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WO2013012271A2 - Procédé permettant de préparer une couche d'absorption de lumière destinée à une cellule solaire, cellule solaire incluant la couche d'absorption de lumière et son procédé de fabrication - Google Patents

Procédé permettant de préparer une couche d'absorption de lumière destinée à une cellule solaire, cellule solaire incluant la couche d'absorption de lumière et son procédé de fabrication Download PDF

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WO2013012271A2
WO2013012271A2 PCT/KR2012/005783 KR2012005783W WO2013012271A2 WO 2013012271 A2 WO2013012271 A2 WO 2013012271A2 KR 2012005783 W KR2012005783 W KR 2012005783W WO 2013012271 A2 WO2013012271 A2 WO 2013012271A2
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electrode
layer
solar cell
light absorbing
light absorption
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PCT/KR2012/005783
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Korean (ko)
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WO2013012271A3 (fr
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김태환
추동철
김대훈
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한양대학교 산학협력단
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Publication of WO2013012271A3 publication Critical patent/WO2013012271A3/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/70—Surface textures, e.g. pyramid structures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for manufacturing a light absorbing layer for a solar cell, a solar cell including the light absorbing layer, and a method for manufacturing the same, and more particularly, using a good solvent and a poor solvent on a surface voluntarily.
  • the present invention relates to a method for manufacturing a light absorbing layer for solar cells that forms irregularities, a solar cell including the light absorbing layer, and a method for manufacturing the same.
  • next-generation energy sources that can solve energy problems because they have less pollution, infinite resources, and can be used semi-permanently.
  • Solar cells are semiconductor devices that convert light energy directly into electrical energy using the photovoltaic effect.
  • the solar cell may be broadly classified into an inorganic solar cell, an dye-sensitized solar cell, and an organic solar cell according to the material of the photoactive layer.
  • silicon-based solar cells which are a kind of inorganic solar cells, face various problems such as photoelectric conversion efficiency reaching a limit and supply of silicon raw materials becomes difficult due to sudden increase in demand. Therefore, active researches on organic solar cells have been conducted as an alternative.
  • the organic solar cell is manufactured by stacking an organic thin film, a flexible substrate can be used, and the organic solar cell can be manufactured in various structures compared to the inorganic solar cell.
  • the absorption coefficient of the organic molecules used as the light absorption layer is high, and even a fine thin film of about 100 nm can sufficiently absorb sunlight. Therefore, the organic solar cell can be easily manufactured as a micro device at low cost, and has excellent advantages in bending property and workability due to the characteristics of the organic material, and can be applied to various fields.
  • the organic solar cell has a junction structure of an electron donor (D) and an electron acceptor (A).
  • D electron donor
  • A electron acceptor
  • the organic solar cell When the organic solar cell is irradiated with light, the light is absorbed to form an electron-hole pair, that is, an exciton, in an excited state.
  • the excitons diffuse in an arbitrary direction and are separated into electrons and holes when they meet the D-A interface.
  • the time taken for the exciton to recombine and disappear is very short, 100 ps (picoseconds)
  • the distance that the exciton can diffuse without recombination is known to be about 10 nm. Therefore, in order for the excitons to be separated without recombination to generate electrons and holes, the excitons must be formed within 10 nm at the D-A junction interface.
  • the thickness of the photoactive layer can be made thin to reduce the exciton travel distance. However, in this case, the amount of light absorption decreases and thus the photoelectric conversion efficiency is lowered.
  • Korean Patent No. 10-0959760 discloses a technique of forming a nano bar using aluminum anodized oxide (AAO) as a nanoporous template.
  • Korean Patent Publication No. 10-2011-0068216 discloses a photoactive layer through chemical vapor deposition (CVD) and chemical dry etching such as LPCVD, PECVD, and hot chemical vapor deposition.
  • CVD chemical vapor deposition
  • PECVD PECVD
  • hot chemical vapor deposition A technique for forming a photoelectric conversion layer pattern composed of a plurality of nanorods is disclosed.
  • the above methods mainly grow the nanorods using chemical methods, many of the structural impurities may be included.
  • the impurities hinder the diffusion of excitons or induce recombination, thereby degrading photoelectric conversion efficiency.
  • the above methods have a problem in that the cost of performing equipment is high, and high vacuum is required, resulting in high manufacturing costs.
  • An object of the present invention is to provide a method for manufacturing a light absorption layer of a solar cell to reduce the recombination of excitons to increase the transport efficiency of the charge to move to the anode and cathode.
  • An object of the present invention is to provide a solar cell having improved photoelectric conversion efficiency by providing irregularities in the surface of the light absorption layer.
  • the problem to be solved by the present invention is to provide a method for manufacturing a solar cell is easy to control the process conditions using a solution process, and low manufacturing cost.
  • One aspect of the present invention to achieve the above object is to prepare a mixed solution containing a good solvent, poor solvent and light absorbing material, agitating the mixed solution to obtain a spontaneously formed nano-aggregate, the nano-aggregate It comprises the step of applying a composition containing a solar cell electrode or an organic thin film layer and the heat treatment of the applied composition to form a light absorption layer having a concave-convex structure.
  • the light absorbing material may be at least one selected from a light absorbing organic material and a light absorbing inorganic material.
  • the light absorbing organic material may be at least one selected from organic semiconductor materials and phosphorescent materials.
  • the light absorbing inorganic material may be an inorganic semiconductor material.
  • One of the good solvent and the poor solvent is selected from the group consisting of chlorobenzene, dichlorobenzene, chloroform, toluene and hexane, and the other is PGMEA, ethylene glycol, tetraethoxysilane, dibutyl ether, dimethylformamide , Xylene, water, methanol, ethanol and propanol.
  • the nano-aggregate may be at least one selected from an inorganic semiconductor material, a combination of an organic semiconductor material and a phosphor, and a combination of an organic semiconductor material and an inorganic semiconductor material.
  • Applying the composition containing the nano-aggregate on the solar cell electrode or the organic thin film layer may be carried out by any one of spin coating, spray coating, dip coating, screen printing, inkjet printing, gravure printing and offset printing.
  • One aspect of the present invention for achieving the above object is a first electrode, a light absorption layer formed on the first electrode, including a light absorbing material, an electron transport layer formed on the light absorbing layer and the second formed on the electron transport layer And an electrode, wherein the light absorbing layer is formed with nanoaggregates protruding in a vertical direction on top of the lower thin film layer to form irregularities, and the electron transport layer fills the space between the nanoaggregates and covers the nanoaggregates.
  • the display device may further include a hole transport layer interposed between the first electrode and the light absorption layer, and further include a charge injection layer interposed between the electron transport layer and the second electrode.
  • the light absorbing material may be at least one selected from light absorbing organics and inorganics.
  • the light absorbing organic material may be at least one selected from an organic semiconductor material and a phosphorescent material, and the light absorbing inorganic material may be an inorganic semiconductor material.
  • the nano-aggregate may be at least one selected from an inorganic semiconductor material, a combination of an organic semiconductor material and a phosphor, and a combination of an organic semiconductor material and an inorganic semiconductor material.
  • a first electrode is formed on a substrate, and a light absorption layer having irregularities on a surface thereof is formed on the first electrode, and an electron transport layer is formed on the light absorption layer. And forming a second electrode on the electron transport layer.
  • the method may further include forming an electron injection layer between forming the second electrode on the electron transport layer.
  • Forming a light absorption layer having irregularities on the surface on the first electrode preparing a mixed solution containing a good solvent, a light absorbing material, a poor solvent, agitated the mixed solution to form a nano-aggregate spontaneously
  • Obtaining a composition applying a composition containing the nano-aggregate on the first electrode and the heat treatment of the applied composition may be included.
  • Applying the composition containing the nano-aggregate on the first electrode may be carried out through any one selected from spin coating, spray coating, dip coating, screen printing, inkjet printing, gravure printing and offset printing.
  • the nano-aggregates are formed on the surface according to the difference in solubility in the good and poor solvents of light-absorbing organic and / or inorganic materials, thereby reducing the recombination of excitons, thereby increasing the efficiency of transporting charges to the anode and the cathode. can do.
  • the solar cell including the light absorbing layer irregularities are spontaneously formed on the surface of the light absorbing layer regularly, thereby suppressing total reflection of incident sunlight, thereby reducing light loss and increasing the light absorbing area to increase photoelectric conversion efficiency. Can be improved.
  • the manufacturing method of the solar cell is easy to control the process conditions, it is possible to optimize the photoelectric conversion efficiency in consideration of the light absorption amount and the self-resistance of the solar cell, it is possible to manufacture a high efficiency solar cell simply and inexpensively.
  • FIG. 1A and 1B are perspective views of a solar cell according to an embodiment of the present invention.
  • FIG. 2 is a flowchart illustrating a method of manufacturing a light absorption layer for a solar cell according to an embodiment of the present invention.
  • 3A to 3D are process diagrams illustrating a method of manufacturing a light absorption layer for a solar cell according to an embodiment of the present invention.
  • 4A to 4F are AFM images of the surface of the light absorption layer manufactured according to one embodiment of the present invention.
  • 5A to 5D are process diagrams illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.
  • FIG. 6 is an energy band diagram of a solar cell according to an embodiment of the present invention.
  • FIG. 7 is a graph showing the I-V curve of the solar cell according to an embodiment of the present invention.
  • a layer is referred to herein as "on" another layer or substrate, it may be formed directly on the other layer or substrate, or a third layer may be interposed therebetween.
  • the directional expression of the upper part, the upper part, and the upper part may be understood as meanings of the lower part, the lower part, the lower part, and the like according to the criteria.
  • the expression of the spatial direction should be understood as a relative direction and should not be construed as limiting the absolute direction.
  • FIG. 1A and 1B are perspective views of a solar cell according to an embodiment of the present invention.
  • the first electrode 100 may be positioned on a substrate (not shown).
  • the substrate is used to support the device and can be removed as needed.
  • the substrate may be a transparent inorganic substrate.
  • the substrate may be selected from glass, quartz, Al 2 O 3 and SiC.
  • the substrate may be a transparent organic substrate.
  • the substrate may be selected from polyethylene terephthlate (PET), polyethersulfone (PES), polystyrene (PS), polycarbonate (PC), polyimide (PI), polyethylene naphthalate (PEN), and polyarylate (PAR).
  • the first electrode 100 serves as an anode for collecting holes generated in the light absorption layer 300 to be described later.
  • the first electrode 100 may be made of a conductive material having a low resistance and having a transparency to transmit light.
  • the first electrode 100 is carbon nanotube (CNT), graphene, ITO, doped ZnO (AZO: Al doping, GZO: Ga doping, IZO: In doping, IGZO: In and Ga doping, MZO: Mg doped), MgO doped with Al or Ga, In 2 O 3 doped with Sn, SnO 2 doped with F, or TiO 2 doped with Nb.
  • CNT carbon nanotube
  • ITO doped ZnO
  • GZO Ga doping
  • IZO In doping
  • IGZO In and Ga doping
  • MZO Mg doped
  • MgO doped with Al or Ga In 2 O 3 doped with Sn
  • SnO 2 doped with F or TiO 2 doped with Nb.
  • the light absorbing layer 300 absorbs the irradiated light and forms an electron-hole pair, that is, an exciton, in an excited state.
  • the light absorbing layer 300 has a structure in which the thin film layer 310 is disposed below and the nanoaggregates 330 are arranged on the thin film layer 310. Therefore, the light absorption layer 300 forms an uneven structure on the surface due to the nano-aggregates 330.
  • the uneven structure may be spontaneously formed by a difference in solubility resulting from dissolving in a solvent (good solvent) that dissolves light absorbing material well and a solvent (poor solvent) that does not dissolve well.
  • the thin film layer 310 positioned below the light absorbing layer 300 includes a light absorbing material evenly dissolved in a good solvent, and the nano-aggregates 330 on the upper side cause the light absorbing material to aggregate in a poor solvent. Is formed.
  • the light absorbing material may be selected from at least one of a light absorbing organic material and an inorganic material.
  • the light absorbing organic material may be at least one selected from organic semiconductor materials and phosphorescent materials.
  • the light absorbing inorganic material may be an inorganic semiconductor material including a quantum dot having a single structure or a dual structure of a core-shell.
  • the light absorbing organic material may be pentacene, PDCDT, PenPTC, ZnPC, CuPC, TiOPC, Coumarin 6, P3HT, P3KT, PT, PTCBI, ADIDI, PTCDA, PTCDI, Spiro-MeOTAD, NTDA, MePTC, HepPTC, At least one selected from the group consisting of F16CuPC, P3OT, MEH-PPV, MDMO-PPV, PFO, PFO-DMP, SubPc, N3, and PBDTTT, and compounds of the Ir, Pt, Eu, or Tb family.
  • the light absorption inorganic material is MgO, MgS, MgSe, MgTe, CaO, CaS, CaSe, CaTe, SrO, SrS, SrSe, SrTe, BaO, BaS, BaSe, BaTE, ZnO, Cu 2 O, ZnS, ZnSe, ZnTe , CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, Al 2 S 3 , Al 2 Se 3 , Al 2 Te 3 , Ga 2 O 3 , Ga 2 S 3 , Ga 2 Se 3 , Ga 2 Te 3 , In 2 O 3 , In 2 S 3 , In 2 Se 3 , In 2 Te 3 , GeO 2 , SnO 2 , SnS, SnSe, SnTe, PbO, Pb O 2, PbS, PbSe, PbTe, AlN, AlP, At least
  • the nano-aggregate 330 may be any one selected from an inorganic semiconductor material, a combination of an organic semiconductor material and a phosphor material, and a combination of an organic semiconductor material and an inorganic semiconductor material.
  • the phosphorescent material or the inorganic semiconductor material combined with the organic semiconductor material may have a nanoparticle form.
  • the nano-aggregate 330 is a combination of an organic semiconductor material and a phosphor material or a combination of an organic semiconductor material and an inorganic semiconductor material, since the phosphor or inorganic semiconductor material in the form of nanoparticles has an excellent light absorption rate, A number of excitons can be produced to increase the photocurrent.
  • triplet excitons with increased diffusion distances can be formed, allowing a greater number of excitons to be separated at the interface.
  • the uneven structure of the light absorption layer 300 increases the area of the interface capable of separating excitons, thereby reducing the recombination rate of the charge. Therefore, the photocurrent can be increased to improve the photoelectric conversion efficiency.
  • the electron transport layer 400 is located on the light absorbing layer 300.
  • the electron transport layer 400 performs a function of capturing electrons in electrons and holes separated at an interface between the light absorption layer 300 and the electron transport layer 400 and transporting the electrons to the second electrode 600.
  • the electron transport layer 400 may contain an organic material or an inorganic material.
  • the electron transport layer 400 is fullerene (C60, C70, C80) or a fullerene derivative PCBM ([6,6] -phenyl-C61 butyric acid methyl ester) (PCBM (C60), PCBM (C70), PCBM ( C80)).
  • the electron transport layer 400 may contain an inorganic material including ZnO, TiO 2 , SnO 2 or carbon nanotubes.
  • the second electrode 600 is located on the electron transport layer 400.
  • the second electrode 600 serves as a cathode for collecting electrons generated in the light absorption layer 300.
  • the second electrode 600 may contain a metal, an alloy, an electrically conductive compound, and a mixture thereof having a small work function.
  • the second electrode 600 may contain any one selected from Al, Au, Cu, Pt, Ag, W, Ni, Zn, Ti, Zr, Hf, Cd, Pd, and alloys thereof.
  • the second electrode 600 may include CuAlO 2 / Ag / CuAlO 2 , ITO / Ag / ITO, ZnO / Ag / ZnO, ZnS / Ag / ZnS, TiO 2 / Ag / TiO 2 , ITO / Au / ITO, It may contain any one selected from WO 3 / Ag / WO 3 and MoO 3 / Ag / MoO 3 .
  • the second electrode 600 may contain any one selected from graphene, carbon nanotubes, conductive polymers, and composites thereof. In particular, when the second electrode 600 is formed of a transparent organic electrode, light reception may be possible even from above.
  • a hole transport layer (HTL) 200 and an electron injection layer 500 may be further included in the configuration of FIG. 1A. Since the description of the components other than the hole transport layer 200 and the electron injection layer 500 is the same as in FIG. 1A, it will be omitted.
  • the hole transport layer 200 may be interposed between the first electrode 100 and the light absorption layer 300.
  • the electron injection layer 500 may be interposed between the electron transport layer 400 and the second electrode 600.
  • the hole transport layer 200 is positioned between the first electrode 100 and the light absorbing layer 300 so as to easily transport holes generated in the light absorbing layer 300 to the first electrode 100.
  • the hole transport layer 200 is preferably made of a compound having excellent hole blocking ability as well as electron blocking properties and thin film formation ability.
  • the hole transport layer 200 may include PEDOT (poly (3,4-ethylenedioxythiophene)), PSS (poly (styrenesulfonate)), polyaniline, phthalocyanine, pentacene, polydiphenyl, acetylene and derivatives thereof At least one conductive polymer such as NPB, TPD, Spiro-TPD, Spiro-NPB, DMFL-TPD, DMFL-NPB, DPFL-TPD, DPFL-NPB, Spiro-TAD, BPAPF, NPAPF, NPBAPF, Spiro-2NPB , PAPB, 2,2'-Spiro-DBP, Spiro-BPA, TAPC, Spiro-TTB or may contain organic substances such as HMTPD, but is not limited thereto. More preferably, the hole transport layer 200 may contain a mixture of PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrenesulf
  • the electron injection layer 500 is positioned between the electron transport layer 400 and the second electrode 600 to improve electron injection.
  • the electron injection layer 500 may be an insulating film having a thin thickness.
  • the electron injection layer 500 may include LiF, Liq, TPBi, PBD, BCP, Bphen, BAlq, Bpy-OXD, BP-OXD-Bpy, TAZ, NTAZ, NBphen, Bpy-FOXD, OXD-7l, 3TPYMB, It may contain any one selected from 2-NPIP, PADN, HNBphen, POPy2, BP4mPy, TmPyPB and BTB.
  • FIG. 2 is a flowchart illustrating a method of manufacturing a light absorption layer of a solar cell according to an embodiment of the present invention.
  • 3A to 3D are process diagrams illustrating a method of manufacturing a light absorption layer of a solar cell according to an embodiment of the present invention.
  • the light absorbing material 310a may be selected from at least one of a light absorbing organic material and a light absorbing inorganic material.
  • the good solvent 340 may refer to a solvent having excellent solubility of the light absorbing material 310a. Therefore, the good solvent 340 preferably has the same polarity as that of the light absorbing material 310a.
  • organic material P3HT poly (3-hexylthiophen)
  • chlorobenzene or dichlorobenzene may be used as the good solvent 340.
  • the poor solvent 350 may refer to a solvent having low solubility of the light absorbing material 310a. Therefore, the poor solvent 350 preferably has a polarity different from that of the light absorbing material 310a.
  • the poor solvent 350 may be added in a constant volume ratio with respect to the good solvent 340, which may be set differently according to experimental conditions.
  • P3HT poly (3-hexylthiophen)
  • PGMEA propylene glycol mono-methyl ether acetate
  • the mixed solution may include a light absorbing organic material or a light absorbing inorganic material having a form of nanoparticles 320.
  • the light absorbing organic material or the light absorbing inorganic material in the form of the nanoparticle 320 may be a phosphor or an inorganic semiconductor material.
  • the inorganic semiconductor material may be a quantum dot having a single structure or a dual structure of a core-shell.
  • the phosphor or quantum dot in the form of nanoparticles 320 has an excellent light absorption, there is an advantage that a greater number of excitons are generated to increase the photocurrent.
  • a good solvent-poor solvent may be used in various combinations for various kinds of light absorbing materials 310a.
  • the nano-aggregate 330 is formed by stirring the mixed solution including the good solvent 340, the light absorbing material 310a, the poor solvent 350, and the light absorbing nanoparticle 320.
  • a portion of the light absorbing material 310a and the light absorbing nanoparticles 320 that are dissolved in the good solvent 340 through the stirring may move to the poor solvent 350, and the nanoaggregate 330 may be formed.
  • the nanoaggregate 330 has a shape in which the nanoparticle 320 surrounds the light absorbing material 310a.
  • the size of the nano-aggregate 330 can be controlled by adjusting the concentration of the solvent, the stirring time, the coating speed and the time.
  • the composition including the nano-aggregate 330 is coated on the electrode or the organic thin film layer (S300).
  • the electrode may be the first electrode 100
  • the organic thin film layer may be the hole transport layer 200.
  • the coating may be carried out by appropriately selecting a coating or printing method such as spin coating, spray coating, dip coating, screen printing, inkjet printing, gravure printing, offset printing, etc. as necessary.
  • a coating or printing method such as spin coating, spray coating, dip coating, screen printing, inkjet printing, gravure printing, offset printing, etc. as necessary.
  • the coated composition is heat-treated to form a light absorption layer 300.
  • the heat treatment may be carried out at a temperature range of 20 °C to 80 °C for 10 to 30 minutes.
  • the light absorbing material 310 remaining in the good solvent 340 through the coating and heat treatment may be formed as a thin film layer 310 at the bottom.
  • the nano-aggregate 330 may be deposited on the thin film layer 310. Therefore, the light absorption layer 300 has a concave-convex structure on the surface due to the nano-aggregates 330 arranged thereon.
  • 4A to 4F are AFM images of the surface of the light absorption layer manufactured according to one embodiment of the present invention.
  • 4A and 4B are AFM images of nano-aggregates formed using P3HT (poly (3-hexylthiophen)), which is a light absorbing organic material, as a light absorbing material and using PGMEA (propylene glycol mono-methyl ether acetate) as a poor solvent.
  • 4C and 4D are AFM images of nano-aggregates formed using ZnSe / InP / ZnS, which are light absorbing inorganic materials, as light absorbing materials and using propylene glycol mono-methyl ether acetate (PGMEA) as a poor solvent.
  • 4F shows nanoparticles formed using P3HT (poly (3-hexylthiophen), a light absorbing organic material, as a light absorbing material, ZnSe, an inorganic nanoparticle, and PGMEA (propylene glycol monomethyl ether acetate) as a poor solvent.
  • P3HT poly (3-hexylthiophen
  • ZnSe zinc absorbing material
  • PGMEA propylene glycol monomethyl ether acetate
  • nanoaggregates having a length of about 3 nm to 25 nm are densely or densely arranged according to the type of light absorbing material and the presence or absence of light absorbing material in the form of nanoparticles to form an uneven structure.
  • the size of the nano-aggregates can be controlled by adjusting the concentration of the solvent, the stirring time, the application rate and time.
  • 5A to 5D are process diagrams illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.
  • a hole transport layer 200 is formed on a substrate (not shown) on which the first electrode 100 is formed.
  • the first electrode 100 may be made of a transparent conductive metal oxide and various carbon materials.
  • the first electrode 100 may be formed on the substrate by using thermal image deposition, electron beam deposition, RF sputtering or magnetron sputtering.
  • the hole transport layer 200 may contain a conductive polymer material.
  • the hole transport layer 200 may be formed using spin coating, spray coating, dipping, sputtering, vacuum deposition, or the like.
  • the light absorption layer 300 is formed on the hole transport layer 200.
  • the light absorption layer 300 may be formed of a thin film layer 310 disposed below and a nano-aggregate 330 arranged thereon.
  • the method of manufacturing the light absorbing layer 300 is the same as described with reference to FIGS. 2 and 3A to 3D, detailed descriptions thereof will be omitted.
  • the electron transport layer 400 is formed on the light absorption layer 300.
  • the electron transport layer 400 may include an organic material or an inorganic material.
  • the electron transport layer 400 may be formed using a solution process.
  • the electron transport layer 400 may be formed using vacuum deposition, spin coating, dip coating, drop coating, spray coating, inkjet printing or screen printing. At this time, it may be formed in an appropriate thickness in consideration of the type and characteristics of the organic material or inorganic material used.
  • a second electrode 600 is formed on the electron transport layer 300.
  • a thin thickness electron injection layer 500 may be further formed to smoothly inject electrons.
  • the electron injection layer 500 is preferably formed of a thin thin film having an insulating property, such as LiF, Liq.
  • the second electrode 600 may be formed to contain various carbon materials and conductive polymer materials, in addition to a metal or an alloy having excellent conductivity. In particular, when the second electrode 600 is formed of a transparent organic electrode, light reception may be possible even from above.
  • the electron injection layer 500 may be formed using vacuum deposition, spin coating, dip coating, drop coating, spray coating, inkjet printing or screen printing.
  • the second electrode 600 may be formed using a thermal image deposition, electron beam deposition, RF sputtering or magnetron sputtering method.
  • ITO transparent electrode was formed on the glass substrate by spin coating, and then ultrasonically washed to remove impurities from the surface of the substrate.
  • the light absorption layer was formed on the PEDOT: PSS hole transport layer.
  • the formation process is as follows.
  • compositions of Samples 1, 2 and 3 were spin-coated on a PEDOT: PSS hole transport layer and heat treated to form a light absorption layer having a planar or uneven structure.
  • FIG. 6 is an energy band diagram of a solar cell according to an embodiment of the present invention.
  • sunlight is absorbed by the light absorbing layer 300, and the light absorbing layer 300 absorbs light energy from sunlight to generate excitons.
  • the generated excitons move and diffuse, and are separated into electrons and holes at the bonding interface between the light absorption layer 300 and the electron transport layer 400.
  • the separated electrons move to the second electrode 600 through the energy level of the electron transport layer 400, and the separated holes move to the first electrode 100 through the energy level of the hole transport layer 200.
  • the charges collected in the first electrode 100 and the second electrode 600 form a photocurrent.
  • FIG. 7 is a graph showing the I-V curve of the solar cell according to an embodiment of the present invention.
  • the short circuit current (J sc ) has a value of 6.2 mAcm ⁇ 2
  • Sample 2 and Sample 3 formed of the uneven structure
  • the values of 7.5 mAcm -2 and 8.6 mAcm -2 respectively. That is, it can be seen that the short-circuit current increased in the solar cell formed of the uneven structure surface.
  • the photovoltaic conversion efficiency ( ⁇ ) of the sample 1 was only 0.8%
  • the uneven structure had values of 1.18% and 1.59%, respectively, and it was confirmed that the solar cell increased significantly.

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Abstract

La présente invention a trait à un procédé permettant de préparer une couche d'absorption de lumière destinée à une cellule solaire, à une cellule solaire incluant la couche d'absorption de lumière et à son procédé de fabrication. Le procédé permettant de préparer une couche d'absorption de lumière destinée à une cellule solaire permet d'augmenter l'efficacité de transport des charges se déplaçant vers les électrodes positive et négative au moyen de la réduction de recombinaison d'exciton en formant de façon spontanée des nanoagrégats en raison d'une différence de solubilité d'un matériau d'absorption de lumière dans un bon solvant et un mauvais solvant. De plus, la cellule solaire permet d'améliorer le photocourant et le rendement de conversion photoélectrique en augmentant la zone d'une interface collée entre la couche d'absorption de lumière et une couche de transport d'électron au moyen de la formation d'une structure irrégulière sur la surface de la couche d'absorption de lumière en raison de l'agencement des nanoagrégats. D'autre part, le procédé de fabrication de la cellule solaire permet de simplifier et de faciliter la fabrication d'une cellule solaire à haut rendement de grande taille à l'aide d'un processus de la présente solution.
PCT/KR2012/005783 2011-07-21 2012-07-19 Procédé permettant de préparer une couche d'absorption de lumière destinée à une cellule solaire, cellule solaire incluant la couche d'absorption de lumière et son procédé de fabrication WO2013012271A2 (fr)

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WO2015065162A1 (fr) * 2013-11-04 2015-05-07 주식회사 엘지화학 Structure conductrice et son procédé de préparation
WO2015076572A1 (fr) * 2013-11-20 2015-05-28 주식회사 엘지화학 Structure conductrice et procédé pour sa fabrication
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WO2015076572A1 (fr) * 2013-11-20 2015-05-28 주식회사 엘지화학 Structure conductrice et procédé pour sa fabrication
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CN104409572B (zh) * 2014-11-24 2017-02-22 新奥光伏能源有限公司 一种异质结太阳能电池的制作方法
KR20160115588A (ko) * 2015-03-27 2016-10-06 주식회사 엘지화학 디스플레이 장치 및 이의 제조방법
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