巴西专利BR112013019158B1 transparent photovoltaic cell, photovoltaic matrix and method for generating electricity

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专利摘要:
PHOTOVOLTAIC CELL, PHOTOVOLTAIC MATRIX, METHOD FOR MANUFACTURING A PHOTOVOLTAIC CELL AND METHOD FOR GENERATING ELECTRICITY. A transparent photovoltaic cell and method for realization are revealed. The photovoltaic cell can include a transparent substrate and a first active material superimposed on the substrate. the first active material may have a first absorption peak at a wavelength greater than approximately 650 nanometers. A second active material is disposed overlapping the substrate, the second active material having a second absorption peak at a wavelength outside the visible light spectrum. The photovoltaic cell can also include a transparent cathode and a transparent anode.
公开号:BR112013019158B1
申请号:R112013019158-9
申请日:2012-01-25
公开日:2021-02-02
发明作者:Vladimir Bulovic；Richard Royal Lunt
申请人:Massachusetts Institute Of Technology；
IPC主号:

专利说明:

CROSS REFERENCE TO THE ORDER PREVIOUSLY DEPOSITED
[001] This request claims priority over the provisional application filed earlier 61/436, 671 filed on January 26, 2011, which is incorporated herein in full by reference. FIELD OF THE INVENTION
[002] This invention refers to the field of photovoltaic devices, and more particularly, organic photovoltaic devices. HISTORIC
[003] The surface area needed to take advantage of solar energy remains an obstacle to counterbalancing a significant portion of non-renewable energy consumption. For this reason, low-cost, transparent and organic photovoltaic (OPV) devices that can be integrated into window panes in homes, skyscrapers and automobiles are desirable. For example, window glasses used in automobiles and in architecture are typically 70-80% and 55-90% transmissive, respectively, to the visible spectrum, for example, light with wavelengths of approximately 450 to 650 nanometers (nm) . The limited mechanical flexibility, the high cost of the module and, most importantly, the band-type absorption of inorganic semiconductors limits its potential utility for transparent solar cells. In contrast, the excitonic character of organic and molecular semiconductors results in absorption spectra that are highly structured with minimal and maximum absorption that is distinctly improbable from the band absorption of their inorganic counterparts. Previous efforts to build semitransparent devices have focused on the use of thin active layers (or physical holes) with absorption focused on the visible spectrum, and therefore have been limited to low efficiencies <1% or low medium visible transmittivity (AVT) to illuminate about 10-35%, since both parameters cannot be optimized simultaneously. SUMMARY OF THE INVENTION
[004] A transparent photovoltaic cell and a method for elaboration are revealed. The photovoltaic cell can include a transparent substrate and a first active material superimposed on the substrate. The first active material may have an absorption peak at a wavelength greater than approximately 650 nanometers. A second active material is disposed overlapping the substrate, the second active material having an absorption peak at a wavelength outside the visible light spectrum. The photovoltaic cell can also include a transparent cathode and a transparent anode.
[005] At least one of the cathodes and anodes can be configured to maximize absorption in the first active material. At least one of the cathodes and anodes can be configured to maximize absorption in the second active material. The first active material and the second active material can be located on separate layers. The first active material may have a second absorption peak at a wavelength of less than approximately 450 nanometers.
[006] The first active material can be a donor and the second active material can be a recipient. The device may also include a mirror that reflects at near-infrared wavelengths. The first active material can comprise an organic material. The first active material can comprise at least one of them: a phthalocyanine, a porphyrin or a naphthalocyanine dye. The first active material may comprise chlorine and aluminum phthalocyanine. The first active layer can comprise tin-phthalocyanine. The second active layer can comprise at least one of 60 carbon (Cee) or a nanotube. The first and second active materials can be configured for use with flexible encapsulation layers.
[007] The photovoltaic cell can include a transparent substrate and a first active material superimposed on the substrate. The first active material may have a first absorption peak at wavelengths greater than about 650 nanometers. The photovoltaic cell can include a second active material superimposed on the substrate, the second active material having a second absorption peak at a wavelength greater than approximately 650 nanometers or less than approximately 450 nanometers. The photovoltaic cell can also include a transparent cathode and a transparent anode.
[008] The photovoltaic cell can include a recombination area arranged between a first and second subcells, each of the first and second subcells having absorption peaks at wavelengths outside the visible light spectrum, a transparent cathode and a transparent anode. The photovoltaic cell can be transparent or semi-transparent.
[009] A method for making a photovoltaic cell may include making a first electrode material on a substrate, the electrode material and the substrate being transparent to visible light. At least one layer can be manufactured, the layer having a first active material with an absorption peak at a wavelength greater than approximately 650 nanometers and a second active material with an absorption peak at a wavelength outside the light spectrum visible. A second electrode can be made of material that is transparent to visible light. The method may include selecting a thickness of at least one of the first or second electrodes so that the absorption of near-infrared light in the active infrared absorption layer is maximized. The method may also include making a multilayer mirror for near-infrared light.
[0010] The method may include making a first and second subcells, each of the first and second subcells having absorption peaks in wavelength outside the visible light spectrum. The recombination area can be arranged between the first and second subcells. A transparent cathode and a transparent anode can also be manufactured. The photovoltaic cell can be transparent or semi-transparent. BRIEF DESCRIPTION OF THE FIGURES
[0011] Figure 1 (a) shows a schematic of a control solar cell;
[0012] Figure 1 (b) shows a schematic of an embodiment of a complete transparent solar cell;
[0013] Figure 1 (c) is a graph showing the extinction coefficient, k, of the active layers shown in Figures 1 (a) and 1 (b);
[0014] Figure 1 (d) is a graph showing the voltage-current curves (J-V) for the ClAlPc-C60 control and transparent cells shown in Figures 1 (a) and 1 (b);
[0015] Figure 2 (a) is a graph showing the series resistance decreases and the fill factor (FF) saturates close to the value for the control cell as the thickness of Indium and Tin Oxide (ITO) is increased;
[0016] Figure 2 (b) is a graph showing an increase in photo current by a factor of 3x at an optimal thickness of 120 nanometers so that the np increases practically the same amount;
[0017] Figure 3 (a) is a graph showing an external quantum efficiency (EQE) as a function of the wavelength for various thicknesses of the ITO and the control layers;
[0018] Figure 3 (b) is a graph that shows the% of transmission as a function of the wavelength for different thicknesses of the ITO and control layers;
[0019] Figure 3 (c) shows the measured solar simulation spectrum showing Xe-lamp characteristics and external quantum efficiency (EQE) mc-Si reported for NREL for the reference diode used to measure the intensity of the solar simulator;
[0020] Figure 3 (d) shows the measured and calculated reflectivity of the distributed Bragg reflector used in this study as the transparent NIR mirror;
[0021] Figures 4a and 4b show arrays of solar cells positioned in front of the image of a "rose" to highlight the transparency of the fully assembled device;
[0022] Figure 4c shows a matrix of solar cell coupled to an LCD Clock;
[0023] Figures 4d and 4e show an alternative realization of a solar cell matrix positioned in front of an image of a "mountain" to highlight the transparency of the fully assembled device;
[0024] Figure 4 (f) is an image of a complete circuit assembly with connections for an LCD clock.
[0025] Figure 5 (a) is a graph showing external quantum efficiency (EQE) as a function of the wavelength for a SnPc device;
[0026] Figure 5 (b) is a graph showing the% transmission as a function of the wavelength for a SnPc device;
[0027] Figure 6 (a) is a graph showing a comparison between SnPc and ClAlPc designs;
[0028] Figure 6 (b) is a graph showing the effect of the thickness of the ITO cathode;
[0029] Figures 6 (c) and 6 (d) show the transfer matrix simulations of the average visible transmission (AVT, left column) and short circuit current (right column) of the transparent OPV architecture as a function of thicknesses the ITO anode and cathode without a NIR mirror;
[0030] Figures 6 (e) and 6 (f) show the transfer matrix simulations of the average visible transmission (AVT, left column) and short circuit current (right column) of the transparent OPV architecture as a function of thicknesses the ITO anode and cathode with a NIR mirror;
[0031] Figure 7 is a block diagram of a mixed layer device including both a donor and a recipient;
[0032] Figure 8 is a block diagram of a tandem device;
[0033] Figures 9 (a) and 9 (b) are graphs showing different band intervals that can be used to optimize a tandem device;
[0034] Figures 10 (a) and 10 (b) are graphs showing practical efficiency limits for several of the achievements revealed here;
[0035] Figure 11 is a diagram showing the solar flow and the photopic response of the human eye; and
[0036] Figure 12 is a diagram showing an electronic reader, smart phone and display screen including a photovoltaic matrix as revealed here. DETAILED DESCRIPTION OF THE INVENTION
[0037] Improved solar cell designs, for example, transparent organic photovoltaic devices (TOPV), are described here. The term transparent used here encompasses an average visible transparency of a direct beam of 45% or more. The term semitransparent used here encompasses an average visible transparency of a direct beam of approximately 10% -45%. In general, the designs include active molecular layers with strong absorption characteristics outside the visible light spectrum, for example, in the ultraviolet (UV) and / or near infrared (NIR) solar spectrum. The devices may include high selective NIR reflectivity and broadband antireflective contact covers. The devices can be formed as heterojunction solar cells with an organic active layer, like chlorine and aluminum phthalocyanine (ClAlPc) or SnPc as a donor and a molecular active layer like C60 acting as a receptor and having a peak absorption in the solar spectrum. UV and NIR. Other materials suitable for the active layers include any phthalocyanine, porphyrin, naphthalocyanine dye, carbon nanotubes or suitable molecular excitonic materials with absorption peaks outside the visible spectrum. Such devices can be formed in a tandem structure with one or more subcells joined together through a recombination area. Such devices can be used in a variety of applications including rigid and flexible computer display screens used on a desktop monitor, laptop or notebook, tablet, cell phone, electronic readers and the like. Other applications include crystal watches, automotive and architectural glass including sunroofs and smoked glass. Photovoltaic devices can be used for active power generation, for example, for fully self-powered applications and battery charging (or battery life extension).
[0038] Near infrared (NIR) as reported here is defined as light having wavelengths ranging from approximately 650 to approximately 850 nanometers (nm). Ultraviolet (UV) as reported here is defined as light having a wavelength less than approximately 450 nanometers. The use of an active layer having absorption in the NIR and in the UV allows the use of mirror coverings of high selective reflectivity close to the infrared to optimize the performance of the device while also allowing the self-transmission of visible light throughout the device. Visible light as reported here is defined as light having wavelengths to which the human eye has a significant response, from approximately 450 to approximately 650 nanometers.
[0039] In one embodiment, the devices were manufactured in 150 nanometers of standardized Indium and Tin Oxide (ITO) (15 Q / sq.) Pre-covered on glass substrates. ITO is a component of an electrode. The ITO was cleaned with solvent and subsequently treated in an oxygen plasma for 30 seconds immediately before loading it into a high vacuum chamber (<1x10-6 Torr). ClAlPc and C60 were purified once by vacuum train sublimation before loading. Batocuproin (BCP) and molybdenum trioxide (MoO3) were used as soon as purchased. MoO3 is another component of an electrode. MoO3 (20 nanometers), ClAlPc (15 nanometers), C60 (30 nanometers), BCP (7.5 nanometers) and a thick Ag 100 nanometer cathode were sequentially deposited through thermal evaporation at a rate of 0.1 nanometers / Mon. The top ITO cathode for the transparent devices was deposited by RF directly into the organic layers at low power (7-25 W) with 10 sccm of Air flow (6 mTorr) and 0.005-0.03 nanometers / second. The cathodes were evaporated by a shadow mask, defining an active area device of 1 millimeter (mm) x 1.2 mm. A distributed Bragg reflector (DBR) near the infrared used as the transparent NIR mirror was growing separately in quartz through the deposit of 7 alternating layers of TiO2 and SiO2 at approximately 0.1 nanometers / second with the thickness centered around a length of 800 nanometer wave (200 nanometer band stop). Broadband antireflective covers (BBAR) pre-covered on quartz substrates (1-side) were attached to the DBRs using the index compatible fluid to reduce additional glass / air interface reflections. The transmission data of the assembled devices were obtained in normal view with a Cary Eclipse 5000 double-beam spectrophotometer without reference samples. The characteristics of current density versus voltage (JV) were measured in the dark and under simulated AM1.5G solar lighting without incompatibility correction (for reference, the incompatibility factor was estimated at ~ 1.05) and measurements of external quantum efficiency (EQE) were collected using an NREL calibrated Si detector. Optical interference modeling was performed according to the method of L. A. A. Pettersson, L. S. Roman and O. Inganas, Journal of Applied Physics 86, 487 (1999), contents which have been incorporated by reference. The diffusion lengths of the exAlciton of ClAlPc and C60 were estimated from the adequacy of the magnitudes of the photo current and EQE being 5 ± 3 nanometers and 10 ± 5 nanometers, respectively.
[0040] Figure 1 (a) shows a schematic of a control solar cell 10. The control solar cell includes a substrate 11, an anode 12, a donor layer 13, for example, ClAlPc, an active layer molecular, for example, C60, acting as a receptor layer 14 and a cathode 15. In this example, anode 15 is opaque, for example, silver. Figure 1 (b) shows a schematic of a complete transparent solar cell 20. Device 20 generally includes a transparent substrate 21, an anode 22, a donor layer 23, for example, ClAlPc, an active molecular layer, for example, C60 , acting as a receptor layer 24, and a cathode 25. The donor layer 23 and the receptor layer 24 have absorption peaks in the ultraviolet (UV) and near infrared (NIR) spectrum. In this example, the substrate is quartz. It should be understood that a variety of rigid and flexible substrates can be used. For example, the substrate can be glass, a rigid or flexible polymer, for example, a screen protector or film, or it can be combined with other layers such as encapsulating layers, anti-reflective layers or the like. In this example, the transparent anode 22 and cathode 25 are formed by conductive oxide, for example, ITO / MoO3. It should be understood that anode 22 and cathode 25 can be formed from other materials such as tin oxides, fluorinated tin oxides, nanotubes, Poli (3,4-ethylenedioxythiophene) (PDOT) or PEDOT: PSS (Poli (3,4- ethylenedioxythiophene) poly (stirenosulfonate)), gallium-doped zinc oxide, aluminum-doped zinc oxide and other materials having adequate transparency and conductivity. Device 20 may also include a DBR 26 near infrared and one or more broadband antireflective covers (BBAR) 27.
[0041] Figure 1 (c) is a graph showing the extinction coefficient, k, of the active layers shown in Figures 1 (a) and 1 (b). Figure 1 (d) is a graph showing the current-voltage (JV) curves for the ClAlPc-C6o control and transparent cells in Figures 1 (a) and 1 (b) for a variation of the ITO thicknesses. The absorption peak for ClAlPc is positioned in the NIR range (~ 740 nanometers). This allows the incorporation of a NIR reflecting mirror and simultaneous optimization of the performance of solar cells and visible transmissivity as diagrammed in Figures 1 (a) and 1 (b). It should be understood that the donor and / or recipient layers may have one or more absorption peaks outside the visual spectrum. In this example, ClAlPc also has a second absorption peak in the UV range. A summary of the device's various performances is provided in Table 1.

[0042] Table 1 generally includes data showing the performance of control OPVs with an Ag cathode, transparent OPVs without an ITO cathode, and OPVs with an ITO cathode and NIR mirror, in 0.8 solar lighting corrected by the incompatible solar spectrum . The short circuit current, JSC, open voltage circuit, VOC, fill factor, FF, power conversion efficiency, Dp, and the average visible transmission, AVT, are indicated. The control device with a thick Ag cathode exhibits a power conversion efficiency (Dp) of 1.9 ± 0.2%, open circuit voltage (Voc) = 0.80 ± 0.02 V, current density short-circuit (Jsc) = 4.7 ± 0.3 mA / cm2, and fill factor (FF) = 0.55 ± 0.03, which is comparable to previous reports.
[0043] When the Ag cathode of the control cell is replaced by ITO, the short-circuit current Jsc drops significantly to 1.5 ± 0.1 mA / cm2, the FF drops to 0.35 ± 0.02, and the open circuit voltage You drop slightly to 0.7 ± 0.02 V leading to Dp = 0.4 ± 0.1%. The FF decreases due to an increase in the series resistances of the thin ITO that is observed in the J-V curve on the bias ahead in Figure 1 (c). Figure 2 (a) is a graph showing the decrease in series resistance and the FF saturation close to the value for the control cell as the ITO thickness is increased. In Figures 2 (a) and 2 (b), the solid lines are from the current simulations, the dotted lines are simply eye guides. The small drop in Voc, regardless of the thickness of ITO, is probably due to a small reduction in the displaced cathode-anode working function. However, it is notable that when we use ITO as both anode and cathode there is a lot of anisotropic deposition as a function of work to support this large Voc and is probably helped by the wide working function of the MoO3 layer.
[0044] The Jsc decreases while the cathode is changed from Ag to ITO due to the reduced cathode reflections that reduced the total absorption by the spectrum in the active layers. Figure 2 (b) is a graph showing an increase in photo current by a factor of 3x at an optimized thickness of 120 nanometers, so this increase in Dp increases approximately the same amount. Adapting these data to the interference model, the optical interference model shows that this behavior detects interference from the rear ITO cathode reflection. Figure 3 (a) is a graph showing EQE as a function of the wavelength for various ITO thicknesses and control layers with and without the NIR reflecting mirrors. The approximate visible photopic variety is highlighted by dashed vertical lines. Figure 3 (b) is a graph showing the% transmission as a function of the wavelength for various thicknesses of ITO and control layers. Comparing EQE and the transmission of ITO-only devices, the absorption for the thinnest thickness and optimized thickness seems equivalent. The inspection of the simulations shows, however, that the distribution of the NIR field is transferred from within the ITO anode to the active layer ClAlPc while the ITO thickness cathode increases, so that the total transmission looks the same even if the absorption active layer changes substantially. This highlights an important aspect of transparent OPV architectures; despite the apparent simple optical configuration, interference management is still crucial for device optimization, particularly for NIR absorption cells and for materials with low exciton diffusion lengths.
[0045] Despite the significant impact on the photo stream, the average visible transmissivity (AVT) shows little variation with ITO thickness (see, for example, Figure 2 (a)). The optical model predicts a small drop in AVT with ITO thicknesses that is not observed experimentally, possibly due to the uncertainties of the model parameter or variant optical constants during thicker ITO growths. Optimized cells without the NIR mirror show min (max) transmission values from 50% (74%) to 450 nanometers (540 nanometers) and an AVT of 65% (standard deviation of 7%). These transmission values decrease slightly with the incorporation of the NIR reflector for minimum (max) transmission values of 47% (68%) to 450 nanometers (560 nanometers) and an AVT of 56% (standard deviation of 5%), where this reduction results from increased visible reflections outside the resonance of the mirror. It is possible to remove reflex oscillations out of resonance in the visible spectrum by designing more complex hot mirror architectures to improve AVT closer to that of the cell without the NIR mirror, but this typically requires a higher number of layers. Hot mirror architectures are described in A. Thelen, Thin Films for Optical Systems 1782, 2 (1993), which is incorporated herein by reference. The high 99% reflectivity between 695-910 nanometers also makes these devices useful for simultaneous NIR rejections in architectural cooling. Additionally, the use of BBAR coverings close to the DBR (coupling outward) and below the substrates (coupling inward), results in a concomitant increase in quantum efficiency of ~ 2-3% and AVT of ~ 4-6%.
[0046] Figure 3 (c) shows the simulated solar spectrum simulator (left axis) showing characteristics of Xe and NREL lamps reported mc-Si of external quantum efficiency (EQE) for the reference diode used to measure the simulated intensity solar (right axis). Due to the responsiveness of the reference diode that extends significantly beyond the response of the OPV cell, the extra NIR light from the solar simulator (compared to the AM1.5G spectrum) results in solar incompatibility factors lower than 1. Figure 3 (d) shows the measured (left axis, circles) and calculated (left axis, solid line) reflectivity of the distributed Bragg reflector used in this study as a transparent NIR mirror. The transmission spectrum (right axis) of broadband antireflective covers (BBAR) is also shown.
[0047] To highlight the transparency of the fully assembled device, Figures 4a and 4b show an array of solar cells in front of an image of a "rose". Both the detail of the image and the clarity of the color are minimally disrupted, so that details of the device's matrix pattern are even more difficult to discern. In this example the matrix has a common cathode 25a and a plurality of anodes 22a. The device also includes an active area 30 which includes the donor layer (s), recipient layer (s) and the reflective mirrors. In this particular example, an array of 10 individual OPV devices is formed on the substrate 21a. Figure 4 (c) shows the matrix connected to the strength of an LCD clock. Figures 4 (d) and 4 (e) show an alternative realization of a solar cell matrix positioned in front of an image of a “mountain” to highlight the transparency of the fully assembled device.
[0048] Figure 4 (f) is an image of a complete circuit assembly (left). The electrical connections are made to the ITO contacts of the OPV device (matrix) using a carbon ribbon. The LCD clock is connected to the circuit (right) that limits the voltage and passes the excess current to a small LED so that the clock works over a wide range of OPV lighting conditions. The LCD clock requires approximately 1.5 V and 10O μA and can be operated by solar cells for intensities> 0.05 suns (note that under ambient light <0.01 sun, the clock turns off).
[0049] Optimizing the transparent OPV structure with only the thickness of the cathode, the power conversion efficiency of 1.0 ± 0.1% is obtained with an average simultaneous transmission of 66 ± 3%. The incorporation of the NIR reflector and BBAR covers with the optimized thickness ITO (see Figure 2 (a)) improves the power conversion efficiency to 1.4 ± 0.1% with an average transmission of 56 ± 2%. With the NIR mirror, the increase in the conversion efficiency of the holding power of the additional NIR photo current in the CLAlPc layer where the EQE shows almost twice the peak of the ClAlPc EQE from 10% to 18% (see Figure 3 (a)). The optimized power efficiency is almost three times that of an existing visible absorption semitransparent planar copper phthalocyanine device while also exhibiting 30% more average transmission, but is slightly less efficient (0.75x) than the heterojunction structures of semitransparent bulk that gain efficiency from the active absorption layer in the visible and subsequently have close to half of the transmission.
[0050] Switching from planar heterojunctions to bulk heterojunctions in these structures, efficiencies of 2-3% may be possible for this set of material with almost identical visible transmission, and is currently under investigation. Tandem stacking of subcells with a deep layer of active absorption in the infrared can also improve these efficiencies; combined with more sophisticated NIR mirrors, efficiencies of up to several percent and average visible transmission> 70% are possible.
[0051] In another embodiment, SnPc, for example, SnPc-C60, can be used to build transparent solar cells. Solar cell designs based on SnPc can achieve> 2% efficiency of solar cells with> 70% visible light transmission (~ 70% of the average transmission across the visible spectrum). The following layers were used in this example: ITO / SnPc (10 nanometers) / C60 (30 nanometers) / BCP (10 nanometers) / ITO (10 nanometers) / DBR. In this example, the ITO was directly deposited. The distributed Bragg reflectors (DBR) were applied with fluid compatible with the index (IMF). Figure 5 (a) is a graph showing EQE as a function of the wavelength for the SnPc device. Figure 5 (b) is a graph showing transmissivity as a function of the wavelength for the complete SnPc TOPV device. A summary of the various device performances is provided in Table 2:
Table 2
[0052] The device may include a NIR mirror (transparent to visible light) composed of both metal / oxide (for example, TiO2 / Ag / TiO2) and dielectric cells (DBRs, for example, consisting of SiO2TiO2). Anti-reflective coatings can be composed of a single or multiple multilayer dielectric materials. As noted above, the active molecular layer can also be made up of any suitable phthalocyanine, porphyrin, naphthalocyanine dye, carbon nanotube, or molecular excitonic materials with absorption peaks outside the visible spectrum.
[0053] Figure 6 (a) is a graph showing a comparison between drawings of SnPc and reference C1A1Pc (opaque). A summary of various device performances is provided in Table 3:
Table 3
[0054] Figure 6 (b) is a graph showing an electric fence and the effect of the ITO cathode thickness. The calculated optical field, | E | 2, from the transparent OVP as a position function at a fixed wavelength close to the absorption peak of the active ClAlPc layer (~ 740 nanometers) for a 20 nanometer (black line) and 120 nanometer (black line) ITO thickness cathode red). Note the improvement of the field in the ClAlPc layer for the optimized thickness ITO, where the absorption is proportional to | E | 2 integrated on the position. In general, there is a strong dependence on the thickness of the ITO.
[0055] Figures 6 (c) and 6 (d) show the transfer matrix simulations of the average visible transmission (AVT, left column) and short-circuit current (right column) of the transparent OPV architecture as a function of thicknesses of the ITO anode and cathode without a NIR mirror. Figures 6 (e) and 6 (f) show the transfer matrix simulations of the medium visible transmission (AVT, left column) and short circuit current (right column) of the transparent OPV architecture as a function of the anode thicknesses and ITO cathode with a NIR mirror. The vertical dashed line indicates the thickness of the ITO anode used in this study. The active layer structure was Anode / MoO3 (20 nanometers) / ClAlPc (15 nanometers) / C60 (30 nanometers) / BCP (7.5 nanometers) / Cathode in which the diffusion lengths of ClAlPc and C60 exon were estimated at from the adequacy of the magnitudes of the photo current and EQE of the control cell being 8 ± 4 nanometers and 15 ± 6 nanometers, respectively.
[0056] The structure shown in Figure 1 (b) includes discrete layers for the donor, for example, ClAlPc or SnPc, and for the recipient, for example, C60. It is to be understood that the donor and the recipient can be combined in a single or mixed layer as generally shown in Figure 7. In this embodiment the device 40 can have a mixed layer 46 including both a donor and a recipient. The mixed layer usually has a mixed thickness as shown. Device 40 can optionally include a discrete donor layer 48 and / or recipient layer 46. Donor layer 48, if present, has a donor thickness as shown. Receptor layer 46, if present, has a receiver thickness as shown. It should be understood that Figure 7 is simplified for the sake of clarity and may include additional layers that are not shown. In this example, device 40 also includes a transparent cathode 42 and a transparent anode 50. The thicknesses of each layer can be selected as generally outlined above. It is to be understood that such a structure may also include other layers including anti-reflective layers and mirror layers as disclosed in the various embodiments here.
[0057] An optimization process can generally be presented as follows: i) Optimize for donor, receiver (total); ii) Fix donor, receiver (total); iii) Variable dimension; iv) Donor d Donor (total) - (mixed / 2); v) dReceptor = dReceptor (total) - (dmixed / 2); and vi) Optimize for relationship (dDoor: dReceptor).
[0058] For devices having only a mixed layer, the optimization can include an adjustment of the thickness of the mixed layer (step iii) and an adjustment of the Donor dReceptor ratio (step vi).
[0059] Figure 8 is a block diagram of a tandem device 60. Device 60 generally includes at least one first and second cells 66, 68. Each cell can have the structure generally disclosed above. Each of the first and second cell functions 66, 68 has transparent subcells. Each can have a variant NIR spectral responsiveness. Each of the first and second cells can have absorption peaks in the wavelength outside the visible light spectrum. The recombination zone 72a is arranged between the first and second cells 66, 68. The recombination area can be composed of a variety of components including, for example, ITO (0.5-10 nanometers), or BCP / Ag (0 , 1-2 nanometers) / MoOx. The additional recombination areas are arranged between subsequent pairs of subcells as generally shown by reference number 72b. It should be understood that that Figure 8 is simplified due to clarity issues and may include additional layers that are not shown. In this example, device 60 also includes a cathode 62 and an anode 70. The device can optionally include a transparent mirror NIR 62. Figures 9 (a) and 9 (b) are graphs showing the different band intervals associated with materials that can be used to optimize a device, for example, US J. Aggregate (Figure 9 (a)) and carbon nanotubes (Figure 9 (b)).
[0060] It should be understood that multiple band intervals can be selected for successive layers stacked on a tandem device to produce a device with the desired efficiency. In such devices, total transparency is improved over devices that are manufactured independently and post-integrated or macroscopically combined. This is possible because such a device benefits from a faithfully compatible index of refraction at each interface between successive layers. The stacked structure can be transparent or semi-transparent.
[0061] Figures 10 (a) and 10 (b) are graphs that show the practical efficiency limits of several achievements revealed here. Figure 11 is a diagram showing the solar flow and the photopic response of the human eye. In general, the photopic response of the human eye's peaks in the green spectrum 530-500 nanometers is affiliated below 450 nanometers to above 650 nanometers.
[0062] Figure 12 is a diagram showing an electronic reader 80, smart phone 82 and display screen 84 including photovoltaic arrays 86, 88 and 90 arranged on their respective display screens. It is to be understood that a variety of devices may incorporate the photovoltaic devices disclosed herein and / or arrays of such devices. Other applications include crystal watches, automotive and architectural glass including sunroofs and smoked glass. Photovoltaic devices can be used for active power generation, for example, for fully self-powered applications and battery charging (or battery life extension).
[0063] In conclusion, near-infrared absorption, transparent planar organic solar cells with a maximum power of 1.4 ± 0.1% and average visible transmission exceeding 55 ± 2% have been demonstrated. This medium visible transmission is sufficiently transparent to be incorporated into architectural glass. The excitonic character of organic semiconductors is advantageously exploited to produce unique photovoltaic architectures that are difficult to access through inorganic semiconductors. By positioning the absorption of the active layer selectively on the NIR it is possible to optimize the architecture using a NIR reflector composed of a DBR mirror centered at 800 nanometers that results in transparent solar cells of efficiency approaching that of a non-transparent control cell. Ultimately these devices provide a guide to achieving high efficiency and high transparency solar cells that can be used in windows to generate power, reduce cooling costs, and sift through energy in a variety of applications.

权利要求:
Claims (32)
[0001]
1. TRANSPARENT PHOTOVOLTAIC CELL, characterized by comprising: a transparent substrate, a first transparent active material superimposed on the transparent substrate, the first transparent active material having an absorption peak at a wavelength greater than approximately 650 nanometers, being the absorption peak the first transparent active material greater than the absorption of the first transparent active material at any wavelength between 450 and 650 nanometers; a second transparent active material superimposed on the transparent substrate, the second transparent active material having an absorption peak at a wavelength between 300 and 450 nanometers or between 650 and 2500 nanometers, the absorption peak of the second transparent active material being greater than the absorption of the second transparent active material at any wavelength between 450 and 650 nanometers; a transparent cathode; and a transparent anode; the transparent photovoltaic cell having at least one absorption peak at a wavelength greater than 650 nanometers which is greater than the absorption of the transparent photovoltaic cell at any wavelength between 450 and 650 nanometers, where the transparent photovoltaic cell is operable for transmit visible light with wavelengths between 450 and 650 nanometers.
[0002]
2. TRANSPARENT PHOTOVOLTAIC CELL, according to claim 1, characterized in that at least one of the transparent cathode and transparent anode is configured to maximize the absorption in the first transparent active material.
[0003]
3. TRANSPARENT PHOTOVOLTAIC CELL, according to claim 1, characterized by at least one of the transparent cathode and the transparent anode being configured to maximize the absorption in the second transparent active material.
[0004]
4. TRANSPARENT PHOTOVOLTAIC CELL, according to claim 1, characterized by the first transparent active material and the second transparent active material being located in separate layers.
[0005]
5. TRANSPARENT PHOTOVOLTAIC CELL, according to claim 1, characterized by the first transparent active material having a second absorption peak at a wavelength less than 450 nanometers.
[0006]
6. TRANSPARENT PHOTOVOLTAIC CELL, according to claim 1, characterized in that the first transparent active material is a donor and the second transparent active material is a recipient.
[0007]
7. TRANSPARENT PHOTOVOLTAIC CELL, according to claim 1, characterized by still comprising a visibly transparent reflector that reflects at wavelengths close to the infrared.
[0008]
8. TRANSPARENT PHOTOVOLTAIC CELL according to claim 1, wherein the first transparent active material is characterized by comprising an organic material.
[0009]
9. TRANSPARENT PHOTOVOLTAIC CELL according to claim 1, wherein the first transparent active material is characterized by comprising at least one among: a phthalocyanine, a porphyrin, a naphthalocyanine dye or nanotubes.
[0010]
10. TRANSPARENT PHOTOVOLTAIC CELL according to claim 1, wherein the first transparent active material is characterized by comprising chlorine and aluminum phthalocyanine.
[0011]
11. TRANSPARENT PHOTOVOLTAIC CELL according to claim 1, wherein the first transparent active material is characterized by comprising tin-phthalocyanine.
[0012]
TRANSPARENT PHOTOVOLTAIC CELL according to claim 1, wherein the second transparent active material is characterized by comprising at least one of the 60 (C60) carbons or a nanotube.
[0013]
13. TRANSPARENT PHOTOVOLTAIC CELL according to claim 1, characterized in that the first and second active transparent materials are configured for use with flexible encapsulation layers.
[0014]
14. TRANSPARENT PHOTOVOLTAIC CELL, according to claim 1, in which the transparent photovoltaic cell is incorporated into one of a display screen, a crystal clock, automotive glass or architectural glass.
[0015]
15. TRANSPARENT PHOTOVOLTAIC CELL, according to claim 1, characterized in that the transparent substrate is flexible.
[0016]
16. TRANSPARENT PHOTOVOLTAIC CELL, characterized by comprising: a transparent substrate; a first active material superimposed on the transparent substrate, the first transparent active material having an absorption peak at a wavelength between 300 and 450 nanometers or between 650 and 2500 nanometers, the absorption peak of the first transparent active material being greater than the absorption the first transparent active material at any wavelength between 450 and 650 nanometers; a second transparent active material superimposed on the transparent substrate, the second transparent active material having an absorption peak at a wavelength greater than 650 nanometers or less than 450 nanometers, the absorption peak of the second transparent active material being greater than any length of wave between 450 and 650 nanometers; a transparent cathode and a transparent anode; the transparent photovoltaic cell having at least one absorption peak at a wavelength greater than 650 nanometers which is greater than the absorption of the transparent photovoltaic cell at any wavelength between 450 and 650 nanometers, where the transparent photovoltaic cell is operable for transmit light with wavelengths between 450 and 650 nanometers.
[0017]
17. TRANSPARENT PHOTOVOLTAIC CELL, according to claim 7, characterized in that the visibly transparent reflector is a Bragg reflector distributed in several layers (DBR).
[0018]
18. TRANSPARENT PHOTOVOLTAIC CELL according to claim 1, characterized in that the transparent anode comprises a transparent conductive oxide.
[0019]
19. TRANSPARENT PHOTOVOLTAIC CELL according to claim 1, characterized in that the transparent cathode comprises a transparent conductive oxide.
[0020]
20. PHOTOVOLTAIC MATRIX, characterized by comprising a plurality of electrically interconnected transparent photovoltaic cells, as defined in claim 1.
[0021]
21. METHOD FOR GENERATING ELECTRICITY, the method being characterized by comprising: the provision of a transparent photovoltaic cell comprising: a transparent substrate, a first transparent active material superimposed on the transparent substrate, the first transparent active material having an absorption peak at a length wavelength greater than 650 nanometers, with the absorption peak of the first transparent active material being greater than the absorption of the first transparent active material at any wavelength between 450 and 650 nanometers; a second transparent active material superimposed on the transparent substrate, the second transparent active material having an absorption peak at a wavelength between 300 and 450 nanometers or between 650 and 2500 nanometers, the absorption peak of the second transparent active material being greater than the absorption of the second transparent active material at any wavelength between 450 and 650 nanometers; a transparent cathode; and a transparent anode; the transparent photovoltaic cell having at least one absorption peak at a wavelength greater than 650 nanometers which is greater than the absorption of the transparent photovoltaic cell at any wavelength between 450 and 650 nanometers, where the transparent photovoltaic cell is operable for transmit visible light with wavelengths between 450 and 650 nanometers; expose the photovoltaic cell to a light source.
[0022]
22. METHOD, according to claim 21, characterized by further comprising the provision of a reflective multilayer to reflect a light close to the infrared.
[0023]
23. METHOD, according to claim 22, characterized in that the multilayer reflector comprises a Bragg reflector with distributed multilayer (DBR).
[0024]
24. METHOD according to claim 21, characterized in that the first transparent active material and the second transparent active material are located on separate layers.
[0025]
25. METHOD according to claim 21, characterized in that the first transparent active material has a second absorption peak at a wavelength less than 450 nanometers.
[0026]
26. METHOD according to claim 21, characterized in that the first transparent active material is a donor and the second transparent active material is a recipient.
[0027]
27. METHOD according to claim 21, characterized in that the first transparent active material comprises an organic material.
[0028]
28. METHOD according to claim 21, characterized in that the first transparent active material comprises at least one among: a phthalocyanine, a porphyrin, a naphthalocyanine dye or nanotubes.
[0029]
29. METHOD, according to claim 21, characterized by the first transparent active material comprising chlorine and aluminum phthalocyanine.
[0030]
30. The method of claim 21, characterized in that the first transparent active material comprises tin-phthalocyanine.
[0031]
31. METHOD according to claim 21, characterized in that the second transparent active material comprises at least one of the 60 (C60) carbons or a nanotube.
[0032]
32. METHOD according to claim 21, characterized in that the transparent substrate is flexible.

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同族专利:

公开号 | 公开日

WO2012103212A3|2013-01-17|

WO2012103212A2|2012-08-02|

EP2668680B1|2022-01-19|

MX339751B|2016-06-08|

AU2012209126A1|2013-08-15|

US20120186623A1|2012-07-26|

US9728735B2|2017-08-08|

MX2013008573A|2015-02-04|

BR112013019158A2|2017-11-07|

JP6576408B2|2019-09-18|

RU2593915C2|2016-08-10|

KR20190086040A|2019-07-19|

KR20210018514A|2021-02-17|

AU2012209126B2|2015-11-26|

JP2020017737A|2020-01-30|

JP2018032872A|2018-03-01|

JP2014505370A|2014-02-27|

EP2668680A2|2013-12-04|

CA2825584A1|2012-08-02|

CN103534831A|2014-01-22|

US10665801B2|2020-05-26|

US20180019421A1|2018-01-18|

RU2013137652A|2015-03-10|

US20200388778A1|2020-12-10|

KR20140021542A|2014-02-20|

CN109244247A|2019-01-18|

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法律状态:
2018-12-18| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2019-11-26| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2020-12-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2021-02-02| 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 25/01/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

US201161436371P| true| 2011-01-26|2011-01-26|

US61/436,371|2011-01-26|

PCT/US2012/022543|WO2012103212A2|2011-01-26|2012-01-25|Transparent photovoltaic cells|

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