CH3NH3PbICl2 and CH3NH3PbIBr2; CH3NH3PbICl2 and CH3NH3PbBrI2; CH3NH3PbBrCl2 and CH3NH3PbIBr2; or CH3NH3PbBrCl2 and CH3NH3PbIBr2.
[0214] The optoelectronic device may comprise two different perovskites, where each perovskite is a perovskite of the formula (H2N = CH - NH2)Pbl3zBr3(1-z), where z is as defined here.
[0215] In some embodiments of the optoelectronic device of the invention, when [B] is a single metal cation that is Pb2+, one of said two or more different halide anions is iodide or fluoride; and when [B] is a single metal cation that is Sn2+ one of said two or more different halide anions is fluoride. Generally, in some embodiments of the optoelectronic device of the invention, one of said two or more different halide anions is iodide or fluoride. Typically, in some embodiments of the optoelectronic device of the invention, one of said two or more different halide anions is iodide and the other of said two or more different halide anions is fluoride or chloride. Often, in some embodiments of the optoelectronic device of the invention, one of said two or more different halide anions is fluoride. Typically, in some embodiments of the optoelectronic device of the invention, each: (a) one of said two or more different anions is fluoride and the other of said two or more different anions is chloride, bromide or iodide; or (b) one of said two or more different anions is odide and the other of said two or more different anions is fluoride or chloride. Typically, [X] is two different halide anions X and X'. Often, in the optoelectronic device of the invention, said divalent metal cation is Sn2+. Alternatively, in the optoelectronic device of the invention, said divalent metal cation may be Pb2+.
[0216] The n-type region in the optoelectronic device of the invention comprises one or more n-type layers. Often the n-type region is an n-type layer, that is, a single n-type layer. In other embodiments, however, the n-type region may comprise an n-type layer and an n-type exciton blocking layer. In cases where an n-type exciton blocking layer is employed, the n-type exciton blocking layer is generally disposed between the n-type layer and the layer(s) comprising the perovskite semiconductor.
[0217] An exciton blocking layer is a material that is of wider band opening than perovskite, but either has its conduction band or valence band closely matched with that of perovskite. If the conduction band (or lower energy levels of the unoccupied molecular orbital) of the exciton blocking layer are closely aligned with the perovskite conduction band, then electrons can pass from the perovskite into and through the exciton blocking layer. , or through the exciton blocking layer and into the perovskite, and we call this an n-type exciton blocking layer. An example of such is batocupoin, as described in {P. Peumans, A. Yakimov, and S. . Forrest, "Small molecular weight organic thin-film photodetectors and solar cells" J. Appl. Phys. 93, 3693 (2001)} and {Masaya Hirade, and Chihaya Adachi, "Small molecular organic photovoltaic cells with exciton blocking layer at anode interface for improved device performance" Appl. Phys. Lett. 99, 153302 (2011)}}.
[0218] An n-type layer is a layer of a material carrying the electron (ie, an n-type). The n-type material may be a single n-type elemental or composite material, or a mixture of two or more n-type elemental or composite materials, which may be doped or undoped with one or more doping elements.
[0219] The n-type layer employed in the optoelectronic device of the invention may comprise an organic or non-organic n-type material.
[0220] A suitable inorganic n-type material can be selected from a metal oxide, a metal sulfide, a metal selenide, a metal telluride, a perovskite, amorphous Si, an n-type group IV semiconductor , an n-type group III-V semiconductor, an n-type group II-VI semiconductor, an n-type group I-VII semiconductor, an n-type group IV-VI semiconductor, a group V semiconductor -VI n-type, an n-type group II-V semiconductor, any of which may be doped or undoped.
[0221] The n-type material can be selected from a metal oxide, a metal sulfide, a metal selenide, a metal telluride, amorphous Si, an n-type group IV semiconductor, a group IV semiconductor n-type III-V, an n-type group II-VI semiconductor, an n-type group I-VII semiconductor, an n-type group IV-VI semiconductor, an n-type group V-VI semiconductor , and an n-type group II-V semiconductor, either of which may be doped or undoped.
[0222] More typically, the n-type material is selected from a metal oxide, a metal sulfide, a metal selenide, and a metal telluride.
[0223] Thus, the n-type layer may comprise an inorganic material selected from titanium oxide, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, or cadmium, or an oxide of a mixture of two or more of said metals. For example, the n-type layer may comprise TiO2, SnO2, ZnO, Nb2O5, Ta2O5, WO3, W2O5, In2O3, Ga2O3, Nd2O3, PbO, or CdO.
[0224] Other suitable n-type materials that may be employed include cadmium, tin, copper, or zinc sulfides, including sulfides of a mixture of two or more of said metals. For example, the sulfide can be FeS2, CdS, ZnS or Cu2ZnSnS4.
[0225] The n-type layer may, for example, comprise a selenide of cadmium, zinc, indium, or gallium or a selenide of a mixture of two or more of said metals; or a telluride of cadmium, zinc, cadmium or tin, or a telluride of a mixture of two or more of said metals. For example, the selenide can be Cu(In,Ga)Se2. Typically, the telluride is a telluride of cadmium, zinc, cadmium or tin. For example, telluride can be CdTe.
[0226] The n-type layer may, for example, comprise an inorganic material selected from titanium oxide, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, cadmium, or an oxide of a mixing two or more of said metals; a cadmium, tin, copper, zinc sulfide or a sulfide of a mixture of two or more of said metals; a selenide of cadmium, zinc, indium, gallium or a selenide of a mixture of two or more of said metals; or a telluride of cadmium, zinc, cadmium or tin, or a telluride of a mixture of two or more of said metals.
[0227] Examples of other semiconductors which may be suitable n-type materials, for example if they are indoped, include semiconductors of group IV compounds; Si amorphous; group III-V semiconductors (eg gallium arsenide); group II-VI semiconductors (eg cadmium selenide); group I-VII semiconductors (e.g. cuprous chloride); group IV-VI semiconductors (eg lead selenide); group V-VI semiconductors (e.g. bismuth telluride); and group II-V semiconductors (eg cadmium arsenide).
[0228] Typically, the n-type layer comprises TiO2.
[0229] When the n-type layer is an inorganic material, for example TiO2 or any of the other materials listed above, it may be a compact layer of said inorganic material. Preferably, the n-type layer is a compact TiO2 layer.
[0230] Other n-type materials may also be employed, including electron-carrying organic and polymeric materials, and electrolytes. Suitable examples include, but are not limited to, a fullerene or a derivative of a fullerene derivative, electron-carrying organic material comprising perylene or a derivative thereof, or poly{[N,N0-bis(2-octyldodecyl)-naphthalene-1, 4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,50-(2,20-bitiophene)} (P(NDI2OD-T2)).
[0231] The p-type region in the optoelectronic device of the invention comprises one or more p-type layers. Often, the p-type region is a p-type layer, that is, a single p-type layer. In other embodiments, however, the p-type region may comprise a p-type layer and a p-type exciton blocking layer. In cases where a p-type exciton blocking layer is employed, the p-type exciton blocking layer is generally disposed between the p-type layer and the layer(s) comprising the perovskite semiconductor. If the valence band (or higher energy levels of the occupied molecular orbital) of the blocking layer of the exciton is closely aligned with the valence band of the perovskite, then holes can pass from the perovskite into and through the blocking layer of the exciton. exciton, or through the exciton blocking layer and into the perovskite, and we call this a p-type exciton blocking layer. An example of such is tris[4-(5-phenylthiophen-2-yl)phenyl]amine, as described in {Masaya Hirade, and Chihaya Adachi, "Small molecular organic photovoltaic cells with exciton blocking layer at anode interface for improved device performance "App. Phys. Lett. 99, 153302 (2011)}}.
[0232] A p-type layer is a layer of a hole-carrying material (ie, a p-type). The p-type material may be a single p-type elemental or composite material, or a mixture of two or more p-type elemental or composite materials, which may be doped or undoped with one or more doping elements.
[0233] The p-type layer employed in the optoelectronic device of the invention may comprise an organic or an inorganic p-type material.
[0234] Suitable p-type materials can be selected from molecular or polymeric hole carriers. The p-type layer employed in the optoelectronic device of the invention may, for example, comprise spiro-OMeTAD (2,2',7,7'-tetracys-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene )), P3HT (poly(3-hexylthiophene)), PCPDTBT (Poly[2,1,3-benzothiadiazol-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1- b:3,4-b']dithiophene-2,6-diyl]]), PVK (poly(N-vinylcarbazole)), HTM-TFSI (1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), Li- TFSI (lithium bis(trifluoromethanesulfonyl)imide) or tBP (tert-butylpyridine). Generally, p-type material is selected from spiro-OMeTAD, P3HT, PCPDTBT and PVK. Preferably, the p-type layer employed in the optoelectronic device of the invention comprises spiro-OMeTAD.
[0235] The p-type layer may, for example, comprise spiro-OMeTAD (2,2',7,7'-tetracys-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene)), P3HT (poly(3-hexylthiophene)), PCPDTBT (Poly[2,1,3-benzothiadiazol-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3) ,4-b']dithiophene-2,6-diyl]]), or PVK (poly(N-vinylcarbazole)).
[0236] Suitable p-type materials also include molecular hole transporters, polymeric hole transporters and copolymer hole transporters. The p-type material may, for example, be a hole-carrying molecular material, a polymer or copolymer comprising one or more of the following moieties: thiophenyl, phenylenyl, dithiazolyl, benzothiazolyl, diketopyrrolopyrrolyl, ethoxydithiophenyl, amino, triphenyl amino, carbozolyl, ethylene dioxythiophenyl, dioxythiophenyl, or fluorenyl. Thus, the p-type layer employed in the optoelectronic device of the invention may, for example, comprise any of the aforementioned hole-carrying polymers, copolymers or molecular materials.
[0237] Suitable p-type materials also include m-MTDATA (4,4',4"-tris(methylphenylphenylamino)triphenylamine), MeOTPD (N,N,N',N'-tetracis(4-methoxyphenyl)-benzidine ), BP2T (5,5'-di(biphenyl-4-yl)-2,2'-bithiophene), Di-NPB (N,N-Di-[(1-naphthyl)-N,N-diphenyl]- 1,1'-bphenyl)-4,4'-diamine), α-NPB (N,N'-di(naphthalen-1-yl)-N,N'-diphenyl-benzidine), TNATA (4,4' ,4"-tris-(N-(naphthylen-2-yl)-N-phenylamino)triphenylamine), BPAPF (9,9-bis[4-(N,N-bis-biphenyl-4-yl-amino)phenyl ]-9H-fluorene), spiro-NPB (N2,N7-Di-1-naphthalenyl-N2,N7-diphenyl-9,9'-spirobi[9H-fluorene]-2,7-diamine), 4P-TPD ( 4,4'-bis-(N,N-diphenylamino)-tetraphenyl), PEDOT:PSS and spiro-OMeTAD.
[0238] The p-type layer can be doped with an ionic salt or a base. The p-type layer can, for example, be doped with an ionic salt selected from HMI-TFSI (1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) and Li-TFSI (lithium bis(trifluoromethanesulfonyl)imide), or with a base which is tBP (tert-butylpyridine).
[0239] Additionally or alternatively, the p-type layer can be doped to increase the density of the hole. The p-type layer can, for example, be doped with NOBF4 (Nitrosonium Tetrafluoroborate), to increase the density of the hole.
[0240] In other embodiments, the p-type layer may comprise an inorganic hole carrier. For example, the p-type layer may comprise an inorganic hole carrier comprising an oxide of nickel, vanadium, copper or molybdenum; CuI, CuBr, CuSCN, Cu22O, CuO or CIS; a perovskite; Si amorphous; a p-type group IV semiconductor, a p-type groups III-V semiconductor, a p-type groups II-VI semiconductor, a p-type groups I-VII semiconductor, a p-type groups IV-VI semiconductor p-type, a p-type group V-VI semiconductor, and a p-type group II-V semiconductor, whose inorganic material can be doped or undoped. The p-type layer may be a compact layer of said inorganic hole carrier.
[0241] The p-type layer may, for example, comprise an inorganic hole carrier comprising an oxide of nickel, vanadium, copper or molybdenum; Cul, CuBr, CuSCN, Cu2O, CuO or CIS; Si amorphous; a p-type group IV semiconductor, a p-type groups III-V semiconductor, a p-type groups II-VI semiconductor, a p-type groups I-VII semiconductor, a p-type groups IV-VI semiconductor p-type, a p-type group V-VI semiconductor, and a p-type group II-V semiconductor, whose inorganic material can be doped or undoped. The p-type layer may, for example, comprise an inorganic hole carrier selected from Cul, CuBr, CuSCN, Cu2O, CuO and CIS. The p-type layer may be a compact layer of said inorganic hole carrier.
[0242] Typically, the p-type layer comprises a molecular or polymeric hole carrier, and the n-type layer comprises an inorganic n-type material. The p-type or polymeric molecular hole transporter can be any suitable molecular or polymeric hole transporter, for example any of those listed above. Likewise, the n-inorganic-type material may be any suitable n-type inorganic, for example, any of those listed above. In one embodiment, for example, the p-type layer comprises spiro-OMeTAD and the n-type layer comprises TiO 2 . Typically, in that embodiment, the n-type layer comprising TiO2 is a compact layer of TiO2.
[0243] In other embodiments, both the n-type layer and the p-type layer comprise the inorganic materials. Thus, the n-type layer may comprise an inorganic n-type material and the p-type layer may comprise an inorganic p-type material. The inorganic p-type material may be any suitable p-type inorganic, for example any of those listed above. Likewise, the n-inorganic-type material may be any suitable n-type inorganic, for example, any of those listed above.
[0244] In still other embodiments, the p-type layer comprises an inorganic p-type material (i.e., an inorganic hole carrier) and the n-type layer comprises a molecular or polymeric hole carrier. The inorganic p-type material may be any suitable p-type inorganic, for example any of those listed above. Likewise, the n-type or polymeric molecular hole transporter can be any n-type or polymeric molecular hole transporter, for example any of those listed above.
[0245] For example, the p-type layer may comprise an inorganic hole carrier and the n-type layer may comprise an electron-carrying material, wherein the electron-carrying material comprises a fullerene or a fullerene derivative, an electrolyte, or an electron transporting organic material, preferably wherein the electron transporting organic material comprises perylene or a derivative thereof, or poly{[N,N0-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis( dicarboximide)-2,6-diyl]-alt-5,50-(2,20-bitiophene)} (P(NDI2OD-T2)). The inorganic hole carrier may, for example, comprise an oxide of nickel, vanadium, copper or molybdenum; Cul, CuBr, CuSCN, Cu2O, CuO or CIS; a perovskite; Si amorphous; a p-type group IV semiconductor, a p-type groups III-V semiconductor, a p-type groups II-VI semiconductor, a p-type groups I-VII semiconductor, a p-type groups IV-VI semiconductor p-type, a p-type group V-VI semiconductor, and a p-type group II-V semiconductor, whose inorganic material can be doped or undoped. More typically, the inorganic hole carrier comprises an oxide of nickel, vanadium, copper or molybdenum; Cul, CuBr, CuSCN, Cu2O, CuO or CIS; a p-type group IV semiconductor, a p-type groups III-V semiconductor, a p-type groups II-VI semiconductor, a p-type groups I-VII semiconductor, a p-type groups IV-VI semiconductor p-type, a p-type group V-VI semiconductor, and a p-type group II-V semiconductor, whose inorganic material can be doped or undoped. Thus, the inorganic hole carrier may comprise an oxide of nickel, vanadium, copper or molybdenum; Cul, CuBr, CuSCN, Cu2O, CuO or CIS.
[0246] The following paragraphs concern the use of a second, p-type perovskite, in the p-type layer, or a second, n-type perovskite, in the n-type layer. (In preferred embodiments, however, neither the p-type layer nor the n-type layer comprises a perovskite. Thus, preferably, neither the p-type region nor the n-type region comprises a perovskite.)
[0247] When the p-type layer comprises an inorganic hole carrier which is a perovskite, the perovskite is different from the perovskite employed in said layer of a semiconductor of perovskite without open porosity, and, when present, in said "first layer " which also comprises the support material. Thus, when the p-type layer comprises an inorganic hole carrier which is a perovskite, the perovskite of the p-type layer is termed here a "second perovskite" (and the perovskite in said layer is a perovskite semiconductor without open porosity). , and, when present, in said first layer, is referred to herein as the "first perovskite").
[0248] Similarly, when the n-type layer comprises an inorganic electron carrier which is a perovskite, the perovskite must be different from the perovskite employed in said layer of a semiconductor of perovskite without open porosity, and, when present, in said " first layer" which also comprises the supporting material. Thus, when the n-type layer comprises an inorganic electron carrier which is a perovskite, the perovskite is referred to herein as a "second perovskite" (and the perovskite in said layer is a perovskite semiconductor without open porosity, and when present , in said "first layer", is referred to herein as the "first perovskite").
[0249] The skilled person will appreciate that the addition of a doping agent to a perovskite can be employed to control the charge transfer properties of that perovskite. Thus, for example, a perovskite which is an intrinsic material can be doped to form a p-type or an n-type material. Thus, the first perovskite and/or the second perovskite may comprise one or more doping agents. Typically the doping agent is a doping element.
[0250] The addition of different doping agents to different samples of the same material may result in different samples having different charge transfer properties. For example, adding a doping agent to a first sample of perovskite material can result in the first sample becoming an n-type material, while adding a different doping agent to a second sample of the same perovskite material may result in the second sample becoming a p-type material.
[0251] Thus, at least one of the first and second perovskites may comprise a doping agent. The first perovskite may, for example, comprise a doping agent which is not present in the or every second perovskite. Additionally or alternatively, the or one of the second perovskites may comprise a doping agent which is not present in the first perovskite. Thus, the difference between the first and second perovskites could be the presence or absence of a doping agent, or it could be the use of a different doping agent in each perovskite. Alternatively, the difference between the first and second perovskites cannot be in the doping agent, but rather the difference may be in the overall structure of the first and second perovskites.
[0252] The second perovskite, when present, may be a perovskite comprising a first cation, a second cation, and at least one anion.
[0253] In some embodiments, the second perovskite that is employed in the n-type or p-type layer, which is different from the first perovskite, is a perovskite compound of formula (IB):
[0254] [A][B][X]3 (IB)
[0255] where:
[0256] [A] is at least one organic cation or at least one Group I metal cation;
[0257] [B] is at least one metal cation; and
[0258] [X] is at least one anion.
[0259] As the learned person will observe, [A] can understand Cs+.
[0260] Generally, [B] comprises Pb2+ or Sn2+. More typically, [B] comprises Pb2+.
[0261] Typically, [X] comprises a halide anion or a plurality of different halide anions.
[0262] Generally, [X] comprises I-.
[0263] In some embodiments, [X] is two or more different anions, eg two or more different halide anions. For example, [X] may comprise I- and F-, I- and Br- or I- and CI-.
[0264] Generally, the perovskite compound of formula IB is CsPbl3 or CsSnI3. For example, the perovskite compound of formula (IB) may be CsPbl3.
[0265] Alternatively, the perovskite compound of formula (IB) may be CsPbI2Cl, CsPblClz, CsPbI2F, CsPbIF2, CsPbI2Br, CsPbIBr2, CsSnI2Cl, CsSnICl2, CsSnI2F, CsSnIF2, CsSnI2Br or CsSnIBr2. For example, the perovskite compound of formula (IB) may be CsPbI2Cl or CsPbICl2. Typically, the perovskite compound of formula (IB) is CsPbICl2.
[0266] In the perovskite compound of formula (IB): [X] may be one, two or more different anions as defined here, for example two or more different anions as defined here for the first perovskite; [A] generally comprises an organic cation as defined herein, as above for the first perovskite; and [B] typically comprises a metal cation as defined herein. The metal cation can be defined as higher for the first perovskite.
[0267] In some embodiments, the second perovskite is a perovskite as defined for the first perovskite above, with the proviso that the second perovskite is different from the first perovskite.
[0268] The support material that is employed in the embodiments of the optoelectronic device of the invention that comprises said first layer, can be a dielectric support material. Generally, the dielectric support material has a range opening of equal to or greater than 4.0 eV.
[0269] Generally, in the optoelectronic device of the invention, the dielectric support material comprises an oxide of aluminum, zirconium, silicon, yttrium or ytterbium. For example, the dielectric support material may comprise zirconium oxide, silica, alumina, ytterbium oxide or yttrium oxide; or alumina silicate. Often, dielectric support material comprises silica, or alumina. More typically, the dielectric support material comprises porous alumina.
[0270] Typically, in the optoelectronic device of the invention, the dielectric support material is mesoporous. Thus, typically, in the optoelectronic device of the invention, the dielectric support material comprises mesoporous alumina.
[0271] Alternatively, the support material may be an inorganic electron-carrying material, such as, for example, titania. Thus, for example, the support material may comprise an oxide of titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium or cadmium. For example, the support material may comprise TiO2, SnO2, ZnO, Nb2O5, Ta2O5, WO3, W2O5, ln2O3, Ga2O3, Nd2O3, PbO, or CdO. Often, the supporting material comprises a mesoporous titanium oxide, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium or cadmium or a mixture thereof. Titania, porous titania, and mesoporous titania are preferred. Typically, in such embodiments, the support material comprises porous, preferably mesoporous, titania.
[0272] The support material may, for example, comprise a hole-carrying inorganic material.
[0273] The support material may, on the other hand, be a hole-carrying inorganic material. Thus, the support material may, for example, comprise an oxide of nickel, vanadium, copper or molybdenum, Cul, CuBr, CuSCN, Cu2O, CuO or CIS.
[0274] The porosity of the support material used in the modalities of the optoelectronic device of the invention, which comprises said first layer, is generally equal to or greater than 50%. For example, the porosity can be about 70%. In one embodiment, the porosity is equal to or greater than 60%, for example, equal to or greater than 70%.
[0275] Typically, in the optoelectronic device of the invention, the thickness of the photoactive region is from 100 nm to 3000 nm, for example from 200 nm to 1000 nm, or, for example, the thickness can be from 300 nm to 800 nm. Often, photoactive layer thickness is from 400 nm to 600 nm. Generally the thickness is about 500 nm.
[0276] The optoelectronic device of the invention generally comprises a first electrode and a second electrode. Thus, the optoelectronic device of the invention typically comprises a first electrode, a second electrode, and, arranged between the first and second electrodes, said photoactive region.
[0277] The first and second electrodes are an anode and a cathode, and usually one or both of the anode and cathode is transparent to allow light to enter. At least one of the electrodes is generally semitransparent across the visible to near infrared region of the solar spectrum. Semi-transparent is typically 80% transparency, and ranging from 40 to 90%. The choice of first and second electrodes of the optoelectronic devices of the present invention may depend on the type of structure. Typically, the first layer of the device is deposited on the first electrode comprising tin oxide, more typically on a fluorine-doped tin oxide (FTO) anode, which is generally a transparent or semi-transparent material. Thus, the first electrode is generally transparent and typically comprises tin oxide, more typically fluorine-doped tin oxide (FTO). Generally, the thickness of the first electrode is from 200 nm to 600 nm, more typically from 300 to 500 nm. For example, the thickness can be 400 nm. Typically, FTO is coated on a sheet of glass. Generally, the second electrode comprises a high metal working function, for example gold, silver, nickel, palladium or platinum, and typically silver. Generally, the thickness of the second electrode is from 50 nm to 250 nm, more generally from 100 nm to 200 nm. For example, the thickness of the second electrode can be 150 nm.
[0278] Often, the first electrode must comprise a transparent or semi-transparent electrically conductive material. For example, the first electrode may comprise a transparent conductive oxide. Transparent conductive oxides include tin oxide, zinc oxide, doped tin oxide and doped zinc oxide. For example, the first electrode may comprise ITO (indium tin oxide, FTO (fluorine-doped tin oxide) or AZO (aluminium-doped tin oxide), preferably FTO. The first electrode may comprise from 90 to 100% by weight of ITO, FTO or AZO, and in some cases the first electrode may consist essentially of ITO, FTO or AZO. Generally, the thickness of the first electrode is from 200 nm to 600 nm, more typically from 300 to 500 nm. for example, the thickness may be 400 nm. The first electrode must often be arranged on a glass substrate. For example, the first electrode may comprise FTO and may be arranged on a glass substrate. In the optoelectronic devices of the invention , light input and/or output typically occurs through the first electrode as it is often transparent or semi-transparent. It is possible for light to enter a device through a metal electrode (such as, the second electrode can often , be), particularly If the metal electrode forms a thin layer.
[0279] Often the second electrode comprises a metal. Generally, the second electrode comprises a high metal working function, for example aluminum, gold, silver, nickel, palladium or platinum, and typically silver or gold. Generally, the thickness of the second electrode is from 50 nm to 250 nm, more generally from 100 nm to 200 nm. For example, the thickness of the second electrode can be 150 nm.
[0280] In an embodiment of the invention, the optoelectronic device of the invention may comprise a first electrode, a second electrode, and, arranged between the first and second electrodes, of said photoactive region; wherein the first electrode is in contact with the n-type region of said photoactive region and the second electrode is in contact with the p-type region of said photoactive region.
[0281] Thereby, the optoelectronic device according to the invention may comprise the following regions in the following order:
[0282] I. a first electrode;
[0283] II. an n-type region comprising at least one n-type layer;
[0284] III. a layer of a perovskite semiconductor without open porosity;
[0285] IV. a p-type region comprising at least one p-type layer; and
[0286] V. a second electrode.
[0287] The term "the regions that follow in the order that follow", as used here, means that each of the regions listed must be present, and that the ordering of each of the layers present must be in the given order. For example, in the above case (I, II, III, IV, V), II follows I, and precedes III, and II is only between I and III (that is, neither IV nor V is between I and III, but II it is). This is the normal understanding of "in the order that follows". The order does not in any way define the orientation in space of the collection of regions: I, II, III is equivalent to III, II, I (that is, "up" and "down" or "left" and " right" are undefined). Regions or layers may be present between each of these regions. For example, I, II, III includes I, la, II, IIa, III and I, la, 1b, II, III. Typically, however, each region (eg, from I to V) is in contact with both the previous and the successor region.
[0288] Regions or layers may be present between each of these regions.
[0289] Typically, however, each region from I to V is in contact with both the previous and the successor region. Each of the regions (a first electrode, an n-type region, a layer of a perovskite semiconductor without open porosity, a p-type region, and a second electrode) can be as defined anywhere here. For example, the optoelectronic device according to the invention may comprise the following regions in the following order:
[0290] I. a first electrode comprising a transparent conductive oxide, preferably FTO;
[0291] II. an n-type region comprising at least one n-type layer;
[0292] III. a layer of a perovskite semiconductor without open porosity;
[0293] IV. a p-type region comprising at least one p-type layer; and
[0294] V. a second electrode comprising a metal, preferably silver or gold.
[0295] In some embodiments, the second electrode may alternatively comprise a transparent conductive oxide. For example, both the first electrode and the second electrode can be selected from ITO, FTO and AZO. If the second electrode comprises a metal, such as silver or gold, the thickness of the second electrode may occasionally be 1 to 10 nm. For example, the first electrode may comprise FTO or ITO and the second electrode may comprise a layer of silver with a thickness from 1 to 10 nm, for example from 5 to 10 nm. A thin layer of silver can be semi-transparent.
[0296] The invention also provides an inverted heterojunction thin film perovskite device. Therefore, in one embodiment, the optoelectronic device of the invention may comprise a first electrode, a second electrode, and, arranged between the first and second electrodes, said photoactive region; wherein the second electrode is in contact with the n-type region of said photoactive region and the first electrode is in contact with the p-type region of said photoactive region. Such an architecture takes what is known as an inverted device. These devices may have the configuration shown schematically in Figure 8. In some circumstances it is desirable to have an inverted device structure in which holes are collected through part of the device substrate. In particular, inverted device architectures may be required for serial applications. Series applications include use with a low number of swath cells with low inorganic PV such as CIGS. The inventors have developed a low temperature, ambient air and solution processable photovoltaic cell based on a semiconductor perovskite absorber. Often p-type and n-type selective contacts can be in the form of PEDOT:PSS and PC60BM respectively. Remarkably, the final electrode configuration is very similar to that employed in "bulky heterojunction" polymer solar cells, albeit with the photoactive layer swapped where the volumetric heterojunction is replaced with a solid perovskite film and energy conversion efficiency in full sun. A very respectable 7.5% is obtained with a lot of scope for further improvement.
[0297] Thin-film photovoltaics based on solution-processable technologies offer the promise of the low-cost, easily manufacturable devices needed to address the world's ever-increasing energy needs. Suitable candidates are photovoltaics with organic, inorganic and hybrid structures. Organic-based photovoltaics, while releasing low-cost and easily processable technology, suffer from reduced performance compared to other thin-film technologies due to fundamental losses in charge generation where a large displacement, preferably, between the donor and acceptor is required to achieve efficient charge separation, limiting the maximum energy conversion efficiency obtainable to just under 11% at a single junction. Thin-film inorganic based photovoltaics may require the use of highly toxic solvents and elevated temperatures of over 500°C, making them undesirable for mass production.
[0298] For these reasons, perovskite-based hybrid photovoltaics are an attractive alternative when they can be processed below 150°C, are fully solid-state and already have high energy conversion efficiencies of over 12%. Perovskite absorbers were previously employed in sensitized solar cells as well as thin-film architectures. Particularly, in the latter configuration, CH3NH3Pbl3-xClx perovskite can act as a combined sensitizer and electron carrier when processed on a mesostructured alumina support, minimizing energy losses simply because electrons are directly transferred to the conducting substrate through the conduction band. from perovskite. In this way, extremely high open circuit voltages of over 1.1V can be obtained.
[0299] Often in perovskite-based photovoltaics, electrons are collected from the FTO substrate at the same time as holes are collected in the metal cathode. This configuration is undesirable for some series applications where holes must be collected at the TCO (Transparent Conductive Oxide) interface. At this point, a new inverted device architecture is demonstrated. It is often based on the nep-type materials generally used for charge collection in organic photovoltaics, that is, [6,6]-Phenyl C61 butyric acid methyl ester (PC60BM) and poly(3,4-ethylenedioxythiophene) poly( styrenesulfonate) (PEDOT:PSS), as well as V2O5 and NiO.
[0300] In one embodiment, the optoelectronic device of the invention comprises a first electrode, a second electrode, and, arranged between the first and second electrodes, said photoactive region; wherein the second electrode is in contact with the n-type region of said photoactive region and the first electrode is in contact with the p-type region of said photoactive region, wherein the first electrode comprises a transparent or semi-transparent electrically conductive material, and wherein the second electrode comprises aluminum, gold, silver, nickel, palladium or platinum.
[0301] Thereby, the optoelectronic device according to the invention may comprise the following regions in the following order:
[0302] I. a second electrode;
[0303] II. an n-type region comprising at least one n-type layer;
[0304] III. a layer of a perovskite semiconductor without open porosity;
[0305] IV. a p-type region comprising at least one p-type layer; and
[0306] V. a first electrode.
[0307] Each of the regions (a second electrode, an n-type region, a layer of a perovskite semiconductor without open porosity, a p-type region, and a first electrode) can be as defined anywhere here.
[0308] For example, the optoelectronic device according to the invention may comprise the following regions in the following order:
[0309] I. a second electrode comprising a metal;
[0310] II. an n-type region comprising at least one n-type layer;
[0311] III. a layer of a perovskite semiconductor without open porosity;
[0312] IV. a p-type region comprising at least one p-type layer; and
[0313] V. a first electrode comprising a transparent conductive oxide.
[0314] For example, the optoelectronic device according to the invention may comprise the following regions in the following order:
[0315] I. a second electrode comprising a metal, preferably silver or gold;
[0316] II. an n-type region comprising at least one n-type layer;
[0317] III. a layer of a perovskite semiconductor without open porosity;
[0318] IV. a p-type region comprising at least one p-type layer; and
[0319] V. a first electrode comprising a transparent conductive oxide, preferably FTO.
[0320] Any of the components in an inverted device according to the invention may be as defined elsewhere herein. For example, the perovskite may be a perovskite according to any one of formulas I, la, II or IIa above. For example, the perovskite may be a perovskite compound selected from CH3NH3PbI3, CH3NH3PbBr3, CH3NH3PbIBr2, CH3NH3SnBrI2, CH3NH3SnICl2, CH3NH3SnF2Cl. alternatively both the first electrode and the second electrode can be selected from ITO, FTO and AZO. If the second electrode comprises a metal such as silver or gold, the thickness of the second electrode may occasionally be 1 to 0 nm. For example, the first electrode may comprise FTO or ITO and the second electrode may comprise a layer of silver with a thickness from 1 to 10 nm, for example from 5 to 10 nm. A thin layer of silver can be semi-transparent.
[0321] The n-type region in an inverted device may comprise at least one n-type layer as defined elsewhere herein for a standard, non-inverted device. For example, an n-type layer may comprise TiO2, SnO2, ZnO, Nb2O5, Ta2O5, WO3, W2O5, ln2O3, Ga2O3, Nd2O3, PbO, or CdO. In one embodiment, the n-type region may comprise a compact layer of titanium dioxide. Often, the n-type region may comprise a compact layer of titanium dioxide and a layer of [60]PCBM ([6,6]-phenyl-C61-butyric acid methyl ester). When the n-type region comprises a layer of titanium dioxide and a layer of [60]PCBM, the compact layer of titanium oxide is typically adjacent to the second electrode and the layer of [60]PCBM is typically adjacent to the layer of one. perovskite semiconductor without open porosity.
[0322] The p-type region in an inverted device may comprise at least one p-type layer as defined elsewhere herein for a standard, non-inverted device. For example, a p-type layer may comprise spiro-OMeTAD (2,2',7,7'-tetracys-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene)), P3HT (poly( 3-hexylthiophene)), PCPDTBT (Poly[2,1,3-benzothiadiazol-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b) ']dithiophene-2,6-diyl]]), PVK (poly(N-vinylcarbazole)), PEDOT (poly(3,4-ethylenedioxythiophene)), or PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly( styrenesulfonate)). Alternatively, the p-type layer may, for example, comprise an inorganic hole carrier comprising an oxide of nickel, vanadium, copper or molybdenum. In particular, the p-type region may comprise a Spiro-OMeTAD layer and/or a PEDOT:PSS layer. In one embodiment, the p-type region comprises a layer of PEDOT:PSS. If the p-type region comprises a layer of a p-type polymeric material (such as PEDOT, or PEDOT:PSS), the p-type layer may be crosslinked. The layer is cross-linked to limit the extent to which it is dissolved in the perovskite precursor solution during device fabrication, i.e., the polymer (eg, PEDOT:PSS) is cross-linked to insolubilize it. For example, the p-type region may comprise a p-type layer comprising a polymeric material wherein the p-type layer is crosslinked. Occasionally, the p-type region may comprise a layer of PEDOT:PSS where the layer is crosslinked. The p-type layer can be cross-linked using a Lewis acid, for example Fe3+. The p-type region may comprise a layer of PEDOT:PSS in which each has been cross-linked using FeCl3.
[0323] An optoelectronic device according to the invention may comprise the following regions in the following order:
[0324] I. a second electrode comprising a metal;
[0325] II. an n-type region comprising a compact layer of titanium dioxide and a layer of [60]PCBM;
[0326] III. a layer of a perovskite semiconductor without open porosity;
[0327] IV. a p-type region comprising a layer of PEDOT:PSS, optionally wherein the layer is crosslinked; and
[0328] V. a first electrode comprising a transparent conductive oxide.
[0329] An optoelectronic device according to the invention may comprise the following regions in the following order:
[0330] I. a second electrode comprising a metal, preferably aluminum, silver or gold;
[0331] II. an n-type region comprising a compact layer of titanium dioxide and a layer of [60]PCBM;
[0332] III. a layer of a perovskite semiconductor without open porosity;
[0333] IV. a p-type region comprising a layer of PEDOT:PSS, optionally wherein the layer is crosslinked; and
[0334] V. a first electrode comprising a transparent conductive oxide, preferably FTO.
[0335] For example, an optoelectronic device according to the invention may comprise the following regions in the following order:
[0336] I. a second electrode comprising aluminum;
[0337] II. a compact layer of titanium dioxide;
[0338] III. a layer of [60]PCBM;
[0339] IV. a layer of a perovskite semiconductor without open porosity;
[0340] V. a layer of PEDOT:PSS lattice; and
[0341] VI. a first electrode comprising FTO.
[0342] Said photoactive region may be the only photoactive region in the device and the optoelectronic device of the invention may therefore be a single junction device.
[0343] Alternatively, the optoelectronic device of the invention may be a series junction optoelectronic device or a multiple junction optoelectronic device.
[0344] Thereby, the optoelectronic device may comprise a first electrode, a second electrode, and, arranged between the first and second electrodes:
[0345] said photoactive region; and
[0346] at least one other photoactive region.
[0347] The other photoactive region or regions may be the same as or different from the photoactive region defined above.
[0348] In some embodiments, the other photoactive region or regions are the same as the photoactive region defined above.
[0349] Thus, the optoelectronic device of the invention may comprise: a first electrode, a second electrode, and, arranged between the first and second electrodes: a plurality of said photoactive regions.
[0350] When the optoelectronic device of the invention is a series or multiple junction device, as the skilled person will observe, it may comprise one or more tunnel junctions. Each tunnel junction is generally arranged between the two photoactive regions.
[0351] A series junction optoelectronic device (or multiple junction optoelectronic device) according to the invention can combine the perovskite thin film technology described herein with known technologies to provide the optimal performance.
[0352] An "all perovskite" multiple junction cell is very attractive, however, even without the need to develop new absorbers, the current system employing CH3NH3Pbl3-xClx is already very well established to combine with crystalline silicon and other thin film technologies, such as CIS, CIGS and CZTSSe, if employed as a superior cell in a series junction. The potential exists to produce optoelectronic devices with efficiencies in excess of 20%. The remarkable aspect of this one is that it does not require a "spectacular advance" in the technology currently presented, simply a little optimization and effective integration. There are many distinct advantages of "overlapping input" to existing technologies; the continuing drop in the cost of existing PV becomes advantageous, the market must be much more willing to adopt "enhanced silicon technology" rather than all new perovskite technology, and last but not least, a fundamental challenge for the wider PV community has been to develop a superior slit-width cell for silicon and thin film technologies. In Figures 16 and 17, schematic illustrations of possible series splicing device configurations are given, for perovskite in c-Si and perovskite in conventional thin film.
[0353] In one embodiment, the invention provides an optoelectronic device comprising a first electrode, a second electrode, and, arranged between the first and second electrodes:
[0354] said photoactive region as defined above; and
[0355] at least one other photoactive region,
[0356] wherein at least one other photoactive region comprises at least one layer of a semiconductor material.
[0357] At least one other photoactive region may be at least one other photoactive region of the photoactive regions employed in conventional and known photovoltaic and optoelectronic devices. For example, it could be a photoactive region of a crystalline silicon photovoltaic cell or a photoactive region of a conventional thin-film gallium arsenide, CZTSSe, CIGS, or CIS photovoltaic device.
[0358] Often, a series optoelectronic device comprises the following regions in the following order:
[0359] I. a first electrode;
[0360] II. a first photoactive region as defined elsewhere above;
[0361] III. a second photoactive region comprising a layer of a semiconductor material; and
[0362] IV. a second electrode.
[0363] The semiconductor material in region III can be any semiconductor material. The term "semiconductor material", as used herein, refers to a material with electrical conductivity intermediate in magnitude between that of a conductor and an insulator. Typically, a semiconductor material is a material that has a conductivity from 103 to 10-8 Scm-1. Standard techniques such as a 4-point conductivity measurement probe can be employed to measure conductivity. Examples of semiconductor materials include an oxide or chalcogenide of a metalloid or metal element; a group IV compound; a compound comprising a group III element and a group V element; a compound comprising a group II element and a group VI element; a compound comprising a group I element and a group VII element; a compound comprising a group IV element and a group VI element; a compound comprising a group V element and a group VI element; a compound comprising a group II element and a group V element; a ternary or quaternary semiconductor compound; a perovskite semiconductor or an organic semiconductor. Typical examples of semiconductor materials include oxides of titanium, niobium, tin, zinc, cadmium, copper or lead; antimony or bismuth chalcogenides; copper zinc tin sulfide; tin zinc copper selenide, tin zinc copper selenide sulfide, indium gallium copper selenide; and indium gallium copper diselenide. Other examples are semiconductors of group IV compounds (eg silicon carbide); group III-V semiconductors (eg gallium arsenide); group II-VI semiconductors (eg cadmium selenide); group I-VII semiconductors (e.g. cuprous chloride); group IV-VI semiconductors (eg lead selenide); group V-VI semiconductors (e.g. bismuth telluride); and group II-V semiconductors (eg, cadmium arsenide); ternary or quaternary semiconductors (eg, indium copper selenide, indium gallium copper diselenide, or copper zinc tin sulfide); semiconductor from perovskite materials (eg CH3NH3Pbl3 and CH3NH3Pbl2Cl); and organic semiconductor materials (e.g. conjugated polymeric compounds including polymers such as polyacetylenes, polyphenylenes and polythiophenes). Examples of organic semiconductors include poly(3,4-ethylenedioxythiophene), 2,2-7,7-tetracys-N,N-di-p-methoxyphenylamine-9,9-spirobifluorene (spiro-OMeTAD) and conjugated organic polymers, such as polyacetylenes, polyphenylenes, polythiophenes or polyanilines. Examples of materials that are not semiconductor materials include, for example, elemental metals, which are natural conductors, and electrical or dielectric insulators such as silica or calcite.
[0364] The term "oxide", as used herein, refers to a compound comprising at least one oxide ion (i.e., O2-) or divalent oxygen atom. It is to be understood that the terms "metal oxide" "an oxide of a metal element" used herein equally encompasses oxides comprising a metal, and also oxides of mixed metals. For the avoidance of doubt, a mixed metal oxide refers to a single oxide compound comprising more than one metal element. Examples of mixed metal oxides include tin and zinc oxide and indium tin oxide. Similarly, it is to be understood that the terms "nonmetal oxide" and "an oxide of a nonmetal element" used herein encompass oxides comprising a nonmetal element as well as mixed nonmetal oxides. For the avoidance of doubt, a mixed metalloid oxide refers to a single oxide compound comprising more than one metalloid element.
[0365] The term "chalcogenide", as used herein, refers to a compound comprising at least one of a sulfide, selenide, or telluride ion (i.e., S2-, Se2-, or Te2-) or a tellurium atom, selenium or divalent sulfur. It is to be understood that the terms "metal chalcogenide" and "a chalcogenide of a metal element" encompass chalcogenides comprising a metal and also chalcogenides of mixed metals. For the avoidance of doubt, a mixed metal chalcogenide refers to a single chalcogenide compound comprising more than one metal element. Similarly, it is to be understood that the terms "nonmetal chalcogenide" and "a chalcogenide of a nonmetal element" used herein encompass chalcogenides comprising a nonmetal and also chalcogenides of mixed metalloids. For the avoidance of doubt, a mixed nonmetal chalcogenide refers to a single chalcogenide compound comprising more than one nonmetal element.
[0366] Occasionally, the semiconductor material comprises an oxide or chalcogenide of a metalloid or metal element. For example, the semiconductor material consists of an oxide or chalcogenide of a nonmetal element or metal. For example, the semiconductor material comprises an oxide of titanium, niobium, tin, zinc, cadmium, copper or lead or any combination thereof; or an antimony, bismuth or cadmium chalcogenide or any combination thereof. For example, the semiconductor material may comprise zinc oxide tin; copper zinc tin sulfide; indium gallium copper selenide, or indium gallium copper diselenide.
[0367] In one embodiment, the semiconductor material may be a doped semiconductor, in which an impurity element is present in a concentration ranging from 0.01 to 40%. If the impurity element acts as an electron donor, then the semiconductor material must be doped to become n-type, if the impurity element acts as an electron acceptor, then the semiconductor material must be doped to become p-type. It is noted that for metal oxides doped with impurity of the nonmetal elements which replace the primary nonmetal element, if the valence of the dopant is greater than the valence of the primary nonmetal element, then the metal oxide must be n-doped, if the valence of the dopant metalloid element is lower than that of the primary metalloid element, then the metal oxide must be p-doped. Any of the above mentioned elements can be employed to dope any of the above mentioned semiconductor materials to different levels of effectiveness and effect.
[0368] Thus, in some cases the semiconductor material comprises an oxide or chalcogenide of a metalloid or metal element; a group IV compound; a compound comprising a group III element and a group V element; a compound comprising a group II element and a group VI element; a compound comprising a group I element and a group VII element; a compound comprising a group IV element and a group VI element; a compound comprising a group V element and a group VI element; a compound comprising a group II element and a group V element; a semiconductor of the ternary or quaternary compound; or an organic semiconductor.
[0369] Often the semiconductor material comprises silicon; an oxide of titanium, niobium, tin, zinc, cadmium, copper or lead; an antimony or bismuth chalcogenide; copper zinc tin sulfide; tin zinc copper selenide, tin zinc copper selenide sulfide, indium gallium copper selenide; copper indium gallium diselenide, silicon carbide, gallium arsenide, cadmium selenide, cuprous chloride, lead selenide, bismuth telluride, or cadmium arsenide. If the semiconductor material comprises silicon, the silicon may be monocrystalline, polycrystalline or amorphous.
[0370] The photoactive region according to the invention can be in series with a traditional silicon solar cell. For example, the semiconductor material may comprise a layer of crystalline silicon.
[0371] In some embodiments, the optoelectronic device comprises the following regions in the following order:
[0372] I. a first electrode;
[0373] II. a first photoactive region as defined elsewhere herein;
[0374] III. a layer (A) of a p-type semiconductor;
[0375] IV. a first intrinsic semiconductor layer;
[0376] V. a layer (B) of a p-type semiconductor or a layer (B) of an n-type semiconductor;
[0377] VI. a second intrinsic semiconductor layer;
[0378] VII. a layer (C) of an n-type semiconductor; and
[0379] VIII. a second electrode.
[0380] Occasionally, the optoelectronic device comprises the following regions in the following order:
[0381] I. a first electrode;
[0382] II. a first region;
[0383] III. a perovskite semiconductor layer without open porosity;
[0384] IV. a third region;
[0385] V. a layer (A) of a p-type semiconductor;
[0386] VI. a first intrinsic semiconductor layer;
[0387] VII. a layer (B) of a p-type semiconductor or a layer (B) of an n-type semiconductor;
[0388] VIII. a second intrinsic semiconductor layer;
[0389] IX. a layer (C) of an n-type semiconductor; and
[0390] X. a second electrode;
[0391] wherein the first region is an n-type region comprising at least one n-type layer and the third region is a p-type region comprising at least one p-type layer; or
[0392] the first region is a p-type region comprising at least one p-type layer and the third region is an n-type region comprising at least one n-type layer.
[0393] Any of the components (eg the perovskite, the first region or the third region) in this series device can be as defined anywhere here. Any intrinsic, p-type, or n-type semiconductor referred to may comprise any semiconductor defined herein which may be appropriately p-doped, n-doped, or undoped.
[0394] Often, the first region is a p-type region comprising at least one p-type layer and the third region is an n-type region comprising at least one n-type layer. Thus, the p-type layer must be adjacent to the first electrode, and the perovskite photoactive region according to the invention must be inverted. Typically, light incident on the device is incident through the first electrode. The n-type region comprising at least one n-type layer may be as defined herein and/or the p-type region comprising at least one p-type layer may be as defined herein.
[0395] Often, in a series optoelectronic device according to the invention, the layer (A) of a p-type semiconductor is a p-type amorphous silicon layer/ or the layer (C) of a p-type semiconductor n is an n-type amorphous silicon layer. Typically, layer (A) of a p-type semiconductor is a p-type amorphous silicon layer and layer (C) of an n-type semiconductor is an n-type amorphous silicon layer. Often, the first intrinsic semiconductor layer is an intrinsic amorphous silicon layer and/or the second intrinsic semiconductor layer is an intrinsic amorphous silicon layer. Sometimes the first intrinsic semiconductor layer is an intrinsic amorphous silicon layer and the second intrinsic semiconductor layer is an intrinsic amorphous silicon layer. In the series device, layer (B) of a p-type semiconductor or layer (B) of an n-type semiconductor can be a p-type crystalline silicon layer by an n-type crystalline silicon layer.
[0396] As defined elsewhere herein, the first electrode typically comprises a transparent conductive oxide and/or the second electrode comprises a metal. Often the first electrode typically comprises a transparent conductive oxide and the second electrode comprises a metal. The transparent conductive oxide may be as defined above and is often FTO, ITO, or AZO, and typically ITO. The metal can be any metal. Generally the second electrode comprises a metal selected from silver, gold, copper, aluminum, platinum, palladium, or tungsten. This list of metals may also apply to other examples of the second electrode here. Often the first electrode material comprises ITO and/or the second electrode comprises silver. Typically, the first electrode material comprises ITO and the second electrode comprises silver.
[0397] Instead of the photoactive region according to the invention comprising a perovskite layer without open porosity being in series with a photoactive region of silicon, it can be in series with a photoactive region of thin film. For example, the optoelectronic device may comprise the following regions in the following order:
[0398] I. a first electrode;
[0399] II. a first photoactive region as defined elsewhere above;
[0400] III. a second photoactive region comprising a layer of a semiconductor material; and
[0401] IV. a second electrode;
[0402] wherein the semiconductor material comprises a layer of tin zinc copper sulfide, tin zinc copper selenide, tin zinc copper selenide, copper indium gallium selenide, copper indium gallium diselenide or copper indium selenide. The layer of a semiconductor material may be a thin film of a semiconductor material.
[0403] In one embodiment, the optoelectronic device comprises the following regions in the following order:
[0404] I. a first electrode;
[0405] II. a first photoactive region as defined above;
[0406] III. a layer of a transparent conductive oxide;
[0407] IV. a layer (D) of an n-type semiconductor;
[0408] V. a layer of tin zinc copper sulphide, tin zinc copper selenide, tin zinc copper selenide sulfide, indium gallium copper selenide, indium gallium copper diselenide or indium copper selenide; and
[0409] VI. a second electrode.
[0410] For example, the optoelectronic device of therefore may comprise the following regions in the following order:
[0411] I. a first electrode;
[0412] II. a first region;
[0413] III. a perovskite semiconductor layer without open porosity;
[0414] IV. a third region;
[0415] V. a layer of a transparent conductive oxide;
[0416] VI. a layer (D) of an n-type semiconductor;
[0417] VII. a layer of tin zinc copper sulfide, tin zinc copper selenide, tin zinc copper selenide sulfide, indium gallium copper selenide, indium gallium copper diselenide or indium copper selenide; and
[0418] VIII. a second electrode;
[0419] wherein the first region is an n-type region comprising at least one n-type layer and the third region is a p-type region comprising at least one p-type layer; or
[0420] the first region is a p-type region comprising at least one p-type layer and the third region is an n-type region comprising at least one n-type layer.
[0421] Layer (D) of an n-type semiconductor may comprise any metal oxide or semiconductor chalcogenide. Often, the layer (D) of an n-type semiconductor comprises cadmium sulfide.
[0422] Typically, in the array device comprising a thin film of a semiconductor, the first region is an n-type region comprising at least one n-type layer, and the third region is a p-type region comprising at least one p-type layer . The n-type region comprising at least one n-type layer may be as defined anywhere herein and/or the p-type region comprising at least one p-type layer may be as defined elsewhere herein.
[0423] The first electrode and/or second electrode may be as defined above. Typically, the first electrode comprises a transparent conductive oxide and/or the second electrode comprises a metal. Often, the first electrode comprises a transparent conductive oxide and the second electrode comprises a metal. Typically, the first electrode comprises ITO and/or the second electrode comprises tungsten, or the first electrode comprises ITO and the second electrode comprises tungsten.
[0424] The optoelectronic device of the invention may be a photovoltaic device; a photodiode; a phototransistor; a photomultiplier; a photoresistor; a photodetector; a light sensitive detector; solid state triode; a battery electrode; a light emitting device; a light-emitting diode; a transistor; a solar cell; a laser; or an injection laser diode.
[0425] In a preferred embodiment, the optoelectronic device of the invention is a photovoltaic device, for example a solar cell.
[0426] The optoelectronic device according to the invention may be a solar cell.
[0427] In another preferred embodiment, the optoelectronic device of the invention is a light-emitting device, for example, a light-emitting diode.
[0428] The perovskite compounds employed in the optoelectronic device of the invention, in said layer of a perovskite semiconductor without open porosity, and/or in said first layer, can be produced by means of a process comprising mixing:
[0429] (a) a first compound comprising (i) a first cation and (ii) a first anion; with
[0430] (b) a second compound comprising (i) a second cation and (ii) a second anion; on what:
[0431] the first and second cations are as defined here for perovskite; and
[0432] the first and second anions can be the same or different anions.
[0433] Perovskites comprising at least one anion selected from halide anions and chalcogenide anions, can, for example, be produced by means of a process comprising mixing:
[0434] (a) a first compound comprising (i) a first cation and (ii) a first anion; with
[0435] (b) a second compound comprising (i) a second cation and (ii) a second anion; on what:
[0436] the first and second cations are as defined here for perovskite; and
[0437] the first and second anions can be the same or different anions selected from halide anions and chalcogenide anions.
[0438] Typically, the first and second anions are different anions. More typically, the first and second anions are different anions selected from halide anions.
[0439] The perovskite produced by the process may comprise other cations or other anions. For example, perovskite may comprise two, three or four different cations, or two, three of four different anions. The process for producing the perovskite may therefore comprise mixing other compounds comprising another cation or another anion. Additionally or alternatively, the process for producing the perovskite may comprise mixing (a) and (b) with: (c) a third compound comprising (i) the first cation and (ii) the second anion; or (d) a fourth compound comprising (i) the second cation and (ii) the first anion.
[0440] Typically, in the process for producing perovskite, the second cation in the mixed anion perovskite is a metal cation. More typically, the second cation is a divalent metal cation. For example, the second cation can be selected from Ca2+, Sr2+, Cd2+, C 2+ Ni2+ Mn2+ F 2+ C 2+ Pd2+ G 2+ Sn2+ Pb2+ Yb2+ E 2+ G r lm nt Cu , Ni , Mn , Fe , Co , Pd , Ge , Sn , Pb , Yb and Eu . Generally, the second cation is selected from Sn2+ and Pb2+.
[0441] Often, in the process for producing perovskite, the first cation in the mixed anion perovskite is an organic cation.
[0442] Generally, the organic cation will have the formula (R1R2R3R4N)+, where:
[0443] R1 is hydrogen, or substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl;
[0444] R2 is hydrogen, or substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl;
[0445] R3 is hydrogen, or substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl; and
[0446] R4 is hydrogen, or substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl.
[0447] Mainly, in the organic cation, R1 is hydrogen, methyl or ethyl, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, methyl or ethyl, and R4 is hydrogen, methyl or ethyl. For example, R1 can be hydrogen or methyl, R2 can be hydrogen or methyl, R3 can be hydrogen or methyl, and R4 can be hydrogen or methyl.
[0448] Alternatively, the organic cation may have the formula (R5NH3)+, wherein: R5 is hydrogen, or substituted or unsubstituted C1-C20 alkyl. For example, R5 can be methyl or ethyl. Typically, R5 is methyl.
[0449] Alternatively, the organic cation may have the formula (R5R6N = CH - NR7R8)+, wherein: R5 is hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl; R6 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl; R7 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl; and R8 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl.
[0450] Typically, R5 in the cation (R5R6N = CH - R7R8)+ is hydrogen, methyl or ethyl, R6 is hydrogen, methyl or ethyl, R7 is hydrogen, methyl or ethyl, and R8 is hydrogen, methyl or ethyl. For example, R5 can be hydrogen or methyl, R6 can be hydrogen or methyl, R7 can be hydrogen or methyl, and R8 can be hydrogen or methyl.
[0451] The organic cation can, for example, have the formula (H2N = CH - NH2)+.
[0452] In the process for producing perovskite, the perovskite is generally a mixed halide perovskite, where the two or more different anions are two or more different halide anions.
[0453] Typically, in the process for producing perovskite, perovskite is a perovskite compound of formula (I):
[0454] [A][B][X]3 (I)
[0455] where:
[0456] [A] is at least one organic cation;
[0457] [B] is at least one metal cation; and
[0458] [X] is the aforementioned two or more different anions; and
[0459] the process comprises mixing:
[0460] (a) a first compound comprising (i) a metal cation and (ii) a first anion; with
[0461] (b) a second compound comprising (i) an organic cation and (ii) a second anion;
[0462] where:
[0463] the first and second anions are different anions selected from halide anions or chalcogenide anions.
[0464] The perovskite of formula (I) may, for example, comprise one, two, three or four different metal cations, typically one or two different metal cations. The perovskite of formula (I) may, for example, comprise one, two, three or four different organic cations, typically one or two different organic cations. The perovskite of formula (I) may, for example, comprise two, three or four different anions, typically two or three different anions. The process may therefore comprise mixing other compounds comprising a cation and an anion.
[0465] Typically, [X] is two or more different halide anions. The first and second anions are thus typically halide anions. Alternatively [X] can be three different halide ions. Thus, the process may comprise mixing a third compound with the first and second compounds, wherein the third compound comprises (i) a cation and (ii) a third halide anion, wherein the third anion is a different anion of halide of the first and second halide anions.
[0466] Often, in the process for producing perovskite, perovskite is a perovskite compound of formula (IA):
[0467] AB[X]3 (IA)
[0468] where:
[0469] A is an organic cation;
[0470] B is a metal cation; and
[0471][X] is the aforementioned two or more different anions,
[0472] The process comprises mixing:
[0473] (a) a first compound comprising (i) a metal cation and (ii) a first halide anion; with
[0474] (b) a second compound comprising (i) an organic cation and (ii) a second halide anion:
[0475] where:
[0476] the first and second halide anions are different halide anions.
[0477] Generally, [X] is two or more different halide anions. Preferably, [X] is two or three different halide anions. More preferably, [X] is two different halide anions. In another embodiment [X] is three different halide anions.
[0478] Typically, in the process for producing perovskite, perovskite is a perovskite compound of formula (II):
[0479] ABX3-yX'y (II)
[0480] where:
[0481] A is an organic cation;
[0482] B is a metal cation;
[0483] X is a first halide anion;
[0484] X' is a second halide anion which is different from the first halide anion; and
[0485] y is from 0.05 to 2.95; and
[0486] The process comprises mixing:
[0487] (a) a first compound comprising (i) a metal cation and (ii) X; with
[0488] (b) a second compound comprising (i) an organic cation and (ii) X':
[0489] where the ratio of X to X' in the mixture is equal to (3- y):y.
[0490] In order to obtain said ratio of X to X' equal to (3-y):y, the process may comprise mixing another compound with the first and second compounds. For example, the process may comprise mixing a third compound with the first and second compounds, wherein the third compound comprises (i) the metal cation and (ii) X'. Alternatively, the process may comprise mixing a third compound with the first and second compounds, wherein the third compound comprises (i) the organic cation and (ii) X.
[0491] Generally, y is from 0.5 to 2.5, for example from 0.75 to 2.25. Typically, y is from 1 to 2.
[0492] Typically, in the process for producing perovskite, the first compound is BX2 and the second compound is AX'.
[0493] Often, the second compound is produced by reacting a compound of the formula (R5NH2), where: R5 is hydrogen, or substituted or unsubstituted C1-C20 alkyl, with a compound of the formula HX'. Typically R5 can be methyl or ethyl, often R5 is methyl.
[0494] Generally, the compound of formula (R5NH2) and the compound of formula HX' are reacted in a 1:1 molar ratio. Often, the reaction takes place under a nitrogen atmosphere and usually in anhydrous ethanol. Typically, anhydrous ethanol is of about grade 200. More typically, 15 to 30 ml of the compound of formula (R5NH2) is reacted with about 15 to 15 ml of HX', usually under a nitrogen atmosphere in 50 to 150 ml. of anhydrous ethanol. The process may also comprise a step of recovering said mixed anion perovskite. A rotary evaporator is often employed to extract crystalline AX'.
[0495] Generally, the step of mixing the initiator and the second compound is a step of dissolving the initiator and the second compound in a solvent. The first and second compounds can be dissolved in a ratio from 1:20 to 20:1, typically a ratio of 1:1. Typically the solvent is dimethylformamide (DMF) or water. When the metal cation is Pb2+ the solvent is usually dimethylformamide. When the metal cation is Sn2+ the solvent is usually water. The use of DMF or water when the solvent is advantageous as these solvents are not very volatile.
[0496] The perovskite semiconductor layer in the inventive devices can be prepared by solution processing or by means of vacuum evaporation. Reduced processing temperature is important for production cost reduction, allowing processing on plastic substrates and processing on top of other layers to allow for the production of serial and multiple junction solar cells. At this point, the inventors demonstrate that the devices of the invention can operate with all layers processed at low temperature including solution processable support.
[0497] The invention provides a process for producing an optoelectronic device comprising a photoactive region, characterized in that the photoactive region comprises:
[0498] an n-type region comprising at least one n-type layer;
[0499] a p-type region comprising at least one p-type layer; and, arranged between the n-type region and the p-type region:
[0500] a layer of a perovskite semiconductor without open porosity,
[0501] whose process comprises:
[0502] (a) provide a first region;
[0503] (b) arranging a second region in the first region, which second region comprises a layer of a perovskite semiconductor without open porosity; and
[0504] (c) place a third region in the second region,
[0505] where:
[0506] the first region is an n-type region comprising at least one n-type layer and the third region is a p-type region comprising at least one p-type layer; or
[0507] the first region is a p-type region comprising at least one p-type layer and the third region is an n-type region comprising at least one n-type layer.
[0508] Often, the first region is an n-type region comprising at least one n-type layer and the third region is a p-type region comprising at least one p-type layer.
[0509] In the process of the invention, the n-type region, n-type layer, p-type region and p-type layer may also be as defined hereinabove for the optoelectronic device of the invention. Likewise, the perovskite semiconductor layer without open porosity, and the perovskite semiconductor itself, can be as defined above.
[0510] In an embodiment of the process of the invention, step (b), of arranging the second region in the first region, comprises:
[0511] produce a solid layer of perovskite in the first region by means of vapor deposition.
[0512] In this embodiment, the step of producing a solid layer by means of vapor deposition typically comprises:
[0513] (i) exposing the first region to vapor, which vapor comprises said perovskite or one or more reagents for producing said perovskite; and
[0514] (ii) allow steam to deposit in the first region, to produce a solid layer of said therein.
[0515] The vapor perovskite may be any of the perovskites discussed above for the optoelectronic device of the invention, and is typically a perovskite of formula (I), (IA) or (II) as defined above.
[0516] One or more reagents for the production of said perovskite may comprise the types of reagents discussed above for the process of synthesizing the perovskite compounds.
[0517] Thus, one or more reagents may comprise:
[0518] (a) a first compound comprising (i) a first cation and (ii) a first anion; and
[0519] (b) a second compound comprising (i) a second cation and (ii) a second anion, as defined above for the production process of the perovskite compounds employed in the optoelectronic device of the invention.
[0520] More particularly, one or more reagents may comprise:
[0521] (a) a first compound comprising (i) a metal cation and (ii) a first anion; with
[0522] (b) a second compound comprising (i) an organic cation and (ii) a second anion; wherein the first and second anions are different anions selected from halide anions or chalcogenide anions, as defined above for the production process of the perovskite compounds employed in the optoelectronic device of the invention.
[0523] For example, one or more reagents may comprise:
[0524] (a) a first compound comprising (i) a metal cation and (ii) a first halide anion; with
[0525] (b) a second compound comprising (i) an organic cation and (ii) a second halide anion; where the first and second halide anions are different halide anions,
[0526] as defined above for the production process of the perovskite compounds employed in the optoelectronic device of the invention.
[0527] For example, when the perovskite to be deposited is CH3NH3Pbl2Cl, one or more reactants typically comprise (a) Pbl2, and (b) CH3NH3Cl.
[0528] The process, generally speaking, also comprises the production of steam by first evaporating said perovskite or evaporating said one or more reactants to produce said perovskite. In this step the perovskite or one or more reagents for producing the perovskite are typically transferred to an evaporation chamber which is subsequently evacuated. The perovskite or one or more reagents for producing the perovskite are typically then heated.
[0529] The resulting vapor is then exposed to and thereby deposited in the first region, to produce a solid layer of said therein. If reagents are employed, they react together in situ to produce perovskite in the first region.
[0530] Typically, vapor deposition is allowed to continue until the solid layer of perovskite has a desired thickness, for example a thickness from 10 nm to 100 μm, or more typically from 10 nm to 10 μm. Preferably, the vapor deposition is allowed to continue until the solid layer of perovskite has a thickness from 50 nm to 1000 nm, or, for example, from 100 nm to 700 nm. For example, deposition can be continued until approximately 100 nm to 300 nm of the powder is deposited in the first region.
[0531] Vapor deposition can continue until the solid layer of perovskite has a thickness of at least 100 nm. Typically, for example, it continues until the solid layer of perovskite has a thickness from 100 nm to 100 μm, or, for example, from 100 nm to 700 nm.
[0532] The inventors have found that a dual source vapor deposition process allows for uniform layers of perovskite to be deposited. Vapor deposition is one of the most common large production ways to deposit thin films of controlled thickness and conventionally refers to deposition of thin films by condensing a vaporized form of the desired film material onto a surface in a vacuum. Inorganic perovskite deposition methods have been well studied, such as pulsed laser deposition and chemical solution deposition. The inorganic organic hybrid perovskite, such as (C6H5C2H4NH3)2Pbl4 or (C6H5C2H4NH3)2PbBr4, was successfully evaporated by single source thermal deposition. However, since the deposition methods of hybrid organic-inorganic perovskite were rarely mentioned because of the significant difference in physical and chemical properties between organic and inorganic materials, thermal deposition from two sources was applied to evaporate the organic source. and inorganic source simultaneously, but independently controlled (VK Dwivedi, JJ Baumberg, and GV Prakash, "Direct deposition of inorganic-organic hybrid semiconductors and their template-assisted microstructures," Materials Chemistry and Physics, vol. 137, no. 3, pp. 941-946, Jan. 2013). Recently, standard assisted electrochemical deposition has been suggested to obtain a new class of a hybrid perovskite (C12H25NH3)2PbI4 in multiple very spectacular structures with strong exciton emission. It has also been suggested that these materials can be directly carved into 2D photonic structures which can be very useful in photovoltaic devices. Deposition of organic-inorganic hybrid perovskite materials is always challenging, because most organic materials are very volatile and decompose easily, and this makes controlling the deposition process more complicated.
[0533] In one embodiment, step (b) of arranging the second region in the first region comprising:
[0534] Produce a solid layer of the perovskite by means of vapor deposition, wherein the vapor deposition is dual source vapor deposition.
[0535] The term "dual source vapor deposition", as employed herein, refers to a vapor deposition process in which the vapor that is deposited on a substrate comprises two or more components that originate from two distinct sources. . Typically a first source will produce a vapor comprising a first component and a second source will produce a vapor comprising a second component. Dual source vapor deposition can also be extended to include three and four sources of vapor deposition, although dual source deposition is usually preferred.
[0536] In one embodiment, step (b) of arranging the second region in the first region comprising:
[0537] (i) exposing the first region to steam, which steam comprises two reagents for the production of said perovskite; and
[0538] (ii) allow steam to deposit in the first region, to produce a solid layer of said therein;
[0539] wherein (i) also comprises producing said vapor comprising two reactants for producing said perovskite by evaporating a first reactant from a first source and evaporating a second reactant from a second source.
[0540] Reagents may be as defined here for the production of a perovskite. The vapor may alternatively comprise three or more reactants. The two sources are typically placed at the same distance from the first region, often 10 to 40 cm.
[0541] Often the first reactant comprises a first compound comprising (i) a first cation and (ii) a first anion; and the second reactant comprises a second compound comprising (i) a second cation and (ii) a second anion. In some cases, the first cation at this point must be a metal cation. In some cases, the second cation at this point must be an organic cation. Thus, the first reactant may comprise a first compound comprising (i) a metal cation and (ii) a first anion; and the second reactant may comprise a second compound comprising (i) an organic cation and (ii) a second anion. Preferably the metal cation is a divalent metal cation. For example, the metal cation can be a cation selected from Ca2+, Sr2+, Cd2+, Cu2+, Ni2+, Mn2+, Fe2+, Co2+, Pd2+, Ge2+, Sn2+, Pb2+, Yb2+ and Eu2+. Of these cations, it is preferred that the divalent metal cation is Pb2+ or Sn2+.
[0542] Often the organic cation has the formula (R1R2R3R4)+, where:
[0543] R1 is hydrogen, or substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl;
[0544] R2 is hydrogen, or substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl;
[0545] R3 is hydrogen, or substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl; and
[0546] R4 is hydrogen, or substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl.
[0547] The organic cation may be as defined anywhere here. Often the organic cation has the formula (R5NH3)+, where: R5 is hydrogen, or substituted or unsubstituted C1-C20 alkyl. For example, the organic cation has the formula (R5NH3)+, wherein: R5 is methyl, ethyl, propyl or butyl, preferably methyl or ethyl. In some cases the organic cation may be a methylammonium cation.
[0548] Alternatively, the organic cation has the formula (R5R6 = CH - NR7R8)+, wherein: R5 is hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl; R6 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl; R7 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl; and R8 is hydrogen, substituted or unsubstituted C1 -C20 alkyl, or substituted or unsubstituted aryl.
[0549] Typically, R5 in the cation (R5R6N = CH - NR7R8)+ is hydrogen, methyl or ethyl, R6 is hydrogen, methyl or ethyl, R7 is hydrogen, methyl or ethyl, and R8 is hydrogen, methyl or ethyl. For example, R5 can be hydrogen or methyl, R6 can be hydrogen or methyl, R7 can be hydrogen or methyl, and R8 can be hydrogen or methyl.
[0550] The organic cation can, for example, have the formula (H2N = CH - NH2)+
[0551] The first and second anions can be any anions, but are typically selected from halide ions (e.g., fluoride, chloride, bromide, and iodide) or chalcogenide ions (e.g., sulfide, selenide, and telluride) . Often the perovskite must be a mixed halide or mixed chalcogenide perovskite and the first and second anions are different anions selected from either halide ions or chalcogenide ions. Preferably the first and second anions are halide anions. Typically, the first and second anions are different anions selected from halide anions. For example, the first anion and the second anion can be one of the following pairs as (first anion: second anion): (fluoride: chloride), (chloride: fluoride), (fluoride: bromide), (bromide: fluoride), (fluoride: iodide), (iodide: fluoride), (chloride: bromide), (bromide: chloride), (chloride: iodide), (iodide: chloride), (bromide: iodide) or (iodide: bromide).
[0552] In some embodiments, the first reagent shall comprise a metal dialect, and the second reagent shall comprise a halide salt of an organic acid. For example, the first reactant may comprise a first compound which is BX2 and the second reactant may comprise a second compound which is AX', where B is a first cation, X is a first anion, A is a second cation and X' is a second anion. Each of the cations and anions can be as defined above. Occasionally, the first reagent comprises a first compound which is BX2 and the second reagent comprises a second compound which is AX', where
[0553] B is a cation selected from Ca2+, Sr2+, 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ Cd , Cu , Ni , Mn , Fe , Co , Pd , Ge , Sn , Pb , Yb and Eu ,
[0554] X is an anion selected from F-, Cl-, Br and I,
[0555] A is a cation of the formula (R5NH3)+, wherein: R5 is hydrogen, or substituted or unsubstituted C1-C20 alkyl,
[0556] X' is an anion selected from F-, CI-, Br - and I-, and
[0557] X and X' are different anions.
[0558] The first reagent may comprise lead halide or tin halide and the second reagent may comprise methyl ammonium halide or ethyl ammonium halide, wherein the halide ion in the first reagent and the second reagent are different. Often, the first reagent comprises stannous fluoride and the second reagent comprises methyl ammonium chloride, methyl ammonium bromide or methyl ammonium iodide;
[0559] the first reagent comprises lead chloride or tin chloride and the second reagent comprises methyl ammonium bromide or methyl ammonium iodide;
[0560] the first reagent comprises lead bromide or tin bromide and the second reagent comprises methyl ammonium chloride or methyl ammonium iodide; or
[0561] the first reagent comprises lead iodide or tin bromide and the second reagent comprises methyl ammonium chloride or methyl ammonium bromide.
[0562] Preferably, the first reagent comprises lead chloride and the second reagent comprises methylammonium iodide.
[0563] These compound pairs also apply to other methods of deposition of a perovskite, eg solution deposition.
[0564] Alternatively, A may be a monovalent inorganic cation. For example, A can be a cation of a metal group, such as Cs+. If A is inorganic, the two halide anions in each reactant may be the same or different. For example, the first reagent may comprise a first compound BX2, and the second reagent may comprise a second compound which is AX, wherein
[0565] B is a cation selected from Ca2+, Sr2+, 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ Cd , Cu , Ni , Mn , Fe , Co , Pd , Ge , Sn , Pb , Yb and Eu ,
[0566] X is an anion selected from F-, Cl-, Br -and I— ,
[0567] A is Cs+,
[0568] X' is an anion selected from F-, CI-, Br - and I-, and
[0569] X and X' are the same or different.
[0570] Double vapor deposition employing these reagents can produce the perovskite layers of formula (IB) as defined above, eg CsSnBr3. Alternatively, CsSnBr3-yIy (where y is as defined in formula II above) can be produced.
[0571] Double vapor deposition allows the evaporation rate (here determined in angstroms per second) of each component to be controlled, thus leading to more controlled deposition. Typically, the evaporation rate of the first reactant (optionally comprising a metal cation) is 0.1 to 10 A/s, or 0.1 to 5 A/s and the evaporation rate of the second reactant (optionally comprising an organic cation ) is 1 to 20 A/s or 1 to 10 A/s. The amount of perovskite disposed can be controlled by changing the amount of time for which the deposition takes place. Typically, a vapor deposition (in both single source or dual source cases) can be performed from 5 to 60 minutes or from 20 to 40 minutes. The deposition time will depend on the evaporation rate used. Often an excess of the second component is preferable, and the molar ratio of the first reactant to the deposited second reactant can be from 1:1 to 1:16, or from 1:4 to 1:16. Vapor deposition can be stopped when the desired layer thickness is achieved.
[0572] Vapor deposition is generally carried out in a chamber with a pressure of less than 10-4 mbar, eg less than 10-5 mbar. The step of arranging the second region in the first region by means of vapor deposition generally also comprising: (iii) heating the solid layer of perovskite so produced.
[0573] The step of heating the solid layer of perovskite generally comprises heating the solid layer of perovskite in an inert atmosphere. Typically, the temperature at which the perovskite solid layer is heated does not exceed 150 °C. In this way, the solid layer of perovskite can be heated to a temperature from 30 °C to 150 °C, and is preferably heated to a temperature from 40 °C to 110 °C. The perovskite solid layer can be heated at said temperature until it has the desired semiconductor properties. Generally, the solid layer of perovskite is heated for at least 30 minutes, preferably for at least 1 hour. In some embodiments, the solid layer of perovskite is heated until the desired semiconductor properties are obtained, which can be measured by routine methods for measuring conductivity and resistivity. The solid layer of perovskite is, in some cases, heated until a color change is observed, which color change indicates that the desired semiconductor properties are obtained. In the case of CH3NH3Pbl2Cl perovskite, the color change is typically from yellow to brown.
[0574] The second region can be arranged in the first region by means of a method comprising disposing a solid layer of a first compound (a first perovskite precursor) in the first region, and then treating the disposed layer with a solution of a second compound (a second perovskite precursor). This is referred to as the "two-step method". The solid layer of a first perovskite precursor can be laid out by means of vacuum deposition. This solid layer is then treated with a solution of a second perovskite precursor. The second precursor in the solution then reacts with the existing solid layer of the first perovskite precursor to produce a solid layer of the perovskite. The solid layer of a first perovskite precursor solution may be treated with a solution comprising the second perovskite precursor, for example, by immersing the solid layer of a first perovskite precursor in a solution comprising the second perovskite precursor. The solid layer of a first perovskite precursor can also be treated by disposing of the solution comprising the second perovskite precursor in the solid layer of the first perovskite precursor.
[0575] The first perovskite precursor is a first compound comprising (i) a first cation and (ii) a first anion and the second perovskite precursor is a second compound comprising (i) a second cation and (ii) a second anion . The first and second cations are generally as defined here for perovskite, and the first and second anions may be the same or different and may be as defined here for the first and second anions.
[0576] In one embodiment, the step of (b) arranging the second region in the first region comprising:
[0577] (i) exposing the first region to vapor, which vapor comprises a first perovskite precursor compound, and allowing the vapor to deposit in the first region to produce a solid layer of the first perovskite precursor compound therein; and
[0578] (ii) treating the resulting solid layer of the first perovskite precursor compound with a solution comprising a second perovskite precursor compound, and thereby reacting the first and second perovskite precursor compounds to produce said semiconductor layer of perovskite without open porosity,
[0579] in which
[0580] the first perovskite precursor compound comprises (i) a first cation and (ii) a first anion and the second perovskite precursor compound comprises (i) a second cation and (ii) a second anion.
[0581] The first cation, first anion, second cation and second anion may be as described anywhere here for perovskite.
[0582] In some cases, the first cation at this point must be a metal cation. In some cases, the second cation at this point must be an organic cation. Thus, the first compound may comprise (i) a metal cation and (ii) a first anion; and the second compound may comprise (i) an organic cation and (ii) a second anion. Preferably the metal cation is a divalent metal cation. For example, the metal cation can be a cation selected from Ca2+, Sr2+, Cd2+, C 2+ Ni2+ M 2+ F 2+ C 2+ Pd2+ G 2+ S 2+ Pb2+ Yb2+ E 2+ D t áti Cu , Ni , Mn , Fe , Co , Pd , Ge , Sn , Pb , Yb and Eu . Of these cations, it is preferred that the divalent metal cation is Pb2+ or Sn2+.
[0583] The first and second anions, which can be the same or different, can be any anions, but are typically selected from halide ions (e.g., fluoride, chloride, bromide, and iodide) or chalcogenide ions. (e.g. sulfide, selenide and telluride).
[0584] Often the perovskite produced must be a mixed halide or mixed chalcogenide perovskite and the first and second anions are different anions selected from either halide ions or chalcogenide ions.
[0585] Preferably the first and second anions are halide anions. Typically, the first and second anions are different anions selected from halide anions. For example, the first anion and the second anion can be one of the following pairs as (first anion: second anion): (fluoride: chloride), (chloride: fluoride), (fluoride: bromide), (bromide: fluoride), (fluoride: iodide), (iodide: fluoride), (chloride: bromide), (bromide: chloride), (chloride: iodide), (iodide: chloride), (bromide: iodide) or (iodide: bromide).
[0586] The organic cation may be selected from (R1R2R3R4N)+, (R5NH3)+, or (R5R6N = CH - NR7R8)+ wherein R1 to R8 may be as defined above.
[0587] Often the first compound has the formula BX2 and the second compound has the formula AX', where
[0588] B is a cation selected from Ca2+, Sr2+, 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ Cd , Cu , Ni , Mn , Fe , Co , Pd , Ge , Sn , Pb , Yb and Eu ,
[0589] X is an anion selected from F-, Cl-, Br -and I-,
[0590] A is a cation of the formula (R5NH3)+, wherein: R5 is hydrogen, or substituted or unsubstituted C1-C20 alkyl,
[0591] X' is an anion selected from F-, CI-, Br - and I-, and
[0592] X and X' are the same or different anions.
[0593] Often the first perovskite precursor compound can be selected from lead fluoride, lead chloride, lead bromide, lead iodide, tin fluoride, tin chloride, tin bromide, or tin iodide. Typically it is lead chloride or lead iodide. Often, the second perovskite precursor compound is selected from methylammonium fluoride, methylammonium chloride, methylammonium bromide, methylammonium iodide, ethylammonium fluoride, ethylammonium chloride, ethylammonium bromide, or ethylammonium iodide. Typically, it is methylammonium iodide.
[0594] Typically, vapor deposition of the first perovskite precursor compound is allowed to continue until the solid layer of the first compound has a desired thickness, e.g. a thickness from 10 nm to 100 μm, or more typically 10 nm at 10 μm. Preferably, vapor deposition is allowed to continue until the solid layer of the first compound has a thickness from 50 nm to 1000 nm, or, for example, from 100 nm to 700 nm. For example, deposition can be continued until approximately 100 nm to 300 nm the first compound is deposited in the first region.
[0595] Vapor deposition may continue until the solid layer of the first perovskite precursor compound has a thickness from 100 nm to 100 μm or from 100 nm to 700 nm.
[0596] The evaporation rate of the first compound can be from 0.1 to 10 A/s, or from 1 to 5 A/s. Vapor deposition is generally carried out in a chamber with a pressure of less than 10-4 mbar, for example less than 10-5 mbar. The temperature at which the first compound is evaporated can be from 200°C to 500°C, or from 250°C to 350°C.
[0597] Typically, step (iii) of exposing the resulting solid layer of the first compound to a solution comprising a second compound to allow the formation of the second region comprises immersing the substrate comprising the solid layer of the first compound in the solution comprising the second compound for a time sufficient to form the second region, that is, the semiconducting perovskite layer without open porosity. Step (iii) may comprise immersing the substrate comprising the solid layer of the first compound in the solution comprising the second compound for from 1 to 60 minutes, or from 5 to 15 minutes.
[0598] Immersion of the substrate comprising the solid layer of the first compound in the solution comprising the second compound may be referred to as dip coating.
[0599] The solution comprising the second perovskite precursor compound comprises a solvent and the second compound. The solvent can be any solvent defined herein. The solvent may be dimethylformamide, ethanol or isopropanol. The solvent may be isopropanol. The concentration of the second compound in the solvent can be from 5 to 50 mg/ml or from 10 to 30 mg/ml.
[0600] After exposing the resulting solid layer of the first perovskite precursor compound to a solution comprising a second compound to allow the formation of the second region (e.g., by dip coating), the substrate can be annealed. For example, the substrate can be heated from 80°C to 200°C or from 100°C to 150°C. Substrates can be heated from 1 to 60 minutes, or from 5 to 15 minutes. Substrates can be annealed in a nitrogen atmosphere.
[0601] Solution deposition methods can be employed to lay out the second region in the first region. Thus, in some embodiments, the step of (b) arranging the second region in the first region comprising:
[0602] (i) arranging one or more precursor solutions in the first region, which one or more precursor solutions comprises: said perovskite dissolved in a solvent, or one or more reagents for producing said perovskite dissolved in one or more solvents; and
[0603] (ii) remove one or more solvents to produce a solid layer of perovskite in the first region.
[0604] Again, the perovskite may be any of the perovskites discussed above for the optoelectronic device of the invention, and is typically a perovskite of formula (I), (IA) or (II) as defined above.
[0605] Likewise, one or more reagents for the production of said perovskite may comprise the types of reagents discussed above for the process of synthesizing the perovskite compounds.
[0606] Thus, one or more reagents may comprise:
[0607] (a) a first compound comprising (i) a first cation and (ii) a first anion; and
[0608] (b) a second compound comprising (i) a second cation and (ii) a second anion, as defined above for the production process of the perovskite compounds employed in the optoelectronic device of the invention.
[0609] More particularly, one or more reagents may comprise:
[0610] (a) a first compound comprising (i) a metal cation and (ii) a first anion; with
[0611] (b) a second compound comprising (i) an organic cation and (ii) a second anion; wherein the first and second anions are different anions selected from halide anions or chalcogenide anions, as defined above for the production process of the perovskite compounds employed in the optoelectronic device of the invention. The organic cation may be as defined above for the perovskite production process.
[0612] For example, one or more reagents may comprise:
[0613] (a) a first compound comprising (i) a metal cation and (ii) a first halide anion; with
[0614] (b) a second compound comprising (i) an organic cation and (ii) a second halide anion; wherein the first and second halide anions are different halide anions, as defined above for the production process of the perovskite compounds employed in the optoelectronic device of the invention.
[0615] For example, when the perovskite to be deposited is CH3NH3Pbl2Cl, one or more reactants typically comprise (a) Pbl2, and (b) CH3NH3Cl.
[0616] Typically, the step of (b) arranging the second region in the first region comprising:
[0617] (i) dispose of a precursor solution in the first region, which precursor solution comprises said perovskite dissolved in a solvent; and
[0618] (ii) remove the solvent to produce in the first region a solid layer of perovskite.
[0619] The perovskite may be any of the perovskites discussed above for the optoelectronic device of the invention, and is typically a perovskite of formula (I), (IA) or (II) as defined above.
[0620] Generally, the steps of (i) disposing of a precursor solution in the first region, and (ii) removing the solvent, comprise spin coating or slotted matrix coating of the precursor solution or solutions in the first region, to produce in the first region of said solid layer of perovskite. Typically, said coating is carried out in an inert atmosphere, for example under nitrogen. Centrifuge coating is generally carried out at a speed from 1000 to 2000 rpm. Spin coating is typically performed for 30 seconds to 2 minutes.
[0621] The precursor solution or solutions can be arranged by spin coating in the first region to produce in the first region said solid layer of perovskite.
[0622] The steps of disposing precursor solution or solutions in the first region and removing the solvent or solvents are carried out until the solid layer of perovskite has a desired thickness, for example, a thickness from 10 nm to 100 μm, more typically from 10 nm to 10 μm. For example, the steps of disposing of the precursor solution or solutions in the first region and removing the solvent or solvents can be carried out until the perovskite solid layer has a thickness from 50 nm to 1000 nm, or, for example, from 50 nm to 1000 nm. 100nm to 700nm.
[0623] The steps of disposing of the precursor solution or solutions in the first region and the removal of the solvent or solvents can be carried out until the solid layer of perovskite has a thickness from 100 nm to 100 μm, or from 100 nm to 700 no.
[0624] The step of arranging the second region in the first region (by means of solution deposition) generally also comprising: (iii) heating the solid layer of perovskite thus produced.
[0625] The step of heating the solid layer of perovskite generally comprises heating the solid layer of perovskite in an inert atmosphere. Typically, the temperature at which the solid layer of perovskite is heated does not exceed 150°C. In this way, the solid layer of perovskite can be heated to a temperature from 30 °C to 150 °C, and is preferably heated to a temperature from 40 °C to 110 °C. The perovskite solid layer can be heated at said temperature until it has the desired semiconductor properties. Generally, the perovskite solid layer is heated for at least 30 minutes, preferably for at least 1 hour. In some embodiments, the solid layer of perovskite is heated until the desired semiconductor properties are obtained, which can be measured by routine methods for measuring conductivity and resistivity. The solid layer of perovskite is, in some cases, heated until a color change is observed, which color change indicates that the desired semiconductor properties are obtained. In the case of CH3NH3Pbl2Cl perovskite, the color change is typically from yellow to brown.
[0626] In some embodiments of the process of the invention (for example, when the photoactive region of the device being produced having no support material), the second region consists of said layer of said semiconductor of perovskite without open porosity.
[0627] In another embodiment of the process of the invention, however, said photoactive region comprises:
[0628] said n-type region;
[0629] said p-type region; and, arranged between the n-type region and the p-type region:
[0630] (i) a first layer comprising a support material and a perovskite semiconductor; and
[0631] (ii) a buffer layer disposed on said first layer, which buffer layer is said layer of a perovskite semiconductor without open porosity,
[0632] where the perovskite semiconductor in the buffer layer is in contact with the perovskite semiconductor in the first layer,
[0633] and the process comprises:
[0634] (a) provide said first region;
[0635] (b) arranging said second region in the first region, wherein the second region comprises:
[0636] (i) a first layer comprising a support material and a perovskite semiconductor; and
[0637] (ii) the buffer layer in said first layer, which buffer layer is said layer of a perovskite semiconductor without open porosity, wherein the perovskite semiconductor in the buffer layer is in contact with the perovskite semiconductor in the first layer; and
[0638] (c) arranging said third region in the second region.
[0639] In general, the support material is porous and said first layer comprises said perovskite semiconductor disposed in the pores of the support material. Thus, typically, in this embodiment, the step of (b) arranging said second region in the first region comprising:
[0640] (i) place a support material in the first region; and
[0641] (ii) disposing said perovskite in the pores of the support material to produce said first layer and also disposing said perovskite in the first layer to produce said buffer layer. Generally, the "arrangement" of said perovskite in the pores of the support material and the "other arrangement" of said perovskite in the first layer are carried out together in a single step, for example by means of the solution deposition step or by means of vapor deposition. They are typically performed by means of solution deposition.
[0642] Typically, step (i) of arranging a support material in the first region comprises:
[0643] arrange a support composition in the first region, which support composition comprises the support material, one or more solvents, and optionally a binder; and
[0644] remove one or more solvents and, when present, the binder.
[0645] The binder is typically a polymer binder, such as, for example, ethyl cellulose.
[0646] This step typically comprises screen printing, doctor blade, slotted die coating or spin coating of the support composition in the first region.
[0647] The films are typically subsequently heated, or to a temperature of around 500°C (and generally held there for around 30 minutes) in order to degrade and remove any polymer binder that is present (high sintering temperature) , or, in the absence of binder, were typically heated to around 120 °C and held there for around 90 minutes (low sintering temperature). The substrates were typically then promptly cooled for perovskite solution deposition.
[0648] Thus, generally, step (i) of arranging the support material in the first region also comprises heating the support composition.
[0649] Of importance to low temperature processing of the mesoporous support layer is the absence of a thermodegradable polymer binder in the nanoparticle slurry during deposition. Instead, the nanoparticles are deposited from a colloidal dispersion in one or more solvents. At low temperatures, the adhesion between the particles and the substrate occurs through the dehydration of the surface hydroxide groups [T. Miyasaka et al., Journal of the Electrochemical Society, vol. 154, p. A455, 2007. The inventors also show that porosity can be tuned by mixing two solvents in the dispersion with different viscosities and boiling points.
[0650] Thus, in a preferred embodiment, the support composition does not comprise a binder and the temperature at which the support composition is heated does not exceed 150°C.
[0651] Thus, typically, step (i) of arranging a support material in the first region comprises:
[0652] arrange a support composition in the first region, whose support composition comprises the support material and one or more solvents; and
[0653] remove one or more solvents.
[0654] Generally, step (i) of disposing the support material in the first region also comprises heating the support composition to a temperature not exceeding 150°C. Typically, the support composition is heated to a temperature from 60°C to 150°C. The support composition is heated at said temperature for a suitable time, for example, until all solvents are removed. Typically, the support composition is heated to said temperature for at least 30 minutes, more typically for at least 1 hour, or for at least 90 minutes.
[0655] Generally, step (i) of arranging the support material in the first region is carried out until the support material that is placed in the first region has a desired thickness, for example, a thickness from 5 nm to 500 nm , preferably from 30 nm to 200 nm.
[0656] The support material employed in the support composition may be as defined above for the optoelectronic device of the invention. Often, the support material used is titania or alumina.
[0657] One or more solvents employed in the support composition may comprise a mixture of two or more solvents with different viscosities and boiling points, for example, a mixture of two solvents with different viscosities and boiling points. The use of two or more solvents with different viscosities and boiling points is advantageous, as the inventors have shown that the porosity of the support material arranged in the first region can be tuned by varying the ratio of the two or more solvents. Two or more solvents may, for example, comprise two or more different alcohols, for example two different alcohols. Thus, for example, two or more solvents may comprise two solvents selected from ethanol, propanol, butanol and terpineol, or from ethanol, iso-propanol, tert-butanol and terpineol.
[0658] Typically, step (ii), of disposing said perovskite in the pores of the support material in order to produce said first layer and also disposing said perovskite in the first layer to produce said buffering layer is carried out until the buffer layer has a desired thickness, for example a thickness from 10 nm to 100 μm, or more typically a thickness from 10 nm to 10 μm, preferably from 50 nm to 1000 nm, or, for example, a thickness from 100 nm to 700 nm.
[0659] Solution deposition methods can be employed to arrange said perovskite in the pores of the support material in order to produce said first layer and also to arrange said perovskite in the first layer to produce said buffer layer. Thus, in some embodiments, step (ii), of disposing said perovskite in the pores of the support material to produce said first layer and also disposing said perovskite in the first layer to produce said buffer layer, comprises :
[0660] to arrange one or more precursor solutions in the support material, which one or more precursor solutions comprises: said perovskite dissolved in a solvent, or one or more reagents for the production of said perovskite dissolved in one or more solvents; and
[0661] remove one or more solvents to produce solid perovskite in the pores of the support material and a solid perovskite buffer layer disposed in the first layer.
[0662] The perovskite may be any of the perovskites discussed above for the optoelectronic device of the invention, and is typically a perovskite of formula (I), (IA) or (II) as defined above.
[0663] Likewise, one or more reagents for the production of said perovskite may comprise the types of reagents discussed above for the process of synthesizing the perovskite compounds.
[0664] Thus, one or more reagents may comprise:
[0665] (a) a first compound comprising (i) a first cation and (ii) a first anion; and
[0666] (b) a second compound comprising (i) a second cation and (ii) a second anion, as defined above for the production process of the perovskite compounds employed in the optoelectronic device of the invention.
[0667] More particularly, one or more reagents may comprise:
[0668] (a) a first compound comprising (i) a metal cation and (ii) a first anion; with
[0669] (b) a second compound comprising (i) an organic cation and (ii) a second anion; wherein the first and second anions are different anions selected from halide anions or chalcogenide anions, as defined above for the production process of the perovskite compounds employed in the optoelectronic device of the invention.
[0670] For example, one or more reagents may comprise:
[0671] (a) a first compound comprising (i) a metal cation and (ii) a first halide anion; with
[0672] (b) a second compound comprising (i) an organic cation and (ii) a second halide anion; where the first and second halide anions are different halide anions,
[0673] as defined above for the production process of the perovskite compounds employed in the optoelectronic device of the invention.
[0674] For example, when the perovskite to be deposited is CH3NH3Pbl2Cl, one or more reactants typically comprise (a) Pbl2, and (b) CH3NH3Cl.
[0675] Typically, step (ii), of disposing said perovskite in the pores of the support material in order to produce said first layer and also disposing said perovskite in the first layer to produce said buffering layer, comprises:
[0676] dispose of a precursor solution in the support material, whose precursor solution comprises said perovskite dissolved in a solvent; and
[0677] remove the solvent to produce solid perovskite in the pores of the support material and a solid perovskite buffer layer disposed in the first layer.
[0678] The perovskite may be any of the perovskites discussed above for the optoelectronic device of the invention, and is typically a perovskite of formula (I), (IA) or (II) as defined above.
[0679] Generally, the steps of disposing a precursor solution on the support material, and removing the solvent or solvents, comprise centrifuge coating or slotted matrix coating of the precursor solution or solutions on the support material, to produce said solid perovskite in the pores of the support material and said solid perovskite buffer layer disposed in the first layer. Typically, the coating is carried out in an inert atmosphere, for example under nitrogen. Centrifuge coating can, for example, be carried out at a speed from 1000 to 2000 rpm. Spin coating is typically performed for 30 seconds to 2 minutes.
[0680] The steps of disposing of the precursor solution or solutions on the support material and removing the solvent or solvents are carried out until the solid perovskite buffer layer has a desired thickness, for example a thickness from 10 nm to 100 µm, or more typically from 10 nm to 10 µm, or, for example, from 50 nm to 1000 nm, preferably from 100 nm to 700 nm.
[0681] Generally, the step of (b) arranging said second region in the first region also comprising: (iii) heating the perovskite.
[0682] The step of heating the perovskite generally comprises heating the perovskite in an inert atmosphere, for example under nitrogen. Typically, the temperature at which perovskite is heated does not exceed 150 °C. In this way, perovskite can be heated to a temperature from 30°C to 150°C, and is preferably heated to a temperature from 40°C to 110°C. The perovskite can be heated at said temperature until it has the desired semiconductor properties. Generally, the perovskite is heated for at least 30 minutes, preferably for at least 1 hour. In some embodiments, the perovskite is heated until the desired semiconductor properties are obtained, which can be measured by routine methods for measuring conductivity and resistivity. Perovskite is, in some cases, heated until a color change is observed, which color change indicates that the desired semiconductor properties have been obtained. In the case of CH3NH3Pbl2Cl perovskite, the color change is typically from yellow to brown.
[0683] Generally, in the process of the invention for the production of an optoelectronic device the first region is arranged on a first electrode. That is to say, the first region is generally already arranged on a first electrode.
[0684] The process of the invention for the production of an optoelectronic device may, however, also comprise a step of:
[0685] Arrange the first region on a first electrode.
[0686] This step is generally performed before the step of placing the second region in the first region.
[0687] The first and second electrodes are an anode and a cathode, one or both of which are transparent to allow light to enter. The choice of the first and second electrodes may depend on the type of structure.
[0688] Typically, the first electrode on which the second region is arranged is tin oxide, more typically fluorine-doped tin oxide (FTO), which is usually a transparent or semi-transparent material. Thus, the first electrode is generally transparent or semi-transparent and typically comprises FTO. Generally, the thickness of the first electrode is from 200 nm to 600 nm, more generally from 300 to 500 nm. For example, the thickness can be 400 nm. Typically, the FTO is coated on a sheet of glass. Often, FTO coated glass sheets are etched with zinc powder and an acid to produce the required electrode pattern. Usually the acid is HCl. Often the concentration of HCl is about 2 molar. Typically, the leaves are cleaned and then generally treated under oxygen plasma to remove any organic residues. Generally, treatment under oxygen plasma is for less than or equal to 1 hour, typically about 5 minutes. The first and second electrodes may be as described elsewhere above, for example the first electrode may comprise FTO, ITO or AZO.
[0689] The steps of disposing the first region in a first electrode and the disposing of the third region in the second region, comprises the deposition of the n-type regions of the p-type, that is, the deposition of one or more layers of the p-type deposition of one or more n-type layers. The n-type and p-type regions, and one or more p-type layers and one or more n-type layers, may be as defined above.
[0690] The step of deposition of a layer of an inorganic compound of n-type or p-type may, for example, comprise deposition of the layer by means of spin coating or by means of slot matrix coating of the compound or a precursor thereof, or by means of pyrolysis spray. For example, a compact layer of titania can be produced by centrifuge coating a (slightly) acidic titanium-isopropoxide solution in a suitable solvent, such as ethanol. Such a solution can be prepared by mixing titanium isopropoxide and anhydrous ethanol with a solution of HCl in anhydrous ethanol. After spin coating, the layer is typically dried at a temperature not exceeding 150°C. Optionally, the compact layer was subsequently heated at 500 °C for 30 minutes on an air hot plate. Alternatively, such a compact layer can be produced by spray pyrolysis deposition. This would typically comprise deposition of a solution comprising titanium diisopropoxide bis(acetylacetonate), generally at a temperature from 200 to 300°C, often at a temperature of around 250°C. Generally the solution comprises titanium diisopropoxide bis(acetylacetonate) and ethanol, typically in a ratio of from 1:5 to 1:20, more typically in a ratio of about 1:10.
[0691] Such methods can be applied to other p-type or n-type inorganic materials to produce p-type or n-type layers in the optoelectronic devices of the invention.
[0692] The deposition of a polymeric, organic, molecular or electron-carrying hole carrier material can be achieved by centrifuge coating a solution of the material in a suitable solvent. The p-type hole carrier, spiro-OMeTAD, for example, is typically dissolved in chlorobenzene. Generally the concentration of spiro-OMeTAD in chlorobenzene is from 150 to 225 mg/ml, more generally the concentration is about 180 mg/ml. An additive can be added to the hole carrier or electron carrier material. The additive may be, for example, tBP, Li-TFSi, an ionic liquid or an ionic liquid with a halide(s) mixed in.
[0693] The process of the invention for producing an optoelectronic device may also comprise: (d) arranging a second electrode in the third region.
[0694] Generally, the second electrode comprises a high working metal function, eg gold, silver, nickel, palladium or platinum, and typically silver. Generally, the thickness of the second electrode is from 50 nm to 250 nm, more generally from 100 nm to 200 nm. For example, the thickness of the second electrode can be 150 nm.
[0695] The second electrode is typically disposed in the third region by means of vapor deposition. Often, the step of producing a second electrode comprises placing a film comprising the hole-carrying material in a thermal evaporator. Generally, the step of producing a second electrode comprises deposition of the second electrode through a shadow mask under a high vacuum. Typically, the vacuum is around 106 mBar.
[0696] The second electrode may, for example, be an electrode with a thickness of 100 to 200 nm. Typically, the second electrode is an electrode with a thickness of 150 nm.
[0697] Alternatively, the process of the invention for producing an optoelectronic device may be a process for producing an inverted optoelectronic device.
[0698] Thus, the invention provides a process for producing an inverted optoelectronic device comprising a photoactive region, characterized in that the photoactive region comprises:
[0699] an n-type region comprising at least one n-type layer;
[0700] a p-type region comprising at least one p-type layer; and, arranged between the n-type region and the p-type region:
[0701] a layer of a perovskite semiconductor without open porosity,
[0702] whose process comprises:
[0703] (a) provide a first region;
[0704] (b) arranging a second region in the first region, which second region comprises a layer of a perovskite semiconductor without open porosity; and
[0705] (c) place a third region in the second region,
[0706] where:
[0707] the first region is a p-type region comprising at least one p-type layer and the third region is an n-type region comprising at least one n-type layer, and the first region is arranged on a first electrode.
[0708] Typically, the first electrode comprises a transparent or semi-transparent material. Typically, the first electrode comprises a transparent conductive oxide, for example FTO, ITO or AZO. Preferably, the first electrode comprises FTO. The first electrode can be arranged on a glass substrate.
[0709] Each of the steps in the process for producing an inverted optoelectronic device may be as defined anywhere herein for a process according to the invention for producing an optoelectronic device. Each of the components employed or present in the process may be as defined for an optoelectronic device in accordance with the invention.
[0710] The first region, which is a p-type region, may be as defined anywhere here for a p-type region. Often, the first region comprises a layer of PEDOT:PSS. Crosslinking can be performed to insolubilize the p-type region so that it is not partially dissolved during disposition of the second region, if the disposition process can lead to the p-type layer being dissolved. Occasionally, for this reason, the layer of PEDOT:PSS comprises cross-linked PEDOT:PSS. Crosslinking can be carried out using a Lewis acid, for example a metal cation such as Fe2+ or Mg2+. For example, (a) may comprise
[0711] (i) provide a first region comprising a layer of PEDOT:PSS and
[0712] (ii) treating the layer with aqueous FeCl 3 to produce a crosslinked PEDOT:PSS layer comprising PEDOT:PSS.
[0713] The second region, which is an n-type region, may be as defined anywhere here for an n-type region. Often, the n-type region comprises a compact layer of an inorganic n-type semiconductor such as the one defined here. Typically, the n-type region comprises a compact layer of titanium dioxide. In some embodiments, the n-type region also comprises a layer of [60]PCBM.
[0714] For this reason, in some modalities, (c) comprises
[0715] (i) arranging in the second region a layer of [60]PCBM; and
[0716] (ii) arrange in the layer of [60]PCBM a compact layer of titanium dioxide.
[0717] In an inverted device, a second electrode can be placed in the third region which is an n-type region. In this way, the process can also include
[0718] (d) arrange a second electrode in the third region.
[0719] The second electrode can be placed directly in the third region, or there can be more intervening layers. Typically, the second electrode is in contact with the third region. The second electrode may be as defined anywhere herein and typically comprises a metal. For example, the second electrode may comprise aluminum, gold, silver, nickel, palladium or platinum, and typically aluminum, silver or gold. In one embodiment, the second electrode comprises silver, gold or aluminum. For example, if the n-type region comprises a compact layer of titanium and a layer of [60]PCBM, the second electrode may comprise aluminum. The second electrode may be disposed by any technique such as that described herein, although it is typically disposed by means of vacuum deposition.
[0720] In this way, the second electrode can be arranged by means of vacuum deposition. Alternatively, the process of the invention for producing an optoelectronic device may be a process for producing a multiple-junction or in-series optoelectronic device which also comprises:
[0721] (d) arrange a tunnel junction in the third region;
[0722] (e) arrange another photoactive region at the tunnel junction which is the same as or different from the photoactive region defined above;
[0723] (f) optionally repeating steps (d) and (e); and
[0724] (g) arrange a second electrode in the other photoactive region arranged in the previous step.
[0725] In a process of producing a multiple junction or series device according to the invention, the other photoactive region may be as defined elsewhere above for optoelectronic devices in series according to the invention. In particular, the other photoactive region may comprise a layer of crystalline silicon, or it may comprise a thin film of CIGS, CIS or CZTSSe.
[0726] In a preferred embodiment, of the process of the invention for the production of an optoelectronic device, the entire process is carried out at a temperature or temperatures not exceeding 150 °C.
[0727] In the process of the invention for producing an optoelectronic device, the optoelectronic device may be as defined above for the optoelectronic device of the invention.
[0728] The invention also provides an optoelectronic device which is obtainable by the process of the invention for producing an optoelectronic device.
[0729] The present invention is also illustrated in the Examples that follow: EXAMPLES EXPERIMENTAL METHODS FOR DEVICE PREPARATION PREPARATION OF AI2O3 PASTE WITH POLYMER BINDING
[0730] An aluminum oxide dispersion was purchased from Sigma-Aldrich (10% by weight in water) and washed as follows: centrifuged at 7500 rpm for 6 hours, and redispersed in Absolute Ethanol (Fisher Chemicals) with an ultrasonic probe; which was operated for a total sonication time of 5 minutes, 2 seconds cycling on, 2 seconds off. This process was repeated 3 times.
[0731] For every 10 g of the original dispersion (1 g of total Al2O3) the following was added: 3.33 g of α-terpineol and 5 g of a 50:50 mixture of 10 cP and 46 cP ethyl cellulose purchased from Sigma Aldrich in ethanol, 10% by weight. After the addition of each component, the mixture was stirred for 2 minutes and sonicated with the ultrasonic probe for 1 minute of sonication, employing a 2-second to 2-second off cycle. Finally, the resulting mixture was introduced into a rotary evaporator to remove excess ethanol and obtain the required thickness when doctor slide, spin coating or screen printing. PREPARATION OF TIO2 PASTE WITH POLYMER BINDING
[0732] A titanium dioxide dispersion containing a polymer binder (DSL 18NR-T) was purchased from Dyesol. It was diluted in a 3:1 weight ratio of absolute ethanol (Fisher Chemicals): DSL 18NR-T with an ultrasonic probe; which was operated for a total sonication time of 5 minutes, cycling off every 2 seconds. PREPARATION OF AI2O3 PASTE WITHOUT POLYMER BINDING
[0733] An aluminum oxide dispersion was purchased from Sigma-Aldrich (20% by weight in isopropanol). This was diluted in 16 volume equivalents of isopropanol. PREPARATION OF TIO PASTE^WITHOUT POLYMER BINDING
[0734] A titanium dioxide powder (P25) was purchased from (Degussa) and dispersed in ethanol at 20 mg/ml. This was diluted in 16 volume equivalents of ethanol. PREPARATION OF METHYLAMONIUM IODIDE PRECURSOR AND PEROVSKITE PRECURSOR SOLUTION
[0735] Methylamine solution (CH3NH2) of 33% by weight in absolute ethanol (Sigma-Aldrich) was reacted with hydroiodic acid of 57% by weight (Sigma-Aldrich) in a 1 :1 molar ratio under nitrogen atmosphere in ethanol anhydrous grade 200 (Sigma-Aldrich). Typical amounts were 24 ml of methylamine, 10 ml of hydroiodic acid and 100 ml of ethanol. Crystallization of methyl ammonium iodide (CHNH3I) was obtained using a rotary evaporator. A white colored precipitate was formed indicating successful crystallization.
[0736] Methylamine can be substituted for other amines such as ethylamine, n-butylamine, tert-butylamine, octylamine etc. in order to change the subsequent perovskite properties. Furthermore, hydroiodic acid can be replaced by other acids to form different perovskites, such as hydrochloric acid.
[0737] To prepare the precursor solution of methylammonium iodide (CHNH3I) and lead(II) chloride (Sigma-Aldrich) precipitate was dissolved in dimethylformamide (C3H7NO) (Sigma-Aldrich) in a molar ratio of 1:1 in 30 % volume. CLEANING AND ENGRAVING THE SUBSTRATE AND TRANSPARENT ELECTRODE
[0738] Fluorine-doped tin oxide (F:SnO2/FTO) coated with glass sheets (TEC 15, 15 Q/square, Pilkington USA) was etched with zinc powder and HCl (2 M) to produce the pattern of electrode needed. The leaves were subsequently cleaned with soap (2% Hellmanex in water), deionized water, acetone, ethanol and finally treated under oxygen plasma for 5 minutes to remove any organic residues. COMPACT TIO2 LAYER DEPOSITION
[0739] The FTO patterned sheets were then coated with a compact layer of TiO2 by spin coating a slightly acidic titanium-isopropoxide solution (Sigma-Aldrich) in ethanol. The solution was prepared by mixing titanium isopropoxide: anhydrous ethanol in a weight ratio of 0.71:4 with a 2M acidic solution of HCl: anhydrous ethanol in a weight ratio of 0.07:4. After spin coating (speed = 2000 rpm, acceleration = 2000 rpm/s, time = 60 s), the substrates were dried at 150 °C on a hot plate for 10 minutes. Optionally, the compact layer was subsequently heated at 500 °C for 30 minutes on an air hot plate. DEPOSITION OF THE FINE LAYER OF MESOPOROUS METAL OXIDE
[0740] The insulating metal oxide paste (for example, the AI2O3 paste) was applied on top of the metal oxide compact layer by screen printing, doctor foil coating or spin coating, through a suitable mesh, doctor blade height or centrifuge speed to create a film with a thickness of ~100 nm. The films were subsequently either heated to 500°C and held there for 30 minutes in order to degrade and remove the polymer binder (high sintering temperature), or, in the absence of binder, heated to 120°C and held there for 90 minutes (low sintering temperature). The substrates were then promptly cooled for deposition of the perovskite solution. DEPOSITION OF THE PEROVSKITE PRECURSOR SOLUTION AND FORMATION OF THE SEMICONDUCTOR PEROVSKITE FINE FILM
[0741] 40 μl of the perovskite precursor solution in dimethylformamide (lead(II) chloride methylammonium iodide (CH3NH3PbCl2l)) at a volume concentration of 30% was dispensed into each prepared and coated mesoporous electrode film by centrifugation at 1500 rpm for 60 s in an inert nitrogen environment. The coated films were then placed on a hot plate set at 100 °C and left for 60 minutes in nitrogen before cooling. During the drying procedure at 100 degrees, the coated electrode changed color from light yellow to dark brown, indicating the formation of the desired perovskite film with semiconducting properties. EVAPORATED DEPOSITION OF THE PRECURSOR OF PEROVSKITE AND FORMATION OF THE FINE FILM OF PEROVSKITE SEMICONDUCTOR
[0742] A 1:1 molar ratio of Pbl2 and CH3NH3Cl was ground with a pestle and mortar for 15 minutes to form a bulk perovskite powder. This formed a powder which was desiccated in a nitrogen environment for >12 hours. A crucible of perovskite powder was transferred to an evaporation chamber which was subsequently evacuated. The crucible was slowly heated to 300 °C. When the source temperature reached 100 °C, a shutter was opened to begin deposition on the substrates. The heater was periodically turned off to maintain a pressure of 10~4 mbar in the chamber. Evaporation continued until a thin film of approximately 100-300 nm was deposited on the substrates. After evaporation, the substrate with the evaporated material was heated at 50 °C for 1 hour in a nitrogen environment. PREPARATION OF PEROVSKITES INCLUDING A FORMAMIDINUM CATION
[0743] As an alternative to ammonium ions, formamidium cations can be employed. Formamidinium iodide (FOI) and formamidinium bromide (FOBr) were synthesized by reacting a 0.5 M molar solution of formamidinium acetate in ethanol with a 3x molar excess of hydroiodic acid (for FOI) or hydrobromic acid. (for FOBr). The acid was added dropwise while stirring at room temperature, and then allowed to stir for another 10 minutes. After drying at 100 °C, a yellowish white powder is formed, which is then dried overnight in a vacuum oven before use. To form FOPbl3 and FOPbBr3 precursor solutions, FOI and Pbl2 or FOBr and PbBr2 were dissolved in anhydrous N,N-dimethylformamide in a 1:1 molar ratio, 0.88 millimoles of each per ml, to produce 0.88 M of perovskite precursor solutions. To form the perovskite precursors FOPbl3zBr3(1-z), the mixtures were made of 0.88 M of the solutions of FOPbl3 and FOPbBr3 in the necessary ratios, where z varies from 0 to 1. The films for characterization or fabrication of the device were coated by centrifugation in a nitrogen-filled glove box, and annealed at 170 °C for 25 minutes in a nitrogen atmosphere. DEPOSITION HOLE CONVEYOR AND DEVICE ASSEMBLY
[0744] The hole carrier material used was 2,2(,7,7(-tetracys-(N,N-dimethoxyphenylamine)9,9(-spirobifluorene)) (spiro-OMeTAD, Lumtec, Taiwan), the which was dissolved in chlorobenzene at a typical concentration of 180 mg/ml Tertbutyl pyridine (tBP) was added directly to the solution with a to mass ratio of 1:26 μl/mg tBP:spiro-MeOTAD. Lithium bis(trifluoromethylsulfonyl)amine salt (Li-TFSI) was pre-dissolved in acetonitrile at 170 mg/ml, and then added to the hole carrier solution at 1:12 μl/mg Li-TFSI:spiro solution -MeOTAD. A small amount (80 μl) of the spiro-OMeTAD solution was dispensed onto each perovskite coated film and centrifuged at 1500 rpm for 30 seconds in air. The films were then placed in a thermal evaporator where 200 nm of Thick silver electrodes were deposited through a shadow mask under high vacuum (10-6 mBar). VARIATIONS OF THE INVESTIGATED DEVICE
[0745] A generic schematic of the device structure is shown in figure 1a. This device can be mounted on any solid substrate material (glass, plastic, foil, metal mesh, etc). In figure 1a, at least one of the metallic electrodes must be transparent / semi-transparent (e.g. doped or mesh metal, non-doped oxide, perovskite, polymer, thin metal, metal, etc.) while the opposite electrode can be transparent / or reflector to semi-transparent. The light absorption of perovskite, which can be n-type, p-type or intrinsic, is sandwiched between an n-type and a p-type semiconductor layer (organic, inorganic, Si amorphous, perovskite, etc. organic/inorganic hybrid ) electron and selective hole extraction respectively. The structure shown can be inverted. Multijunction cells can be produced by stacking a repeating structure.
[0746] Certain embodiments of the devices of the present invention have the specific structure shown in Figure 1b. When used, the thin metal oxide layer is generally permeable to solution-processed perovskite, to ensure direct contact of perovskite with selective electron contact. Each of the preparation variations investigated here are summarized in Table 1. TABLE 1. SUMMARY OF VARIATIONS FOR THE LAYERS INVESTIGATED

RESULTS AND DISCUSSION POROSITY CONTROL OF LOW TEMPERATURE SINTERIZED MESOPOROUS AL2O3
[0747] The porosity of a mesoporous layer of AI2O3 can be controlled by mixing two solvents with different viscosities and different evaporation rates, using nanoparticle dispersion. After deposition of the dispersion and removal of the solvent, the refractive index of a mesoporous thin film composite of Al2 O3 and air depends on the volume fraction of the two components, i.e., porosity. The refractive indices of films formed by spin-coating dispersions with varying content of terpineol and t-butanol on glass slides are shown in Table 2, below, indicated as equivalents by volume. A lower refractive index is indicative of a higher volume fraction of air i.e. more porous film. The addition of a secondary solvent is generally found to increase the porosity of the resulting mesoporous film. TABLE 2. SUMMARY OF POROSITY VARIATION WITH A VARIING QUANTITY OF ADDED VOLUME EQUIVALENTS OF A SECONDARY SOLVENT IN THE ALUMINA DISPERSION AS INDICATED BY MEANS OF REFRACTIVE INDEX MEASURED OF THE RESULTING FILM

X-RAY DIFFRACTION
[0748] The XRD patterns of thin perovskite films, based on the different investigated sublayer variations are shown in Figure 2a. All samples were prepared on smooth glass and, when thin mesoporous oxides are specified, without compact layers. Both the 110 and 220 perovskite peaks are prominent according to our earlier demonstration of this perovskite [Lee et al., Science, Submitted 2012]. Figure 2b shows the XRD pattern of perovskite when evaporated. Corresponding peaks for the mixed halide perovskites are present in addition to those occurring from Pbl2. UV-VIS SPECTROSCOPY
[0749] The UV-vis patterns for thin perovskite films, based on the different investigated sublayer variations are shown in Figure 3. All samples were prepared in flat glass and, in which the thin mesoporous oxides are specified, without compact layers . The spectra show normalized extinction (ε = log10 [I0/ I1i]). - All spectra show an onset of absorption at a wavelength of ~800 nm confirming the presence of perovskite. Although diffraction peaks corresponding to Pbl2 XRD were observed for the evaporated perovskite, the UV-vis spectrum indicates that most of the light is absorbed by the perovskite. The shapes of the spectra agree with our previous demonstration of this perovskite type [M. Lee et al., Science, Presented 2012]. CURRENT-VOLTAGE CHARACTERISTICS
[0750] The voltage and current density (JV) characteristics of some devices representing each investigated variation are presented in Figure 4. A summary of the parameters extracted from these results is presented in Table 3. The thickness of the thin oxide layer (tmesoporous) and the perovskite leveling layer (t-perovskite buffer) as measured with a surface profilometer are also shown in Table 3. For thickness measurements, samples were prepared on flat glass and in which fine mesoporous oxides are specified , without compact layers. The ratio of these thicknesses suggests that most of the light absorption will occur in the leveling layer forming a flat heterojunction with the carrier material hole. TABLE 3. SUMMARY OF PARAMETERS EXTRACTED FROM THE JV CHARACTERISTICS OF THE MOST EFFICIENT DEVICES
SCANNING ELECTRON MICROSCOPY
[0751] Cross-sectional micrographs of solar cells are shown in Figure 5 (a) - (f). The distinct layers shown in the cross-sections are, from right to left: glass, FTO, compact layer, mesoporous layer, the perovskite leveling layer, spiro-OMeTAD and Ag. Planar images of the mesoporous layers are shown in Figure 6 (a) - (f) and in Figure 7 (a) and (b). Where AI2O3 is used, both with and without binder and sintered at high and low temperatures, the images clearly show a mesoporous structure allowing perovskite infiltration and seeding. Compact layers shown in Figures 6 (e) and 6 (f) characteristic features appear in the resolution of the instrument. Where TiO2 is used, with binder the film appears mesoporous. However, in the absence of a binding agent, the nanoparticles aggregate forming a sub-no layer. CONCLUSION
[0752] The Examples show that it is possible to create planar n-type / perovskite absorber / p-type structured optoelectronic devices. Growth of a perovskite light absorber was achieved in a thin support or in the absence of support deposition solution. Devices that incorporate a thin layer of seeds can be fully processed at temperatures not exceeding 150 °C, which is important for flexible and/or tandem/multijunction devices. Furthermore, it has been shown that perovskite can be formed by evaporation from a bulk powder. INVERTED HETEROJUNCTION PEROVSKITE SOLAR CELLS SUBSTRATE PREPARATION:
[0753] Fluorine doped tin oxide (FTO) coated glass sheets (7 Q/D Pilkington) were etched with zinc dust and HCl (2 Molar) to obtain the required electrode pattern. The leaves were then washed with soap (2% Hellmanex in water), deionized water, acetone, methanol and finally treated under an oxygen plasma for 5 minutes to remove the last traces of organic residue. PRECURSOR SOLUTION WITH FLAT TiOx FILM
[0754] The TiOx flat film precursor solution consists of 0.23M titanium isopropoxide (Sigma Aldrich, 99.999%) and 0.013M HCl solution in ethanol (>99.9% Fisher Chemicals). To prepare this solution, titanium isopropoxide was diluted in 0.46 M ethanol. Separately, a 2M HCl solution was diluted with ethanol to reach a concentration of 0.026 M. Finally, the acidic solution was added dropwise to the solution. titanium precursor under heavy agitation. MANUFACTURE OF REGULAR ARCHITECTURE:
[0755] The etched FTO substrates were coated with a compact layer of TiO2 deposited by centrifuge coating the precursor solution with TiOx flat film at 2000 rpm for 60 seconds and subsequently heating at 500 °C for 30 minutes to form titania stoichiometric anatase. Then, the mesostructured support was deposited by a colloidal dispersion of ~20 nm Al2O3 nanoparticles in isopropanol spin coating, followed by drying at 150 °C for 10 minutes. After cooling to room temperature, the perovskite was deposited by spin coating from a DMF solution of methylammonium iodide and PbCl2 (3:1 molar ratio), which formed the perovskite after heating at 100 °C for 45 minutes. The hole-carrying layer was deposited by spin coating 7% by volume of Spiro-OMeTAD (2,2',7,7'-tetracys(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene ) in chlorobenzene with solution were added 80 mM tert-butylpyridine (TBP) and 25 mM bis-lithium (trifluoromethanesulfonyl) imide (LITFS1) at 1000 rpm for 45 s. Finally, the devices were filled with high vacuum evaporation of Ag contact electrodes through a shadow mask. MANUFACTURE OF INVERTED ARCHITERURE: PEDOT.PSS:
[0756] The etched FTO substrates were coated with a thin film of PEDOT:PSS deposited via spin coating of a 25:75 by volume solution of PEDOT:PSS (Clevios):isopropanol (>99.9%, Fisher Chemicals) at 2000 rpm for 60 seconds and subsequently annealed at 150°C for 20 minutes or cross-linked by submerging the substrates for 5 minutes in a 0.25M aqueous solution of FeCl3, subsequently washed and 2 sequential baths of deionized water and then finally dried with nitrogen. NiO
[0757] The spin coating precursor for the thin film of NiO was prepared by dissolving nickel acetate tetrahydrate and monoethanolamines in ethanol both at a concentration of 0.1M under stirring in an air-sealed vial on a plate of heating at 70°C for 4 hours. The solution appeared homogeneous and deep green. V205:
[0758] The etched FTO substrates were coated with a thin film of V2O5 deposited via spin coating of a 1:35 by volume solution of vanadium(V)oxytriisopropoxide (Sigma Aldrich) in isopropanol and subsequently heated to 500° C to obtain the crystalline vanadium oxide layers. PEROVSKITE AND TYPE N CONTACT DEPOSITION:
[0759] After cooling/drying, the perovskite precursor solution was spin coated at 2000 rpm for 20 seconds and then heated at 100°C for 45 minutes to form the structure.
[0760] Electron selective contact was deposited by centrifuge coating a 20 mgmL-1 solution of [60] PCBM in chlorobenzene (Anidrosa, Sigma Aldrich) at 1000 rpm for 45 seconds. The TiOx flat film precursor solution was then spin coated at 3000 rpm for 60 seconds and the films were annealed at 130°C for 10 minutes. Finally, the devices were filled with high vacuum evaporation of Al contact electrodes through a shadow mask. RESULTS AND DISCUSSION
[0761] Perovskite-based thin-film photovoltaic devices have recently been reported with an architecture developed from solid-state dye-sensitized solar cells, in which holes are collected through the metal cathode and electrons through the FTO anode ( Ball, JM; Lee, MM; Hey, A.; Snaith, H. Low-Temperature Processed Mesosuperstructured to Thin-Film Perovskite Solar Cells. Energy & Environmental Science 2013). In this configuration, a thin film of mesoporous alumina is deposited under TiO2 compacted FTO coated substrates to aid in perovskite film formation, and then an organic hole carrier is deposited under the formed structure to provide hole-selective contact. However, since the holes are collected through the top of the metal cathode, this configuration has limited applications in series solar cells, where immediate improvements can be achieved by employing "wide band gap" perovskites. " in the case of a low-gap inorganic top cell, (Beiley, ZM; McGehee, MD Modeling low cost hybrid tandem photovoltaics with the potential for efficiencies exceeding 20%. Energy & Environmental Science 2012, J, 9173-9179) that , is usually constructed in a "substrate" configuration with electrons being collected on top of the metal contacts.
[0762] Typical materials used in organic photovoltaics as selective hole contacts for mixtures are PEDOT:PSS, V205 and NiO, while generally PC60BM and more recently poly[(9,9-bis(3'-(N ,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) are used as electron acceptors. In order to determine whether these materials will work in the complete device, a good first step to verify that charge transfer to these interlayers is possible to measure the efficiency of steady-state PL quenching, similarly to what has become routine in all cells. organic solar. These data are presented in Figure 9 and the results are summarized in Table 4. It can be clearly seen that all p-type layers chosen in this work quench the perovskite PL more efficiently than the spiro-OMeTAD model, with similar values for PEDOT:PSSe V205 of 99.87% quenching efficiency. All n-type layers show significantly higher extinction rates than the model TiO2 system, which only show an extinction efficiency of 45% at steady state. All cells manufactured in this work use a centrifuge coated PC60BM layer as the n-type contact, since solar cells manufactured with a PFN interlayer yielded extremely poor photovoltaic performance.
TABLE 4. STABLE STATE PHOTOLUMINESCENCE EXTINGUISHING EFFICIENCY FOR BOTH TYPE NE LAYERS OF THE TYPE NEO PEROVSKITE ABSORBER PEDOT:PSS AS TYPE P CONTACT
[0763] The first example of an inverted architecture with perovskite as both light absorber and carrier charge uses a thin PEDOT: PSS as the contact-type powder layer and a bi-layer of PC60BM and compact TiOx as the type n contact. To be able to process these structures in air, the top of the Interlay TiOx er was needed to achieve good contact with the top of the Al anode. A cross-sectional SEM image of the optimized structure is shown in Figure 10. Uniform coverage of the perovskite structure is essential for manufacturing optimal photovoltaic devices and is strongly affected by the substrate it is formed on. When mounted on annealed PEDOT: PSS underlayers, macrocrystals of more than 30 μni perovskite length are formed, as shown in figure 1 ib) and 1 id). While this can be beneficial for transporting charge across the layer, there are somewhat large micronized gaps between crystals that allow direct contact between PCeoBM and the PEDOT:PSS inner layer, which is not beneficial for device performance. PEDOT: PSS is soluble in DMF and for this reason has been cross-linked by immersion in a 0.25 M FeCi3 aqueous solution to prevent re-dissolving of the layer when the perovskite precursor in DMF is deposited. When the PEDOT:PSS is crosslinked, surprisingly the resulting film perovskite coverage increases significantly while the average crystal/feature size for that material has been reduced considerably. The crystal size and resulting coverage is shown in Figure 11a) and 11c), which was found to be 80 ± 1% for annealed PEDOT: PSS films and 97 ± 1% for crosslinked films estimated directly from the SEM images.
[0764] When the performance of the resulting devices are compared, as shown in Figure 12a), it is found that the devices processed in PEDOT:PSS lattice present open circuit voltages of about 0.8 V, while the annealed devices PEDOT: PSS just reached about 0.64V. This is consistent with a reduction in the rate of recombination between the charges on the PCBM layer and the PEDOT:PSS overlay layer, due to the improved perovskite film. Devices employing crosslinked PEDOT: PSS show a slight reduction in short-circuit current of 16.2 mAcm-2, compared to annealed PEDOT: PSS devices that exhibit 17.2 mAcm2, although the difference is small, and, within the experimental variation. PSS devices that reached 5.6%: finally, the energy conversion efficiency of the devices optimal values above 6.7%, surpassing annealed PEDOT severely reached. V2O5 AND NIO AS P-TYPE CONTACTS
[0765] Both V2O5 and NiO are common p-type materials currently in use for high efficiency and stable organic photovoltaic devices. Here, the inventors have the devices manufactured by spincoating the appropriate precursor solution into the FTO with a subsequent sintering step at 500°C, to ensure a fully crystalline metal oxide layer. Surface coverage of the perovskite solution can be a problem for this material, as can be seen in the SEM images in Figure 13.
[0766] The PV performance of devices incorporating these layers is shown in Figure 14. COMPARISON WITH REGULAR ARCHITECTURES
[0767] Finally, the champion inverted device, which is incorporates PEDOT: PSS as the accept hole and PCeoBM layer as the electron extraction layer, is compared with a device that normally comprises an architecture of TiO2 electron accept layer and spiro- OMeTAD as the hole transport layer in Figure 15b). Both systems achieve short circuit currents over an astonishing 17.5 mAcm-2, and high open circuit voltages above 0.9 V. The main difference in power conversion efficiency of 11.8% for the architecture normal and 7.54% for inverted devices are the bottom filling. Factors of the latter and this is likely due to either leakage problems between PEDOT: PSS and PCBM as shown in Figure 5. A or series resistance losses, likely due to the need to use an outer TiOx layer to be able to process the devices. ambient air conditions.
[0768] The presented devices described offer a completely new approach to architectural design, particularly when the materials employed are generally employed and mass-produced at present for the organic photovoltaic industry and must, for that reason, develop at high speed from a mass-produced system. CONCLUSION
[0769] Inverted device structures, where holes are collected through the FTO, are required for tandem applications for use with inorganic photovoltaic bottom cells. Shown here is a low temperature, ambient air and photovoltaic cell solution processable based on a perovskite semiconductor absorber and N-type and p-type selective contacts in the form of PEDOT: PSS and [60] PCBM. An energy conversion efficiency of 7.5% is achieved by these inverted structures. In a sense, this demonstrates the versatility of perovskite thin film technology to the wide variety of possible device configurations, and just as importantly, it removes any barriers to the adoption of perovskite technology from the organic photovoltaic community. STEAM DEPOSITION FROM TWO SOURCES SUBSTRATE PREPARATION
[0770] The substrate preparation process was carried out in air. Fluorine-doped tin oxide (FTO) coated glass was modeled by etching with Zn metal powder and 2 M HCl diluted in milliQ water, and then cleaned with 2% hellmanex solution diluted in milliQ water. , rinsed with milliQ water, acetone and ethanol and dried with clean, dry air. Oxygen plasma was subsequently treated for 10 minutes. A compact layer of T1O2 was an acidic solution of titanium isopropoxide in ethanol coated by centrifugation, and then sintered at 150 °C for 10 minutes and then at 500 °C for 30 minutes. STEAM DEPOSITION
[0771] The system used is dual-source evaporation to better manage the organic source and inorganic source separately. The evaporator was the Kurt J. Lesker Mini Spectros Deposition System with ceramic crucibles (OLED sources), housed in a nitrogen filled dry glove (Figure 18). Therefore, all processes were operated in an oxygen-free environment. The operating chamber is designed to work under a pressure of 5E-6mbar where the vapor particles are able to travel directly to the substrate. The samples were kept face down in a rack above crucibles containing the parent powders. Two crystal monitor sensors are located just 10 cm above the crucibles to control the deposition speed of each source separately, without interfering with each other. Measurements are served as feedback to adjust the heating temperature for the source chemicals. Another crystal sensor is available close to the substrate support which can be used to measure the total thickness deposited. MEASUREMENT OF THE DURABILITY FACTOR
[0772] Since the distance from the source to the monitor is different from the distance from the source to the substrate, the tooling factor (ratio of materials deposited on the sensors to that in the samples) of each source was calibrated individually. The density of CH3NH3I was assumed to be 1 g/cm3, due to its unavailability. Configuration and results are shown in Table 5.
TABLE 5: MEASUREMENT OF THE DURABILITY FACTOR
[0773] Note that it was difficult to evaporate the organic source CH3NH3I constantly due to its instability during the evaporation process and its deposition rate had up to +/- 20% derivation from the set value. Physical thickness was measured by Veeco Dektak 150 film thickness probe. DEPOSITION OF PEROVSKITE FROM TWO SOURCES
[0774] The inventors aimed to investigate 'flat junction' perovskite solar cells by means of evaporation in the dual source deposition system. The evaporated perovskite can be deposited on top of the TiO2 compact layer directly without the mesoporous layer (Figure 20b and 20c).
[0775] The organic CH3NH3I source and inorganic PbCk source were weighed at approximately 200 mg and at 100 mg, and loaded into the two crucibles respectively. Samples were face down inserted into the substrate holder. Once the pressure in the chamber was evacuated to 5E-6 mbar, the shutters of the two OLED sources were opened, while heating the sources. Once the two sources reached the defined values, the shutter of the substrate was opened with the rotation of the support, in order to obtain a thin and uniform film.
[0776] After completing the evaporation, the color of the samples was changed corresponding to the composition of the two sources. All samples were then placed on the hot plate to dry at 100°C for 50 minutes to crystallize perovskite crystal before spin-coating the hole-carrier layer. Figure 21 shows the surface image after annealing the perovskite crystal on the hot plate. In the experiment so far, 7% spiro-OMeTAD solution in chlorobenzene with added tert-butylpyridine (TBP) and bis(trifluoromethanesulfonyl)imide (Li-TDI) was used as the carrier port and was spin-coated at 2000 rpm for 45 s. In the end, the devices were completed with the evaporation of Ag contact electrodes (Figure 20a).
[0777] Comparing the evaporated perovskite with the conventional spin coated perovskite, the perovskite had evaporated from the surface more uniformly and smooth with fewer holes (Figure 21). The full coverage of the evaporate perovskite not only completely contacts the TiO2 compact layer, but also insulates the hole transport layer from the compact layer. It will certainly help the photocurrent as well as voltage through the system. DEVICE CHARACTERIZATION
[0778] The experiment started with the composition varying from CH3NH3I to PbCl2 from 4:1 to 16:1 in molar ratio under constant total thickness. Once the composition was optimized, the desired thickness under best composition was investigated.
[0779] The best performance was obtained at 13% electrical energy efficiency by setting the deposition rate at 5.3 A/s for CH3NH3I and 1 A/s for PbCl2 which ideally should have given 9.3:1 in the molar ratio if the durability factor is taken into account. However, as mentioned above, since the evaporation of the organic source of dH3NH3I always has the deviation, the final thickness shown on Sensor 1 for CH3NH3I was 44.4 kA instead of the expected 42.4 kA. In other words, the actual average deposition rate for CH3NH3I should be 5.6 A/s instead of the stated value of 5.3 A/s. In this case, the film was actually deposited under the CH3NH3I to PbCl2 molar ratio of 9.8:1 which gave a physical thickness of 230 nm as measured by the DekTak probe.
[0780] The best performance gave a short circuit photocurrent Jsc of 21.47 mA/cm2, open circuit voltage Voc of 1.07 Volts and a fill factor (FF) of 0.67 producing electrical energy conversion efficiency of up to 15.36 % as shown in Figure 22. Current Voltage characteristics were measured (2400 Series SourceMeter, Keithley Instruments) under simulated 1.5G AM sunlight at irradiance at 100 mW^cm-2 and the solar cells were masked with a metal aperture to define the active area which was typically 0.076 cm2 and measured on a light-impervious sample holder to minimize any edge effects.
[0781] In order to define the content of the evaporated film, the XRD pattern of the surface of the evaporated perovskite was measured and then compared to the XRD pattern for the conventional rotational coating of perovskite and other essential chemicals as shown in Figure 23.
[0782] According to XRD standards, it clearly shows that the evaporated perovskite is almost identical to the processed solution of the perovskite film processed from CH3NH3I and PbCl2 precursors in DMF (named 330) which indicates that the evaporated perovskite has the same crystal structure like centrifuge coated perovskite.
[0783] The last measurement in Figure 24 was a comparison of the absorbance between 200 nm of the evaporated film and the spin coated film. The absorbance of the two 200nm 'flat junction' evaporated perovskite has similar absorbance shape as the 200nm 'flat junction' spin coated perovskite, but the evaporated perovskite has much larger units in absorption. CONCLUSION
[0784] At this point, organic inorganic hybrid perovskite evaporated in flat junction solar cells with more than 15% energy conversion efficiency is demonstrated, by properly controlling the deposition rate of CH3NH3I and PbCl2 and the thickness deposited on the substrate. The realization of using the evaporation technique to produce the perovskite solar cells goes beyond the solution process limits of finding a suitable solution to dissolve the chemicals and thus also helps in the commercialization of hybrid inorganic organic solar cells.
[0785] In general, it is considered to be advantageous to maintain a 3D crystal structure in the perovskite, as opposed to creating layered perovskites which will inevitably have higher exciton binding energies (Journal of Luminescence 60&61 (1994) 269 274). It is also advantageous to be able to tune the perovskite band gap. The band gap can be altered either by altering metal cations or halides, which directly influence electron orbitals and crystal structure alike. Alternatively, by altering the organic cation (eg, from a methylammonium cation to a formamidium cation), the crystal structure can be altered. Anyway, in order to fit the perovskite crystal, the following geometric condition must be satisfied:

[0786] where RA, B, & X are the ionic radios of ABX ions. The inventors have unexpectedly found that the formamidinium (FO) cation actually forms the perovskite structure in a 3D crystal structure in a FOPbBr3 (tetragonal crystal) or FOPbl3 (cubic crystal) perovskite, and their mixed halide perovskites. PRODUCTION OF TWO STAGE PEROVSKITE LAYER SUBSTRATE PREPARATION
[0787] An electrode pattern was etched onto glass substrates coated with fluorine-doped tin oxide (FTO, TEC 7 Pilkington Glass) employing a mixture of Zn powder and 2M HCl. They were then sequentially cleaned in Hallmanex, deionized water, acetone, propan-2-ol, and O2 plasma. DEPOSITION OF THE SELECTIVE ELECTRON LAYER
[0788] A thin layer (approximately 50 nm) of TiO2 served as the electron selective layer. It was deposited on the substrate by centrifuge coating (speed = 2000 rpm, acceleration = 2000 rpm/s, time = 60s) of a filtered solution (0.45 μm PTPE filter) containing Ti-isopropoxide in ethanol with added HCl. These films were heated at 500°C for 30 minutes. EVAPORATION OF Pbl2 AND PbCl2
[0789] Thin films (approximately 150 nm) of Pbl2 or PbCl2 were deposited via thermal evaporation through a shadow mask onto substrates at a pressure of approximately 10-6 mbar at a rate of approximately 2A/s. Evaporation temperatures were approximately 270 °C and 310 °C for Pbl2 and PbCl2 respectively. CONVERSION OF PEROVSKITE BY IMMERSION COATING
[0790] For dip coating, substrates pre-coated in Pbl2 or PbCl2 were immersed in a 20 mg/ml solution of methylammonium iodide in anhydrous propan-2-ol in a nitrogen-filled glove box. The immersion time was constant for all devices at 10 minutes. After immersion coating, the substrates were annealed at 120 °C in a nitrogen atmosphere for 10 minutes. Immersion times can vary from 10 seconds to 2 hours, for the example given in this patent, the immersion time was 10 minutes. DEPOSITION OF HOLE TRANSPORT MATERIAL
[0791] The hole carrier material, 2,2',7,7'-tetracis-(N,N-di-methoxyphenylamine)9,9'-spirobifluorene (spiro-OMeTAD), was deposited via coating by centrifugation (speed = 2000 rpm, acceleration = 2000 rpm/s, time = 60s) of an 80 mM chlorobenzene solution containing 80 mol % tert-butylpyridine (tBP) and 30 mol % lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) as additives in a nitrogen-filled glove box. TOP ELECTRODE DEPOSITION
[0792] The upper silver electrode was deposited by thermal evaporation (pressure approx. 5 μTorr) to a thickness of 150 nm at approx. 2A/s. CURRENT-VOLTAGE CHARACTERIZATION DEVICE
[0793] For the measurement of solar cell performance, simulated AM 1.5 sunlight was generated with an AAB ABET class solar simulator calibrated to produce AM 1.5 simulator, of 106.5 mW/cm2 of equivalent irradiance, employing a solar cell. of filtered silicon reference of KG5 calibrated with NREL. The imbalance factor was calculated to be 1.065 between 300 to 900 nm, which is beyond the operating range of both the KG5 filtered silicon reference cell and the perovskite test cells. Current-voltage curves were recorded with a source meter (Keithley 2400, USA). The solar cells were masked with a metal opening defining the active area (0.0625 cm2) of the solar cells. The voltage and current density characteristics of the devices are shown in Figure 32 (for Pbl2 as the photoactive layer (dashed line) and CH3NH3PDI3 after dip coating as the photoactive layer (solid line)) and Figure 33 (for PbCl2 as the photoactive layer (dashed line) and CH3NH3PbI3-xClx after dip coating as the photoactive layer (solid line)). X-RAY DIFFRACTION
[0794] X-ray diffraction (XRD) spectra were obtained from devices without silver electrodes (FTO coated glass, TiO2, photoactive layer, spiro-OMeTAD) using a Panalytical X'Pert Pro x-ray diffractometer. The results are shown in Figure 31. SCANNING ELECTRON MICROSCOPY
[0795] Scanning electron microscopy (SEM) images were obtained from devices without silver electrodes (FTO coated glass, TiO2, photoactive layer, spiro-OMeTAD) using a Hitachi S-4300. Electron micrographs are shown in Figure 29 (for (a) PbCl2 and (b) CH3NH3Pbl3-xClx after dip coating) and Figure 30 (for (a) Pbl2 and (b) CH3NH3Pbl3 after dip coating). RESULTS AND DISCUSSION
[0796] The two-step method allows the production of uniform films of perovskite employing the economical techniques that are already readily available in the glass industry. After an initial deposition of a metal dialect, uniform flat films of perovskite can be produced by infiltrating the metal dialect with the organic halide. Figure 31 shows the thin-film X-ray diffraction spectra of (a) PbCl2, (b) CH3NH3PbI3-xClx, (c) Pbl2, and (d) CH3NH3PbI3. After dip coating, the films of both precursors show a decrease in the relative intensity of the peaks corresponding to the precursor lattice and a relative increase in the perovskite lattice (absent in the precursor XRD spectra) indicating predominant conversion of the precursor films to the perovskite.
[0797] Figure 29 shows the cross-section of the scanning electron microscopy of the devices showing, from the bottom to the top, the glass substrates, FTO, TiO2 electron selective layer, photoactive layer, spiro-OMeTAD. The photoactive layers are (a) PbCl2, and (b) CH3NH3PbI3-xClx after dip coating. Figure 30 shows the cross-section of the scanning electron microscopy of the devices showing, from bottom to top, the glass substrates, FTO, TiO2 electron selective layer, photoactive layer, spiro-OMeTAD. The photoactive layers are (a) PbI2, and (b) CH3NH3PbI3 after dip coating. In both examples, the perovskites produced by dip coating show relative uniformity.
[0798] The voltage and current density characteristics of the devices are shown in Figures 32 and 33. In Figure 32, the characteristics are shown for a device made employing Pbl2 as the active layer (dashed line) and a device in which Pbl2 evaporated was converted to CH3NH3PbI3 (solid line) by immersion coating in a solution of methylammonium iodide in propan-2-ol. The performance parameters for Pbl2 are Jsc = 1.6 mA/cm2, PCE = 0.80%, Voc = 0.97 V, FF = 0.57. The performance parameters for CH3NH3PbI3 are Jsc = 5.3 mA/cm2, PCE = 2.4%, Voc = 0.82 V, FF = 0.61. In Figure 33 the voltage and current density characteristics of a device made employing PbCl2 as the active layer (dashed line) and a device in which the evaporated PbCl2 was converted to CH3NH3PbI3-xClx (solid line) by immersion coating in a solution of methylammonium iodide in propan-2-ol are shown. The performance parameters for PbCl2 are Jsc = 0.081 mA/cm2, PCE = 0.006%, Voc = 0.29 V, FF = 0.27. The performance parameters for CH3NH3PbI3-xClx are Jsc = 19.0 mA/cm2, PCE = 7.0%, Voc = 0.8 V, FF = 0.49. In both cases, it is shown that viable devices are produced by this two-step method. ESTIMATED LENGTH OF DIFFUSION OF THE LOAD CARRIER
[0799] For a charge (or electron the hole) to be generated from absorbing light and efficiently collected from a thin solid film, the lifetime of the charge species the time from bound to before recombination with a oppositely charged species) must be longer than the time required to diffuse through the film and flow into the electrode. The product of the diffusion coefficient (De) and the lifetime (te) can be used to estimate the diffusion length (LD) that follows

[0800] Photoluminescence (PL) quenching has previously been successfully employed with organic semiconductors in order to determine the diffusion length of the photoexcited bound electron-hole pair (the exciton). By simply fabricating the solid thin films in the presence or absence of an exciton quenching layer, and modeling the photoluminescence falls into a diffusion equation, it is possible to precisely determine the exciton lifetime, diffusion rate, and diffusion length. . A cross-sectional SEM image of a thick 270 nm mixed halide absorption layer with an upper hole quenching layer of Spiro-OMeTAD is shown in Figure 36.
[0801] The dynamics of PL disintegration were modeled by calculating the number and distribution of excitations in the film n(x,t) according to the 1-D diffusion equation (eq. 1),

[0802] where D is the diffusion coefficient and k(t) is the rate of disintegration of PL in the absence of any extinguishing material. The total decay rate k was determined by fitting a stretched exponential decay to the PL data from the PMMA-coated perovskite layers. The quenching layer effect was included by assuming that all photogenerated carriers reaching the interface are quenched, giving the boundary condition n(L,t) = 0, where x = 0 at the glass/perovskite interface and L is the perovskite film thickness. As the samples were photoexcited on the glass substrate side of the samples, the initial distribution of photoexcitations was given for n(x,0) = noexp(-αx), where α is the absorption coefficient. The diffusion length of the species was then determined from
on what
is the recombination of the lifetime in the absence of an extinguisher. If free charges are predominantly created after photoexcitation, the PL decay represents the depopulation of charge carriers and the diffusion coefficients for holes or electrons can be estimated depending on which quenching layer is employed. The results of the diffusion model adjustments are shown in Figure 34 and Figure 35. And the parameters summarized in Table 6 (D is the diffusion constant and LD is the diffusion length). TABLE 6

[0803] Mixed halide (CH3NH3PbI3-xClx) and triiodide (CH3NH3PbI3) perovskites are compared in Figure 37 which shows the photoluminescence disintegration for a CH3NH3PbI3-xClx mixed organolead trihalide perovskite film (black squares) and a film of CH3NH3PbI3 organolead triiodide perovskite (gray squares), coated with PMMA. Lifetimes Tβ quoted as the time taken to reach 1/e of the initial intensity.
[0804] Surprisingly, the diffusion lengths of both electrons and holes in mixed halide perovskite are greater than 1 μm, which is significantly greater than the absorption depth of 100 to 200 nm. This indicates that there should be no need for meso or nanostructure with this specific perovskite absorber. The triiodide perovskite CH3NH3PbI3 films have a shorter diffusion length of about 100 nm for both electrons and holes. The large diffusion lengths of mixed halide perovskite allow photovoltaic devices with perovskite layers with thicknesses in excess of 100 nm to be crafted that exhibits excellent device characteristics. METHODS PREPARATION OF PEROVSKITE PRECURSOR:
[0805] Methylamine iodide (MAI) was prepared by reacting methylamine, 33% by weight in ethanol (Sigma-Aldrich), with hydroiodic acid (HI) 57% by weight in water (Sigma-Aldrich), at temperature environment. HI was added dropwise while stirring. After drying at 100 °C, a white powder was formed, which was dried overnight in a vacuum oven and recrystallized from ethanol before use. To form the precursor solution CH3NH3PbI3-xClx or CH3NH3PbI3, methylammonium iodide and either lead(II) chloride (Sigma-Aldrich) or lead(II) iodide iodide (Sigma-Aldrich) were dissolved in anhydrous N,N-Dimethylformamide ( DMF) in a 3:1 molar ratio of MAI to PbCl2/ Pbl2, with final concentrations of 0.88 M lead chloride/iodide and 2.64 M methylammonium iodide. SUBSTRATE PREPARATION:
[0806] Glass substrates for absorption, TA and PL measurements were cleaned sequentially in 2% hallmanex detergent, acetone, propan-2-ol and oxygen plasma. Devices were fabricated in fluorine-doped tin oxide (FTO) coated glass (Pilkington, 7Q^-'). Initially the FTO was removed from the regions under the anode contact, to prevent drift in contact with measuring pins, by etching the FTO with 2M HCl and zinc dust. The substrates were then cleaned and plasma etched as above. A hole blocking layer of the compact TiO2 was deposited by spin coating a slightly acidic solution of titanium isopropoxide in ethanol, and annealed at 500°C for 30 minutes. Centrifuge coating was performed at 2000 rpm for 60 seconds. PEROVSKITE DEPOSITION:
[0807] To form the perovskite layer for spectroscopy measurements, the non-stoichiometric precursor was centrifuged coated at 2000 rpm in air. For CH3NH3Pbl3-xClx, the precursor was used as is; for CH3NH3Pbl3, the precursor was diluted in DMF in a 1:1 ratio of precursor solution to DMF. After spin coating, the CH3NH3Pbl3-xClx films were annealed at 100°C for 45 minutes, and CH3NH3Pbl3 at 150°C for 15 minutes. The upper extinguishers were then deposited into the air through spin coating chlorobenzene solutions with the following conditions: polymethylmethacrylate) (PMMA; Sigma-Aldrich) at 10 mg/ml and phenyl-C61-butyric acid methyl ester (PCBM; Solenne BV) at 30 mg/ml, both coated by centrifugation at 1000 rpm, and 2,2',7,7'-tetracys-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene (spiro- OMeTAD; Borun Chemicals) in 0.46 M coated by centrifugation at 2000 rpm. DESCRIPTION:
[0808] A field emission scanning electron microscope (Hitachi S-4300) was employed to acquire the SEM images. Sample thicknesses were measured using a Veeco Dektak 150 surface profilometer. PHOTOLUMINESCENCE MEASUREMENTS AND ADJUSTMENTS:
[0809] Time-resolved and steady-state PL measurements were acquired employing a time-correlated single photon counting (TCSPC) step (FluoTime 300, PicoQuant GmbH). The film samples were photoexcited with a 507 laser head (LDH-PC-510, PicoQuant GmbH) pulsed at frequencies between 0.3-10 MHz, with a pulse duration of 117 ps and fluence of ~30nJ/cm2. PL was collected using a high resolution monochromator and hybrid photomultiplier detector set (PMA Hybrid 40, PicoQuant GmbH). The parameters describing dynamic photoluminescence in the absence of any extinguisher are necessary inputs into the diffusion model. These were obtained by fitting the base correlated PL measured from the PMMA capped perovskite films with a stretched exponential decay function of the shape,

[0810] The errors in the adjustment parameters were determined by examining the reduced X surface obtained by independently varying each adjustment parameter. A cutoff value of XR2 (p)/ XR2 = 1.2 was used in each case to obtain the limits at a confidence level of 68%. For ease of comparison of lifetimes between samples with different extinguishers, Te is defined as the time taken after excitation for the PL intensity to drop to 1/e of its peak intensity. The error in the accuracy of this lifetime was taken to be the half of the range of points whose mean value lies within one standard deviation of the 1/e line. The dynamic photoluminescence results are shown in Figures 34, 35 and 37. THE DIFFUSION MODELING:
[0811] The dynamic disintegration of the PL was modeled by calculating the number and distribution of excitations in the film. n(x,t) according to the 1-D diffusion equation,

[0812] where D is the diffusion coefficient and k(t) is the rate of disintegration of PL in the absence of any extinguishing material. The total decay rate, k = 1/kf + 1/knr = βT'-βtβ'1 , was determined by fitting a stretched exponential decay to the LP data from the perovskite layers with PMMA and assumed independent of the buffering material. The quenching layer effect was included assuming that all excitons reaching the interface are quenched with unity efficiency (n(L,t) = 0, where x = 0 at the glass/perovskite interface and L is the perovskite film thickness). As the excitation pulse was on the glass substrate side of the samples, the initial distribution of excitons was taken to be n(x,0) = n0exp(-αx), where α=A/L (absorbance at 507 nm / thickness of the perovskite layer). Any deviation from this distribution due to reflection of the laser pulse at the perovskite/extinguisher interface was assumed to be negligible. In order to calculate the LD diffusion length, the diffusion coefficient was varied to minimize the reduced chi-square value,

[0813] where y(t) and yc(t) are the measure and intensities of the PL calculated at time t, n is the number of data points and p is the number of fit parameters. The equation was numerically solved using the Crank-Nicholson algorithm and the number of excitons integrated across the entire film in order to determine the intensity of the total PL at time t. Likewise, the stretched exponential and 1-D diffusion models were fitted to the experimental TCSPC data by means of iterative reconvolution with the instrument response function (IRF) that was recorded separately, so that the observed PL intensity,
is the result of the real disintegration curve, f(t), convolved with the IRF, g(t). The average diffusion length LD is determined by
, on what
is the time required for PL to drop to 1/e of its initial intensity in the absence of any extinguisher.

权利要求:
Claims (25)
[0001]
1. Photovoltaic device comprising a photoactive region, characterized in that the photoactive region comprises: an n-type region comprising at least one n-type layer; a p-type region comprising at least one p-type layer; and, arranged between the n-type region and the p-type region: a layer of a perovskite semiconductor without open porosity, wherein the layer of the perovskite semiconductor without open porosity has a thickness from 10 nm to 100 μm and forms a flat heterojunction with the n-type region or the p-type region.
[0002]
Photovoltaic device according to claim 1, characterized in that the thickness of the perovskite semiconductor layer without open porosity is from 100 nm to 100 μm, and is preferably from 100 nm to 700 nm.
[0003]
A photovoltaic device according to claim 1 or claim 2, characterized in that the perovskite semiconductor has a three-dimensional crystal structure, and optionally wherein the perovskite semiconductor has a band gap equal to or less than 3.0 eV.
[0004]
Photovoltaic device according to any one of claims 1 to 3, characterized in that the perovskite semiconductor layer without open porosity is a layer consisting of the perovskite semiconductor.
[0005]
Photovoltaic device according to any one of the preceding claims, characterized in that the perovskite semiconductor layer without open porosity is in contact with the n-type region and the p-type region, and preferably the perovskite semiconductor layer without open porosity. which forms a first flat heterojunction with the n-type region and a second flat heterojunction with the p-type region.
[0006]
6. Photovoltaic device according to any one of claims 1 to 4, characterized in that the photoactive region comprises: said n-type region; said p-type region; and, disposed between the n-type region and the p-type region: (i) a first layer comprising a porous material and a perovskite semiconductor disposed in the pores of the porous material; and (ii) a buffer layer disposed on said first layer, which buffer layer is said layer of a perovskite semiconductor without open porosity, wherein the perovskite semiconductor in the buffer layer is in contact with the perovskite semiconductor in the first layer; optionally wherein the porous material is mesoporous, optionally wherein the porous material is a dielectric material having a band gap equal to or greater than 4.0 eV, and optionally wherein the porous material is a charge-carrying material.
[0007]
A photovoltaic device according to claim 6, characterized in that the perovskite semiconductor in the first layer contacts one of the ne-type regions of the p-type, and the perovskite semiconductor in the buffer layer contacts the other of the ne-type regions of the p-type. p-type, and preferably wherein the perovskite semiconductor in the buffer layer forms a flat heterojunction with the p-top region or the n-type region.
[0008]
Photovoltaic device according to claim 6 or claim 7, characterized in that the thickness of the buffer layer is greater than the thickness of the first layer, optionally wherein the thickness of the buffer layer is from 100 nm to 700 nm, and preferably from 100 nm to 700 nm, and optionally wherein the thickness of the first layer is from 5 nm to 1000 nm, and preferably from 30 nm to 200 nm.
[0009]
9. Photovoltaic device according to any one of the preceding claims, characterized in that: (i) n-type region comprises any: an n-type layer; and an n-type layer and an n-type exciton blocking layer, preferably wherein the n-type exciton blocking layer is arranged between the n-type layer and the layer(s) comprising the perovskite semiconductor; and (ii) p-type region comprises any: a p-type layer; and a p-type exciton blocking layer, preferably wherein the p-type exciton blocking layer is disposed between the p-type layer and the layer(s) comprising the perovskite semiconductor.
[0010]
10. Photovoltaic device according to any one of the preceding claims, characterized in that the perovskite comprises at least one anion selected from halide anions or chalcogenide anions; preferably wherein the perovskite comprises a first cation, a second cation, and said at least one anion, optionally wherein the second cation is a metal cation selected from Sn2+, Pb2+ and Cu2+, preferably wherein the cation metal is selected from Sn2+ and Pb2+, and optionally wherein the first cation is an organic cation.
[0011]
11. Photovoltaic device according to claim 10, characterized in that the perovskite is a mixed anion perovskite comprising two or more different anions selected from halide anions and chalcogenide anions, and preferably wherein the perovskite is a perovskite of mixed halide, where the two or more different anions are two or more different halide anions.
[0012]
12. Photovoltaic device according to any one of the preceding claims, characterized in that it is a series junction or multiple junction photovoltaic device, wherein the device comprises a first electrode, a second electrode, and arranged between the first and the second electrode. second electrodes: the referred photoactive region; and at least one other photoactive region, preferably wherein at least one other photoactive region comprises at least one layer of a semiconductor material; and more preferably wherein the semiconductor material comprises a layer of crystalline silicon, tin zinc sulfide copper, tin zinc copper selenide, tin zinc copper selenide sulfide, indium gallium copper selenide, indium gallium copper diselenide or copper selenide. indian copper.
[0013]
A photovoltaic device according to claim 12, characterized in that it comprises any: (a) the following regions in the following order: I. a first electrode; II. a first photoactive region as defined in any one of claims 1 to 11; III. a layer (A) of a p-type semiconductor; IV. a first intrinsic semiconductor layer; V. a layer (B) of a p-type semiconductor or a layer (B) of an n-type semiconductor; SAW. a second intrinsic semiconductor layer; VII. a layer (C) of an n-type semiconductor; and VIII. a second electrode; and (b) the following regions in the following order: I. a first electrode; II. a first photoactive region as defined in any one of claims 1 to 11; III. a layer of a transparent conductive oxide; IV. a layer (D) of an n-type semiconductor; V. a layer of tin zinc copper sulfide, tin zinc copper selenide, tin zinc copper selenide sulfide, indium gallium copper selenide, indium gallium copper diselenide or indium copper selenide; and VI. a second electrode.
[0014]
14. Process for producing a photovoltaic device, characterized in that it comprises a photoactive region, which photoactive region comprises: an n-type region comprising at least one n-type layer; a p-type region comprising at least one p-type layer; and, arranged between the n-type region and the p-type region: a layer of a perovskite semiconductor without open porosity, wherein the layer of the perovskite semiconductor without open porosity, whose layer has a thickness from 10 nm to 100 μm and forms a flat heterojunction with the n-type region or the p-type region, which process comprises: (a) providing a first region; (b) arranging a second region in the first region, which second region comprises said layer of a perovskite semiconductor without open porosity; and (c) arranging a third region in the second region, wherein: the first region is said n-type region comprising at least one n-type layer and the third region is said p-type region comprising at least one p-type layer ; or the first region is said p-type region comprising at least one p-type layer and the third region is said n-type region comprising at least one n-type layer.
[0015]
A process according to claim 14, characterized by the step of (b) disposing the second region in the first region, comprising: producing a solid layer of the perovskite in the first region by means of vapor deposition; preferably wherein the step of producing a solid layer of the perovskite in the first region by means of vapor deposition comprising: (i) exposing the first region to vapor, which vapor comprises said perovskite or one or more reagents for producing said perovskite; and (ii) allowing steam to deposit in the first region to produce a solid layer thereof; and preferably also comprising producing steam by evaporating said perovskite or evaporating one or more reagents for producing said perovskite.
[0016]
A process according to claim 14 or claim 15, characterized by step (b) of arranging the second region in the first region comprising: producing a solid layer of the perovskite by means of vapor deposition, wherein the vapor deposition is a dual source vapor deposition; preferably wherein the step of producing a solid layer of the perovskite in the first region through dual source vapor deposition comprises: (i) exposing the first region to vapor, which vapor comprises two reactants for producing said perovskite; and (ii) allowing steam to deposit in the first region to produce a solid layer thereof; wherein (i) also comprises producing said vapor comprising two reactants for producing said perovskite by evaporating a first reactant from a first source and evaporating a second reactant from a second source; and preferably wherein the first reactant comprises a first compound comprising (i) a metal cation and (ii) a first anion; and the second reactant comprises a second compound comprising (i) an organic cation and (ii) a second anion.
[0017]
Process according to claim 16, characterized in that the first and second anions are different anions selected from halide ions or from chalcogenide ions, and preferably wherein the first and second anions are different anions selected from of halide anions.
[0018]
Process according to claim 14, characterized by the step of (b) disposing the second region in the first region comprising: (i) exposing the first region to steam, which steam comprises a first perovskite precursor compound, and allowing the depositing the vapor in the first region to produce a solid layer of the first perovskite precursor compound therein; and (ii) treating the resulting solid layer of the first perovskite precursor compound with a solution comprising a second perovskite precursor compound, and thereby reacting the first and second perovskite precursor compounds to produce said layer of the perovskite semiconductor. without open porosity, wherein the first perovskite precursor compound comprises (i) a first cation and (ii) a first anion and the second perovskite precursor compound comprises (i) a second cation and (ii) a second anion.
[0019]
Process according to claim 14, characterized by the step of (b) disposing the second region in the first region comprising: (i) disposing one or more precursor solutions in the first region, which one or more precursor solutions comprises: said perovskite dissolved in a solvent, or one or more reagents for producing said perovskite dissolved in one or more solvents; and (ii) removing one or more solvents to produce a solid layer of the perovskite in the first region; and preferably wherein it comprises spin coating the precursor solution or solutions in the first region, to produce in the first region said solid layer of perovskite.
[0020]
A process according to any one of claims 15 to 17 and 19, characterized by the step of (b) arranging the second region in the first region, also comprising: (111) heating the solid layer of perovskite. optionally wherein the step of heating the perovskite solid layer comprises heating the perovskite solid layer in an inert atmosphere; and optionally wherein the temperature at which the solid layer of perovskite is heated does not exceed 150°C, preferably wherein the solid layer of perovskite is heated to a temperature from 30°C to 150°C, and more preferably at a temperature from 40 °C to 110 °C.
[0021]
Process according to claim 14, characterized in that said photoactive region comprises: said n-type region; said p-type region; and, disposed between the n-type region and the p-type region: (i) a first layer comprising a porous material and a perovskite semiconductor disposed in the pores of the porous material; and (ii) a buffer layer disposed on said first layer, which buffer layer is said layer of a perovskite semiconductor without open porosity, wherein the perovskite semiconductor in the buffer layer is in contact with the perovskite semiconductor in the the first layer, wherein the process comprises: (a) providing said first region; (b) arranging said second region in the first region, wherein the second region comprises: (i) a first layer comprising a porous material and a perovskite semiconductor disposed in the pores of the porous material; and (ii) a buffer layer in said first layer, which buffer layer is said layer of a perovskite semiconductor without open porosity, wherein the perovskite semiconductor in the buffer layer is in contact with the perovskite semiconductor in the first layer; and (c) arranging said third region in the second region; and preferably wherein the step of (b) arranging said second region in the first region comprising: 1.) arranging a porous material in the first region; and 11.) disposing said perovskite in the pores of the porous material to produce said first layer and also disposing said perovskite in the first layer to produce said buffering layer, and preferably disposing said perovskite in the pores of the porous material and also arranging said perovskite in the first layer are carried out together in a single step.
[0022]
Process according to claim 21, characterized in that step (i) of disposing a porous material in the first region comprises: disposing of a composition in the first region, which composition comprises the porous material, a solvent, and optionally a binder; and removing the solvent and, when present, the binder; and preferably further comprising heating the composition.
[0023]
A process according to claim 21 or claim 22 wherein it comprises step (ii): disposing one or more precursor solutions in the porous material, which one or more precursor solutions comprises: said perovskite dissolved in a solvent, or a or more reagents for the production of said perovskite dissolved in one or more solvents; and removing one or more solvents to produce the solid perovskite in the pores of the porous material and a solid perovskite buffer layer disposed in the first layer.
[0024]
A process according to any one of claims 21 to 23, characterized by the step of (b) arranging the second region in the first region, also comprising: (111) heating the perovskite. optionally wherein the step of heating the perovskite comprising heating the perovskite in an inert atmosphere, and Optionally wherein the temperature at which the perovskite is heated does not exceed 150 °C, preferably wherein the perovskite is heated to a temperature from 30°C to 150°C, preferably at a temperature from 40°C to 110°C.
[0025]
Process according to any one of claims 14 to 23, characterized by producing a photovoltaic series-junction or multiple-junction device, which also comprises: (d) arranging a tunnel junction in the third region; (e) arranging another photoactive region at the tunnel junction which is the same as or different from the photoactive region defined in claim 14 or claim 21; (f) optionally repeating steps (d) and (e); and (g) arranging a second electrode in the other photoactive region arranged in the previous step.

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同族专利:

---

公开号 | 公开日

---

EP2898553A1|2015-07-29|

---

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---

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---

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---

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---

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---

PL2898553T3|2019-05-31|

---

CN106684246B|2020-01-21|

---

JP6660930B2|2020-03-11|

---

SA515360164B1|2017-02-05|

---

AU2013319979A1|2015-03-19|

---

KR102118475B1|2020-06-03|

---

KR20180100722A|2018-09-11|

---

JP6263186B2|2018-01-17|

---

EP2898553B1|2018-11-14|

---

JP2018041987A|2018-03-15|

---

CN104769736B|2016-08-24|

---

EP3413365A1|2018-12-12|

---

JP2020074485A|2020-05-14|

---

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---

AU2016204753A1|2016-07-28|

---

KR102296283B1|2021-08-31|

---

AU2013319979B2|2016-08-25|

---

US20180315870A1|2018-11-01|

---

US10069025B2|2018-09-04|

---

SA516371519B1|2018-02-28|

---

WO2014045021A1|2014-03-27|

---

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---

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---

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---

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---

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---

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---

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---

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---

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

DE59700595D1|1996-04-26|1999-11-25|Forschungszentrum Juelich Gmbh|PIN LAYER SEQUENCE ON A PEROWSKIT|

---

US5721634A|1996-10-09|1998-02-24|Boeing North American, Inc.|Cesium-germanium halide salts forming nonlinear optical crystals|

---

US5882548A|1997-05-08|1999-03-16|International Business Machines Corporation|Luminescent organic-inorganic perovskites with a divalent rare earth metal halide framework|

---

US5871579A|1997-09-25|1999-02-16|International Business Machines Corporation|Two-step dipping technique for the preparation of organic-inorganic perovskite thin films|

---

US6027666A|1998-06-05|2000-02-22|The Governing Council Of The University Of Toronto|Fast luminescent silicon|

---

US6180956B1|1999-03-03|2001-01-30|International Business Machine Corp.|Thin film transistors with organic-inorganic hybrid materials as semiconducting channels|

---

US6150536A|1999-07-08|2000-11-21|International Business Machines Corporation|Dye doped organic-inorganic hybrid materials|

---

US6420056B1|1999-07-08|2002-07-16|International Business Machines Corporation|Electroluminescent device with dye-containing organic-inorganic hybrid materials as an emitting layer|

---

AT324662T|1999-08-04|2006-05-15|Fuji Photo Film Co Ltd|ELECTROLYTE COMPOSITION AND PHOTO-ELECTROCHEMICAL CELL|

---

JP2001148491A|1999-11-19|2001-05-29|Fuji Xerox Co Ltd|Photoelectric conversion element|

---

US6429318B1|2000-02-07|2002-08-06|International Business Machines Corporaiton|Layered organic-inorganic perovskites having metal-deficient inorganic frameworks|

---

US20050268962A1|2000-04-27|2005-12-08|Russell Gaudiana|Flexible Photovoltaic cells, systems and methods|

---

JP3542077B2|2000-09-08|2004-07-14|独立行政法人科学技術振興機構|Organic ammonium / inorganic layered perovskite compound and production method thereof|

---

JP4278080B2|2000-09-27|2009-06-10|富士フイルム株式会社|High sensitivity light receiving element and image sensor|

---

JP2002198551A|2000-12-27|2002-07-12|Mitsubishi Heavy Ind Ltd|Optical-to-electrical transducer element and device thereof using it as well as method for manufacturing the same|

---

JP2002299063A|2001-04-03|2002-10-11|Japan Science & Technology Corp|Electroluminescent element with lead bromide system layered perovskite compound as luminescent layer|

---

US6709929B2|2001-06-25|2004-03-23|North Carolina State University|Methods of forming nano-scale electronic and optoelectronic devices using non-photolithographically defined nano-channel templates|

---

US7105360B2|2002-03-08|2006-09-12|International Business Machines Corporation|Low temperature melt-processing of organic-inorganic hybrid|

---

CN1288794C|2002-06-14|2006-12-06|松下电工株式会社|Photoelectric transducer and its manufacturing method|

---

EP1537445B1|2002-09-05|2012-08-01|Nanosys, Inc.|Nanocomposites|

---

JP4259081B2|2002-10-10|2009-04-30|セイコーエプソン株式会社|Manufacturing method of semiconductor device|

---

WO2004112440A1|2003-06-13|2004-12-23|Matsushita Electric Industrial Co., Ltd.|Light-emitting device, method for producing same, and display|

---

US7045205B1|2004-02-19|2006-05-16|Nanosolar, Inc.|Device based on coated nanoporous structure|

---

WO2005114748A2|2004-04-13|2005-12-01|Solaris Nanosciences, Inc.|Plasmon enhanced sensitized photovoltaic cells|

---

US8592680B2|2004-08-11|2013-11-26|The Trustees Of Princeton University|Organic photosensitive devices|

---

WO2006034561A1|2004-09-27|2006-04-06|The State Scientific Institution 'institute Of Molecular And Atomic Physics Of The National Academy Of Science Of Belarus'|High-efficient small-aperture light converter|

---

JP2007031178A|2005-07-25|2007-02-08|Utsunomiya Univ|Cadmium-tellurium oxide thin film and its forming method|

---

US8034745B2|2005-08-01|2011-10-11|Amit Goyal|High performance devices enabled by epitaxial, preferentially oriented, nanodots and/or nanorods|

---

US20070028961A1|2005-08-04|2007-02-08|General Electric Company|Organic dye compositions and use thereof in photovoltaic cells|

---

JP2007095488A|2005-09-29|2007-04-12|Toshiba Corp|Light emitting element and method of manufacturing same|

---

KR100838158B1|2007-01-04|2008-06-13|한국과학기술연구원|Photo-electrodes equipped meso porous metal oxide layer for dye-sensitized photovoltaic cell and method for preparing the same|

---

JP2008189947A|2007-01-31|2008-08-21|National Institute For Materials Science|Perovskite thin film and manufacturing method of the same|

---

KR20080079894A|2007-02-28|2008-09-02|삼성에스디아이 주식회사|Dye-sensitized solar cell and preparing method thereof|

---

JP2009006548A|2007-06-27|2009-01-15|Saga Univ|Organic/inorganic layer-shaped perovskite compound thin film, and method for producing the same|

---

AT498203T|2007-07-23|2011-02-15|Basf Se|PHOTOVOLTAIC TANDEM CELL|

---

US20090032097A1|2007-07-31|2009-02-05|Bigioni Terry P|Enhancement of dye-sensitized solar cells using colloidal metal nanoparticles|

---

US8193704B2|2008-02-19|2012-06-05|National Institute Of Advanced Industrial Science And Technology|Perovskite oxide thin film EL element|

---

JP2010009786A|2008-06-24|2010-01-14|Sharp Corp|Dye sensitized solar cell, and dye sensitized solar cell module|

---

CN101635203B|2008-07-27|2011-09-28|比亚迪股份有限公司|Semiconductor electrode, manufacture method thereof and solar cell containing same|

---

TWI375333B|2009-02-26|2012-10-21|Nat Applied Res Laboratories|

---

US20110089402A1|2009-04-10|2011-04-21|Pengfei Qi|Composite Nanorod-Based Structures for Generating Electricity|

---

KR101061970B1|2009-05-25|2011-09-05|한국과학기술연구원|Photoelectrode using conductive nonmetallic film and dye-sensitized solar cell comprising same|

---

GB0909818D0|2009-06-08|2009-07-22|Isis Innovation|Device|

---

GB0916037D0|2009-09-11|2009-10-28|Isis Innovation|Device|

---

JP5489621B2|2009-09-29|2014-05-14|ヤヱガキ醗酵技研株式会社|Photoelectric conversion element and photovoltaic device using the photoelectric conversion element|

---

GB0920918D0|2009-11-27|2010-01-13|Isis Innovation|Device|

---

GB201004106D0|2010-03-11|2010-04-28|Isis Innovation|Device|

---

CN102468413B|2010-11-09|2014-10-29|四川新力光源股份有限公司|Alternating current LED light-emitting device|

---

GB201020209D0|2010-11-29|2011-01-12|Isis Innovation|Device|

---

KR101172374B1|2011-02-14|2012-08-08|성균관대학교산학협력단|Dye-sensitized solar cell based on perovskite sensitizer and manufacturing method thereof|

---

US9484475B2|2011-10-11|2016-11-01|The Trustees Of The University Of Pennsylvania|Semiconductor ferroelectric compositions and their use in photovoltaic devices|

---

US9181475B2|2012-02-21|2015-11-10|Northwestern University|Photoluminescent compounds|

---

GB201203881D0|2012-03-05|2012-04-18|Isis Innovation|Mesoporous single crystal semiconductore|

---

GB201208793D0|2012-05-18|2012-07-04|Isis Innovation|Optoelectronic device|

---

EP2850627B1|2012-05-18|2016-04-06|Isis Innovation Limited|Optoelectronic device comprising porous scaffold material and perovskites|

---

ES2566914T3|2012-05-18|2016-04-18|Isis Innovation Limited|Photovoltaic device comprising perovskites|

---

EP2897178A4|2012-09-12|2016-05-25|Korea Res Inst Chem Tech|Solar cell having light-absorbing structure|

---

BR112015005926B1|2012-09-18|2022-01-25|Oxford University Innovation Limited|optoelectronic device|

---

GB2528831A|2014-06-05|2016-02-10|Univ Swansea|Perovskite pigments for solar cells|US9181475B2|2012-02-21|2015-11-10|Northwestern University|Photoluminescent compounds|

---

GB201208793D0|2012-05-18|2012-07-04|Isis Innovation|Optoelectronic device|

---

BR112015005926B1|2012-09-18|2022-01-25|Oxford University Innovation Limited|optoelectronic device|

---

JP6103183B2|2012-10-10|2017-03-29|ペクセル・テクノロジーズ株式会社|Electroluminescent device using perovskite compound|

---

JP6099036B2|2012-10-17|2017-03-22|ペクセル・テクノロジーズ株式会社|Organic EL devices using perovskite compounds|

---

US10079356B2|2012-12-20|2018-09-18|Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd.|Perovskite schottky type solar cell|

---

JP2014236045A|2013-05-31|2014-12-15|積水化学工業株式会社|Organic thin-film solar cell|

---

EP3042402A4|2013-09-04|2017-05-31|Dyesol Ltd|A photovoltaic device|

---

JP6304980B2|2013-09-10|2018-04-04|大阪瓦斯株式会社|Photoelectric conversion device using perovskite materials|

---

US9997714B2|2013-10-02|2018-06-12|Merck Patent Gmbh|Hole transport material|

---

WO2015057885A1|2013-10-16|2015-04-23|OmniPV, Inc.|Photovoltaic cells including halide materials|

---

WO2015116297A2|2013-11-12|2015-08-06|The Regents Of The University Of California|Sequential processing with vapor treatment of thin films of organic-inorganic perovskite materials|

---

WO2016183273A1|2015-05-13|2016-11-17|Hunt Energy Enterprises, L.L.C.|Titanate interfacial layers in perovskite material devices|

---

US9416279B2|2013-11-26|2016-08-16|Hunt Energy Enterprises, L.L.C.|Bi- and tri-layer interfacial layers in perovskite material devices|

---

US9520512B2|2013-11-26|2016-12-13|Hunt Energy Enterprises, L.L.C.|Titanate interfacial layers in perovskite material devices|

---

US9425396B2|2013-11-26|2016-08-23|Hunt Energy Enterprises L.L.C.|Perovskite material layer processing|

---

EP3320571B1|2015-07-10|2020-09-02|Hunt Perovskite Technologies, L.L.C.|Perovskite material layer processing|

---

US11180660B2|2013-11-26|2021-11-23|Cubic Perovskite Llc|Mixed cation perovskite material devices|

---

KR101877975B1|2014-11-21|2018-08-17|히 솔라, 엘.엘.씨.|Bi- and tri-layer interfacial layers in perovskite material devices|

---

US9136408B2|2013-11-26|2015-09-15|Hunt Energy Enterprises, Llc|Perovskite and other solar cell materials|

---

ES2776161T3|2013-12-17|2020-07-29|Univ Oxford Innovation Ltd|Photovoltaic device comprising a metal halide perovskite and a passivating agent|

---

WO2015187225A2|2014-03-12|2015-12-10|The University Of Akron|Ultrasensitive solution-processed perovskite hybrid photodetectors|

---

CN104979421B|2014-04-11|2017-09-26|中国科学院大连化学物理研究所|A kind of lamination solar cell|

---

KR101645872B1|2014-04-23|2016-08-04|주식회사 엘지화학|Inorganic-organic hybrid solar cell|

---

US9966198B2|2014-04-24|2018-05-08|Northwestern University|Solar cells with perovskite-based light sensitization layers|

---

KR101757198B1|2014-04-28|2017-07-11|성균관대학교산학협력단|Precursor for preparing perovskite and preparing method of the same, and perovskite solar cell and preparing method of the cell|

---

TWI474992B|2014-04-29|2015-03-01|Univ Nat Central|Method for preparing perovskite thin film and solar cell|

---

CN103956431B|2014-04-30|2017-10-20|华南理工大学|A kind of organic-inorganic planar heterojunction solar cell of solution processing and its preparation|

---

GB201407606D0|2014-04-30|2014-06-11|Cambridge Entpr Ltd|Electroluminescent device|

---

CN106463625B|2014-05-05|2019-04-26|学校法人冲绳科学技术大学院大学学园|For manufacturing the system and method for being used for the perovskite film of solar battery purposes|

---

EP3149765B1|2014-05-28|2019-03-13|Alliance for Sustainable Energy, LLC|Methods for producing perovskite materials|

---

GB2528831A|2014-06-05|2016-02-10|Univ Swansea|Perovskite pigments for solar cells|

---

US9564593B2|2014-06-06|2017-02-07|The Board Of Trustees Of The Leland Stanford Junior University|Solar cells comprising 2d-perovskites|

---

GB201410542D0|2014-06-12|2014-07-30|Isis Innovation|Heterojunction device|

---

CN104051629B|2014-06-28|2017-10-20|福州大学|A kind of method that Ca-Ti ore type solar cell is prepared based on spraying coating process|

---

US20160005987A1|2014-07-01|2016-01-07|Sharp Laboratories Of America, Inc.|Planar Structure Solar Cell with Inorganic Hole Transporting Material|

---

GB201412201D0|2014-07-09|2014-08-20|Isis Innovation|Two-step deposition process|

---

EP2966703A1|2014-07-11|2016-01-13|Ecole Polytechnique Fédérale de Lausanne |Template enhanced organic inorganic perovskite heterojunction photovoltaic device|

---

CN105280817B|2014-07-16|2017-11-07|财团法人工业技术研究院|The formed method of solar cell|

---

WO2016009450A2|2014-07-17|2016-01-21|Indian Institute Of Technology Bombay|Photonic devices by organo-metallic halides based perovskites material and its method of preparation|

---

JP2016025170A|2014-07-18|2016-02-08|学校法人桐蔭学園|Photoelectric conversion element consisting of organic-inorganic hybrid structure|

---

WO2016012274A1|2014-07-21|2016-01-28|Basf Se|Organic-inorganic tandem solar cell|

---

WO2016014845A1|2014-07-23|2016-01-28|The University Of Akron|Ultrasensitive solution-processed perovskite hybrid photodetectors|

---

CN104124291B|2014-07-24|2016-08-31|华中科技大学|A kind of perovskite solar cell and preparation method thereof|

---

CN104157786A|2014-07-31|2014-11-19|清华大学|Perovskite type solar battery and preparation method thereof|

---

US9305715B2|2014-08-01|2016-04-05|Hunt Energy Enterprises Llc|Method of formulating perovskite solar cell materials|

---

US20170226641A1|2014-08-07|2017-08-10|Okinawa Institute Of Science And Technology School Corporation|System and method based on multi-source deposition for fabricating perovskite film|

---

GB201414110D0|2014-08-08|2014-09-24|Isis Innovation|Thin film production|

---

TWI527259B|2014-08-13|2016-03-21|國立清華大學|Method of fabricating perovskite solar cell|

---

KR101869212B1|2014-08-21|2018-06-19|각코호진 오키나와가가쿠기쥬츠다이가쿠인 다이가쿠가쿠엔|System and method based on low-pressure chemical vapor deposition for fabricating perovskite film|

---

CN104201284B|2014-08-29|2017-08-25|国家纳米科学中心|A kind of integrated solar cell based on perovskite solar cell and bulk heterojunction solar cell and preparation method thereof|

---

US10930442B2|2014-09-02|2021-02-23|University Of Tokyo|Light-transmitting electrode having carbon nanotube film, solar cell, method for producing light-transmitting electrode having carbon nanotube film, and method for manufacturing solar cell|

---

CN104269452A|2014-10-11|2015-01-07|中国科学院半导体研究所|Perovskite solar battery made of silicon-based thin-film materials and manufacturing method thereof|

---

JP2016082003A|2014-10-14|2016-05-16|積水化学工業株式会社|Method for manufacturing thin-film solar battery|

---

CN106796992B|2014-10-21|2020-08-14|住友化学株式会社|Organic photoelectric conversion element and method for manufacturing same|

---

KR101969659B1|2014-11-05|2019-04-16|각코호진 오키나와가가쿠기쥬츠다이가쿠인 다이가쿠가쿠엔|Doping engineered hole transport layer for perovskite-based device|

---

JP2016096277A|2014-11-15|2016-05-26|ペクセル・テクノロジーズ株式会社|Photoelectric conversion element arranged by use of perovskite compound, and method for manufacturing the same|

---

EP3024042B1|2014-11-21|2017-07-19|Heraeus Deutschland GmbH & Co. KG|PEDOT in perovskite solar cells|

---

CN104409642B|2014-11-21|2017-04-26|北京科技大学|Preparation method of perovskite/P-type quantum dot composite solar cell|

---

GB201421133D0|2014-11-28|2015-01-14|Cambridge Entpr Ltd|Electroluminescent device|

---

US10535791B2|2014-12-03|2020-01-14|The Board Of Trustees Of The Leland Stanford Junior University|2-terminal metal halide semiconductor/C-silicon multijunction solar cell with tunnel junction|

---

WO2016088019A1|2014-12-03|2016-06-09|Saule Sp. Z O.O.|A film-forming compostion and a method for manufacturnig a photoactive film|

---

JP2016115880A|2014-12-17|2016-06-23|積水化学工業株式会社|Organic/inorganic hybrid solar cell|

---

JP2016119468A|2014-12-17|2016-06-30|積水化学工業株式会社|Organic inorganic hybrid solar cell|

---

CN107210367B|2014-12-19|2020-01-21|联邦科学和工业研究组织|Method of forming photoactive layer of optoelectronic device|

---

CN107210372B|2014-12-23|2020-02-28|荷兰应用自然科学研究组织 Tno|Method of manufacturing an interconnected solar cell array|

---

NL2014097B1|2015-01-08|2016-09-30|Univ Delft Tech|Hole transport azomethine molecule.|

---

US20170365417A1|2015-01-22|2017-12-21|Sumitomo Chemical Company, Limited|Photoelectric conversion device and production method thereof|

---

TWI693732B|2015-01-29|2020-05-11|日商積水化學工業股份有限公司|Solar battery and method for manufacturing solar battery|

---

EP3051600A1|2015-01-30|2016-08-03|Consejo Superior De Investigaciones Científicas|Heterojunction device|

---

JP2016149472A|2015-02-13|2016-08-18|ペクセル・テクノロジーズ株式会社|Photoelectric conversion element using perovskite compound|

---

US9997707B2|2015-02-26|2018-06-12|Nanyang Technological University|Perovskite thin films having large crystalline grains|

---

US9701696B2|2015-02-27|2017-07-11|Alliance For Sustainable Energy, Llc|Methods for producing single crystal mixed halide perovskites|

---

JP6486719B2|2015-03-03|2019-03-20|株式会社東芝|Method for manufacturing photoelectric conversion element|

---

WO2016144883A1|2015-03-06|2016-09-15|The Regents Of The University Of California|Efficient and stable of perovskite solar cells with all solution processed metal oxide transporting layers|

---

CN104733618A|2015-03-06|2015-06-24|中国科学院大学|Method for preparing perovskite solar cell absorption layer|

---

JP6537850B2|2015-03-09|2019-07-03|大阪瓦斯株式会社|Method of forming light absorbing layer in photoelectric conversion device|

---

JP6339037B2|2015-03-18|2018-06-06|株式会社東芝|Photoelectric conversion element and manufacturing method thereof|

---

JP6486737B2|2015-03-19|2019-03-20|株式会社東芝|Photoelectric conversion element|

---

WO2016152705A1|2015-03-25|2016-09-29|積水化学工業株式会社|Solar cell|

---

JP6554300B2|2015-03-27|2019-07-31|株式会社カネカ|Method for manufacturing photoelectric conversion device|

---

WO2016158698A1|2015-03-30|2016-10-06|住友化学株式会社|Photoelectric conversion element|

---

WO2016157979A1|2015-03-31|2016-10-06|株式会社カネカ|Photoelectric conversion device and photoelectric conversion module|

---

JPWO2016158838A1|2015-03-31|2017-12-14|株式会社カネカ|Photoelectric conversion device, method for manufacturing photoelectric conversion device, and photoelectric conversion module|

---

JP6434847B2|2015-03-31|2018-12-05|株式会社東芝|Method and apparatus for manufacturing photoelectric conversion element|

---

US10586659B2|2015-04-06|2020-03-10|Board Of Trustees Of Northern Illinois University|Perovskite photovoltaic device|

---

WO2016172211A1|2015-04-20|2016-10-27|The Regents Of The University Of California|Perovskite-based optoelectronic device employing non-doped small molecule hole transport materials|

---

US10910569B2|2015-05-19|2021-02-02|Alliance For Sustainable Energy, Llc|Organo-metal halide perovskites films and methods of making the same|

---

CN104993059B|2015-05-28|2017-11-10|中山大学|A kind of silicon substrate perovskite heterojunction solar battery and preparation method thereof|

---

KR101693192B1|2015-05-29|2017-01-05|한국과학기술연구원|Perovskite solar cell and preparation method thereof|

---

WO2016200897A1|2015-06-08|2016-12-15|The Florida State University Research Foundation, Inc.|Single-layer light-emitting diodes using organometallic halide perovskite/ionic-conducting polymer composite|

---

KR101654310B1|2015-06-09|2016-09-05|포항공과대학교 산학협력단|Method for manufacturing of electrode layer using anodization, and method for manufacturing of perovskite solar cell comprising the same|

---

WO2016198898A1|2015-06-12|2016-12-15|Oxford Photovoltaics Limited|Multijunction photovoltaic device|

---

EP3496173B1|2015-06-12|2020-04-08|Oxford Photovoltaics Limited|Perovskite material|

---

JP6489950B2|2015-06-12|2019-03-27|シャープ株式会社|Photoelectric conversion element and manufacturing method thereof|

---

GB201510351D0|2015-06-12|2015-07-29|Oxford Photovoltaics Ltd|Method of depositioning a perovskite material|

---

CN104934503B|2015-06-12|2017-03-08|辽宁工业大学|A kind of preparation method of perovskite solar cell light absorption layer material methyl amine lead bromide|

---

EP3316327A4|2015-06-26|2018-07-04|FUJI-FILM Corporation|Photoelectric conversion element, solar battery, metal salt composition, and manufacturing method for photoelectric conversion element|

---

KR20180023975A|2015-06-30|2018-03-07|캠브리지 엔터프라이즈 리미티드|Light emitting device|

---

JP6352223B2|2015-07-03|2018-07-04|国立大学法人京都大学|Method for producing perovskite solar cell|

---

JP2017028028A|2015-07-17|2017-02-02|積水化学工業株式会社|Solid-state junction photoelectric conversion element and p type semiconductor layer for solid-state junction photoelectric conversion element|

---

JP2017028027A|2015-07-17|2017-02-02|積水化学工業株式会社|Solid-state junction photoelectric conversion element and p type semiconductor layer for solid-state junction photoelectric conversion element|

---

JP6572039B2|2015-07-22|2019-09-04|積水化学工業株式会社|Thin film solar cell and method for manufacturing thin film solar cell|

---

KR102323243B1|2015-07-22|2021-11-08|삼성디스플레이 주식회사|Organic light emitting diode and organic light emitting diode display including the same|

---

JP2017028138A|2015-07-24|2017-02-02|公立大学法人 滋賀県立大学|Solar cell and method of manufacturing the same|

---

WO2017022687A1|2015-07-31|2017-02-09|積水化学工業株式会社|Solar cell|

---

JP6725221B2|2015-07-31|2020-07-15|積水化学工業株式会社|Thin film solar cell|

---

JP6725219B2|2015-07-31|2020-07-15|積水化学工業株式会社|Solar cell|

---

WO2017031193A1|2015-08-20|2017-02-23|The Hong Kong University Of Science And Technology|Organic-inorganic perovskite materials and optoelectronic devices fabricated by close space sublimation|

---

CN105206749A|2015-08-31|2015-12-30|中国电子科技集团公司第四十八研究所|Perovskite solar cell and preparation process thereof|

---

KR101686342B1|2015-09-01|2016-12-14|연세대학교 산학협력단|Semitransparent perovskite solar cells and fabrication thereof|

---

US9911935B2|2015-09-04|2018-03-06|International Business Machines Corporation|Transparent conducting oxide as top-electrode in perovskite solar cell by non-sputtering process|

---

KR20170029370A|2015-09-07|2017-03-15|주식회사 레이언스|X-ray detector|

---

WO2017043871A1|2015-09-07|2017-03-16|주식회사 레이언스|X-ray detector|

---

KR101629729B1|2015-09-07|2016-06-13|한국기계연구원|Perovskite solar cell|

---

JP6382781B2|2015-09-15|2018-08-29|株式会社東芝|Semiconductor element manufacturing method and manufacturing apparatus|

---

JP2017059647A|2015-09-15|2017-03-23|株式会社東芝|Photoelectric conversion element and solar cell|

---

US10573690B2|2015-09-17|2020-02-25|Koninklijke Philips N.V.|Method for producing a radiation detector and radiation detector|

---

EP3358637A4|2015-09-30|2019-06-19|Kaneka Corporation|Multi-junction photoelectric conversion device and photoelectric conversion module|

---

US10476017B2|2015-10-11|2019-11-12|Northwestern University|Phase-pure, two-dimensional, multilayered perovskites for optoelectronic applications|

---

CN105374941B|2015-10-13|2018-06-12|上海科技大学|A kind of semi-conducting material with cubic perovskite structure and preparation method thereof|

---

WO2017083077A1|2015-10-22|2017-05-18|The Board Of Trustees Of The Leland Stanford Junior University|Solar cell comprising an oxide-nanoparticle buffer layer and method of fabrication|

---

CN106676476B|2015-11-11|2019-10-25|清华大学|Vacuum deposition method|

---

CN106676474B|2015-11-11|2019-09-13|清华大学|Vacuum deposition method|

---

CN106676475B|2015-11-11|2019-09-03|清华大学|Vacuum deposition apparatus|

---

EP3168877A1|2015-11-13|2017-05-17|TWI Limited|A wire shaped coaxial photovoltaic solar cell|

---

CN105226187B|2015-11-15|2018-01-30|河北工业大学|Film crystal silicon perovskite heterojunction solar battery and preparation method thereof|

---

CN105244442A|2015-11-15|2016-01-13|河北工业大学|Thin film crystal silicon perovskite heterojunction solar cell manufacturing method|

---

CN105449103B|2015-11-15|2018-06-22|河北工业大学|A kind of film crystal silicon perovskite heterojunction solar battery and preparation method thereof|

---

CN105428535A|2015-11-15|2016-03-23|河北工业大学|Manufacturing method for thin film crystal silicon perovskite heterojunction solar cell|

---

CN105405974A|2015-11-17|2016-03-16|华中科技大学|P-type doped perovskite-based photoelectric functional material and application thereof|

---

CN105470400B|2015-11-19|2018-06-22|华北电力大学|A kind of preparation method and application of perovskite film|

---

DE102015015017A1|2015-11-19|2017-05-24|Institut Für Solarenergieforschung Gmbh|A solar cell and method of making a solar cell having a plurality of absorbers interconnected by charge carrier selective contacts|

---

WO2017087611A1|2015-11-20|2017-05-26|Alliance For Sustainable Energy, Llc|Multi-layered perovskites, devices, and methods of making the same|

---

KR101853342B1|2015-11-25|2018-04-30|재단법인 멀티스케일 에너지시스템 연구단|Perovskite solar cell and preparing method of same|

---

GB201520972D0|2015-11-27|2016-01-13|Isis Innovation|Mixed cation perovskite|

---

EP3182466B1|2015-12-14|2020-04-08|Oxford Photovoltaics Limited|Photovoltaic module encapsulation|

---

CN106910830A|2015-12-23|2017-06-30|昆山工研院新型平板显示技术中心有限公司|A kind of organic electroluminescence device and preparation method thereof|

---

JP6431513B2|2015-12-24|2018-11-28|旭化成株式会社|Composition|

---

US10622161B2|2016-01-06|2020-04-14|Nutech Ventures|Narrow band perovskite single crystal photodetectors with tunable spectral response|

---

CN108417720B|2016-01-26|2020-03-27|南京工业大学|Perovskite material|

---

US10714688B2|2016-02-25|2020-07-14|University Of Louisville Research Foundation, Inc.|Methods for forming a perovskite solar cell|

---

US10937978B2|2016-02-25|2021-03-02|University Of Louisville Research Foundation, Inc.|Methods for forming a perovskite solar cell|

---

CN105655443A|2016-02-29|2016-06-08|苏州大学|Method for enhancing solar cell efficiency based on light induced field inductive effect|

---

CN105742507B|2016-02-29|2018-02-13|上海科技大学|Semi-conducting material with cubic perovskite structure and preparation method thereof|

---

JP6722007B2|2016-03-14|2020-07-15|株式会社カネカ|Stacked photoelectric conversion device and manufacturing method thereof|

---

WO2017160955A1|2016-03-15|2017-09-21|Nutech Ventures|Insulating tunneling contact for efficient and stable perovskite solar cells|

---

CN105826476B|2016-03-17|2018-07-31|华北电力大学|A kind of preparation method of the perovskite solar cell based on composite hole transporting layer|

---

WO2017158551A2|2016-03-18|2017-09-21|Ecole Polytechnique Federale De Lausanne |High efficiency large area perovskite solar cells and process for producing the same|

---

WO2017165434A1|2016-03-21|2017-09-28|Nutech Ventures|Sensitive x-ray and gamma-ray detectors including perovskite single crystals|

---

EP3223323A1|2016-03-24|2017-09-27|Ecole Polytechnique Fédérale de Lausanne |High efficiency large area perovskite solar cells and process for producing the same|

---

EP3442037B1|2016-04-07|2021-02-24|Kaneka Corporation|Method for manufacturing multijunction photoelectric conversion device|

---

CN105789449B|2016-05-12|2019-07-26|西安穿越光电科技有限公司|A kind of perovskite solar cell and preparation method thereof|

---

CN105826473B|2016-05-12|2019-06-21|东莞市联洲知识产权运营管理有限公司|A kind of Ca-Ti ore type solar battery and preparation method thereof|

---

US10892106B2|2016-05-13|2021-01-12|University of Pittsburgh—of the Commonwealth System of Higher Education|Highly stable electronic device employing hydrophobic composite coating layer|

---

US10453988B2|2016-06-03|2019-10-22|University Of Utah Research Foundation|Methods for creating cadmium tellurideand related alloy film|

---

WO2018005749A1|2016-06-29|2018-01-04|Alliance For Sustainable Energy, Llc|Methods for making perovskite solar cells having improved hole-transport layers|

---

JP6708493B2|2016-06-30|2020-06-10|浜松ホトニクス株式会社|Radiation detector and manufacturing method thereof|

---

TWI626768B|2016-08-01|2018-06-11|國立成功大學|Light-emitting diode and method for fabricating the same|

---

CN106229411A|2016-08-02|2016-12-14|天津工业大学|A kind of perovskite solar cell of backlight substrate and preparation method thereof|

---

CN106252513A|2016-08-02|2016-12-21|天津工业大学|Perovskite solar cell based on matte light regime structure and preparation method thereof|

---

WO2018025445A1|2016-08-04|2018-02-08|花王株式会社|Light absorption layer, photoelectric conversion element, dispersion, photoelectric conversion element, solar cell, and method for manufacturing light absorption layer|

---

CN109699193A|2016-08-05|2019-04-30|维深半导体公司|Photodetector and manufacturing method|

---

KR102146212B1|2016-08-11|2020-08-20|아반타마 아게|Luminescent crystals and manufacturing thereof|

---

WO2018036914A1|2016-08-22|2018-03-01|Merck Patent Gmbh|Organic semiconducting compounds|

---

JP6843719B2|2016-09-06|2021-03-17|旭化成株式会社|Organic inorganic metal compounds|

---

CN106282922A|2016-09-07|2017-01-04|中国工程物理研究院材料研究所|A kind of coevaporation prepares the method for inorganic non-lead halogenide perovskite thin film|

---

CN106252516B|2016-09-20|2019-05-14|华南理工大学|A kind of translucent hybrid perovskite solar cell device of planar inverted and preparation method|

---

JPWO2018056295A1|2016-09-21|2019-07-04|積水化学工業株式会社|Solar cell|

---

JP6530360B2|2016-09-23|2019-06-12|株式会社東芝|Photoelectric conversion element|

---

WO2018064235A1|2016-09-27|2018-04-05|Massachusetts Institute Of Technology|Tunable light emitting diodes utilizing quantum-confined layered perovskite emitters|

---

JP2019531380A|2016-10-05|2019-10-31|メルク パテント ゲーエムベーハー|Organic semiconductor compounds|

---

EP3523308A1|2016-10-05|2019-08-14|Merck Patent GmbH|Organic semiconducting compounds|

---

EP3306690A1|2016-10-05|2018-04-11|Merck Patent GmbH|Organic semiconducting compounds|

---

WO2018068102A1|2016-10-13|2018-04-19|Newsouth Innovations Pty Limited|A photovoltaic cell and a method of forming a photovoltaic cell|

---

GB2554908A|2016-10-13|2018-04-18|Univ Of Kent|Photovoltaically active perovskite materials|

---

US10611783B2|2016-10-14|2020-04-07|Alliance For Sustainable Energy, Llc|Oriented perovskite crystals and methods of making the same|

---

CN106549106A|2016-10-21|2017-03-29|中国科学院上海应用物理研究所|A kind of thin-film solar cells based on laminated perovskite structure material and preparation method thereof|

---

EP3533089A1|2016-10-31|2019-09-04|Merck Patent GmbH|Organic semiconducting compounds|

---

US10276820B2|2016-11-14|2019-04-30|Boe Technology Group Co., Ltd.|Quantum dots light emitting diode and fabricating method thereof, display panel and display apparatus|

---

EP3331029B1|2016-12-02|2021-09-01|LG Electronics Inc.|Tandem solar cell and method of manufacturing the same|

---

EP3333170B1|2016-12-06|2020-04-29|Merck Patent GmbH|Asymmetrical polycyclic compounds for use in organic semiconductors|

---

CN106653927B|2016-12-23|2018-01-02|济南大学|One kind is based on Cs2SnI6＆ CH3NH3PbI3The preparation method of the solar cell of bulk heterojunction|

---

EP3565015A4|2016-12-28|2019-12-25|Panasonic Intellectual Property Management Co., Ltd.|Solar cell, light-absorbing layer, and method for forming light-absorbing layer|

---

CN108305949A|2017-01-11|2018-07-20|南京工业大学|A kind of method of adjustment and its application that multiple quantum wells perovskite material Quantum Well trap is wide and device|

---

JP2018117008A|2017-01-17|2018-07-26|積水化学工業株式会社|Solid junction type photoelectric conversion element and solid junction type photoelectric conversion element P type semiconductor layer|

---

KR20180090116A|2017-02-02|2018-08-10|삼성전자주식회사|Light filter and Spectrometer comprising the same|

---

GB2559800B|2017-02-20|2019-06-12|Oxford Photovoltaics Ltd|Multijunction photovoltaic device|

---

US10457148B2|2017-02-24|2019-10-29|Epic Battery Inc.|Solar car|

---

JP6378383B1|2017-03-07|2018-08-22|株式会社東芝|Semiconductor device and manufacturing method thereof|

---

EP3592748A1|2017-03-09|2020-01-15|Merck Patent GmbH|Organic semiconducting compounds|

---

CN106684247A|2017-03-15|2017-05-17|中南大学|Perovskite solar cell and preparation method thereof|

---

CN107425122B|2017-03-20|2019-08-16|中节能万润股份有限公司|A kind of doping type perovskite solar battery and preparation method thereof|

---

US11271123B2|2017-03-27|2022-03-08|The Board Of Trustees Of The Leland Stanford Junior University|Alloyed halide double perovskites as solar-cell absorbers|

---

US10587221B2|2017-04-03|2020-03-10|Epic Battery Inc.|Modular solar battery|

---

US20180301288A1|2017-04-14|2018-10-18|Hunt Energy Enterprises, L.L.C.|Photovoltaic Device Encapsulation|

---

GB201706285D0|2017-04-20|2017-06-07|Univ Oxford Innovation Ltd|Semiconductor device comprising halometallate|

---

EP3401305A1|2017-05-12|2018-11-14|Dottikon Es Holding Ag|Indane derivatives and their use in organic electronics|

---

TW201900845A|2017-05-12|2019-01-01|瑞士商多蒂孔股份有限公司|Decane derivatives and their use in organic electronic products|

---

KR101895166B1|2017-05-19|2018-10-18|울산과학기술원|Pb-free perovskite based hole transport material composites, solar cells comporising the same, and method for manufactureing the same|

---

US20200111982A1|2017-05-19|2020-04-09|Florida State University Research Foundation, Inc.|Halide perovskite thin films and methods for production thereof|

---

KR20180130397A|2017-05-29|2018-12-07|엘지전자 주식회사|Method of manufacturing perovskite silicon tandem solar cell|

---

CN110998888A|2017-08-11|2020-04-10|默克专利股份有限公司|Organic semiconducting polymers|

---

EP3681889A1|2017-09-13|2020-07-22|Merck Patent GmbH|Organic semiconducting compounds|

---

KR20190036937A|2017-09-28|2019-04-05|엘지디스플레이 주식회사|Lighe emitting diode and light emitting device having thereof|

---

US11249203B2|2017-09-29|2022-02-15|Northwestern University|Thick alkali metal halide perovskite films for low dose flat panel x-ray imagers|

---

CN107742661A|2017-10-19|2018-02-27|辽宁科技大学|The method that inorganic tin based perovskites solar cell is prepared with physical vaporous deposition|

---

EP3474339A1|2017-10-20|2019-04-24|Siemens Healthcare GmbH|X-ray image sensor with adhesion promotive interlayer and soft-sintered perovskite active layer|

---

KR102093718B1|2017-10-27|2020-03-26|이화여자대학교 산학협력단|Photodetector including quasi-2d perovskite film|

---

EP3704176A1|2017-11-02|2020-09-09|Merck Patent GmbH|Organic semiconducting compounds|

---

CN107749432A|2017-11-06|2018-03-02|成都中建材光电材料有限公司|A kind of CdTe thin film solar cell and preparation method thereof|

---

WO2019091995A1|2017-11-10|2019-05-16|Merck Patent Gmbh|Organic semiconducting compounds|

---

GB201721066D0|2017-12-15|2018-01-31|Oxford Photovoltaics Ltd|Multi-function photovoltaic device|

---

CN108230908A|2018-01-03|2018-06-29|京东方科技集团股份有限公司|A kind of display panel and display device|

---

WO2019154973A1|2018-02-12|2019-08-15|Merck Patent Gmbh|Organic semiconducting compounds|

---

CN108376745B|2018-03-01|2020-08-18|京东方科技集团股份有限公司|Quantum dot light-emitting diode, preparation method thereof and display panel|

---

CN112236882A|2018-03-28|2021-01-15|天光材料科技股份有限公司|Organic semiconductor compound|

---

US20210070770A1|2018-03-28|2021-03-11|Raynergy Tek Inc.|Organic semiconducting compounds|

---

CN108493341A|2018-03-30|2018-09-04|苏州大学|The preparation of perovskite solar cell using tantalum pentoxide as electron transfer layer|

---

WO2019206926A1|2018-04-27|2019-10-31|Merck Patent Gmbh|Organic semiconducting polymers|

---

CN108649124B|2018-05-23|2020-03-17|中南大学|High-efficiency inorganic perovskite solar cell and preparation method thereof|

---

US20210125790A1|2018-06-07|2021-04-29|The Governing Council Of The University Of Toronto|Doped metal halide perovskites with improved stability and solar cells comprising same|

---

GB201811537D0|2018-07-13|2018-08-29|Univ Oxford Innovation Ltd|Turnable blue emitting lead halide perovskites|

---

GB201811538D0|2018-07-13|2018-08-29|Univ Oxford Innovation Ltd|Stabilised a/m/x materials|

---

WO2020011831A1|2018-07-13|2020-01-16|Merck Patent Gmbh|Organic semiconducting compounds|

---

GB201811539D0|2018-07-13|2018-08-29|Univ Oxford Innovation Ltd|Fabrication process for a/m/x materials|

---

DE102018212305A1|2018-07-24|2020-01-30|Siemens Aktiengesellschaft|Organometallic perovskite solar cell, tandem solar cell and manufacturing process therefor|

---

DE102018212304A1|2018-07-24|2020-01-30|Siemens Aktiengesellschaft|Organometallic perovskite solar cell, tandem solar cell and manufacturing process therefor|

---

CN112955456A|2018-09-06|2021-06-11|天光材料科技股份有限公司|Organic semiconductor compound|

---

CN109346611A|2018-09-26|2019-02-15|杭州电子科技大学|A kind of preparation method of optical detector antetype device|

---

EP3650438A1|2018-11-09|2020-05-13|Dottikon Es Holding Ag|Di-, tri- and tetraphenylindane derivatives and their use in organic electronics|

---

US10907050B2|2018-11-21|2021-02-02|Hee Solar, L.L.C.|Nickel oxide sol-gel ink|

---

EP3896751A4|2018-12-12|2022-03-09|Jfe Steel Corp|Method for producing laminate and method for producing perovskite solar cell|

---

GB201820427D0|2018-12-14|2019-01-30|Univ Oxford Innovation Ltd|Device interlayer|

---

EP3918639A2|2019-01-30|2021-12-08|NUtech Ventures|Conversion of halide perovskite surfaces to insoluble, wide-bandgap lead oxysalts for enhanced solar cell stability|

---

WO2020161052A1|2019-02-06|2020-08-13|Merck Patent Gmbh|Organic semiconducting polymers|

---

JP2019071496A|2019-02-12|2019-05-09|株式会社東芝|Photoelectric conversion element and manufacturing method thereof|

---

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---

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---

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---

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---

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---

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---

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---

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---

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---

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法律状态:
2018-01-02| B25D| Requested change of name of applicant approved|Owner name: OXFORD UNIVERSITY INNOVATION LIMITED (GB) |

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2018-01-16| B25I| Requirement for requested change of headquarter|Owner name: OXFORD UNIVERSITY INNOVATION LIMITED (GB) |

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2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-03-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-11-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-01-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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GB201216605A|GB201216605D0|2012-09-18|2012-09-18|Optoelectronic device|

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GB1216605.4|2012-09-18|

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GB201309409A|GB201309409D0|2013-05-24|2013-05-24|Optoelectronic device|

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GB1309409.9|2013-05-24|

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PCT/GB2013/052425|WO2014045021A1|2012-09-18|2013-09-17|Optoelectronic device|

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