WO2015037856A1 - 태양전지 광흡수층 제조용 금속 칼코게나이드 나노 입자 및 이의 제조방법 - Google Patents

태양전지 광흡수층 제조용 금속 칼코게나이드 나노 입자 및 이의 제조방법 Download PDF

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WO2015037856A1
WO2015037856A1 PCT/KR2014/008181 KR2014008181W WO2015037856A1 WO 2015037856 A1 WO2015037856 A1 WO 2015037856A1 KR 2014008181 W KR2014008181 W KR 2014008181W WO 2015037856 A1 WO2015037856 A1 WO 2015037856A1
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Prior art keywords
metal chalcogenide
nanoparticles
thin film
chalcogenide nanoparticles
metal
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PCT/KR2014/008181
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English (en)
French (fr)
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박은주
윤석희
윤석현
이호섭
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주식회사 엘지화학
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Priority to US14/917,265 priority Critical patent/US20160218231A1/en
Priority to ES14844680T priority patent/ES2834993T3/es
Priority to CN201480048450.6A priority patent/CN105518872B/zh
Priority to JP2016540801A priority patent/JP6246373B2/ja
Priority to EP14844680.0A priority patent/EP3026714B1/en
Publication of WO2015037856A1 publication Critical patent/WO2015037856A1/ko
Priority to US15/638,240 priority patent/US10170649B2/en

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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
    • H01L31/0256—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 the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • 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
    • H01L31/0256—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 the material
    • H01L31/0264—Inorganic materials
    • H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
    • 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
    • H01L31/0256—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 the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
    • 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
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to metal chalcogenide nanoparticles for producing a solar cell light absorption layer and a method of manufacturing the same.
  • CIGS copper-knot-gallium-sulfo-die-salenide, Cu (In, Ga) (S, Se) 2
  • CIGS layer-described solar cell has a power conversion efficiency of more than 19%.
  • the potential for CIGS-based thin film solar cells is high. Nevertheless, due to the cost and supply shortage of indium (In), it is a major obstacle to the wide range of applications and applicability of thin-film solar cells using CIGS-based light absorption layers. Battery development is urgent.
  • CZTS Cu 2 ZnSn (S, Se) 4
  • the CZTS has a direct bandgap of about 1.0 to 1.5 eV. gap) and absorption coefficient of 10 4 cm- 1 or more, and has the advantage of using Sn and Zn which are relatively rich in reserve and low in price.
  • PCT / US / 2010-035792 describes ink containing CZTS / Se nanoparticles.
  • the nano-particles used in the thin film is Cu, Zn, including, but Sn, to take the form of non-CZTS crystal, tends to metal nanoparticles oxide nyung 'consisting of a single metal element, since an excess of Se and high There is a disadvantage in that oxygen removal process using temperature is required. In case of mixing and mixing chalcogenides containing respective metals, non-uniform composition ratio of metals may be a problem.
  • the present invention aims to solve the above-mentioned problems of the prior art and technical problems that have been requested from the past.
  • Metallic chalcogenide nanoparticles comprising a first phase consisting of copper (Cu) -tin (Sn) chalcogenide and a second phase consisting of zinc (Zn) chalcogenide were developed.
  • a first phase consisting of copper (Cu) -tin (Sn) chalcogenide
  • a second phase consisting of zinc (Zn) chalcogenide
  • Metal chalcogenide nanoparticles forming a light absorption layer comprising: a first phase consisting of copper (Cu) -tin (Sn) chalcogenide, and a second phase formed of zinc (Zn) chalcogenide )).
  • chalcogenide refers to a substance containing a group VI element, for example, sulfur (S) or selenium (Se).
  • the copper (Cu) -tin (Sn) chalcogenide may be Cu a SnS b (1.2 ⁇ a ⁇ 3.2, 2.5 ⁇ b ⁇ 4.5), and / or Cu x SnSe y (1.2 ⁇ x ⁇ 3.2, 2.5 ⁇ y ⁇ 4.5), and zinc ( Zn) containing chalcogenide may be ZnS and / or ZnSe.
  • Two phases of the metal chalcogenide nanoparticles are one metal.
  • the composition ratio of the metal in the metal chalcogenide nanoparticles can be determined in the range of 0.5 ⁇ Cu (Zn + Sn) ⁇ 1.5, a5 ⁇ Zn / Sn ⁇ 2.0, Specifically, it can be determined in the range of 0.7 ⁇ Cu / (Zn + Sn) ⁇ 1.2 and 0.8 ⁇ Zn / Sn ⁇ 1.4.
  • first and second phases may be uniformly distributed, and the first and second phases exist in bulk, so that the complex is formed.
  • the metal chalcogenide nano is observed in the area observed when SEM-EDX or TEM-EDX is observed for the metal chalcogenide inner region.
  • the composition ratio of the metal in the particles can be determined in the range of 0.5 ⁇ Cu / (Zn + Sn) ⁇ 1.5, a5 ⁇ Zn / Sn ⁇ 2.0, and in detail 0.7 ⁇ Cu / (Zn + Sn) ⁇ 1.2, 0.8 Zn / Sn ⁇ 1.4 can be determined.
  • the core diameter may be 5 nanometers to 200 nanometers, and the thickness of the shell may be determined based on the particle size of the core. And it is formed in a range corresponding to the volume occupied in the second phase or the nanoparticles, it can be 1 to 100 nanometers.
  • the voids between the particles become large, and if the core size is too small, not only the coarseness between the particles, but also the thickness of the shell to make the final film have an appropriate composition ratio is too thin. Therefore, when forming a shell, it is difficult to form an appropriate thickness, which is not preferable.
  • composition ratio of the first phase and the second phase in the metal chalcogenide nanoparticles in the whole metal chalcogenide nanoparticles is
  • the metal chalcogenide nanoparticles may contain from 0.5 to 3 moles of chalcogenide elements based on 1 mole of metal elements when all kinds of metals are collectively referred to as metal elements. .
  • the present invention also provides a method for synthesizing the metal chalcogenide nanoparticles.
  • the method for producing metal chalcogenide nanoparticles according to the present invention is a solution process rather than a conventional vacuum process, which can drastically lower the process cost and is also toxic as a solvent for preparing the solution.
  • the absence of hydrazine can also eliminate the risks associated with conventional solution processing.
  • the Group VI source is 0.5 mole to 1 mole of a metal element.
  • the first solution contains a sufficient Group VI source, no additional Group VI source is required when mixing the third solution; otherwise, to resolve the partial deficiency of the Group VI element,
  • a Group VI source may be added, wherein the Group VI source is prepared by the first solution and the second solution.
  • the solvent of the first solution, the second solution, and the third solution is water, alcohols, diethylene glycol, oleylamine,
  • the alcohol solvent may be one to one carbon atom in detail. It may be 8 having methanol, ethanol, propane, butanol, pentanol, nucleool, heptanol, and octanol.
  • the copper (Cu), tin (Sn) salts, and zinc (Zn) salts are independently chloride, bromide, iodide, or nitrate salts. nitrate, nitrite, sulfate, acetate, acetate, sulfite, acetylacetoante, and
  • It may be one or more of the forms selected from the group consisting of hydroxides, and in the case of tin (Sn) salts, both divalent and tetravalent salts may be used but are not limited.
  • the Group VI source is Se, Na 2 Se, K 2 Se, CaSe, (CH 3 ) 2 Se, SeO 2, SeCl 4 , H 2 Se0 3 , H 2 Se0 4 , Na 2 S, K 2 S, CaS, (CH 3 ) 2 S, H 2 S0 4 , S, Na 2 S 2 0 3 , NH 2 S0 3 H and their hydrates, thiourea, thioacetamide (thioacetamide), selenoacetamide and selenourea may be one or more selected from the group consisting of.
  • the first solution to the third solution may further include a capping agent. have.
  • the capping agent not only regulates the size and phase of the metal chalcogenide nanoparticles synthesized by being included in the solution process, but also contains atoms such as N, 0, S and so on.
  • the binding of chalcogenide nanoparticles on the surface of the chalcogenide nanoparticles prevents the oxidation of metal chalcogenide nanoparticles.
  • Polyvinylpyrrolidone PVP
  • sodium L-tartrate dibasic dehydrate potassium sodium tartrate
  • sodium mesoxalate antenna "sodium acrylate )
  • Plylidone Poly (vinyl pyrrolidone)
  • sodium citrate Trisodium citrate, disodium citrate, sodium gluconate, sodium ascorbate )
  • the invention also provides a light absorption layer comprising the metal chalcogenide nanoparticles.
  • An ink composition for manufacturing is provided, and a method for producing a thin film using the ink composition is provided.
  • a metal chalcogenide comprising a first phase consisting of copper (Cu) -tin (Sn) chalcogenide and a second phase consisting of zinc (Zn) chalcogenide Dispersing nanoparticles in a solvent to prepare an ink;
  • the solvent of step (i) above is a general organic solvent.
  • alkanes alkenes, alkynes, aromatic compounds, ketons, nitriles, ethers ( ethers), esters,
  • An organic solvent selected from sulfoxides, and amides may be used alone or in a mixed form of one or more organic solvents selected from these stones.
  • the alcohol solvent is ethanol, 1-propanol (l-propanol),
  • the amine solvent is triethyl amine, dibutyl amine, dipropyl amine, butylamine, ethanolamine,
  • DETA Diethylenetriamine
  • TETA Triethylenetetraine
  • It may be one or more mixed solvents selected from tris (2-aminoethyl) amine.
  • the thiol solvent may be one or more mixed solvents selected from 1,2-ethanedithiol, pentanethiol, hexanethiol, and mercaptoethanol. have.
  • the alkane solvent may be one or more mixed solvents selected from hexane, heptane, and octaneosis.
  • aromatic compounds solvents are toluene, xylene,
  • It may be one or more mixed solvents selected from nitrobenzene, pyridineosis.
  • the organic halide solvent may include one or more traces selected from chloroform, methylene chloride, tetrachloromethane, dichloroethane, and chlorobenzene. It can be a solvent.
  • the nitrile solvent may be acetonitrile.
  • the ketone solvent may be one or more mixed solvents selected from acetone, cyclohexanone, cyclopentanone, and acetylacetone.
  • the ether solvent is ethyl ether
  • It may be one or more mixed solvents selected from tetrahydrofurane, and 1,4-dioxane.
  • the sulfoxides solvent is DMSO (dimethyl sulfoxide), and
  • It may be one or more mixed solvents selected from sulfolane.
  • the amide solvent is F (dimethyl formamide), and
  • NMP n-methyl-2-pyrrolidone
  • the ester solvent is ethyl lactate
  • It may be one or more mixed solvents selected from r-butyrolactone, and ethyl acetoacetate.
  • the carboxylic acid solvent is propionic acid, hexanoic acid, meso-2,3-dimercaptosuccinic acid, thiolactic acid. It may be one or more mixed solvents selected from thiolactic acid, and thioglycolic acidosis.
  • the solvents may be one example and are not limited thereto.
  • it may be prepared by further adding an additive to the ink of step (i).
  • the additives include, for example, dispersants, surfactants, polymers, binders, crosslinkers, emulsifiers, antifoaming agents, drying agents, layering agents, extenders, thickeners, film conditioners, antioxidants, glidants, smoothing additives, And at least one selected from the group consisting of corrosion inhibitors, specifically polyvinylpyrrolidone (PVP), poly vinylalcohol, anti-terra 204, anti-terra
  • Anti-terra 205 ethyl cellulose
  • It may be one or more selected from the group consisting of DispersBYKllO.
  • the method of forming the coating layer of the above process (U) may include, for example, wet coating, spray coating, spin coating, doctor blade coating, contact printing, upper feed reverse printing, and lower printing.
  • Feed reverse printing, nozzle feed reverse printing, gravure printing, micro gravure printing, reverse micro gravure printing, roller coating, slot die Can be any one selected from the group consisting of coating, capillary coating, inkjet printing, jet deposition and spray deposition.
  • the heat treatment of the process (Hi) can be performed in the silver range of 400 to 900 degrees Celsius.
  • the selenization process may be accomplished by a variety of methods.
  • the condition in which the S or Se element is present is possible by supplying the gas in the form of H 2 S or H 2 Se, or by heating the Se or S to a gas.
  • step (iii) is performed.
  • the deposition can be accomplished by a solution process or by a variety of other deposition methods.
  • the present invention also provides a thin film manufactured by the above method.
  • the thin film may have a thickness in the range of 0.5 / m to 3.0; and more specifically, the thin film may have a thickness of 0.5 fm to 2.5.
  • the thickness of the thin film is less than 0.5 um, the density and quantity of the light absorbing layer are not sufficient, so that the desired photoelectric efficiency cannot be obtained. If the thin film exceeds 3.0, the distance of the carriers increases. The higher the probability of recombination, the lower the efficiency.
  • the present invention provides a thin film solar cell manufactured using the thin film.
  • Example 1 is a SEM photograph of Cu 2 SnS 3 -ZnS nanoparticles formed by Example 1;
  • FIG. 2 is a TEM photograph of Cu 2 SnS 3 -ZnS nanoparticles formed by Example 1; FIG.
  • Example 3 is an XRD graph of Cu 2 SnS 3 -ZnS nanoparticles formed by Example 1;
  • FIG. 5 is an XRD graph of Cu 2 SnS 3 -ZnS nanoparticles formed by Example 7; FIG.
  • FIG. 6 is an SEM photograph of the thin film prepared in Example 17;
  • Example 7 is an XRD graph of the thin film prepared in Example 17.
  • Example 10 is an IV characteristic graph of the thin film solar cell manufactured in Example 18;
  • Synthesized particles were purified by centrifugation to obtain Cu 2 SnS 3 particles. Separately, ZnCl 2 , Thioacetamide and PVP were dissolved in Diethyene Glycol solution and heated at 175 degrees for 2.5 hours. Synthesized particles
  • the Cu 2 SnS 3 -ZnS particles prepared in Example 8 were dispersed in a mixed solvent composed of an alcoholic solvent to prepare an ink, and then coated on a glass substrate coated with molybdenum (Mo). After drying the coating film, the Se substrate was heated together with the E-deposited glass substrate to form a Se atmosphere, followed by RTA (Rapid Thermal Annealing) at 575 ° C to prepare a CZTSSe-based thin film.
  • a mixed solvent composed of an alcoholic solvent
  • Mo molybdenum
  • the ink was prepared, it was coated on a soda lime glass substrate coated with molybdenum (Mo). The coated film was dried and then thermally treated at 450 ° C. under a Se atmosphere to prepare a CZTSSe-based thin film.
  • An XRD graph of the obtained thin film is shown in FIG. 8.
  • RTA Rapid Thermal Annealing
  • Example 17 After etching the CZTSSe-based thin film prepared in Example 17 with potassium cyanide (KCN) solution, a CdS layer (Thickness: 50 nm) was raised using a chemical bath deposition (CBD) method, and then sputtering was used.
  • the ZnO layer (Thickness: 100 nm) and the A1 doped ZnO layer (Thickness: 500 nm) were sequentially laminated to manufacture a thin film, and an aluminum (A1) electrode was formed on the thin film to manufacture a thin film solar cell.
  • a current-voltage (IV) characteristic graph obtained from the thin film solar cell is shown in FIG. 10.
  • the CZTSSe-based thin film prepared in Comparative Example 3 was prepared by raising a CdS layer by using a CBD (Chemical Bath Deposition) method and then laminating a ZnO layer and a ⁇ layer by using a sputtering method to manufacture a thin film. An electrode was formed to manufacture a thin film solar cell. A current-voltage (IV) characteristic graph obtained from the thin film solar cell is shown in FIG. 11.
  • the CZTSSe-based thin film prepared in Comparative Example 4 was prepared by raising a CdS layer by using a CBD (Chemica I bath deposition) method and then laminating a ZnO layer and an ITO layer by sputtering in order to manufacture a thin film. An electrode was formed to manufacture a thin film solar cell.
  • the current-voltage (IV) characteristic graph obtained from the thin film solar cell is shown in FIG. 12.
  • variable J sc which determines the efficiency of the solar cell described in Table 1, represents the current density.
  • V oc means open circuit voltage measured at zero output current
  • photoelectric efficiency refers to the ratio of the cell output to the amount of energy of light incident on the solar panel
  • FF Frill factor
  • the metal chalcogenide nanoparticles according to the present invention include a first phase consisting of copper (Cu) -tin (Sn) chalcogenide, and zinc (Zn) chalcogenide.
  • the second phase of the particles is contained in one particle, and when the thin film is manufactured using this, it is possible to suppress the occurrence of secondary phases and to include all the metals in one particle, so that the film can have a more uniform composition as a whole.
  • the inclusion of S or Se in the nanoparticles itself makes it stable for oxidation and increases the content of ⁇ ⁇ [group elements in the final thin film, and higher density due to the increase in particle volume as the group VI elements are added during selenization. It is effective to grow the thin film.
  • metal chalcogenide nanoparticles according to the present invention are prepared by a solution process.
  • the process cost can be significantly lowered compared to the existing vacuum process, and the use of toxic reducing agents such as hydrazine eliminates the risk.

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Abstract

본 발명은 태양전지의 광흡수층을 형성하는 금속 칼코게나이드 나노 입자로서, 구리 (Cu)-주석 (Sn)칼코게나이드로 이루어진 제 1상 (phase),및아연 (Zn) 칼코게나이드로 이루어진 제 2상 (phase)을 포함하는 것을 특징으로 하는 금속 칼코게나이드 나노 입자 및 이의 제조 방법에 관한 것이다.

Description

명세서
발명의명칭:태양전지광흡수층제조용금속칼코게나이드나노 입자및이의제조방법
기술분야
[1] 본발명은태양전지광흡수층제조용금속칼코게나이드나노입자및이의 제조방법에관한것이다.
배경기술
[2] 태양전지는개발초기때부터비싼제조과정의광흡수층및반도체물질로서 규소 (Si)를사용하여제작되어왔다.태양전지를더욱경제적으로산업에이용 가능하도록제조하기위해，박막태양전지의구조물로저비용의
CIGS (구리-인듭-갈륨-설포-다이-샐레나이드， Cu(In, Ga)(S, Se)2)와같은광흡수 물질을이용한제품이개발되어왔다.상기 CIGS계의태양전지는전형적으로 후면전극층， n-형접합부，및 P-형흡광층으로구성된다.이렇게 CIGS층이 기재된태양전지는 19%를초과하는전력변환효율을갖는다.그러나, CIGS계의박막태양전지에대한잠재성에도불구하고，인듐 (In)의원가와 공급량부족으로인하여 CIGS계의광흡수층을이용한박막태양전지의 광범위한용도및적용성에주요한장애가되고있는바, In-free나 In-less의저가 범용원소를이용하는태양전지개발이시급한실정이다.
[3] 따라서，최근에는상기 CIGS계의광흡수층에대한대안으로초저가금속
원소인구리，아연，주석，황,또는셀레늄원소를포함하는 CZTS(Cu2ZnSn(S,Se)4 )계태양전지가주목받고있다.상기 CZTS는약 1.0내지 1.5eV의직접 밴드갭 (direct band gap)및 104 cm-1이상의흡수계수를갖고있고，상대적으로 매장량이풍부하고가격이저렴한 Sn과 Zn을사용하는장점을가지고있다.
[4] 1996년에처음 CZTS헤테로 -접합 PV전지가보고되었지만,현재까지도
CZTS를기반으로한태양전지의기술은 CIGS의태양전지의기술보다뒤처져 있고, CZTS전지에대한광전효율은 10%이하로 CIGS의그것에비해아직많이 부족한상태이다. CZTS의박막은스퍼터링 (sputtering),하이브리드
스퍼터링 (hybrid sputtering),펼스레이저 (pulse laser)증착법,분무열분해법, 전착 /열황화 (thermal sulfurization), E-빔 (E-beam) Cu/Zn/Sn/열황화，및
졸-겔 (sol-gel)의방법들을이용하여제조되어왔다.
[5] 한편， PCT/US/2010-035792에서는 CZTS/Se나노입자를포함하는잉크를
이용하여기재상에열처리하여박막을형성시킨내용을개시하고있는데， 일반적으로， CZTS/Se나노입자를사용하여 CZTS박막을형성하는경우,이미 형성된결정이작기때문에이후박막을형성하는과정에서결정의크기를 키우기가힘들고，이와같이각각의그레인 (grain)이작은경우에는경계면이 늘어나게되고，경계면에서생기는전자의손실때문에효율이떨어질수밖에 없다.
[6] 따라서 ,박막에사용되는나노입자는 Cu, Zn, Sn을포함하되 , CZTS결정이 아닌형태를취해야하는데，단일금속원소로구성된금속나노입자늉 ' 산화되기쉽고，이후과량의 Se와높은온도를이용한산소의제거공정이 필요하다는단점이있으며，각각의금속을포함하는칼코게나이드를각각 합성하여흔합하는경우에는금속의불균일한조성비가문제될수있다.
[7] 따라서，산화에안정할뿐아니라균일한조성으로결점을최소화시킨높은 효율의광흡수층을형성할수있는박막태양전지에대한기술의필요성이높은 실정이다.
발명의상세한설명
기술적과제
[8] 본발명은상기와같은종래기술의문제점과과거로부터요청되어온기술적 과제를해결하는것을목적으로한다.
[9] 본출원의발명자들은심도있는연구와다양한실험을거듭한끝에,
구리 (Cu)-주석 (Sn)칼코게나이드로이루어진제 1상 (phase),및아연 (Zn) 칼코게나이드로이루어진제 2상 (phase)을포함하는금속칼코게나이드나노 입자를개발하였고,이를사용하여박막을제조하는경우，박막내에이차상의 발생을억제하고전체적으로균일한조성을가질수있을뿐아니라,나노입자 자체에 S또는 Se를포함함으로써산화에안정하며,최종박막내에 VI족원소의 함유량을높인양질의박막을제조할수있는것을확인하고，본발명을 완성하기에이르렀다.
과제해결수단
[10] 따라서，본발명에따른금속칼코게나이드나노입자는，태양전지의
광흡수층을형성하는금속칼코게나이드나노입자로서,구리 (Cu)-주석 (Sn) 칼코게나이드로이루어진제 1상 (phase),및아연 (Zn)칼코게나이드로이투어진 제 2상 (phase)을포함하는것을특징으로한다.
[11] 본발명에서칼코게나이드는 VI족원소，예를들어,황 (S)또는샐레늄 (Se)을 포함하는물질을의미하는바,하나의구체적인예에서，상기구리 (Cu)-주석 (Sn) 칼코게나이드는 CuaSnSb(1.2≤a≤3.2, 2.5<b<4.5),및 /또는 CuxSnSey(1.2≤x≤3.2, 2.5≤y≤4.5)일수있고,아연 (Zn)함유칼코게나이드는 ZnS및 /또는 ZnSe일수 있다.
[12] 상기금속칼코게나이드나노입자를이루는 2개의상들은하나의금속
칼코게나이드나노입자내에서독립적으로존재하며 ,금속칼코게나이드나노 입자내에서의금속의조성비는 0.5≤Cu (Zn+Sn)≤1.5, a5≤Zn/Sn≤2.0이되는 범위에서정해질수있고,상세하게는 0.7≤Cu/(Zn+Sn)≤1.2, 0.8≤Zn/Sn≤1.4가 되는범위에서정해질수있다.
[13] 이러한금속칼코게나이드나노입자의구조，즉，제 1상및제 2상의분포 형태는,특별히한정되지아니하나，도 13내지도 15에서보는바와같이제 1상 및제 2상이균일하게분포되어있을수도있고,제 1상및제 2상이벌크 (bulk) 형태로존재하여，복합체를이를수도있고,제 1상이코어를이루고，제 2상이 쉘올이루는코어-쉘구조를가질수도있다.
[14] 상기금속칼코게나이드나노입자가균일하게분포되어있는경우에는，상기 금속칼코게나이드내임의의영역을 SEM-EDX나 TEM-EDX로관찰하였을때, 관찰된영역에서금속칼코게나이드나노입자내에서의금속의조성비는 0.5<Cu/(Zn+Sn)≤1.5, a5≤Zn/Sn≤2.0이되는범위에서정해질수있고， 상세하게는 0.7≤Cu/(Zn+Sn)≤1.2, 0.8≤Zn/Sn≤1.4가되는범위에서정해질수 있다.
[15] 상기금속칼코게나이드나노입자가코어-쉘구조를갖는경우에는，상기 코어의입경은 5나노미터내지 200나노미터일수있고，상기쉘의두께는 코어의입경을고려하여，제 1상및제 2상이나노입자내에서차지하는부피에 대응되는범위에서형성되는바， 1나노미터내지 100나노미터일수있다.
[16] 상기범위를벗어나코어의크기가너무큰경우에는쉘까지형성한금속
칼코게나이드나노입자크기가너무커져 1마이크로미터내지 2
마이크로미터의두께를갖는최종박막에서의입자들사이의공극이커지고, 코어의크기가너무작은경우에는입자들사이의웅집이쉬을뿐만아니라, 최종박막이적절한조성비를갖게하기위한쉘의두께가너무얇아지므로쉘을 형성시킬때，적절한두께로형성시키기어려운바，바람직하지않다.
[17] 한편,상기형태에상관없이，금속칼코게나이드나노입자전체에서상기제 1 상및제 2상이금속칼코게나이드나노입자내에서차지하는조성비는
0.5≤Cu/(Zn+Sn)≤1.5, 0.5≤Zn/Sn≤2.0이되는범위에서정해질수있고, 상세하게는 0.7≤Cu/(Zn+Sn)≤1.2, 0.8≤Zn/Sn≤1.4가되는범위에서정해질수 있다.
[18] 하나의구체적인예에서，상기금속칼코게나이드나노입자는,모든종류의 금속을금속원소로총칭할때,금속원소 1몰을기준으로칼코게나이드 원소들을 0.5몰내지 3몰로포함할수있다.
[19] 상기범위를벗어나,금속원소들이너무많이포함되는경우 , VI족원소의 충분한제공이불가능하므로금속칼코게나이드와같은안정한상이형성되지 못하는바，이후공정에서상이변해 이차상을 형성시키거나분리된금속이 산화될수있는문제가있고，반대로,칼코게나이드원소가너무많이포함되는 경우에는박막을제조하기위한열처리공정에서 VI족소스가증발하면서최종 박막에공극이과도하게형성될수있으므로바람직하지않다.
[20] 본발명은또한,상기금속칼코게나이드나노입자를합성하는방법을
제공하고，상기합성방법은구체적으로，
[21] (i)황 (S)또는샐레늄 (Se)을포함하는화합물로이루어진군에서선택되는 1종 이상의 VI족소스를포함하는제 1용액을준비하는과정; [22] (ii)구리 (Cu)염및주석 (Sn)염을포함하는제 2용액과，아연 (Zn)염을포함하는 제 3용액을준비하는과정 ;
[23] (iii)상기제 1용액과제 2용액을혼합하여반웅시키는과정；및
[24] (iv)상기과정 (iii)의반웅생성물에상기제 3용액을혼합하여반웅시키는 과정;
[25] 을포함할수있다.
[26] 즉， 본발명에따른금속 칼코게나이드나노입자의제조방법은기존의진공 공정이아닌용액공정으로이루어지므로공정비용을획기적으로 낮출수있을 뿐아니라,용액을제조하기위한용매로서유독한하이드라진을사용하지 않으므로기존의용액공정에서발생할수있는위험성을제거할수도있다.
[27] 하나의구체적인예에서，상기과정 (iv)의제 3용액을혼합시 VI족소스를
추가로첨가할수있다.
[28] 상기에서언급한바와같이 , VI족소스는금속원소 1몰에대해 0.5몰내지
3몰로포함되어야하므로,제 1용액이충분한 VI족소스를포함하고있는 경우에는제 3용액의혼합시추가적인 VI족소스가필요없지만,그렇지못한 경우에는， VI족원소의부분적인부족을해결하기위해추가로 VI족소스를 첨가할수있고，이때,상기 VI족소스는제 1용액과제 2
용액의 반웅 생성물에 잔류하는 ^족원소의양을감안하여첨가될수있다.
[29] 하나의구체적인예에서，상기제 1용액，제 2용액,및제 3용액의용매는물, 알콜류,디에틸렌글리콜 (diethylene glycol),오레일아민 (oleylamine),
에틸렌글리콜 (ethylene glycol),트리에틸렌글리콜 (triethylene glycol),
디메틸설폭사이드 (dimethyl sulfoxide),디메틸포름아마이드 (dimethyl formamide) 및 NMP(N-methyl-2-pyrrolidoneᅵ로이루어진군에서선텍되는하나이상일수 있고，상기알코을류용매는상세하게는,탄소수 1개내지 8개를갖는메탄올， 에탄올,프로판을，부탄올,펜탄올，핵산올，헵탄올,및옥탄올일수있다.
[30] 하나의구체적인예에서,상기구리 (Cu)염과주석 (Sn)염및아연 (Zn)염은각각 독립적으로염화물 (chloride),브롬화물 (bromide),요오드화물 (iodide), 질산염 (nitrate),아질산염 (nitrite),황산염 (sulfate),아세트산염 (acetate), 아황산염 (sulfite),아세틸아세토네이트염 (acetylacetoante)및
수산화물 (hydroxide)로이루어진군에서선택되는하나이상의형태일수있고， 주석 (Sn)염의경우에는 2가및 4가의염이한정되지아니하고모두사용 가능하다.
[31] 하나의구체적인예에서,상기 VI족소스는 Se, Na2Se, K2Se, CaSe, (CH3)2Se, SeO 2, SeCl4, H2Se03, H2Se04, Na2S, K2S, CaS, (CH3)2S, H2S04, S, Na2S203, NH2S03H및 이들의수화물과，티오요소 (thiourea),티오아세트아미드 (thioacetamide), 샐레노아세트아미드 (selenoacetamide)및셀레노유레아 (selenourea)로이루어진 군에서선택되는하나이상일수있다.
[32] 한편,상기제 1용액내지제 3 용액에는캡핑제 (capping agent)가더포함될수 있다.
[33] 상기캡핑제는용액공정증에포함됨으로써합성되는금속칼코게나이드나노 입자의크기와입자의상을조절할뿐만아니라， N, 0， S등의원자를포함하고 있으므로상기원자들의비공유전자쌍 (lone pair electron)에의해금속
칼코게나이드나노입자표면에쉽게바인딩 (binding)하여표면을감싸므로금속 칼코게나이드나노입자의산화를방지해줄수있다.
[34] 이러한캡핑제는특별히한정되지는않으나 ,예를들어，
폴리비닐피로리돈 (polyvinylpyrrolidone: PVP), L-주석산나트륨 (sodium L-tartrate dibasic dehydrate),타르타르산나트륨칼晉 (potassium sodium tartrate),소듐 메조옥살레이트 (sodium mesoxalate),소듬이"크릴산 (sodium acrylate),
폴리 (아크릴산소듐염 )(Poly(acrylic acid sodium salt)),폴리 (비닐
피를리돈) (Poly(vinyl pyrrolidone)),시트르산나트륨 (sodium citrate),시트르산 삼나트륨 (trisodium citrate),시트르산디나트륨 (disodium citrate),글루콘산 나트晉 (sodium gluconate),아스코르브산나트륨 (sodium ascorbate),
소비틀 (sorbitol),트리에틸포스페이트 (triethyl phosphate),에틸렌디아민 (ethylene diamine),프로필렌디아민 (propylene diamine),에탄디티올 (1,2-ethanedithiol),및 에탄티을 (ethanethiol)로이루어진군에서선택되는하나이상일수있다.
[35] 본발명은또한,상기금속칼코게나이드나노입자를포함하는광흡수층
제조용잉크조성물을제공하고,상기잉크조성물을사용하여박막을제조하는 방법을제공한다.
[36] 본발명에따른박막의제조방법은，
[37] (i)구리 (Cu)-주석 (Sn)칼코게나이드로이루어진제 1상 (phase),및아연 (Zn) 칼코게나이드로이루어진제 2상 (phase)을포함하는금속칼코게나이드나노 입자를용매에분산하여잉크를제조하는과정 ;
[38] (ii)전극이형성된기재상에상기잉크를코팅하는과정 ;및
[39] (iii)상기전극이형성된기재상에코팅된잉크를건조한후열처리하는과정；
[40] 을포함할 수 있다.
[41] 하나의구체적인예에서，상기과정 (i)의용매는일반적인유기용매라면
특별한 한정없이사용할수있는데， 구체적으로, 알칸계 (alkanes), 알켄계 (alkenes),알킨계 (alkynes),방향족화합물계 (aromatics),케톤계 (ketons), 니트릴계 (nitriles),에테르계 (ethers),에스테르계 (esters),
유기할로겐화물계 (organic halides),알코을계 (alcohols),아민계 (amines), 티올계 (thiols),카르복실산계 (carboxylic acids),수소화인계 (phosphines), 아인산계 (phosphites),인산염계 (phosphates),술폭시화물계 (sulfoxides),및 아미드계 (amides)중에서선택된유기용매를단독으로사용하거나이돌중에서 선택된하나이상의유기용매가혼합된형태로사용할수있다.
[42] 구체적으로,상기알코올계용매는에탄올， 1-프로판올 (l-propanol),
2-프로판올 (2-propanol), 1-펜타놀 (l-pentanol), 2-펜타놀 (2-pentanoI), 1-핵사놀 (l-hexanol), 2-핵사놀 (2-hexanol), 3-핵사놀 (3-hexanol),헵타놀 (heptanol), 옥타놀 (octanol), EG(ethylene glycol), DEGMEE(diethylene glycol monoethyl ether), EGMME(ethylene glycol monomethyl ether), EGMEE(ethylene glycol monoethyl ether), EGDME(ethylene glycol dimethyl ether), EGDEE(ethylene glycol diethyl ether), EGMPE(ethylene glycol monopropyl ether), EGMBE(ethylene glycol monobutyl ether), 2-메틸 -1-프로판을 (2-methyl-l-propanol),
시클로펜탄올 (cyclopentanol),시클로핵산올 (cyclohexanol), PGPE(propyiene glycol propyl ether), DEGDME(diethylene glycol dimethyl ether), 1 ,2-PD( 1 ,2-propanediol), 1 ,3-PD( 1 ,3-propanediol), 1 ,4-BD( 1 ,4-butanediol), 1,3-BD(1 ,3-butanediol), 알파테르피네올( S -terpineol), DEG (diethylene glycol),글리세롤 (glycerol),
2-에틸아미노에탄을 (2-(ethylamino)ethanol),
2- (메틸아미노)에탄올 (2-(methylamino)ethanol),및
2-아미노 -2-메틸 -1-프로판올 (2-amino-2-methyl-l-propanol)중에서선택되는하나 이상의혼합용매일수있다.
[43] 상기아민계용매는트리에틸아민 (triethyl amine),디부틸아민 (dibutyl amine), 디프로필아민 (dipropyl amine),부틸아민 (butylamine),에탄올아민 (ethanolamine),
DETA(Diethylenetriamine), TETA(Triethylenetetraine),
트리에탄올아민 (Triethanolamine), 2-아미노에틸피페라진 (2-aminoethyl piperazine), 2-하드록시에틸피페라진 (2-hydroxy ethyl piperazine),
다이부틸아민 (dibutylamine),및
트리스 (2-아미노에틸)아민 (tris(2-aminoethyl)amine)증에서선택되는하나이상의 혼합용매일수있다.
[44] 상기티올계용매는 1,2-에탄디티을 (1,2-ethanedithiol),펜탄티올 (pentanethiol), 핵산티올 (hexanethiol),및메르캅토에탄올 (mercaptoethanol)중에서선택되는 하나이상의흔합용매일수있다.
[45] 상기알칸계 (alkane)용매는핵산 (hexane),헵탄 (heptane),옥탄 (octane)증에서 선택되는하나이상의흔합용매일수있다.
[46] 상기방향족화합물계 (aromatics)용매는톨루엔 (toluene),자일렌 (xylene),
니트로벤젠 (nitrobenzene),피리딘 (pyridine)증에서선택되는하나이상의혼합 용매일수있다.
[47] 상기유기할로겐화물계 (organic halides)용매는클로로포름 (chloroform),메틸렌 클로라이드 (methylene chloride),테트라클로로메탄 (tetrachloromethane), 디클로로에탄 (dichloroethane),및클로로벤젠 (chlorobenzene)중에서선택되는 하나이상의흔합용매일수있다.
[48] 상기니트릴계 (nitrile)용매는아세토니트릴 (acetonitrile)일수있다.
[49] 상기케톤계 (ketone)용매는아세톤 (acetone),시클로핵사논 (cyclohexanone), 시클로펜타논 (cyclopentanone)，및아세틸아세론 (acetyl acetone)중에서선택되는 하나이상의혼합용매일수있다. Ί
[50] 상기에테르계 (ethers)용매는에틸에테르 (ethyl ether),
테트라하이드로퓨란 (tetrahydrofurane),및 1,4-다이옥산 (1,4-dioxane)중에서 선택되는하나이상의혼합용매일수있다.
[51] 상기술폭시화물계 (sulfoxides)용매는 DMSO(dimethyl sulfoxide),및
술포란 (sulfolane)증에서선택되는하나이상의혼합용매일수있다.
[52] 상기아미드계 (amide)용매는 F(dimethyl formamide),및
NMP(n-methyl-2-pyrrolidone)중에서선택되는하나이상의흔합용메일수있다.
[53] 상기에스테르계 (ester)용매는에틸락테이트 (ethyl lactate),
r-부틸로락톤 (r-butyrolactone),및에틸아세토아세테이트 (ethyl acetoacetate) 증에서선택되는하나이상의흔합용매일수있다ᅳ
[54] 상기카르복실산계 (carboxylic acid)용매는프로피온산 (propionic acid),핵산 산 (hexanoic acid),메소 -2,3-디메르갑토숙신산 (meso-2,3-dimercaptosuccinic acid), 티오락틱산 (thiolactic acid),및티오글리콜산 (thioglycolic acid)증에서선택되는 하나이상의흔합용매일수있다.
[55] 그러나,상기용매들은하나의예시일수있으며이에한정되지않는다.
[56] 경우에따라서는，상기과정 (i)의잉크에첨가제를더첨가하여제조될수있다.
[57] 상기첨가제는예를들어，분산제，계면활성제，증합체,결합제，가교결합제， 유화제,소포제,건조제，층전제，증량제，증점화제，필름조건화제，항산화제, 유동제，평활성첨가제,및부식억제제로이루어진군에서선택되는어느하나 이상일수있고,상세하게는폴리비닐피로리돈 (polyvinylpyrrolidone: PVP), 폴리비닐알코올 (Poly vinylalcohol),안티테라 204(Anti-terra 204),안티테라
205(Anti-terra 205),에틸셀를로오스 (ethyl cellulose)ᅳ및
디스퍼스 BYKllO(DispersBYKllO)으로이루어진군에서선택되는어느하나 이상일수있다.
[58] 상기과정 (U)의코팅층을형성하는방법은,예를들어,습식코팅，분무코팅， 스핀코팅，닥터블레이드 (doctor blade)코팅，접촉프린팅,상부피드리버스 (feed reverse)프린팅，하부피드리버스 (feed reverse)프린팅，노즐피드리버스 (nozzle feed reverse)프린팅，그라비어 (gravure)프린팅，마이크로그라비어 (micro gravure) 프린팅，리버스마이크로그라비어 (reverse micro gravure)프린팅，롤러코팅，슬롯 다이 (slot die)코팅，모세관코팅，잉크젯프린팅，젯 (jet)침착,분무침착으로 이루어진군에서선택되는어느하나일수있다.
[59] 상기과정 (Hi)의열처리는섭씨 400내지 900도범위의은도에서수행될수
있다.
[60] 한편，더욱높은밀도의태양전지의박막을제조하기위해서는선택적으로 셀렌화공정이포함될수있고，상기샐렌화공정은다양한방법에의해 이루어질수있다.
[61] 첫번째예에서,상기과정 (i)에서금속칼코게나이드나노입자와함께 S
및 /또는 Se를입자형태로용매에분산하여잉크를제조하고,과정 ( )의 열처리를통함으로써달성될수있다.
[62] 두번째예에서，상기과정 (iii)의열처리를 S또는 Se가존재하는조건에서 수행함으로써달성될수있다.
[63] 상세하게는,상기 S또는 Se원소가존재하는조건은 H2S또는 H2Se의가스 형태로공급하거나, Se또는 S를가열하여기체로공급함으로써가능하다.
[64] 세번째예에서 ,상기과정 (ii)이후에 S또는 Se를증착한후과정 (iii)을
진행하여달성될수있다.상세하게는，상기증착은용액공정에의하여 이루어질수있고그 밖의 다양한증착방법에의해이루어질수도있다.
[65] 본발명은또한， 상기방법으로제조된박막을제공한다.
[66] 상기박막은 0.5 /m내지 3.0； 의범위내에서두께를가질수있으며，더욱 상세하게는박막의두께는 0.5 fm내지 2.5 일수있다.
[67] 박막의두께가 0.5 um미만인경우에는광흡수층의밀도와양이층분치못해 소망하는광전효율을얻을수없고，박막이 3.0 를초과하는경우에는， 전하운반자 (carrier)가이동하는거리가증가함에따라재결합 (recombination)이 일어날확률이높아지므로이로인한효율저하가발생하게된다.
[68] 더나아가，본발명은상기박막을사용하여제조되는박막태양전지를
제공한다.
[69] 박막의태양전지를제조하는방법은당업계에이미알려져있으므로본 명세서에는그에대한설명을생략한다.
도면의간단한설명
[70] 도 1은실시예 1에의해형성된 Cu2SnS3-ZnS나노입자의 SEM사진이다;
[71] 도 2는실시예 1에의해형성된 Cu2SnS3-ZnS나노입자의 TEM사진이다;
[72] 도 3은실시예 1에의해형성된 Cu2SnS3-ZnS나노입자의 XRD그래프이다;
[73] 도 4는실시예 7에의해형성된 Cu2SnS3-ZnS나노입자의 SEM사진이다;
[74] 도 5는실시예 7에의해형성된 Cu2SnS3-ZnS나노입자의 XRD그래프이다;
[75] 도 6는실시예 17에서제조된박막의 SEM사진이다;
[76] 도 7은실시예 17에서제조된박막의 XRD그래프이다;
[77] 도 8은비교예 3에서제조된박막의 XRD그래프이다;
[78] 도 9는비교예 4에서제조된박막의 XRD그래프이다;
[79] 도 10은실시예 18에서제조된박막태양전지의 IV특성그래프이다;
[80] 도 1 1은비교예 5에서제조된박막태양전지의 IV특성그래프이다;
[81] 도 12는비교예 6에서제조된박막태양전지의 IV특성그래프이다;
[82] 도 13은본발명에따라합성된입자에서금속이균일하게분포됨을보여주는
Cu2SnS3-ZnS나노입자의 SEM-EDX결과를나타낸표이다;
[83] 도 14는본발명에따라합성된입자에서금속이균일하게분포됨을보여주는
Cu2SnS3-ZnS나노입자의 EDS맵핑 (mapping)결과이다;
[84] 도 15는본발명에따라합성된입자에서금속이균일하게분포됨을보 주는 Cu2SnS3-ZnS나노입자의조성에대한라인스캔 (line-scan)결과이다.
발명의실시를위한형태
[85] 이하,본발명의실시예를참조하여설명하지만，하기실시예는본발명을 예시하기위한것이며，본발명의범주가이들만으로한정되는것은아니다.
[86]
[87] <실시예 1>
[88] Cu,SnSrZnS입자의합성
[89] 10 mm이의 CuQ2를포함하는 DEG용액， 5 mm이의 SnCl2를포함하는 DEG 용액에 30 mm이의티오아세트아미드 (thioacetamide)를포함하는 DEG용액을 넣고， 175도까지온도를올린후 3시간동안교반하여반웅시키고，다시 상온에서상기반웅용액에 7 mm이의 ¾을포함하는 DEG용액을천천히 적가한다음， 180도이상으로가열하고,온도를유지하며 3시간동안교반한후, 원심분리법으로정제하여 Cu2SnS3-ZnS나노입자를얻었다.형성된입자를 분석한전자현미경사진 (SEM),투과전자현미경사진 (TEM)및 XRD그래프를도 1내지도 3에나타내었다.
[90]
[91] <실시예 2>
[92] Cu,SnS,-ZnS입자의합성
[93] 10 mm이의 CuS04를포함하는 DEG용액， 5 mm이의 SnCl2를포함하는 DEG 용액에 30 mm이의티오아세트아미드 (thioacetamide)를포함하는 DEG용액을 넣고， 175도까지온도를올린후 3시간동안교반하여반웅시키고,다시 상온에서상기반웅용액에 7 mm 의 ZnCl2을포함하는 DEG용액을천천히 적가한다음， 180도이상으로가열하고，온도를유지하며 3시간동안교반한후, 원심분리법으로정제하여 Cu2SnS3-ZriS나노입자를얻었다.
[94]
[95] <실시예 3>
[96] Ci SnS ZnS입자의합성
[97] 10 mm이의 CuS04를포함하는 DEG용액, 5 mm이의 Sn(OAc)2를포함하는 DEG 용액에 30 mm이의티오아세트아미드 (thioacetamide)를포함하는 DEG용액을 넣고， 175도까지은도를올린후 3시간동안교반하여반웅시키고，다시 상온에서상기반웅용액에 7 mm이의 ZnCl2을포함하는 DEG용액을천천히 적가한다음， 180도이상으로가열하고，온도를유지하며 3시간동안교반한후， 원심분리법으로정제하여 Cu2SnS3-ZiiS나노입자를얻었다.
[98]
[99] <실시예 4>
[100] Ci SnS ZnS입자의함성
[101] 10 mm이의 CuCl2를포함하는 DEG용액， 5 mm이의 SnCl2를포함하는 DEG 용액에 30 mm이의티오요소 (thiourea)를포함하는 DEG용액을넣고, 175도까지 온도를올린후 3시간동안교반하여반웅시키고，다시상은에서상기반웅 용액에 7 mm이의 ZnCl2을포함하는 DEG용액을천천히적가한다음， 180도 이상으로가열하고，온도를유지하며 3시간동안교반한후，원심분리법으로 정제하여 Cu2SnS3-ZnS나노입자를얻었다.
[102]
[103] <실시예 5>
[104] Cu,SnS,-ZnS ¾자의합성
[105] 10 mm이의 CuC12를포함하는 DEG용액， 5 mm이의 SnCl2를포함하는 DEG 용액에 15 mm이의티오아세트아미드 (thioacetamide)를포함하는 DEG용액을 넣고， 175도까지온도를올린후 5시간동안교반하여반웅시키고，다시 상온에서상기반웅용액에 6 mm이의 ZnCl2을포함하는 DEG용액, 6 mmol의 티오아세트아미드를포함하는 DEG용액을천천히적가한다음, 180도이상으로 가열하고,온도를유지하며 3시간동안교반한후，원심분리법으로정제하여 Cu2 SnS3-ZnS나노입자를얻었다.
[106]
[107] <실시예 6>
[108] Cu,SnSvZnS입자의합성
[109] 10 mm이의 CuCl2를포함하는 DEG용액, 5 mm이의 SnCl2를포함하는 DEG
용액에 20 mm이의티오아세트아미드 (thioacetamide)를포함하는 DEG용액을 넣고， 175도까지온도를올린후 3시간동안교반하여반웅시키고,다시 상온에서상기반웅용액에 6 mm 의 ZnCl2을포함하는 DEG용액, 12 mmd의 티오아세트아미드를포함하는 DEG용액을천천히적가한다음， 180도이상으로 가열하고,온도를유지하며 3시간동안교반한후,원심분리법으로정제하여 Cu2 SnS3-ZnS나노입자를얻었다.
[110]
[111] <실시예 7>
[112] Cu,SnS,-ZnS 자의합성
[113] 10 mm이의 CuCl2를포함하는 DEG용액, 5 mm이의 SnCl2를포함하는 DEG
용액에 20 mm이의티오아세트아미드 (thioacetamide)를포함하는 DEG용액을 넣고， 175도까지은도를올린후 6시간동안교반하여반웅시키고，다시 상온에서상기반웅용액에 6 mm이의 ZnCl2을포함하는 DEG용액, 12 mmol의 티오아세트아미드를포함하는 DEG용액을천천히적가한다음, 180도이상으로 가열하고,온도를유지하며 3시간동안교반한후，원심분리법으로정제하여 Cu2 SnS3-ZnS나노입자를얻었다.형성된입자를분석한전자현미경사진 (SEM)및 XRD그래프를도 4및도 5에나타내었다.
[114]
[115] <실시예 8> [116] CU,SnS,-ZnS입자의함^
[117] 10 mm이의 CuCl2를포함하는 EG용액, 5 mm이의 SnCl2를포함하는 EG용액에 30 mm이의티오아세트아미드 (thioacetamide)를포함하는 EG용액을넣고， 175도까지온도를올린후 3시간동안교반하여반응시키고，다시상온에서상기 반웅용액에 6 mm이의 ZnCl2을포함하는 EG용액을천천히적가한다음, 180도 이상으로가열하고,온도를유지하며 3시간동안교반한후,원심분리법으로 정제하여 Cu2SnSrZnS나노입자를얻었다.
[Π8]
[119] <실시예 9>
[120] Cu,SnS,-ZnS입자의합성
[121] 10 mm이의 CuCl2를포함하는 DEG용액, 5 mm이의 SnCl2를포함하는 DEG용액， 1 mm이의 PVP를포함하는 DEG용액에 30 mm이의
티오아세트아미드 (thioacetamide)를포함하는 DEG용액을넣고， 175도까지 온도를올린후 3시간동안교반하여반웅시키고,다시상온에서상기반웅 용액에 7 mm이의 ZnCl2을포함하는 DEG용액을천천히적가한다음， 180도 이상으로가열하고,온도를유지하며 3시간동안교반한후，원심분리법으로 정제하여 Cu2SnS3-ZnS나노입자를얻었다.
[122]
[123] <실시예 10>
[124] Cu,SnS,-ZnS입자의합성
[125] 10 mm 의 CuCl2를포함하는 H20용액， 5 mn l의 SnCl2를포함하는 0
용액에 30 mm이의티오아세트아미드 (thioacetamide)를포함하는 H20용액을 넣고， 100도까지온도를올린후 3시간동안교반하여반웅시키고,다시 상온에서상기반웅용액에 6 mm이의 ZnCl2을포함하는 H20용액을천천히 적가한다음， 100도로가열하고，온도를유지하며 3시간동안교반한후， 원심분리법으로정제하여 CU2SnS3-ZnS나노입자를얻었다.
[126]
[127] <실시예 11>
[128] Cu2SnS ZnS입자의합성
[129] 10 mm이의 CuCl2를포함하는 H20용액， 5 mm이의 SnCl2를포함하는 H20용액, 10 mm이의시트르산나트륨 (sodium citrate)을포함하는 H20용액에 30 mm이의 티오아세트아미드 (thioacetamide)를포함하는 H20용액을넣고, 100도까지 온도를올린후 6시간동안교반하여반웅시키고,다시상온에서상기반웅 용액에 6 mm이의 ZnCl2을포함하는 H20용액, 12 mm이의티오아세트아미드를 포함하는 ¾0용액을천천히적가한다음， 100도로가열하고,온도를유지하며 3시간동안교반한후,원심분리법으로정제하여 Cu2SnS3-ZnS나노입자를 얻었다.
[130] [131] <실시예 12>
[132] Cu,SnS,-ZnS입자의합석
[133] 10 mm이의 1^03)2를포함하는 H20용액， 5 mm이의 SnCl2를포함하는 H20 용액， 10 mm이의소듬메조옥살레이트 (sodium mesoxalate)을포함하는 ¾0 용액에 30 mm이의티오아세트아미드 (thioacetamide)를포함하는 H20용액을 넣고， 100도까지은도를올린후 6시간동안교반하여반웅시키고，다시 상온에서상기반웅용액에 6 nun이의 Zn(OAc)2을포함하는 H20용액， 12 nun이의 티오아세트아미드를포함하는 0용액을천천히적가한다음， 100도로 가열하고，온도를유지하며 5시간동안교반한후,원심분리법으로정제하여 Cu2 SnS3-ZnS나노입자를얻었다.
[134]
[135] <실시예 13>
[136] Cu,SnSvZnS입자의함성
[137] 10 mm이의 0 12를포함하는 0용액, 5 mm이의 SnCl2를포함하는 H20
용액에 30 mm이의 Na2S를포함하는 0용액을넣고,상온에서 3시간동안 교반하여반웅시키고,다시상온에서상기반웅용액에 6 mm이의 ZnCl2을 포함하는 0용액을천천히적가한다음，상온에서 3시간동안교반한후， 원심분리법으로정제하여 Cu2SnS3-ZnS나노입자를얻었다.
[138]
[139] <실시예 14>
[140] Cu,SnS,-ZnS입자의합성
[141] 10 mm이의 CuS04를포함하는 0용액， 5 mm이의 SnCl2를포함하는 H20용액, 15 mm이의시트르산나트륨 (sodium citrate)을포함하는 H20용액에 30 mm이의 Na2S를포함하는 ¾0용액을넣고，상온에서 3시간동안교반하여반웅시키고， 다시상온에서상기반응용액에 6 mmd의 ZnCl2을포함하는 H20용액을천천히 적가한다음，상온에서 3시간동안교반한후,원심분리법으로정제하여 Cu2SnS3 -ZnS나노입자를얻었다.
[142]
[143] <실시예 15>
[144] Ci SnS,-ZnS입자의합성
[145] 10 mm이의 CuS04를포함하는 H20용액， 5 mm이의 SnCl2를포함하는 H20
용액에 30 mm이의 Na2S를포함하는 H20용액을넣고,상온에서 3시간동안 교반하여반응시키고，다시상온에서상기반웅용액에 6 mm이의 ZnCl2을 포함하는、 0용액을천천히적가한다음，상온에서 3시간동안교반한후, 원심분리법으로정제하여 Cu2SnS3-ZnS나노입자를얻었다.
[146]
[147] <실시예 16>
[148] Cu,SnS,-ZnS입자의합성 [149] 10 mm이의 Cu(N03)2를포함하는 H20용액， 5 mm이의 SnCl2를포함하는 ¾0 용액에 30 mm이의 Na2S를포함하는 H20용액을넣고，상온에서 3시간동안 교반하여반웅시키고，다시상온에서상가반응용액에 6 mm이의 ZnCl2올 포함하는 ¾0용액을천천히적가한다음,상온에서 3시간동안교반한후， 원심분리법으로정제하여 Cu2SnS3-ZnS나노입자를얻었다.
[150]
[151] <비교예 1>
[152] Cu(acac)2 (cupric acetylacetonate), Zn(OAc)2 (zinc acetate),및 Sn(acac)2Br2을
올레일아민 (oleylamine)용액에녹인후， 225도까지승은시켰고，이때, S원소가 녹아있는올레일아민용액을추가로상기승온된용액에적가하였다.형성된 입자를원심분리법으로정제하여 CZTS나노입자를제조하였다.
[153]
[154] <비교예 2>
[ 155] CuCl2.2H20, SnCl2,그리고 Thioacetamide를 Diethylene Glycol용액에녹인후,
175도에서 2.5시간가열하였다.합성된입자를원심분리법으로정제하여 Cu2SnS 3입자를얻었다.또한,별도로 ZnCl2, Thioacetamide그리고 PVP를 Diethyene Glycol용액에녹인후， 175도에서 2.5시간가열하였다.합성된입자를
원심분리법으로정제하여 ZiiS입자를얻었다.
[156]
[157] <실시예 17>
[158] 박막의제조
[159] 실시예 8에서제조된 Cu2SnS3-ZnS입자를알콜계용매로이루어진흔합용매에 분산하여잉크를제조한후,몰리브덴 (Mo)이코팅된유리기판 (glass substrate) 위에코팅하였다.상기코팅막을건조시킨후， Se이증착된유리기판과함께 가열하여 Se분위기가조성될수있도록한후 575°C로 RTA(Rapid Thermal Annealing)하여 CZTSSe계박막을제조하였다.얻어진박막을분석한
전자현미경 (SEM)사진및 XRD그래프를도 6과도 7에나타내었다.
[160]
[161] <비교예 3>
[162] 박막의제조
[163] 비교예 1에서제조된 CZTS나노입자를톨루엔 (toluene)용매에분산하여
잉크를제조한후,몰리브덴 (Mo)이코팅된소다라임유리기판 (soda lime glass substrate)위에코팅하였다.상기코팅막을건조시킨후, Se분위기하에서 450°C로열처리하여 CZTSSe계박막을제조하였다.얻어진박막을분석한 XRD 그래프를도 8에나타내었다.
[164]
[165] <비교예 4>
[166] 받막의체조 [167] 비교예 2에서제조된 Cu2SnS3나노입자및 ZnS나노입자를알콜계용매로 이루어진흔합용매에분산하여잉크를제조한후,몰리브덴 (Mo)이코팅된유리 기판 (glass substrate)위에코팅하였다.상기코팅막을건조시킨후， Se이증착된 유리기판과함께가열하여 Se분위기가조성될수있도록한후 575°C로
RTA(Rapid Thermal Annealing)하여 CZTSSe계박막을제조하였다.얻어진 박막을분석한 XRD그래프를도 9에나타내었다.
[168]
[169] <실시예 18>
[170] 받막태양저지의제조
[171] 실시예 17에서제조된 CZTSSe계박막을사이안화칼륨 (KCN)용액으로에칭한 후， CBD(Chemical bath deposition)방법을이용하여 CdS층 (Thickness: 50 nm)을 올린후스퍼터링법을이용하여 ZnO층 (Thickness: 100 nm)및 A1가도핑된 ZnO층 (Thickness: 500 nm)을차례로적층하여박막을제조하고，상기박막에 알루미늄 (A1)전극을형성시켜박막태양전지를제조하였다.상기박막 태양전지로부터얻어진전류 -전압 (I-V)특성그래프를도 10에나타내었다.
[172]
[173] <비교예 5>
[174] 박막태양저지의제조
[175] 비교예 3에서제조된 CZTSSe계박막에 CBD(Chemical bath deposition)방법을 이용하여 CdS층을올린후스퍼터링법을이용하여 ZnO층및 ΠΌ층을차례로 적층하여박막을제조하고,상기박막에전극을형성시켜박막태양전지를 제조하였다.상기박막태양전지로부터얻어진전류 -전압 (I-V)특성그래프를도 11에나타내었다.
[176]
[177] <비교예 6>
[178] 박막태양저지의체조
[179] 비교예 4에서제조된 CZTSSe계박막에 CBD(ChemicaI bath deposition)방법을 이용하여 CdS층을올린후스퍼터링법을이용하여 ZnO층및 ITO층을차례로 적층하여박막을제조하고,상기박막에전극을형성시켜박막태양전지를 제조하였다.상기박막태양전지로부터얻어진전류 -전압 (I-V)특성그래프를도 12에나타내었다.
[180]
[181] <실험예 1>
[182] 실시예 18및비교예 5， 6에서제조된박막태양전지의광전효율을측정하였고， 그결과를하기표 1,도 10내지도 12에나타내었다.
[183] 표 1 [Table 1]
Figure imgf000016_0001
[184] 상기표 1에기재된태양전지의효율을결정하는변수인 Jsc는전류밀도를
의미하고， Voc는제로출력전류에서측정된개방회로전압을의미하며 , 광전효율은태양전지판에입사된빛의에너지량에따른전지출력의비율을 의미하고， FF(Fill factor)는최대전력점에서의전류밀도와전압값의곱을 Voc와 Jsc 의곱으로나눈값을의미한다.
[185] 표 1에서볼수있듯이，본발명에따라제조된금속칼코게나이드나노입자를 광흡수층을형성하는데사용한경우,기존의방법에의해제조된금속
칼코게나이드나노입자를사용한경우에비해，전류밀도및전압이높아 우수한광전효율을나타냄을알수있다.
[186]
[187] 본발명이속한분야에서통상의지식을가진자라면상기내용을바탕으로본 발명의범주내에서다양한웅용및변형을행하는것이가능할것이다.
산업상이용가능성
[188] 이상에서설명한바와같이,본발명에따른금속칼코게나이드나노입자는, 구리 (Cu)-주석 (Sn)칼코게나이드로이루어진제 1상 (phase),및아연 (Zn) 칼코게나이드로이루어진제 2상 (phase)을한입자내에포함하는바，이를 사용하여박막을제조하는경우，이차상의발생을억제할수있고한입자내에 금속을모두포함하고있어박막전체적으로보다균일한조성을가질수있을 뿐아니라,나노입자자체에 S또는 Se를포함함으로써산화에안정하고최종 박막내에 \^[족원소의함유량을높일수있으며,셀렌화과정에서 VI족원소를 첨가함에따라입자부피의증가로인해더높은밀도의박막을성장시킬수 있는효과가있다.
[189] 또한,본발명에따른금속칼코게나이드나노입자는용액공정을통하여
제조되므로기존의진공공정대비공정비용을획기적으로낮출수있고, 히드라진과같은유독한환원제를사용하지않아,위험성을제거할수있는 효과가있다.

Claims

청구범위
태양전지의광흡수층을형성하는금속칼코게나이드나노 입자로서,구리 (Cu)-주석 (Sn)칼코게나이드로이루어진제 1 상 (phase),및아연 (Zn)칼코게나이드로이루어진제 2상 (phase)을 포함하는것을특징으로하는금속칼코게나이드나노입자. 제 1항에있어서，구리 (Cu)-주석 (Sn)칼코게나이드는 CuaSnSb
(1.2<a<3.2, 2.5<b<4.5),및 /또는 CuxSnSey(1.2≤x≤3.2, 2.5≤y≤4.5)인 것을특징으로하는금속칼코게나이드나노입자.
제 1항에있어서,아연 (Zn)함유칼코게나이드는 ZnS,및 /또는
ZnSe인것을특징으로하는금속칼코게나이드나노입자. 제 1항에있어서,상기제 1상및제 2상은독립적으로존재하는 것을특징으로하는금속칼코게나이드나노입자.
제 1항에있어서，상기금속칼코게나이드나노입자내에서의 금속의조성비는 0.5≤Cu/(Zn+Sn)≤1.5, 0.5≤Zn/Sn≤2.0이되는 범위에서정해지는것을특징으로하는금속칼코게나이드나노 입자.
제 1항에있어서，상기제 1상및제 2상은금속칼코게나이드 나노입자내에서균일하게분포되어있는것을특징으로하는 금속칼코게나이드나노입자.
제 6항에있어서，상기금속칼코게나이드내임의의영역을 관찰하였을때,상기영역에서금속칼코게나이드나노입자 내에서의금속의조성비는 0.5≤Cu/(Zn+Sn)≤1.5, 0.5≤Zn/Sn≤2.0이 되는범위에서정해지는것을특징으로하는금속칼코게나이드 나노입자.
제 7항에있어서,상기영역에서금속칼코게나이드나노입자 내에서의금속의조성비는 a7<Cu/(Zn+Sn)<1.2, ().8<Zn/Sn<L4가 되는범위에서정해지는것을특징으로하는금속칼코게나이드 나노입자.
제 1항에있어서，상기금속칼코게나이드나노입자는제 1상및 제 2상이벌크 (bulk)형태로존재하는복합체인것을특징으로 하는금속칼코게나이드나노입자.
제 1항에있어서，상기금속칼코게나이드나노입자는제 1 상으로이루어진코어 (core)와,제 2상으로이루어진쉘 (shell)을 포함하는코어-쉘구조의나노입자인것을특징으로하는금속 칼코게나이드나노입자.
제 10항에있어서,상기코어의입경은 5나노미터내지 200 나노미터인것을특징으로하는금속칼코게나이드나노입자. [청구항 12] 제 10항에있어서,상기쉘의두께는 1나노미터내지 100
나노미터인것을특징으로하는금속칼코게나이드나노입자. [청구항 13] 제 1항에따른금속칼코게나이드나노입자를합성하는
방법으로서,
(1)황 (S)또는셀레늄 (Se)을포함하는화합물로이루어진군에서 선택되는 1종이상의 VI족소스를포함하는제 1용액을준비하는 과정;
(ii)구리 (Cu)염및주석 (Sri)염을포함하는제 2용액과， 아연 (Zn)염을포함하는제 3용액을준비하는과정;
(iii)상기제 1용액과제 2용액을흔합하여반웅시키는과정 ;및
(iv)상기과정 (iii)의반응생성물에상기제 3용액을흔합하여 반웅시키는과정 ;
을포함하는것을특징으로하는금속칼코게나이드나노입자의 합성방법.
[청구항 14] 제 13항에있어서,상기과정 (iv)의제 3용액을혼합시추가로
VI족소스를첨가하는것을특징으로하는금속칼코게나이드 나노입자의합성방법 .
[청구항 15] 제 13항에있어서,상기제 1용액，제 2용액,및제 3용액의
용매는물,디에틸렌글리콜 (diethylene glycol),메탄올 (methanol), 에탄올 (ethanol),오레일아민 (oleylamine),에틸렌글리콜 (ethylene glycol),트리에틸렌글리콜 (triethylene glycol), 디메틸설폭사이드 (dimethyl sulfoxide),
디메틸포름아마이드 (dimethyl formamide)및
NMP(N-methyl-2-pyrrolidone)로이루어진군에서선택되는하나 이상인것을특징으로하는금속칼코게나이드나노입자의 합성방법.
[청구항 16] 제 13항에있어서,상기구리 (Cu)염과주석 (Sn)염및아연 (Zn)염은 각각독립적으로염화물 (chloride),브롬화물 (bromide), 요오드화물 (iodide),질산염 (nitrate),아질산염 (nitrite),
황산염 (sulfate),아세트산염 (acetate),아황산염 (sulfite),
아세틸아세토네이트염 (acetylacetoante)및수산화물 (hydroxide)로 이루어진군에서선택되는하나이상의형태인것을특징으로 하는금속칼코게나이드나노입자의합성방법 .
[청구항 17] 제 13항에있어서,상기 VI족소스는 Se, Na2Se, K2Se, CaSe, (CH3)2
Se, Se02, SeCl4, H2Se03, ¾Se04, Na2S, K2S, CaS, (CH3)2S, H2S04, S,
Na2S203, NH2S03H및이돌의수화물과,티오요소 (thiourea), 티오아세트아미드 (thioacetamide),
샐레노아세트아미드 (sdenoacetamide)및 셀레노유레아 (sdenourea)로이루어진군에서선택되는하나
이상인것을특징으로하는금속칼코게나이드나노입자의 합성방법.
[청구항 18] 제 1항에따른금속칼코게나이드나노입자를포함하는것을 특징으로하는광흡수층제조용잉크조성물.
[청구항 19] 제 18항에따른광흡수층제조용잉크조성물을사용하여박막을 제조하는방법으로서 ,
(i)구리 (Cu)-주석 (Sn)칼코게나이드로이루어진제 1상 (phase),및 아연 (Zn)칼코게나이드로이루어진제 2상 (phase)을포함하는 금속칼코게나이드나노입자를용매에분산하여잉크를제조하는 과정;
(ii)전극이형성된기재상에상기잉크를코팅하는과정;및
(iii)상기전극이형성된기재상에코팅된잉크를건조한후 열처리하는과정;
을포함하는것을특징으로하는박막의제조방법 .
[청구항 20] 제 19항에있어서,상기과정 (i)의용매는알칸계 (alkanes),
알켄계 (alkenes),알킨계 (alkynes),방향족화합물계 (aromatics), 케톤계 (ketons),니트릴계 (nitriles),에테르계 (ethers),
에스테르계 (esters),유기할로겐화물계 (organic halides),
알코올계 (alcohols),아민계 (amines),티올계 (thiols),
카르복실산계 (carboxylic acids),수소화인계 (phosphines), 인산염계 (phosphates),황산화물계 (sulfoxides),및아미드계 (amides) 이루어진군으로부터선택된하나이상의유기용매인것을 특징으로하는박막의제조방법 .
[청구항 21] 제 19항에있어서,상기과정 (i)의잉크는첨가제를더포함하여 제조되는것을특징으로하는박막의제조방법 .
[청구항 22] 제 19항에있어서,상기첨가제는
폴리비닐피로리돈 (Polyvinylpyrrolidone: PVP),
폴리비닐알코올 (Polyvinylalcohol),안티테라 204(Anti-terra 204)， 안티테라 205(Anti-terra 205),에틸셀를로오스 (ethyl cellulose),및 디스퍼스 BYKl lO(DispersBYKllO)으로이루어진군에서선택되는 어느하나이상인것을특징으로하는박막의제조방법 .
[청구항 23] 제 19항에있어서,상기과정 (ii)의코팅은습식코팅，분무코팅， 닥터블레이드 (doctor blade)코팅，또는잉크젯프린팅에의해 이루어지는것을특징으로하는박막의제조방법 .
[청구항 24] 제 19항에있어서,상기과정 (iii)의열처리는섭씨 400내지 900도 범위의온도에서수행되는것을특징으로하는박막의제조방법. [청구항 25] 제 19항에있어서,상기과정 (i)에서금속칼코게나이드나노 입자와함께 S및 /또는 Se를입자형태로용매에분산하여잉크를 제조하는것을특징으로하는박막의제조방법 .
[청구항 26] 제 19항에있어서，상기과정 (iii)의열처리는 S또는 Se가
존재하는조건에서이루어지는것을특징으로하는박막의제조 방법.
[청구항 27] 제 26항에있어서ᅳ상기 S또는 Se가존재하는조건은 H2S또는 ¾
Se의가스형태로공급되거나， Se또는 S를가열하여기체로 공급됨으로써이루어지는것을특징으로하는박막의제조방법.
[청구항 28] 제 19항에있어서，상기과정 (ii)이후에 S또는 Se를증착하는 과정을추가로포함하는것을특징으로하는박막의제조방법 .
[청구항 29] 제 19항내지제 28항증어느하나에따른방법으로제조된것을 특징으로하는박막.
[청구항 30] 제 29항에따른박막을사용하여제조되는박막태양전지 .
PCT/KR2014/008181 2013-09-12 2014-09-02 태양전지 광흡수층 제조용 금속 칼코게나이드 나노 입자 및 이의 제조방법 WO2015037856A1 (ko)

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EP14844680.0A EP3026714B1 (en) 2013-09-12 2014-09-02 Method for preparing metal chalcogenide nanoparticles for manufacturing optical absorption layer for solar cell
US15/638,240 US10170649B2 (en) 2013-09-12 2017-06-29 Metal chalcogenide nanoparticles for preparing light absorption layer of solar cells and method of preparing the same

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US10170649B2 (en) 2019-01-01
US20160218231A1 (en) 2016-07-28
KR20150030598A (ko) 2015-03-20
EP3026714A1 (en) 2016-06-01
ES2834993T3 (es) 2021-06-21
EP3026714A4 (en) 2017-04-12
CN105518872A (zh) 2016-04-20
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CN105518872B (zh) 2018-04-27
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