WO2013002605A2 - Composite particles for a photoactive layer of a solar cell and method for manufacturing same - Google Patents

Composite particles for a photoactive layer of a solar cell and method for manufacturing same Download PDF

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Publication number
WO2013002605A2
WO2013002605A2 PCT/KR2012/005194 KR2012005194W WO2013002605A2 WO 2013002605 A2 WO2013002605 A2 WO 2013002605A2 KR 2012005194 W KR2012005194 W KR 2012005194W WO 2013002605 A2 WO2013002605 A2 WO 2013002605A2
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group
metal
photoactive layer
metals
solar cell
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PCT/KR2012/005194
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French (fr)
Korean (ko)
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WO2013002605A3 (en
Inventor
정선호
이병석
최영민
류병환
정택모
김창균
서영희
조예진
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한국화학연구원
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Publication of WO2013002605A2 publication Critical patent/WO2013002605A2/en
Publication of WO2013002605A3 publication Critical patent/WO2013002605A3/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
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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 a composite particle for a photovoltaic active layer of a solar cell and a method for manufacturing the same, which can produce a high quality photoactive layer through a simple, safe and easy process in detail and satisfying the stoichiometric ratio. It is possible to manufacture single-phase photoactive layer, to have composite stability and uniformity at a temperature within the process tolerance of 550 o C or less, to have a fine structure, and to produce a photoactive layer composed of coarse grains. It's about how.
  • a method of preparing photoactive fillers through a particle-based solution process for producing a CI (G) S film by coating a mixture of oxide nanoparticles or a mixture of metal oxides and non-oxide particles on a substrate and then reacting them under a reducing atmosphere and a Se gas atmosphere. Is being tried.
  • the purpose of the present invention is to provide a compact and low-temperature heat treatment under the process tolerance of 550 ° C,
  • the present invention provides a composite particle which can be prepared in a single phase and has a stoichiometric ratio-based photoactive layer, a manufacturing method thereof, and an ink containing the same.
  • Another purpose of the present invention is to provide a low temperature heat treatment of less than 550 ° C.
  • the composite particles according to the present invention are for solar cell photoactive layers.
  • Satisfactory Group 11 metal chalcogenide compounds are common particles in the medium.
  • ⁇ is one or more selected from Group 11 metals, ⁇ is a chalcogen element,
  • X is a real number that satisfies 1-2.
  • the medium is a chalcogenide compound of at least one element selected from Group 11 metals and Groups 12-14.
  • It may contain an intermetallic chalcogenide compound.
  • the medium may contain an intermetallic chalcogenide compound satisfying the following Chemical Formula 2 or the following Chemical Formula 3.
  • M ' is one or more metals selected from Group 11 metals, and ⁇ "is
  • One or more metals selected from Group 13 One or more metals selected from Group 13.
  • M ' is one or more metals selected from Group 11 metals
  • ⁇ "' is
  • the volume 11 may contain the Group 11 metal chalcogenideol.
  • the composite particle may contain a Group 11 metal: Group 12-14 metal: chalcogen element at a molar ratio of 0.8 to 1.3: 0.8 to 1.3: 1.7 to 2.3. have.
  • the Group 11 metal may be Cu.
  • the metal of Group 12 to 14 may be In or In and Ga, and the chalcogen element may be Se.
  • the Group 11 metal chalcogenide compound may contain CuSe, CuSe 2, or a mixture thereof.
  • the composite particle has a molar ratio of Group 11 metals: Group 12-14 metals: chalcogen elements of 8 to 1.3: 0.8 to 1.3: 1.7 to 2.3.
  • Each of the metal precursors and the chalcogenide precursors can be prepared by irradiating microwaves in a mixture mixed in a semi-aqueous solvent having a boiling point of 200 ° C or higher.
  • the present invention includes an ink for a solar cell photoactive layer containing the above-mentioned composite particles.
  • the manufacturing method of the composite particles for solar cell photoactive layer according to the present invention includes a) each metal such that the molar ratio of Group 11 metals: Group 12-14 metal: chalcogen element is 0.8-1.3: 0.8-1.3: 1.7-2.3.
  • Precursors and chalcogenide precursors are compatible with semi-aqueous solvents with boiling points above 200 ° C.
  • M is one or more selected from Group 11 metals, A is a chalcogenide and X is a real number satisfying 1 or 2.
  • step b) may be performed for 15 to 40 minutes at 200 to 30 ° C. by irradiating microwaves to the mixture.
  • the reaction solvent of step a) may include one or more solvents selected from poly-based solvents, amine-based solvents and phosphine-based solvents.
  • Group 11 metals satisfying a molar ratio of 0.8-1.3: 0.8-1.3: 1.7-2.3 may be Cu
  • Group 12-14 metals may be In or In and Ga
  • the chalcogenide element may be Se.
  • the composite particle of step b) is CuSe, CuSe in a medium containing an intermetallic chalcogenide compound satisfying the following formula (2) or (3) It may be a particle having a Group 11 metal chalcogenide compound, which is 2 or a combination thereof.
  • M ' is one or more metals selected from Group 11 metals
  • M ' is one or more metals selected from Group 11 metals
  • the method of manufacturing a solar cell photoactive layer according to the present invention may include c) applying the ink described above to a substrate to form a coating film; and d) heat treating the coating film to prepare a photoactive layer.
  • the heat treatment of step d) may be performed at 400 to 550 ° C. in a chalcogen atmosphere.
  • the present invention includes a photoactive layer for solar cells manufactured by the method for producing a photovoltaic active layer described above.
  • the present invention includes a solar cell equipped with the photoactive layer described above.
  • the composite particles according to the present invention have a low melting point, which is a chalcogenide compound of Group 11 metal.
  • the chalcogenide compound is a mixed particle in the medium, a high quality plural chalcogenide compound is obtained through an extremely simple, safe and easy process of heat-treating the coating film containing the composite particle at a temperature within the process tolerance of 550 ° C or below.
  • (Photoactive layer) can be manufactured, and the composition of the photoactive layer can be controlled by the composition of the composite particles, and only by heat treatment of the coating film containing the composite particles, it is possible to manufacture the photoactive layer satisfying the stoichiometric ratio. It has excellent compositional stability and uniformity, has a dense fine structure, and has the advantage of manufacturing a single-phase photoactive layer composed of coarse grains.
  • Example 1 shows the results of X-ray diffraction analysis of the composite particles prepared in Example 1
  • FIG. 2 shows the results of X-ray diffraction analysis of the photoactive layer prepared in Example 1
  • Example 3 is a scanning electron micrograph of the photoactive layer prepared in Example 1,
  • FIG. 5 shows the X-ray diffraction of the composite particles prepared in Examples 1 and 4 to 6.
  • FIG. 6 is a diagram showing an X-ray diffraction analysis result of the particles prepared in Comparative Example 1
  • FIG. 7 is a diagram showing an X-ray well analysis result of the photoactive layer prepared in Comparative Example 1.
  • FIG. 8 is a scanning electron micrograph of the photoactive layer prepared in Comparative Example 1.
  • FIG. 9 illustrates solar cell characteristics (efficiency: 8.3%) fabricated using the ink composition-based CuInSe 2 thin film of Example 1.
  • the low melting point chalcogenide compound when the low melting point chalcogenide compound is mixed with the mixed particles in the medium to produce the photoactive layer, the low temperature heat treatment below the process tolerance temperature of 550 ° C. It is possible to manufacture a photoactive layer composed of a single plural chalcogenide compound, a dense and uniform photoactive layer can be prepared, a photoactive layer composed of coarse grains, and a composition ratio satisfying the stoichiometric ratio can be prepared. In this regard, the present invention has been applied for.
  • the composite particle for solar cell photoactive layer according to the present invention satisfies the following formula (1).
  • Group 11 metal chalcogenides are particles mixed in the medium.
  • ⁇ is one or more selected from Group 11 metals, A is a chalcogen element, and X is a real number satisfying 1-2.
  • the composite particle according to the embodiment of the present invention is a group 11 satisfying the medium and formula (1).
  • the metal chalcogenide compound may be commonly present as a single particle at the same time as the synthesis.
  • the composite particles according to one embodiment of the present invention are formed at the stage of synthesis of the Group 11 metal chalcogenide compound satisfying the medium and formula (1).
  • the media and Group 11 metal chalcogenide compounds can be formed and aggregated.
  • the particles may refer to secondary particles in which several crystals and / or amorphous particles form a grain boundary with each other, and in terms of the in-situ, the nucleation and growth of the medium material and Nucleation and growth of the Group 11 metal chalcogenide occurs frequently, and such nucleation may occur by the nucleation site of another nucleus that has been generated and grown immediately.
  • the medium is a chalcogenide compound of at least one element selected from Group 11 metals and Groups 12-14.
  • It may contain an intermetallic chalcogenide compound.
  • the Group 11 metal may include Cu.
  • Group 12 metals may include Zn
  • Group 13 metals may include Ga and In
  • Group 14 metals may include Sn, i.e., Groups 12 to 14 may contain Zn, Ga, In and Sn.
  • One or more selected elements from Groups 12 to 14 may be In; Ga; In and Ga; Zn; Sn; or may be Zn and Sn.
  • a chalcogen of a chalcogen compound in a composite particle according to an embodiment of the present invention may include S, Se or S and Se.
  • the composite particle according to an embodiment of the present invention is a chalcogenide compound of one or two or more elements selected from Group 11 metals and Groups 12 to 14
  • a chalcogen compound (hereinafter referred to as Group 1 chalcogen compound);
  • the intermetallic chalcogenide compound and the Group 11 chalcogenide compound may be composite particles common to a single particle.
  • the intermetallic chalcogenide compound is
  • the composite particles may be particles in which a chalcogen compound and a group 11 chalcogen compound including all metal elements constituting the photoactive layer are found in a single particle.
  • an intermetallic chalcogenide compound which is a chalcogenide compound of at least one element selected from Group 11 metals and Groups 12 to 14, is a compound semiconductor-based optical activity to be prepared. Having stoichiometric ratio of layer
  • It may be an intermetallic chalcogenide compound.
  • the intermetallic chalcogenide compound may be an intermetallic chalcogenide compound satisfying the stoichiometric ratio according to the following Chemical Formula 2 or the following Chemical Formula 3.
  • M ' is a metal selected from one or more than one group 11 metal, ⁇ "is
  • M ' may be copper and ⁇ "may be a real number In y Ga ⁇ O y ⁇ ),
  • A may be a real number Se n S 0 ⁇ n ⁇ l).
  • M ' is one or more metals selected from Group 11 metals, and ⁇ ' "is
  • M ' may be copper
  • M "' may be Zn m Sn 2 _ m (real number 0 ⁇ m ⁇ 2)
  • A may be a real number Se n S 0 ⁇ n ⁇ l).
  • the intermetallic chalcogenide compound may be CuInSe, CuInS or CuInSe ⁇ .
  • the Group 11 chalcogenide compound may form a molten phase (liquid phase) at a thermal treatment temperature for manufacturing a photoactive layer of a solar cell.
  • the heat treatment temperature for producing a solar cell photoactive layer may be 400 to 550 ° C
  • Group 1 chalcogenide compound may form a molten phase at 400 to 550 ° C, more specifically ,
  • the melting point of the Group 11 chalcogenene compound may be 220 to 550 ° C.
  • the Group 1 Group 1 metal may include copper.
  • the Group 11 chalcogenide compound may include CuSe, CuSe 2 or a combination thereof.
  • the Group 11 metal may be Cu.
  • the metal of Group 12 to 14 may be In, In, and Ga, and the chalcogen element may be Se.
  • the Group 11 metal may be Cu.
  • the metal of Group 12 to 14 may be Zn, Sn or Zn and Sn, chalcogen element may be S, Se or S.
  • the composite particles according to one embodiment of the present invention contain all metal elements of the photoactive layer to be manufactured, such as CIS (Cu-in- (S, Se)), and the photoactive activity to be manufactured.
  • the medium contains intermetallic chalcogenides having a stoichiometric ratio of the layer as a medium, and the low melting point Group 11 chalcogenides forming the medium and the liquid phase are mixed in a single particle, the step of the photoactive layer in the composite particle step without further processing is required.
  • the composition can be adjusted to the desired composition.
  • the composite particles according to the embodiment of the present invention are formed by the composition of the composite particles themselves.
  • the Group 11 chalcogenide forming a molten phase can produce a very fast and homogeneously dense structure of the photoactive layer.
  • the loss of the chalcogenide element can be prevented to obtain compositional stability.
  • the heterogeneous distribution of the molten phase leads to the formation of a nonuniform fine structure of the finally produced photoactive layer.
  • the formation of locally excessive molten phases may lead to the composition uniformity of the photoactive layer.
  • the composite particles in accordance with one embodiment of the present invention is a Group 11 metal: 12 to Group 14 metal: the molar ratio of the knife kojen element 0.8 ⁇ 1.3: 0.8 ⁇ 1.3: 1.7 ⁇ 2.3, preferably, 0.8 ⁇ 1.3: 1 : It can be 2 days.
  • the element ratio of the photoactive layer produced by the molar ratio (element ratio) of each metal and calcolian element contained in the composite particle can be specified. Accordingly, the pole using the composite particle having the stoichiometric ratio of the target photoactive insect. Through a simple and simple method, it is possible to manufacture a photoactive layer having a desired composition.
  • the complex particles may be formed of all of the photoactive layers to be manufactured, such as CIS (Cu-In- (S, Se)).
  • CIS Cu-In- (S, Se)
  • the low melting group 11 chalcogenide compound containing the intermetallic chalcogenide of the metal elements as a medium and mixed into the single particle forms the composition of the photoactive layer at the compound particle stage without further processing. Can be adjusted with
  • the composite particle according to one embodiment of the present invention is a Group 11 metal, which is Cu: In or
  • the molar ratio of 12 to 14 metals of In and Ga: Se incalcogen element was 0.8-1.3: 0.8-1.3: 1.7-2.3, preferably 0.8-1.3: 1: 1.
  • the composite particles according to one embodiment of the present invention are a Group 11 metal of Cu: Zii, Sn, or a Group 12 to 14 metal of Zn and Sn: a molar ratio of S, Se, or S and Se incalcogen elements.
  • the composite particles may contain Cu: In: Se in a molar ratio of 0.8 to 1.3: 0.8 to 1.3: 1.7 to 2.3.
  • the composite particles may contain a Cu: In: Se in a molar ratio of 8 to 1.3: 1: 1.
  • the electrical properties of the light absorption layer are controlled to reduce It is possible to improve the efficiency of the porcelain, and there is a risk of deterioration of characteristics due to the separation of the crystal phase at the ratio of less than 0.8. It can promote the growth of grains that make up.
  • the composite particle may contain 1 to 20% by volume of the Group 11 chalcogen compound.
  • the Group 11 chalcogen compound contained in the composite particle may be heat treated to form a photoactive layer. It may be a low melting point compound that forms a commercial melting phase, and in the case of having a volume ratio described above the Group 11 chalcogen compound contained in the composite particles, a single phase poly-chalcogen compound may be generated very rapidly and homogeneously by the molten phase, and in excessive liquid phase formation It is possible to prevent the formation of heterogeneous microstructures and to prevent composition loss by obtaining chalcogenene elements.
  • the composite particles according to one embodiment of the present invention may contain an intermetallic compound and a Group 11 chalcogen compound having a stoichiometric ratio of the photoactive layer to be manufactured, wherein the intermetallic compound and 11 It may contain other residual compounds other than the family chalcogen compounds.
  • the residual compound is an intermetallic compound
  • Group 11 chalcogenides are simultaneously produced, grown, and bound together to form composite particles, they may be minor by-products during synthesis, and as the composition of the overall composite particles satisfies the composition of the photoactive layer to be prepared,
  • It may be a by-product formed with the formation of a Group 11 chalcogen compound.
  • the residual compound may remain as a by-product when synthesized
  • Residual Compounds A chalcogenide compound of Group 11 metal that does not satisfy Formula 1, at least one selected from Group 12 to 14 metals; intermetallic chalcogenide compound; one or more selected from oxides and chalcogens of at least one metal selected from Group 12 to 14 metals; More than one substance may be selected.
  • the chalcogenide compound of Group 11 metal that does not satisfy Formula 1 may be Cu 2 Se, and the oxide of at least one metal selected from Group 12 to 14 metal is indium.
  • the oxide of the selected metal may be one or more selected from indium oxide, gallium oxide, tin oxide, zinc oxide, rhythm-gallium oxide and tin-zinc oxide, and the chalcogen may be S or Se.
  • the residual compound may be selected from Cu 2 Se, In 2 Se 3 , In 2 O 3 and Se.
  • the composite particle is 1 to 20
  • the medium may comprise a volume 11 group 11 chalcogen compound and a medium of 80 to 99 volume%
  • the medium may be composed of an intermetallic chalcogenide compound, or a metal chalcogenide compound and a residual compound.
  • the medium may be at least 40%. It may contain an intermetallic chalcogenide in a volume of « 3 ⁇ 4 or more, and the medium may be less than 60% by volume.
  • Residual compounds may be contained, i.e., the medium may contain from 40 to 100% by volume of the intermetallic chalcogenide compound based on the total volume of the medium, and may contain from 0 to 60% by volume of the residual compound.
  • the composite particles may contain 1 to 20% by volume of the Group 11 chalcogenide compound.
  • It may contain 40 to 95% by volume of intermetallic chalcogenides and 5 to 60% by volume of the residual compound, based on the total volume of the medium excluding the low melting point n-group chalcogenides.
  • the composite particle may be a nanoparticle and an average particle size may be 5 to 500 nm. As described above, the composite particle may be formed in a material synthesis step. In-situ group 11 chalcogen compound
  • the intermetallic chalcogenide compounds may be infrequent and bound by multiple nucleation and growth at the same time, and may be made of nanoparticles with an average particle size of 5 to 500 nm by this synthesis.
  • the composite particles may have a molar ratio of Cu : In : Se of 0.8 to 1.3: 0.8 to 1.3: 1.7 to 2.3, preferably 0.8 to 1.3: 1: 1.
  • Copper, indium and selenium compounds can be prepared by irradiating microwaves in a mixed solution mixed with a reaction solvent.
  • the reaction solvent has a boiling point of 200 ° C. or higher and practically 200 to 450. ° C is preferred, boiling point is 200 ⁇
  • the reaction solvent may include one kind or two or more kinds selected from poly solvents, amine solvents, and phosphine solvents.
  • the poly-based solvent may be selected from the group consisting of diethylene glycol,
  • Butyl ether diethylene glycol buthyl ether
  • triethylene glycol polyethylene glycol
  • poly (ethylene glycol) diacrylate And one or more selected from the group consisting of polyethylene glycol dibenzonate, dipropylene glycol, tripropylene glycol, and glycerol. can do.
  • the amine solvent may be selected from diethyl amine,
  • It may include one or two or more selected from the group consisting of hexamethylene tetramine.
  • the phosphine solvent is trioctylphosphine or
  • It may be a mixed solvent of any one or two of trioctylphosphineoxide.
  • the content of the Group 11 chalcogen compound contained in the composite particles by one or more factors selected from the heating temperature of the mixed solution by microwave irradiation and the reaction time at which the heating temperature is maintained. This can be controlled.
  • the multiparticulates of the present invention preferably contain 1 to 20% by volume of Group 11 chalcogenide compound,
  • reaction time for 15 to 40 minutes at a temperature of 200 to 300 ° C. by microwave irradiation.
  • the present invention provides an ink for a photovoltaic layer of a solar cell containing the above-mentioned composite particles.
  • An ink according to an embodiment of the present invention may contain the above-described composite particles.
  • the composite particles contained in the ink contain all metal elements constituting the desired photoactive layer.
  • the intercalating chalcogenide compound, which is a chalcogenide compound, and the low melting point Group 11 chalcogenide compound are homogeneously dispersed, and the composition of the photoactive layer is determined by the composition of the composite particles (pre-determined).
  • the effective material for forming the photoactive layer may be a composite particle.
  • the ink may be An effective substance that is involved in the formation of the photoactive layer, and may contain only composite particles.
  • chalcogenide compound an intermetallic chalcogenide
  • each metal and chalcogen element can be formed to satisfy the composition of the target compound semiconductor-based photoactive layer.
  • the complex particles are homogeneously dispersed and bound together in the group 11 chalcogen compound forming a liquid phase in the preparation of the photoactive layer in a medium containing an intermetallic chalcogen compound, the particles are dense alone. It is possible to produce a homogeneous, single phase photoactive layer.
  • the ink is an effective substance involved in the formation of the photoactive layer, and the composition containing only the composite particles is determined by the characteristics of the composite particles contained in the ink according to the present invention. It is possible and, if necessary, may contain other effective substances other than the composite particles as long as they do not interfere with the effects caused by the composite particles described above.
  • the concentration of elements (eg, Ga) in the thickness of the photoactive layer varies.
  • composite particles of various compositions with different metal-to-metal molar ratios and with different approaches, to control the composite particles and concentration profiles of uniform composition (e.g., The precursor of cha) or the chalcogenide of the element to which the concentration profile is to be adjusted can be used together.
  • uniform composition e.g., The precursor of cha
  • chalcogenide of the element to which the concentration profile is to be adjusted can be used together.
  • the ink is prepared by the above-described ink.
  • the photoactive layer may be CIS (Cu-In-Se or Cu-In-S), CIGS (Cu-In-Ga-Se or Cu-In-Ga-S), CIGSS (Cu-In-Ga-Se-S), CZTS (Cu-Zn-Sn-Se or Cu-Zn-Sn-S) or
  • CZTSS Cu-Zn-Sn-Se-S
  • the photoactive layer may have a stoichiometric ratio
  • a solvent for forming a dispersion medium is
  • the solvent may be a solvent used in a general ink composition containing particulates and performing a coating process.
  • the solvent may be a nonpolar solvent, a poly solvent, an amine solvent, a phosphine solvent, an alcohol solvent, or a polar solvent. It may contain more than one solvent selected.
  • poly-based solvents capable of forming a dispersion medium of ink include ethylene glycol, diethylene glycol, diethylene glycol ethyl ether and diethylene glycol butyl.
  • Dicer glycol buthyl ether diethylene glycol
  • polyethylene glycol polyethylene glycol (Mw: 200-100,000)
  • polyethylene glycol polyethylene glycol (Mw: 200-100,000)
  • Diacrylate poly (ethylene glycol) diacrylate
  • polyethylene glycol polyethylene glycol
  • It may include a solvent selected from dibenzonate, dipropylene glycol, dipropylene glycol, dipropylene glycol and glycerol (glycerol).
  • the amine solvent is capable of forming a dispersion medium of the ink
  • One or more solvents selected from hexamethylene tetramine, ethanolamine, diethanolamine, and triethanolamine may be included.
  • phosphine-based solvents which can form a dispersion medium of ink
  • It may include one or more solvents selected from trioctylphosphineoxide.
  • an alcoholic solvent capable of forming a dispersion medium of the ink may be methyl cellosolve, ethyl cellosolve or butyl.
  • Butyl solve (Butyl Cellosolve) and having from 1 to 8 carbon atoms
  • It may include a solvent selected from one or more than alcohol (Alcohol).
  • a nonpolar solvent capable of forming a dispersion medium of the ink capable of forming a dispersion medium of the ink
  • One or more solvents selected from dichlorobenzene, anisole, xylene, and hydrocarbon solvent having 6 to 14 carbon atoms may be included.
  • a polar solvent capable of forming a dispersion medium of ink is
  • the ink (I or II) may further contain a dispersant and an organic binder.
  • the dispersant and the organic provider are sufficient to be a dispersant and an organic binder used in a conventional ink composition which contains particulates and is subjected to an application process.
  • the dispersant may be a fatty acid salt (soap), an ⁇ -sulfofatty acid ester salt (MES),
  • MES ⁇ -sulfofatty acid ester salt
  • ABS alkylbenzenesulfonates
  • LAS straight chain alkylbenzene sulfonates
  • AS alkylsulfates
  • AES alkylethersulfate ester salts
  • anionic compounds Fatty acid to tanol amide
  • Low molecular weight non-ionic compounds including polyoxy ethylene alkyl ether (AE), polyoxy ethylene alkyl phenyl ether (APE), sorbbi and sorbitan; Low molecular cationic compounds including alkyltri methylammonium salts, dialkyldimethylammonium chlorides and alkylpyridinium chlorides; Low molecular positive compound containing alkylcarboxybetaine, sulfobetaine and lecithin; Formal aqueous condensates of naphthalene sulfonates, polystyrene sulfonates, polyacrylates, polymeric salts of vinyl compounds and carboxylic acid monomers, carboxymethylcellulose and polyvinyl alcohol; polyacrylic acid Polymeric non-aqueous dispersants comprising partially alkyl esters and poly alkylenepolyamines; and polymeric cationic dispersants comprising polyethylene imine and aminoalkyl methacrylate copolymers;
  • the dispersant may be a commercial product, a specific example,
  • DisperBYKlOl DisperBYK102, DisperBYK106, DisperBYK108, DisperBYKl ll, DisperBYK116, DisperBYK130, DisperBYKHO, DisperBYK142, DisperBYK145, DisperBYK162, DisperBYK162, DisperBYK162, DisperBYK162 DisperBYK171, DisperBYK174, DisperBYK180, DisperBYK182, DisperBYK192, DisperBYK193, DisperBYK2000, DisperBYK2001, DisperBYK2020, DisperBYK2025, DisperBYK2050, DisperBYK2070,
  • the organic binder is polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinyl pyridone (PVP), polyvinylidene fluoride (PVDF), self-crosslinked acrylic resin emulsion, hydroxy Ethyl cellulose (HEC), carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), copolymer of C1-10 alkyl (meth) acrylate and unsaturated carboxylic acid, nitrocellulose, gelatin ( gelatine),
  • the ink may contain 200 to 900 parts by weight of a solvent with respect to 100 parts by weight of particulates including the composite particles described above.
  • the content of the solvent, optionally the dispersant and the organic binder, based on the particulate phase according to the above-described embodiment, is a mechanical strength to maintain the shape of the coating film while the coating process is performed smoothly, adhesion to the substrate to which the ink is applied, drying and It is the content to prevent the film quality deterioration by the organic matter which is decomposed and removed during heat treatment.
  • the ink contains particulates.
  • It can be produced by methods commonly used in the field of ink manufacturing methods, and can be produced by non-limiting examples, by mixing particulates and solvents, optionally, dispersants and organic binders and homogeneously mixing them with milling.
  • the present invention provides a method for producing the composite particles described above.
  • the composite particles according to the embodiment of the present invention are manufactured at the manufacturing stage.
  • the chalcogenide compound of the low melting point Group 11 metal satisfying Chemical Formula 1 may be mixed in the in-situ medium to have a uniform distribution and binding of the chalcogenide compound of the Group 11 metal.
  • a method for producing a composite particle according to an embodiment of the present invention is a) a group 11 metal : 12 to 12
  • M is one or more selected from Group 11 metals, A is a chalcogen element,
  • X is a real number that satisfies 1-2.
  • the metal of group 12 to 14 of step a) means one or more metals selected from group 12 to 14.
  • the composite particles prepared in step b) are similar to those described above, detailed description thereof will be omitted.
  • the mixture of step a) may contain all the elements constituting the target compound semiconductor-based photoactive layer, and the composite particles synthesized in step b) contain all the constituent elements constituting the photoactive layer.
  • the photoactive layer may be prepared using the composite particles (only) prepared in step b) as an active material as described above.
  • the composite particles are determined by the molar ratio of each metal precursor (a precursor of a Group 11 metal and one or more metals selected from Groups 12 to 14 metals) and a chalcogen element precursor to be added to the semi-solvent in step a).
  • the molar ratio of each metal and chalcogen element contained in is defined, and the element ratio of the photoactive layer produced by the composite particles can be defined. This makes it possible to manufacture the photoactive layer having the target composition by an easy and simple method of introducing each precursor into the semi-aqueous solvent so as to have a stoichiometric ratio of the target photoactive layer.
  • the boiling point of the reaction solvent in step a) may be 200 ° C or more, and substantially 200 to 450 ° C.
  • a desired compound semiconductor-based photoactive layer for example, CIS
  • Containing all metal elements eg Cu and In
  • Composite particles containing intermetallic chalcogenides and low melting point Group 11 metal chalcogenides can be prepared.
  • composite particles containing a low melting point Group 11 metal chalcogenide compound can be prepared.
  • the semi-aqueous solvent may include one or two or more selected from a poly-based solvent, an amine-based solvent, and a phosphine-based solvent.
  • the poly-based solvent may include diethylene glycol, Diethyleneglycol ethyl ether, diethylene glycol buthyl ether,
  • Triethylene glycol polyethylene glycol, molecular weight; 200 to 100,000
  • polyethylene glycol diacrylate polyethylene glycol diacrylate
  • polyethylene glycol dibenzoate dipropylene glycol
  • It may include one or two or more selected from the group consisting of tripropylene glycol, glycerol (glycerol).
  • the amine solvents include diethyl amine, triethylamine, 1,3-propane diamine, 1,4-butanediamine ( l, 4 _butane diamine), 1,5-pentane diamine, 1,6-hexane diamine (1,6-hexane diamine), 1,7-heptane diamine (1,7-heptane diamine), 1,8-octane diamine,
  • Diethylene diamine diethylene triamine, toluene diamine, m-phenylenediamine, diphenyl methane diamine, hexamethylene Diamine (hexamethylene diamine), triethylene tetramine,
  • phosphine-based solvent is one or two of trioctylphosphine or trioctylphosphine oxide (trioctylphosphine oxide) It may be a mixed solvent.
  • the precursor of the Group 11 metal and the precursor of one or more metals selected from Group 12 to 14 metal are independently of each other, oxide, hydroxide, acetate, nitrate, Sulfate, perchlorate, halides and hydrates thereof may be selected from the group consisting of one or two or more, chalcogenide precursors are hydrogen chalcogenide, sodium chalcogenide, potassium chalcogenide, calcium chalcogenide, dimethyl One or more may be selected from the group consisting of chalcogenides and their hydrates.
  • the Group 11 metal may be Cu
  • the precursor of the Group 11 metal may be a Cu precursor
  • the Group 12 to 14 metal may be In or In and Ga
  • the precursor of the Group 12 to 14 metal may be an In precursor or an In precursor and a Ga precursor.
  • the chalcogen element may be Se
  • the precursor of the chalcogen element may be a Se precursor.
  • the Group 11 metal may be Cu
  • the precursor of the Group 11 metal may be a Cu precursor
  • the Group 12 to 14 metal may be Zn, Sn or Zii and Sn
  • the precursor of the Group 12 to 14 metal is a Zn precursor, Sn precursor or Zn precursor
  • the chalcogen element may be Se
  • the precursor of the chalcogen element may be Se precursor.
  • the metal precursors added to the semi-aqueous solution may be copper precursors and rhythm precursors.
  • It may include one or two or more selected from the group consisting of, indium precursor is ln 2 0 3 , In (OH) 3 , In (CH 3 COO) 3 , InF 3 , InCl, InCl 3 , InBr, InBr 3 , Inl, Inl 3 , In (C10 4 ) 3 , In (N0 3 ) 3 , In 2 (S0
  • the content of the low melting point Group 11 metal chalcogenide compound contained in the composite particles is determined by the temperature and heating time (ie,
  • the microwave power may be in the range of, for example, 500 to 900 W.
  • a secondary phase which is a low melting group 11 metal chalcogenide
  • the molar ratio of each element is determined by the molar ratio of each metal precursor introduced and the precursor of the chalcogenide element, and the stoichiometric ratio (0.8 to 1.3: 0.8-1.3: 1.7 -23) of the whole particle is extremely easy. Can be controlled.
  • the manufacturing method according to the embodiment of the present invention is applied to the reaction solvent.
  • the molar ratio of elements constituting the composite particles can be determined, and the composition of the photoactive layer can be determined by the composition of the composite particles, the molar ratio of each precursor injected into the semi-aqueous solvent is properly adjusted in consideration of the composition of the target photoactive layer.
  • the copper precursor rhythm precursor: the precursor of the chalcogenide element is Cu: In: (Se and / Or a molar ratio of Se) of 0.8-1.3: 0.8-1.3: 1.7-2.3, preferably 0.8-1.3: 1: 1.
  • the method for producing a photovoltaic active layer of a solar cell according to the present invention includes the steps of c)
  • the photoactive layer comprises a plurality of elements of one or more selected elements from Group 11 metals and Groups 12-14. It may be a chalcogenide film.
  • Manufacturing methods include vacuum evaporation, sputtering + selenization, and chemical thin film manufacturing methods, such as electrodeposition. In each method, various manufacturing methods are used depending on the type of raw materials.
  • the manufacturing method of the present invention is based on the formation of a photoactive layer by the ink containing the composite particles, or the characteristics of the present invention. It is possible to produce high-quality multi-factor chalcogenide compounds (photoactive layers) through an extremely simple, safe and easy process of coating inks containing only composite particles as effective active substances and low temperature heat treatment of coating films. By using a satisfactory ink, there is an advantage of producing a photoactive layer having a stoichiometric ratio by simple application and thermal treatment of the ink.
  • the manufacturing method of the present invention uses the ink described above to form a photoactive layer.
  • the substrate on which the ink is applied is an insulator substrate commonly used in the solar cell field, and a back electrode commonly used in the solar cell field is used.
  • Laminated substrates may be laminated. Examples of insulated substrates include glass substrates, soda-lime glass, ceramic substrates, or semiconductor substrates. For example, back electrodes formed on insulated substrates. Molybdenum (Mo) layer.
  • the ink is coated by spin coating, bar coating, dip coating, drop casting, ink-jet printing, fine contact printing ( One or more selected from micro-contact printing, imprinting, gravure printing, gravure-offset printing, flexography printing and screen printing It can be done in a way.
  • a step of drying the coating film after step c) and before step d) may be further performed.
  • the drying of coating film is 60 to 90 o in air. Can be performed in C.
  • a substrate the ink is applied is formed coating film the heat treatment to 400 to 550 ° C, preferably in a knife kojen atmosphere, of 500 to 530 o C
  • the heat treatment time can be properly adjusted according to the thickness of the coating film, for example, 30 minutes to 2 hours.
  • the film is densified, crystal grows, and becomes single by heat treatment of the coated film.
  • Phase transitions to chalcogenides can occur.
  • the manufacturing method can be used to produce a pure single phase photoactive layer without post-treatment or complex compositional control, using composite particles that already meet the intended composition of the optical active layer, and heat treatment within the process tolerance of 550 ° C or less.
  • An extremely dense and homogeneous photoactive layer can also be produced in the drawing.
  • the heat treatment of the coating film is carried out in a chalcogen atmosphere.
  • the chalcogen atmosphere includes an atmosphere in which sulfur (S), selenium (Se) or a mixture thereof is present.
  • the heat treatment of the coating film can supply the chalcogen-containing gas or heat-treat the chalcogen powder together with the coating film to use the chalcogen powder as a source of the chalcogen gas.
  • the heat treatment of the coating film includes an atmosphere in which the chalcogen atmosphere includes sulfur (S), selenium (Se), or a mixed gas thereof, and the chalcogen gas atmosphere is H 2 S or H 2 Se.
  • a chalcogen-containing gas containing H 2 S, H 2 Se, chalcogen element (S, Se) vapor, or a mixed gas thereof may be used at a flow rate of 5 to 300 sccm.
  • the chalcogen powder when the chalcogen powder itself is formed by evaporating the chalcogen powder including S powder, Se powder or a mixture thereof, the chalcogen powder is heated.
  • the temperature can be the same as the temperature of the coating film being heat treated and can be different from each other.
  • the chalcogen powder when used as a chalcogen gas source, the chalcogen powder may be heated to 80 to 250 0 C.
  • the powder may be placed in an area different from the area in which the coating film is located, where the heat treatment is provided with a heating element and controller equipped to independently form two or more uniform zones in a single heat treatment space where fluid flow is possible.
  • the heating of the chalcogen powder can be controlled by adjusting the position of the chalcogen powder in a conventional heat treatment device forming a single unit zone.
  • the heat treatment of the coating film may be performed at any pressure, but one non-limiting example may be heat treatment at vacuum or atmospheric pressure.
  • the heat treatment apparatus of the coating film may be a furnace using conventional heat generation (IR) or a rapid thermal annealing system (RTP) using light such as tungsten and halogen.
  • the chalcogenide compound may contain CuIn x Ga 1-x Se y S 1-y days (real number 0 ⁇ 1, real number 0 ⁇ y ⁇ l), and CuZn m Sn ⁇ Se ⁇ CO i ⁇ ? Real numbers, 0 ⁇ 1 real numbers).
  • a medium containing CuInSe 2 and CuSe, CuSe 2 or a combination thereof For example, a medium containing CuInSe 2 and CuSe, CuSe 2 or a combination thereof.
  • 11 jokkal kojen compound can be prepared for CuInSe 2-indan daily multi knife kojen phosphorescent compound of the active layer by using the ink containing the composite particles heunjae to a single particle.
  • Group 11 chalcogenide compound which is a mixture of these CuIn x Ga ,.
  • a photoactive layer which is a single-phase, polychalcogen compound of x Se 2 (real number of 0 ⁇ x ⁇ l), can be prepared.
  • a compound mixed with a medium containing Cu 2 Zn m Sn 2-m Se 4 (a real number of 0 ⁇ m ⁇ 2 ) and CuSe, CuSe 2 or a mixture of Group 11 chalcogenide single particles Cu 2 Zn m Sn 2 . m Se 4 (0 ⁇ m ⁇ 2 real number)
  • the present invention includes a photoactive layer prepared by the above-mentioned manufacturing method.
  • the present invention relates to a solar cell having a photoactive layer manufactured by the above-described manufacturing method.
  • a solar cell according to an embodiment of the present invention includes a photoactive layer described above formed on a substrate (substrate formed with a lower electrode); a buffer layer formed on the photoactive layer; a window layer formed on the buffer layer; a grid formed on the window layer Electrode; may include.
  • the buffer layer comprises a photoactive layer that is a first conductive semiconductor (eg, p-type in CIGS).
  • a photoactive layer that is a first conductive semiconductor (eg, p-type in CIGS).
  • the buffer layer can be used.
  • the buffer layer can be a CdS thin film.
  • the window layer is a layer having a semiconductor characteristic complementary to the photoactive layer, and may be used as the window layer used in conventional compound semiconductor-based solar cells capable of pn junction with the photoactive layer.
  • the window layer is ZnO. It may be a thin film.
  • the grid electrode is for collecting current on the surface of the solar cell, which may include finger electrodes and busbar electrodes, and may be any front electrode structure and material used in conventional compound semiconductor-based solar cells.
  • the grid electrode may have a bone structure and may be A1 or Ni / Al.
  • a solar cell according to an embodiment of the present invention is formed on a grid electrode.
  • Anti-reflective coatings may be included, and may be used as anti-reflective coatings used in conventional compound semiconductor-based solar cells. It may be a silicon oxide film.
  • the present invention includes the above-described method for manufacturing a solar cell.
  • a method of manufacturing a solar cell according to an embodiment of the present invention includes forming a photoactive layer according to the above-described method of manufacturing a photoactive layer on a substrate on which a lower electrode is formed; over the photoactive layer, a buffer layer, a window layer, and the like. Sequentially forming the front electrode layer.
  • the formation of the buffer layer, the window layer, and the front electrode layer may be performed using materials and methods known in the solar cell field.
  • the buffer layer may be performed through a deposition process using solution deposition.
  • the front electrode layers can be independently performed through chemical vapor deposition (CVD), physical vapor deposition (PVD) including sputtering, or plasma deposition (PECVD).
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • PECVD plasma deposition
  • the present invention includes solar cell modules equipped with one or more of the above described solar cells.
  • a solar cell module focuses light on a solar cell.
  • a condenser for irradiating and a sal portion in which two or more solar cells are arranged and electrically connected in series and / or in parallel.
  • the condenser condenses light.
  • the cell portion is a solar cell array, the solar cell array spaced at a plurality of solar cell intervals It may comprise a fixed and / or supporting support and an electrical connection which connects several solar cells in series and / or in parallel.
  • the prepared mixture was heated for 2 minutes at a power of 800 W using microwave, and then reacted for 25 minutes at 280 ° C. and then cooled for 20 minutes to produce a composite particle. Ethanol was used to recover the synthesized particles. After centrifugation at 25000rpm for 30 minutes, washing and particle recovery were performed, and the particles were recovered three times. The recovered particles were dried in a vacuum oven at 40 ° C. [205]
  • An ink was prepared using the composite particles prepared above.
  • CIS particles prepared to be 15% by weight were added to a solvent mixture of 785g ethylene glycol i.785g and 0.765g ethanol, and at 20 Hz for homogeneous mixing of the ink.
  • An ink prepared on a soda-lime glass substrate on which the Mo electrode was deposited was coated with a bar, dried at 80 ° C., and the substrate was thermally treated to prepare a photoactive layer.
  • the Se powder was heated to 230 0 C and the ink coated glass substrate was 530 o C.
  • the photoactive layer was prepared by heat treatment at temperature for 1 hour at which time the pressure in the heat treatment chamber was 10 5 torr.
  • CdS thin film was deposited using chemical bath deposition, and ZnO and Al-doped ZnO thin films were deposited by sputtering on top of the CdS thin film.
  • An A1 electrode was deposited on the ZnO thin film by thermal evaporation.
  • Example 1 The same procedure as in Example 1 was performed except that the temperature was raised to 800 W using a microwave to react at 250 ° C., and the rest was performed in the same manner as in Example 1.
  • Example 1 The same procedure as in Example 1 was performed except that the temperature was raised to 800 W using a microwave and the reaction was repeated at 200 ° C., and the rest was performed in the same manner as in Example 1.
  • Example 1 The same procedure as in Example 1 was performed, but the temperature was raised to 800 W using a microwave, and the reaction was repeated for 30 minutes. The rest was performed in the same manner as in Example 1.
  • Example 2 The same implementation as in Example 1 was carried out using a microwave to 800W output.
  • Indium acetate: selenium powder (Se powder) is weighed in a molar ratio of 1: 1: 2, and 3.2 g of the mixed compound is added to 20 g of ethylene glycol (T b 197 0C), and then 1 Stirring was carried out for a period of time.
  • the mixed solution was heated for 2 minutes at a power of 800 W using microwave, the reaction was performed for 25 minutes at 280 ° C., and then cooled for 20 minutes to prepare particles. Ethanol was used to recover the synthesized particles. 30 minutes at 25000rpm was used for centrifugation to wash and recover the particles, but repeated three times to recover the particles.
  • the recovered particles were dried in a vacuum oven at 40 ° C to obtain CuInSe 2 (CIS) particles.
  • the XRD analysis was performed for the phase analysis of the prepared CIS particles, and the results are shown in Fig. 6.
  • the prepared CIS particles were a single phase and Cu: In: Se was 26:26:48 by stoich
  • a photoactive layer and a solar cell were prepared in the same manner as in Example 1 except that CIS particles manufactured in place of the composite particles were used.
  • FIG. 1 shows the results of X-ray diffraction analysis of the composite particles prepared in Example 1, where composite particles containing a Group 11 chalcogenide compound containing CuInSe 2 (CIS) and CuSe were prepared.
  • the prepared composite particles contained a secondary phase containing CuSe. This is the result of the presence of secondary phases controlled by the nature of the transition reaction solvent to the CuInSe 2 phase. Even if such secondary phases exist, Cu
  • the ratio of: In: Se is The results of EDX (Energy Dispersive X-ray Spectrometer) were not significantly different from the composition ratio of the added precursor. The EDX results showed that the composite particles had a molar ratio of Cu: In: Se of 29: 28:43, and the small ratio of Se was found to exist as an oxide (In 2 0 3 in Fig. 1).
  • the stoichiometry of Cu: In: Se is 1: 1: 2 by heat treatment in a Se atmosphere, which is a post-process. Rain could easily be optimized.
  • Example 3 is a scanning electron micrograph of the photoactive layer prepared in Example 1, as shown in the results of FIGS. 2 and 3, wherein the photoactive layer has a single layer of CuInSe 2 and a film having a fine microstructure is formed. I could see that.
  • EDX measurement results The composition of the photoactive layer prepared in Example 1 was Cu: In: Se 7 ⁇ 25:23:52 in terms of stoichiometric ratio.
  • Example 3 reaction temperature 200 ° C.
  • Example 2 reaction temperature 250 ° C.
  • c is the analysis result of Example 1 (reaction temperature 280 ° C.).
  • Example 5 (reaction time 20 minutes), c) Example 1 (reaction time 25 minutes), d)
  • reaction temperature and reaction time control the type and content of secondary phases contained in the composite particles.
  • the analysis results show that the composite particles contain 1 to 20% by volume of low melting point copper chalcogenide compounds (CuSe and / or CuSe 2 ) and are based on the total volume of the medium excluding low melting point copper chalcogenide compounds. It was found that CuInSe 2 contained 40 to 95% by volume. Residual compounds other than the low melting point copper calcogen compound were 5 to 5 In 2 Se 3 , In 2 0 3 , Se, and Cu 2 Se. 60 volumes ⁇ 3 ⁇ 4 were found.
  • the content of the low melting point copper calogen compound can be controlled according to the reaction temperature.
  • a composite particle containing a copper chalcogen compound is produced, where a lower reaction temperature of less than 200 may cause most of the synthesized particles to be secondary phase, and when the reaction temperature exceeds 300 ° C., a low melting point copper calogen may be produced.
  • the content of the compound can be extremely small, dense, the composition of the composite particles is maintained, there is a risk that the single-phase photoactive layer is not produced.
  • the content of the low melting point copper chalcogenide can be controlled according to the reaction time.
  • a composite particle containing a copper chalcogen compound is produced, in which case the reaction time is less than 15, and most of the synthesized particles may be formed in the second phase, and if it exceeds 40 minutes, a low melting point of the copper chalcogen compound is produced.
  • the content can be extremely small, compact, maintaining the composition of the composite particles, and the single phase photoactive layer There is a risk of manufacturing failure.
  • FIG. 6 shows X-ray diffraction analysis results of CIS particles prepared in Comparative Example 1
  • FIG. 7 shows X-ray diffraction analysis results of photoactive layer prepared in Comparative Example 1
  • FIG. 8 shows Comparative Example 1 Scanning electron micrographs of photoactive layers prepared in.
  • the CIS particles prepared by Comparative Example 1 were CIS particles composed of CuInSe 2 single phase without secondary phase. Also, the CIS particles prepared by Comparative Example 1 were stoichiometric. Cu: In: Se was 26:26:48.
  • the stoichiometric ratio of the photoactive layer manufactured by the comparative example 1 was 25:26:49 in Cu: In: Se.
  • the solar cell is manufactured in the comparative example in terms of solar cell characteristics.
  • Example 1 While no heterojunction is generated, the optical conversion efficiency of 0% is shown, while the photo-active layer-based solar cell having excellent stoichiometry, crystallinity, microstructure, etc. produced in Example 1 is improved to 8.2%. It shows the light conversion efficiency.

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Abstract

The present invention relates to composite particles for a photoactive layer of a solar cell, and to a method for manufacturing same. More particularly, the composite particles for a photoactive layer of a solar cell according to the present invention are characterized in that group 11 metal chalcogenides are mixed with a medium, wherein the group 11 metal chalcogenides satisfy M1 AX (where M is one or more selected from group 11 metals, A is a chalcogen element, and x is a real number which satisfies 1 and 2).

Description

명세서  Specification
발명의명칭:태양전지광활성층용복합입자및이의제조방법 기술분야  Name of invention: Composite particles for solar cell photoactive layer and method for manufacturing same
[1] 본발명은태양전지태양전지광활성층용복합입자및이의제조방법에관한 것으로,상세하게，간단하고안전하며용이한공정을통해고품질의광활성층을 제조할수있으며，화학양론비를만족하는단일상의광활성층을제조할수 있으며 ,550oC이하의공정허용온도이내의온도에서조성적안정성및 균일도가우수하고치밀한미세구조를가지며，조대결정립으로이루어진 광활성층을제조할수있는복합입자및이의제조방법에관한것이다. [1] The present invention relates to a composite particle for a photovoltaic active layer of a solar cell and a method for manufacturing the same, which can produce a high quality photoactive layer through a simple, safe and easy process in detail and satisfying the stoichiometric ratio. It is possible to manufacture single-phase photoactive layer, to have composite stability and uniformity at a temperature within the process tolerance of 550 o C or less, to have a fine structure, and to produce a photoactive layer composed of coarse grains. It's about how.
배경기술  Background
[2] 기존의기상증착법기반의화합물반도체광활성층 (CIG(S,Se), CZT(S,Se))의 제조공정은우수한특성에도불구하고，높은공정비용이소요되는한계를 지니고있다.이에의해，화합물반도체를이용한태양전지의상업화를이루기 위해서는용액공정을이용한 CIG(S,Se),CZT(S,Se)광활성층의제조가  [2] The manufacturing process of the conventional semiconductor vapor deposition-based compound semiconductor photoactive layer (CIG (S, Se), CZT (S, Se)), despite its excellent characteristics, has a high process cost limit. In order to achieve commercialization of solar cells using compound semiconductors, the production of CIG (S, Se) and CZT (S, Se) photoactive layers using a solution process is required.
필수기술로고려되고있다.  It is considered an essential technology.
[3] 미국등록특허제 6127202호및미국등록특허계 6268014호와같이，금속  [3] metals, such as US Pat. No. 6,127,202 and US Pat.
산화물나노입자의혼합물또는금속산화물과산화물이아닌입자의흔합물을 기판에코팅한후환원분위기및 Se기체분위기하에서반웅시켜 CI(G)S막을 제조하는입자기반의용액공정을통한광활성충제조방법이시도되고있다.  A method of preparing photoactive fillers through a particle-based solution process for producing a CI (G) S film by coating a mixture of oxide nanoparticles or a mixture of metal oxides and non-oxide particles on a substrate and then reacting them under a reducing atmosphere and a Se gas atmosphere. Is being tried.
[4] 하지만금속산화물기반용액공정을이용하여광활성층을제조하는경우， 부수적인환원공정이필수적으로이루어져야하며，환원공정시막에결함이 생기는문제가있으며，이는 Se기체열처리공정시반웅의불균일성을  [4] However, when the photoactive layer is manufactured by using a metal oxide-based solution process, an additional reduction process is indispensable, and there is a problem in that a defect occurs in the film during the reduction process. of
야기한다.  Cause.
[5] 따라서，공정허용은도인 550°C내의의열처리과정을통해치밀하면서  [5] Therefore, the process tolerance is closely controlled through the heat treatment within 550 ° C.
단일상의 CIG(S,Se), CZT(S,Se)막을제조할수있는새로운경제적인접근 방법에대한연구개발이필수적이다.  Research and development of new economical approaches to manufacturing single-phase CIG (S, Se) and CZT (S, Se) films is essential.
발명의상세한설명  Detailed description of the invention
기술적과제  Technical task
[6] 본발명의목적은공정허용온도인 550°C이하의저온열처리를통해치밀하고， [6] The purpose of the present invention is to provide a compact and low-temperature heat treatment under the process tolerance of 550 ° C,
' 단일상으로이루어지며，화학양론비를갖는반도체화합물기반광활성층을 제조할수있는복합입자，이의제조방법및이를함유하는잉크를제공하는 것이다. The present invention provides a composite particle which can be prepared in a single phase and has a stoichiometric ratio-based photoactive layer, a manufacturing method thereof, and an ink containing the same.
[7] 본발명의다른목적은공정허용온도인 550oC이하의 저은열처리를통해 [7] Another purpose of the present invention is to provide a low temperature heat treatment of less than 550 ° C.
치밀하고，단일상으로이루어지며,화학양론비를갖는반도체화합물기반 광활성층을경제적이며단순한공정으로제조할수있는광활성층의제조방법 및이를통해제조된광활성층을제공하는것이다. 과제해결수단 It is to provide a method for producing a photoactive layer that can produce a compact, single-phase, stoichiometric, semiconductor compound-based photoactive layer in an economical and simple process, and to provide a photoactive layer produced thereby. Task solution
[8] 본발명에따른복합입자는태양전지광활성층용이며，하기화학식 1을  [8] The composite particles according to the present invention are for solar cell photoactive layers.
ᅳ 만족하는 11족금속칼코젠화합물이매질에흔재된입자이다.  Satisfactory Group 11 metal chalcogenide compounds are common particles in the medium.
[9] (화학식 1) [9] (Formula 1)
[10] Μ,Α,  [10] Μ, Α,
[11] Μ은 11족금속에서하나또는둘이상선택된것이며， Α는칼코젠원소이며, [11] Μ is one or more selected from Group 11 metals, Α is a chalcogen element,
X는 1내지 2를만족하는실수이다. X is a real number that satisfies 1-2.
[12] 본발명의일실시예에따른복합입자에있어,상기매질은 11족금속및 12족 내지 14족에서하나또는둘이상선택된원소의칼코젠화합물인 [12] In the composite particle according to the embodiment of the present invention, the medium is a chalcogenide compound of at least one element selected from Group 11 metals and Groups 12-14.
금속간칼코젠화합물을함유할수있다.  It may contain an intermetallic chalcogenide compound.
[13] 본발명의일실시예에따른복합입자에 있어，상기매질은하기화학식 2또는 하기화학식 3을만족하는금속간칼코젠화합물을함유할수있다. In the composite particle according to the embodiment of the present invention, the medium may contain an intermetallic chalcogenide compound satisfying the following Chemical Formula 2 or the following Chemical Formula 3.
[14] (화학식 2) [14] (Formula 2)
[15] Μ',Μ'ΊΑζ [15] Μ ', Μ'ΊΑζ
[16] 화학식 2에서 M'는 11족금속에서하나또는둘이상선택된금속이며, Μ"는 [16] In Formula 2, M 'is one or more metals selected from Group 11 metals, and Μ "is
13족에서하나또는둘이상선택된금속이다. One or more metals selected from Group 13.
[17] (화학식 3) [17] (Formula 3)
[18] Μ'2Μ"Ά4 [18] Μ ' 2 Μ "Ά 4
[19] 화학식 3에서 M'는 11족금속에서하나또는둘이상선택된금속이며 ,Μ "'는 [19] In Formula 3, M 'is one or more metals selected from Group 11 metals, and Μ "' is
12족및 14족에서하나또는둘이상선택된금속이다. At least one metal selected from Groups 12 and 14;
[20] 본발명의일실시예에따른복합입자에있어，상기복합입자는 1내지 20 [20] A composite particle according to one embodiment of the present invention, wherein the composite particle is 1 to 20
부피 %의상기 11족금속칼코젠화합물올함유할수있다.  The volume 11 may contain the Group 11 metal chalcogenideol.
[21] 본발명의일실시예에따른복합입자에있어，상기복합입자는 11족금속 : 12 내지 14족금속：칼코젠원소를 0.8~1.3:0.8~1.3:1.7~2.3의몰비로함유할수있다.  [21] In a composite particle according to an embodiment of the present invention, the composite particle may contain a Group 11 metal: Group 12-14 metal: chalcogen element at a molar ratio of 0.8 to 1.3: 0.8 to 1.3: 1.7 to 2.3. have.
[22] 본발명의일실시예에따른복합입자에있어,상기 11족금속은 Cu일수  [22] In the composite particle according to the embodiment of the present invention, the Group 11 metal may be Cu.
있으며， 12내지 14족금속은 In또는 In과 Ga일수있으며，칼코젠원소는 Se일수 있다.  The metal of Group 12 to 14 may be In or In and Ga, and the chalcogen element may be Se.
[23] 본발명의일실시예에따른복합입자에있어,상기 11족금속칼코젠화합물은 CuSe, CuSe2또는이들의흔합물을함유할수있다. In the composite particle according to the embodiment of the present invention, the Group 11 metal chalcogenide compound may contain CuSe, CuSe 2, or a mixture thereof.
[24] 본발명의일실시예에따른복합입자에 있어，상기복합입자는 11족금속 : 12 내지 14족금속 :칼코젠원소의몰비가으8~1.3:0.8~1.3:1.7~2.3이되도록각금속 전구체및칼코젠원소전구체가끓는점이 200°C이상인반웅용매에흔합된 흔합액에마이크로파를조사하여제조될수있다.  [24] In a composite particle according to an embodiment of the present invention, the composite particle has a molar ratio of Group 11 metals: Group 12-14 metals: chalcogen elements of 8 to 1.3: 0.8 to 1.3: 1.7 to 2.3. Each of the metal precursors and the chalcogenide precursors can be prepared by irradiating microwaves in a mixture mixed in a semi-aqueous solvent having a boiling point of 200 ° C or higher.
[25] 본발명은상술한복합입자를함유하는태양전지광활성층용잉크를포함한다.  [25] The present invention includes an ink for a solar cell photoactive layer containing the above-mentioned composite particles.
[26] 본발명에따른태양전지광활성층용복합입자의제조방법은 a) 11족금속 : 12 내지 14족금속 :칼코젠원소의몰비가 0.8~1.3:0.8~1.3:1.7~2.3이되도록각금속 전구체및칼코젠원소전구체가끓는점이 200°C이상인반웅용매에흔합된 혼합액을제조하는단계 ;및 b)상기흔합액에마이크로파를조사하여하기 화학식 1을만족하는 11족금속칼코젠화합물이매질에흔재된태양전지 광활성층용복합입자를제조하는단계;를포함한다. ¬식 1)[26] The manufacturing method of the composite particles for solar cell photoactive layer according to the present invention includes a) each metal such that the molar ratio of Group 11 metals: Group 12-14 metal: chalcogen element is 0.8-1.3: 0.8-1.3: 1.7-2.3. Precursors and chalcogenide precursors are compatible with semi-aqueous solvents with boiling points above 200 ° C. Preparing a mixed solution; and b) irradiating microwaves to the mixed solution to produce a composite particle for a solar cell photoactive layer having a Group 11 metal chalcogenide satisfying Formula 1 below. ¬Equation 1)
Figure imgf000005_0001
Figure imgf000005_0001
M은 11족금속에서하나또는둘이상선택된것이며 , A는칼코젠원소이며, X는 1내지 2를만족하는실수이다.  M is one or more selected from Group 11 metals, A is a chalcogenide and X is a real number satisfying 1 or 2.
본발명의일실시예에따른태양전지광활성층용복합입자의제조방법에 있어, b)단계는상기흔합액에마이크로파를조사하여 200내지 30C C에서 15 내지 40분동안수행될수있다.  In the method for producing a composite particle for solar cell photoactive layer according to an embodiment of the present invention, step b) may be performed for 15 to 40 minutes at 200 to 30 ° C. by irradiating microwaves to the mixture.
본발명의일실시예에따른태양전지광활성층용복합입자의제조방법에 있어， a)단계의상기반응용매는폴리을계용매，아민계용매및포스핀계 용매로부터하나또는둘이상선택된용매를포함할수있다.  In the method for producing a composite particle for solar cell photoactive layer according to an embodiment of the present invention, the reaction solvent of step a) may include one or more solvents selected from poly-based solvents, amine-based solvents and phosphine-based solvents.
본발명의일실시예에따른태양전지광활성층용복합입자의제조방법에 있어，상기 11족금속 : 12내지 14족금속：칼코젠원소를  In the method for producing a composite particle for solar cell photoactive layer according to an embodiment of the present invention, the Group 11 metal: 12 to 14 metal: Chalcogen element
0.8~1.3:0.8~1.3:1.7~2.3의몰비를만족하는 11족금속은 Cu일수있으며, 12내지 14족금속은 In또는 In과 Ga일수있으며,칼코젠원소는 Se일수있다.  Group 11 metals satisfying a molar ratio of 0.8-1.3: 0.8-1.3: 1.7-2.3 may be Cu, Group 12-14 metals may be In or In and Ga, and the chalcogenide element may be Se.
본발명의일실시예에따른태양전지광활성층용복합입자의제조방법에 있어， b)단계의상기복합입자는하기화학식 2또는하기화학식 3을만족하는 금속간칼코젠화합물을함유하는매질에 CuSe, CuSe2또는이들의흔합물인 11족 금속칼코젠화합물이흔재된입자일수있다.In the method of manufacturing a composite particle for solar cell photoactive layer according to an embodiment of the present invention, the composite particle of step b) is CuSe, CuSe in a medium containing an intermetallic chalcogenide compound satisfying the following formula (2) or (3) It may be a particle having a Group 11 metal chalcogenide compound, which is 2 or a combination thereof.
Figure imgf000005_0002
(화학식 2)
Figure imgf000005_0002
(Formula 2)
Figure imgf000005_0003
Figure imgf000005_0003
화학식 2에서 M'는 11족금속에서하나또는둘이상선택된금속이며， M"는 13족에서하나또는둘이상선택된금속이다. In Formula 2, M 'is one or more metals selected from Group 11 metals, and M "is one or more metals selected from Group 13 metals.
Figure imgf000005_0004
(화학식 3)
Figure imgf000005_0004
(Formula 3)
Figure imgf000005_0005
Figure imgf000005_0005
화학식 3에서 M'는 11족금속에서하나또는둘이상선택된금속이며， Μ'"는 12족및 14족에서하나또는둘이상선택된금속이다.  In Formula 3, M 'is one or more metals selected from Group 11 metals, and M' "is one or more metals selected from Groups 12 and 14.
본발명에따른태양전지광활성층의제조방법은 c)상술한잉크를기판에 도포하여도포막을형성하는단계;및 d)상기도포막을열처리하여광활성층을 제조하는단계;를포함할수있다.  The method of manufacturing a solar cell photoactive layer according to the present invention may include c) applying the ink described above to a substrate to form a coating film; and d) heat treating the coating film to prepare a photoactive layer.
본발명의일실시예에따른태양전지광활성층의제조방법에 있어,상기 d) 단계의열처리는칼코젠분위기에서， 400내지 550°C에서수행될수있다. 본발명은상술한태양전지광활성층의제조방법으로제조된태양전지용 광활성층을포함한다.  In the method of manufacturing a solar cell photoactive layer according to one embodiment of the present invention, the heat treatment of step d) may be performed at 400 to 550 ° C. in a chalcogen atmosphere. The present invention includes a photoactive layer for solar cells manufactured by the method for producing a photovoltaic active layer described above.
본발명은상술한광활성층이구비된태양전지를포함한다. The present invention includes a solar cell equipped with the photoactive layer described above.
Figure imgf000005_0006
발명의효과
Figure imgf000005_0006
Effects of the Invention
[45] 본발명에따른복합입자는 11족금속의칼코젠화합물인저융점  [45] The composite particles according to the present invention have a low melting point, which is a chalcogenide compound of Group 11 metal.
칼코젠화합물이매질에혼재된입자임에따라，복합입자를함유하는도포막을 550°C이하의공정허용온도이내의온도에서열처리하는극히간단하고 안전하며용이한공정을통해고품질의다원칼코젠화합물 (광활성층)을제조할 수있으며，복합입자의조성에의해광활성층의조성이제어될수있고，단지 복합입자를함유하는도포막을열처리함으로써，화학양론비를만족하는 광활성층의제조가가능하며，조성적안정성및균일도가우수하고치밀한미세 구조를가지며，조대결정립으로이루어진단일상의광활성층을제조할수있는 장점이있다.  Since the chalcogenide compound is a mixed particle in the medium, a high quality plural chalcogenide compound is obtained through an extremely simple, safe and easy process of heat-treating the coating film containing the composite particle at a temperature within the process tolerance of 550 ° C or below. (Photoactive layer) can be manufactured, and the composition of the photoactive layer can be controlled by the composition of the composite particles, and only by heat treatment of the coating film containing the composite particles, it is possible to manufacture the photoactive layer satisfying the stoichiometric ratio. It has excellent compositional stability and uniformity, has a dense fine structure, and has the advantage of manufacturing a single-phase photoactive layer composed of coarse grains.
[46]  [46]
도면의간단한설명  Brief description of the drawings
[47] 도 1은실시예 1에서제조된복합입자의 X선회절분석결과를도시한 1 shows the results of X-ray diffraction analysis of the composite particles prepared in Example 1
도면이며,  Drawing,
[48] 도 2는실시예 1에서제조된광활성층의 X-선회절분석결과를도시한  FIG. 2 shows the results of X-ray diffraction analysis of the photoactive layer prepared in Example 1
도면이며，  Drawing.
[49] 도 3은실시예 1에서제조된광활성층의주사전자현미경사진이며，  3 is a scanning electron micrograph of the photoactive layer prepared in Example 1,
[50] 도 4는실시예 1내지 3에서제조된복합입자의 X-선회절분석결과를도시한 도면이며， 4 is a view showing the results of X-ray diffraction analysis of the composite particles prepared in Examples 1 to 3,
[51] 도 5는실시예 1및실시예 4내지 6에서제조된복합입자의 X-선회절  FIG. 5 shows the X-ray diffraction of the composite particles prepared in Examples 1 and 4 to 6.
분석결과를도시한도면이며，  A diagram showing the results of the analysis.
[52] 도 6은비교예 1에서제조된입자의 X-선회절분석결과를도시한도면이며, [53] 도 7은비교예 1에서제조된광활성층의 X-선회잘분석결과를도시한 FIG. 6 is a diagram showing an X-ray diffraction analysis result of the particles prepared in Comparative Example 1, and FIG. 7 is a diagram showing an X-ray well analysis result of the photoactive layer prepared in Comparative Example 1.
도면이며，  Drawing.
[54] 도 8은비교예 1에서제조된광활성층의주사전자현미경사진이다.  FIG. 8 is a scanning electron micrograph of the photoactive layer prepared in Comparative Example 1. FIG.
[55] 도 9는실시예 1의잉크조성물기반 CuInSe2박막을이용하여제작된태양전지 특성 (효율: 8.3%)을나타낸것이다. 9 illustrates solar cell characteristics (efficiency: 8.3%) fabricated using the ink composition-based CuInSe 2 thin film of Example 1. FIG.
[56]  [56]
발명의실시를위한형태  Mode for Carrying Out the Invention
[57] 이하첨부한도면들올참조하여본발명의잉크및광활성층의제조방법을 상세히설명한다.다음에소개되는도면들은당업자에게본발명의사상이 층분히전달될수있도록하기위해예로서제공되는것이다.따라서，본발명은 이하제시되는도면들에한정되지않고다른형태로구체화될수도있으며，이하 제시되는도면들은본발명의사상을명확히하기위해과장되어도시될수 있다.이때,사용되는기술용어및과학용어에있어서다른정의가없다면，이 발명이속하는기술분야에서통상의지식을가진자가통상적으로이해하고 있는의미를가지며,하기의설명및첨부도면에서본발명의요지를 불필요하게흐릴수있는공지기능및구성에대한설명은생략한다. Reference is made to the accompanying drawings, in which the ink and photoactive layers of the present invention will be described in detail. The following drawings are provided as an example to fully convey the concept of the present invention to those skilled in the art. Therefore, the present invention may be embodied in other forms, not limited to the drawings presented below, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. Unless otherwise defined in the context of the present invention, the present invention has a meaning generally understood by those skilled in the art to which the invention belongs, and the subject matter of the present invention in the following description and attached drawings. Omit descriptions of known functions and configurations that may be unnecessarily blurred.
[58]  [58]
[59] 본출원인은화합물반도체기반태양전지광활성층에대한연구를심화한  [59] The present applicant has deepened the research on compound semiconductor-based solar cell photoactive layers.
결과，놀랍게도입자의합성단계에서저융점칼코젠화합물이매질내에혼재된 복합입자를이용하여광활성층을제조하는경우，공정허용온도인 550oC이하의 저온열처리를통해고품질의광활성층의제조가가능하며,단일상의다원 칼코젠화합물로이루어진광활성층이제조될수있고，치밀하고균일한 광활성층이제조될수있으며，조대결정립으로이루어지고，화학양론비를 만족하는조성비를갖는광활성층이제조될수있음을발견하여,본발명을 출원하기에이르렀다. As a result, when the low melting point chalcogenide compound is mixed with the mixed particles in the medium to produce the photoactive layer, the low temperature heat treatment below the process tolerance temperature of 550 ° C. It is possible to manufacture a photoactive layer composed of a single plural chalcogenide compound, a dense and uniform photoactive layer can be prepared, a photoactive layer composed of coarse grains, and a composition ratio satisfying the stoichiometric ratio can be prepared. In this regard, the present invention has been applied for.
剛 剛
[61] 본발명에따른태양전지광활성층용복합입자는하기화학식 1을만족하는 [61] The composite particle for solar cell photoactive layer according to the present invention satisfies the following formula (1).
11족금속칼코젠화합물이매질에혼재된입자이다. Group 11 metal chalcogenides are particles mixed in the medium.
[62] (화학식 1) [62] (Formula 1)
[63] Μ,Αχ [63] Μ, Αχ
[64] Μ은 11족금속에서하나또는둘이상선택된것이며， Α는칼코젠원소이며， X는 1내지 2를만족하는실수이다.  [64] Μ is one or more selected from Group 11 metals, A is a chalcogen element, and X is a real number satisfying 1-2.
[65] 본발명의일실시예에따른복합입자는매질및화학식 1을만족하는 11족  [65] The composite particle according to the embodiment of the present invention is a group 11 satisfying the medium and formula (1).
금속칼코젠화합물이합성과동시에，단일한입자상으로서로흔재되어있을수 있다.즉，본발명의일실시예에따른복합입자는매질및화학식 1을만족하는 11족금속칼코젠화합물의합성단계에서인 -시츄 (in-situ)로단일한입자형태로 매질과 11족금속칼코젠화합물이흔재및응집되어형성될수있다.  The metal chalcogenide compound may be commonly present as a single particle at the same time as the synthesis. In other words, the composite particles according to one embodiment of the present invention are formed at the stage of synthesis of the Group 11 metal chalcogenide compound satisfying the medium and formula (1). In situ, in the form of a single particle, the media and Group 11 metal chalcogenide compounds can be formed and aggregated.
[66] 이때,상기입자는다수개의결정체및 /또는비정질체가서로입계를이루며 웅집된 2차입자를의미할수있으며，상기인-시츄 (in-situ)의측면에서,매질 물질의핵생성및성장과 11족금속칼코젠화합물의핵생성및성장이동시 다발적으로발생하며，이러한핵생성이,직전생성되어성장하는다른핵을 핵생성자리로하여발생할수있다.이에따라，핵생성및성장단계에서서로 웅집되어단일한입자를형성하며매질과 11족금속칼코젠화합물이혼재하는 복합입자일수있다.  In this case, the particles may refer to secondary particles in which several crystals and / or amorphous particles form a grain boundary with each other, and in terms of the in-situ, the nucleation and growth of the medium material and Nucleation and growth of the Group 11 metal chalcogenide occurs frequently, and such nucleation may occur by the nucleation site of another nucleus that has been generated and grown immediately. To form a single particle and may be a mixed particle in which a medium and a Group 11 metal chalcogenide compound are mixed.
[67] 본발명의일실시예에따른복합입자에 있어,상기매질은 11족금속및 12족 내지 14족에서하나또는둘이상선택된원소의칼코젠화합물인  In a composite particle according to an embodiment of the present invention, the medium is a chalcogenide compound of at least one element selected from Group 11 metals and Groups 12-14.
금속간칼코젠화합물을함유할수있다.  It may contain an intermetallic chalcogenide compound.
[68] 본발명의일실시예에따른복합입자에있어， 11족금속은 Cu를포함할수  In a composite particle according to an embodiment of the present invention, the Group 11 metal may include Cu.
있으며, 12족금속은 Zn을포함할수있으며, 13족금속은 Ga및 In을포함할수 있으며, 14족금속은 Sn을포함할수있다.즉， 12족내지 14족은 Zn, Ga, In및 Sn을포함할수있으며, 12족내지 14족에서하나또는둘이상선택된원소는 In; Ga; In과 Ga; Zn; Sn;또는 Zn과 Sn일수있다.  Group 12 metals may include Zn, Group 13 metals may include Ga and In, and Group 14 metals may include Sn, i.e., Groups 12 to 14 may contain Zn, Ga, In and Sn. One or more selected elements from Groups 12 to 14 may be In; Ga; In and Ga; Zn; Sn; or may be Zn and Sn.
[69] 본발명의일실시예에따른복합입자에있어，칼코젠화합물의칼코젠또는 칼코젠 원소는 S, Se 또는 S와 Se를 포함할 수 있다. [69] A chalcogen of a chalcogen compound in a composite particle according to an embodiment of the present invention, The chalcogen element may include S, Se or S and Se.
[70] 상술한 바와 같이 , 본 발명의 일 실시 예에 따른 복합입자는 11족 금속 및 12족 내지 14족에서 하나 또는 둘 이상 선택된 원소의 칼코젠화합물인  As described above, the composite particle according to an embodiment of the present invention is a chalcogenide compound of one or two or more elements selected from Group 11 metals and Groups 12 to 14
금속간칼코젠화합물；과 상기 화학식 1을 만족하는 11족 금속  An intermetallic chalcogenide compound and a Group 11 metal satisfying Chemical Formula 1
칼코젠화합물 (이하， 1 1족칼코젠화합물);을 함유하며，상기  A chalcogen compound (hereinafter referred to as Group 1 chalcogen compound);
금속간칼코젠화합물과 상기 11족칼코젠화합물이 단일한 입자내에 흔재된 복합입자일 수 있다.  The intermetallic chalcogenide compound and the Group 11 chalcogenide compound may be composite particles common to a single particle.
[71] 본 발명 의 일 실시 예에 따른 복합입자에 있어，금속간칼코젠화합물은  [71] In the composite particle according to the embodiment of the present invention, the intermetallic chalcogenide compound is
제조하고자 하는 광활성층을 구성하는 모든 금속원소를 포함하는  Containing all metal elements constituting the photoactive layer to be prepared
칼코젠화합물일 수 있다. 즉, 복합입자는 광활성층을 구성하는 모든 금속원소를 포함하는 칼코젠화합물과 11족칼코젠화합물이 단일한 입자 내에 흔재된 입자일 수 있다.  It may be a chalcogen compound. That is, the composite particles may be particles in which a chalcogen compound and a group 11 chalcogen compound including all metal elements constituting the photoactive layer are found in a single particle.
[72] 본 발명의 일 실시 예에 따른 복합입자에 있어， 11족 금속 및 12족 내지 14족에서 하나 또는 둘 이상 선택된 원소의 칼코젠화합물인 금속간칼코젠화합물은 제조하고자 하는 화합물 반도체 기 반 광활성층의 화학양론비를 갖는  In a composite particle according to an embodiment of the present invention, an intermetallic chalcogenide compound, which is a chalcogenide compound of at least one element selected from Group 11 metals and Groups 12 to 14, is a compound semiconductor-based optical activity to be prepared. Having stoichiometric ratio of layer
금속간칼코젠화합물일 수 있다.  It may be an intermetallic chalcogenide compound.
[73] 보다 상세하게，금속간칼코젠화합물은 하기 화학식 2 또는 하기 화학식 3에 따른 화학양론비를 만족하는 금속간칼코젠화합물일 수 있다.  More specifically, the intermetallic chalcogenide compound may be an intermetallic chalcogenide compound satisfying the stoichiometric ratio according to the following Chemical Formula 2 or the following Chemical Formula 3.
[74] (화학식 2)  [74] (Formula 2)
[75] ΜΊΜ'ΊΑ2 [75] ΜΊΜ'ΊΑ 2
[76] 화학식 2에서 M'는 11족 금속에서 하나 또는 둘 이상 선택된 금속이며 , Μ"는 In Formula 2, M 'is a metal selected from one or more than one group 11 metal, Μ "is
13족에서 하나 또는 들 이상 선택된 금속이다. One or more metals selected from Group 13;
[77] 상세하게, M'는 구리 일 수 있으며， Μ"는 InyGa^O y^인 실수)일 수 있으며，In detail, M 'may be copper and Μ "may be a real number In y Ga ^ O y ^),
A는 SenS 0≤n≤l인 실수)일 수 있다. A may be a real number Se n S 0 ≦ n ≦ l).
[78] (화학식 3) [78] (Formula 3)
[79] M'2M'"A4 [79] M ' 2 M'"A4
[80] 화학식 3에서 M'는 11족 금속에서 하나 또는 둘 이상 선택된 금속이며 , Μ'"는 [80] In Formula 3, M 'is one or more metals selected from Group 11 metals, and Μ' "is
12족 및 14족에서 하나 또는 둘 이상 선택된 금속이다. At least one metal selected from Groups 12 and 14;
[81] 상세하게, M'는 구리 일 수 있으며 , M"'은 ZnmSn2_m(0≤m≤2인 실수)일 수 있으며，In detail, M 'may be copper, M "' may be Zn m Sn 2 _ m (real number 0≤m≤2),
A는 SenS 0≤n≤l인 실수)일 수 있다. A may be a real number Se n S 0 ≦ n ≦ l).
[82] 실질적 인 일 예로，금속간칼코젠화합물은 CuInSe, CuInS 또는 CuInSe^^ [82] As a practical example, the intermetallic chalcogenide compound may be CuInSe, CuInS or CuInSe ^^.
(0≤η≤1인 실수)일 수 있다.  (Real number 0 ≦ η ≦ 1).
[83] 본 발명 의 일 실시 예에 따른 복합입자에 있어，태양전지 광활성층 제조를 위한 열처 리 온도에서 11족칼코젠화합물은 용융상 (액상)을 형성 할 수 있다. In the composite particle according to the embodiment of the present invention, the Group 11 chalcogenide compound may form a molten phase (liquid phase) at a thermal treatment temperature for manufacturing a photoactive layer of a solar cell.
[84] 상세하게，태양전지 광활성층 제조를 위 한 열처 리 온도는 400 내지 550°C일 수 있으며 , 1 1족칼코젠화합물은 400 내지 550°C에서 용융상을 형성 할 수 있으며， 보다 상세하게， 11족칼코젠화합물의 융점은 220 내지 550 °C일 수 있다. In detail, the heat treatment temperature for producing a solar cell photoactive layer may be 400 to 550 ° C, Group 1 chalcogenide compound may form a molten phase at 400 to 550 ° C, more specifically , The melting point of the Group 11 chalcogenene compound may be 220 to 550 ° C.
[85] 본 발명의 일 실시 예에 따른 복합입자에 있어， 1 1족 금속은 구리를 포함할 수 있으며, 11족칼코젠화합물은 CuSe, CuSe2또는이들의흔합물을포함할수있다. In the composite particle according to the embodiment of the present invention, the Group 1 Group 1 metal may include copper. And the Group 11 chalcogenide compound may include CuSe, CuSe 2 or a combination thereof.
[86] 본발명의일실시예에따른복합입자에있어,상기 11족금속은 Cu일수 In the composite particle according to the embodiment of the present invention, the Group 11 metal may be Cu.
있으며, 12내지 14족금속은 In또는 In과 Ga일수있으며，칼코젠원소는 Se일수 있다.  The metal of Group 12 to 14 may be In, In, and Ga, and the chalcogen element may be Se.
[87] 본발명의일실시예에따른복합입자에있어,상기 11족금속은 Cu일수  In the composite particle according to the embodiment of the present invention, the Group 11 metal may be Cu.
있으며, 12내지 14족금속은 Zn, Sn또는 Zn과 Sn일수있으며，칼코젠원소는 S, Se또는 S와 수있다.  The metal of Group 12 to 14 may be Zn, Sn or Zn and Sn, chalcogen element may be S, Se or S.
[88] 상술한바와같이，본발명의일실시예에따른복합입자는 CIS(Cu-in-(S,Se))와 같이제조하고자하는광활성층의모든금속원소들을함유하며，제조하고자 하는광활성층의화학양론비를갖는금속간칼코젠화합물을매질로함유하고， 매질과액상을형성하는저융점의 11족칼코젠화합물이단일입자내에 혼재됨에따라，별도의추가공정없이복합입자단계에서광활성층의조성을 원하는조성으로조절할수있다.  As described above, the composite particles according to one embodiment of the present invention contain all metal elements of the photoactive layer to be manufactured, such as CIS (Cu-in- (S, Se)), and the photoactive activity to be manufactured. As the medium contains intermetallic chalcogenides having a stoichiometric ratio of the layer as a medium, and the low melting point Group 11 chalcogenides forming the medium and the liquid phase are mixed in a single particle, the step of the photoactive layer in the composite particle step without further processing is required. The composition can be adjusted to the desired composition.
[89] 즉，본발명의일실시예에따른복합입자는복합입자자체의조성에의해  That is, the composite particles according to the embodiment of the present invention are formed by the composition of the composite particles themselves.
광활성층의조성을설계 (결정)할수있는장점이있으며 ,복합입자가광활성층 제조를위한열처리시고상을유지하는광활성층의모든금속원소들의금속간 ' 칼코젠화합물을함유하는매질과액상을형성하는 11족칼코젠화합물이흔재된 입자상임에따라,광활성층제조를위한열처리시조성변화가방지될수있는 장점이있다.  It has the advantage of designing (determining) the composition of the photoactive layer, and the complex particles form a medium and liquid phase containing the metal-to-metal chalcogen compound of all the metal elements of the photoactive layer which are thermally treated to maintain the phase. Since the group chalcogenide compound is a common particle, there is an advantage that the composition change during heat treatment for the production of the photoactive layer can be prevented.
[90] 또한，금속간칼코젠화합물과액상을형성할수있는 11족칼코젠화합물이  [90] In addition, a Group 11 chalcogen compound capable of forming a liquid phase with the intermetallic chalcogen compound
단일한입자내균질하게분산및결합된입자상을가짐에따라,용융상을 형성하는 11족칼코젠화합물에의해매우빠르고균질하게치밀한구조의 광활성층을제조할수있다.또한고상을유지하며이미광활성층의  By having homogeneously dispersed and bound granular phases within a single particle, the Group 11 chalcogenide forming a molten phase can produce a very fast and homogeneously dense structure of the photoactive layer.
화학양론비를갖는금속간칼코젠화합물과 11족칼코젠화합물이극히균질하게 단일입자내에혼재되어있음에따라，칼코젠원소의손실이방지되어조성적 안정성을획득할수있다.  Since the intermetallic chalcogenide and group 11 chalcogenide having a stoichiometric ratio are mixed in a very homogeneous single particle, the loss of the chalcogenide element can be prevented to obtain compositional stability.
[91] 이러한효과는본발명의일실시예에따른복합입자에기인한것으로，  This effect is due to the composite particles according to the embodiment of the present invention.
11족칼코젠화합물입자와금속간칼코젠화합물입자가서로독립적으로합성된 후，단지물리적으로혼합된경우,용융상의불균질한분포로인해，최종적으로 제조되는광활성층의불균일한미세구조형성을야기하며，국부적으로과도한 용융상의형성에의해광활성층의조성블균일을야기할수있다.  If the Group 11 chalcogenide particles and the intermetallic chalcogenide particles are independently synthesized and then only physically mixed, the heterogeneous distribution of the molten phase leads to the formation of a nonuniform fine structure of the finally produced photoactive layer. The formation of locally excessive molten phases may lead to the composition uniformity of the photoactive layer.
[92] 본발명의일실시예에따른복합입자는 11족금속： 12내지 14족금속：칼코젠 원소의몰비가 0.8~1.3:0.8~1.3:1.7~2.3，바람직하게' 0.8~1.3： 1： 2일수있다. 상세하게，복합입자에함유된각금속및칼코롄원소의몰비 (원소비)에의해 제조되는광활성층의원소비가규정될수있다.이에따라，목표하는광활성충의 화학양론비를갖는복합입자를이용하는극이용이하고간단한방법을통해， 목표하는조성을갖는광활성층의제조가가능해진다. [92] The composite particles in accordance with one embodiment of the present invention is a Group 11 metal: 12 to Group 14 metal: the molar ratio of the knife kojen element 0.8 ~ 1.3: 0.8 ~ 1.3: 1.7 ~ 2.3, preferably, 0.8 ~ 1.3: 1 ： It can be 2 days. Specifically, the element ratio of the photoactive layer produced by the molar ratio (element ratio) of each metal and calcolian element contained in the composite particle can be specified. Accordingly, the pole using the composite particle having the stoichiometric ratio of the target photoactive insect. Through a simple and simple method, it is possible to manufacture a photoactive layer having a desired composition.
[93] 즉,복함입자는， CIS(Cu-In-(S,Se))와같이제조하고자하는광활성층의모든 금속원소들의금속간칼코젠화합물을매질로함유하고,매질과액상을 형성하는저융점의 11족칼코젠화합물이단일입자내에혼재됨에따라,별도의 추가공정없이복합입자단계에서광활성층의조성올원하는조성으로조절할 수있다. That is, the complex particles may be formed of all of the photoactive layers to be manufactured, such as CIS (Cu-In- (S, Se)). The low melting group 11 chalcogenide compound containing the intermetallic chalcogenide of the metal elements as a medium and mixed into the single particle forms the composition of the photoactive layer at the compound particle stage without further processing. Can be adjusted with
[94] 상세하게,본발명의일실시예에따른복합입자는 Cu인 11족금속： In또는  In detail, the composite particle according to one embodiment of the present invention is a Group 11 metal, which is Cu: In or
In과 Ga인 12내지 14족금속: Se인칼코젠원소의몰비가 0.8~1.3:0.8~1.3:1.7~2.3， 바람직하게 0.8 -1.3： 1： 2일수았다.  The molar ratio of 12 to 14 metals of In and Ga: Se incalcogen element was 0.8-1.3: 0.8-1.3: 1.7-2.3, preferably 0.8-1.3: 1: 1.
[95] 상세하게，본발명의일실시예에따른복합입자는 Cu인 11족금속 : Zii, Sn또는 Zn과 Sn인 12내지 14족금속: S, Se또는 S와 Se인칼코젠원소의몰비가  Specifically, the composite particles according to one embodiment of the present invention are a Group 11 metal of Cu: Zii, Sn, or a Group 12 to 14 metal of Zn and Sn: a molar ratio of S, Se, or S and Se incalcogen elements.
0.8-1.3:0.8-1.3:1.7-2.3,바람직하게 0.8 -1.3： 1： 2일수있다.  0.8-1.3: 0.8-1.3: 1.7-2.3, preferably 0.8 -1.3: 1: 1.
[96] 일예로,제조하고자하는광활성층이 CuIn(S,Se)2인경우，상기복합입자는 Cu： In： Se를 0.8~1.3:0.8~1.3:1.7~2.3의몰비로함유할수있다.바람직하게，상기 복합입자는 Cu： In： Se를으8 ~ 1.3： 1： 2의몰비로함유할수있다.이때， Cu의 몰비가이 0.8 ~ 1.0의범위로제어될경우광흡수층의전기적특성이제어되어 광소자의효율을향상시킬수있으며， 0.8미만의비율에서는결정상의분리로 인해특성저하가발생할위험이있다.또한， Cu의몰비가 1.0~ 1.3범위로제어될 경우, 11족칼코젠화합물의액상형성에의한광흡수층을구성하는결정입 성장을촉진시킬수있다. For example, when the photoactive layer to be manufactured is CuIn (S, Se) 2 , the composite particles may contain Cu: In: Se in a molar ratio of 0.8 to 1.3: 0.8 to 1.3: 1.7 to 2.3. Preferably, the composite particles may contain a Cu: In: Se in a molar ratio of 8 to 1.3: 1: 1. At this time, when the molar ratio of Cu is controlled in the range of 0.8 to 1.0, the electrical properties of the light absorption layer are controlled to reduce It is possible to improve the efficiency of the porcelain, and there is a risk of deterioration of characteristics due to the separation of the crystal phase at the ratio of less than 0.8. It can promote the growth of grains that make up.
[97] 본발명의일실시예에따른복합입자에 있어 ,복합입자는 1내지 20부피 %의 11족칼코젠화합물을함유할수있다.복합입자에함유되는 11족칼코젠화합물은 광활성층형성을위한열처리시용융상을형성하는저융점화합물일수있는데, 복합입자내함유되는 11족칼코젠화합물이상술한부피비를갖는경우， 용융상에의해매우빠르고균질하게단일상다원칼코젠화합물이생성될수 있으며，과도한액상형성에의한불균질한미세구조형성을방지할수있으며， 칼코젠원소의손실이방지되어조성적안정성을획득할수있다.  In a composite particle according to an embodiment of the present invention, the composite particle may contain 1 to 20% by volume of the Group 11 chalcogen compound. The Group 11 chalcogen compound contained in the composite particle may be heat treated to form a photoactive layer. It may be a low melting point compound that forms a commercial melting phase, and in the case of having a volume ratio described above the Group 11 chalcogen compound contained in the composite particles, a single phase poly-chalcogen compound may be generated very rapidly and homogeneously by the molten phase, and in excessive liquid phase formation It is possible to prevent the formation of heterogeneous microstructures and to prevent composition loss by obtaining chalcogenene elements.
[98] 상술한바와같이，본발명의일실시예에따른복합입자는제조하고자하는 광활성층의화학양론비를갖는금속간화합물및 11족칼코젠화합물을함유할수 있는데，이때,금속간화합물및 11족칼코젠화합물이외의다른잔류화합물을더 함유할수있다.  As described above, the composite particles according to one embodiment of the present invention may contain an intermetallic compound and a Group 11 chalcogen compound having a stoichiometric ratio of the photoactive layer to be manufactured, wherein the intermetallic compound and 11 It may contain other residual compounds other than the family chalcogen compounds.
[99] 상기잔류화합물은상술한바와같이，합성단계에서금속간화합물및  As described above, the residual compound is an intermetallic compound and
11족칼코젠화합물이동시에생성및성장하고서로결착하여복합입자화됨에 따라，합성시미량존재할수있는부생성물일수있으며，전체적인복합입자의 조성이제조하고자하는광활성층의조성을만족함에따라,  As Group 11 chalcogenides are simultaneously produced, grown, and bound together to form composite particles, they may be minor by-products during synthesis, and as the composition of the overall composite particles satisfies the composition of the photoactive layer to be prepared,
11족칼코젠화합물의생성과함께형성되는부생성물일수있다 .  It may be a by-product formed with the formation of a Group 11 chalcogen compound.
[100] 상술한바와같이,상기잔류화합물은합성시부산물로잔류하거나， As described above, the residual compound may remain as a by-product when synthesized,
광활성층의조성을갖도록복합입자를제조함에따라부산물로잔류하는 것임에따라，제조하고자하는광활성층의물질,조성에따라존재여부， 화합물의형태및 /또는그함량이달라질수있다.일예로，상기잔류화합물은 상기화학식 1을만족하지않는 11족금속의칼코젠화합물, 12내지 14족 금속에서하나이상선택돤금속간의금속간칼코젠화합물， 12내지 14족 금속에서하나이상선택된금속의산화물및칼코젠에서하나또는둘이상 선택된물질일수있다. Depending on the composition of the photoactive layer, the composite particles remain as a by-product, and depending on the material and composition of the photoactive layer to be produced, the presence, the form and / or the content of the compound may vary. Residual Compounds A chalcogenide compound of Group 11 metal that does not satisfy Formula 1, at least one selected from Group 12 to 14 metals; intermetallic chalcogenide compound; one or more selected from oxides and chalcogens of at least one metal selected from Group 12 to 14 metals; More than one substance may be selected.
[101] 일예로,화학식 1을만족하지않는 11족금속의칼코젠화합물은 Cu2Se일수 있으며， 12내지 14족금속에서하나이상선택된금속의산화물은인듐 [101] For example, the chalcogenide compound of Group 11 metal that does not satisfy Formula 1 may be Cu 2 Se, and the oxide of at least one metal selected from Group 12 to 14 metal is indium.
칼코젠화합물，갈륨칼코젠화합물，주석칼코젠화합물，아연칼코젠화합물， 인듐 -갈륨칼코젠화합물및주석 -아연칼코젠화합물에서하나또는둘이상 선택된것일수있으며, 12내지 14족금속에서하나이상선택된금속의 산화물은인듐산화물,갈륨산화물,주석산화물，아연산화물,인듬 -갈륨산화물 및주석 -아연산화물에서하나또는둘이상선택된것일수있으며,칼코젠은 S 또는 Se일수있다.  One or more selected from chalcogen compounds, gallium chalcogen compounds, tin chalcogen compounds, zinc chalcogen compounds, indium-gallium chalcogen compounds and tin-zinc chalcogen compounds, and at least one of 12 to 14 metals. The oxide of the selected metal may be one or more selected from indium oxide, gallium oxide, tin oxide, zinc oxide, rhythm-gallium oxide and tin-zinc oxide, and the chalcogen may be S or Se.
[102] 보다실질적인일예로，상기잔류화합물은 Cu2Se, In2Se3, In203및 Se에서하나 또는둘이상선택될수있다. In a more practical example, the residual compound may be selected from Cu 2 Se, In 2 Se 3 , In 2 O 3 and Se.
[103] 본발명의일실시예에따른복합입자에있어，상기복합입자는 1내지 20  [103] In the composite particle according to the embodiment of the present invention, the composite particle is 1 to 20
부피 %의 11족칼코젠화합물과 80내지 99부피 %의매질을포함할수있으며， 상기매질은금속간칼코젠화합물로이루어지거나,금속칼코젠화합물과 잔류화합물로이루어질수있다.상세하게，상기매질은적어도 40부피 «¾이상의 금속간칼코젠화합물을함유할수있으며，상기매질은 60부피%이하의 It may comprise a volume 11 group 11 chalcogen compound and a medium of 80 to 99 volume%, the medium may be composed of an intermetallic chalcogenide compound, or a metal chalcogenide compound and a residual compound. In detail, the medium may be at least 40%. It may contain an intermetallic chalcogenide in a volume of « ¾ or more, and the medium may be less than 60% by volume.
잔류화합물을함유할수있다.즉，상기매질은매질의전체부피를기준으로 40 내지 100부피 %의상기금속간칼코젠화합물을함유할수있으며, 0내지 60 부피 %의잔류화합물을함유할수있다.  Residual compounds may be contained, i.e., the medium may contain from 40 to 100% by volume of the intermetallic chalcogenide compound based on the total volume of the medium, and may contain from 0 to 60% by volume of the residual compound.
[104]. 실질적인일예로，상기복합입자는 11족칼코젠화합물을 1내지 20부피 %  [104]. As a practical example, the composite particles may contain 1 to 20% by volume of the Group 11 chalcogenide compound.
함유할수있으며，저융점의 n족칼코젠화합물을제외한매질의전체부피를 기준으로금속간칼코젠화합물을 40내지 95부피 %로함유하고,잔류화합물을 5 내지 60부피 %로함유할수있다.  It may contain 40 to 95% by volume of intermetallic chalcogenides and 5 to 60% by volume of the residual compound, based on the total volume of the medium excluding the low melting point n-group chalcogenides.
[105] 본발명의일실시예에따른복합입자에있어,상기복합입자는나노입자일수 있으며，평균입자크기가 5내지 500nm일수있다.또한,상술한바와같이，상기 복합입자는물질합성단계에서인-시츄로 11족칼코젠화합물과  In a composite particle according to an embodiment of the present invention, the composite particle may be a nanoparticle and an average particle size may be 5 to 500 nm. As described above, the composite particle may be formed in a material synthesis step. In-situ group 11 chalcogen compound
금속간칼코젠화합물이서로동시다발적인핵생성및성장에의해흔재및 결착된것일수있으며，이러한합성에의해평균입자크기가 5내지 500nm인 나노입자로제조된것일수있다.  The intermetallic chalcogenide compounds may be infrequent and bound by multiple nucleation and growth at the same time, and may be made of nanoparticles with an average particle size of 5 to 500 nm by this synthesis.
[106] 본발명의복합입자에따른일실시예에있어，상기복합입자는 Cu:In:Se의 몰비가 0.8~1.3:0.8~1.3:1.7~2.3,바람직하게, 0.8 ~ 1.3： 1： 2이되도록구리화합물, 인듐화합물및샐레늄화합물이반웅용매에흔합된흔합액에마이크로파를 조사하여제조될수있다.이때，상기반응용매는끓는점 (boiling point)이 200°C 이상，실질적으로 200내지 450°C인것이바람직하며 ,끓는점이 200내지 In one embodiment according to the composite particles of the present invention, the composite particles may have a molar ratio of Cu : In : Se of 0.8 to 1.3: 0.8 to 1.3: 1.7 to 2.3, preferably 0.8 to 1.3: 1: 1. Copper, indium and selenium compounds can be prepared by irradiating microwaves in a mixed solution mixed with a reaction solvent. At this time, the reaction solvent has a boiling point of 200 ° C. or higher and practically 200 to 450. ° C is preferred, boiling point is 200 ~
450oC인고비점반웅용매를이용함으로써，매질에 U족칼코젠화합물이혼재된 입자상이 제조될 수 있다. By using a 450 o C high boiling point reaction solvent, Particulate phases can be produced.
[107] 반응 용매는, 폴리 을계 용매，아민계 용매 및 포스핀계 용매로부터 선택된 1종 또는 2종 이상을 포함할 수 있다.  The reaction solvent may include one kind or two or more kinds selected from poly solvents, amine solvents, and phosphine solvents.
[108] 보다 상세하게 폴리을계 용매는 디 에 틸렌글리콜 (diethylene glycol),  In more detail, the poly-based solvent may be selected from the group consisting of diethylene glycol,
디에 틸렌글리콜 에 틸이서 (diethylene glycol ethyl ether), 디에 틸렌글리콜  Diethylene glycol ethyl ether, diethylene glycol
부틸이서 (diethylene glycol buthyl ether), 트리에 틸렌글리콜 (triethylene glycol), 폴리에 틸렌 글리콜 (poly(ethyleneglycol), 분자량; 200 ~ 100,000), 폴리에 틸렌 글리콜 다이아크릴 레이트 (poly(ethylene glycol) diacrylate), 폴리에 틸렌 글리콜 다이 벤조네이트 (polyethylene glycol) dibenzonate), 디프로필렌글리콜 (dipropylene glycol), 트리프로필렌글리콜 (dipropylene glycol), 글리세를 (glycerol)로 이루어 진 군으로부터 선택된 1종 또는 2종 이상을 포함할 수 있다.  Butyl ether (diethylene glycol buthyl ether), triethylene glycol (polyethylene glycol), poly (ethyleneglycol, molecular weight; 200 ~ 100,000), poly (ethylene glycol) diacrylate And one or more selected from the group consisting of polyethylene glycol dibenzonate, dipropylene glycol, tripropylene glycol, and glycerol. can do.
[109] 보다 상세하게 아민계 용매는 디 에 틸아민 (diethyl amine),  [109] More specifically, the amine solvent may be selected from diethyl amine,
트리에 틸아민 (triethylamine), 1,3-프로판디아민 (l,3-propane diamine),  Triethylamine, 1,3-propanediamine,
1，4-부탄디아민 (1,4-butane diamine), 1,5-펜탄디 아민 (1,5-pentane diamine),  1,4-butanediamine, 1,5-pentane diamine, 1,5-pentane diamine,
1 ,6-핵산디아민 ( 1 ,6-hexane diamine), 1 ,7-헵탄디아민 ( 1 ,7-heptane diamine),  1,6-hexane diamine (1,6-hexane diamine), 1,7-heptane diamine,
1,8-옥탄디아민 (octane diamine), 디 에 틸렌디아민 (diethylene diamine),  1,8-octane diamine, diethylene diamine,
디에 틸렌트리아민 (diethylene triamine), 를루엔 디아민 (toluene diamine), m-페닐렌디아민 (mphenylenediamine), 디페닐메탄 디 아민 (diphenyl methane diamine), 핵사메틸렌 디 아민 (hexame thy lene diamine),  Diethylene triamine, toluene diamine, m-phenylenediamine, diphenyl methane diamine, hexamethylene diamine,
트리에 틸렌테트라아민 (triethylene tetramine),  Triethylene tetramine,
테트라에 틸렌펜타아민 (tetraethylenepentamine),  Tetraethylenepentamine,
핵사메 틸렌테트라아민 (hexamethylene tetramine)으로 이루어진 군으로부터 선택된 1종 또는 2종 이상을 포함할 수 있다.  It may include one or two or more selected from the group consisting of hexamethylene tetramine.
[110] 보다 상세하게，포스핀계 용매는 트리옥틸포스핀 (trioctylphosphine) 또는 [110] More specifically, the phosphine solvent is trioctylphosphine or
트리옥틸포스핀 옥사이드 (trioctylphosphineoxide) 중 어느 하나 또는 둘의 혼합 용매일 수 있다.  It may be a mixed solvent of any one or two of trioctylphosphineoxide.
[111] 이 때，마이크로파의 조사에 의 한 흔합액의 가열 온도 및 가열 온도가 유지 되는 반응시간에서 하나 또는 둘 이상 선택된 인자 (factor)에 의 해 상기 복합입자에 함유되는 11족칼코젠화합물의 함량이 제어될 수 있다.  [111] At this time, the content of the Group 11 chalcogen compound contained in the composite particles by one or more factors selected from the heating temperature of the mixed solution by microwave irradiation and the reaction time at which the heating temperature is maintained. This can be controlled.
[112] 본 발명의 복합입 자에 따른 일 실시 예에 있어，복합입자는 1 내지 20 부피 %의 11족칼코젠화합물을 함유하는 것이 바람직하며 , 복합입자 내  In one embodiment according to the multiparticulates of the present invention, the multiparticulates preferably contain 1 to 20% by volume of Group 11 chalcogenide compound,
11족칼코젠화합물을 1 내지 20 부피 %로 제어하기 위해，마이크로파 조사에 의해 200 내지 300oC의 온도로 15 내지 40분간 반응이 유지 (반웅시간)되는 것 이 바람직하다. In order to control the Group 11 chalcogenene compound to 1 to 20% by volume, it is preferable that the reaction is maintained (reaction time) for 15 to 40 minutes at a temperature of 200 to 300 ° C. by microwave irradiation.
[113]  [113]
[1 14] 본 발명은 상술한 복합입자를 함유하는 태양전지 광활성층용 잉크를 제공한다.  [1 14] The present invention provides an ink for a photovoltaic layer of a solar cell containing the above-mentioned composite particles.
[115] 본 발명의 일 실시 예에 따른 잉크는 상술한 복합입자를 함유할 수 있다. 잉크에 함유되는 복합입자는 목적하는 광활성층을 구성하는 모든 금속원소를 함유하는 칼코젠화합물인금속간칼코젠화합물과저융점의 11족칼코젠화합물이 균질하게분산된복합입자이며，복합입자의조성에의해광활성층의조성이기 결정됨 (pre-determined)에따라，잉크는분삼성，점도，물리적결착성등，도포공정 및막형성을위한보조적 첨가물질이외，실질적으로광활성층을형성하기 위한유효물질이복합입자일수있다.즉，본발명에따른잉크의일실시예에 있어，잉크는광활성층의형성에관여하는유효물질로,복합입자만을함유할수 있다. An ink according to an embodiment of the present invention may contain the above-described composite particles. The composite particles contained in the ink contain all metal elements constituting the desired photoactive layer. The intercalating chalcogenide compound, which is a chalcogenide compound, and the low melting point Group 11 chalcogenide compound are homogeneously dispersed, and the composition of the photoactive layer is determined by the composition of the composite particles (pre-determined). In addition to the auxiliary additives for the coating process and film formation, such as viscosity, physical binding, etc., the effective material for forming the photoactive layer may be a composite particle. In other words, in one embodiment of the ink according to the present invention, the ink may be An effective substance that is involved in the formation of the photoactive layer, and may contain only composite particles.
[116] 이는,복합입자가목표하는화합물반도체기반광활성층을구성하는모든  [116] This means that all of the components that make up the compound semiconductor-based photoactive layer targeted by the composite particle
금속원소를함유하는칼코젠화합물 (금속간칼코젠화합물)을함유하며, 목표하는화합물반도체기반광활성층의조성을만족하도록각금속및 칼코젠원소의조성을가질수있기때문이다.  This is because it contains a chalcogenide compound (an intermetallic chalcogenide) containing a metal element, and each metal and chalcogen element can be formed to satisfy the composition of the target compound semiconductor-based photoactive layer.
[117] 또한,복합입자가금속간칼코젠화합물을함유하는매질에광활성층의제조시 액상을형성하는 11족칼코젠화합물이균질하게분산및서로결착된상태임에 따라，복합입자단독으로도치밀하고，균질하며,단일상의광활성층의제조가 가능할수있다.  In addition, since the complex particles are homogeneously dispersed and bound together in the group 11 chalcogen compound forming a liquid phase in the preparation of the photoactive layer in a medium containing an intermetallic chalcogen compound, the particles are dense alone. It is possible to produce a homogeneous, single phase photoactive layer.
[118] 그러나，본발명의일실시예에따른잉크에 있어,잉크가광활성층의형성에 관여하는유효물질로,복합입자만을함유하는구성은본발명에따른잉크에 함유되는복합입자의특징에의해가능한것이며，상술한복합입자에의해 야기되는효과들을저해하지않는한，필요시,복합입자이외의다른유효물질을 더함유할수있다.  However, in the ink according to one embodiment of the present invention, the ink is an effective substance involved in the formation of the photoactive layer, and the composition containing only the composite particles is determined by the characteristics of the composite particles contained in the ink according to the present invention. It is possible and, if necessary, may contain other effective substances other than the composite particles as long as they do not interfere with the effects caused by the composite particles described above.
[119] 일예로,광활성층의두께별원소 (일예로, Ga)농도가달라지는  For example, the concentration of elements (eg, Ga) in the thickness of the photoactive layer varies.
그레디언트 (gradient)광활성층을제조하고자할경우,서로다른금속간몰비를 갖는다양한조성의복합입자를사용할수있으며,다른접근으로，일정조성을 갖는복합입자와농도프로파일을조절하고자하는원소 (일예로, Ga)의전구체 또는농도프로파일을조절하고자하는원소의칼코젠화합물을함께사용할수 있다.  For the production of gradient photoactive layers, it is possible to use composite particles of various compositions with different metal-to-metal molar ratios, and with different approaches, to control the composite particles and concentration profiles of uniform composition (e.g., The precursor of cha) or the chalcogenide of the element to which the concentration profile is to be adjusted can be used together.
[120] 본발명의일실시예에따른잉크에 있어,상술한잉크에의해제조되는  [120] In the ink according to one embodiment of the present invention, the ink is prepared by the above-described ink.
광활성층은 CIS(Cu-In-Se또는 Cu-In-S), CIGS(Cu-In-Ga-Se또는 Cu-In-Ga-S), CIGSS(Cu-In-Ga-Se-S), CZTS(Cu-Zn-Sn-Se또는 Cu-Zn-Sn-S)또는  The photoactive layer may be CIS (Cu-In-Se or Cu-In-S), CIGS (Cu-In-Ga-Se or Cu-In-Ga-S), CIGSS (Cu-In-Ga-Se-S), CZTS (Cu-Zn-Sn-Se or Cu-Zn-Sn-S) or
CZTSS(Cu-Zn-Sn-Se-S)일수있다.이때，광활성층은화학양론비를가질수있다.  It may be CZTSS (Cu-Zn-Sn-Se-S), wherein the photoactive layer may have a stoichiometric ratio.
[121] 본발명의일실시예에따른잉크에 있어，분산매질을형성하는용매는  [121] In the ink according to one embodiment of the present invention, a solvent for forming a dispersion medium is
입자상을함유하며도포공정이수행되는통상의잉크조성물에사용되는 용매이면족하며，일예로，용매는무극성용매,폴리을계용매，아민계용매， 포스핀계용매,알코올계용매및극성용매중하나또는둘이상선택되는 용매를함유할수있다.  The solvent may be a solvent used in a general ink composition containing particulates and performing a coating process. For example, the solvent may be a nonpolar solvent, a poly solvent, an amine solvent, a phosphine solvent, an alcohol solvent, or a polar solvent. It may contain more than one solvent selected.
[122] 실질적인일예로,잉크의분산매질을형성할수있는，폴리을계용매는에틸렌 글리콜 (ethylene glycol),디에틸렌글리콜 (diethylene glycol),디에틸렌글리콜 에틸이서 (diethylene glycol ethyl ether),디에틸렌글리콜부틸이서 (diethylene glycol buthyl ether), 트리 에 틸렌글리콜 (Methylene glycol), 폴리에 틸렌 글리콜 (poly(ethylene glycol), Mw: 200-100,000), 폴리에 틸렌 글리콜 [122] As a practical example, poly-based solvents capable of forming a dispersion medium of ink include ethylene glycol, diethylene glycol, diethylene glycol ethyl ether and diethylene glycol butyl. Dicer glycol buthyl ether), polyethylene glycol, polyethylene glycol (Mw: 200-100,000), polyethylene glycol
다이아크릴레 이트 (poly(ethylene glycol) diacrylate), 폴리 에 틸렌 글리콜  Diacrylate (poly (ethylene glycol) diacrylate), polyethylene glycol
다이 벤조네이트 (polyethylene glycol) dibenzonate), 디프로필렌글리콜 (dipropylene glycol), 트리프로필렌글리콜 (dipropylene glycol) 및 글리세를 (glycerol)로부터 하나 또는 둘 이상 선택되는 용매를 포함할 수 있다.  It may include a solvent selected from dibenzonate, dipropylene glycol, dipropylene glycol, dipropylene glycol and glycerol (glycerol).
[123] 실질적 인 일 예로，잉크의 분산매질을 형성 할 수 있는，아민계열 용매는 [123] As a practical example, the amine solvent is capable of forming a dispersion medium of the ink
디에 틸아민 (diethyl amine), 트리 에 틸아민 (triethylamine),  Diethyl amine, triethylamine,
1,3-프로판디아민 (1,3-propane diamine), 1,4-부탄디 아민 (1,4-butane diamine), 1,5-펜탄디 아민 (1,5-pentane diamine), 1,6-핵산디 아민 (1,6-hexane diamine), 1,7-헵탄디아민 (1,7-heptane diamine), 1，8-옥탄디아민 (octane diamine)을 포함하는 디에 틸렌디 아민 (diethylene diamine), 디에 틸렌트리 아민 (diethylene triamine), 를루엔 디 아민 (toluene diamine), m-페닐렌디아민 (m-phenylenediamine), 디페닐메탄 디아민 (diphenyl methane diamine), 핵사메틸렌 디아민 (hexamethylene diamine), 트리에 틸렌테트라아민 (triethylene tetramine),  1,3-propane diamine, 1,4-butanediamine, 1,5-pentane diamine, 1,5-pentane diamine, 1,6 Diethylene diamine, including 1,6-hexane diamine, 1,7-heptane diamine, and 1,8-octane diamine , Diethylene triamine, toluene diamine, m-phenylenediamine, diphenyl methane diamine, hexamethylene diamine, Triethylene tetramine,
테트라에 틸렌펜타아민 (tetraethylenepentamine),  Tetraethylenepentamine,
핵사메틸렌테트라아민 (hexamethylene tetramine), 에 탄올 아민 (ethanolamine), 다이에 탄올 아민 (diethanolamine) 및 트리에 탄올아민 (triethanolamine)으로부터 하나 또는 둘 이상 선택되는 용매를 포함할 수 있다.  One or more solvents selected from hexamethylene tetramine, ethanolamine, diethanolamine, and triethanolamine may be included.
[124] 실질적 인 일 예로，잉크의 분산매질을 형성 할 수 있는, 포스핀계 용매는 As a practical example, phosphine-based solvents, which can form a dispersion medium of ink,
트리옥틸포스핀 (trioctylphosphine) 및  Trioctylphosphine and
트리옥틸포스핀옥사이드 (trioctylphosphineoxide)으로부터 하나 또는 둘 이상 선택되는 용매를 포함할 수 있다.  It may include one or more solvents selected from trioctylphosphineoxide.
[125] 실질적 인 일 예로, 잉크의 분산매질을 형성 할 수 있는，알코올계 용매는 메틸 샐로솔브 (Methyl Cellosolve), 에 틸 샐로솔브 (Ethyl Cellosolve), 부틸  As a practical example, an alcoholic solvent capable of forming a dispersion medium of the ink may be methyl cellosolve, ethyl cellosolve or butyl.
샐로솔브 (Butyl Cellosolve) 및 1 내지 8의 탄소수를 가지는  Butyl solve (Butyl Cellosolve) and having from 1 to 8 carbon atoms
알코올 (Alcohol)로부터 하나 또는 둘 이상 선택되는 용매를 포함할 수 있다.  It may include a solvent selected from one or more than alcohol (Alcohol).
[126] 실질적 인 일 예로，잉크의 분산매질을 형성 할 수 있는，무극성 용매는  [126] As a practical example, a nonpolar solvent capable of forming a dispersion medium of the ink
를루엔 (toluene), 클로로품 (chloroform), 클로로벤젠 (chlorobenzene),  Toluene, chloroform, chlorobenzene,
다이클로로벤젠 (dichlorobenzene), 애니솔 (anisole), 자일 렌 (xylene) 및 6 내지 14의 탄소수를 가지는 탄화수소계 용매로부터 하나 또는 둘 이상 선택되는 용매를 포함할 수 있다.  One or more solvents selected from dichlorobenzene, anisole, xylene, and hydrocarbon solvent having 6 to 14 carbon atoms may be included.
[127] 실질적 인 일 예로，잉크의 분산매질을 형성 할 수 있는, 극성 용매는  As a practical example, a polar solvent capable of forming a dispersion medium of ink is
포름아마이드 (formamide), 다이포름아마이드 (diformamide),  Formamide, diformamide,
아세토나이트릴 (acetonitrile), 테트라하이드로퓨란 (tetrahydrofuran),  Acetonitrile, tetrahydrofuran,
다이 메틸설폭사이드 (dimethylsulfoxide), 아세톤 (acetone), α-터피 네올 (Terpineol), β_터피 네올，다이 하이드로 터피 네올 (Dihydro-terpineol) 및 물로부터 하나 또는 둘 이상 선택되는 용매를 포함할 수 있다. [128] 본 발명의 일 실시 예에 따른 잉크에 있어 , 잉크 (I 또는 II)는 분산제 및 유기 바인더를 더 함유할 수 있다. It may include one or more solvents selected from dimethylsulfoxide, acetone, α-terpineol, β_terpineol, dihydro-terpineol and water. . In the ink according to the embodiment of the present invention, the ink (I or II) may further contain a dispersant and an organic binder.
[129] 분산제 및 유기 바이더는 입자상을 함유하며 도포 공정 이 수행되는 통상의 잉크 조성물에 사용되는 분산제 및 유기 바인더 이면 족하다. The dispersant and the organic provider are sufficient to be a dispersant and an organic binder used in a conventional ink composition which contains particulates and is subjected to an application process.
[130] 일 예로，분산제는 지 방산염 (비누), α-술포지방산 에스테르염 (MES), [130] For example, the dispersant may be a fatty acid salt (soap), an α-sulfofatty acid ester salt (MES),
알킬벤젠술폰산염 (ABS), 직 쇄 (直鎖) 알킬벤젠 술폰산염 (LAS), 알킬황산염 (AS), 알킬에 테르황산에스테르염 (AES) 및 알킬황산트리 에 탄올을 포함하는 저분자 음이온성 (anionic) 화합물; 지방산 에 탄올 아미드,  Low molecular anionics, including alkylbenzenesulfonates (ABS), straight chain alkylbenzene sulfonates (LAS), alkylsulfates (AS), alkylethersulfate ester salts (AES), and alkylsulfate triethanol ( anionic compounds; Fatty acid to tanol amide,
폴리옥시 에 틸렌알킬에 테르 (AE), 폴리옥시에 틸렌알킬페닐에 테르 (APE), 솔비를 및 솔비 탄을 포함하는 저분자 비 (非)이온계 화합물; 알킬트리 메틸암모늄염， 디 알킬디 메틸암모늄클로라이드 및 알킬피 리 디늄클로라이드를 포함하는 저분자 양이온성 (cationic) 화합물; 알킬카르복실베타인，술포베타인 및 레시 틴을 포함하는 저분자 양성 계 화합물; 나프탈렌술폰산염 의 포르말린 축합물， 폴리스티 렌술폰산염，폴리아크릴산염，비 닐화합물과 카르복실산계 단량체의 공중합체염，카르복시 메틸셀롤로오스 및 플리 비 닐알콜을 포함하는 고분자 수계 분산제；폴리아크릴산 부분 알킬 에스테르 및 폴리 알킬렌폴리아민를 포함하는 고분자 비수계 분산제；및 폴리 에틸렌이 민 및 아미노알킬메타크릴레 이트 공중합체를 포함하는 고분자 양이온계 분산제；에서 하나 또는 둘 이상 선택된 물질을 포함할 수 있다.  Low molecular weight non-ionic compounds including polyoxy ethylene alkyl ether (AE), polyoxy ethylene alkyl phenyl ether (APE), sorbbi and sorbitan; Low molecular cationic compounds including alkyltri methylammonium salts, dialkyldimethylammonium chlorides and alkylpyridinium chlorides; Low molecular positive compound containing alkylcarboxybetaine, sulfobetaine and lecithin; Formal aqueous condensates of naphthalene sulfonates, polystyrene sulfonates, polyacrylates, polymeric salts of vinyl compounds and carboxylic acid monomers, carboxymethylcellulose and polyvinyl alcohol; polyacrylic acid Polymeric non-aqueous dispersants comprising partially alkyl esters and poly alkylenepolyamines; and polymeric cationic dispersants comprising polyethylene imine and aminoalkyl methacrylate copolymers;
[131] 비 한정 적 인 일 예로，분산제는 상용제품일 수 있으며 , 구체적 인 일 예로， [131] In one non-limiting example, the dispersant may be a commercial product, a specific example,
EFKA4008, EFKA4009, EFKA4010, EFKA4015, EFKA4046, EFKA4047,  EFKA4008, EFKA4009, EFKA4010, EFKA4015, EFKA4046, EFKA4047,
EFKA4060, EFKA4080, EFKA7462, EFKA4020, EFKA4050, EFKA4055,  EFKA4060, EFKA4080, EFKA7462, EFKA4020, EFKA4050, EFKA4055,
EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4300, EFKA4330,  EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4300, EFKA4330,
EFKA4340, EFKA6220, EFKA6225, EFKA6700, EFKA6780, EFKA6782,  EFKA4340, EFKA6220, EFKA6225, EFKA6700, EFKA6780, EFKA6782,
EFKA8503(EFKA ADDITIVES B. V. 제품), TEXAPHOR-UV21,  EFKA8503 (product of EFKA ADDITIVES B. V.), TEXAPHOR-UV21,
TEXAPHOR-UV61(코그니스 재팬 가부시키가이샤 제품), DisperBYKlOl, DisperBYK102, DisperBYK106, DisperBYK108, DisperBYKl l l, DisperBYK116, DisperBYK130, DisperBYKHO, DisperBYK142, DisperBYK145, DisperBYK161, DisperBYK162, DisperBYK163, DisperBYK164, DisperBYK166, DisperBYK167, DisperBYK168, DisperBYKHO, DisperBYK171, DisperBYK174, DisperBYK180, DisperBYK182, DisperBYK192, DisperBYK193, DisperBYK2000, DisperBYK2001, DisperBYK2020, DisperBYK2025, DisperBYK2050, DisperBYK2070,  TEXAPHOR-UV61 (made by Cogness Japan), DisperBYKlOl, DisperBYK102, DisperBYK106, DisperBYK108, DisperBYKl ll, DisperBYK116, DisperBYK130, DisperBYKHO, DisperBYK142, DisperBYK145, DisperBYK162, DisperBYK162, DisperBYK162, DisperBYK162 DisperBYK171, DisperBYK174, DisperBYK180, DisperBYK182, DisperBYK192, DisperBYK193, DisperBYK2000, DisperBYK2001, DisperBYK2020, DisperBYK2025, DisperBYK2050, DisperBYK2070,
DisperBYK2155, DisperBYK2164, BYK220S, BYK300, BYK306, BYK320, BYK322, BYK325, BYK330, BYK340, BYK350, BYK377, BYK378, BYK380N, BYK410, BYK425, BYK430(빅 케미 재팬 가부시 키가이샤 제품)， FTX-207S, FTX-212P, FTX-220P, FTX-220S, FTX-228P, FTX-710LL, FTX-750LL,  DisperBYK2155, DisperBYK2164, BYK220S, BYK300, BYK306, BYK320, BYK322, BYK325, BYK330, BYK340, BYK350, BYK377, BYK378, BYK380N, BYK410, BYK425, BYK430 212P, FTX-220P, FTX-220S, FTX-228P, FTX-710LL, FTX-750LL,
프터 전트 (ftergent) 212P, 프터 전트 220P, 프터 전트 222F, 프터 전트 228P, 프터 전트 245F, 프터 전트 245P, 프터 전트 250，프터 전트 251，프터 전트 710FM, 프터전트 730FM,프터전트 730LL,프터전트 730LS,프터전트 750DM, 프터전트 750FM (가부시키가이샤네오스제품)，메가팩 (MEGAFACE)F-477, 메가팩 480SF또는메가팩 F-482(DIC가부시키가이샤제품)을사용할수있다. Xergent 212P, Xergent 220P, Xergent 222F, Xergent 228P, Xergent 245F, Xergent 245P, Xergent 250, Xergent 251, Xergent 710FM, Giant 730FM, Giant 730LL, Giant 730LS, Giant 750DM, Giant 750FM (MegaFace), Mega Pack F-477, Mega Pack 480SF or Mega Pack F-482 (Made by DIC Corporation) can be used.
[132] 일예로，유기바인더는폴리비닐알콜 (PVA),폴리비닐부티랄 (PVB),폴리비닐 피를리돈 (PVP),폴리불화비닐리덴 (PVDF)，자기가교성아크릴수지에멀전， 하이드록시에틸샐를로스 (HEC)，카르복시메틸샐를로스 (CMC)，스티렌 부타디엔고무 (SBR), C1-10알킬 (메타)아크릴레이트와불포화카르복실산의 공중합체，니트로셀를로오스 (nitrocellulose),젤라틴 (gelatine),  [132] For example, the organic binder is polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinyl pyridone (PVP), polyvinylidene fluoride (PVDF), self-crosslinked acrylic resin emulsion, hydroxy Ethyl cellulose (HEC), carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), copolymer of C1-10 alkyl (meth) acrylate and unsaturated carboxylic acid, nitrocellulose, gelatin ( gelatine),
폴리비닐부티랄 (polyvinylbutyral),틴소톤 (Thixoton),스타치 (starch),  Polyvinylbutyral, thixoton, starch,
폴리에테르-폴리올，아민기가말단처리되어있는폴리스티렌 (PS-NH2), 하이드록시셀를로오스,메틸샐를로오스,니트로셀를로오스，에틸셀를로오스， 에틸하이드록시에틸셀를로오스 (ethylhydroxyethylcellulose),  Polyether-polyol, polystyrene (PS-NH2) with amine groups terminated, hydroxycellulose, methylsalulose, nitrocellulose, ethylcellulose, ethylhydroxyethylcellulose,
폴리에틸렌옥사이드，폴리우레탄，카르복실기를포함하는수지，페놀성수지， 에틸셀롤로오스와페놀성수지의혼합물，에스터중합체,메타크릴레이트 중합체，에틸렌성불포화기를갖는공중합체，에틸셀롤로스계,아크릴레이트계 및에폭시수지계에서하나또는둘이상선택되는물질을포함할수있다ᅳ  Polyethylene oxide, polyurethane, resins containing carboxyl groups, phenolic resins, mixtures of ethyl cellulose and phenolic resins, ester polymers, methacrylate polymers, copolymers with ethylenically unsaturated groups, ethylcelluloses, and acrylates And may contain one or more selected substances from the epoxy resin system.
[133] 본발명의일실시예에따른잉크에 있어，잉크는상술한복합입자를포함하는 입자상 100중량부에대해 200내지 900중량부의용매를함유할수있다.  In the ink according to one embodiment of the present invention, the ink may contain 200 to 900 parts by weight of a solvent with respect to 100 parts by weight of particulates including the composite particles described above.
[134] 본발명의일실시예에따른잉크에 있어，분산제및유기바인더를더함유하는 경우，상술한복합입자를포함하는입자상 100중량부에대해으5내지 10 중량부의분산제및 0.5내지 10중량부의유기바인더를함유할수있다.  5 to 10 parts by weight of dispersant and 0.5 to 10 parts by weight of 100 parts by weight of particulates containing the above-described composite particles in the ink according to one embodiment of the present invention. It can contain negative organic binders.
[135] 상술한일실시예에따른입자상을기준으로한용매，선택적으로분산제및 유기바인더의함량은도포공정이원활히수행되면서도막의형상을유지하는 기계적강도，잉크가도포되는기판과의접착력，건조및열처리시분해되어 제거되는유기물에의한막질저하를방지할수있는함량이다.  The content of the solvent, optionally the dispersant and the organic binder, based on the particulate phase according to the above-described embodiment, is a mechanical strength to maintain the shape of the coating film while the coating process is performed smoothly, adhesion to the substrate to which the ink is applied, drying and It is the content to prevent the film quality deterioration by the organic matter which is decomposed and removed during heat treatment.
[136] 본발명의일실시예에따른잉크에 있어，상기잉크는입자상을함유하는  [136] In the ink according to one embodiment of the present invention, the ink contains particulates.
잉크의제조방법분야에서통상적으로사용되는방법을통해제조될수있으며， 비한정적인일예로，입자상과용매,선택적으로，분산제및유기바인더를 혼합하고밀링을이용하여서로균질하게흔합함으로써제조될수있다.  It can be produced by methods commonly used in the field of ink manufacturing methods, and can be produced by non-limiting examples, by mixing particulates and solvents, optionally, dispersants and organic binders and homogeneously mixing them with milling.
[137]  [137]
[138] 본발명은상술한복합입자의제조방법을제공한다.  The present invention provides a method for producing the composite particles described above.
[139] 상술한바와같이,본발명의일실시예에따른복합입자는제조단계에서  As described above, the composite particles according to the embodiment of the present invention are manufactured at the manufacturing stage.
인-시츄로매질에화학식 1을만족하는저융점 11족금속의칼코젠화합물이 혼재되어매질에 11족금속의칼코젠화합물이균일하게분포및결착된상태를 가질수있다.  The chalcogenide compound of the low melting point Group 11 metal satisfying Chemical Formula 1 may be mixed in the in-situ medium to have a uniform distribution and binding of the chalcogenide compound of the Group 11 metal.
[140] 본발명의일실시예에따른복합입자의제조방법은 a) 11족금속 : 12내지 [140] A method for producing a composite particle according to an embodiment of the present invention is a) a group 11 metal : 12 to 12
14족금속 :칼코젠원소의몰비가 0.8~1.3:0.8~1.3:1.7~2.3이되도록각금속 전구체및칼코젠원소전구체가반응용매에흔합된흔합액을제조하는단계; 및 b) 상기 흔합액에 마이크로파를 조사하여 하기 화학식 1을 만족하는 11족 금속 칼코젠화합물이 매질에 흔재된 태양전지 광활성층용 복합입자를 제조하는 단계 ;를 포함할 수 있다. Preparing a mixed solution in which each metal precursor and the chalcogenide precursor are mixed in the reaction solvent such that the molar ratio of the Group 14 metal to the chalcogenide is 0.8 to 1.3: 0.8 to 1.3: 1.7 to 2.3; And b) irradiating microwaves to the mixture to produce composite particles for a photovoltaic layer of a solar cell, in which a Group 11 metal chalcogenide compound satisfying Formula 1 is common in a medium.
[141] (화학식 1)  [141] (Formula 1)
[142] M,AX [142] M, A X
[143] M은 11족 금속에서 하나 또는 둘 이상 선택된 것이며， A는 칼코젠 원소이며， [143] M is one or more selected from Group 11 metals, A is a chalcogen element,
X는 1 내지 2를 만족하는 실수이 다. X is a real number that satisfies 1-2.
[144] 이 때， a) 단계의 12 내지 14족 금속은 12족 내지 14족에서 하나 또는 둘 이상 선택된 금속을 의 미 한다. 또한， b) 단계에서 제조되는 복합입자는 상술한 바와 유사함에 따라，이에 대한 상세한 설명은 생략한다. In this case, the metal of group 12 to 14 of step a) means one or more metals selected from group 12 to 14. In addition, since the composite particles prepared in step b) are similar to those described above, detailed description thereof will be omitted.
[145] a) 단계의 흔합액은 목표하는 화합물 반도체 기 반 광활성층을 구성하는 모든 원소를 함유할 수 있으며， b)단계에서 합성되는 복합입자는 광활성층을 구성하는 모든 구성 원소를 함유하며，목적하는 광활성층의 조성을 만족함과 동시 에 극히 향상된 저온 반웅성을 가짐 에 따라，상술한 바와 같이 b) 단계에서 제조되는 복합입자 (만)을 유효 물질로 하여 광활성 층이 제조될 수 있다.  The mixture of step a) may contain all the elements constituting the target compound semiconductor-based photoactive layer, and the composite particles synthesized in step b) contain all the constituent elements constituting the photoactive layer. As it satisfies the composition of the desired photoactive layer and at the same time has an extremely improved low temperature reaction, the photoactive layer may be prepared using the composite particles (only) prepared in step b) as an active material as described above.
[146] 또한， a) 단계의 반웅용매에 투입되는 각 금속 전구체 (11족 금속의 전구체 및 12 내지 14족 금속에서 하나 또는 둘 이상 선택된 금속의 전구체) 및 칼코젠 원소 전구체 몰비 에 의 해 복합입자에 함유된 각 금속 및 칼코젠 원소의 몰비가 규정되며，복합입자에 의해 제조되는 광활성층의 원소비가 규정 될 수 있다. 이에 따라，목표하는 광활성층의 화학양론비를 갖도록 각 전구체를 반웅용매에 투입하는 극이 용이하고 간단한 방법을 통해，목표하는 조성을 갖는 광활성층의 제조가 가능해진다.  In addition, the composite particles are determined by the molar ratio of each metal precursor (a precursor of a Group 11 metal and one or more metals selected from Groups 12 to 14 metals) and a chalcogen element precursor to be added to the semi-solvent in step a). The molar ratio of each metal and chalcogen element contained in is defined, and the element ratio of the photoactive layer produced by the composite particles can be defined. This makes it possible to manufacture the photoactive layer having the target composition by an easy and simple method of introducing each precursor into the semi-aqueous solvent so as to have a stoichiometric ratio of the target photoactive layer.
[147] 본 발명의 일 실시 예에 따른 제조방법 에 있어， a) 단계의 상기 반응용매의 끓는 점 (boiling point)은 200°C이상, 실질적으로 200 내지 450°C일 수 있다. 상기 반응용매로, 끓는 점 이 200 내지 450oC인 고비 점 용매를 사용함으로써， b) 단계의 마이크로파 조사에 의 한 반응시 , 목적하는 화합물 반도체 기 반 광활성층 (일 예로, CIS)을 구성하는 모든 금속 원소들 (일 예로， Cu 및 In)을 함유하는 In the manufacturing method according to an embodiment of the present invention, the boiling point of the reaction solvent in step a) may be 200 ° C or more, and substantially 200 to 450 ° C. As the reaction solvent, by using a high boiling point solvent having a boiling point of 200 to 450 o C, upon reaction by microwave irradiation in step b), a desired compound semiconductor-based photoactive layer (for example, CIS) is formed. Containing all metal elements (eg Cu and In)
' 금속간칼코젠화합물과 저융점의 11족 금속 칼코젠화합물이 흔재된 복합입자가 제조될 수 있다.  Composite particles containing intermetallic chalcogenides and low melting point Group 11 metal chalcogenides can be prepared.
[148] 즉, 흔합액의 용매로 고비 점 용매를 사용함과 동시에 , 마이크로파 조사에 의 해 가온하는 구성에 의해, 저융점의 11족 금속 칼코젠화합물이 흔재된 복합입자를 제조할 수 있다.  In other words, by using a high boiling point solvent as the solvent for the mixed solution and heating by microwave irradiation, composite particles containing a low melting point Group 11 metal chalcogenide compound can be prepared.
[149] 상세하게, 반웅용매는 폴리을계 용매，아민계 용매 및 포스핀계 용매로부터 선택된 1종 또는 2종 이상을 포함할 수 있는데, 보다 상세하게 폴리을계 용매는 디 에 틸렌글리콜 (diethylene glycol), 디 에 틸렌글리콜 에 틸이서 (diethyleneglycol ethyl ether), 디 에 틸렌글리콜 부틸이서 (diethylene glycol buthyl ether),  In detail, the semi-aqueous solvent may include one or two or more selected from a poly-based solvent, an amine-based solvent, and a phosphine-based solvent. More specifically, the poly-based solvent may include diethylene glycol, Diethyleneglycol ethyl ether, diethylene glycol buthyl ether,
트리 에 틸렌글리콜 (triethylene glycol,), 폴리 에 틸렌 글리콜 (polyethylene glycol), 분자량; 200 ~ 100,000), 폴리에틸렌 글리콜 다이아크릴 레 이트 (polyethylene glycol) diacrylate), 폴리 에 틸렌 글리콜 다이 벤조네이트 (polyethylene glycol) dibenzonate), 디프로필렌글리콜 (dipropylene glycol), Triethylene glycol, polyethylene glycol, molecular weight; 200 to 100,000), polyethylene glycol diacrylate (polyethylene glycol) diacrylate), polyethylene glycol dibenzoate, dipropylene glycol,
트리프로필렌글리콜 (dipropylene glycol), 글리세를 (glycerol)로 이루어진 군으로부터 선택된 1종 또는 2종 이상을 포함할 수 있다.  It may include one or two or more selected from the group consisting of tripropylene glycol, glycerol (glycerol).
[150] 또한, 아민계 용매는 디에 틸아민 (diethyl amine), 트리 에 틸아민 (triethylamine), 1，3-프로판디 아민 (1,3-propane diamine), 1,4-부탄디 아민 (l,4_butane diamine), 1 ,5-펜탄디아민 ( 1 ,5-pentane diamine), 1 ,6-핵산디 아민 ( 1 ,6-hexane diamine), 1,7-헵탄디아민 (1,7-heptane diamine), 1，8-옥탄디아민 (octane diamine), [150] In addition, the amine solvents include diethyl amine, triethylamine, 1,3-propane diamine, 1,4-butanediamine ( l, 4 _butane diamine), 1,5-pentane diamine, 1,6-hexane diamine (1,6-hexane diamine), 1,7-heptane diamine (1,7-heptane diamine), 1,8-octane diamine,
디 에 틸렌디아민 (diethylene diamine), 디에 틸렌트리 아민 (diethylene triamine), 를루엔 디 아민 (toluene diamine), m-페닐렌디아민 (mphenylenediamine), 디페닐메탄 디아민 (diphenyl methane diamine), 헥사메틸렌 디아민 (hexamethylene diamine), 트리 에 틸렌테트라아민 (triethylene tetramine),  Diethylene diamine, diethylene triamine, toluene diamine, m-phenylenediamine, diphenyl methane diamine, hexamethylene Diamine (hexamethylene diamine), triethylene tetramine,
테트라에 틸렌펜타아민 (tetraethylenepentamkie),  Tetraethylenepentamkie,
핵사메틸렌테트라아민 (hexamethylenetetramine)으로 이루어진 군으로부터 선택된 1종 또는 2종 이상을 포함할 수 있으며，포스핀계 용매는 트리옥틸포스핀 (trioctylphosphine) 또는 트리옥틸포스핀 옥사이드 (trioctylphosphineoxide) 증 어느 하나 또는 둘의 흔합 용매일 수 있다.  It may include one or two or more selected from the group consisting of hexamethylenetetramine, phosphine-based solvent is one or two of trioctylphosphine or trioctylphosphine oxide (trioctylphosphine oxide) It may be a mixed solvent.
[151] 본 발명의 일 실시 예에 따른 제조방법에 있어 , 11족 금속의 전구체 및 12 내지 14족 금속에서 하나 또는 둘 이상 선택된 금속의 전구체는 서로 독립적으로, 산화물，수산화물, 아세트산염，질산염 , 황산염，과염소산염 , 할로겐화물 및 이들의 수화물로 이루어진 군으로부터 하나 또는 둘 이상 선택될 수 있으며， 칼코젠 원소 전구체는 칼코젠화수소，칼코젠화나트륨, 칼코젠화칼륨，칼코젠화 칼슘，디 메틸칼코제나이드 및 이들의 수화물로 이루어 진 군으로부터 하나 또는 둘 이상 선택될 수 있다. In the manufacturing method according to an embodiment of the present invention, the precursor of the Group 11 metal and the precursor of one or more metals selected from Group 12 to 14 metal are independently of each other, oxide, hydroxide, acetate, nitrate, Sulfate, perchlorate, halides and hydrates thereof may be selected from the group consisting of one or two or more, chalcogenide precursors are hydrogen chalcogenide, sodium chalcogenide, potassium chalcogenide, calcium chalcogenide, dimethyl One or more may be selected from the group consisting of chalcogenides and their hydrates.
[152] 본 발명 의 일 실시 예에 따른 제조방법 에 있어 , 상기 11족 금속은 Cu일 수  In the manufacturing method according to an embodiment of the present invention, the Group 11 metal may be Cu
있으며 , 상기 11족 금속의 전구체는 Cu 전구체일 수 있고, 상기 12 내지 14족 금속은 In 또는 In과 Ga일 수 있으며 , 상기 12 내지 14족 금속의 전구체는 In 전구체 또는 In 전구체와 Ga 전구체 일 수 있고，상기 칼코젠 원소는 Se일 수 있으며，상기 칼코젠 원소의 전구체는 Se 전구체 일 수 있다.  The precursor of the Group 11 metal may be a Cu precursor, the Group 12 to 14 metal may be In or In and Ga, and the precursor of the Group 12 to 14 metal may be an In precursor or an In precursor and a Ga precursor. The chalcogen element may be Se, and the precursor of the chalcogen element may be a Se precursor.
[153] 본 발명의 일 실시 예에 따른 제조방법에 있어 , 상기 11족 금속은 Cu일 수  In a manufacturing method according to an embodiment of the present invention, the Group 11 metal may be Cu
있으며，상기 11족 금속의 전구체는 Cu 전구체일 수 있고，상기 12 내지 14족 금속은 Zn, Sn 또는 Zii과 Sn일 수 있으며 , 상기 12 내지 14족 금속의 전구체는 Zn전구체， Sn 전구체 또는 Zn 전구체와 Sn 전구체 일 수 있고，상기 칼코젠 원소는 Se일 수 있으며，상기 칼코젠 원소의 전구체는 Se 전구체 일 수 있다.  The precursor of the Group 11 metal may be a Cu precursor, the Group 12 to 14 metal may be Zn, Sn or Zii and Sn, the precursor of the Group 12 to 14 metal is a Zn precursor, Sn precursor or Zn precursor And Sn precursor, the chalcogen element may be Se, and the precursor of the chalcogen element may be Se precursor.
[154] 일 예로，목적하는 광활성층이 CIS(CuInSe2, CuInS2 또는 CuIn(Se,S)2)인 경우, 반웅용액에 투입 되는 금속 전구체는 구리 전구체 및 인듬 전구체일 수 있으며， 구리 전구체는 CuO, Cu02, CuOH, Cu(OH)2, Cu(CH3COO), Cu(CH3COO)2, CuF2, CuCl, CuCl2, CuBr, CuBr2, Cul, Cu(C104)2, Cu(N03)2, CuS04 및 이들의 수화물로 이루어진군으로부터선택된 1종또는 2종이상을포함할수있고,인듐 전구체는 ln203, In(OH)3, In(CH3COO)3, InF3, InCl, InCl3, InBr, InBr3, Inl, Inl3, In(C104)3, In(N03)3, In2(S04)3및이들의수화물로이루어진군으로부터선택된 1종또는 2종이상을포함할수있으며，칼코젤원소의전구체는 H2Se, Na2Se, K2 Se, Ca2Se, (CH3)2Se , H2S, Na2S, K2S, Ca2S, (CH3)2S및이들의수화물로이루어진 군으로부터선택된 1종또는 2종이상을포함할수있다. For example, when the target photoactive layer is CIS (CuInSe 2 , CuInS 2 or CuIn (Se, S) 2 ), the metal precursors added to the semi-aqueous solution may be copper precursors and rhythm precursors. CuO, Cu0 2 , CuOH, Cu (OH) 2 , Cu (CH 3 COO), Cu (CH 3 COO) 2 , CuF 2 , CuCl, CuCl 2 , CuBr, CuBr 2 , Cul, Cu (C10 4 ) 2 , Cu (N0 3 ) 2 , CuS0 4 and their hydrates It may include one or two or more selected from the group consisting of, indium precursor is ln 2 0 3 , In (OH) 3 , In (CH 3 COO) 3 , InF 3 , InCl, InCl 3 , InBr, InBr 3 , Inl, Inl 3 , In (C10 4 ) 3 , In (N0 3 ) 3 , In 2 (S0 4 ) 3 and one or more selected from the group consisting of hydrates thereof, and may contain one or more Precursors are H 2 Se, Na 2 Se, K 2 Se, Ca 2 Se, (CH 3 ) 2 Se, H 2 S, Na 2 S, K 2 S, Ca 2 S, (CH 3 ) 2 S and their It may comprise one or two or more selected from the group consisting of hydrates.
[155] 본발명의일실시예에따른제조방법에 있어, b)단계에서제조되는  [155] In the manufacturing method according to the embodiment of the present invention,
복합입자에함유되는저융점 11족금속칼코젠화합물의함량은조사되는 마이크로파의조사에의해가열되는흔합액의온도및가열시간 (즉，  The content of the low melting point Group 11 metal chalcogenide compound contained in the composite particles is determined by the temperature and heating time (ie,
반웅시간)에의해제어될수있다.  Reaction time).
[156] 상세하게， a)단계의흔합액에마이크로파를조사하여， 200 ~ 300°C에서 15 ~ 40분동안반응시켜 1내지 20부피 %의저융점 11족금속칼코젠화합물을 함유하는복합입자를제조할수있다.  In detail, irradiating the microwave mixture to the mixture of step a) for 15-40 minutes at 200-300 ° C. to produce composite particles containing 1 to 20% by volume of low melting point Group 11 metal chalcogenide compound. Can be manufactured.
[157] 마이크로파의출력은，예컨대 500 ~900W의범위일수있다.이때，상술한바와 같이，마이크로파조사및고비점용매를통해저융점 11족금속칼코젠화합물인 이차상이형성되더라도복합입자를구성하는각원소의몰비는초기투입된각 금속전구체및칼코젠원소의전구체의몰비에의해결정됨에따라，전체적인 입자 (복합입자)의화학양론비 (0.8 ~ 1.3： 0.8 - 1.3： 1.7 -23)는극히용이하게 제어될수있다.  The microwave power may be in the range of, for example, 500 to 900 W. As described above, even if a secondary phase, which is a low melting group 11 metal chalcogenide, is formed through microwave irradiation and a high boiling point solvent, The molar ratio of each element is determined by the molar ratio of each metal precursor introduced and the precursor of the chalcogenide element, and the stoichiometric ratio (0.8 to 1.3: 0.8-1.3: 1.7 -23) of the whole particle is extremely easy. Can be controlled.
[158] 상술한바와같이，본발명의일실시예에따른제조방법은반응용매에  As described above, the manufacturing method according to the embodiment of the present invention is applied to the reaction solvent.
투입되는각전구체의몰비를제어하는단순한방법에의해,제조되는  Manufactured by a simple method of controlling the molar ratio of each precursor injected
복합입자를구성하는원소의몰비가결정될수있으며,복합입자의조성에의해 광활성층의조성이결정될수있음에따라，반웅용매에투입되는각전구체의 몰비는목적하는광활성층의조성을고려하여적절히조절될수있다.  As the molar ratio of elements constituting the composite particles can be determined, and the composition of the photoactive layer can be determined by the composition of the composite particles, the molar ratio of each precursor injected into the semi-aqueous solvent is properly adjusted in consideration of the composition of the target photoactive layer. Can be
[159] 일예로，목적하는광활성층이 CIS(CuInSe2, CuInS2또는 CuIn(Se,S)2)인경우， 구리전구체：인듬전구체：칼코젠원소의전구체는 Cu： In： (Se및 /또는 Se)의 몰비가 0.8 ~ 1.3： 0.8 ~ 1.3： 1.7 - 2.3이되도록투입될수있으며，바람직하게， 0.8 -1.3: 1： 2가되도록투입될수있다. [159] For example, when the target photoactive layer is CIS (CuInSe 2 , CuInS 2 or CuIn (Se, S) 2 ), the copper precursor: rhythm precursor: the precursor of the chalcogenide element is Cu: In: (Se and / Or a molar ratio of Se) of 0.8-1.3: 0.8-1.3: 1.7-2.3, preferably 0.8-1.3: 1: 1.
[160]  [160]
[161] 이하,상술한잉크를이용한태양전지광활성층의제조방법을상술한다.  Hereinafter, a method for producing a solar cell photoactive layer using the above-described ink will be described.
[162] 본발명에따른태양전지광활성층의제조방법은 c)상술한잉크를기판에  [162] The method for producing a photovoltaic active layer of a solar cell according to the present invention includes the steps of c)
도포하여도포막을형성하는단계;및 d)상기도포막을열처리하여광활성층을 제조하는단계를포함할수있다.이때,광활성층은 11족금속및 12족내지 14족에서하나또는둘이상선택된원소의다원칼코젠화합물막일수있다.  Forming a coating film by coating; and d) heat treating the coating film to produce a photoactive layer, wherein the photoactive layer comprises a plurality of elements of one or more selected elements from Group 11 metals and Groups 12-14. It may be a chalcogenide film.
[163] 통상적인화합물반도체 (CIG(S,Se))또는 CZT(S,Se))기반광활성충은  [163] Conventional compound semiconductors (CIG (S, Se)) or CZT (S, Se) based photoactive insects
다원화합물이기때문에제조공정이매우까다롭다.물리적인박막  Because it is a multi-element compound, the manufacturing process is very demanding.
제조방법으로는진공증발법 (Evaporation),스퍼터링 -셀렌화법 (Sputtering + Selenization),화학적인박막제조방법으로는전착법 (Electrodeposition)이있고， 각방법에있어서원료의종류에따라다양한제조방법이사용되고있다. Manufacturing methods include vacuum evaporation, sputtering + selenization, and chemical thin film manufacturing methods, such as electrodeposition. In each method, various manufacturing methods are used depending on the type of raw materials.
[164] 그러나，본발명의제조방법은고가이며취급이어려운기상의유기  [164] However, the manufacturing method of the present invention is expensive and difficult to handle.
금속화합물또는고가의진공장비를사용하지않으며,다층증착과같이고도의 복잡한공정이불필요하다.즉，본발명의제조방법은복합입자를함유하는 잉크,또는본발명의특징에의해광활성층형성에관여하는유효물질로 복합입자만을함유하는잉크를도포하고，도포막을저온열처리하는극히 간단하고안전하며용이한공정을통해양질의다원칼코젠화합물 (광활성층)을 제조할수있으며，이미광활성층의조성을만족하는잉크를사용함에따라， 잉크의단순도포및열처리에의해화학양론비를갖는광활성층을제조할수 있는장점이 있다.  It does not use metal compounds or expensive vacuum equipment and does not require highly complex processes such as multi-layer deposition. In other words, the manufacturing method of the present invention is based on the formation of a photoactive layer by the ink containing the composite particles, or the characteristics of the present invention. It is possible to produce high-quality multi-factor chalcogenide compounds (photoactive layers) through an extremely simple, safe and easy process of coating inks containing only composite particles as effective active substances and low temperature heat treatment of coating films. By using a satisfactory ink, there is an advantage of producing a photoactive layer having a stoichiometric ratio by simple application and thermal treatment of the ink.
[165] 또한,본발명의제조방법은상술한잉크를이용하여광활성층을  In addition, the manufacturing method of the present invention uses the ink described above to form a photoactive layer.
제조함으로써， 550°C이하의공정허용온도보다낮은온도에서단일상의다원 칼코젠화합물로이루어진광활성층을제조할수있으며 ,화학양론비를 만족하며，균일도가우수하고치밀한미세구조를갖는광활성층을제조할수 있는장점이있다.  By manufacturing, it is possible to manufacture a photoactive layer consisting of a single phase of multiple chalcogenide compounds at a temperature lower than the process allowable temperature below 550 ° C, to satisfy the stoichiometric ratio, and to produce a photoactive layer having excellent uniformity and a fine structure. There are advantages to doing this.
[166] 본발명의일실시예에따른태양전지광활성층의제조방법에있어,잉크가 도포되는기판은태양전지분야에서통상적으로사용되는부도체기재에， 태양전지분야에서통상적으로사용되는후면전극이적층된，적층기판을 포함할수있다.부도체기판의일예로,유리기판，소다석회유리기판 (soda-lime glass),세라믹기판또는반도체기판을들수있다.부도체기판에형성된후면 전극의일예로，몰리브덴 (Mo)층을들수있다.  In the method of manufacturing a photovoltaic active layer of a solar cell according to an embodiment of the present invention, the substrate on which the ink is applied is an insulator substrate commonly used in the solar cell field, and a back electrode commonly used in the solar cell field is used. Laminated substrates may be laminated. Examples of insulated substrates include glass substrates, soda-lime glass, ceramic substrates, or semiconductor substrates. For example, back electrodes formed on insulated substrates. Molybdenum (Mo) layer.
[167] 본발명의일실시예에따른태양전지광활성층의제조방법에 있어,잉크의 도포는스핀코팅，바코팅，딥코팅，드랍캐스팅，잉크젯프린팅 (ink-jet printing), 미세접촉프린팅 (micro-contact printing),임프린팅 (imprinting),그라비아 프린팅 (gravure printing),그라비아 -읍셋프린팅 (gravure-offset printing),플렉소 프린팅 (Flexography printing)및스크린프린팅 (screen printing)에서하나또는둘 이상선택된방법으로수행될수있다.  In the method of manufacturing a solar cell photoactive layer according to an embodiment of the present invention, the ink is coated by spin coating, bar coating, dip coating, drop casting, ink-jet printing, fine contact printing ( One or more selected from micro-contact printing, imprinting, gravure printing, gravure-offset printing, flexography printing and screen printing It can be done in a way.
[168] 본발명의일실시예에따른태양전지광활성층의제조방법에있어， c)단계후 및 d)단계전,도포막을건조하는단계가더수행될수있다.건조단계는 도포막에함유된액상을휘발제거하기위한것으로，잉크의도포에의한 막 (film)올형성하는분야에서통상적으로사용하는건조방법이면사용 가능하다.비한정적인일예로，도포막의건조는공기중 60내지 90oC에서수행될 수있다. In the method of manufacturing a solar cell photoactive layer according to an embodiment of the present invention, a step of drying the coating film after step c) and before step d) may be further performed. For the volatilization of liquid phase, it is possible to use any drying method that is commonly used in the field of forming film by ink application. In one non-limiting example, the drying of coating film is 60 to 90 o in air. Can be performed in C.
[169] 본발명의일실시예에따른태양전지광활성층의제조방법에 있어，기판상 잉크가도포되어형성된도포막의열처리는칼코젠분위기에서 400내지 550°C, 바람직하게， 500내지 530oC에서수행될수있다.이때，열처리시간은도포막의 두께에따라적절히조절될수있으며，일예로, 30분내지 2시간동안수행될수 있다. [170] 본발명의일실시예에따른태양전지광활성층의제조방법에있어，도포된 도포막의열처리에의해,막의치밀화,결정성장및단일한다원 [169] in the production method of the one solar cell optically active layer according to an embodiment of the present invention, a substrate the ink is applied is formed coating film the heat treatment to 400 to 550 ° C, preferably in a knife kojen atmosphere, of 500 to 530 o C At this time, the heat treatment time can be properly adjusted according to the thickness of the coating film, for example, 30 minutes to 2 hours. In the method for manufacturing a photovoltaic active layer of a solar cell according to an embodiment of the present invention, the film is densified, crystal grows, and becomes single by heat treatment of the coated film.
칼코젠화합물로의상전이가이루어질수있다.  Phase transitions to chalcogenides can occur.
[171] 상술한바와같이,본발명의일실시예에따른태양전지광활성층의 As described above, according to the solar cell photoactive layer according to an embodiment of the present invention,
제조방법은목적하는광활상층의조성을이미만족하는복합입자를사용하여， 후처리또는복잡한조성제어없이순수한단일한상 (phase)의광활성층을 제조할수있으며， 550°C이하의공정허용온도이내의열처리은도에서도극히 치밀하고균질한광활성층이제조될수있다.  The manufacturing method can be used to produce a pure single phase photoactive layer without post-treatment or complex compositional control, using composite particles that already meet the intended composition of the optical active layer, and heat treatment within the process tolerance of 550 ° C or less. An extremely dense and homogeneous photoactive layer can also be produced in the drawing.
[172] 본발명에따른제조방법에있어，도포막의열처리는칼코젠분위기에서 [172] In the manufacturing method according to the present invention, the heat treatment of the coating film is carried out in a chalcogen atmosphere.
수행될수있다.칼코젠분위기는황 (S),셀레늄 (Se)또는이들의흔합기체가 존재하는분위기를포함한다.  The chalcogen atmosphere includes an atmosphere in which sulfur (S), selenium (Se) or a mixture thereof is present.
[173] 상세하게,도포막의열처리는칼코젠함유기체를공급하거나,칼코젠분말을 도포막과함께열처리하여칼코젠분말을칼코젠기체의소스 (source)로사용할 수있다. In detail, the heat treatment of the coating film can supply the chalcogen-containing gas or heat-treat the chalcogen powder together with the coating film to use the chalcogen powder as a source of the chalcogen gas.
[174] 보다상세하게,도포막의열처리는칼코젠분위기는황 (S),썰레늄 (Se)또는 이들의흔합기체가존재하는분위기를포함하며，칼코젠기체분위기는 H2S 또는 H2Se와같이칼코젠원소 (S, Se)를함유하는기체의공급하거나,칼코젠 원소 (S, Se)를휘발시킨후공급하거나，또는칼코젠원소의분말상인칼코젠 분말을도포막과함께열처리하여，칼코젠분말을칼코젠기체의소스 (source)로 사용하여형성될수있다. In more detail, the heat treatment of the coating film includes an atmosphere in which the chalcogen atmosphere includes sulfur (S), selenium (Se), or a mixed gas thereof, and the chalcogen gas atmosphere is H 2 S or H 2 Se. Supplying a gas containing a chalcogen element (S, Se), or by supplying a volcanic element (S, Se) after volatilization, or by heating the chalcogen powder, which is a powder of the chalcogen element, with a coating film It can be formed by using chalcogen powder as a source of chalcogen gas.
[175] 실질적인일예로,칼코젠기체를공급하는경우 5내지 300sccm의유량으로 H 2S, H2Se,칼코젠원소 (S, Se)증기또는,이들의흔합가스를포함하는칼코젠 함유가스를공급할수있다. As a practical example, in the case of supplying a chalcogen gas, a chalcogen-containing gas containing H 2 S, H 2 Se, chalcogen element (S, Se) vapor, or a mixed gas thereof may be used at a flow rate of 5 to 300 sccm. Can supply
[176] 실질적인일예로，도포막의열처리가이루어지는챔버내에서， S분말， Se분말 또는이들의흔합분말을포함하는칼코젠분말자체를기화시켜칼코젠 분위기를조성하는경우，칼코젠분말이가열되는온도는열처리되는도포막의 온도와동일할수있으며，서로상이할수있다.  As a practical example, when the chalcogen powder itself is formed by evaporating the chalcogen powder including S powder, Se powder or a mixture thereof, the chalcogen powder is heated. The temperature can be the same as the temperature of the coating film being heat treated and can be different from each other.
[177] 상세하게，칼코젠분말을칼코젠기체소스로이용하는경우,칼코젠분말은 80 내지 2500C로가열될수있다. In detail, when the chalcogen powder is used as a chalcogen gas source, the chalcogen powder may be heated to 80 to 250 0 C.
[178] 칼코젠분말을켈코젠기체소스로이용하는경우，열처리장치내칼코젠  [178] When using chalcogen powder as a chalcogen gas source, chalcogen in heat treatment apparatus
분말은도포막이위치하는영역과상이한영역에놓일수있다.이때，열처리는 유체의유동이가능한단일한열처리공간내에서로독립적으로둘이상의 유니폼존을형성할수있도록발열체및컨트를러가구비된장치를이용하여 수행될수있으며,단일한유니품존을형성하는통상의열처리장치내에서 칼코젠분말이놓이는위치를조절하여칼코젠분말의가열은도가조절될수 있다.  The powder may be placed in an area different from the area in which the coating film is located, where the heat treatment is provided with a heating element and controller equipped to independently form two or more uniform zones in a single heat treatment space where fluid flow is possible. The heating of the chalcogen powder can be controlled by adjusting the position of the chalcogen powder in a conventional heat treatment device forming a single unit zone.
[179] 도포막의열처리는어떠한압력에서수행되어도무방하나，비한정적인일 예로，진공내지대기압에서열처리가수행될수있다. [180] 도포막의열처리장치는통상적인발열체의줄열 (IR)을이용하는퍼니스또는 고주파유도가열또는텅스덴과할로겐과같은광을이용한급속열처리장치 (RTP; Rapid Thermal annealing system)일수있다. The heat treatment of the coating film may be performed at any pressure, but one non-limiting example may be heat treatment at vacuum or atmospheric pressure. The heat treatment apparatus of the coating film may be a furnace using conventional heat generation (IR) or a rapid thermal annealing system (RTP) using light such as tungsten and halogen.
[181] 본발명의일실시예에따른태양전지광활성층의제조방법에있어,다원  [181] A method of manufacturing a solar cell photoactive layer according to an embodiment of the present invention,
칼코젠화합물은 CuInxGa1-xSeyS1-y일 (0≤χ≤1인실수, 0≤y≤l인실수)를포함할수 있으며， CuZnmSn^ Se^^CO i^?인실수, 0≤η≤1인실수)를포함할수있다. The chalcogenide compound may contain CuIn x Ga 1-x Se y S 1-y days (real number 0≤χ≤1, real number 0≤y≤l), and CuZn m Sn ^ Se ^^ CO i ^? Real numbers, 0≤η≤1 real numbers).
[182] 일예로， CuInSe2를함유하는매질및 CuSe, CuSe2또는이들의흔합물인 [182] For example, a medium containing CuInSe 2 and CuSe, CuSe 2 or a combination thereof.
11족칼코젠화합물단일한입자에흔재된복합입자를함유하는잉크를이용하여 CuInSe2인단일상의다원칼코젠화합물인광활성층을제조할수있다. 11 jokkal kojen compound can be prepared for CuInSe 2-indan daily multi knife kojen phosphorescent compound of the active layer by using the ink containing the composite particles heunjae to a single particle.
[183] 일예로， CuInxGa^Se^C x^인실수)를함유하는매질및 CuSe, CuSe2또는 [183] For example, a medium containing CuIn x Ga ^ Se ^ C x ^ and a number of CuSe, CuSe 2 or
이들의혼합물인 11족칼코젠화합물단일한입자에혼재된복합입자를함유하는 잉크를이용하여 CuInxGa,.xSe2(0≤x≤l인실수)인단일상의다원칼코젠화합물인 광활성층올제조할수있다. Group 11 chalcogenide compound which is a mixture of these CuIn x Ga ,. A photoactive layer, which is a single-phase, polychalcogen compound of x Se 2 (real number of 0 ≦ x ≦ l), can be prepared.
[184] 일예로, Cu2ZnmSn2-mSe4(0≤m≤2인실수)를함유하는매질및 CuSe, CuSe2또는 이들의혼합물인 11족칼코젠화합물단일한입자에혼재된복합입자를함유하는 잉크를이용하여 Cu2ZnmSn2.mSe4(0≤m≤2인실수)인단일상의다원 [184] For example, a compound mixed with a medium containing Cu 2 Zn m Sn 2-m Se 4 (a real number of 0 ≦ m ≦ 2 ) and CuSe, CuSe 2 or a mixture of Group 11 chalcogenide single particles. Cu 2 Zn m Sn 2 . m Se 4 (0 ≤ m ≤ 2 real number)
칼코젠화합물인광활성층을제조할수있다.  It is possible to prepare a photoactive layer which is a chalcogen compound.
[185] 본발명은상술한제조방법으로제조된광활성층을포함한다.  The present invention includes a photoactive layer prepared by the above-mentioned manufacturing method.
[186] 본발명은상술한제조방법으로제조된광활성층이구비된태양전지를  [186] The present invention relates to a solar cell having a photoactive layer manufactured by the above-described manufacturing method.
포함한다.  Include.
[187] 본발명의일실시예에따른태양전지는기판 (하부전극이형성된기판)상부에 형성된상술한광활성층;광활성층상부에형성된버퍼층;버퍼층상부에형성된 원도우층;상기원도우층상부에형성된그리드전극;을포함할수있다.  A solar cell according to an embodiment of the present invention includes a photoactive layer described above formed on a substrate (substrate formed with a lower electrode); a buffer layer formed on the photoactive layer; a window layer formed on the buffer layer; a grid formed on the window layer Electrode; may include.
[188] 버퍼층은제 1도전형반도체 (일예로, CIGS의경우 p-type)인광활성층과  The buffer layer comprises a photoactive layer that is a first conductive semiconductor (eg, p-type in CIGS).
제 2도전형반도체인원도우층 (일예로, ZnO박막의경우， n-type)간의 p-n접합시, 두층간의격자상수및밴드갭에너지차이를완화시키기위해，통상적인 화합물반도체기반태양전지에서사용되는버퍼층이면사용가능하다.일예로， 버퍼층은 CdS박막일수있다.  Used in conventional compound semiconductor-based solar cells to reduce the lattice constant and band gap energy difference between the two layers when pn-bonding between the second conductive semiconductor chain layers (for example, n-type for ZnO thin films) The buffer layer can be used. For example, the buffer layer can be a CdS thin film.
[189] 원도우층은광활성층과상보적인반도체특성을갖는층으로,광활성충과 p-n 접합을이를수있는통상적인화합물반도체기반태양전지에서사용되는 원도우층이면사용가능하다.일예로,원도우층은 ZnO박막일수있다.  [189] The window layer is a layer having a semiconductor characteristic complementary to the photoactive layer, and may be used as the window layer used in conventional compound semiconductor-based solar cells capable of pn junction with the photoactive layer. For example, the window layer is ZnO. It may be a thin film.
[190] 그리드전극은태양전지표면에서의전류를수집하기위한것으로,핑거전극및 버스바전극을포함할수있으며，통상적인화합물반도체기반태양전지에서 사용되는전면전극구조및물질이면사용가능하다.일예로，그리드전극은 어골구조를가질수있으며 , A1또는 Ni/Al재질일수있다.  The grid electrode is for collecting current on the surface of the solar cell, which may include finger electrodes and busbar electrodes, and may be any front electrode structure and material used in conventional compound semiconductor-based solar cells. The grid electrode may have a bone structure and may be A1 or Ni / Al.
[191] 본발명의일실시예에따른태양전지는그리드전극상부에형성된  [191] A solar cell according to an embodiment of the present invention is formed on a grid electrode.
반사방지막더포함할수있으며，통상적인화합물반도체기반태양전지에서 사용되는반사방지막이면사용가능하다.일예로，반사방지막은 실리콘산화물막일수있다. Anti-reflective coatings may be included, and may be used as anti-reflective coatings used in conventional compound semiconductor-based solar cells. It may be a silicon oxide film.
[192]  [192]
[193] 본발명은상술한태양전지의제조방법을포함한다.  The present invention includes the above-described method for manufacturing a solar cell.
[194] 본발명의일실시예에따른태양전지의제조방법은하부전극이형성된기판 상에상술한광활성층의제조방법에따라광활성층을형성하는단계;상기 광활성층상부로，버퍼층，원도우층및전면전극층을순차적으로형성하는 단계;를포함할수있다.  [194] A method of manufacturing a solar cell according to an embodiment of the present invention includes forming a photoactive layer according to the above-described method of manufacturing a photoactive layer on a substrate on which a lower electrode is formed; over the photoactive layer, a buffer layer, a window layer, and the like. Sequentially forming the front electrode layer.
[195] 상기버퍼층，원도우층및전면전극층의형성은태양전지분야에서공지된 물질및방법을사용하여수행될수있으며，일예로，버퍼층은용액침적을 이용한증착공정을통해수행될수있으며,원도우층및전면전극층은서로 독립적으로화학적증착 (CVD),스퍼터링을포함하는물리적증착 (PVD),또는 플라즈마증착 (PECVD)을통해수행될수있다.  The formation of the buffer layer, the window layer, and the front electrode layer may be performed using materials and methods known in the solar cell field. For example, the buffer layer may be performed through a deposition process using solution deposition. The front electrode layers can be independently performed through chemical vapor deposition (CVD), physical vapor deposition (PVD) including sputtering, or plasma deposition (PECVD).
[196] 본발명은하나이상의상술한태양전지가구비된태양전지모들을포함한다.  [196] The present invention includes solar cell modules equipped with one or more of the above described solar cells.
[197] 본발명의일실시예에따른태양전지모들은광을집광하여 태양전지에  [197] According to one embodiment of the present invention, a solar cell module focuses light on a solar cell.
조사하는집광부;및둘이상의태양전지가배열되어전기적으로직렬및 /또는 병렬로연결된샐부;를포함할수있으며，상기집광부는광을집광하고  And a condenser for irradiating; and a sal portion in which two or more solar cells are arranged and electrically connected in series and / or in parallel. The condenser condenses light.
태양전지에조사하기위한광경로를제어할수있는，태양전지모들분야에서 통상적으로사용되는광학부품들로이루어질수있으며，상기셀부는다수개의 태양전지일정간격으로이격배열된태양전지어레이,상기태양전지어레이를 고정및 /또는지지하는지지체및다수개의 태양전지를서로직렬및 /또는병렬 연결하는전기적연결부를포함할수있다.  It can be composed of optical components commonly used in the field of solar cells, which can control the optical path for irradiating solar cells, wherein the cell portion is a solar cell array, the solar cell array spaced at a plurality of solar cell intervals It may comprise a fixed and / or supporting support and an electrical connection which connects several solar cells in series and / or in parallel.
[198]  [198]
[199] 이하,실제조예를기반으로본발명을상술하나，이는본발명의보다전반적인 이해를돕기위해서제공된것일뿐，본발명은하기의제조예에의해한정되는 것은아니며，본발명이속하는분야에서통상의지식을가진자라면이러한 기재로부터다양한수정및변형이가능하다.  [199] Hereinafter, the present invention will be described based on actual examples, which are provided only for the purpose of better understanding of the present invention, and the present invention is not limited by the following preparation examples, but in the field to which the present invention belongs. Those skilled in the art can make various modifications and variations from this description.
[200]  [200]
[201] (실시예 1)  [201] (Example 1)
[202] CIS입자의제조 [202] production of CIS particles
[203] 구리아세테이트모노하이드레이트 (Cu acetate monohydrate)：  [203] Cu acetate monohydrate:
인듐아세테이트 (Indium acetate)：셀레늄파우더 (Se powder)를 1:1:2의몰비로 평량한후흔합한흔합물 3.2g을 20g의폴리에틸렌글리콜 (polyethylene glycol, M.W. = 400,Tb=250°C)에투입한후 1시간동안교반하여흔합액을제조하였다. Indium acetate: selenium powder (Se powder) is weighed in a molar ratio of 1: 1: 2, and 3.2 g of the mixed compound is 20 g of polyethylene glycol (MW = 400, T b = 250 ° C). After the addition, the mixture was stirred for 1 hour to prepare a mixed solution.
[204] 제조된흔합액을마이크로파를이용하여 800W의출력으로 2분동안승온시켜 280oC에서 25분간반웅시킨후 20분간냉각시켜복합입자를제조하였다.합성된 입자를회수하기위하여에탄올을이용하여 25000rpm으로 30분을원심분리를 실시하여세정및입자회수를하되 , 3회반복실시하여입자를회수하였다ᅳ 회수된입자는 40°C의진공오본에서건조를실시하였다. [205] The prepared mixture was heated for 2 minutes at a power of 800 W using microwave, and then reacted for 25 minutes at 280 ° C. and then cooled for 20 minutes to produce a composite particle. Ethanol was used to recover the synthesized particles. After centrifugation at 25000rpm for 30 minutes, washing and particle recovery were performed, and the particles were recovered three times. The recovered particles were dried in a vacuum oven at 40 ° C. [205]
[206] CIS막및태양전지셀제조  [206] CIS film and solar cell manufacturing
[207] 상기제조된복합입자이용하여잉크를제조하였다.  An ink was prepared using the composite particles prepared above.
[208] 에틸렌글리콜 i.785g과에탄올 0.765g을혼합한용매에 15중량%가되도록 제조된 CIS입자를첨가하였으며，잉크의균질한혼합을위해 20 Hz의조건에서 [208] CIS particles prepared to be 15% by weight were added to a solvent mixture of 785g ethylene glycol i.785g and 0.765g ethanol, and at 20 Hz for homogeneous mixing of the ink.
60분동안볼밀링을수행하였다. Ball milling was performed for 60 minutes.
[209] Mo전극이증착된소다라임유리 (Soda-lime Glass)기판상에제조한잉크를바 코팅하고， 80oC에서건조한후,기판을열처리하여광활성층을제조하였다. An ink prepared on a soda-lime glass substrate on which the Mo electrode was deposited was coated with a bar, dried at 80 ° C., and the substrate was thermally treated to prepare a photoactive layer.
[210] 상세하게, Se분말을 2300C로가열하며잉크가도포된유리기판을 530oC [210] Specifically, the Se powder was heated to 230 0 C and the ink coated glass substrate was 530 o C.
온도에서 1시간동안열처리하여광활성층을제조하였다.이때열처리챔버내 압력은 105torr이었다. The photoactive layer was prepared by heat treatment at temperature for 1 hour at which time the pressure in the heat treatment chamber was 10 5 torr.
[211] 태양전지셀제작을위해서,광활성층이형성된기판상부에,화학적용액 [211] A chemical solution on a substrate on which a photoactive layer is formed for manufacturing a solar cell
성장법 (chemical bath deposition)을이용하여 CdS박막을증착하고， CdS박막 상부에스퍼터링법을이용하여 ZnO및 Al-doped ZnO박막을증착하고， Al-doped CdS thin film was deposited using chemical bath deposition, and ZnO and Al-doped ZnO thin films were deposited by sputtering on top of the CdS thin film.
ZnO박막상부에열증착법을이용하여 A1전극을증착하였다. An A1 electrode was deposited on the ZnO thin film by thermal evaporation.
[212]  [212]
[213] (실시예 2)  [213] (Example 2)
[214] CIS입자의제조 [214] CIS Particle Manufacturing
[215] 상기실시예 1과동일하게실시하되마이크로파를이용하여 800W출력으로 승온시켜 250oC에서반응시킨것에차이가있으며，나머지는상기실시예 1과 동일하게실시하였다. The same procedure as in Example 1 was performed except that the temperature was raised to 800 W using a microwave to react at 250 ° C., and the rest was performed in the same manner as in Example 1.
[216] CIS막제조  [216] CIS film manufacturing
[217] 상기실시예 1과동일하게실시하였다.  It carried out similarly to Example 1 above.
[218] [218]
[219] (실시예 3)  [219] (Example 3)
[220] CIS입자의제조 [220] CIS Particle Manufacturing
[221] 상기실시예 1과동일하게실시하되마이크로파를이용하여 800W출력으로 승온시켜 200oC에서반웅시킨것에차이가있으며,나머지는상기실시예 1과 동일하게실시하였다. The same procedure as in Example 1 was performed except that the temperature was raised to 800 W using a microwave and the reaction was repeated at 200 ° C., and the rest was performed in the same manner as in Example 1.
[222] CIS막제조  [222] CIS film manufacturing
[223] 상기실시예 1과동일하게실시하였다.  The same implementation as in Example 1 was carried out.
[224] (실시예 4) [224] (Example 4)
[225] CIS입자의제조 [225] CIS Particle Manufacturing
[226] 상기실시예 1과동일하게실시하되마이크로파를이용하여 800W출력으로 승온시켜 30분동안반웅시킨것에차이가있으며，나머지는상기실시예 1과 동일하게실시하였다.  The same procedure as in Example 1 was performed, but the temperature was raised to 800 W using a microwave, and the reaction was repeated for 30 minutes. The rest was performed in the same manner as in Example 1.
[227] CIS막제조  [227] CIS film production
[228] 상기실시예 1과동일하게실시하였다. [229] (실시예 5) It carried out similarly to Example 1 above. [229] (Example 5)
[230] CIS입자의제조 [230] CIS Particle Manufacturing
[231] 상기실시예 1과동일하게실시하되마이크로파를이용하여 800W출력으로  The same implementation as in Example 1 was carried out using a microwave to 800W output.
승온시켜 20분동안반웅시킨것에차이가있으며，나머지는상기실시예 1과 동일하게실시하였다.  There was a difference in temperature and reaction for 20 minutes, and the rest was carried out in the same manner as in Example 1.
[232] CIS막제조  [232] CIS film manufacturing
[233] 상기실시예 1과등일하게실시하였다.  The same procedure as in Example 1 was carried out.
[234] (실시예 6) [234] (Example 6)
[235] CIS입자의제조 [235] CIS Particle Manufacturing
[236] 상기실시예 1과동일하게실시하되마이크로파를이용하여 800W출력으로  In the same manner as in Example 1, but using a microwave to 800W output
승온시켜 15분동안반응시킨것에차이가있으며,나머지는상기실시예 1과 동일하게실시하였다.  There was a difference in the reaction for 15 minutes by raising the temperature, and the rest was carried out in the same manner as in Example 1.
[237] CIS막제조  [237] CIS film manufacturing
[238] 상기실시예 1과동일하게실시하였다.  The same implementation as in Example 1 was carried out.
[239] [239]
[240] (비교예)  [240] (Comparative Example)
[241] CIS입자의제조  [241] CIS Particle Manufacturing
[242] 구리아세테이트모노하이드레이트 (Cu acetate monohydrate):  [242] Cu acetate monohydrate:
인듐아세테이트 (Indium acetate)：셀레늄파우더 (Se powder)를 1:1:2의몰비로 평량한후흔합한흔합물 3.2g을 20g의에틸렌글리콜 (ethylene glycol, Tb=197 0C)에투입한후 1시간동안교반을실시하였다.흔합된용액을마이크로파를 이용하여 800W의출력으로 2분동안승온시켜 280°C에서 25분간반웅시킨후 20분간냉각시켜입자를제조하였다.합성된입자를회수하기위하여에탄올을 이용하여 25000rpm으로 30분을원심분리를실시하여세정및입자회수를하되 3회반복실시하여입자를회수하였다.회수된입자는 40°C의진공오본에서 건조를실시하여 CuInSe2(CIS)입자를제조하였다.제조된 CIS입자의상분석을 위하여 XRD분석을실시하였고그결과를하기도 6에나타내었다.상기제조된 CIS입자는단일상이었으며화학양론비로 Cu:In:Se는 26:26:48이었다. Indium acetate: selenium powder (Se powder) is weighed in a molar ratio of 1: 1: 2, and 3.2 g of the mixed compound is added to 20 g of ethylene glycol (T b = 197 0C), and then 1 Stirring was carried out for a period of time. The mixed solution was heated for 2 minutes at a power of 800 W using microwave, the reaction was performed for 25 minutes at 280 ° C., and then cooled for 20 minutes to prepare particles. Ethanol was used to recover the synthesized particles. 30 minutes at 25000rpm was used for centrifugation to wash and recover the particles, but repeated three times to recover the particles. The recovered particles were dried in a vacuum oven at 40 ° C to obtain CuInSe 2 (CIS) particles. The XRD analysis was performed for the phase analysis of the prepared CIS particles, and the results are shown in Fig. 6. The prepared CIS particles were a single phase and Cu: In: Se was 26:26:48 by stoichiometric ratio. .
[243] CIS막제조및태양전지셀제작  [243] CIS film and solar cell manufacturing
[244] 복합입자대신제조된 CIS입자를사용한것을제외하고,실시예 1과동일하게 실시하여광활성층및태양전지셀을제조하였다.  A photoactive layer and a solar cell were prepared in the same manner as in Example 1 except that CIS particles manufactured in place of the composite particles were used.
[245]  [245]
[246] 도 1은실시예 1에서제조된복합입자의 X선회절분석결과로， CuInSe2(CIS)와 CuSe를포함하는 11족칼코젠화합물이흔재된복합입자가제조됨을확인하였다. FIG. 1 shows the results of X-ray diffraction analysis of the composite particles prepared in Example 1, where composite particles containing a Group 11 chalcogenide compound containing CuInSe 2 (CIS) and CuSe were prepared.
[247] 도 1에서알수있듯이,끓는점이높은폴리에틸렌글리콜을반웅용매로  As can be seen in Figure 1, a high boiling point polyethylene glycol as a reaction solvent
합성하였을때，제조된복합입자는 CuSe를포함하는이차상을함유하였다.이는 CuInSe2상으로의전이반웅이용매의특성에의해서제어되어이차상들이 존재하게되는결과이다.이러한이차상이존재할지라도 Cu:In:Se의비율은 EDX(Energy Dispersive X-ray Spectrometer)축정결과첨가된원료전구체의 조성비와크게상이하지않았다. EDX측정결과복합입자는 Cu： In： Se가 29： 28 :43의몰비를가짐을알수있었으며， Se의비율이조금작게측정되는것은 산화물 (도 1의 In203)로존재하는이차상의존재에기인하는결과이고，도 2의 실시예 1에서제조된광활성층의 X-선회절분석결과에서알수있듯이, 후공정인 Se분위기에서의열처리에의해서 Cu:In:Se가 1:1:2의화학양론비는 쉽게최적화될수있었다. When synthesized, the prepared composite particles contained a secondary phase containing CuSe. This is the result of the presence of secondary phases controlled by the nature of the transition reaction solvent to the CuInSe 2 phase. Even if such secondary phases exist, Cu The ratio of: In: Se is The results of EDX (Energy Dispersive X-ray Spectrometer) were not significantly different from the composition ratio of the added precursor. The EDX results showed that the composite particles had a molar ratio of Cu: In: Se of 29: 28:43, and the small ratio of Se was found to exist as an oxide (In 2 0 3 in Fig. 1). As a result of the X-ray diffraction analysis of the photoactive layer manufactured in Example 1 of FIG. 2, the stoichiometry of Cu: In: Se is 1: 1: 2 by heat treatment in a Se atmosphere, which is a post-process. Rain could easily be optimized.
[248] 도 3은실시예 1에서제조된광활성층의주사전자현미경사진으로，도 2및도 3의결과에서알수있듯이,광활성층이 CuInSe2단일상을가지면서치밀한 미세구조를가지는막이형성되는것을알수있었다. EDX측정결과실시예 1에서제조된광활성층의조성은화학양론비로 Cu:In:Se 7} 25:23:52였다. 3 is a scanning electron micrograph of the photoactive layer prepared in Example 1, as shown in the results of FIGS. 2 and 3, wherein the photoactive layer has a single layer of CuInSe 2 and a film having a fine microstructure is formed. I could see that. EDX measurement results The composition of the photoactive layer prepared in Example 1 was Cu: In: Se 7} 25:23:52 in terms of stoichiometric ratio.
[249] 도 4는실시예 1내지 4에서제조된복합입자의 X-선회절분석결과를통합  4 shows the results of X-ray diffraction analysis of the composite particles prepared in Examples 1 to 4.
도시한도면으로， a)는실시예 3(반응온도 200oC), b)는실시예 2(반응온도 250oC), c)는실시예 1(반웅온도 280°C)의분석결과이다. As shown in the figure, a) is Example 3 (reaction temperature 200 ° C.), b) is Example 2 (reaction temperature 250 ° C.), and c) is the analysis result of Example 1 (reaction temperature 280 ° C.). .
[250] 도 5는실시예 1및실시예 4내지 6에서제조된복합입자의 X-선회절  5 shows the X-ray diffraction of the composite particles prepared in Examples 1 and 4 to 6.
분석결과를통합도시한도면으로, a)는실시예 6(반웅시간 15분), b)는  In the integrated drawing of the analysis results, a) is Example 6 (reaction time 15 minutes), b) is
실시예 5(반웅시간 20분)， c)는실시예 1(반응시간 25분)， d)는  Example 5 (reaction time 20 minutes), c) Example 1 (reaction time 25 minutes), d)
실시예 4(반웅시간 30분)의분석결과이다.  The analysis result of Example 4 (reaction time 30 minutes).
[251] 도 4및도 5에서알수있듯이，반응온도및반웅시간을통해복합입자내에 함유되는이차상의종류및함량이제어됨을알수있으며, X-선회절  4 and 5, it can be seen that the reaction temperature and reaction time control the type and content of secondary phases contained in the composite particles.
분석결과를통해，복합입자가저융점의구리칼코젠화합물 (CuSe및 /또는 CuSe2 )를 1내지 20부피 %함유함을알수있으며，저융점의구리칼코젠화합물을 제외한매질의전체부피를기준으로 CuInSe2를 40내지 95부피 %로함유함을알 수있었다.또한,저융점의구리칼코젠화합물이외의잔류화합물로 ,In2Se3,In203, Se, Cu2Se를 5내지 60부피 <¾로함유함을알수있었다. The analysis results show that the composite particles contain 1 to 20% by volume of low melting point copper chalcogenide compounds (CuSe and / or CuSe 2 ) and are based on the total volume of the medium excluding low melting point copper chalcogenide compounds. It was found that CuInSe 2 contained 40 to 95% by volume. Residual compounds other than the low melting point copper calcogen compound were 5 to 5 In 2 Se 3 , In 2 0 3 , Se, and Cu 2 Se. 60 volumes < ¾ were found.
[252] 도 4에서알수있듯이반웅온도에따라,저융점의구리칼코젠화합물의함량이 제어될수있음을알수있는데,반응온도가낮을수록보다다량의  As can be seen from FIG. 4, it can be seen that the content of the low melting point copper calogen compound can be controlled according to the reaction temperature.
구리칼코젠화합물을함유하는복합입자가제조됨을알수있다.이때， 200 의 반웅온도미만에서는합성된입자의대부분이이차상으로이루어질수있으며, 300°C반웅온도를초과하는경우，저융점의구리칼코젠화합물의함량이극히 미미할수있어，치밀하고，복합입자의조성이유지되며，단일상의광활성층이 제조되지못할위험이 있다.  It can be seen that a composite particle containing a copper chalcogen compound is produced, where a lower reaction temperature of less than 200 may cause most of the synthesized particles to be secondary phase, and when the reaction temperature exceeds 300 ° C., a low melting point copper calogen may be produced. The content of the compound can be extremely small, dense, the composition of the composite particles is maintained, there is a risk that the single-phase photoactive layer is not produced.
[253] 도 5에서알수있듯이반응시간에따라，저융점의구리칼코젠화합물의함량이 제어될수있음을알수있는데,반웅시간이짧을수록보다다량의  As can be seen from FIG. 5, it can be seen that the content of the low melting point copper chalcogenide can be controlled according to the reaction time.
구리칼코젠화합물을함유하는복합입자가제조됨을알수있다.이때， 반응시간을 15미만인경우，합성된입자의대부분이이차상으로이루어질수 있으며， 40분을초과하는경우，저융점의구리칼코젠화합물의함량이극히 미미할수있어，치밀하고，복합입자의조성이유지되며，단일상의광활성층이 제조되지못할위험이있다. It can be seen that a composite particle containing a copper chalcogen compound is produced, in which case the reaction time is less than 15, and most of the synthesized particles may be formed in the second phase, and if it exceeds 40 minutes, a low melting point of the copper chalcogen compound is produced. The content can be extremely small, compact, maintaining the composition of the composite particles, and the single phase photoactive layer There is a risk of manufacturing failure.
[254] 따라서，도 4및도 5에서알수있듯이， iInSe2가주상으로존재하면서 1내지 20부피 %의저융점구리칼코젠화합물을함유하기위해서는 200내지 300oC의 반웅온도로, 15분내지 40분동안합성이이루어지는것이바람직함을알수 있다. Thus, as can be seen in FIGS. 4 and 5, in order to contain 1 to 20% by volume of low-melting copper calogenous compounds with iInSe 2 as the main phase, at a reaction temperature of 200 to 300 o C, 15 minutes to 40 It can be seen that it is desirable to have synthesis for minutes.
[255] 도 6은비교예 1에서제조된 CIS입자의 X-선회절분석결과를나타낸것이며， 도 7은비교예 1에서제조된광활성층의 X-섰회절분석결과를나타낸것이며, 도 8은비교예 1에서제조된광활성층의주사전자현미경사진을나타낸것이다.  FIG. 6 shows X-ray diffraction analysis results of CIS particles prepared in Comparative Example 1, FIG. 7 shows X-ray diffraction analysis results of photoactive layer prepared in Comparative Example 1, and FIG. 8 shows Comparative Example 1 Scanning electron micrographs of photoactive layers prepared in.
[256] 도 6에서알수있듯이，비교예 1에의해제조된 CIS입자는이차상이존재하지 않는 CuInSe2단일상으로이루어진 CIS입자임을알수있었다.또한비교예 1에 의해제조된 CIS입자는화학양론비로 Cu:In:Se가 26:26:48이었다. 6, it can be seen that the CIS particles prepared by Comparative Example 1 were CIS particles composed of CuInSe 2 single phase without secondary phase. Also, the CIS particles prepared by Comparative Example 1 were stoichiometric. Cu: In: Se was 26:26:48.
[257] 도 7및도 8에서확인할수있듯이비교예 1에의해제조된광활성층은  As shown in FIGS. 7 and 8, the photoactive layer prepared by Comparative Example 1
단일상이나，치밀도가현저히떨어지는미세구조를가지는것을알수있다. 비교예 1에서제조된광활성층의화학양론비는 Cu:In:Se가 25:26:49였다.  It can be seen that it has a single phase or a fine structure with a significantly lower density. The stoichiometric ratio of the photoactive layer manufactured by the comparative example 1 was 25:26:49 in Cu: In: Se.
[258] 이러한,미세구조의근복적인차이점으로인해,태양전지특성측면에서， 비교예에서제작된다공성광활성층기반태양전지의경우바람직한  Due to the near difference of the microstructure, the solar cell is manufactured in the comparative example in terms of solar cell characteristics.
이종접합이생성되지않아 0%의광전환효율을보이는반면,도 9에보이듯이 실시예 1에서제작된화학양론비,결정성，미세구조등이우수한광활성층기반 태양전지의경우 8.2%으로획기적으로개선된광전환효율을보임을알수있다.  While no heterojunction is generated, the optical conversion efficiency of 0% is shown, while the photo-active layer-based solar cell having excellent stoichiometry, crystallinity, microstructure, etc. produced in Example 1 is improved to 8.2%. It shows the light conversion efficiency.
[259] 이상，실제조예에기반하여본발명을상술하였으나，본발명의사상은설명된 제조예에국한되어정해져서는아니되며 ,후술하는특허청구범위뿐아니라이 특허청구범위와균등하거나등가적변형이있는모든것들은본발명사상의 범주에속한다고할것이다.  [259] While the present invention has been described above based on actual manufacturing examples, the spirit of the present invention should not be limited to the described manufacturing examples, and the claims described below, as well as equivalent or equivalent modifications to the scope of the claims. Everything that exists would fall within the scope of the present invention.

Claims

청구범위 [청구항 1] 하기 화학식 1을 만족하는 11족 금속 칼코젠화합물이 매질에 흔재된 태양전지 광활성층용 복합입자. Claims [Claim 1] A composite particle for a solar cell photoactive layer in which a Group 11 metal chalcogenide compound satisfying the following Formula 1 is common in a medium.
(화학식 1)  (Formula 1)
M,AX M, A X
(M은 11족 금속에서 하나 또는 둘 이상 선택된 것이 며 , A는 칼코젠 원소이며 , X는 1 내지 2를 만족하는 실수이다.)  (M is one or more selected from Group 11 metals, A is a chalcogen element, and X is a real number that satisfies 1-2.)
[청구항 2] 제 1항에 있어서，  2. The method of claim 1,
상기 매질은 11족 금속 및 12족 내지 14족에서 하나 또는 둘 이상 선택된 원소의 칼코젠화합물인 금속간칼코젠화합물을 함유하는 복합입자.  The medium is a composite particle containing an intermetallic chalcogenide compound which is a chalcogenide compound of at least one element selected from Group 11 metal and Groups 12 to 14.
[청구항 3] 제 2항에 있어서，  [Claim 3] The method of claim 2,
상기 매질은 하기 화학식 2 또는 하기 화학식 3을 만족하는 금속간칼코젠화합물을 함유하는 복합입자.  The medium is a composite particle containing an intermetallic chalcogenide compound satisfying the following formula (2) or (3).
(화학식 2)  (Formula 2)
ΜΊΜ",Α2 ΜΊΜ ", Α 2
(화학식 2에서 M'는 11족 금속에서 하나 또는 둘 이상 선택된 금속이 며 , Μ"는 13족에서 하나 또는 둘 이상 선택된 금속이다.) (화학식 3)  (In Formula 2, M 'is one or more metals selected from Group 11 metals and Μ "is one or more metals selected from Group 13).
Μ'2Μ"Ά4 Μ ' 2 Μ "Ά 4
(화학식 3에서 M'는 11족 금속에서 하나 또는 둘 이상 선택된 금속이며， Μ'"는 12족 및 14족에서 하나 또는 둘 이상 선택된 금속이 다.)  (In Formula 3, M 'is one or more metals selected from Group 11 metals and Μ' "is one or more metals selected from Groups 12 and 14.)
[청구항 4] 제 2항에 있어서，  [Claim 4] The method of claim 2,
상가 복합입자는 1 내지 20 부피 %의 상기 11족 금속  The additive multiparticulate is 1-20% by volume of the Group 11 metal.
칼코젠화합물을 함유하는 복합입자.  Multiparticulates containing chalcogenide compounds.
[청구항 5] 제 2항에 있어서，  5. The method of claim 2,
상기 복합입자는 11족 금속 : 12 내지 14족 금속：칼코젠 원소를 0.8~1.3:0.8~1.3:1.7~2.3의 몰비로 함유하는 복합입자.  The said composite particle is a composite particle which contains the Group 11 metal: Group 12-14 metal: chalcogen element in molar ratio of 0.8-1.3: 0.8-1.3: 1.7-2.3.
[청구항 6] 제 2항에 있어서 ,  [Claim 6] The method according to claim 2,
상기 11족 금속은 Cu이며， 12 내지 14족 금속은 In 또는 In과 Ga이며 , 상기 칼코젠 원소는 Se인 복합입자.  The Group 11 metal is Cu, the Group 12-14 metals are In or In and Ga, the chalcogen element is Se.
[청구항 7] 제 2항에 있어서 ,  [Claim 7] The method according to claim 2,
상기 U족 금속 칼코젠화합물은 CuSe, CuSe2 또는 이들의 흔합물을 포함하는 복합입자. The Group U metal chalcogenide compound includes CuSe, CuSe 2 or a mixture thereof.
[청구항 8] 제 2항에 있어서 ,  8. The method of claim 2,
상기 복합입자는 11족 금속： 12 내지 14족 금속：칼코젠 원소의 몰비가 0.8~1.3:0.8~1.3:1.7~2.3이 되도록 각 금속 전구체 및 칼코젠 원소 전구체가 끓는점 이 200°C이상인 반웅 용매에 혼합된 혼합액에 마이크로파를 조사하여 제조되는 복합입자. The composite particles are a Group 11 metal: a Group 12 to 14 metal: a chalcogen element. A composite particle prepared by irradiating microwaves to a mixed solution mixed with a reaction liquid having a boiling point of 200 ° C. or more, in which each metal precursor and chalcogen element precursor have a molar ratio of 0.8 to 1.3: 0.8 to 1.3: 1.7 to 2.3.
[청구항 9] 제 1항 내지 제 8항에서 선택된 어느 한 항에 따른 복합입자를 함유하는 태양전지 광활성층용 잉크.  Claim 9 The ink for solar cell photoactive layers containing the composite grain | particle of any one of Claims 1-8.
[청구항 10] a) 11족 금속： 12 내지 14족 금속：칼코젠 원소의 몰비가  Claim 10: a) Group 11 metal: Group 12-14 metal: The molar ratio of the chalcogen element
0.8~1.3:0.8~1.3:1.7~2.3이 되도록 각 금속 전구체 및 칼코젠 원소 전구체가 끓는점 이 200oC이상인 반웅 용매에 흔합된 흔합액을 제조하는 단계；및 Preparing a mixed solution mixed in a reaction mixture having a boiling point of 200 ° C. or higher at each metal precursor and a chalcogenide precursor such that 0.8 to 1.3: 0.8 to 1.3: 1.7 to 2.3; and
b) 상기 흔합액에 마이크로파를 조사하여 하기 화학식 1을 만족하는 11족 금속 칼코젠화합물이 매질에 흔재된 태양전지 광활성층용 복합입자를 제조하는 단계 ;  b) irradiating microwaves to the mixture to prepare composite particles for a photovoltaic active layer of a solar cell in which a Group 11 metal chalcogenide compound satisfying the following Formula 1 is common in a medium;
를 포함하는 태양전지 광활성층용 복합입자의 제조방법 .  Method for producing a composite particle for solar cell photoactive layer comprising a.
(화학식 1)  (Formula 1)
(M은 1 1족 금속에서 하나 또는 둘 이상 선택된 것 이 며， A는 칼코젠 원소이 며 , χ는 1 내지 2를 만족하는 실수이 다.) (M is one or more selected from Group 1 metals, A is a chalcogen element, and χ is a real number satisfying 1 to 2.)
[청구항 11] 제 10항에 있어서 ,  11. The method of claim 10,
b) 단계는 상기 흔합액에 마이크로파를 조사하여 200 내지  b) step 200 to the microwave by irradiating the mixture
300°C에서 15 내지 40분 동안 수행되는 복합입자의 제조방법 . Method for producing a composite particle is carried out at 300 ° C for 15 to 40 minutes.
[청구항 12] 제 10항에 있어서 , 12. The method of claim 10, wherein
a) 단계의 상기 반응 용매는 폴리을계 용매，아민계 용매 및 포스핀계 용매로부터 하나 또는 둘 이상 선택된 용매를 포함하는 복합입자의 제조방법 .  The method of claim 1, wherein the reaction solvent of step a) comprises one or more solvents selected from poly solvents, amine solvents and phosphine solvents.
[청구항 13] 제 10항에 있어서 , 13. The method of claim 10,
상기 11족 금속은 Cu이며 , 12 내지 14족 금속은 In 또는 In과 The Group 11 metal is Cu, the Group 12 to 14 metal is In or In and
Ga이며，상기 칼코젠 원소는 Se인 복합입자. Ga, and the chalcogen element is Se.
[청구항 14] 제 10항에 있어서， 14. The method of claim 10,
b) 단계의 상기 복합입자는 하기 화학식 2 또는 하기 화학식 3을 만족하는 금속간칼코젠화합물을 함유하는 매질에 CuSe, CuSe2 또는 이들의 흔합물인 11족 금속 칼코젠화합물이 흔재된 복합입자의 제조방법 . The composite particle of step b) is a method for producing a composite particle containing CuSe, CuSe 2 or a Group 11 metal chalcogenide compound in a medium containing an intermetallic chalcogenide compound satisfying the following Formula 2 or .
(화학식 2)  (Formula 2)
M M' A2 MM 'A 2
(화학식 2에서 M'는 11족 금속에서 하나 또는 둘 이상 선택된 금속이며ᅳ M"는 13족에서 하나 또는 둘 이상 선택된 금속이다.) (화학식 3)  (In Formula 2, M 'is one or two or more metals selected from Group 11 metals and M' is one or more metals selected from Group 13).
Μ'2Μ"Ά4 (화학식 3에서 M'는 11족금속에서하나또는둘이상선택된 금속이며 ,Μ'"는 12족및 14족에서하나또는둘이상선택된 금속이다.) Μ ' 2 Μ "Ά 4 (In Formula 3, M 'is one or more metals selected from Group 11 metals, and Μ'"is one or more metals selected from Groups 12 and 14.)
[청구항 15] c)제 9항에따른잉크를기판에도포하여도포막을형성하는 단계;및.  [Claim 15] c) forming a coating film by applying the ink according to claim 9 onto a substrate; and
d)상기도포막을열처리하여광활성층을제조하는단계; 를포함하는태양전지광활성층의제조방법.  d) heat treating the coating film to produce a photoactive layer; Method for producing a solar cell photoactive layer comprising a.
[청구항 16] 제 15항에있어서，  [Claim 16] In Section 15,
상기 d)단계의열처리는칼코젠분위기에서 , 400내지 550°C로 수행되는광활성층의제조방법.  The heat treatment of step d) is carried out in a chalcogen atmosphere, 400 to 550 ° C. Method for producing a photoactive layer.
[청구항 17] 제 15항의제조방법으로제조된태양전지용광활성층.  Claim 17 The photoactive layer for solar cells manufactured by the manufacturing method of Claim 15.
[청구항 18] 제 17항의광활성층이구비된태양전지. Claim 18 The solar cell provided with the photoactive layer of Claim 17.
PCT/KR2012/005194 2011-06-30 2012-06-29 Composite particles for a photoactive layer of a solar cell and method for manufacturing same WO2013002605A2 (en)

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