• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    An organic or hybrid electronic device with a NIP structure, such as an organic light-emitting diode, an organic photodetector, or an organic photovoltaic cell, comprising successively: a transparent substrate (100); a transparent and electrically conductive first electrode (101) an N-type layer (102), preferably of metal oxide, having a thickness ranging, for example, from 5 nm to 95 nm, an active layer (103) comprising a polyethyleneimine (200) and: a donor material; electrons and an electron acceptor material, ○ or perovskite material, - a P-type layer (104), - a second electrode (105).
    公开号:FR3073088A1
    申请号:FR1760100
    申请日:2017-10-26
    公开日:2019-05-03
    发明作者:Noella Lemaitre
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    (54) ORGANIC OR HYBRID ELECTRONIC DEVICE AND ITS MANUFACTURING METHOD.
    (57) Organic or hybrid electronic device, with NIP structure, such as an organic light-emitting diode, an organic photodetector, or an organic photovoltaic cell, successively comprising:
    - a transparent substrate (100),
    - a first transparent and electrically conductive electrode (101),
    an N-type layer (102), preferably made of metal oxide, having a thickness ranging, for example, from 5 nm to 95 nm,
    an active layer (103) comprising a polyethyleneimine (200) and:
    O an electron donor material and an electron acceptor material,
    O or a perovskite material,
    - a P-type layer (104),
    - a second electrode (105).
    ORGANIC OR HYBRID ELECTRONIC DEVICE
    AND MANUFACTURING METHOD THEREOF
    DESCRIPTION
    TECHNICAL AREA AND PRIOR ART
    The invention relates to the field of organic electronic devices such as organic photovoltaic cells (OPV), organic light-emitting diodes (OLED), and organic photodetectors (OPD), and to the field of hybrid electronic devices, and more particularly electronic devices. organic or hybrid with NIP structure.
    The invention also relates to a method for producing such organic or hydride electronic devices.
    Nowadays, the conversion yields of a single junction photovoltaic cell reach 10%. Improving not only the conversion yields but also the stability of the photovoltaic cells is essential in order to be able to meet the service life requirements of commercial devices and to widen the fields of application of this technology, for example to nomadic objects, ioT (“internet of things”), with street furniture, or even for building integration ...
    To respond to this double challenge, research is particularly directed towards the study of active materials and the architectures of organic photovoltaic cells and hybrid photovoltaic cells.
    The reverse type structure (also called NIP) was developed in order to improve the stability of the organic photovoltaic cell. It is the one which, to date, achieves the longest lifespan for this type of device. As shown in FIG. 1A, the reverse type structure comprises a substrate 1 on which are arranged:
    a first electrode 2 (cathode) of an electrically conductive transparent material, also called a lower electrode, conventionally made of indium tin oxide (ITO),
    - an N 3 type semiconductor layer called “electron transport layer” (or EIL for “Electron Injection Layer”) or N type layer,
    an active layer 4, which has the function of absorbing the photons and generating the free charges, comprising at least two materials: an N type material, electron acceptor, and a P type material, electron donor (hole carrier); the PN type heterojunction in volume is replaced by a perovskite material in the case of a hydride photovoltaic cell,
    a P-type semiconductor layer 5 called “hole transport layer” (or HTL for “Hole transporting Layer”) or P-type layer,
    - A second electrode 6 (anode) of an electrically conductive material also called the upper electrode.
    The N 3 type layer may be a monolayer of metal oxide, optionally doped, for example in ZnO, in ZnO doped (AZO, ZnO doped in Aluminum) or in polyethyleneimine (PEI) (FIG. IA). It can also be a bilayer comprising, for example, a layer of metal oxide 3a, such as a layer of ZnO, associated with a layer of PEI 3b (FIG. 1B).
    For example, in the article by Jin et al. (Highly stable and efficcient inverted organic solar cells based on low-temperature solution processed PEIE and ZnO bilayers J. Mater. Chem. A, 2016, 4, 3784), the active layer in PTB7 / PC 7 iBM is deposited on a bilayer of ethoxylated polyethyleneimine (PEIE) and ZnO.
    In the article by Courtright et al. (Polyethylenimine Interfacial Layers in Inverted Organic Photovoltaic Devices: Effects of Ethoxylation and Molecular Weight on Efficiency and Temporal Stability ACS Appl. Mater. Interfaces 2015, 7, 26167) it has been shown that the performance of organic solar cells based on PBDTTTFTTE: PC 70 BM are improved by the addition of a ZnO / PEI bi-layer. The increase in the molar mass of the PEI from 800 to 750,000 g.mol 1 leads to a lowering of the output work of the ITO / ZnO and to an increase in the temporal stability of the devices.
    However, as the PEI is electrically insulating, it must be used in a very thin layer, typically of the order of 5 nm, in order to allow the extraction of the charges while limiting the series resistances. However, the control of nanometric deposition is often critical, which complicates the cell manufacturing process. In addition, with such thin layers, there is a risk of forming a non-continuous layer, and therefore that there is contact between the active layer 4 and the first electrode 2, which shortens the lifetime of the cells. .
    As shown in FIG. 1C, another solution consists in directly incorporating the PEI 10 into the active layer 4a, 4b. This approach is, for example, described in the article by Kang et al. (Simplified Tandem Polymer Solar Cells with an Idéal Self-Organized Recombination Layer Adv. Mater. 2015, 27, 1408) with photovoltaic cells with simplified tandem structure, comprising a substrate 1, covered by a layer 2 of ITO, a first layer active 4a, a P type layer 5a in PEDOT: PSS, a second active layer 4b, a second P type layer 5b in MoOx, a second electrode 6. To develop the active layers 4a and 4b, a solution called PEI containing water and a branched PEI is diluted to 0.1% by mass in 2-methoxyethanol. In parallel, an active layer solution is prepared by adding PTB7-Th and PC 70 BM (1: 1.5) to a mixture of chlorobenzene / 1.8-diiodooctane (97: 3 vol%). The so-called PEI solution is added to the active layer solution with a volume ratio of 10: 90. The mixture obtained is then deposited by spinning deposition ("spin-coating"). It seems that the PEI is self-organizing in the active layer towards the ITO / active layer interface. The cells have good conversion yields. However, the process requires the use of chlorinated solvents, which makes it difficult to industrialize.
    STATEMENT OF THE INVENTION
    It is therefore an object of the present invention to provide an organic or hybrid electronic device, with a NIP structure, having good stability and not containing a thin layer of PEI.
    This goal is achieved by an organic or hybrid electronic device, with PIN structure, successively comprising:
    - a transparent substrate,
    - a first transparent and electrically conductive electrode,
    - an N-type layer,
    an active layer comprising a polyethyleneimine and o an electron donor material and an electron acceptor material, o or a perovskite material,
    - a P-type layer,
    - a second electrode.
    The organic photovoltaic cell is fundamentally distinguished from the prior art by the presence of both the N-type layer and by the presence of polyethyleneimine (PEI) in the active layer.
    The inventors have shown that, even if PEI, which is an electrically insulating material, is added to the active layer of a photovoltaic cell further comprising an N-type layer, the photovoltaic cell exhibits good efficiency and very good stability.
    The inventors have shown that the stability of the organic device according to the invention is improved compared to a device having an N type layer in the form of a ZnO / PEl bilayer, or compared to an N type layer formed of a mixture of ZnO and PEI.
    By transparent, it is meant that the substrate and the first electrode have a transmittance greater than 70% in the visible range, i.e. from 350nm to 750nm, and preferably greater than 90% in the visible range.
    Advantageously, the polyethyleneimine represents from 0.005% to 0.5%, and preferably from 0.01% to 0.1% by mass relative to the electron donor material or relative to the perovskite material of the active layer. Such percentages make it possible to improve the stability of the organic electronic device, and without increasing the series resistances within the device or the defects which are comparable to areas of recombination.
    Advantageously, the polyethylenimine is an ethoxylated polyethylenimine.
    Advantageously, the electron acceptor material is an N-type polymer or a soluble fullerene derivative, such as methyl [6,6] -phenyl-C 6 i-butyrate, and the electron donor material is chosen from poly (3-hexyl) thiophene (P3HT), poly [N-9'-heptadecanyl-2,7-carbazole-alt-5,5- (4,7-di-2-thienyl-2 ', l' , 3'benzothiadiazole] (PCDTBT), poly [[4,8-bis [(2-ethylhexyl) oxy] benzo [1,2- b: 4,5b '] dithiophene-2,6-diyl] [3- fluoro-2 - [(2-ethylhexyl) carbonyl] thieno [3,4- b] thiophenediyl]] (PTB7), Poly ([2,6'-4,8-di (5-ethylhexylthienyl) benzo [l, 2-b; 3,3-b] dithiophene] {3-fluoro2 [(2-ethylhexyl) carbonyl] thieno [3,4-b] thiophenediyl}) (PTB7-Th).
    Advantageously, the active layer has a thickness ranging from 100 nm to 500 nm.
    Advantageously, the N-type layer is made of metal oxide, preferably ZnO, optionally doped.
    Advantageously, the N-type layer has a thickness ranging from 5 nm to 95 nm, and preferably from 40 nm to 50 nm. Such layers are easy to deposit compared to thin layers (less than 5nm). There is less risk of forming a discontinuous layer.
    Advantageously, the substrate is made of glass, or of polymer, for example chosen from poly (ethylene terephthalate), ethylene polynaphthalate, and cyclo olefinic copolymers. The use of these materials makes it possible to produce flexible substrates. By flexible is meant that the substrate can be conformable, that is to say that it can be curved without being damaged.
    Advantageously, the organic electronic device is an organic light-emitting diode, an organic photodetector, or an organic photovoltaic cell.
    Advantageously, the device has a tandem architecture, that is to say that the device comprises two subassemblies, each having a reverse structure, stacked one on the other according to the PIN / PIN scheme.
    The invention also relates to a method for manufacturing an organic or hybrid electronic device which does not require depositing a thin layer of PEI, which is easy to apply and can be applied on a large scale.
    This object is achieved by a method of manufacturing an organic or hybrid electronic device, with a PIN structure, comprising at least the following successive steps:
    a) supply of a transparent substrate successively covered by a first transparent and electrically conductive electrode and by an N-type layer of metal oxide,
    b) formation of an active layer by depositing a solution containing a polyethyleneimine (200), a non-chlorinated solvent, and, an electron donor material and an electron acceptor material, or a perovskite material, then annealed.
    The process does not require the use of chlorinated solvents and can be easily industrialized. It makes it possible to manufacture flexible organic electronic devices with an improved lifespan without the need to carry out a step of depositing a thin layer of PEI which is difficult to control.
    Advantageously, the deposition of the active layer is carried out by spinner deposition, by printing or by coating.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Other characteristics and advantages of the invention will emerge more clearly from the description which follows and from the appended drawings in which:
    FIGS. 1A, 1B and 1C, previously described, represent partial views, in section and in profile, of organic photovoltaic cells, according to the prior art,
    FIG. 2 represents a partial view, in section and in profile, of an organic photovoltaic cell according to a first particular embodiment of the invention,
    FIG. 3 represents a partial view, in section and in profile, of an organic photovoltaic cell according to a second particular embodiment of the invention,
    - Figure 4 shows the evolution of the conversion efficiency under continuous illumination of different organic photovoltaic cells according to different embodiments of the invention, as well as an organic photovoltaic cell without PEI and an organic photovoltaic cell having a bilayer ZnO / PEI,
    - Figure 5 shows the evolution of the conversion efficiency under continuous illumination of different organic photovoltaic cells according to different embodiments of the invention, as well as a reference organic photovoltaic cell without PEI.
    The different parts shown in the figures are not necessarily shown on a uniform scale, to make the figures more readable.
    DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS
    Subsequently, the invention will be described for a photovoltaic cell, organic or hybrid, with a PIN structure. A person skilled in the art can transpose this teaching to any other organic electronic device such as an organic light-emitting diode (OLED), an organic photodetector (OPD). These electronic devices can have a tandem architecture.
    First of all, reference is made to FIG. 2 which represents a photovoltaic cell with a PIN structure. The cell successively comprises, and preferably consists of:
    - a transparent substrate 100,
    a first transparent and electrically conductive electrode 101, an N 102 type layer,
    an active layer 103 comprising either an electron donor material and an electron acceptor material and a polyethyleneimine 200 or a perovskite material and a polyethyleneimine 200,
    - a P 104 type layer,
    a second electrically conductive electrode 105.
    The substrate 100 is preferably flexible.
    The substrate 100 is, for example, made of glass, or of polymer, for example chosen from poly (ethylene terephthalate) (PET), ethylene polynaphthalate (PEN), and cyclo olefinic copolymers (CCO or COC for "Cyclic Olefin Copolymer").
    The substrate 100 has two main faces parallel to each other. By parallel is meant parallel or substantially parallel.
    One of the main faces is intended to receive the light rays (represented by arrows), it is the front face. The front face is not textured in the figures. However, to better trap the light, the front face could be textured.
    The rear face of the substrate 100 is covered by the first electrode 101.
    The first electrode 101, also called the lower electrode, is disposed between the substrate and the active layer. It must be transparent, so as to let the photons pass to the active layer, and electrically conductive. It can be made of transparent conductive oxide (OTC) or a semiconductor material. This electrode can be made of indium tin oxide (ITO), zinc oxide, zinc oxide doped with aluminum also called AZO (ZnO: AI), or it can be formed from a transparent conductive polymer. including silver nanowires for example.
    The first electrode 101 is electrically connected to the N-type layer.
    The N 102 type layer, also called the electron injection layer (EIL), can be made of metal oxide, native or doped. It is, for example, zinc oxide (ZnO), zinc oxide doped with aluminum (ZnO: AI), titanium oxide (TiO 2 ) or tin oxide (SnO 2 ).
    The N 102 type layer has a thickness ranging from 5 nm to 95 nm, and preferably ranging from 40 nm to 50 nm.
    The cell has no thin PEI layer at the active layer / N-type layer interface.
    The active layer 103 absorbs the photons and generates the free charges. It has a thickness ranging, for example, from 100nm to 500nm.
    The active layer 103 is a volume heterojunction comprising an electron donor material and an electron acceptor material.
    The electron donating material is a P type material, for example a P type polymer. Among the electron donating polymers, mention may be made, for example, of poly (3-hexyl) thiophene (P3HT), poly [2 -methoxy-5- (3,7-dimethyloctyloxy) -
    1.4- phenylene-vinylene] (MDMO-PPV), or poly [N- 9'-heptadecanyl-2,7-carbazole-alt-
    5.5- (4,7-di-2-thienyl-2 ', l', 3'-benzothiadiazole] (PCDTBT) and PBTZT-stat-BDTT-8 (also known as PV-D4610, marketed by the Among the active polymer families, mention may also be made of the PTB7 family, including PTB7-Th, or else the PBDTBDD, PDBT-T1, PPDT2FBT, PffBT4T2OD, and DT-PDPP2T- families. TT.
    The acceptor material is an N-type material, for example, an N-type polymer, graphene, semiconductor carbon nanotubes, fullerene or a mixture of fullerenes (C 60 , and / or C 70 and / or C 84 ), or a soluble fullerene derivative such as [6,6] -phenyl-C 6 methyl i-butyrate (PCBM).
    When it is a hybrid photovoltaic cell, the active layer includes a perovskite material playing the role of heterojunction in volume.
    The active layer based on perovskite advantageously comprises at least one organic-inorganic hybrid perovskite material. Advantageously, perovskite is a material comprising 1, 2 or 3 cations and anions, for example halogens, in particular Cl, Br, I, and their mixtures.
    The perovskite is advantageously of the ABX 3 type (A and B representing two different cations, and X representing three halogens) in which:
    A advantageously represents at least one organo-ammonium ion, for example of the methylammonium (MA) or formamidinium (FA) type or else a mixture of the two, optionally combined with cesium and / or rubidium,
    B advantageously represents lead, tin, bismuth or antimony,
    - X is advantageously chosen from: Cl, Br, I or a combination of these halides.
    For example, the perovskite can be of the MAPbl 3 , or MAFAPbl 3 or MAFACsPbl 3 type . It can also be MAPbl 3 . x Cl x with x between 0 and 10 or MAPbl 3 . x Br x with x between 0 and 100.
    Perovskite can be two-dimensional or three-dimensional.
    The active layer based on perovskite has a thickness advantageously between 50 nanometers and 1000 nanometers, more advantageously between 200 nanometers and 500 nanometers.
    The active layer 103 also comprises a polyethyleneimine (PEI) 200. In general, the PEI can have a number-average molar mass Mn ranging from 500 to 20,000 g / mol, for example from 500 to 10000 g / mol.
    The PEI 200 can be linear, connected or branched.
    The connected PEI 200 includes secondary amines. The connected PEI can have a number-average molar mass Mn varying from 500 to 5000 g / mol, preferably from 1000 to 2000 g / mol, and even more preferably from 1200 g / mol to 1800 g / mol. The number-average molar mass Mn represents the average of the molar masses weighted by the number of chains of each length.
    The PEI can otherwise be defined by the average molar mass by mass Mw which corresponds to the average of the molar masses weighted by the mass of chains of each length. For example, a number-average molar mass Mn ranging from 1200g / mol to 1800g / mol corresponds to a mass-average molar mass Mw ranging from 1300g / mol to 2000g / mol respectively.
    The branched PEI 200 comprises primary, secondary and tertiary amines. The branched PEI can have an average molar mass of the order of lOOOOg / mol, corresponding to a weight-average molar mass of 25000g / mol.
    According to a particular embodiment, the PEI 200 can be an ethoxylated polyethyleneimine (PEIE).
    We assume a vertical segregation of PEI 200 in the active layer 113 with a PEI 200 concentration gradient which increases towards the active layer 113 / N 102 type layer interface.
    The P 104 type layer, also called the hole transport layer (HTL), is made of a P type material. It is, for example, Poly (3,4ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS) or d a metal oxide such as a molybdenum oxide, a vanadium oxide or a tungsten oxide.
    The P-type layer 104 is electrically connected to the second electrode 105.
    As the second electrode 105, also called the upper electrode, is positioned on the rear face, behind the active layer 103, with respect to the radiation, it can be opaque or of limited transparency, for example, made of metal. It is, for example, in silver, gold, chromium, aluminum or a mixture of these metals.
    As shown in FIG. 3, in the case of an organic photovoltaic cell with reverse structure and with tandem architecture (PIN / PIN), the cell according to the invention successively comprises and preferably consists of:
    - a transparent substrate 100,
    a first transparent and electrically conductive electrode 101,
    - a first layer of type N 102,
    a first active layer 103 comprising: an electron donor material, an electron acceptor material and a polyethyleneimine 200,
    - a first layer of type P 104,
    - a second layer of type N 112,
    a second active layer 113 comprising: an electron donor material, an electron acceptor material and a polyethyleneimine 200,
    - a second P 114 type layer,
    a second electrically conductive electrode 105.
    The materials used to make the photovoltaic cell with tandem architecture can be the same as in the case of a photovoltaic cell with simple reverse structure, as previously described.
    The first active layer 103 and the second active layer 113 may have the same composition or different compositions. They can have the same thickness or different thicknesses. The PEI of the first active layer 103 may be identical to or different from that of the second active layer 113.
    The same applies to the first N 102 type layer and the second N 112 type layer.
    The same also applies to the first P 104 type layer and the second P 114 type layer.
    The conversion yields of different OPV cells with simple reverse structure, as shown in FIG. 2, were measured. The active layer 103 of the OPV cells contains PV-D4610 sold by Merck, PCBM and 0.01% PEI relative to the weight of donor polymer in a binary mixture of non-chlorinated solvents. The layer of type N 102 is made of ZnO. Three PEIs were studied: two weakly connected PEIs with molar mass Mn 1200g / mol (noted 'PEI connected 1' in the figure
    4) and 1800 g / mol (denoted 'PEI branched 2') and a highly branched PEI of molar mass Mn lOOOOg / mol (denoted 'branched PEI').
    The evolution of the conversion efficiency of OPV cells (active surface = 0.1256 cm 2 ) is shown in Figure 4. The experimental conditions are as follows: continuous illumination AMI.5, power of 1000W / m 2 , temperature of 40 ° C .
    The cells were compared with a reference cell which comprises a ZnO layer and an active layer without PEI (denoted 'reference without ΡΕΓ in FIG. 4) and a cell which comprises a ZnO / PEl bilayer and an active layer without PEI ( noted 'reference ZnO / ΡΕΓ). For these reference cells, the PEI is a branched PEI. The PEI represents 0.01% by weight relative to the weight of the donor polymer of the active layer.
    For all the implementation conditions tested, the initial performances of the cells of the invention are lower than those of the reference cells, but they do not exhibit significant initial degradation unlike the reference cells. For the cells of the invention, the photovoltaic yields increase and reach a plateau beyond 6% on average (maximum at 7.5%). This represents an improvement of 2% absolute after 100 h under continuous illumination compared to the reference cell without PEI.
    The results with the cell according to the invention are also superior compared to a cell having a ZnO / PEI bilayer. The concentration gradient in the active layer is favorable to stability compared to a well-defined layer of the same material at the ZnO / active layer interface.
    The conversion yields of OPV cells with an N-type layer formed of a PEI / ZnO mixture were also measured. The yields and intrinsic stability of the cells of the invention is better.
    The addition of PEI, branched or branched, in the active layer of an OPV device also having an N-type layer, improves the stability of the device compared to the reference devices.
    The invention also relates to a method for producing an organic or hybrid photovoltaic cell comprising at least the following successive steps:
    a) supply of a transparent substrate 100 covered, successively, by a first transparent and electrically conductive electrode 101, and by an N-type layer 102,
    b) formation of an active layer 103 by the wet method, by deposition of a solution containing a polyethyleneimine 200 and a non-chlorinated solvent, and either an electron donor material and an electron acceptor material, or a perovskite material, then annealed,
    c) deposition of a P 104 type layer,
    d) depositing a second electrically conductive electrode 105.
    By non-chlorinated solvent is meant a non-chlorinated solvent or a mixture of several non-chlorinated solvents. The non-chlorinated solvent is, for example, chosen from o-xylene, 1-methylnaphthalene, tetralin, and mesitylene, or one of their mixtures. The choice of solvent will be made according to the material (s) forming the active layer in order to allow good solubilization of the material (s).
    The solution deposited in step b) can be prepared by mixing:
    a first solution comprising a non-chlorinated solvent and either the donor material and the acceptor material or the perovskite material, and
    - a second solution comprising PEI, optionally hydrated, and a non-chlorinated solvent.
    The deposition of the N 102 type layer and / or the active layer 103 and / or the P 104 type layer can be carried out at ambient temperature or at moderate temperature. By ambient temperature is meant a temperature of 20-25 ° C, and by moderate temperature is meant a temperature above 25 ° C and up to 70 ° C.
    The deposition of the active layer 103 and / or of the N-type layer 102 and / or of the P-type layer 104 can be carried out wet. It can, for example, be produced by any printing and / or coating technique such as inkjet deposition, by screen printing, by passage through a slot (“slot-die”), by spraying ( “Spray coating”), with a doctor blade, or by spinning, also called spin coating.
    The stack can be subjected to one or more annealing steps. For example, it may be an annealing carried out after step b) or c) or several annealing operations carried out after each wet layer deposition. Annealing after each wet layer deposition allows better drying of the different layers and / or microsegregation of phases in the case of the active layer. The annealing step promotes the formation of the PEI concentration gradient in the active layer. It is advantageously possible to carry out an annealing step of these different layers.
    The annealing step can be carried out in several ways:
    rapid annealing directly at a relatively high set temperature but advantageously below 150 ° C and, preferably, around 120 ° C, annealing in several phases: a drying phase which can be in air or at temperature moderate (for example 50 ° C) and an annealing phase at a higher temperature but, advantageously, less than 150 ° C and, preferably, around 120 ° C.
    Annealing allows the solvent to evaporate, but it also has an impact on the morphology of the active layer.
    In the case of oragnic devices, it makes it possible to obtain good phase segregation between the materials forming the active layer.
    In the case of hybrid devices, the crystallization of the perovskite material is improved, in particular by varying the size of the crystals.
    The temperature of the heat treatment for drying the active layer ranges, for example, from 80 ° C to 160 ° C, depending on the nature of the polymer. For example, for an active layer 103 of P3HT: PCBM, the annealing temperature is 100-150 ° C. The duration of the annealing can be a few minutes, for example of the order of 2 minutes.
    For a tandem type architecture, the method described above comprises, between step c) and step d), the successive deposits of a second layer of type N 112, of a second active layer 113 and of a second layer of type P 114.
    This process is particularly interesting for OPV solar cells manufactured by sheet-by-sheet or unwound processes, by inkjet printing or coating techniques, where limiting the number of deposition steps is crucial and controlling layers of very small thickness is critical, and for which the lifespan is essential.
    Advantageously, the method can include a subsequent step in which the photovoltaic cell is encapsulated to be protected from external elements, in particular from air (water vapor and oxygen).
    The implementation of the encapsulation is carried out by positioning the cells between two layers of so-called “gas barrier” materials or by protecting only on the front face. Gas barrier materials are typically dense layers (for example glass or metal plates) or multilayer films associating thin dense inorganic layers placed between organic layers. The barrier film or rigid insulation layer (glass or metal) can be maintained on the photovoltaic cell by means of a pressure-sensitive adhesive, a liquid adhesive or a thermoplastic polymer used by vacuum laminating for example. An example of a thermoplastic polymer is an ethylene / vinyl acetate EVA copolymer film. This encapsulating film has a thickness typically between 50 µm and 500 µm.
    Since the encapsulation techniques are well known to those skilled in the art, they will not be detailed here.
    Illustrative and nonlimiting example of a process for manufacturing an organic photovoltaic cell device:
    By way of illustration and without limitation, a PIN type photovoltaic cell can be produced according to the following steps:
    - formation of a first electrode 101 in TCO on a substrate 100 in PET of 180 μm thick,
    formation of a layer of type N 102, for example in ZnO of approximately 50 nm thickness, by the wet method on the upper electrode 110, followed by annealing at 120 ° C,
    formation of an active layer 103, by depositing a solution containing PV-D4610 and PCBM formulated in a mixture of non-chlorinated solvents and comprising a linear or branched PEI 200, the active layer 103 having a thickness of 300 nm on the type N layer, followed by annealing at 50 ° C, and annealing at 120 ° C,
    formation of a layer of type P 104, in HTL of type PEDOT: PSS, with a thickness of 80 nm, then annealing at 100 ° C.,
    - formation of a second electrode 105,
    - encapsulation, for example by laminating a gas barrier film and an encapsulant on the front face.
    FIG. 5 represents the evolution of the conversion efficiency for different anneals. Annealing A corresponds to an annealing of 2 min at 120 ° C. Annealing B corresponds to free drying followed by annealing for 2 min at 120 ° C. Annealing C corresponds to a 2 min annealing at 50 ° C followed by a 2 min annealing at 120 ° C. The way in which the active layer 5 is dried has little impact on the conversion yield.
    权利要求:
    Claims (12)
    [1" id="c-fr-0001]
    1. Organic or hybrid electronic device, with PIN structure, successively comprising:
    - a transparent substrate (100),
    - a first transparent and electrically conductive electrode (101),
    - an N-type layer (102),
    - an active layer (103) comprising a polyethyleneimine (200) and:
    o an electron donor material and an electron acceptor material, o or a perovskite material,
    - a P-type layer (104),
    - a second electrode (105).
    [2" id="c-fr-0002]
    2. Electronic device according to claim 1, characterized in that the polyethyleneimine (200) represents from 0.005% to 0.5%, and preferably from 0.01% to 0.1% by mass relative to the electron donor material or relative to the perovskite material of the active layer (103).
    [3" id="c-fr-0003]
    3. Electronic device according to one of claims 1 and 2, characterized in that the polyethyleneimine (200) is an ethoxylated polyethyleneimine.
    [4" id="c-fr-0004]
    4. Electronic device according to any one of the preceding claims, characterized in that the electron-accepting material is an N-type polymer or a soluble fullerene derivative, such as [6,6] -phenyl-C 6 i -methyl butyrate, and in that the electron donor material is chosen from poly (3-hexyl) thiophene, poly [N- 9'-heptadecanyl-2,7-carbazole-alt-5,5- ( 4,7-di-2-thienyl-2 ', l', 3'benzothiadiazole], poly [[4,8-bis [(2-ethylhexyl) oxy] benzo [1,2- b: 4,5- b '] dithiophene-2,6 diyl] [3-fluoro-2 - [(2-ethylhexyl) carbonyl] thieno [3,4-bjthiophenediyl]], and Poly ([2,6'-4,8di (5 -ethylhexylthienyl) benzo [1,2-b; 3,3-b] dithiophene] {3-fluoro-2 [(2-ethylhexyl) carbonyl] thieno [3,4-b] thiophenediyl}).
    [5" id="c-fr-0005]
    5. Electronic device according to any one of the preceding claims, characterized in that the active layer (103) has a thickness ranging from 100 nm to 500 nm.
    [6" id="c-fr-0006]
    6. Electronic device according to any one of the preceding claims, characterized in that the N-type layer (102) is made of metal oxide, preferably ZnO, optionally doped.
    [7" id="c-fr-0007]
    7. Electronic device according to any one of the preceding claims, characterized in that the N-type layer (102) has a thickness ranging from 5 nm to 95 nm, and preferably from 40 nm to 50 nm.
    [8" id="c-fr-0008]
    8. Electronic device according to any one of the preceding claims, characterized in that the substrate (100) is made of glass, or of polymer, for example chosen from poly (ethylene terephthalate), ethylene polynaphthalate, and cyclo olefinic copolymers.
    [9" id="c-fr-0009]
    9. Electronic device according to any one of the preceding claims, characterized in that the organic electronic device is an organic light-emitting diode, an organic photodetector, or an organic photovoltaic cell.
    [10" id="c-fr-0010]
    10. Electronic device according to any one of the preceding claims, characterized in that the device has a tandem architecture.
    [11" id="c-fr-0011]
    11. Method for manufacturing an organic or hybrid electronic device, with PIN structure, comprising at least the following successive steps:
    a) supply of a transparent substrate (100) covered, successively, by a first electrode (101) transparent and electrically
    5 conductive, and by an N-type layer (102),
    b) formation of an active layer (103) by deposition of a solution containing a polyethyleneimine (200), a non-chlorinated solvent, and, an electron donor material and an electron acceptor material, or a perovskite material, then annealed.
    10
    [0012]
    12. Method according to claim 11, characterized in that the deposition of the active layer (103) is carried out by deposition with a spinner, by printing or by coating.
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    同族专利:
    公开号 | 公开日
    EP3477721A1|2019-05-01|
    FR3073088B1|2019-11-22|
    US10707425B2|2020-07-07|
    JP2019080064A|2019-05-23|
    EP3477721B1|2020-07-29|
    US20190131545A1|2019-05-02|
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    US20170229518A1|2014-08-11|2017-08-10|Newsouth Innovations Pty Limited|A Photovoltaic Cell and a Method of Forming a Photovoltaic Cell|
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    法律状态:
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    2019-05-03| PLSC| Search report ready|Effective date: 20190503 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1760100A|FR3073088B1|2017-10-26|2017-10-26|ORGANIC OR HYBRID ELECTRONIC DEVICE AND METHOD FOR MANUFACTURING THE SAME|
    FR1760100|2017-10-26|FR1760100A| FR3073088B1|2017-10-26|2017-10-26|ORGANIC OR HYBRID ELECTRONIC DEVICE AND METHOD FOR MANUFACTURING THE SAME|
    EP18201697.2A| EP3477721B1|2017-10-26|2018-10-22|Electronic or hybrid device and fabrication method|
    US16/169,031| US10707425B2|2017-10-26|2018-10-24|Organic or hybrid electronic device and manufacturing method thereof|
    JP2018200649A| JP2019080064A|2017-10-26|2018-10-25|Organic or hybrid electronic device and manufacturing method thereof|
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