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    • 专利摘要:
    The invention relates to a method for producing a stack of the first electrode / active layer / second electrode type for an electronic device, in particular of the organic photodetector or organic solar cell type, comprising the following steps: (a) deposition of a first layer (2) of conductive material on the front face of a substrate, to form the first electrode, (b) deposition of an active layer (3), in the form of an organic semiconductor thin layer, this layer comprising non-continuous zones, characterized in that this method also comprises the following steps: (d) depositing a resin layer (4) on the face of the stack opposite the substrate which is at least partially transparent, ( e) exposing the resin layer (4) by the rear face (10) of said substrate, (f) developing the resin layer and (g) depositing a second layer (5) of conductive material to form the second electr ode conductive.
    公开号:FR3037723A1
    申请号:FR1555480
    申请日:2015-06-16
    公开日:2016-12-23
    发明作者:Jean-Marie Verilhac；Simon Charlot
    申请人:Commissariat a lEnergie Atomique CEA；Isorg SA；Trixell SAS；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] The invention relates to conductive / thin organic / conductive layer stacks conventionally used in electronic devices. These devices may for example be current-rectifying diodes, solar cells, photodetector cells, capacitors, laser diodes, sensor-type devices, memories, transistors, or light-emitting diodes. These include devices of organic electronics on flexible plastic substrate. The invention applies more particularly to the field of diode stacks used in organic solar cells or organic photodetectors. In the devices known in the state of the art, it can be seen the appearance of electric leakage currents through the organic thin layer which is supposed to electrically isolate the two conductive electrodes, also called active layer. These leakage currents depend on the one hand, the intrinsic properties of the active layer, in particular its conductivity, the presence of electrical traps, the positioning of the HOMO-LUMO energy levels with respect to the output of the electrodes, or its morphology. and, on the other hand, extrinsic parameters such as parasitic electrical leakage currents. These parasitic currents are not controlled. They come mainly from topological defects, that is to say, holes or morphological defects, that is to say areas of greater free volume. They are generated during the formation of the active layer. Thus, the presence of holes in the active layer may cause the two conductive electrodes to be locally short-circuited. In addition, areas of different morphology are more conducive to electrical breakdown. These defects in the active layer may be due to the materials used to form the layer, which are in the form of a solution which may comprise aggregates, i.e., portions of the material poorly dissolved in the solution. They can also result from defects present on the substrate, such as peaks or topological defects of the surface or areas with different surface voltages. These parasitic leakage currents are very detrimental when they occur in organic photodetectors or current-rectifying diodes. Indeed, in this case, the current in reverse regime of the diode and in the dark must be very low (of the order of nA / cm2). Thus, the slightest electrical leakage through the defects of the active layer can increase this current by several decades and degrade the performance of the diode drastically and irreversibly. These parasitic leakage currents are also penalizing for organic solar cells, but to a lesser extent. For such a device, the lower the leakage current of the diode, the more the solar cell will respond to low illumination. Thus, solutions have already been proposed for minimizing parasitic leakage currents in the active layer of a stack. In particular, it has been proposed to increase the thickness of the active layer, to filter the solutions prior to deposition to form the active layer and to use substrates with few defects. However, the proposed solutions have disadvantages. Indeed, an excessive increase in the thickness of the active layer tends, for example, to degrade the performance of the devices.
    [0002] This is why the thickness of the active layer is generally of the order of 200-300 nm. Moreover, a filtration requires a solution having a good solubility which is not the case of all materials currently available for the active layers. In addition, the filtration step is difficult to implement at the industrial level. Finally, substrates with few defects are substrates with planarizing layers that are expensive.
    [0003] One can also cite the document FR-2991505 which describes a method of making a stack of the first electrode / active layer / second electrode type for reducing parasitic electrical leakage currents.
    [0004] This process consists firstly of depositing a first layer of conductive material on a substrate, to form the first electrode, then an active layer, in the form of an organic semiconductor thin layer, this layer having defects. This process then consists in locally removing, by chemical etching, the first conductive layer, through the defects of the active layer. A second layer of conductive material is then deposited on the active layer to form the second conductive electrode. Due to the local elimination of the conductive layer, at the level of the defects of the active layer, the two electrodes can no longer be in contact and therefore can not create an electrical short circuit through the active layer. . Electric leakage currents are therefore considerably reduced. This method thus makes it possible to reduce the risks of short circuits. However, it is not suitable in the case where the second conductive layer is very liquid. Indeed, it is then likely to infiltrate under the organic layer and come into contact with the first conductive layer beyond the engraved area under the defect.
    [0005] In addition, the method requires that the first conductive layer be fully etched at the defects to avoid a short circuit. Thus, to be effective, the method requires that the first conductive layer is substantially supergravated with respect to the size of the opening in the active layer, since when the second conductive layer is deposited, it infiltrates a little under the layer. active and can thus generate a short circuit.
    [0006] Thus, the object of the invention is to further reduce parasitic electrical leakage currents through the active layer of a conductive / active / conductive layer stack, while maintaining the performance of the corresponding devices.
    [0007] The subject of the invention is a method for producing a first electrode / active layer / second electrode stack intended for an electronic device, in particular of the organic photodetector or organic solar cell type, comprising the following steps: (a) deposition of a first layer of conductive material on the front face 10 of a substrate, to form the first electrode, (b) depositing an active layer, in the form of an organic semiconductor thin layer, this layer comprising non-conductive zones. According to the invention, this method also comprises the following steps: (d) depositing a layer of resin on the face of the stack opposite to the substrate which is at least partially transparent, (e) insolation of the layer resin by the back side of said substrate, (f) developing the resin layer and (g) depositing a second layer of conductive material to form the second conductive electrode. e. In a first mode of implementation of the method, the resin is negative and step (f) leads to the formation of resin pads on the non-continuous zones.
    [0008] Alternatively, a buffer layer is deposited between steps (b) and (d). In a second embodiment of the process, the resin is positive, the step (f) leading to the formation of holes in the layer of the resin at the non-continuous zones and the step (g) being carried out. between steps (b) and (d), a step (h) of etching the second conductive electrode being performed after step (f).
    [0009] In a first variant, the method comprises an additional step (i) of removing the resin after the etching step (h). In another variation, the method includes a further step of depositing a passivation layer on the second conductive electrode prior to step (d) of depositing the resin layer. In a third embodiment of the process according to the invention, the resin is positive, step (f) leading to the formation of holes in the resin at the non-continuous zones, and the process comprises two complementary steps. between steps (f) and (g), a step (j) of depositing a passivation layer on the resin layer and a step (k) of resurfacing the resin. In a first variant, before step (j), a step (I) is provided for etching the active layer through the holes formed in the resin. In another variant, a buffer layer is deposited on the active layer between steps (b) and (d), a step of etching the buffer layer being provided between steps (k) and (g). In a particular embodiment of the method according to the invention, the step (c) of local elimination by chemical etching of the first conductive layer, through the non-continuous zones of the active layer is provided after the step (b). The invention will be better understood and other objects, advantages and characteristics thereof will appear more clearly on reading the description which follows and which is made with reference to the appended drawings, in which: FIGS. 1 and 2 are sectional views, representing the steps (a) to (c) of the method according to the invention, - Figures 3 to 6 are sectional views, showing the steps (d) to (g) of the first mode of implementation. FIGS. 7 to 12 are sectional views showing the steps of a first variant of the first embodiment of the method illustrated in FIGS. 3 to 6, FIGS. 13 to 18 are views in FIG. section and represent the steps (d) to (h) of the second embodiment according to the invention, - Figures 19 to 24 are sectional views, showing the steps (d) to (k) of the third mode of Embodiments of the invention, FIGS. 25 to 28 are sectional views showing the steps of FIG. a variant of the third mode of implementation of the method according to the invention, - Figure 29 is a top view of a detail of Figure 2, - Figure 30 is a sectional view illustrating a matrix of 10 pixels. obtained by the second embodiment of the method according to the invention, - Figure 31 is a top view of a matrix of pixels obtained by the second embodiment of the method according to the invention, - the figures 32 to 34 are sectional views showing a variant of the second embodiment of the method according to the invention for obtaining a matrix of pixels. The elements common to the different figures will be designated by the same references. Steps (a) to (c) of the process according to the invention will be described with reference to FIGS. 1 to 3. They are common to all the embodiments of the process according to the invention. Figure 1 illustrates a substrate 1 which can be rigid or flexible. It must have a transmittance of at least 20% at the insolation wavelength of the resin which will be used in the following process. In general, the method may use any type of substrate that is not completely opaque at the wavelength of this resin. Preferably, this transmittance is at least 40%, or even at least 70%, at this length. wave. This is, for example, a rigid glass substrate or FOP type (Fiber On Plate in Anglosaxon terminology), or a flexible plastic substrate, for example of the PET type.
    [0010] On the substrate 1, during a step (a), a layer 2 of a conductive material was deposited. This layer 2 will form the first conductive electrode. This electrode must be opaque to the wavelength of the resin used in the rest of the process. In general, it is opaque in the insolation range of the resins used. The corresponding wavelengths are in the UV range (UVA, UVB, UVC). It will be noted that the wavelength of 365 nm corresponds to the wavelength of insolation used for the resins 10 most used in photolithography. The term "opaque electrode" is understood here to mean an electrode which has a transmittance of less than 20% at the wavelength used for insolating the resin. This transmittance is preferably less than 10% or even 5% at this wavelength.
    [0011] The thickness of this layer 2 is between 1 nm and several microns meters. Preferably, it will be strictly greater than 5 nm and less than 500 nm. This layer 2 may consist of a single layer or a multilayer with specific interface layers.
    [0012] The material of layer 2 may be a metal, for example Au, Pd, Pt, Cr, Ti, Al or TiW. The metal layer can be a massive layer. In this case, the thickness of the layer is preferably strictly greater than 5 nm.
    [0013] The material of layer 2 can also be a conductive oxide with a degraded transmittance in UVA, or with a low natural transmittance in UVB or UVC: for example, ITO, AZO, TiO2 doped Nb, FTO, GZO or IZO. Several types of multilayers can be envisaged.
    [0014] It may first be a conductive or semiconductor oxide stack: for example ITO / TiOx, AZO / TiOx, ITO / MoO3, ITO / V205, AZO / ZnO or FTO / NiO.
    [0015] It is also possible to envisage a stack of at least two layers made of a metal and a metal oxide. The following combinations can for example be envisaged: Cr / ZnO, Au / TiO 2, Au, MoO 3 or Cr / WO 3.
    [0016] In particular, it may be a stack of three layers, for example of the type: ITO / Ag / ITO, AZO / Ag / AZO or ZnO / Ag / ZnO. In this case, the thicknesses of the stack are adjusted so as to modulate the optical spectrum of the stack and, in particular, to cut at the wavelength targeted for insolation of the resin. For example, optical simulations on Optilayer show that a tri-layer stack of AZO / Ag / AZO type with thicknesses of 300 nm / 10 nm / 300 nm would have a transmittance of 17% at 365 nm, whereas a stack with thicknesses of 600 nm / 10 nm / 600 nm would have a transmittance of 4% at 365 nm. It is therefore possible to modulate the thickness to ensure that the tri-layer cuts at the right wavelength. It is also conceivable to use more than three layers to make a Bragg mirror that cuts at the desired wavelength. The layer 2 also consists of a stack of a metal layer and a layer of an organic material to modulate its work output. It is recalled here that the work of output of a metal is the energy necessary to extract the electrons from the layer or to move them from their bound state in the metal to an unbonded state corresponding to the energy of the vacuum. . The organic material may be PEI, PEIE, a conjugated polyelectrolyte (poly [9,9-bis (3 '- (N, N-dimethylamino) propyl) -2,7-fluorene-alt-2,7- ( 9,9-dioctylfluorene)] (PFN)) or not (Nafion) or SAM (self assembled layer). The layer 2 can be deposited by conventional vacuum techniques, for example by evaporation or sputtering. It can also be deposited by means of a liquid, for example by a screen printing technique, in the atomic form or in the form of a dispersion of particles. Other liquid deposition techniques are for example centrifugal coating, better known by its English name: 303772.3 9 "spin-coating", the flat-die coating better known by its English name of: "slot- die ", heliography, flexography, inkjet, scraping, blade spreading, better known by its English name of" doctor blade "or dip coating better known by its name 5 English of: "dip-coating". In the remainder of the description, the English terms will be used again. In general, this first electrode 1 may act as anode or cathode. In addition, it must be able to be etched by liquid or vapor, through the through defects of the active layer, without impact or weakly impacting the properties of this active layer. Layer 2 is usually a layer that is spatially localized. FIG. 1 shows that, on layer 2, an active layer 3 is deposited during a step (b).
    [0017] The thickness of this layer 3 is preferably between 10 nm and several micrometers. In the case of organic photodetectors and organic solar cells, the active layer consists of at least one material which is semiconductor in nature.
    [0018] It advantageously consists of a mixture of an electron donor material and an electron acceptor material. The donor semiconductor material may be a conjugated organic molecule, oligomer, or organic polymer, i.e. alternating single bonds and double bonds. The mixture conventionally used is the regio-regular poly (3-hexylthiophene) (P3HT RR) and the [6,6] -PhenylC61 butyric acid methyl ester ([60] PCBM). Other donor polymers with a high gap (PFB, TFB, PTAA, PCDTBT, etc.) or with a small gap (PDPP3T, PCPDTBT, Si-PCPDTBT, PDDTT, etc.) can advantageously be used. Similarly, for the acceptor material, other materials may advantageously be used, of the C60, C70 or C80 derivative type (PCBM, indene-C60, indene-C60 bis adduct), acene diimide-type molecules, or polymer ( F8BT, N2200) or any other inorganic compound.
    [0019] Thus, the active layer may be a heterojunction of an electron donor material and an electron acceptor material in the form of a layer or a stack of several layers. It may also be a nanoscale mixture of the two materials in the form of heterojunction by volume, i.e., an intimate mixture of the two materials at the nanoscale. The layer 3 may be deposited in a continuous layer or spatially located. The active layer may be deposited by evaporation or co-evaporation, (case of molecules of low molar masses) or by liquid means (materials in the form of molecules, oligomers and polymers). In a non-exhaustive manner, liquid coating techniques are of the spin-coating, slot-die, heliography, flexography, screen printing, inkjet, doctor blade or dip-coating type.
    [0020] In some cases, the active layer may be crosslinked so as to render it insoluble in the solvents present in the various layers deposited and / or used during the various etching steps provided for in the process. Several routes may be used to crosslink the active layer. These pathways are well described in the following document: Guillaume Wantz et al, Polym Int, 63 (2014) 1346-1361. For example, P3HT and PCBSD can be mixed in a weight ratio of 1: 1 and deposited at a thickness of 200 nm. The layer is then annealed at 160 ° C for 30 minutes to become insoluble in the usual solvents. In general, this active layer 3 must have a transmittance greater than 5% at the wavelength of the resin that will be used in the following process. Preferably, this transmittance is at least 20% or even at least 50% at this wavelength. As indicated above, the active layer 3 comprises non-continuous zones, or defects, referenced 30 in FIG.
    [0021] These defects may consist of micrometric holes or areas with large free volumes. It may be porosity or volumes that are not occupied by the polymer chains. They have dimensions of between 1 nm and several 100 microns. FIG. 2 illustrates another step (c) of the method in which the conductive layer 2 is locally removed through the defects 30. As will be explained later, this step (c) may, in practice, be omitted. This local elimination will be obtained by a technique of etching preferably wet, that is to say by placing in contact with an etching solution. In a particular case of the invention, etching may be carried out by exposing the sample to vapors of the etching solution. In some cases, this elimination is obtained with a solvent. However, it is the term of etching solution that will generally be used in the following description. Of course, the etching solution must be chosen so as not to degrade the electrical, optical and mechanical properties of the active layer. The electrical properties of the active layer may be degraded due to an increase or decrease in its conductivity, or the generation of intrinsic or extrinsic electrical traps to the active layer. The degradation of the optical properties of the active layer may for example result in a decrease in the absorption properties of the light at the desired wavelength. Finally, the degradation of the mechanical properties can be reflected in particular by detachment, cracking or loss of flexibility of the active layer. Thus, in general, the etching solution used will be selective, that is to say, it will be able to etch the conductive layer 2, without etching or attacking the active layer 3. In general, the solution of etching engraving will be an acid or a base. It may be pure or diluted in water or in a solvent orthogonal to the active layer, that is to say a solvent that is not likely to attack or dissolve the active layer. An orthogonal solvent may be of the methanol, ethanol, ethylene glycol, di-ethylene glycol or isopropanol type. Preferably, the etching solution will be diluted in water and, preferably, in deionized water to avoid possible contamination with ions, especially metal ions (Na +, etc.). The person skilled in the art knows how to choose the nature and the concentration of the strong acid (of the type HNO3, HCl, H2SO4, KI, oxalic acid or H3PO4) or weak (of the oxalic acid, CH3CO2H or NH4 + type), or of the strong base (of the NaOH or KOH type) or weak (of the NH3 or CH3CO2- type), depending on the nature of the conductive electrode and the etching rate. Reference is made in this connection to the book "Thin Film Processes" edited by John L. Vossen and Werner Kern, Academic Press, New York, 1978. In general, the engraving speed is between 1 15 and 1,000 A / s. The etching solution is provided on the active layer 3 and penetrates through the non-continuous zones 30 of this active layer. The etching solution can be provided over the entire surface of the active layer or in a localized manner. A localized deposit can be implemented in the case where several different devices are on the same matrix, some of them being sensitive to the etching solution. The etching solution then reaches the conductive layer 2 through the zones 30, which makes it possible to locally eliminate the layer 2, in the zones identified in FIG. 2.
    [0022] Depending on the composition of the electrode 2, the latter may be etched in one or more steps and with one or more different etching solutions. Etching is usually done concentrically from the defect in the active layer.
    [0023] In general, the duration of the etching will be chosen so that the area of the etched area or aperture 20 in the layer 2, through a defect 30 of the active layer 3, is at least equal to the surface area. of this defect. The surfaces are here measured in the plane of the layers 2 and 3. This is illustrated by FIG. 29 which shows, seen from above, the layer 3, at the level of a defect 30. This is a micrometric hole whose input is schematically represented by a disk. The latter has a diameter dl. Furthermore, FIG. 29 shows, delimited by a dashed line, the zone 20 of the layer 2 which has been etched and which is therefore devoid of conducting material. This area 20 is schematically represented as a disk of diameter d2 which is larger than d1. Thus, in the case of a hole, d2 is at least equal to d1 and it will preferably be at least 2 dl or even 5 d1. Of course, the non-continuous area 30 may have a shape different from that of a disc. It may especially be an elongated crack. In all cases, the zone 20 has at least the dimensions of the defect and preferably a dimension at least 2 times or 5 times larger. It should also be noted that, when the layer 2 is in the form of a stack of several layers of different materials, different etching solutions may also be used successively, so as to be able to completely etch the entire Once the etching is complete, the stack illustrated in FIG. 2 will be rinsed, so as to stop the etching reaction and to eliminate any residual traces of etching solution in the active layer 3. This step of rinsing will be carried out by dipping in at least one deionized water bath, an orthogonal solvent or an orthogonal water / solvent mixture. Alternatively, the rinsing solution 30 may be slightly acidic (if the prior etching is basic) and vice versa to buffer the pH of the solution during rinsing.
    [0024] Naturally, the rinsing of the stack can also be carried out by spraying a suitable liquid, alternatively by soaking in a bath. For example, an electrode 2 made of conductive oxides ZnO type doped aluminum (AZO) or multi-layer type (AZO / Ag / AZO ...) can be advantageously used because of its ease to be etched (a thickness of 125 nm can be etched in less than 30 s in an etching solution at 50 ° C) in dilute aqueous solutions of HCl or HCl / FeCl 3 (especially sold under the name: TE100 from the manufacturer Transene). The different modes of implementation of the method according to the invention will now be detailed. Reference is first made to FIGS. 3 to 6 relating to the additional steps of the first mode of implementation of the method according to the invention. Thus, FIG. 3 illustrates another step (d) of this first embodiment of the method according to the invention, in which a layer 4 of a negative resin is deposited on the active layer 3. By convention and definition, a negative resin is a resin that remains in place in the insolated areas, and a positive resin is a resin that leaves in the insolated areas. The thickness of this layer 4 is between 10 nm and 100 μm and, preferably, between 0.2 μm and 5 μm. In general, the thickness of this layer 4 must be sufficient to cover the topology of the defects on the active layer. This resin may be a fluororesin, for example a resin marketed under the name OSCoR4000 Orthogonal manufacturer. This resin may be a non-fluorinated resin of the SU8 range.
    [0025] The resin may be deposited on the active layer 3 by evaporation or, preferably, by a liquid route. Preferably, this resin will be deposited by slot-die, spin-coating or spray-coating.
    [0026] FIG. 4 illustrates another step (e) during which the resin is insolated through the rear face 10 of the substrate. Consequently, it will be insolated in the zones corresponding to those where the electrode 2 is not present and in particular in the zones 20 in which the electrode 2 has been etched, as explained with reference to FIG. Insolation doses are those recommended in the resin data sheets and are typically of the order of 50-100 mJ. Preferably, the dose to crosslink the resin will be adjusted according to the transmittance of the underlying layers (substrate 1, electrode 10, active layer 3) to the insolation wavelength of the resin. Preferably, the insolation will take place in an inert atmosphere, with a limited rate of oxygen, in order to limit the photooxidation of the active layer. Figure 5 illustrates a next step (f) of the process in which the areas of the resin layer 4 that have not been insolated are developed. This development is carried out thanks to a developer that must be orthogonal to the underlying layers and, in particular, to the active layer 3. In other words, the components of this developer do not dissolve or very little underlying layers . By way of example, for a resin of the SU8 type, the developer 20 may be a product marketed by MicroChem under the name SU-8 Developer which is based on PGMEA. For a resin marketed under the name OSCoR4000, the developer may be a product marketed under the name Orthogonal Developer 103 Solution by Orthogonal.
    [0027] FIG. 5 shows that after this step (f) of development, negative resin studs 40 are obtained which are situated above the etched zones of the layer 2 and therefore, above the defects 30 present in the active layer 3. These studs 40 of negative resin can pass electrically non-continuous or defect areas 30, that is to say electrically isolate these areas 30 may create electric leakage currents in the stack .
    [0028] Figure 6 illustrates step (g) in which a layer 5 of a conductive material is deposited which will form the second conductive electrode. This second electrode 5 may serve as anode or cathode. The thickness of this layer 5 is between 5 nm and 500 μm, preferably between 8 nm and 30 μm. For some applications that require absorption from the top of the stack, this layer 5 will be semi-transparent. It can also be opaque. Thus, when the stack is intended to form a photodiode, the latter can absorb the photons through this electrode. The term "semitransparent electrode" herein refers to an electrode having a transmittance greater than 10% to the desired wavelength of absorption of the photodiode. This transmittance is preferably greater than 40% or even 70% at this wavelength. This electrode 5 may be formed by an organic, inorganic material or a mixture of both. Thus, this layer 5 may be in the form of a monolayer of one of these materials, a mixture based on several of these materials or a stack of layers of these different materials, alone or in mixing, with specific interface layers. It can be deposited by the same techniques as those used for the deposition of the layer 2.
    [0029] By way of example, the electrode 5 may be a monolayer or a multilayer comprising at least one of the following layers: metals (for example Ca, Ba, Au, Al, Ag, Pd, Pt, Ti or TiW), with a thickness of less than 10 nm in the case where the electrode must be semi-transparent, metal oxides in the form of monolayers (for example ITO, GZO, AZO 30 or ZnMgO) or trilayers (for example ITO / Ag / ITO , ZnO / Ag / ZnO or AZO / Ag / AZO), conductive polymers of the PANI, PEDOT / PSS or Plexcore 0C1100 type, carbon-based conductive materials of the graphene type or carbon nanotubes. The previously described materials may be in the form of continuous films or percolating networks of nanowires (for example: Ag, Cu, Au or ITO nanowires). Interface layers may possibly be deposited before the electrode 5 in order, for example, to block its output work. For example, for the final device to have a diode behavior, it is preferable that the electrodes 2 and 5 have different output work. For this purpose, either the output work of the conductive layer used is used, or an interface layer is placed which modulates the output work of the electrode so as to block the same output work to the desired value for the electrode. device. As an example, an interface layer may be mentioned: LiF, Ca, Ba, with thicknesses of less than 5 nm; PEI or PEIE, metal oxides (TiOX, ZnOx, Mo03, CsCO3, WO3), conjugated polyelectrolytes (PFN) or Nafion. In a variant of the first embodiment of the process according to the invention illustrated in FIGS. 7 to 12, a passivation layer 6 is deposited on the active layer between steps (c) and (d) previously described in FIG. FIGS. 7 and 8 show that this buffer or passivation layer 6 is deposited between the active layer 3 and the resin layer 4. This layer 6 serves to protect the active layer 3 of the resin. This layer 6 is of electrically insulating nature. It can be deposited by liquid or by evaporation. It has a thickness between 1 nm and 20 pm. It may be, for example, Parylene®, an oxide layer made by ALD (metal oxide type A1203, SiN-type metal nitride) or a fluoropolymer of the type sold under the name Cytop® by ASAHI.
    [0030] FIGS. 9 and 10 illustrate the steps (e) and (f) of insolation and development of the resin which are identical to those described with reference to FIGS. 4 and 5. This layer 6 is then etched by a liquid route. or by plasma, after the steps (e) and (f) of insolation and development of the resin. This etching step is illustrated in FIG. 11. The layer 6 thus present under the resin pads 40 which overhangs the defect areas 30.
    [0031] FIG. 12 illustrates the step (g) of forming the second conductive electrode which is identical to that described with reference to FIG. 6. A first example of this first embodiment of the method according to the invention will now to be described. It makes it possible to produce organic photodiodes on a rigid glass substrate. The first electrode 2 is made of aluminum and has a thickness of 100 nm. It is deposited by sputtering and then localized with the standard techniques of microelectronics. The electrode 2 is then etched with RIE plasma treatment. An active layer 3 of the heterojunction type volume of a thickness of 150 nm is deposited on the entire surface of the electrode 2 by spin-coating, or by other printing techniques of the slot die type, screen printing, gravure printing, jet ink or spray.
    [0032] The active layer is a donor / acceptor mixture, the donor may be a regioregular poly (3-hexylthiophene) type conjugate polymer and the acceptor a type molecule derived from the 60PCBM fullerene. The donor and the acceptor have a ratio of 1: 1 in the mixture. The stack is then dipped in an aluminum etch solution (for example Fujifilm's Alu Etch 1960 (25 vol H3PO4 + 1 vol HNO3 + 5 vol CH3COOH + H2O) at a temperature of 60 ° C, the speed of etching being v = 7 nm / s) The layer 3 is then thoroughly rinsed with deionized water and dried. A resin 4 of the type marketed under the name OSCoR4000 by Orthogonal is deposited by spin-coating on the active layer 3 to obtain a thickness of 1 .mu.m. The resin layer 4 obtained is annealed at 90 ° C for 1 min. It is then insolated by the rear face 10 of the substrate, with a wavelength of 365 nm and a dose of 100 mJ / cm 2. A so-called post-back step of 1 min at 90 ° C. is carried out. It makes it possible to finish hardening the resin in the insolated zones so that it does not leave during the development stage. The resin layer 4 is then developed in the non-insolated zones for 90 s and with the aid of the developer marketed under the name "Developer 103" supplied by Orthogonal. Finally, the second electrode 5 (anode) is deposited.
    [0033] It comprises a 100 nm interface layer made of PEDOT-PSS, on which is deposited an evaporated Ag layer whose thickness is 8 nm. In another example of the first embodiment of the method according to the invention, the substrate 1 is a flexible PET substrate. In addition, the first electrode 2 (the cathode) is composed of two layers: a first opaque Cr-conducting layer with a thickness of 100 nm, and a second layer, called an interface layer, made of ZnO with a thickness of 30 nm. These two layers are deposited by cathodic sputtering and then localized with the standard techniques of microelectronics.
    [0034] The active layer has the same characteristics as in the previous example, the acceptor possibly being a PCBSD-type fullerene-type molecule. In addition, the active layer is annealed at 160 ° C for 30 min to crosslink and make it insoluble. In a first step, the stack is dipped in a solution for etching ZnO (for example the solution marketed under the name TE100 by Transene) for 30 s.
    [0035] In a second step, the stack is dipped in an etching solution of Cr. (for example, Chrome Etch (5-10% Nitric Acid) / Diammonium hexanitratocerate (20-25%), with an etching rate of V = 10 nm / min). This active layer is then thoroughly rinsed with deionized water. then dried A resin of the SU-8 type is deposited by spin-coating on the active layer to obtain a thickness of 2 μm This layer is then annealed at 100 ° C. for 1 min.
    [0036] It is then insolated by the back side of the substrate, with a wavelength of 365 nm and a dose of 100 mJ / cm 2. The resin is then developed in the non-insolated zones for 90 s and using a PGMEA-based developer. Finally, the electrode 5 (anode) is deposited. It has a 100 nm PEDOT-PSS interface layer on which is deposited a semitransparent layer of Ag nanowire in the form of a 2D percolating network. An example of the variant of the first embodiment illustrated in FIGS. 7 to 12 will now be described. This variant makes it possible to produce organic photodiodes on a rigid glass substrate. The first electrode (cathode) 2 is made of a stack of three layers AZO / Ag / AZO, these three layers having respectively a thickness of 600 nm, 10 nm and 600 nm. This first electrode 2 is deposited by cathode sputtering and then localized with the standard techniques of microelectronics. The active layer 3 has the same characteristics as those of the first example described above. The stack is then dipped in an AZO etching solution (for example the solution sold under the name TE100 by the company Transene), then in an Ag-etching solution (for example, a solution of the type 4CH3COH + 1 NH4OH + 1H2O2, with an etching rate of v = 6nm / s) and finally, for 60 s in an AZO etching solution. The layer 3 is then rinsed thoroughly with deionized water and then dried.
    [0037] A buffer or passivation layer made of Cytop® is deposited on the active layer 3 by spin-coating, to obtain a thickness of 300 nm. The surface of the layer 3 is activated by plasma to make it wetting.
    [0038] A SU8 type resin is deposited on the layer to obtain a thickness of 1 μm. The resin is then insolated by the rear face of the substrate, with a wavelength of 365 nm and a dose of 100 mJ / cm. The resin is finally developed using a PGMEA based developer in non-insolated areas for 40 seconds. The buffer layer 6 is etched by soaking for 30 seconds in a fluorinated solvent (for example sold under the name CT-SOLV 180) and using the resin pads as a mask. The second electrode 5 is made as described in the first example. It should be noted that, in the context of this first embodiment of the method, step (c) in which the first electrode is locally removed, by etching through the non-continuous zones of the zone, may be omitted. active.
    [0039] In this case, the resin is insolated through the electrode 2 and in the zones corresponding to those of the defects 30 in the active layer 3. Reference is now made to FIGS. 13 to 18 relating to the additional steps of the second embodiment. implementation of the method according to the invention. The first electrode (layer 2) is therefore opaque.
    [0040] Thus, FIG. 13 illustrates a step (g) of this second embodiment of the method according to the invention, in which the second electrode 5 is made directly on the active layer 3, after the steps (a). (c) illustrated in FIGS. 1 and 2. This second electrode 5 may have the same characteristics as that described with reference to FIG. 6, specifying that it must be at least transparent to the wavelength of the resin . It can also be filed using the same techniques. The electrode 5 may be designed to cut the wavelength of the resin but without cutting the wavelength of absorption of the photodiode.
    [0041] In practice, this means that, in this second embodiment of the method, step (g) is performed between steps (c) and (d), this step (d) being now described with reference to the FIG. 14. This step (d) consists in depositing a layer 7 of a positive resin on the second electrode 5.
    [0042] This layer 7 may be deposited by evaporation or, preferably, by the liquid route, and in particular by slot-die, spin-coating or spray coating. The thickness of this layer 7 is between 10 nm and 10 μm and, preferably, between 0.2 μm and 5 μm.
    [0043] This resin may be a resin sold under the names Shipley S1818, Shipley S1814, Shipley S1828, Shipley Megaposit SPR220, AZ9260 series or AZTX1311-DUV by Microchemicals. Fig. 15 illustrates another step (e) during which the resin is insolated through the rear face 10 of the substrate. Consequently, it will be insolated in the areas where the first electrode 2 is not present and in particular in the zones 20 in which the electrode 2 has been etched. Since the electrode 2 is spatially located, there are areas around the electrode 2 that may be transparent to the wavelength of the resin. As a result, the resin will be insolated in the areas around the electrode 2.
    [0044] The insolation conditions of this resin layer are identical to those described for the resin layer 5 described with reference to Figures 3 to 6 and will not be described in detail. Figure 16 illustrates step (f) of the method in which resin layer 7 is developed. This step is carried out using a developer that is orthogonal to the underlying layers and in particular to the active layer 3 and the second electrode 5. By way of example, mention may be made of the developers 10 marketed under the name MF319 (Shipley), AZ® 726 MIF (Clariant), MF-26A (Shipley). Thus, FIG. 16 shows that at the end of step (f), the resin layer 7 has zones or holes 70 situated above the defects of the active layer 3, in which the resin is absent. . In practice, at the level of these defects 30 and on either side of the assembly formed by the active layer 3 and the second electrode 5, no material is present, because of the existence of the zones 20 and 20. 70. FIG. 17 illustrates a step (h) of etching the second electrode 5.
    [0045] This etching is performed in the holes 70 formed in the resin layer 7. This etching step is carried out chemically and / or physically. The chemical route is to use etching solutions or solvents. The physical way is to use RIE type plasmas, for example. The etching may stop, either at the level of the upper surface of the active layer 3, or in the thickness of the active layer 3, or at the level of the first electrode 2 after complete etching of the active layer.
    [0046] FIG. 17 illustrates the situation in which the etching stops at the upper surface of the active layer 3. It leads to forming openings 50 in the second electrode 5. FIG. 17 shows that the second electrode 5 is located mainly in the areas opposite those where the first electrode 3 is present. In other words, thanks to the deposition of the resin layer 7, it has been possible to etch the second electrode 5 in the regions surrounding the defect areas. Thus, these zones 30 are electrically insulated from both the first electrode 2 through the formation of the apertures 20 and the second electrode 5 through the apertures 50. Fig. 18 illustrates an additional step (i) of this method of remove the resin after step (h) etching. This step is carried out using a solvent orthogonal to the underlying layers, for example acetone. This step is optional. It should be noted that, in the context of this second mode of implementation of the method, step (c) described with reference to FIG. 2 can also be omitted, the resin being isolated through the electrode 2, and in the 20 zones corresponding to the defects 30 in the active layer 3. In an alternative embodiment of the method illustrated in FIGS. 13 to 18, a passivation layer is deposited on the second electrode 5, that is to say between steps (g) and (d). This passivation layer serves to protect the resin, both the first electrode 2, the active layer 3 and the electrode 5. It can be conductive or insulating. It must have the property of allowing the wavelength of insolation of the resin to pass. Thus, this passivation layer can be made of a thin metal (<15 nm), for example Ag, Au, Al or Ti or an evaporation-deposited dielectric material (for example Parylene® or metals), by PECVD, 3037723 CVD, ALD, or deposited in solution (for example polystyrene, polyvinylphenol, Cytop, cycloolefin or PMMA). This passivation layer will be etched chemically or physically between the step (f) of developing the resin illustrated in FIG. 16 and the etching step (h) illustrated in FIG. The process has the following advantages over the first embodiment described with reference to FIGS. 1 to 12. Firstly, it makes it possible to use positive resins whose choice is wider than the resins. negative. In addition, it is easier to deposit the resin layer on the second electrode 5 than on the active layer. Indeed, the resins are in organic solvents that can dissolve the material constituting the active layer. On the other hand, the different types of electrode 5 (metal, metal oxide, conductive polymers, etc.) are not or only slightly sensitive to organic solvents. Finally, the second electrode 5 protects the active layer of solvents of the resin which are used in steps (f) and (i). An example of this second mode of implementation of the method 20 according to the invention will now be described. It leads to the production of organic photodiodes on a rigid glass substrate. The first electrode 2 is made of gold and has a thickness of 100 nm.
    [0047] This first electrode 2 is deposited by cathodic sputtering and then localized with the standard techniques of microelectronics. The electrode 2 is then covered with a PEIE layer having a thickness of 20 nm which is deposited by spin-coating. This layer is thoroughly rinsed with deionized water to leave only one monolayer of PEIE absorbed on the surface of the electrode 2.
    [0048] Next, an active layer 3 of heterojunction volume type with a thickness of about 150 nm is deposited on the entire surface of the electrode 2 by spin-coating, or by other slot-like printing techniques. screen printing, rotogravure, inkjet or spray.
    [0049] The active layer is a donor / acceptor mixture, the donor may be a PCPDTBT conjugate polymer and the acceptor a type molecule derived from 60PCBM fullerene. The donor and the acceptor have a ratio of 1: 1.5 in the mixture. The stack is then dipped in a gold etching solution for 10 minutes. The etching solution is a commercial mixture based on KI / 12 (for example of the VOLUSOL type, which makes it possible to burn 100 nm of Au in 100 s). The active layer 3 is then rinsed thoroughly with deionized water and then dried. The second electrode 5 (anode) is then deposited. It is composed of a 100 nm interface layer made of PEDOT-PSS, on which is deposited a layer whose thickness is 8 nm of evaporated Ag. A layer of resin sold under the name S1818 by Shipley is deposited on the second electrode 5 by spinning. This layer has a thickness of 1 μm. The resin is then insolated by the rear face 10 of the substrate, with a wavelength of 365 nm and a dose of 100 mJ / cm 2. The resin is then developed using the developer marketed under the name MF319 for 40 s. The electrode 5 is then etched entirely using an oxygen plasma in RIE (Reactive Ion Ecthing). Finally, the resin is removed by being immersed for 30 seconds in an acetone bath.
    [0050] It has previously been indicated with regard to FIG. 17 that the second electrode 5 was mainly located in zones opposite those in which the first electrode 2 was present. The consequences will be different for single devices, such as unit diodes, or for pixel arrays. For unit diodes which are of macroscopic size (diameter -1 mm), the consequence is that the electrical contact on the electrode 5 will have to be on the active surface of the diode which corresponds to the area of overlap between the electrode 5 and the electrode 2.
    [0051] In the case where it is desired to deport the electrical contact on the electrode 5, it will be necessary to add a third conductive layer, or third electrode which will connect the electrode 5 to an electrical contact recovery pad. The third electrode connects the electrode 5 to a small surface of the diode so that the electrode 5 does not short circuit the initially passivated defects. For a matrix of pixels, at the end of the step (h) of etching, the second electrode 5 no longer forms a continuous layer. As a result, the pixels are disconnected from each other. Fig. 30 is a sectional view showing such a matrix of pixels. Thus, Figure 30 illustrates a line of pads 22 of the first electrode 2 arranged in a line, between which are arranged pads 21 of line. The pads 22 of the first electrode and the pads 21 of line 25 (or column) are opaque areas. Thus, after the implementation of steps (d) to (h), the matrix illustrated in FIG. 30 is obtained. It shows a defect 30 in the active layer 3 and an area 220 of a stud 22 opposite the defect. 30, in which the stud has been etched.
    [0052] In the case of the matrices, it is therefore necessary to provide an additional step after step (i) to ensure that the electrode 5 becomes continuous again.
    [0053] A first solution consists in redepositing at least one conductive layer (of the same nature as that of the electrode 5 or not), in order to reconnect all the pads of the electrode 5 with each other and to obtain a continuous conductive layer.
    [0054] FIG. 31 illustrates this conductive layer 8 and shows that this layer is localized, insofar as it consists of conductive lines electrically connecting the pads of the second electrode 5. In practice, it is necessary for this conductive layer 8 to be located to prevent it from shunting the first electrode 2 to Io through the defects present in the active layer 3. Another variant is to make opaque to the wavelength of insolation of the resin, the spaces between the pads of the first electrode 2. Thus, as illustrated in FIG. 32, a layer 11 of a material 15 opaque at this wavelength can be deposited between the pads 22 of the first electrode 2, the steps (g) and (d) being carried out as has been described with reference to FIGS. 13 and 14. For a wavelength of the order of 365 nm, this localized layer 10 may be made of polyimide, for example marketed under the name NISSAN SE5291, or a SK-3000L type negative resin (Fujifilm), this layer 10 having a thickness of 0.1 pm to 5 pm. This opaque layer 11 serves as a mask. Thus, during step (e), the resin layer can be insolated only in the area above the pads of the first electrode 2 and to the extent that defects are present. Figure 33 illustrates the matrix after step (e) of insolation of the resin through the substrate 1 and the step (f) of developing the resin. These steps (e) and (f) are carried out as described with reference to FIGS. 15 and 16. FIG. 34 illustrates this matrix after steps (h) for etching the second electrode 5 and (i) removing the resin. as described with reference to Figures 17 and 18.
    [0055] FIG. 34 shows that, even after this step of etching the second electrode 5, the latter remains in the form of a continuous layer. It is therefore not necessary to deposit a third localized electrode, such as that illustrated in Figure 31. This variant is advantageously used for matrices having a low pitch of repetition between the pixels. Reference is now made to FIGS. 19 to 24 which illustrate the additional steps corresponding to the third mode of implementation of the method according to the invention.
    [0056] FIG. 19 illustrates another step (d) of this third embodiment of the method according to the invention, in which a layer 7 of a positive resin is deposited on the active layer 3, after the steps (a). (c) illustrated in FIGS. 1 and 2. This resin layer may have the same characteristics as that described with reference to FIG. 14. It may also be deposited using the same techniques. The layer 7 of resin will therefore not be described in more detail. Figures 20 and 21 illustrate steps (e) of insolation and (f) development of the resin layer. These steps (e) and (f) can be carried out as has been described with reference to FIGS. 15 and 16. These two steps will therefore not be described in more detail. FIG. 21 shows that, at the end of step (f), holes 70 are formed in layer 7, these holes being opposite zones 20 in which electrode 2 has been engraved during step (c). FIG. 22 illustrates an additional step (j) of this method of depositing an electrically insulating passivation layer 9 on the resin layer 7 and the active layer 3 at the holes 70 made in the resin layer 7 This passivation layer may be an insulating polymer of fluorinated polymer or cyclic polyolefin type, or a layer deposited by ALD 3037723 (for example a metal oxide of the A1203 type, a SiN type metal nitride), or a layer deposited by evaporation. (eg Parylene®). Insofar as this layer 9 conforms to the surface of the stack, it makes it possible to cover the defects 30 of the active layer 3.
    [0057] FIG. 23 illustrates a complementary step (k) of this process consisting in locally removing the passivation layer 9 by the removal of the resin 7. This shrinkage is carried out by dissolving the resin by soaking the resin in one of its solvents (type acetone), a method known in English as "lift off". In the rest of the description, the English terms io will be used again. The solvent will infiltrate under the layer 9, dissolve the resin and take the layer 9 to the dissolved zones. In order to promote this removal step, the passivation layer may be non-continuous and open in areas of the sample outside the electrode 2. These openings may be additively, by direct localization during the deposit of the passivation layer, or subtractively, by laser ablation, for example. FIG. 23 shows that after this step (k), pads 90 of electrically insulating material are obtained which are situated above the etched areas of layer 2 and defects present in active layer 3. These pads 90 electrically isolate the areas 30 likely to create electrical leakage currents in the stack. FIG. 24 illustrates the last step (g) of this process in which the second electrode 5 is deposited on the active layer 3. This second electrode 5 may have the same characteristics as those described with reference to FIG. can also be filed using the same techniques. This second electrode 5 will not be described in more detail. It should be noted that, in the context of this third mode of implementation of the process, step (c) described with reference to FIG. 2 can also be omitted, the resin being isolated through the electrode 2 and in the zones corresponding to the defects 30 in the active layer 3.
    [0058] Alternatively, another passivation layer may be deposited between steps (c) and (d). This passivation layer is deposited on the active layer 3 and serves to protect the first electrode 2 and the active layer 3 of the resin. This passivation layer must be electrically insulating and have the property of allowing the insolation wavelength of the resin to pass. It may be made of a dielectric material deposited by evaporation (for example Parylene®), by PECVD, CVD, ALD, or deposited in solution (polystyrene, polyvinylphenol or Cytop® or cyclooelfin ...). This passivation layer is then etched chemically or physically between steps (k) and (g) illustrated in FIGS. 23 and 24. An example of this third embodiment of the process according to the invention will now be described. It makes it possible to produce organic photodiodes on a rigid glass substrate. The first electrode 2 (the anode) is made of chromium and has a thickness of 10 nm. It is deposited by sputtering and then localized with the standard techniques of microelectronics. Electrode 2 is etched with RIE plasma treatment. An active layer 3 of the heterojunction volume type with a thickness of 150 nm is deposited on the entire surface of the first electrode 2 by spin-coating or other printing techniques of the slot 25 die type, screen printing, gravure printing, jet ink or spray. The active layer is a donor / acceptor mixture, the donor may be a PBDTTT-C conjugated polymer and the acceptor a C60 fullerene molecule. The donor and the acceptor have a ratio of 1: 2 in the mixture.
    [0059] The stack is then dipped in a Cr etching solution for 10 minutes. The etching solution is, for example, a mixture of the type: 1 g of Ce (SO42-2 (NI-14) 2 -SO4-2H20 +5 ml HNO3 + 25 ml H2O, the etching is carried out at 28 ° C. and the etching rate is 8.5 nm / min The layer 3 is then thoroughly rinsed with deionized water and then dried A resin layer of the type sold under the name S1814 by Shipley is deposited on the active layer. is then insolated by the rear face of the substrate with a wavelength of 365 nm and a dose of 80 mJ / cm 2. The resin layer is developed using the developer marketed under the name MF319 (Shipley) for 40 s .
    [0060] A passivation layer of A1203 having a thickness of 50 nm is deposited by ALD. The passivation layer is opened in places on surfaces less than 50 μm in diameter, in areas outside the electrode 2, and using ablation using an excimer laser. These open areas will allow the solvent to dissolve the resin, seep through the buffer layer and perform the lift off step. The resin is then stripped in an acetone bath for 1 min. The electrode 5 (the cathode) composed of PEDOT / PSS and having a thickness of 50 nm is finally deposited by spin-coating.
    [0061] Figures 25 to 28 illustrate a variant of this third embodiment of the method according to the invention. This variant occurs after the steps (a) to (c) described with reference to Figures 1 and 2 and the steps (d) and (f) described with reference to Figures 19 to 21.
    [0062] This variant comprises a step (I) for etching the active layer 3. This step (I) is illustrated in FIG. 25. This etching is performed in the holes 70 formed in the resin layer 7.
    [0063] It is carried out by liquid means, for example by dissolving in solvents, or physically, using RIE type plasmas in particular.
    [0064] Thus, as shown in FIG. 25, the stack is completely hollowed out at the zones 20 of the first electrode 2 which have been etched. Fig. 26 illustrates the next step (j) in which a passivation layer 9 is deposited on the stack. This layer 9 may have the same characteristics as the passivation layer described with reference to FIG. 22. It may also be deposited using the same techniques. It will not be described in more detail.
    [0065] FIG. 26 shows that this layer 9 conforms to the surface of the stack and therefore comes into contact with the substrate 1 in the zones 20 of the first electrode 2 which have been previously etched. FIG. 27 illustrates the step (k) of removal of the resin present in layer 7.
    [0066] This removal of the resin can be carried out as previously described with respect to Fig. 23 and will not be described in more detail. FIG. 27 shows that, thanks to the deposition of the resin layer 7, the active layer 3 could be etched at the defects 30 which were therefore eliminated. Moreover, the passivation layer 9 makes it possible to isolate the first electrode 2 and the second electrode 5. FIG. 28 illustrates the step (g) in which the second conductive electrode 5 is deposited on the stack. This step (g) can be performed as previously described with respect to FIG. 6 and will not be described in more detail. It is also possible to combine the two variants of this third embodiment of the process according to the invention, by providing another passivation layer on the active layer 3, this passivation layer being etched before step (I). ) of etching the active layer, as shown in Figure 25.
    [0067] It should be noted that, in the context of this third embodiment of the method according to the invention, if the first electrode 1 is designed to cut the wavelength of the resin, without cutting the length absorption wave of the photodiode, the transmittance of the second electrode 5 does not matter. An exemplary implementation of the variant described with reference to Figures 25 to 28 will now be described. It makes it possible to produce organic photodiodes on a rigid glass substrate.
    [0068] The first electrode 2 (the anode) is made of gold and has a thickness of 100 nm. It is deposited by sputtering and then localized with the standard techniques of microelectronics. An active layer 3 of heterojunction type volume of a thickness of 10 nm is deposited on the entire surface of the electrode 2 by spin-coating or other printing techniques slot die types, screen printing, gravure printing, jet printing. ink or spray. The active layer is a donor / acceptor mixture, the donor being a TFB conjugate polymer and the acceptor a PCBSD type fullerene derived molecule. The donor and the acceptor have a ratio of 1: 2 in the mixture. The active layer is annealed at 160 ° C for 30 min to crosslink and become insoluble. The stack is then dipped in the Au etching solution for 10 minutes. The etching solution is a commercial mixture based on KI / 12. (for example of the VOLUSOL type, an etching of 100 nm Au being obtained in 100 s). The layer 3 is then rinsed thoroughly with deionized water and then dried. A resin layer of the type sold under the name S / 818 by Shipley is deposited on the active layer 3037723 and then insolated by the rear face of the substrate with a wavelength of 365 nm and a dose of 80 mJ / cm 2 . The resin layer is developed using the developer marketed under the name MF319 for 40 s.
    [0069] The active layer is then etched with an Argon RIE plasma. A 50 nm passivation layer of Al 2 O 3 having a thickness of 50 nm is then deposited by ALD. The passivation layer is opened in places on surfaces less than 50 μm in diameter, in areas outside the electrode 1, and using ablation with an excimer laser. These open areas will allow the dissolving solvent of the resin to infiltrate through the buffer layer and perform the lift off step. The resin is then stripped in an acetone bath for 1 min.
    [0070] The electrode 5 (the cathode) composed of an Al layer with a thickness of 3 nm and an Ag layer with a thickness of 7 nm is finally deposited by vacuum evaporation. It should be noted that in all embodiments of the method according to the invention, the resin layer may be deposited on the entire surface of the stack or only in localized areas. This localized deposit can be made using a mask. On reading the various embodiments of the method according to the invention, it is understood that this method makes it possible to solve the problem of parasitic electrical leakage currents through an organic semiconductor layer of a stack, by electrically passivating the fragile areas of this organic layer, whether holes or zones of different morphologies. For this, the method can provide, as in FR-2 991 505, locally etching an electrode zone under the active layer, through the defects of this layer. This local etching step (c) makes the process even more efficient for passing the defects of the active layer.
    [0071] In addition, this method provides for the deposition of a positive or negative resin which is insolated through the electrode present under the active layer. Thus, the method allows to open a positive resin or to deposit a negative resin, precisely above the fragile areas, at the origin of the electric leakage currents. The opening or the deposition of the resin is thus self-indexed on the defects present on the active layer. The resin allows, thanks to specific steps, to electrically isolate faults that can create electric leakage currents in the stack by repairing them locally.
    [0072] In general, the first mode of implementation of the invention constitutes a preferred mode. Indeed, it is this process that has the least steps and is the easiest to implement. In particular, it does not include a step of etching the second electrode 5 or the active layer 3 which are, in addition, difficult steps to achieve. Finally, this method is best suited to obtaining pixel matrices. The method according to the invention may advantageously be used to increase the performance and decrease the defects of organic electronic devices used in discrete components or in more complex systems of the passive or active matrix type. These devices 20 may be organic or hybrid organic / inorganic type. It may especially be current rectifying diodes, solar cells, photodiodes, capacitance, memories, lasers, light emitting diodes or field effect transistors. The reference signs inserted after the technical features contained in the claims are intended solely to promote understanding of the latter and can not limit its scope.
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. A method of producing a first electrode / active layer / second electrode stack for an electronic device, particularly of the organic photodetector or organic solar cell type, comprising the following steps: (a) deposition of a first layer (2) of conductive material on the front face of a substrate, for forming the first electrode, (b) deposition of an active layer (3), in the form of an organic semiconductor thin layer, this layer comprising non-continuous zones, characterized in that, this method also comprises the following steps: (d) depositing a resin layer (4, 7) on the face of the stack opposite the substrate, which is at least partially transparent, (e) insolation of the resin layer (4, 7) through the rear face (10) of said substrate, (f) developing the resin layer and (g) depositing a second layer (5) of conductive material to form the second electrode conductr ice.
    [0002]
    2. The method of claim 1, wherein the resin (4) is negative and the step (f) leads to the formation of resin pads (40) on the non-continuous areas (30).
    [0003]
    The method of claim 2, wherein a buffer layer (6) is deposited between steps (b) and (d).
    [0004]
    The method of claim 1, wherein the resin (7) is positive, the step (f) leading to the formation of holes (70) in the resin layer (7) at the non-continuous zones (30). ), and step (g) being performed between steps (b) and (d), a step (h) of etching the second conductive electrode (5) being performed after step (f).
    [0005]
    The method of claim 4, comprising a further step (i) of removing the resin (7) after the etching step (h).
    [0006]
    The method of claim 4 or 5, including a further step of depositing a passivation layer on the second conductive electrode, prior to step (d) of depositing the resin layer (7).
    [0007]
    The method of claim 1, wherein the resin is positive, wherein the step (f) results in the formation of holes (70) in the resin layer (7) at the non-continuous zones (30). process comprising two complementary steps between steps (f) and (g), a step (j) of depositing a passivation layer (9) on the resin layer and a step (k) of removing the resin.
    [0008]
    The method of claim 7, wherein prior to step (j) there is provided a step (I) of etching the active layer (3) through the holes (70) formed in the resin.
    [0009]
    9. The method of claim 7 or 8, wherein a buffer layer is deposited on the active layer between steps (b) and (d), a step of etching the buffer layer being provided between steps (k) and (boy Wut).
    [0010]
    Method according to one of claims 1 to 9, wherein a step (c) of local elimination by chemical etching of the first conductive layer, through the non-continuous zones (30) of the active layer, is carried out after the step (b) .20
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1555480|2015-06-16|
    FR1555480A|FR3037723B1|2015-06-16|2015-06-16|METHOD FOR MAKING A STACK OF THE FIRST ELECTRODE / ACTIVE LAYER / SECOND ELECTRODE TYPE.|FR1555480A| FR3037723B1|2015-06-16|2015-06-16|METHOD FOR MAKING A STACK OF THE FIRST ELECTRODE / ACTIVE LAYER / SECOND ELECTRODE TYPE.|
    KR1020187001181A| KR20180019165A|2015-06-16|2016-06-16|Method for producing a first electrode/active layer/second electrode stack|
    EP19175695.6A| EP3550625B1|2015-06-16|2016-06-16|Method for producing a first electrode/active layer/second electrode type stack|
    EP16731102.6A| EP3311428B1|2015-06-16|2016-06-16|Process to realise a stack comprisinga first electrode/ an active layer/ a second electrode|
    PCT/EP2016/063922| WO2016202938A1|2015-06-16|2016-06-16|Method for producing a first electrode/active layer/second electrode stack|
    US15/736,266| US10559771B2|2015-06-16|2016-06-16|Method for producing a first electrode/active layer/second electrode stack|
    CN201680047027.3A| CN107925005A|2015-06-16|2016-06-16|Method for the lamination for manufacturing first electrode/active layer/second electrode|
    JP2017565844A| JP6830453B2|2015-06-16|2016-06-16|Method for manufacturing first electrode / active layer / second electrode stack|
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