WO2015167230A1 - Cellule solaire et son procédé de fabrication - Google Patents

Cellule solaire et son procédé de fabrication Download PDF

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WO2015167230A1
WO2015167230A1 PCT/KR2015/004268 KR2015004268W WO2015167230A1 WO 2015167230 A1 WO2015167230 A1 WO 2015167230A1 KR 2015004268 W KR2015004268 W KR 2015004268W WO 2015167230 A1 WO2015167230 A1 WO 2015167230A1
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electrode
buffer layer
metal
solar cell
present specification
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PCT/KR2015/004268
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English (en)
Korean (ko)
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방지원
이재철
이행근
김진석
장송림
최두환
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주식회사 엘지화학
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Priority to CN201580022750.1A priority Critical patent/CN106233483B/zh
Publication of WO2015167230A1 publication Critical patent/WO2015167230A1/fr

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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
    • 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
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • 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 specification relates to a solar cell and a method of manufacturing the same.
  • the main energy sources currently used are oil, coal and gas. This represents 80% of the total energy source used.
  • the current depletion of petroleum and coal energy is becoming a serious problem, and the increasing emissions of carbon dioxide and other greenhouse gases into the air are causing serious problems.
  • the use of renewable energy, pollution-free green energy is still only about 2% of the total energy source. Therefore, the worries for solving the problem of the energy source is accelerating the research on new and renewable energy development.
  • renewable energy such as wind, water and sun
  • solar energy the most attention is solar energy. Solar cells using solar energy are expected to be an energy source that can solve future energy problems due to low pollution, infinite resources and a semi-permanent lifetime.
  • Solar cells are devices that can directly convert solar energy into electrical energy by applying the photovoltaic effect.
  • Solar cells can be divided into inorganic solar cells and organic solar cells according to the material constituting the thin film.
  • Typical solar cells are made of p-n junctions by doping crystalline silicon (Si), an inorganic semiconductor. Electrons and holes generated by absorbing light diffuse to the p-n junction and are accelerated by the electric field to move to the electrode.
  • the power conversion efficiency of this process is defined as the ratio of the power given to the external circuits and the solar power entered into the solar cell, and is now up to 24% when measured under standardized virtual solar irradiation conditions.
  • the conventional inorganic solar cell has already shown a limit in the economic and material supply and demand, organic solar cells with easy processing, low cost and various functionalities are spotlighted as long-term alternative energy sources.
  • the organic solar cell has the advantage that the monomolecular organic material or the polymer material used is easy, fast and inexpensive and large area process is possible.
  • the organic solar cell has a disadvantage of low energy conversion efficiency. Therefore, efficiency improvement is very important to secure competitiveness with other solar cells at this time.
  • the present specification provides a solar cell and a method of manufacturing the same that can improve current density and charge rate.
  • An exemplary embodiment of the present specification includes a first electrode; Second electrode; A photoactive layer provided between the first electrode and the second electrode; And
  • An electrode buffer layer disposed between the first electrode and the photoactive layer, wherein the electrode buffer layer includes a matrix including a metal oxide and one or more metal particles, and the metal particles are provided in direct contact with the matrix.
  • One embodiment of the present specification comprises the steps of preparing a preparation 1 electrode; menstruum; Metal oxide precursors; And preparing a solution comprising a metal salt; Coating the solution on the first electrode and then performing heat treatment to form an electrode buffer layer; Forming a photoactive layer on the electrode buffer layer; And forming a second electrode on the photoactive layer, wherein the electrode buffer layer comprises a matrix including a metal oxide and one or more metal particles, wherein the metal particles are provided in direct contact with the matrix.
  • the electrode buffer layer comprises a matrix including a metal oxide and one or more metal particles, wherein the metal particles are provided in direct contact with the matrix.
  • the metal particles in the electrode buffer layer have an advantage of being uniformly dispersed without a phase separation phenomenon with the matrix.
  • the electrode buffer layer suppresses recombination of electrons and holes at a low built in potential due to high electron conductivity, so that the current density and fill rate of the solar cell factor: FF).
  • the electrode buffer layer may achieve high light conversion efficiency by condensing light having a wavelength in the visible light region with the photoactive layer.
  • the electrode buffer layer can be formed by a simple method to achieve a reduction in process time and process cost.
  • FIG. 1 illustrates a schematic diagram of a solar cell according to an exemplary embodiment of the present specification.
  • FIG 2 shows the optical characteristics of the electrode buffer layer prepared according to the embodiment.
  • Figure 3 shows the current density according to the voltage of the solar cell according to the embodiment and the comparative example.
  • An exemplary embodiment of the present specification includes a first electrode; Second electrode; A photoactive layer provided between the first electrode and the second electrode; And an electrode buffer layer provided between the first electrode and the photoactive layer, the electrode buffer layer comprising a matrix comprising a metal oxide and one or more metal particles, wherein the metal particles are provided in direct contact with the matrix.
  • a battery Provide a battery.
  • the electrode buffer layer forms a stable structure by forming a continuous phase structure in which a matrix including metal oxide and metal particles are not phase separated. Further, the metal particles in the electrode buffer layer are uniformly dispersed in the matrix, and have uniform light transmittance and uniform electrical conductivity. In addition, since the electrode buffer layer is uniformly dispersed in the matrix without agglomeration of metal particles, the shape of the electrode buffer layer may be kept constant. Therefore, another member provided on the electrode buffer layer can be easily formed.
  • the metal particles may not be combined with an additive for dispersing the metal particles on the surface.
  • the metal particles may not include a surfactant on the surface.
  • the metal particles may not be bonded to a ligand on the surface of the metal particles.
  • the metal particles may be made of a metal derived from a metal salt.
  • the matrix may mean a layer in which the metal particles may be provided. Specifically, the matrix may mean a layer in which the metal particles may be embedded. In addition, the matrix may be made of a metal oxide. That is, the matrix may be a metal oxide matrix.
  • the metal oxide matrix as the electrode buffer layer has an advantage of excellent electrical conductivity and excellent stability since the metal oxide forms a crystal structure. On the contrary, in the case of the polymer matrix, the stability is greatly reduced, and electrical conductivity is also low.
  • the present inventors have prepared a buffer layer by coating a surfactant on the surface of the metal particles so that the metal particles can be uniformly dispersed in the electrode buffer layer in the buffer layer, but the electrical conductivity of the electrode buffer layer is lowered by the surfactant. Found.
  • the present inventors have attempted to increase the dispersibility of the metal particles in the buffer layer by bonding a substituent to the surface ligand of the metal particles, but in the case of the metal particles to which the substituent is bonded, the electrical conductivity is lowered, and the dispersibility is not greatly improved. there was.
  • the present inventors add a metal salt to a solution containing a metal oxide precursor for forming a buffer layer, so that the metal particles can be uniformly dispersed in the electrode buffer layer, and then the metal in the matrix containing the metal oxide through a heat treatment method.
  • a method of growing particles has been developed.
  • the metal particles may provide high electrical conductivity to the electrode buffer layer. Furthermore, since the metal particles are not gasified and included in the matrix precursor solution, that is, the solution including the metal oxide precursor, the metal particles may be evenly dispersed in the buffer layer.
  • the electrode buffer layer may include anion or negative atomic group ions at a concentration of 50 ppm or more and 500000 ppm or less with respect to the electrode buffer layer.
  • the anion or negative atomic group ion may be a residual anion or negative atomic group ion derived from a metal salt for forming the metal particles.
  • the atomic ions of the anion or negative is Cl -, No 3 -, I -, F -, Br - , and (C 2 H 7 O 2) - may be at least one of.
  • the content of the metal particles may be 0.005% by volume or more and 50% by volume or less with respect to the total volume of the electrode buffer layer.
  • the average particle diameter of the metal particles may be 1 nm or more and 5 ⁇ m or less.
  • the particle diameter may mean the size of the metal particles, and may mean the maximum length passing through the inside of the metal particles.
  • the shape of the metal particles may be in the form of a sphere, plate, rod, or prism.
  • the spherical shape means having a spherical shape as a whole, and does not necessarily mean a perfect spherical shape.
  • the plate shape may mean that the thickness is smaller than the maximum diameter of the particles, the maximum diameter of the particles may mean the maximum diameter based on the widest surface of the plate-shaped particles.
  • the rod form includes rod and wire forms, and may include all forms having an aspect ratio of more than one.
  • the prism shape means a shape having a triangle in cross section, and may include all shapes such as a triangular pyramid and a triangular pyramid.
  • the thickness of the electrode buffer layer may be 1 nm or more and 10 ⁇ m or less. Specifically, according to the exemplary embodiment of the present specification, the thickness of the electrode buffer layer may be 1 nm or more and 200 nm or less.
  • the electrode buffer layer may be provided in physical contact with the first electrode.
  • an additional layer may be provided between the electrode buffer layer and the first electrode.
  • FIG. 1 illustrates a schematic diagram of a solar cell according to an exemplary embodiment of the present specification. Specifically, FIG. 1 illustrates that the electrode buffer layer 301, the photoactive layer 401, and the anode 201 are sequentially stacked on the cathode 101. According to one embodiment of the present specification, it is not limited to the structure of FIG. 1, and an additional member may be further included to form a solar cell.
  • the electrode buffer layer includes metal particles, and has excellent electrical conductivity. Therefore, by the buffer layer of the electrode, the solar cell can suppress the recombination of electrons and holes at a low built in potential, and the current density and the fill factor (FF) of the solar cell can be improved. .
  • the solar cell may achieve high light conversion efficiency.
  • the solar cell further includes a substrate, the first electrode may be provided on the substrate, and the first electrode may be a cathode.
  • the solar cell may be an inverted solar cell.
  • the first electrode is a transparent electrode
  • the solar cell may absorb light via the first electrode.
  • the first electrode may be provided on a transparent substrate.
  • the maximum condensing wavelength of the electrode buffer layer may be included in the light absorption wavelength band of the photoactive layer.
  • the metal particles included in the electrode buffer layer have an effect of condensing light of a specific wavelength band due to the surface plasmon resonance effect. Therefore, the light conversion efficiency of the photoactive layer may be increased by including metal particles capable of collecting light in the wavelength band absorbed by the photoactive layer in the electrode buffer layer.
  • the metal particles may include one or more metals selected from the group consisting of Ag, Au, Al, Pt, W, and Cu. Specifically, according to one embodiment of the present specification, the metal particles may include Ag.
  • the maximum condensing wavelength of the buffer layer may be 400 nm or more and 1,000 nm or less.
  • the metal oxide is titanium oxide (TiO x ); Zinc oxide (ZnO); It may include one or more selected from the group consisting of molybdenum oxide (MoO 3 ) and cesium carbonate (Cs 2 CO 3 ).
  • the electrode buffer layer may be a cathode buffer layer including metal particles in a matrix including ZnO.
  • An exemplary embodiment of the present specification provides a method of manufacturing the solar cell.
  • One embodiment of the present specification comprises the steps of preparing a first electrode; menstruum; Metal oxide precursors; And preparing a solution comprising a metal salt; Coating the solution on the first electrode and then performing heat treatment to form an electrode buffer layer; Forming a photoactive layer on the electrode buffer layer; And forming a second electrode on the photoactive layer, wherein the electrode buffer layer comprises a matrix including a metal oxide and one or more metal particles, wherein the metal particles are provided in direct contact with the matrix.
  • the electrode buffer layer comprises a matrix including a metal oxide and one or more metal particles, wherein the metal particles are provided in direct contact with the matrix.
  • the metal salt is reduced in the solution to grow into metal particles, and at the same time, a matrix may be formed.
  • an electrode buffer layer free of impurities such as a reducing agent, a surfactant, and a substituent may be formed, and the metal particles may be uniformly distributed in the matrix without aggregation.
  • the metal salt may include at least one selected from the group consisting of Ag metal salt, Au metal salt, Al metal salt, Cu metal salt, W metal salt and Pt metal salt.
  • the Ag metal salt may include one or more selected from the group consisting of AgCl, AgNO 3 and AgI.
  • the present invention is not limited thereto.
  • the Au metal salt may include one or more selected from the group consisting of HAuCl 4 , AuCl and AuCl 3 .
  • the present invention is not limited thereto.
  • the Cu metal salt may include one or more selected from the group consisting of CuI, CuF 3 and CuNO 3 .
  • the present invention is not limited thereto.
  • the Pt metal salt may include one or more selected from the group consisting of PtCl 2 , PtCl 4 , PtBr 2, and Pt (C 5 H 7 O 2 ) 2 .
  • the present invention is not limited thereto.
  • the solvent may be used without limitation so long as it is a solvent capable of dissolving the metal salt.
  • the solvent may be a water-soluble solvent or an organic solvent.
  • the content of the metal oxide precursor may be 0.1 wt% or more and 50 wt% or less with respect to the solution. Specifically, the content of the metal oxide precursor may be 0.5 wt% or more and 10 wt% or less with respect to the solution.
  • the content of the metal oxide precursor is 0.1 wt% or less, voids may exist on the metal oxide film, and when the content of the metal oxide precursor is 50 wt% or more, a metal oxide thin film having a non-uniform thickness may be formed. have.
  • the metal oxide precursor may include at least one or more of zinc salts, titanium salts, and molybdenum salts.
  • the metal oxide precursor is zinc acetate, titanium isopropoxide, or bis (2,4-pentanedionate) molybdenum (VI).
  • Dioxide Bis (2,4-pentanedionato) molybdenum (VI) Dioxide
  • VI Dioxide
  • the content of the metal salt may be 0.0001 wt% or more and 10 wt% or less with respect to the solution. Specifically, the content of the metal salt may be 0.001% by weight or more and 10% by weight or less with respect to the solution.
  • the metal salts When the content of the metal salt is less than 0.0001% by weight, the metal salts do not aggregate and it is difficult to form the metal nanoparticles, and when the content of the metal salt is 10% by weight or more, a metal electrode is formed in the metal oxide buffer layer to short the device. This can happen.
  • the forming of the electrode buffer layer may include applying the solution to a thickness of 1 nm or more and 1 ⁇ m or less.
  • the forming of the electrode buffer layer may include applying the solution to a thickness of 1 nm or more and 200 nm or less.
  • the heat treatment may be performed at a temperature of 50 ° C. or more and 400 ° C. or less. Specifically, the heat treatment may be performed at a temperature of more than 80 °C 200 °C. When the heat treatment is 80 °C or less, it is difficult to form the metal nanoparticles, the metal nanoparticles may be oxidized above 200 °C may inhibit the characteristics of the metal nanoparticles.
  • the solar cell may further include a substrate.
  • the substrate may be provided under the first electrode.
  • the substrate may use a substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness.
  • a glass substrate, a thin film glass substrate, or a transparent plastic substrate may be used.
  • the plastic substrate may include a film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone (PEEK), and polyimide (PI) in the form of a single layer or a multilayer.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PEEK polyether ether ketone
  • PI polyimide
  • the substrate is not limited thereto, and a substrate commonly used in solar cells may be used.
  • the first electrode may be an anode, and the second electrode may be a cathode.
  • the first electrode may be a cathode, and the second electrode may be an anode.
  • the first electrode may be a transparent electrode.
  • the first electrode When the first electrode is a transparent electrode, the first electrode may be a conductive oxide such as tin indium oxide (ITO) or zinc indium oxide (IZO). Furthermore, the first electrode may be a translucent electrode. When the first electrode is a translucent electrode, it may be made of a translucent metal such as Ag, Au, Mg, Ca or an alloy thereof. When the translucent metal is used as the first electrode, the solar cell may have a microcavity structure.
  • the electrode of the present specification is a transparent conductive oxide layer
  • the electrode is in addition to glass and quartz plate, polyethylene terephthalate (PET), polyethylene naphthelate (PEN), polyperopylene (PP), polyimide (PI), polycarbonate (PC), PS ( conductive on flexible and transparent materials such as polystylene, POM (polyoxyethlene), AS resin (acrylonitrile styrene copolymer), ABS resin (acrylonitrile butadiene styrene copolymer) and plastics including TAC (Triacetyl cellulose), PAR (polyarylate), etc. Doped materials may be used.
  • ITO indium tin oxide
  • FTO fluorine doped tin oxide
  • AZO aluminum doped zink oxide
  • IZO indium zink oxide
  • ZnO-Ga 2 O 3 ZnO-Al 2 O 3 and antimony tin oxide (ATO)
  • ATO antimony tin oxide
  • the forming of the transparent electrode may sequentially wash the patterned ITO substrate with a detergent, acetone, and isopropanol (IPA), and then, in the heating plate, at a temperature of 100 to 250 ° C. for 1 to 30 ° C.
  • the surface of the substrate can be modified to be hydrophilic if it is dried for 10 minutes, specifically at 250 ° C. for 10 minutes and the substrate is thoroughly cleaned.
  • Pretreatment techniques for this are a) surface oxidation using parallel planar discharge, b) oxidation of the surface through ozone generated using UV ultraviolet light in a vacuum state, and c) oxygen radicals generated by plasma. To oxidize.
  • the bonding surface potential can be maintained at a level suitable for the surface potential of the hole injection layer, the formation of the polymer thin film on the ITO substrate can be facilitated, and the quality of the thin film can be improved.
  • One of the above methods is selected according to the state of the substrate. In any of these methods, the effective effect of pretreatment can be expected by preventing oxygen escape from the surface of the substrate and restraining the remaining of moisture and organic matter as much as possible.
  • the surface modification method of the patterned ITO substrate in this invention does not need to specifically limit, Any method may be used as long as it is a method of oxidizing a substrate.
  • the second electrode may be a metal electrode.
  • the metal electrode may be silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium ( It may include one or two or more selected from the group consisting of Pd).
  • the solar cell may have an inverted structure.
  • the second electrode may be silver (Ag), MoO 3 / Al, MoO 3 / Ag, MoO 3 / Au, or Au.
  • the inverted solar cell of the present specification may mean that the anode and the cathode of the solar cell of the general structure are configured in the reverse direction.
  • Al layer used in the solar cell of the general structure is very vulnerable to oxidation reaction in the air, it is difficult to ink and there is a limitation in commercializing it through the printing process.
  • the inverted solar cell according to the exemplary embodiment of the present specification may use Ag instead of Al, and is more stable in oxidation reaction than the solar cell having a general structure, and easy to manufacture Ag ink. There is an advantage.
  • the solar cell may have a normal structure.
  • the second electrode may be Al.
  • the organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer and an electron injection layer.
  • the electron transport layer may include one or two or more selected from the group consisting of a conductive oxide and a metal.
  • the conductive oxide of the electron transport layer may be electron-extracting metal oxides, specifically, titanium oxide (TiO x ); Zinc oxide (ZnO); And cesium carbonate (Cs 2 CO 3 ) It may include one or more selected from the group consisting of.
  • the electron transport layer may be formed by being applied to one surface of the first electrode or coated in a film form using sputtering, E-Beam, thermal deposition, spin coating, screen printing, inkjet printing, doctor blade or gravure printing.
  • the electron transport layer may be a cathode buffer layer.
  • the solar cell may include an organic material in the photoactive layer.
  • the solar cell may include a quantum dot in the photoactive layer.
  • the photoactive layer includes a quantum dot
  • CdSe, CdTe, ZnTe, PbS PbSe, InP, Ag 2 S and Ag 2 Se may include one or more selected quantum dots
  • the quantum dots It may be dispersed in the conductive polymer matrix.
  • the solar cell may include a material of a perovskite structure in the photoactive layer.
  • the photoactive layer includes a material having a perovskite structure
  • CH 3 NH 3 PbI 3 , CH 3 NH 3 PbBr 3 , CH 3 NH 3 PbI x Br 3 -x and CH 3 NH 3 PbI ( Br) 3 may include one or more materials selected from the group consisting of.
  • the photoactive layer may include a material of the perovskite structure and a conductive polymer.
  • the photoactive layer may have a material of the perovskite structure dispersed in a conductive polymer matrix.
  • the photoactive layer may include an electron donor material and an electron acceptor material as a photoactive material.
  • the photoactive material may mean the electron donor material and the electron acceptor material.
  • the photoactive layer forms excitons in which the electron donor material pairs electrons and holes by photoexcitation, and the excitons are separated into electrons and holes at the interface of the electron donor / electron acceptor.
  • the separated electrons and holes move to the electron donor material and the electron acceptor material, respectively, and are collected by the first electrode and the second electrode, respectively, so that they can be used as electrical energy from the outside.
  • the photoactive layer may be a bulk heterojunction structure or a double layer junction structure.
  • the bulk heterojunction structure may be a bulk heterojunction (BHJ) junction type
  • the bilayer junction structure may be a bi-layer junction type.
  • the mass ratio of the electron donor material and the electron acceptor material may be 1:10 to 10: 1. Specifically, the mass ratio of the electron acceptor material and the electron donor material of the present specification may be 1: 0.5 to 1: 5.
  • the electron donor material is at least one electron donor; Or a polymer of at least one kind of electron acceptor and at least one kind of electron donor.
  • the electron donor may include at least one kind of electron donor.
  • the electron donor includes a polymer of at least one kind of electron acceptor and at least one kind of electron donor.
  • the electron donor material is thiophene-based, fluorene-based, carbazole-based, starting with MEH-PPV (poly [2-methoxy-5- (2'-ethyl-hexyloxy) -1,4-phenylene vinylene]) It may be a variety of polymer materials and monomolecular materials such as.
  • the monomolecular substance is copper (II) phthalocyanine, zinc phthalocyanine, tris [4- (5-dicynomethylidemethyl-2-thienyl) phenyl] Amine (tris [4- (5-dicyanomethylidenemethyl-2-thienyl) phenyl] amine), 2,4-bis [4- (N, N-dibenzylamino) -2,6-dihydroxyphenyl] squalane (2,4-bis [4- (N, N-dibenzylamino) -2,6-dihydroxyphenyl] squaraine), benz [b] anthracene, and pentacene It may include one or more materials.
  • the polymer material is poly 3-hexyl thiophene (P3HT: poly 3-hexyl thiophene), PCDTBT (poly [N-9'-heptadecanyl-2,7-carbazole-alt-5,5- (4'-) 7'-di-2-thienyl-2 ', 1', 3'-benzothiadiazole)]), PCPDTBT (poly [2,6- (4,4-bis- (2, ethylhexyl) -4H-cyclopenta [2, 1-b; 3,4-b '] dithiophene) -alt-4,7- (2,1,3-benxothiadiazole)]), PFO-DBT (poly [2,7- (9,9-dioctyl-fluorene) ) -alt-5,5- (4,7-di 2-thienyl-2,1,3-benzothiadiazole)]), PTB7 (Poly [[4,8-bis
  • the electron acceptor material may be a fullerene derivative or a nonfullerene derivative.
  • the fullerene derivative is a fullerene derivative of C60 to C90.
  • the fullerene derivative may be a C60 fullerene derivative or a C70 fullerene derivative.
  • the C60 fullerene derivative or C70 fullerene derivative are each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted or unsubstitute
  • the fullerene derivative may be selected from the group consisting of C76 fullerene derivative, C78 fullerene derivative, C84 fullerene derivative, and C90 fullerene derivative.
  • the C76 fullerene derivative, C78 fullerene derivative, C84 fullerene derivative, and C90 fullerene derivative are each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstitute
  • the fullerene derivative has an ability to separate electron-hole pairs (exciton, electron-hole pair) and charge mobility compared to the non-fullerene derivative, which is advantageous for efficiency characteristics.
  • the electron donor material and the electron acceptor material may form a bulk heterojunction (BHJ).
  • the photoactive layer of the present specification may be annealed at 30 ° C. to 300 ° C. for 1 second to 24 hours to maximize properties after the electron donor material and the electron acceptor material are mixed.
  • the photoactive layer is a poly 3-hexyl thiophene [P3HT: poly 3-hexyl thiophene] as an electron donor material, [6,6] -phenyl-C 61 -butyl acid methyl ester (PC 61 BM) and / or [6,6] -phenyl-C 71 -butyl acid methyl ester (PC 71 BM) as the electron acceptor material.
  • P3HT poly 3-hexyl thiophene
  • the mass ratio of the electron donor material and the electron acceptor material may be 1: 0.4 to 1: 2, specifically 1: 0.7.
  • the photoactive layer is not limited to the above material.
  • the photoactive materials are dissolved in an organic solvent and then the solution is introduced into the photoactive layer in a thickness ranging from 50 nm to 280 nm by spin coating or the like.
  • the photoactive layer may be applied to a method such as dip coating, screen printing, spray coating, doctor blade, brush painting.
  • the electron acceptor may include other fullerene derivatives such as C70, C76, C78, C80, C82, C84, including PC 61 BM, and the coated thin film may be heat-treated at 80 ° C. to 160 ° C. to determine the conductive polymer. It is good to increase the sex.
  • the solar cell of the present specification has an inverted structure, and in this case, pre-annealing may be performed at 120 ° C.
  • the hole transport layer and / or the electron transport layer material of the present specification may be a material that increases the probability that the generated charge is transferred to the electrode by efficiently transferring electrons and holes to the photoactive layer, but is not particularly limited.
  • the hole transport layer may be an anode buffer layer.
  • a hole transport layer may be introduced through spin coating, dip coating, inkjet printing, gravure printing, spray coating, doctor blade, bar coating, gravure coating, brush painting, thermal deposition, and the like.
  • poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate) [PEDOT: PSS] is mainly used as a conductive polymer solution, and is used as a hole-extracting metal oxides material.
  • Molybdenum oxide (MoO x ), vanadium oxide (V 2 O 5 ), nickel oxide (NiO), tungsten oxide (WO x ) and the like can be used.
  • the hole transport layer may be formed with a thickness of 5 nm to 10 nm through MoO 3 through a thermal deposition system.
  • ITO glass was prepared as a first electrode.
  • Acid zinc (zinc acetate) 1g and 0.28 g ethanol amine after forming a ZnO precursor solution was added to 2-methoxyethanol solvent of ethanol 10 ml, AgNO 3 30 mL was added to the ZnO precursor solution and applied by spin coating on the first electrode.
  • heat treatment was performed at 200 ° C. for 10 minutes to form an electrode buffer layer including Ag nanoparticles in the ZnO metal oxide matrix.
  • a photoactive layer was formed on the buffer layer using PC 60 BM, and a MoO 3 layer was formed on the photoactive layer.
  • a second electrode was formed using Ag to manufacture a solar cell.
  • FIG. 2 shows optical characteristics of the electrode buffer layer prepared according to the above embodiment. Specifically, FIG. 2 shows the light condensing characteristics due to Ag particles in the electrode buffer layer, and it can be seen that the light having the maximum wavelength for condensing is around 450 nm wavelength. More specifically, FIG. 2 shows that blue-based visible light resonates with free electrons of Ag nanoparticles contained in a ZnO metal oxide matrix, and thus the electromagnetic wave density of visible light is increased around Ag nanoparticles, thereby reducing the light absorbing ability of the photoactive layer. It shows what can be improved.
  • V oc denotes an open voltage
  • J sc denotes a short circuit current
  • FF denotes a fill factor
  • PCE denotes an energy conversion efficiency.
  • the open-circuit and short-circuit currents are the X- and Y-axis intercepts in the four quadrants of the voltage-current density curve, respectively. The higher these two values, the higher the efficiency of the solar cell.
  • the fill factor is the area of the rectangle drawn inside the curve divided by the product of the short circuit current and the open voltage. By dividing these three values by the intensity of the emitted light, the energy conversion efficiency can be obtained, and higher values are preferable.
  • the solar cell according to the embodiment shows excellent efficiency compared to the solar cell according to the comparative example.
  • the solar cell according to the embodiment improves the current density by improving the light absorption capacity of the photoactive layer due to the light condensing effect of the Ag nanoparticles, the conductivity of the buffer layer is improved by the Ag nanoparticles Since the decrease in current density due to the voltage is small, it can be confirmed that the charging rate is large.

Abstract

L'invention concerne une cellule solaire et un procédé de fabrication de celle-ci.
PCT/KR2015/004268 2014-04-30 2015-04-28 Cellule solaire et son procédé de fabrication WO2015167230A1 (fr)

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