WO2018186542A1 - Hole transport material and photoelectric element comprising same - Google Patents

Hole transport material and photoelectric element comprising same Download PDF

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WO2018186542A1
WO2018186542A1 PCT/KR2017/009997 KR2017009997W WO2018186542A1 WO 2018186542 A1 WO2018186542 A1 WO 2018186542A1 KR 2017009997 W KR2017009997 W KR 2017009997W WO 2018186542 A1 WO2018186542 A1 WO 2018186542A1
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hole transport
poly
transport material
transport layer
layer
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PCT/KR2017/009997
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French (fr)
Korean (ko)
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이슬기
이정현
박현수
임종찬
니콜라스제이로빈
와트에이알앤드류
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대주전자재료 주식회사
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
    • H01L31/035218—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions

Definitions

  • [1] relates to hole transport materials and photoelectric devices comprising them.
  • [2] solar cells are typical for converting them into electrical energy using light energy
  • Solar cells are first generation solar cells containing crystalline and polycrystalline silicon systems, second generation solar cells including organic solar cells, dye-sensitized solar cells, and compound semiconductor thin film solar cells, and third generation solar cells including quantum dots. Can be divided into batteries
  • the quantum dot is characterized by a single material absorbing wavelengths above the bandgap in all areas, and a low bandgap through quantum confinement to a size below the bohr radius.
  • the band gap of the bulk material can be easily controlled.
  • the quantum dots can easily be separated into electrons and holes due to the high dielectric constant, and a single photon generates a large number of excitons.
  • the solution process can be implemented as a low cost process.
  • An embodiment of the present invention provides a photoelectric conversion efficiency (PCE) of a photovoltaic device such as a solar cell.
  • PCE photoelectric conversion efficiency
  • An object is to provide a hole transport material which can be improved and a photoelectric device comprising the same.
  • the photoelectric element including the hole transport material of one embodiment of the present invention can be improved in stability.
  • An embodiment of the present invention provides a hole transport material comprising a non-conductive polymer matrix; and a composite of carbon nano-nouvves and hole transport materials located in the non-conductive polymer matrix.
  • the nonconductive polymer is poly (methyl methacrylate) (poly (methyl methacrylate),
  • PMMA ethylene-vinyl acetate
  • EVA polyvinyl chloride
  • PE polyethylene
  • PC polycarbonate
  • PB polybutylene
  • the hole transport material is P3HT (poly (3-hexylthiophene)
  • Another embodiment of the present invention is a transparent electrode; located on the transparent electrode
  • An electron transport layer a photoactive layer positioned on the electron transport layer; a hole transport layer located on the photoactive layer; and a counter electrode positioned on the hole transport layer, wherein the hole transport layer comprises: a non-conductive polymer matrix; and the non-conductive
  • a photoelectric device comprising a composite of carbon nanotubes and hole transport materials located in a polymer matrix.
  • the non-conductive polymer is poly (methyl methacrylate) (PMMA), ethylene-vinyl acetate (EVA), polyvinyl chloride (PVC), polyethylene (polyethylene, PE),
  • PC polycarbonate
  • PB polybutylene
  • the hole transport material is P3HT (poly (3-hexylthiophene)
  • the carbon nanotubes may be selected from single wall carbon nanotubes,
  • the photoactive layer may be a quantum dot layer.
  • the quantum dot is CdS, CdSe, CdTe, PbS, PbSe, PbS x S ei . x (0 ⁇ x ⁇ l), Bi 2 S 3 , Bi 2 Se 3 , InP, InCuS 2 , In (CuGa) Se 2 , Sb 2 S 3 , Sb 2 Se 3 , SnS x (l ⁇ x ⁇ 2) , NiS, CoS, FeS x (l ⁇ x ⁇ 2), In 2 S 3 , MoS, MoSe, or combinations thereof.
  • the quantum dot may include an inorganic ligand on the surface.
  • the inorganic ligand may be Iodide.
  • the electron transport layer may include Ti0 2 , Sn0 2 , ZnO, W0 3 , Nb 2 0 5 , TiSr0 3 , ln 2 0 3 , or a combination thereof.
  • the thickness of the hole transport layer may be 40 nm or more and 200 nm or less.
  • the thickness of the photoactive layer may be 150 nm or more and 300 nm or less.
  • the hole transport material according to one embodiment of the present invention has excellent selective transport ability for holes formed in the photoactive layer of a solar cell photovoltaic device, thereby improving the photoelectric conversion efficiency of the photoelectric device. Can be improved.
  • Absorption capacity may be improved, and stability of the photoelectric device including the same may be improved.
  • FIG. 1 is a schematic diagram of a solar cell of one embodiment of the present invention.
  • FIG 3 shows the surface of the SWNT / P3HT solution-drop coated surface during the manufacturing process of the embodiment.
  • FIG. 5 is light absorption measurement data of solar cells of Examples and Comparative Examples.
  • parts such as layers, membranes, areas, and plates are “on” or “on” other parts.
  • An embodiment of the present invention provides a hole transport material comprising a nonconductive polymer matrix; and a composite of carbon nano-nouvves and hole transport materials located in the nonconductive polymer matrix.
  • an optoelectronic device including the same is provided.
  • the photoelectric device 100 is specifically, a transparent electrode 20 as illustrated in FIG. 1; an electron transport layer positioned on the transparent electrode 20.
  • a photoactive layer 40 positioned on the electron transport layer 30; a hole transport layer 50 located on the photoactive layer 40; and a counter electrode disposed on the hole transport layer 50; 60); and the hole transport layer 50 may include the hole transport material.
  • the photoelectric device 100 may be a solar cell, but is not limited thereto.
  • Various photovoltaic elements 100 other than batteries may be used.
  • a case where the photovoltaic element 100 is a solar cell will be described.
  • the composite of carbon nanotubes and hole transport material is carbon nanotubes and
  • the hole transport material is uniformly dispersed in the non-conductive polymer matrix
  • the hole transport material may be in the form or specifically the form in which the hole transport material is wrapped around the carbon nano-lloves, but is not limited to such a form.
  • the carbon nano-rloves and the hole transport material form a complex, the complexes are incorporated into the matrix.
  • a hole transport path can be formed, and carbon nanotubes are thought to contribute to the selective transport of holes.
  • Electron Reference Energy Band Diagram The energy level of each layer (transparent electrode, electron transport layer, photoactive layer, hole transport layer, counter electrode) constituting the state-positive cell affects the spontaneous separation and spontaneous movement of photoelectrons and light holes. remind
  • the matching of energy levels of these layers can be improved, thereby improving the selective transfer efficiency of the holes created in the photoactive layer 40.
  • the short-circuit current density of the circuit can be significantly improved, the photoelectric conversion efficiency (PCE) can be improved significantly, the open voltage of the solar cell is improved, and the life time of the carrier including electrons and holes is increased. The recombination of electrons and holes decreases,
  • the hole transport layer 50 may improve light absorption through reinforcement interference with the photoactive layer 40.
  • the hole transport layer 50 may be formed by the physical structure formed by the hole transport layer 50 including carbon nanotubes.
  • the carbon nano-lube in the hole transport layer 50 can scatter the light to extend the light path in the solar cell. As a result, the light absorption efficiency can be improved. Intra-cell travel path of incident light increases, the amount of reflected light out of the cell decreases, and the light absorption rate may increase.
  • the hole transport layer 50 comprises a non-conductive polymer matrix
  • the non-conductive polymer is an electrically insulating polymer, poly (methyl methacrylate) (PMMA), ethylene-vinyl acetate (EVA), polyvinyl chloride (polyvinyl chloride). , PVC), Polyethylene (polyethylene, PE), polycarbonate (PC), polybutylene (PB), or a combination of these; more specifically, it may be PMMA, but not limited to Other polymer matrices can be employed as long as the above-described effects can be achieved by having a matrix-like property that can disperse the composite of carbon nanotubes and hole transport materials inside.
  • the hole transport material may be an organic hole transport material, and specifically, may be a thiophene-based organic material. More specifically, P3HT (poly (3-hexylthiophene)),
  • the hole transport material is a hole transport function It is possible, but not limited to, to employ other organic hole transport materials that can be used.
  • the carbon nano-lube may be a multi-wall carbon nanotube
  • MWCNTs or single wall carbon nanotubes (SWCNTs), but is not limited to this, although it may be desirable that they are single wall carbon nanotubes. This is because of the metallic and p-type semiconductor properties due to the symmetry of the two-dimensional carbon lattice.
  • the hole transport layer 50 is formed on the photoactive layer 40, carbon nanotubes, and the like.
  • It can be formed by applying a precursor solution containing a hole transport material, followed by application and drying of a non-conductive polymer solution.
  • the solvent of the precursor solution can be appropriately employed depending on the type of hole transport material used. If the hole transport material is PEDOT: PSS, a polar solvent containing water can be used. If the hole transport material is P3AT, a nonpolar solvent such as toluene, chlorobenzene, or chloroform can be used to prepare the precursor solution. In polymeric polymer solutions, chlorobenzene can be used as an example solvent when the non-conductive polymer is PMMA.
  • the precursor solution is coated with a composite of carbon nanotubes and hole transport materials.
  • the coating of the above-mentioned nonconductive polymer solution is conventional.
  • Processes such as printing, doctor blades and Langmuir Blodgett can be used, but are not limited to this.
  • the thickness of the hole transport layer 50 may be a thickness in which the photoactive layer 40 and the counter electrode 60 are physically and safely separated, and smooth hole transfer is performed.
  • the hole transport layer 50 may be formed.
  • the thickness can be 40 nm to 200 nm.
  • the photoactive layer 40 may be a quantum dot layer.
  • the photoactive layer 40 may include a hole transport material according to an embodiment of the present invention. The photoelectric conversion efficiency can be improved.
  • the quantum dot is CdS, CdSe, CdTe, PbS, PbSe, PbS x Se,. x (0 ⁇ x ⁇ l), Bi 2 S 3 , Bi 2 Se 3 , InP, InCuS 2 , In (CuGa) Se 2 , Sb 2 S 3 , Sb 2 Se 3 , SnS x (l ⁇ x ⁇ 2) , NiS, CoS, FeS x (l ⁇ x ⁇ 2), In 2 S 3 , MoS, MoSe, or a combination thereof, but may not be limited thereto.
  • the element selected from group 13 may be a doped material.
  • the quantum dot may further include an oleic acid or an oleyamine-bound ligand which acts as a surfactant on the surface to secure a stable solvent dispersed phase of the quantum dot.
  • the ligand is conductive. Since the quantum point can be used as a short-length ligand-ligand substituted, the contact resistance between the quantum points can be reduced.
  • the quantum dot may include an inorganic iodide ligand on the surface. By including the iodide ligand, the mobility of the carrier is improved. As a result, the battery characteristics of the solar cell may be improved.
  • the type of ligand is not limited thereto.
  • the quantum dots more specifically include PbS containing iodide ligands on the surface.
  • It can be a quantum dot, but it is not limited to it.
  • PbS quantum dots containing iodide ligands can be prepared by subjecting ligand exchange reactions to quantum dots on which organic ligands, such as oleate, have been formed.
  • Ligand-formed PbS quantum dots can be prepared by mixing a methylammonium iodide solution. A solution containing the surface-treated quantum dots is then applied to the electron transport layer 30 and dried.
  • Quantum dot layer can be formed by application of conventional coating methods, such as spin coating, dip coating, spray coating, dropping, Processes such as dispensing, printing, doctor blades, and Tangmuk Blodgett can be used, but are not limited to these.
  • the thickness of the photoactive layer 40 may be 150 nm or more and 300 nm or less, but is not limited thereto.
  • the electron transport layer 30 may include Ti0 2 , Sn0 2 , ZnO, W0 3 , Nb 2 0 5 , TiSr0 3 , ln 2 0 3, or
  • It may be a combination of these or a substance doped with an element selected from Group 15 of the periodic table, but it is not limited thereto.
  • the electron transport layer 30 may be formed by coating and drying a precursor solution containing the material on the transparent electrode.
  • the coating may be performed by a conventional coating method. For example, spin coating may be performed. coating, dip coating, spray coating, dropping, dispensing, printing, Processes such as doctor blades and Langmuir Blodgett can be used, but are not limited to these.
  • the thickness of the electron transport layer 30 may be 50 nm to 150 nm in consideration of the efficiency of the solar cell, but is not limited thereto.
  • a solar cell of one embodiment of the present invention is provided at the bottom of the transparent electrode 20.
  • the transparent substrate 10 may further include a transparent substrate 10 positioned thereon.
  • the transparent substrate 10 serves as a support for supporting a structure on the substrate and may be used as long as the substrate transmits light.
  • a glass substrate may be a rigid substrate.
  • Polyethylene terephthalate, polyimide which include, as a flexible substrate
  • Triacetyl cellulose Triacetyl cellulose, polyether sulfone substrate, and the like.
  • the transparent electrode 20 disposed on the transparent substrate includes: indium tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, May contain, but is not limited to, indium zinc oxide.
  • the counter electrode 60 may include platinum, gold, aluminum, silver, titanium, cream, nickel, or the like, and may have a single layer of the same metal or a multi-layer structure including different metals. However, this is not a limitation.
  • the counter electrode 60 may be formed on the hole transport layer 50 through a deposition method.
  • the counter electrode 60 may be formed by physical deposition or chemical deposition, and may be formed by thermal deposition.
  • the present invention is not limited thereto, and a patterning process may be added depending on the desired shape of the electrode.
  • the solution mixed with bis (trimethylsilyl) sude was added and stirred, followed by cooling at room temperature.
  • the prepared PbS quantum dots were recovered by centrifugation, and the washing solution was washed. Acetone, nucleic acid, and two methanols were used in chronological order. The final concentration was 50 mg / ml. Dispersed in octane.
  • N, N-di methylformamide DMF
  • octane N, N-di methylformamide
  • three washes were performed by centrifugation using octane. After the last wash, 0.2 mL of octane was removed. After replacing the solvent with luene, centrifugation was performed again, and the obtained nanoparticle precipitate was dried in a nitrogen atmosphere. Then, 160 uL of butylamine was added to dissolve it.
  • the prepared nanoparticles were washed twice with centrifugation using methanol, and dissolved in a mixture of 5 ml of chloroform and 5 ml of methanol.
  • P3HT was added to chlororobenzene to prepare a solution at a concentration of 0.6 jng / ml, and 2.5 mg of SWCNT was added. Ultra-sonication was performed for 10 minutes while cooling the solution. Thereafter, 5 ml of chlororobenzene was added. 8 minutes at 10000 g
  • the supernatant was recovered using a centrifuge. Toluene 10 ml was added to the collected solution and left at 70 ° C. for 30 minutes. The solution was removed, centrifuged at 16000 g for 4 minutes, and the precipitate was recovered. Repeated. Dispersed in Chloroform at a ratio of 1: 8 to the weight of the final precipitate. The solution was used after 10 minutes of ultrasonication at 10% power.
  • the PbS mixture prepared in (2) of Preparation Example was spin-coated at 2500 rpm for 90 seconds thereon, and then dried at 100 ° C. for 10 minutes to form a quantum dot layer of 220 nm.
  • a solar cell was manufactured in the same manner as in the above example, except that a hole transport layer was formed without using a SWNT P3HT solution.
  • SEM scanning electron microscope
  • FIG 3 shows the surface of the SWNT / P3HT solution-drop coated surface during the manufacturing process of the embodiment.
  • the transmission electron microscope (TEM) photograph shows that the SWNT / P3HT complex is uniformly coated on the quantum dot layer. Afterwards, the SWNT / P3HT complex is uniformly distributed on the PMMA through spin coating and drying of the PMMA solution.
  • the electrical characteristics of the solar cells of the above examples and comparative examples were measured. Specifically, the short circuit current density (Jsc), the open circuit voltage (Voc), the fill factor (FF), and
  • Photoelectric conversion efficiency was measured and the measurements were made under standard conditions (100 mW / Cm 2 ).
  • FIG. 4 shows the results of the electrical characteristics measurement.
  • the photoelectric conversion efficiency is compared with the comparative example by the remarkable improvement of the short-circuit current density and the open-circuit voltage in the embodiment with the hole transport layer of the present invention. It can be seen that the improvement is about 1.5 times.
  • the absorption rate of the embodiment is improved in the entire wavelength region.
  • the solar cell of Examples and Comparative Examples was operated in an ambient air without humidity control for 35 days and the change of electrical characteristics was measured.
  • the measurement method was the same as in Example 2. Is shown in Figure 6.
  • 'control' is a comparative example, and 'SWNT' represents an embodiment.
  • the solar cell of the embodiment maintains stable electrical characteristics for 35 days compared to the comparative example.
  • photoelectric element 10 substrate 20: transparent electrode

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Abstract

The present invention relates to a hole transport material and a photoelectric element comprising same, and may provide a hole transport material and a photoelectric element comprising same, the hole transport material comprising: a non-conductive polymer matrix; and a composite of a hole transport substance and a carbon nanotube located in the non-conductive polymer matrix.

Description

명세서  Specification
발명의명칭:정공수송재료및이를포함하는광전소자 기술분야  Name of invention: hole transport material and photoelectric device technology including the same
[1] 정공수송재료및이를포함하는광전소자에관한것이다.  [1] relates to hole transport materials and photoelectric devices comprising them.
배경기술  Background
[2] 태양전지는광에너지를이용하여 전기에너지로변환시켜주는대표적인  [2] solar cells are typical for converting them into electrical energy using light energy
광전소자이다.태양전지는결정질및다결정질실리콘계를포함하는 1세대 태양전지，유기태양전지，염료감웅태양전지 및화합물반도체박막태양전지를 포함하는 2세대태양전지，그리고양자점을포함하는 3세대태양전지로구분될 수있다ᅳ  Solar cells are first generation solar cells containing crystalline and polycrystalline silicon systems, second generation solar cells including organic solar cells, dye-sensitized solar cells, and compound semiconductor thin film solar cells, and third generation solar cells including quantum dots. Can be divided into batteries
[3] 이중,양자점태양전지는양자점의소재특성으로인해최근많은연구가  [3] Due to the material properties of quantum dots, dual and quantum dot solar cells have recently been studied.
이루어지고있다.양자점 (quantum dot)은단일물질이밴드갭이상의파장을 전영역에서흡수하는특징을가지고있으며，보어반지름 (bohr radius)이하의 크기로양자구속화 (quantum confinement)를통해낮은밴드갭을가지는벌크 물질의 밴드갭을쉽게제어할수있다.또한，양자점은높은유전상수로인해 생성된액시톤이쉽게전자와정공으로분리될수있으며，하나의광자 (photon)가 다수의 엑시톤을생성하는다증여기자 (MEG, multiple exciton generation)의 생성이가능할뿐더러，용액공정올통해저가공정으로구현가능하다.  The quantum dot is characterized by a single material absorbing wavelengths above the bandgap in all areas, and a low bandgap through quantum confinement to a size below the bohr radius. In addition, the band gap of the bulk material can be easily controlled. In addition, the quantum dots can easily be separated into electrons and holes due to the high dielectric constant, and a single photon generates a large number of excitons. In addition to the generation of multiple exciton generation (MEG), the solution process can be implemented as a low cost process.
[4] 그러나현재까지개시된양자점 태양전지의경우에는양자점간의결정립계 문제등으로인하여발생되는전하들이손실및왜곡되는현상때문에  [4] However, in the case of quantum point solar cells, which have been disclosed so far, charges caused by grain boundary problems between quantum points are lost and distorted.
광전변환효율이상대적으로낮다는문제점이 있었다.이에，양자점 태양전지의 광전변환효율을높이기위한연구가지속적으로이루어지고있는실정이다. 발명의상세한설명  There is a problem that the photoelectric conversion efficiency is relatively low, and research into the quantum dot solar cell to improve the photoelectric conversion efficiency is continuously conducted. Detailed description of the invention
기술적과제  Technical task
[5] 본발명의 일구현예는,태양전지등광전소자의광전변환효율 (PCE)를  [5] An embodiment of the present invention provides a photoelectric conversion efficiency (PCE) of a photovoltaic device such as a solar cell.
향상시킬수있는정공수송재료및이를포함하는광전소자를제공하고자한다.  An object is to provide a hole transport material which can be improved and a photoelectric device comprising the same.
[6] 나아가，본발명의 일구현예의정공수송재료를포함하는광전소자는안정성이 향상될수있다.  [6] Furthermore, the photoelectric element including the hole transport material of one embodiment of the present invention can be improved in stability.
과제해결수단  Task solution
[7] 본발명의 일구현예는,비전도성고분자매트릭스;및상기 비전도성고분자 매트릭스내위치하는탄소나노류브와정공수송물질의복합체；를포함하는 것인정공수송재료를제공한다.  [7] An embodiment of the present invention provides a hole transport material comprising a non-conductive polymer matrix; and a composite of carbon nano-nouvves and hole transport materials located in the non-conductive polymer matrix.
[8] 상기 비전도성고분자는，폴리 (메틸메타크릴레이트) (poly(methyl methacrylate), [8] The nonconductive polymer is poly (methyl methacrylate) (poly (methyl methacrylate),
PMMA),에틸렌 -비닐아세테이트 (ethylene-vinyl acetate, EVA),폴리비닐 클로라이드 (polyvinyl chloride, PVC),폴리에틸렌 (polyethylene, PE), PMMA), ethylene-vinyl acetate (EVA), polyvinyl chloride (PVC), polyethylene (polyethylene, PE),
폴리카보네이트 (polycarbonate, PC),폴리부틸렌 (Polybutylene, PB),또는이들의 혼합물인것일수있다. Polycarbonate (PC), polybutylene (PB), or their It may be a mixture.
[9] 상기정공수송물질은, P3HT(poly(3-hexylthiophene)), [9] The hole transport material is P3HT (poly (3-hexylthiophene)),
P3AT(poly(3-alkylthiophene)), P30T(poly(3-octylthiophene), PEDOT:PSS  Poly (3-alkylthiophene) (P3AT), poly (3-octylthiophene), PEDOT: PSS
(Poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate)),또는이들의혼합물인 것일수있다.  (Poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate)), or a mixture thereof.
[10] 상기탄소나노류브는，단일벽탄소나노튜브 (single wall carbon nanotube,  [10] The carbon nano rebe, single wall carbon nanotube,
SWCNT)인것일수있다.  SWCNT).
[11] 본발명의다른일구현예는,투명전극;상기투명전극상에위치하는  [11] Another embodiment of the present invention is a transparent electrode; located on the transparent electrode
전자수송층;상기전자수송층상에위치하는광활성층;상기광활성층상에 위치하는정공수송층;및상기정공수송층상에위치하는대향전극을포함하고， 상기정공수송층은，비전도성고분자매트릭스;및상기비전도성고분자 매트릭스내위치하는탄소나노튜브와정공수송물질의복합체；를포함하는 것인광전소자를제공한다.  An electron transport layer; a photoactive layer positioned on the electron transport layer; a hole transport layer located on the photoactive layer; and a counter electrode positioned on the hole transport layer, wherein the hole transport layer comprises: a non-conductive polymer matrix; and the non-conductive Provided is a photoelectric device comprising a composite of carbon nanotubes and hole transport materials located in a polymer matrix.
[12] 상기비전도성고분자는，폴리 (메틸메타크릴레이트) (poly(methyl methacrylate), PMMA),에틸렌-비닐아세테이트 (ethylene-vinyl acetate, EVA),폴리비닐 클로라이드 (polyvinyl chloride, PVC),폴리에틸렌 (polyethylene, PE),  [12] The non-conductive polymer is poly (methyl methacrylate) (PMMA), ethylene-vinyl acetate (EVA), polyvinyl chloride (PVC), polyethylene (polyethylene, PE),
폴리카보네이트 (polycarbonate, PC),폴리부틸렌 (Polybutylene, PB),또는이들의 흔합물인것일수있다.  It may be polycarbonate (PC), polybutylene (PB), or a combination thereof.
[13] 상기정공수송물질은， P3HT(poly(3-hexylthiophene)),  [13] The hole transport material is P3HT (poly (3-hexylthiophene)),
P3AT(poly(3-alkylthiophene)), P30T(poly(3-octylthiophene), PEDOT:PSS  Poly (3-alkylthiophene) (P3AT), poly (3-octylthiophene), PEDOT: PSS
(Poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate)),또는이들의혼합물인 것일수있다.  (Poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate)), or a mixture thereof.
[14] 상기탄소나노튜브는,단일벽탄소나노류브 (single wall carbon nanotube,  [14] The carbon nanotubes may be selected from single wall carbon nanotubes,
SWCNT)인것일수있다.  SWCNT).
[15] 상기광활성층은，양자점층인것일수있다. The photoactive layer may be a quantum dot layer.
[16] 상기양자점은， CdS, CdSe, CdTe, PbS, PbSe, PbSxSei.x(0<x<l), Bi2S3, Bi2Se3, InP, InCuS2, In(CuGa)Se2, Sb2S3, Sb2Se3, SnSx(l<x<2), NiS, CoS, FeSx(l<x<2), In2S3, MoS , MoSe,또는이들의흔합물을포함하는것일수있다. [16] The quantum dot is CdS, CdSe, CdTe, PbS, PbSe, PbS x S ei . x (0 <x <l), Bi 2 S 3 , Bi 2 Se 3 , InP, InCuS 2 , In (CuGa) Se 2 , Sb 2 S 3 , Sb 2 Se 3 , SnS x (l <x <2) , NiS, CoS, FeS x (l <x <2), In 2 S 3 , MoS, MoSe, or combinations thereof.
[17] 상기양자점은,표면에무기리간드를포함하는것일수있다.  The quantum dot may include an inorganic ligand on the surface.
[18] 상기무기리간드는， Iodide인것일수있다.  [18] The inorganic ligand may be Iodide.
[19] 상기 전자수송층은， Ti02, Sn02, ZnO, W03, Nb205, TiSr03, ln203,또는이들의 흔합물을포함하는것일수있다. The electron transport layer may include Ti0 2 , Sn0 2 , ZnO, W0 3 , Nb 2 0 5 , TiSr0 3 , ln 2 0 3 , or a combination thereof.
[20] 상기정공수송층의두께는， 40nm이상및 200nm이하인것일수있다. The thickness of the hole transport layer may be 40 nm or more and 200 nm or less.
[21] 상기광활성층의두께는， 150nm이상및 300nm이하인것일수있다. [21] The thickness of the photoactive layer may be 150 nm or more and 300 nm or less.
발명의효과  Effects of the Invention
[22] 본발명의일구현예의정공수송재료는,태양전지둥광전소자의광활성층에서 형성된정공에대한선택적수송능력이뛰어나，광전소자의광전변환효율을 향상시킬수있다. [22] The hole transport material according to one embodiment of the present invention has excellent selective transport ability for holes formed in the photoactive layer of a solar cell photovoltaic device, thereby improving the photoelectric conversion efficiency of the photoelectric device. Can be improved.
[23] 또한,본발명의일구현예의정공수송재료의독특한형태에의하여，빛의  [23] In addition, due to the unique form of the hole transport material of one embodiment of the present invention,
흡수능이향상될수있으며,이를포함하는광전소자의안정성이향상될수 있다.  Absorption capacity may be improved, and stability of the photoelectric device including the same may be improved.
도면의간단한설명  Brief description of the drawings
[24] 도 1은본발명의일구현예의 태양전지의모식도이다. 1 is a schematic diagram of a solar cell of one embodiment of the present invention.
[25] 도 2는실시예에서제조된태양전지의주사전자현미경사진이다. 2 is a scanning electron micrograph of the solar cell manufactured in the embodiment.
[26] 도 3는실시예의제조과정중 SWNT/P3HT용액이드랍코팅된표면의 3 shows the surface of the SWNT / P3HT solution-drop coated surface during the manufacturing process of the embodiment.
투과전자현미경사진이다.  Transmission electron micrograph.
[27] 도 4는실시예및비교예의 태양전지의 전기적특성측정데이터이다. 4 shows electrical characteristics measurement data of solar cells of Examples and Comparative Examples.
[28] 도 5는실시예및비교예의 태양전지의빛흡수율측정 데이터이다. FIG. 5 is light absorption measurement data of solar cells of Examples and Comparative Examples. FIG.
[29] 도 6은실시예및비교예의태양전지의안정성평가데이터이다. 6 shows stability evaluation data of solar cells of Examples and Comparative Examples.
발명의실시를위한형태  Mode for Carrying Out the Invention
[30] 다른정의가없다면본명세서에서사용되는모든용어 (기술및과학적용어를 포함)는본발명이속하는기술분야에서통상의지식을가진자에게공통적으로 이해될수있는의미로사용될수있을것이다.명세서 전체에서어떤부분이 어떤구성요소를 "포함"한다고할때，이는특별히반대되는기재가없는한다른 구성요소를제외하는것이아니라다른구성요소를더포함할수있는것을 의미한다.또한단수형은문구에서특별히언급하지않는한복수형도포함한다.  [30] Unless otherwise defined, all terms used in this specification (including technical and scientific terms) may be used as meanings that may be commonly understood by persons of ordinary knowledge in the technical field to which this invention belongs. When a part of the term "contains" a component, it means that it is possible to include other components, not to exclude other components that do not have a special mention. In addition, the singular is not specifically mentioned in a phrase. Unless otherwise included
[31] 본명세서에서소개되는도면들은당업자에게본발명의사상이충분히 전달될 수있도록하기위해예로서제공되는것이다.따라서，본발명은이하제시되는 도면들에한정되지않고다른형태로구체화될수도있으며，이하제시되는 도면들은본발명의사상을명확히하기위해과장되어도시될수있다.또한 명세서전체에걸쳐서동일한참조번호들은동일한구성요소들을나타낸다.  [31] The drawings introduced in this specification are provided as examples to ensure that the spirit of the present invention is fully communicated to those skilled in the art. Thus, the present invention may be embodied in other forms, not limited to the drawings presented below. In addition, the drawings presented below may be exaggerated to clarify the spirit of the present invention. Throughout the specification the same reference numerals represent the same components.
[32] 본명세서에서층，막,영역，판등의부분이다른부분 "위에"또는 "상에"  [32] In this specification, parts such as layers, membranes, areas, and plates are "on" or "on" other parts.
있다고할때，이는다른부분 "바로위에"있는경우뿐아니라그중간에또다른 부분이 있는경우도포함한다.  If so, this includes not only other parts "directly above" but also other parts in between.
[33]  [33]
[34] 본발명의 일구현예는，비전도성고분자매트릭스;및상기 비전도성고분자 매트릭스내위치하는탄소나노류브와정공수송물질의복합체；를포함하는 것인정공수송재료를제공하며，본발명의다른일구현예로，이를포함하는 광전소자를제공한다.상기광전소자 (100)는구체적으로，도 1에 예시된바와 같이투명전극 (20);상기투명전극 (20)상에위치하는전자수송층 (30);상기 전자수송층 (30)상에위치하는광활성층 (40);상기광활성층 (40)상에위치하는 정공수송층 (50);및상기정공수송층 (50)상에위치하는대향전극 (60);을 포함하고，상기정공수송층 (50)이상기정공수송재료를포함하는것일수있다.  [34] An embodiment of the present invention provides a hole transport material comprising a nonconductive polymer matrix; and a composite of carbon nano-nouvves and hole transport materials located in the nonconductive polymer matrix. In another embodiment, an optoelectronic device including the same is provided. The photoelectric device 100 is specifically, a transparent electrode 20 as illustrated in FIG. 1; an electron transport layer positioned on the transparent electrode 20. A photoactive layer 40 positioned on the electron transport layer 30; a hole transport layer 50 located on the photoactive layer 40; and a counter electrode disposed on the hole transport layer 50; 60); and the hole transport layer 50 may include the hole transport material.
[35] 상기광전소자 (100)는,태양전지일수있으나，이에한정하는것은아니고태양 전지 이외의다양한광전소자 (100)일수있다.이하,상기광전소자 (100)가 태양전지인경우를예로들어설명한다. The photoelectric device 100 may be a solar cell, but is not limited thereto. Various photovoltaic elements 100 other than batteries may be used. Hereinafter, a case where the photovoltaic element 100 is a solar cell will be described.
[36] 상기탄소나노튜브와정공수송물질의복합체는，탄소나노튜브및  [36] The composite of carbon nanotubes and hole transport material is carbon nanotubes and
정공수송물질이상기비전도성고분자매트릭스에균일하게분산된  The hole transport material is uniformly dispersed in the non-conductive polymer matrix
형태이거나，구체적으로상기정공수송물질이탄소나노류브를감싸고 (wrapped) 있는형태일수있다.다만，이러한형태에한정하는것은아니다.이와같이 탄소나노류브및정공수송물질이복합체를이루면서,복합체들이매트릭스 내에분산됨에따라정공수송경로가형성될수있고，탄소나노튜브가정공의 선택적인전달향상에기여하는것으로생각된다.  It may be in the form or specifically the form in which the hole transport material is wrapped around the carbon nano-lloves, but is not limited to such a form. As such, the carbon nano-rloves and the hole transport material form a complex, the complexes are incorporated into the matrix. As it is dispersed, a hole transport path can be formed, and carbon nanotubes are thought to contribute to the selective transport of holes.
[37] 전자기준에너지밴드다이어그램상태양전지를구성하는각층 (투명 전극, 전자수송층,광활성층，정공수송층,대향전극)의에너지 레벨은광전자및 광정공의자발적분리및자발적이동에영향을미친다.이때상기  [37] Electron Reference Energy Band Diagram The energy level of each layer (transparent electrode, electron transport layer, photoactive layer, hole transport layer, counter electrode) constituting the state-positive cell affects the spontaneous separation and spontaneous movement of photoelectrons and light holes. remind
정공수송재료를정공수송층 (50)으로포함하는태양전지에서 ,이러한각층의 에너지 레벨의매칭성이향상되어，광활성층 (40)에서만들어진정공의선택적인 전달효율이향상될수있다.이에,태양전지의단락전류밀도가현저히 향상되어，광전변환효율 (PCE)이현저히향상될수있다.또한태양전지의 개방 전압이향상되고，전자및정공을포함하는캐리어 (carrier)의수명 (life time)이 증가되어,전자와정공의재결합 (recombination)이감소하고，이는곧  In solar cells comprising a hole transport material as the hole transport layer 50, the matching of energy levels of these layers can be improved, thereby improving the selective transfer efficiency of the holes created in the photoactive layer 40. The short-circuit current density of the circuit can be significantly improved, the photoelectric conversion efficiency (PCE) can be improved significantly, the open voltage of the solar cell is improved, and the life time of the carrier including electrons and holes is increased. The recombination of electrons and holes decreases,
단락전류밀도의향상으로이어질수있다.  This can lead to an improvement in short circuit current density.
[38] 또한,상기정공수송층 (50)은광활성층 (40)과의보강간섭을통해광흡수율을 향상시킬수있다.나아가，정공수송층 (50)이탄소나노튜브를포함함에따라 형성되는물리적인구조에의해,광흡수율이향상되어광전변환효율이향상될 수있다.구체적으로，정공수송층 (50)내탄소나노류브는빛을산란 (scattering) 시켜태양전지내에서빛의이동경로를확장시킬수있다.그결과，입사된광의 전지내이동경로가증가하고,전지밖으로반사되는양이감소하며， 광흡수율이증가할수있다.  In addition, the hole transport layer 50 may improve light absorption through reinforcement interference with the photoactive layer 40. Further, the hole transport layer 50 may be formed by the physical structure formed by the hole transport layer 50 including carbon nanotubes. In this case, the carbon nano-lube in the hole transport layer 50 can scatter the light to extend the light path in the solar cell. As a result, the light absorption efficiency can be improved. Intra-cell travel path of incident light increases, the amount of reflected light out of the cell decreases, and the light absorption rate may increase.
[39] 상기 정공수송층 (50)이비전도성고분자매트릭스를포함함에따라,태양  [39] As the hole transport layer 50 comprises a non-conductive polymer matrix,
전지의구동안정성이향상될수있다.태양전지로의수분또는산소의유입은 양자점 태양전지의경우광활성층 (50)인양자점층내양자의  Qualitative properties can be improved over the life of the cell. The influx of moisture or oxygen to the solar cell is due to the quantum dot layer in the quantum dot layer,
나노결정 (nanocrystal)표면및표면의 리간드에표면결함을일으킬수있다. 이러한표면결함에따라캐리어의재결합 (recombination)이유발되는등의 문제가발생하여，전지효율이 저하될수있다.그러나，비전도성고분자 매트릭스를정공수송층 (50)에포함함에따라,수분또는산소의유입이차단될 수있다.이에，전지의구동안정성이향상되어，장기간높은효율을유지할수 있는고수명특성을나타낼수있다.  Surface defects can occur on the surface of nanocrystals and on ligands on the surface. Such surface defects may cause problems such as carrier recombination, which may reduce battery efficiency. However, incorporation of a non-conductive polymer matrix into the hole transport layer 50 may lead to the influx of moisture or oxygen. This can be blocked, which improves battery life, resulting in high lifespan characteristics that can maintain high efficiency over long periods of time.
[40] 상기비전도성고분자는，전기절연성고분자로서，폴리 (메틸메타크릴레이트) (poly(methyl methacrylate), PMMA),에틸렌-비닐아세테이트 (ethylene-vinyl acetate, EVA),폴리비닐클로라이드 (polyvinyl chloride, PVC),폴리에틸렌 (polyethylene, PE),폴리카보네이트 (polycarbonate, PC),폴리부틸렌 (Polybutylene, PB),또는이들의흔합물인것일수있다.보다구체적으로는 PMMA인것일수 있다.다만，이에한정하는것은아니고,탄소나노튜브및정공수송물질의 복합체를내부에분산시킬수있는매트릭스형태의물성을가짐으로써상술한 효과를구현할수있다면，다른고분자매트릭스의채용이가능하다. [40] The non-conductive polymer is an electrically insulating polymer, poly (methyl methacrylate) (PMMA), ethylene-vinyl acetate (EVA), polyvinyl chloride (polyvinyl chloride). , PVC), Polyethylene (polyethylene, PE), polycarbonate (PC), polybutylene (PB), or a combination of these; more specifically, it may be PMMA, but not limited to Other polymer matrices can be employed as long as the above-described effects can be achieved by having a matrix-like property that can disperse the composite of carbon nanotubes and hole transport materials inside.
[41] 상기정공수송물질은，유기정공수송물질일수있으며，구체적으로는티오펜계 유기물일수있다.보다구체적으로는 P3HT(poly(3-hexylthiophene)),  [41] The hole transport material may be an organic hole transport material, and specifically, may be a thiophene-based organic material. More specifically, P3HT (poly (3-hexylthiophene)),
P3AT(poly(3-alkylthiophene)), P30T(poly(3-octylthiophene), PEDOT:PSS  Poly (3-alkylthiophene) (P3AT), poly (3-octylthiophene), PEDOT: PSS
(Poly (3 ,4-ethylenedioxythiophene)poly (styrenesulfonate)), ΞΕ 이들의혼합물일수 있다.보다구체적으로는 P3HT(!K)ly(3-hexyUhiophene)일수있다.그러나，상기 정공수송물질은정공수송기능을수행할수있는다른유기정공수송물질의 채용이가능할수있으며,이에한정하는것은아니다.  (Poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate)), ΞΕ It may be a mixture of these. More specifically, it may be P3HT (! K) ly (3-hexyUhiophene) .However, the hole transport material is a hole transport function It is possible, but not limited to, to employ other organic hole transport materials that can be used.
[42] 상기탄소나노류브는,다증벽탄소나노류브 (multi wall carbon nanotube,  [42] The carbon nano-lube may be a multi-wall carbon nanotube,
MWCNT),또는단일벽탄소나노류브 (single wall carbon nanotube, SWCNT)인 것일수있으나,이에한정하는것은아니다.다만,단일벽탄소나노튜브인것인 바람직할수있는데，이는단일벽탄소나노튜브는직경, 2차원탄소격자의 대칭성등의구조에의해금속성및 p-type반도체성질을갖기때문이다.  MWCNTs, or single wall carbon nanotubes (SWCNTs), but is not limited to this, although it may be desirable that they are single wall carbon nanotubes. This is because of the metallic and p-type semiconductor properties due to the symmetry of the two-dimensional carbon lattice.
[43] 상기 정공수송층 (50)은상기광활성층 (40)상에 ,탄소나노튜브및  The hole transport layer 50 is formed on the photoactive layer 40, carbon nanotubes, and the like.
정공수송물질을포함하는전구체용액을도포한뒤,곧이어비전도성고분자 용액을도포및건조함으로써형성할수있다.상기전구체용액의용매는 사용되는정공수송물질의종류에따라적절히 채용될수있다.예를들면， 정공수송물질이 PEDOT:PSS인경우물을포함하는극성용매를이용할수 있으며，정공수송물질이 P3AT인경우톨루엔，클로로벤젠，클로로폼과같은 무극성용매를이용하여전구체용액을제조할수있다.상기비전도성고분자 용액에서，비전도성고분자가 PMMA인경우예시적인용매로클로로벤젠을 사용할수있다.  It can be formed by applying a precursor solution containing a hole transport material, followed by application and drying of a non-conductive polymer solution. The solvent of the precursor solution can be appropriately employed depending on the type of hole transport material used. If the hole transport material is PEDOT: PSS, a polar solvent containing water can be used. If the hole transport material is P3AT, a nonpolar solvent such as toluene, chlorobenzene, or chloroform can be used to prepare the precursor solution. In polymeric polymer solutions, chlorobenzene can be used as an example solvent when the non-conductive polymer is PMMA.
[44] 상기전구체용액의코팅은,탄소나노튜브및정공수송물질의복합체가  [44] The precursor solution is coated with a composite of carbon nanotubes and hole transport materials.
균일하게분산될수있도록드랍코팅 (drop coating)방식으로코팅할수있으나, 이에한정하는것은아니다.상기비전도성고분자용액의도포는，통상적인 It can be coated by a drop coating method so that it can be uniformly dispersed, but not limited thereto. The coating of the above-mentioned nonconductive polymer solution is conventional.
' 도포방법에의할수있다.예를들어,스핀코팅 (spin coating),딥코팅 (dip coating), 스프레이코팅 (spray coating),드롭핑 (dropping),디스편！싱 (dispensing), Can be of the "method of application, for example, spin coating (spin coating), dip coating (dip coating), spray coating (spray coating), dropping (dropping), display piece! Singh (dispensing),
프린팅 (printing),닥터블레이드 (doctor blade),랭뮤어블로젯 (Langmuir Blodgett) 등의공정을이용할수있으나이에한정하는것은아니다.  Processes such as printing, doctor blades and Langmuir Blodgett can be used, but are not limited to this.
[45] 상기정공수송층 (50)의두께는,광활성층 (40)과대향전극 (60)이물리적으로 안전하게분리되며원활한정공의전달이 이루어지는두께일수있다.구체적 일 예로,정공수송층 (50)의두께는 40nm내지 200 nm일수있다.  The thickness of the hole transport layer 50 may be a thickness in which the photoactive layer 40 and the counter electrode 60 are physically and safely separated, and smooth hole transfer is performed. In one embodiment, the hole transport layer 50 may be formed. The thickness can be 40 nm to 200 nm.
[46] 상기 태양전지에서，상기광활성층 (40)은양자점층인것일수있다.이에,본 발명의 일구현예에따른정공수송재료를포함함으로써，양자점 태양전지의 광전변환효율을향상시킬수있다. In the solar cell, the photoactive layer 40 may be a quantum dot layer. The photoactive layer 40 may include a hole transport material according to an embodiment of the present invention. The photoelectric conversion efficiency can be improved.
[47] 상기 양자점은， CdS, CdSe, CdTe, PbS, PbSe, PbSxSe,.x(0<x<l), Bi2S3, Bi2Se3, InP, InCuS2, In(CuGa)Se2, Sb2S3, Sb2Se3, SnSx(l<x<2), NiS, CoS, FeSx(l≤x<2), In2S3, MoS , MoSe,또는이들의흔합물을포함하는것일수있으나，이에한정하는 것은아니다.또한,상기양자점은상기물질에주기율표상 13족에서선택되는 원소가도핑된물질일수있다. The quantum dot is CdS, CdSe, CdTe, PbS, PbSe, PbS x Se,. x (0 <x <l), Bi 2 S 3 , Bi 2 Se 3 , InP, InCuS 2 , In (CuGa) Se 2 , Sb 2 S 3 , Sb 2 Se 3 , SnS x (l <x <2) , NiS, CoS, FeS x (l≤x <2), In 2 S 3 , MoS, MoSe, or a combination thereof, but may not be limited thereto. The element selected from group 13 may be a doped material.
[48] 또한，상기양자점은양자점의안정적인용매분산상을확보하기위해표면에 계면활성제역할을하는올레산 (oleic acid),올레아민 (oleyamine)둥의리간드를 더포함할수있다.그러나，상기리간드는전도성이 없기때문에전자와정공의 이동에대해저항으로작용할수있다.이를방지하기위해，상기양자점은 길이가짧은리간드로리간드치환된것을사용할수있다.이에,양자점간의 거리를좁혀，양자점사이의접촉저항을줄일수있다.구체적으로，상기 양자점은표면에무기물질인요오드화물 (iodide)리간드를포함할수있다.상기 요오드화물 (iodide)리간드를포함함으로써,캐리어 (carrier)의이동도 (mobility)가 향상되어,태양전지의전지특성이향상될수있다.다만,리간드의종류를이에 한정하는것은아니다.  In addition, the quantum dot may further include an oleic acid or an oleyamine-bound ligand which acts as a surfactant on the surface to secure a stable solvent dispersed phase of the quantum dot. However, the ligand is conductive. Since the quantum point can be used as a short-length ligand-ligand substituted, the contact resistance between the quantum points can be reduced. Specifically, the quantum dot may include an inorganic iodide ligand on the surface. By including the iodide ligand, the mobility of the carrier is improved. As a result, the battery characteristics of the solar cell may be improved. However, the type of ligand is not limited thereto.
[49] 상기양자점은보다구체적으로표면에 iodide리간드를포함하는 PbS  [49] The quantum dots more specifically include PbS containing iodide ligands on the surface.
양자점일수있나,이에한정하는것은아니다.  It can be a quantum dot, but it is not limited to it.
[50] 상기 iodide리간드를포함하는 PbS양자점은,올레이트와같은유기 리간드가 형성된양자점을리간드교환반웅 (ligand exchange reaction)처리하여제조할수 있다.비한정적인예시로，표면에올레이트와같은유기 리간드가형성된 PbS 양자점을메틸암모니움아이오다이드 (methylammonium iodide)용액과 흔합시키는방식에의해제조될수있다.이후，상기표면처리된양자점을 포함하는용액을상기전자수송층 (30)상에도포및건조시켜 양자점층을 형성시킬수있다.도포는통상적인도포방법에의할수있다.예를들어， 스핀코팅 (spin coating),딥코팅 (dip coating),스프레이코팅 (spray coating), 드롭핑 (dropping),디스펜싱 (dispensing),프린팅 (printing),닥터블레이드 (doctor blade),탱뮤어블로젯 (Langmuk Blodgett)등의공정을이용할수있으나이에 한정하는것은아니다.  PbS quantum dots containing iodide ligands can be prepared by subjecting ligand exchange reactions to quantum dots on which organic ligands, such as oleate, have been formed. Ligand-formed PbS quantum dots can be prepared by mixing a methylammonium iodide solution. A solution containing the surface-treated quantum dots is then applied to the electron transport layer 30 and dried. Quantum dot layer can be formed by application of conventional coating methods, such as spin coating, dip coating, spray coating, dropping, Processes such as dispensing, printing, doctor blades, and Tangmuk Blodgett can be used, but are not limited to these.
[51] 상기광활성층 (40)의두께는， 150nm이상및 300nm이하인것일수있으나, 이에한정하는것은아니다.  [51] The thickness of the photoactive layer 40 may be 150 nm or more and 300 nm or less, but is not limited thereto.
[52] 상기전자수송층 (30)은, Ti02, Sn02, ZnO, W03, Nb205, TiSr03, ln203.또는 The electron transport layer 30 may include Ti0 2 , Sn0 2 , ZnO, W0 3 , Nb 2 0 5 , TiSr0 3 , ln 2 0 3, or
이들의흔합물이거나，상기물질들에주기율표상 15족에서선택되는원소가 도핑된물질일수있다.다만，이에한정하는것은아니다.  It may be a combination of these or a substance doped with an element selected from Group 15 of the periodic table, but it is not limited thereto.
[53] 상기전자수송층 (30)은해당물질을포함하는전구체용액을상기투명 전극 상에도포및건조시켜형성시킬수있다.도포는통상적인도포방법에의할수 있다.예를들어，스핀코팅 (spin coating),딥코팅 (dip coating),스프레이코팅 (spray coating),드롭핑 (dropping),디스 싱 (dispensing),프린팅 (printing), 닥터블레이드 (doctor blade),랭뮤어블로젯 (Langmuir Blodgett)등의공정을 이용할수있으나이에한정하는것은아니다. The electron transport layer 30 may be formed by coating and drying a precursor solution containing the material on the transparent electrode. The coating may be performed by a conventional coating method. For example, spin coating may be performed. coating, dip coating, spray coating, dropping, dispensing, printing, Processes such as doctor blades and Langmuir Blodgett can be used, but are not limited to these.
[54] 상기전자수송층 (30)의두께는태양전지의효율을고려하여 50nm내지 150nm 일수있으나，이에한정하는것은아니다.  [54] The thickness of the electron transport layer 30 may be 50 nm to 150 nm in consideration of the efficiency of the solar cell, but is not limited thereto.
[55] 상기본발명의 일구현예의 태양전지는상기투명전극 (20)의하부에  A solar cell of one embodiment of the present invention is provided at the bottom of the transparent electrode 20.
위치하는투명기판 (10)을더포함할수있다.투명기판 (10)은기판상부의 구조물을지지하기위한지지체의 역할을수행하며광이투과되는기판이면 사용가능하다.일예로,리지드기판으로유리기판을들수있으며,플렉시블 기판으로포함하는폴리에틸렌테레프탈레이트，폴리이미드,  The transparent substrate 10 may further include a transparent substrate 10 positioned thereon. The transparent substrate 10 serves as a support for supporting a structure on the substrate and may be used as long as the substrate transmits light. For example, a glass substrate may be a rigid substrate. Polyethylene terephthalate, polyimide, which include, as a flexible substrate
폴리에틸렌나프탈레이트，폴리카보네이트，폴리프로필렌，  Polyethylene naphthalate, polycarbonate, polypropylene,
트리아세틸셀를로오스，폴리에테르술폰기판등을들수있다.다만이에 한정하는것은아니다.  Triacetyl cellulose, polyether sulfone substrate, and the like.
[56] 상기투명기판상에위치하는투명전극 (20)은,인듐주석산화물 (indium tin oxide),불소 -도핑주석산화물 (fluorine doped tin oxide),알루미늄 -도핑 아연 산화물 (aluminum doped zinc oxide),인듐아연산화물 (indium zinc oxide)등을 포함할수있으나，이에한정하는것은아니다.  The transparent electrode 20 disposed on the transparent substrate includes: indium tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, May contain, but is not limited to, indium zinc oxide.
[57] 상기대향전극 (60)은，백금,금，알루미늄,은，티타늄，크름,니켈등을포함할 수있으며，동일금속의단일층，또는서로다른금속을포함하는다층구조를 가질수있다.다만，이에한정하는것은아니다.  The counter electrode 60 may include platinum, gold, aluminum, silver, titanium, cream, nickel, or the like, and may have a single layer of the same metal or a multi-layer structure including different metals. However, this is not a limitation.
[58] 상기대향전극 (60)은,상기정공수송층 (50)상에증착방식을통해형성될수 있으며,예를들면，물리적증착또는화학적중착방식에의해형성될수있으며， 열증착에의해형성될수있다.다만，이에한정하는것은아니다.또한，전극의 목적하는형상에따라패터닝공정이부가될수있다.  The counter electrode 60 may be formed on the hole transport layer 50 through a deposition method. For example, the counter electrode 60 may be formed by physical deposition or chemical deposition, and may be formed by thermal deposition. However, the present invention is not limited thereto, and a patterning process may be added depending on the desired shape of the electrode.
[59]  [59]
[60] 이하본발명의바람직한실시예및비교예를기재한다.그러나하기실시예는 본발명의바람직한일실시예일뿐본발명이하기실시예에한정되는것은 아니다.  [0060] Hereinafter, preferred embodiments and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.
[61]  [61]
[62] 제조예  [62] Preparation
[63] [63]
[64] (1) PbS콜로이달양자점의합성  [64] (1) synthesis of PbS colloidal quantum dots
[65] 10g의 1-옥타데센 (1-octadecene)에 2.1mm이의 PbO와 5.7mm이의올레익산 (oleic add)를흔합한후，진공에서 90°C에서 2시간동안유지하였다.이후，흔합액의 온도를 105oC로조절하고， 5g의 1-옥타데센에 1mm이의 [65] 10 g of 1-octadecene was mixed with 2.1 mm of PbO and 5.7 mm of oleic acid, followed by holding at 90 ° C for 2 hours in a vacuum. The temperature is adjusted to 105 o C and 5 g of 1-octadecene is less than 1 mm.
비스 (트리메틸실릴)설파이드 (bis(trimethylsilyl)su de)가혼합된용액을 투입하여교반한후,상온에서 냉각하였다.이렇게제조된올레이트리간드가 형성된 PbS양자점을원심분리를통해회수하였으며 ,세척용액은순서대로 아세톤，핵산，두차례의메탄올을사용하였다.최종적으로 50mg/ml의농도로 옥탄 (octane)에분산시켰다. The solution mixed with bis (trimethylsilyl) sude was added and stirred, followed by cooling at room temperature. The prepared PbS quantum dots were recovered by centrifugation, and the washing solution was washed. Acetone, nucleic acid, and two methanols were used in chronological order. The final concentration was 50 mg / ml. Dispersed in octane.
[66]  [66]
[67] (2) PbS콜로이달양자점의리간드교환 (ligand exchange)  [67] (2) Ligand exchange of PbS colloidal quantum stores
[68] 상기 (1)에서제조된 PbS콜로이달양자점 0.8mL에용매인옥탄을가하여, lOmg/ml농도의 4mL용액으로희석하였다.이희석액을강한교반하에 0.63M의 메틸암모니움아이오다이드 (methylammonium iodide)용액 (용매는  [68] The solvent phosphorus octane was added to 0.8 mL of the PbS colloidal quantum dot prepared in (1) above, and diluted with 4 mL solution of lOmg / ml concentration. The dilution solution was 0.63 M of methylammonium iodide under strong stirring. methylammonium iodide)
N,N-di methylformamide, DMF)과흔합하였다.옥탄에서 DMF로 PbS나노입자의 이동이완료된후,옥탄을이용해원심분리를통해 3차례세척하였다.마지막 세척 이후옥탄을제거 한후, 0.2mL의를루엔으로용매를교체한후，원심분리를 재차수행한뒤,얻어진나노입자침전물을질소분위기에서건조하였다.이후， 160uL의뷰틸아민 (butylamine)을투입하여용해시켰다.  N, N-di methylformamide (DMF). After the transfer of PbS nanoparticles from octane to DMF was completed, three washes were performed by centrifugation using octane. After the last wash, 0.2 mL of octane was removed. After replacing the solvent with luene, centrifugation was performed again, and the obtained nanoparticle precipitate was dried in a nitrogen atmosphere. Then, 160 uL of butylamine was added to dissolve it.
[69]  [69]
[70] (3) ZnO나노입자의합성  [70] (3) ZnO nanoparticle synthesis
[71] 125 ml메탄올에 13.4mmol의 Zinc acetate dihydrate이녹아있는용액과， 65ml의 메탄올에 26.9mm이의 potassium hydroxide가녹아있는용액을제조하고，각각 60°C에서교반하였다.이후,상기 potassium hydroxide용액을상기 Zinc acetate dehydrate용액에점적투입 (dropwise)하고, 2.5시간동안 60°C에서교반하였다.  A solution in which 13.4 mmol of zinc acetate dihydrate was dissolved in 125 ml methanol and 26.9 mm of potassium hydroxide dissolved in 65 ml of methanol was prepared and stirred at 60 ° C., respectively. Was added dropwise to the zinc acetate dehydrate solution and stirred at 60 ° C. for 2.5 hours.
[72] 이후,제조된 ΖιιΟ나노입자를메탄올을이용해 2차례원심분리로세척하고， 5ml의클로로폼 (chloroform)및 5ml의메탄올의흔합액에녹였다.  Subsequently, the prepared nanoparticles were washed twice with centrifugation using methanol, and dissolved in a mixture of 5 ml of chloroform and 5 ml of methanol.
[73]  [73]
[74] (4)단일벽탄소나노류브P3HT용액의제조  [74] (4) manufacture of single-walled carbon nanofluid P3HT solution
[75] Chlorobenzene에 P3HT를첨가하여 0.6jng/ml의농도의용액으로제조하고, SWCNT 2.5mg을첨가하였다.이용액을냉각하면서 Ultra-sonication을 10분간 실시하였다.이후, Chlorobenzene 5ml를첨가하였다. 10000g로 8분간  P3HT was added to chlororobenzene to prepare a solution at a concentration of 0.6 jng / ml, and 2.5 mg of SWCNT was added. Ultra-sonication was performed for 10 minutes while cooling the solution. Thereafter, 5 ml of chlororobenzene was added. 8 minutes at 10000 g
원심분리기를이용해상층액을회수하였다.회수한용액에 Toluene 10ml를 첨가하고， 70°C에서 30분간방치하였다.용액을꺼내 16000g로 4분간원심분리를 하고，침전물을회수하였다.위과정을 5번반복하였다.최종침전물의무게에 맞춰 1:8의비율로 Chloroform에분산한다.만들어진용액을 10%의 power로 2분간 Ultra-sonication과정을거친후사용하였다.  The supernatant was recovered using a centrifuge. Toluene 10 ml was added to the collected solution and left at 70 ° C. for 30 minutes. The solution was removed, centrifuged at 16000 g for 4 minutes, and the precipitate was recovered. Repeated. Dispersed in Chloroform at a ratio of 1: 8 to the weight of the final precipitate. The solution was used after 10 minutes of ultrasonication at 10% power.
[76]  [76]
[77] 실시예  [77] Example
[78] ITO코팅된유리기관상에상기제조예의 (3)에서제조된 ZnO용액을  [78] The ZnO solution prepared in (3) above was prepared on an ITO coated glass engine.
2000rpm으로 30초동안스핀코팅한후, 100°C에서 10분간건조하여 lOOnm의 전자수송층을형성하였다.  After spin coating at 2000 rpm for 30 seconds, it was dried at 100 ° C for 10 minutes to form an electron transport layer of 100 nm.
[79] 이후，상기제조예의 (2)에서제조된 PbS흔합액을그위에 2500rpm으로 90초 동안스핀코팅한후, 100oC에서 10분간건조하여 220nm의양자점층을 형성하였다. Thereafter, the PbS mixture prepared in (2) of Preparation Example was spin-coated at 2500 rpm for 90 seconds thereon, and then dried at 100 ° C. for 10 minutes to form a quantum dot layer of 220 nm.
[80] 다음으로，상기제조예의 (4)에서제조된 SWNT/P3HT용액 200uL를상기 양자점층상에 3000rpm으로 90초간드랍코팅 (drop coating)하고，바로이어서 0.65mg/tnl의 PMMA용액 (용매는클로로벤젠)을 2000rpm으로 45초간스핀 코팅한뒤, 100°C에서 10분간건조하여 70nm두께의 정공수송층을형성하였다ᅳ[80] Next, 200uL of the SWNT / P3HT solution prepared in (4) above was Drop coating on quantum dot layer at 3000rpm for 90 seconds, followed by spin coating for 0.6 seconds at 0.65mg / tnl PMMA solution (chlorobenzene) at 2000rpm for 45 seconds, and drying at 100 ° C for 10 minutes to 70nm thickness. Formed a hole transport layer of ᅳ
[81] 이후,열증착을이용하여 lOOnm두께의 Au전극을형성하였다. After that, an Au electrode having a thickness of 100 nm was formed by thermal evaporation.
[82]  [82]
[83] 비교예  [83] Comparative Example
[84] SWNT P3HT용액을사용하지않고정공수송층을형성한점을제외하고는， 상기실시예와같은방법으로태양전지를제조하였다.  A solar cell was manufactured in the same manner as in the above example, except that a hole transport layer was formed without using a SWNT P3HT solution.
[85]  [85]
[86] 실험예  [86] Experimental Example
[87] [87]
[88] (1)주사전자현미경 (Scanning Electron Microscope, SEM)및  [88] (1) Scanning Electron Microscope (SEM) and
투과전자현미경 (transmission electron microscope, TEM)사진  Transmission electron microscope (TEM)
[89] 도 2는실시예에서제조된태양전지의주사전자현미경 (SEM)사진이다.  2 is a scanning electron microscope (SEM) photograph of the solar cell manufactured in the example.
[90] 투명전극상에， ZnO전자수송층， Iodide리간드치환된 PbS양자점층및  [90] A ZnO electron transport layer, an Iodide ligand-substituted PbS quantum dot layer on a transparent electrode,
SWNT/P3HT-PMMA정공수송층이 형성된모습을확인할수있다.  It can be seen that the SWNT / P3HT-PMMA hole transport layer is formed.
[91] 도 3은실시예의제조과정중， SWNT/P3HT용액이드랍코팅된표면의  3 shows the surface of the SWNT / P3HT solution-drop coated surface during the manufacturing process of the embodiment.
투과전자현미경 (TEM)사진이다.양자점층상에， SWNT/P3HT복합체가 균일하게코팅된것을확인할수있다.이후 PMMA용액의스핀코팅및건조를 통해 PMMA에상기 SWNT/P3HT복합체가균일하게분포되며， P3HT가  The transmission electron microscope (TEM) photograph shows that the SWNT / P3HT complex is uniformly coated on the quantum dot layer. Afterwards, the SWNT / P3HT complex is uniformly distributed on the PMMA through spin coating and drying of the PMMA solution. P3HT
SWNT를감싸고있는형태의정공수송층이형성된것으로보인다.  It appears that a hole transport layer of a type surrounding the SWNT is formed.
[92]  [92]
[93] (2)광전변환효율 (Power Conversion Efficiency, PCE)측정  [93] (2) Power Conversion Efficiency (PCE) Measurement
[94] 상기실시예및비교예의태양전지의전기적특성을측정하였다.구체적으로, 단락전류밀도 (Jsc),개방전압 (Voc),필팩터 (Fill Factor, FF),및  The electrical characteristics of the solar cells of the above examples and comparative examples were measured. Specifically, the short circuit current density (Jsc), the open circuit voltage (Voc), the fill factor (FF), and
광전변환효율 (PCE)를측정하였으며,측정은표준조건 (100mW/Cm2)하에서 이루어졌다. Photoelectric conversion efficiency (PCE) was measured and the measurements were made under standard conditions (100 mW / Cm 2 ).
[95] 도 4는전기적특성측정 결과를나타내는그림이다.도 4로부터 알수있듯이， 본발명의정공수송층을구비한실시예의경우단락전류밀도및개방전압의 현저한향상에의해광전변환효율이비교예에비해약 1.5배향상된것을확인할 수있다.  4 shows the results of the electrical characteristics measurement. As can be seen from FIG. 4, the photoelectric conversion efficiency is compared with the comparative example by the remarkable improvement of the short-circuit current density and the open-circuit voltage in the embodiment with the hole transport layer of the present invention. It can be seen that the improvement is about 1.5 times.
[96]  [96]
[97] (3)빛흡수율 (Absorbance)측정  [97] (3) Absorbance measurement
[98] 상기실시예및비교예의 태양전지의파장에따른빛흡수율을측정하였다.그 결과는도 5와같다.도 5에서, 'control'은비교예이고， 'SWNT'는실시예를 나타낸다.  The light absorption rate according to the wavelength of the solar cell of Examples and Comparative Examples was measured. The results are shown in FIG. 5. In FIG. 5, 'control' is a comparative example and 'SWNT' represents an embodiment.
[99] 도 5에서알수있듯이，전파장영역에서실시예의흡수율이향상된것을  As can be seen from FIG. 5, the absorption rate of the embodiment is improved in the entire wavelength region.
확인할수있다.특히,약 500내지 650nm대빛에 대한흡수율이증가한것을알 있다. In particular, we found that the absorption rate increased for the 500 to 650 nm range. have.
[100]  [100]
[101] (4)셀안정성측정  [101] (4) cell stability measurement
[102] 상기실시예및비교예의태양전지를 35일간습도조절이없는통상적인 환경 (ambient air)에서작동시키면서，전기적특성의변화를측정하였다ᅳ측정 방식은상기실험예 2에서와같다.그결과를도 6에나타내었다.도  The solar cell of Examples and Comparative Examples was operated in an ambient air without humidity control for 35 days and the change of electrical characteristics was measured. The measurement method was the same as in Example 2. Is shown in Figure 6.
6에서, 'control'은비교예이고, 'SWNT는실시예를나타낸다.  In 6, 'control' is a comparative example, and 'SWNT' represents an embodiment.
[103] 도 6에서알수있듯이，실시예의 태양전지의경우,비교예에비해 35일내내 안정적인전기적특성을유지하는것을알수있다.  As can be seen from FIG. 6, it can be seen that the solar cell of the embodiment maintains stable electrical characteristics for 35 days compared to the comparative example.
[104]  [104]
[105] [부호의설명]  [105] [Description of the Signs]
[106] 100 :광전소자 10 :기판 20 :투명전극  100: photoelectric element 10: substrate 20: transparent electrode
[107] 30：전자수송층 40：광활성층 50：정공수송층  [107] 30: electron transport layer 40: photoactive layer 50: hole transport layer
[108] 60 :대향전극  [108] 60: counter electrode

Claims

청구범위 Claim
[청구항 1] 비전도성고분자매트릭스;및상기비전도성고분자매트릭스내  [Claim 1] Non-conductive polymer matrix; and in the non-conductive polymer matrix
위치하는탄소나노류브와정공수송물질의복합체；를포함하는것인， 정공수송재료.  A hole transport material, comprising a composite of carbon nano-rive and hole transport material located.
[청구항 2] 제 1항에서，  [Claim 2] In paragraph 1,
상기비전도성고분자는，  The non-conductive polymer is
폴리 (메틸메타크릴레이트) (poly(methyl methacrylate), PMMA), 에틸렌-비닐아세테이트 (ethylene-vinyl acetate, EVA),폴리비닐 클로라이드 (polyvinyl chloride, PVC),폴리에틸렌 (polyethylene, PE), 폴리카보네이트 (polycarbonate, PC),폴리부틸렌 (Polybutylene, PB),또는 이들의흔합물인것인，  Poly (methyl methacrylate) (PMMA), ethylene-vinyl acetate (EVA), polyvinyl chloride (PVC), polyethylene (PE), polycarbonate ( polycarbonate, PC), polybutylene (PB), or a combination thereof
정공수송재료.  Hole transport material.
[청구항 3] 제 1항에서， [Claim 3] In paragraph 1,
상기정공수송물질은,  The hole transport material,
P3HT(poly(3-hexylthiophene)), P3AT(poly(3-alkylthiophene)),  Poly (3-hexylthiophene) (P3HT), poly (3-alkylthiophene) (P3AT),
P30T(poly(3-octylthiophene), PEDOT:PSS  P30T (poly (3-octylthiophene), PEDOT: PSS
(Poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate)),또는이들의 흔합물인것인，  (Poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate)), or a mixture thereof
정공수송재료.  Hole transport material.
[청구항 4] 제 1항에서, [Claim 4] In Clause 1,
상기탄소나노류브는,  The carbon nano-leave,
단일벽탄소나노튜브 (single wall carbon nanotube, SWCNT)인것인, 정공수송재료.  A hole transport material, which is a single wall carbon nanotube (SWCNT).
[청구항 5] 투명 전극; Claim 5 A transparent electrode;
상기투명전극상에위치하는전자수송층;  An electron transport layer on the transparent electrode;
상기전자수송층상에위치하는광활성층;  A photoactive layer positioned on the electron transport layer;
상기광활성층상에위치하는정공수송층;및  A hole transport layer on the photoactive layer; and
상기정공수송층상에위치하는대향전극을포함하고， 상기정공수송층은，비전도성고분자매트릭스;및상기비전도성고분자 매트릭스내위치하는탄소나노류브와정공수송물질의복합체；를 포함하는것인，  A counter electrode located on the hole transport layer, wherein the hole transport layer comprises a non-conductive polymer matrix; and a composite of carbon nano-leubes and a hole transport material located in the non-conductive polymer matrix;
광전소자.  Photoelectric device.
[청구항 6] 제 5항에서, [Claim 6] In Clause 5,
상기비전도성고분자는，  The non-conductive polymer is
폴리 (메틸메타크릴레이트) (poly(methyl methacrylate), PMMA), 에틸렌-비닐아세테이트 (ethylene-vinyl acetate, EVA),폴리비닐 클로라이드 (polyvinyl chloride, PVC),폴리에틸렌 (polyethylene, PE), 폴리카보네이트 (polycarbonate, PC),폴리부틸렌 (Polybutylene, PB),또는 이들의흔합물인것인, Poly (methyl methacrylate) (PMMA), ethylene-vinyl acetate (EVA), polyvinyl chloride (PVC), polyethylene (PE), Polycarbonate (PC), polybutylene (PB), or a combination thereof,
광전소자.  Photoelectric device.
[청구항 7] 제 5항에서， [Claim 7] In paragraph 5,
상기정공수송물질은，  The hole transport material is,
P3HT(poly(3-hexylthiophene)), P3AT(poly(3-alkylthiophene)),  Poly (3-hexylthiophene) (P3HT), poly (3-alkylthiophene) (P3AT),
P30T(poly(3-octylthiophene), PEDOT:PSS  P30T (poly (3-octylthiophene), PEDOT: PSS
(Poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate)),또는이들의 흔합물인것인，  (Poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate)), or a mixture thereof
광전소자.  Photoelectric device.
[청구항 8] 제 5항에서， [Claim 8] In paragraph 5,
상기탄소나노튜브는,  The carbon nanotubes,
단일벽탄소나노류브 (single wall carbon nanotube, SWCNT)인것인, 광전소자.  A photovoltaic device, which is a single wall carbon nanotube (SWCNT).
[청구항 9] 제 5항에서， [Claim 9] In paragraph 5,
상기광활성층은，  The photoactive layer is,
양자점층인것인，  Quantum dot layer,
광전소자ᅳ  Optoelectronic device
[청구항 10] 제 9항에서, [Claim 10] In Section 9,
상기 양자점은，  The quantum dot is,
CdS, CdSe, CdTe, PbS, PbSe, PbSxSe,.x(0<x<l), Bi2S3) Bi2Se3, InP, InCuS2, In(CuGa)Se2, Sb2S3, Sb2Se3, SnSx(l<x<2), NiS, CoS, FeSx(l <x<2), In2S3, MoS, MoSe,또는이들의혼합물을포함하는것인， CdS, CdSe, CdTe, PbS, PbSe, PbS x Se ,. x (0 <x <l), Bi 2 S 3) Bi 2 Se 3 , InP, InCuS 2 , In (CuGa) Se 2 , Sb 2 S 3 , Sb 2 Se 3 , SnS x (l <x <2) , NiS, CoS, FeS x (l <x <2), In 2 S 3 , MoS, MoSe, or a mixture thereof,
광전소자.  Photoelectric device.
[청구항 U] 제 10항에서, [Claim U] In claim 10,
상기 양자점은，  The quantum dot is,
표면에무기리간드를포함하는것인,  Which contains inorganic ligands on the surface,
광전소자.  Photoelectric device.
[청구항 1 제 11항에서,  [In claim 1 Clause 11,
상기무기리간드는，  The inorganic ligand,
Iodide인것인,  Being Iodide,
광전소자.  Photoelectric device.
[청구항 제 5항에서， [In claim 5,
상기 전자수송층은，  The electron transport layer,
Ti02, Sn02, ZnO, W03, Nb205, TiSr03, ln203,또는이들의흔합물을 포함하는것인, Ti0 2 , Sn0 2 , ZnO, W0 3 , Nb 2 0 5 , TiSr0 3 , ln 2 0 3 , or a combination thereof,
광전소자.  Photoelectric device.
[청구항 14] 제 5항에서， 상기정공수송층의두께는, 40nm이상및 200nm이하인것인， 광전소자. [Claim 14] In paragraph 5, The hole transport layer has a thickness of 40 nm or more and 200 nm or less.
[청구항 I5] 제 5항에서, [Claim I 5 ] in paragraph 5,
상기광활성층의두께는，  The thickness of the photoactive layer is
150nm이상및 300nm이하인것인 광전소자.  Optoelectronic device having more than 150nm and less than 300nm.
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