WO2023048117A1 - Cellule solaire - Google Patents

Cellule solaire Download PDF

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Publication number
WO2023048117A1
WO2023048117A1 PCT/JP2022/034907 JP2022034907W WO2023048117A1 WO 2023048117 A1 WO2023048117 A1 WO 2023048117A1 JP 2022034907 W JP2022034907 W JP 2022034907W WO 2023048117 A1 WO2023048117 A1 WO 2023048117A1
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layer
solar cell
electrode
charge transport
transport layer
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PCT/JP2022/034907
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English (en)
Japanese (ja)
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暢 入江
良太 三島
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株式会社カネカ
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to solar cells.
  • a basic perovskite solar cell consists of a substrate, a first electrode (anode or cathode), a first charge transport layer (hole transport layer or electron transport layer), a photoelectric conversion layer (perovskite layer), a second charge transport layer. (electron transport layer or hole transport layer) and a second electrode (cathode or anode) are laminated in this order. Furthermore, by providing a first buffer layer between the first electrode and the first charge transport layer, or providing a second buffer layer between the second charge transport layer and the second electrode, the photoelectric conversion efficiency can be improved. It is also known that it can be improved.
  • At least one of the first and second electrodes of the perovskite solar cell is a transparent electrode that can be made of metal oxide such as ITO.
  • a transparent electrode can be formed, for example, by a physical vapor deposition method such as sputtering.
  • a physical vapor deposition method such as sputtering.
  • the organic substance may be damaged and the performance of the solar cell may be deteriorated. .
  • a transparent electrode is laminated as a first electrode on a transparent base material, a layer that can contain an organic substance such as a photoelectric conversion layer is laminated, and finally a second electrode is laminated with silver. It is formed of paste or the like, and is often configured to receive light from the substrate side.
  • perovskite solar cells that receive light from the opposite side of the substrate.
  • US Pat. No. 6,300,001 describes a tandem solar cell using a crystalline silicon solar cell as the substrate.
  • the tandem solar cell utilizes the fact that the wavelengths of light photoelectrically converted by the perovskite solar cell and the crystalline silicon solar cell are different.
  • a crystalline silicon solar cell photoelectrically converts the light of the wavelength.
  • both the first electrode and the second electrode of the perovskite solar cell need to be transparent electrodes.
  • a thin film such as SnO 2 is deposited as the second buffer layer by atomic layer deposition (ALD: Atomic Layer Deposition) can suppress a decrease in photoelectric conversion efficiency.
  • ALD Atomic Layer Deposition
  • atomic layer deposition takes a long process time, it is difficult to improve production efficiency.
  • An object of the present invention is to provide a solar cell that has high production efficiency and receives light on the side opposite to the substrate.
  • a solar cell includes a substrate, a first electrode layer, a first charge transport layer, a photoelectric conversion layer containing a perovskite compound, a second charge transport layer, and an organic material.
  • a buffer layer, a contact layer made of polycrystalline ITO, and a second electrode layer made of amorphous ITO are provided in this order.
  • the doping amount of tin oxide in the second electrode layer may be larger than the doping amount of tin oxide in the contact layer.
  • the second charge transport layer may contain fullerene.
  • the contact layer may have a thickness of 3 nm or more and 20 nm or less
  • the second electrode layer may have a thickness of 10 nm or more and 200 nm or less.
  • the substrate may be a crystalline silicon solar cell.
  • the present invention it is possible to provide a solar cell that has high production efficiency and receives light on the side opposite to the substrate.
  • FIG. 1 is a schematic cross-sectional view showing a layer structure of a solar cell according to one embodiment of the present invention
  • FIG. 4 is a graph showing output characteristics of an example of the present invention
  • FIG. 1 is a schematic cross-sectional view showing the layer structure of a solar cell 1 according to one embodiment of the invention.
  • the solar cell 1 includes a base material 10, a perovskite solar cell part 20 laminated on the surface of the base material 10, a back surface collection electrode 31 laminated on the back surface of the base material 10, and a part on the surface of the perovskite solar cell part 20. and an antireflection layer 33 covering the surface of the perovskite solar cell section 20 and the surface collector electrode 32 . Light enters the solar cell 1 through the antireflection layer 33 and performs photoelectric conversion in the perovskite solar cell section 20 .
  • the base material 10 is a structure that supports the perovskite solar cell part 20, and may have a photoelectric conversion function.
  • the substrate 10 may be, for example, a glass substrate, a resin sheet, or the like, but in the solar cell 1 of this embodiment, the substrate 10 is a crystalline silicon solar cell.
  • the solar cell 1 light incident through the antireflection layer 33 is first photoelectrically converted by the perovskite solar cell section 20 , and light having a wavelength transmitted through the perovskite solar cell section 20 is photoelectrically converted by the crystalline silicon solar cell 10 .
  • the crystalline silicon solar cell Since the crystalline silicon solar cell has sufficient strength, it can function as the base material 10 that supports the perovskite solar cell portion 20, and converts the light that has passed through the perovskite solar cell portion 20 into electricity. Conversion efficiency can be improved.
  • the crystalline silicon solar cell and the perovskite solar cell portion 20 are connected in series by laminating the perovskite solar cell portion 20 on the crystalline silicon solar cell serving as the substrate 10.
  • the base material 10 of the present embodiment includes a semiconductor substrate 11, a first semiconductor layer 12 laminated on the front surface side of the semiconductor substrate 11, and a second semiconductor layer 13 laminated on the back surface side of the semiconductor substrate 11.
  • the perovskite solar cell section 20 includes, from the substrate 10 side, a first electrode layer 21, a first charge transport layer 22, a photoelectric conversion layer 23, a second charge transport layer 24, a buffer layer 25, and a contact layer 26. , and the second electrode layer 27 are provided in this order.
  • the first electrode layer 21 is one electrode of the perovskite solar cell section 20, and is a positive electrode in this embodiment.
  • the first electrode layer 21 can be formed of a transparent conductive oxide (TCO) having electrical conductivity and optical transparency, a thin semiconductor layer, or the like.
  • TCO transparent conductive oxide
  • dopants examples include Sn, W, Zn, Ti, Ce, Zr, Mo, Al, Ga, Ge, As, Si, S and the like.
  • ITO Indium Tin Oxide
  • tin is added to indium oxide
  • the first electrode layer 21 can be laminated on the substrate 10 by a method such as sputtering or vacuum deposition.
  • the thickness of the first electrode layer can be, for example, 1 nm or more and 200 nm or less when electric power is output from the perovskite solar cell section 20 to the base material 10 (when current flows in the thickness direction).
  • the first charge transport layer 22 is a layer that allows passage of charges of the first polarity generated in the photoelectric conversion layer 23, and in this embodiment, a hole transport layer (HTL) that transmits holes to the first electrode layer 21. is.
  • HTL hole transport layer
  • metal oxides such as nickel oxide (NiO) and copper oxide (Cu 2 O), for example, PTAA (Poly(bis(4-phenyl)( 2,4,6-trimethylphenyl)amine)) and Spiro-MeOTAD.
  • the first charge transport layer 22 includes, for example, 2PACz ([2-(9H-Carbazol-9-yl)ethyl]phosphonic Acid), MeO-2PACz ([2-(3,6-Dimethoxy-9H-carbazol-9 SAM: Self-Assembled Monolayers). Also, the first charge transport layer 22 may have a multilayer structure.
  • the first charge transport layer 22 can be formed by a method such as sputtering or vacuum deposition. Also, the first charge transport layer 22 containing an organic substance can be formed by a method such as applying a solution of an organic substance and drying it.
  • the thickness of the first charge transport layer 22 may vary greatly depending on the material, the structure of adjacent layers, etc., but can be, for example, 1 nm or more and 200 nm or less. thickness.
  • Photoelectric conversion layer 23 contains a perovskite compound.
  • a perovskite compound an organic atom A containing at least one of monovalent organic ammonium ions and amidinium ions, a metal atom B that generates a divalent metal ion, an iodide ion I, a bromide ion Br, and a chloride
  • a compound represented by ABX 3 containing a halogen atom X containing at least one of a compound ion Cl and a fluoride ion F can be used.
  • the organic atom A is preferably methylammonium MA(CH 3 NH 3 )
  • the metal atom B is preferably lead Pb
  • the halogen atom X is preferably At least one of iodide I, bromide ion Br and chloride ion Cl is preferred.
  • preferred perovskite compounds include methylammonium lead halide MAPbX 3 (CH 3 NH 3 PbX 3 ), MAPbI 3 , MAPbBr 3 and MAPbCl 3 .
  • halogen atom X multiple types may be included. Examples of perovskite compounds containing iodide I and other halogen atoms X include methylammonium lead iodide MAPbI y X (3-y) (CH 3 NH 3 PbI y X (3-y) ), MAPbI y Br ( 3-y) , MAPbI y Cl (3-y) , etc. (y is any positive integer).
  • the photoelectric conversion layer 23 is made of lead halide (PbX 2 ) material and methylammonium halide (MAX) material in order. can be formed by coating and reacting thin films of these materials at reaction temperatures.
  • the photoelectric conversion layer 23 is, for example, a lead halide (PbX2 ) material and a methylammonium iodide (MAI) material, and reacting thin films of these materials at the reaction temperature.
  • the photoelectric conversion layer 23 can also be formed by a method such as a sol-gel method for synthesizing a perovskite compound in a liquid-phase coating film, or a coating method for applying a solution containing a pre-synthesized perovskite compound.
  • the thickness of the photoelectric conversion layer 23 is preferably 100 nm or more and 1000 nm or less in order to increase the light absorptivity and reduce the travel distance of the generated charges, although it depends on the forming material.
  • the second charge transport layer 24 is a layer that allows passage of charges of the second polarity generated in the photoelectric conversion layer 23.
  • the second charge transport layer 24 transfers electrons to the second electrode layer 27 through the buffer layer 25 and the contact layer 26.
  • An electron transport layer (ETL) examples of the main material of the second charge transport layer 24, which is an electron transport layer, include fullerene.
  • fullerenes include C60, C70, their hydrides, oxides, metal complexes, alkyl group-added derivatives such as PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester). be done.
  • PCBM [6,6]-Phenyl-C61-Butyric Acid Methyl Ester
  • the second charge transport layer 24 can be formed, for example, by a sol-gel method, a coating method, or the like.
  • the thickness of the second charge transport layer 24 may be, for example, 3 nm or more and 30 nm or less.
  • the buffer layer 25 prevents recombination of the first charge and the second charge by blocking passage of charges of the first polarity, and blocking holes in this embodiment.
  • the buffer layer 25 prevents the metals of the contact layer 26 and the second electrode layer 27 from diffusing into the second charge transport layer 24 and thus from recombination of charges.
  • the buffer layer 25 also functions as a buffer layer for preventing damage to the second charge transport layer 24 when the contact layer 26 and the second electrode layer 27 are formed by sputtering or the like.
  • the buffer layer 25 is made of an organic material that blocks charges of the first polarity, for example, an organic material that has a hole blocking function due to its HOMO (valence band) having a lower energy level than the HOMO of the second charge transport layer 24 . can be formed from In addition, good characteristics tend to be obtained by using a material having a wide HOMO-LUMO (band) gap and high insulating properties as a material for forming the buffer layer 25 .
  • Specific organic materials for forming the buffer layer 25 include, for example, bathocuproine (2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline) and Bphen (4,7-Diphenyl-1,10-phenanthroline).
  • TPBi (1,3,5-Tris(1-phenyl-1Hbenzimidazol-2-yl)benzene
  • TMPyPB (1,3,5-Tris(3-pyridyl-3-phenyl)benzene)
  • FPI fluorinated polyimide
  • the buffer layer 25 can be formed by a method such as vacuum deposition.
  • the thickness of the buffer layer 25 can be, for example, 3 nm or more and 30 nm or less, preferably 10 nm or less. By making the thickness of the buffer layer 25 equal to or greater than the lower limit, pinholes in the buffer layer 25 can be prevented. Further, by setting the thickness of the buffer layer 25 to be equal to or less than the upper limit, the carrier transmission efficiency can be improved.
  • the contact layer 26 is provided to improve adhesion between the buffer layer 25 and the second electrode layer 27 .
  • Contact layer 26 is formed from polycrystalline ITO.
  • Polycrystalline ITO produces a single peak between 30 and 31° in the in-plane XRD measurement, which does not occur with amorphous ITO.
  • Such polycrystalline ITO can exhibit sufficient adhesion to the buffer layer 25 made of bathocuproine.
  • the contact layer 26 can be formed by a sputtering method. In other words, it is possible to control whether the ITO is polycrystalline or amorphous depending on the sputtering conditions. Specifically, ITO can be polycrystallized by setting the back pressure of the process chamber to be low. Also, the smaller the amount of tin oxide doped into ITO, the easier it is to crystallize ITO. The doping amount of tin oxide in the contact layer 26 can be, for example, 2% by mass or more and 4% by mass or less. In addition, crystallization of ITO can be promoted by increasing the output of the sputtering apparatus.
  • the crystallization of ITO can be promoted by setting the flow rate of oxygen during sputtering to be less than the amount of oxygen (bottom oxygen amount) at which the sheet resistance of ITO becomes the lowest.
  • the contact layer 26 is formed in a plurality of steps, the crystallization of ITO is inhibited. Therefore, it is preferable to form the contact layer 26 at one time.
  • the lower limit of the thickness of the contact layer 26 is preferably 3 nm, more preferably 5 nm.
  • the upper limit of the thickness of the contact layer 26 is preferably 25 nm, more preferably 20 nm.
  • the second electrode layer 27 is an electrode paired with the first electrode layer 21 of the perovskite solar cell section 20, and is a negative electrode in this embodiment.
  • the second electrode layer 27 is a transparent electrode that transmits incident light through the antireflection layer 33, and is made of amorphous ITO.
  • the second electrode layer 27 can be formed by a sputtering method. More specifically, the second electrode layer 27 is formed by using the same sputtering apparatus as the sputtering for forming the contact layer 26, and the conditions such as the back pressure of the process chamber, the doping amount of tin oxide, the output of the sputtering apparatus, and the oxygen flow rate are different. can be formed by A plurality of conditions may be different between the formation of the second electrode layer 27 and the formation of the contact layer 26 . By doing so, it becomes easy to polycrystallize the ITO forming the contact layer 26 and to make the ITO forming the second electrode layer 27 amorphous.
  • the lower limit of the thickness of the second electrode layer 27 is preferably 10 nm, more preferably 20 nm.
  • the upper limit of the thickness of the second electrode layer 27 is preferably 200 nm, more preferably 100 nm.
  • the back collector electrode 31 and the front collector electrode 32 are electrode pairs for extracting electric power from the laminate of the crystalline silicon solar cell and the perovskite solar cell and outputting it to the outside.
  • the back collector electrode 31 may be laminated over the entire surface, while the front collector electrode 32 is composed of a plurality of linear portions arranged at intervals to allow light to enter the perovskite solar cell portion 20 . , so-called finger electrodes.
  • the back collector electrode 31 and the front collector electrode 32 are made of a conductive material.
  • a method for forming the back surface collection electrode 31 and the front surface collection electrode 32 for example, a known method such as sputtering or plating can be used.
  • a method for forming the pattern it is preferable to form by printing and baking a conductive paste such as a silver paste.
  • the thickness of the back collector electrode 31 and the front collector electrode 32 can be, for example, 100 nm or more and 300 nm or less.
  • the antireflection layer 33 reduces reflection of light on the light receiving surface of solar cell 1 .
  • the antireflection layer 33 can be made of a low refractive index material such as magnesium fluoride (MgF 2 ), silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), cerium fluoride (CeF 2 ), or the like. can.
  • the antireflection layer 33 may be a multilayer film in which a low refractive index material and a high refractive index material are alternately laminated.
  • the thickness of the antireflection layer 33 can be, for example, 50 nm or more and 200 nm or less.
  • the second electrode layer 27 formed of transparent amorphous ITO is provided on the side of the perovskite solar cell portion 20 opposite to the substrate 10, and the second electrode layer 27 side receives light to generate photoelectric conversion. Transformation can be done. Also, in the solar cell 1, between the buffer layer 25 made of bathocuproine and the second electrode layer 27 made of amorphous ITO, relatively high adhesion to both the buffer layer 25 and the second electrode layer 27 is achieved. Since the contact layer 26 made of polycrystalline ITO that can exert force is interposed, the peeling of the second electrode layer 27 can be prevented. Further, the buffer layer 25 made of bathocuproine, the contact layer 26 made of polycrystalline ITO, and the second electrode layer 27 made of amorphous ITO can be formed by a general film forming apparatus. The solar cell 1 has high production efficiency.
  • solar cells according to the invention may include layers that prevent undesired inter-layer migration of charges or materials (e.g. a buffer layer that may be provided between the first electrode layer and the first charge transport layer, a substrate and a second layer). an intermediate layer that may be provided between one electrode layer), a layer for providing a dopant to a particular layer (e.g. a thin lithium fluoride layer that may be provided for providing lithium fluoride to an electron-transporting layer comprising fullerenes). ) and the like.
  • layers that prevent undesired inter-layer migration of charges or materials e.g. a buffer layer that may be provided between the first electrode layer and the first charge transport layer, a substrate and a second layer.
  • an intermediate layer that may be provided between one electrode layer
  • a layer for providing a dopant to a particular layer e.g. a thin lithium fluoride layer that may be provided for providing lithium fluoride to an electron-transporting layer comprising fullerenes.
  • Example 1 A first electrode layer made of ITO, a first charge transport layer made of a self-assembled monolayer containing 2PACz, a photoelectric conversion layer containing a perovskite compound, a second charge transport layer containing fullerene, and bathocuproine on a glass substrate.
  • a buffer layer made of polycrystalline ITO, a contact layer made of polycrystalline ITO, a second electrode layer made of amorphous ITO, and a surface collection electrode made of a sintered silver paste are laminated in this order, Example 1 of a solar cell was produced as a trial.
  • a comparative example of a solar cell was obtained by laminating in this order a buffer layer formed of layer-deposited tin oxide, a second electrode layer formed of amorphous ITO, and a surface collection electrode formed of a sintered body of silver paste. 1 was prototyped.
  • Comparative example 2 A first electrode layer made of ITO, a first charge transport layer made of a self-assembled monolayer containing 2PACz, a photoelectric conversion layer containing a perovskite compound, a second charge transport layer containing fullerene, and bathocuproine on a glass substrate. Comparative Example 2 of a solar cell was fabricated by laminating in this order a buffer layer formed of , a second electrode layer formed of amorphous ITO, and a surface collection electrode formed of a sintered body of silver paste.
  • Example 1 Comparative Example 2, and Comparative Example 3 of the solar cell, light was irradiated from the surface collecting electrode side, and the output characteristics between the first electrode layer and the surface collecting electrode were measured. This result is shown in FIG. As shown in the figure, in Example 1 in which a contact layer made of polycrystalline ITO was formed between the buffer layer and the second electrode layer, the buffer layer formed from bathocuproine was damaged during lamination of the second electrode layer. Not only was a photoelectric conversion efficiency higher than that of Comparative Example 2 conceivable, but even compared to Comparative Example 1 having a buffer layer formed by atomic layer deposition, a photoelectric conversion efficiency higher than the maximum efficiency by 9.3% was obtained. was taken.

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Selon un aspect de la présente invention, une cellule solaire (1) présente un rendement de production élevé et reçoit de la lumière sur un côté opposé à un matériau de base. La cellule solaire (1) comprend, dans l'ordre suivant, un matériau de base (10), une première couche d'électrode (21), une première couche de transport de charge (22), une couche de conversion photoélectrique (23) comprenant un composé de pérovskite, une seconde couche de transport de charge (24), une couche tampon (25) constituée d'un matériau organique, une couche de contact (26) constituée d'un ITO polycristallin, et une seconde couche d'électrode (27) constituée d'un ITO amorphe.
PCT/JP2022/034907 2021-09-22 2022-09-20 Cellule solaire WO2023048117A1 (fr)

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JP2021-154364 2021-09-22
JP2021154364 2021-09-22

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000082831A (ja) * 1998-06-30 2000-03-21 Canon Inc 光起電力素子
JP2008305529A (ja) * 2007-05-09 2008-12-18 Victor Co Of Japan Ltd 光情報記録媒体及び光情報記録媒体の製造方法
JP2017135379A (ja) * 2016-01-21 2017-08-03 株式会社東芝 透明電極、電子デバイス、および電子デバイスの製造方法
JP2017168499A (ja) * 2016-03-14 2017-09-21 株式会社カネカ 光電変換装置およびその製造方法
JP2018120922A (ja) * 2017-01-24 2018-08-02 株式会社東芝 光電変換素子およびその製造方法
US20200058811A1 (en) * 2013-02-22 2020-02-20 International Business Machines Corporation Electrode formation for heterojunction solar cells
CN112490368A (zh) * 2020-12-15 2021-03-12 华能新能源股份有限公司 一种优化电荷收集能力的电极、电池及制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000082831A (ja) * 1998-06-30 2000-03-21 Canon Inc 光起電力素子
JP2008305529A (ja) * 2007-05-09 2008-12-18 Victor Co Of Japan Ltd 光情報記録媒体及び光情報記録媒体の製造方法
US20200058811A1 (en) * 2013-02-22 2020-02-20 International Business Machines Corporation Electrode formation for heterojunction solar cells
JP2017135379A (ja) * 2016-01-21 2017-08-03 株式会社東芝 透明電極、電子デバイス、および電子デバイスの製造方法
JP2017168499A (ja) * 2016-03-14 2017-09-21 株式会社カネカ 光電変換装置およびその製造方法
JP2018120922A (ja) * 2017-01-24 2018-08-02 株式会社東芝 光電変換素子およびその製造方法
CN112490368A (zh) * 2020-12-15 2021-03-12 华能新能源股份有限公司 一种优化电荷收集能力的电极、电池及制备方法

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