WO2012169621A1 - 光吸収層形成用塗布液、及び光吸収層形成用塗布液の製造方法 - Google Patents
光吸収層形成用塗布液、及び光吸収層形成用塗布液の製造方法 Download PDFInfo
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- WO2012169621A1 WO2012169621A1 PCT/JP2012/064813 JP2012064813W WO2012169621A1 WO 2012169621 A1 WO2012169621 A1 WO 2012169621A1 JP 2012064813 W JP2012064813 W JP 2012064813W WO 2012169621 A1 WO2012169621 A1 WO 2012169621A1
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- hydrazine
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- light absorption
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- 239000007788 liquid Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 146
- 150000004770 chalcogenides Chemical class 0.000 claims abstract description 61
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 238
- 238000000576 coating method Methods 0.000 claims description 80
- 239000011248 coating agent Substances 0.000 claims description 74
- 230000031700 light absorption Effects 0.000 claims description 47
- 239000011669 selenium Substances 0.000 claims description 47
- 229910052798 chalcogen Inorganic materials 0.000 claims description 33
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- 239000012043 crude product Substances 0.000 claims description 26
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- 229910052711 selenium Inorganic materials 0.000 claims description 12
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 11
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- 238000001914 filtration Methods 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims 2
- 238000000605 extraction Methods 0.000 claims 1
- 239000010949 copper Substances 0.000 description 40
- 239000011135 tin Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- 239000011701 zinc Substances 0.000 description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000010408 film Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 10
- 229910008772 Sn—Se Inorganic materials 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 7
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- 150000003346 selenoethers Chemical class 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
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- 239000002244 precipitate Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 238000000224 chemical solution deposition Methods 0.000 description 3
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- 238000004090 dissolution Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 238000010549 co-Evaporation Methods 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
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- -1 respectively Chemical compound 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- KTLOQXXVQYUCJU-UHFFFAOYSA-N [Cu].[Cu].[Se] Chemical compound [Cu].[Cu].[Se] KTLOQXXVQYUCJU-UHFFFAOYSA-N 0.000 description 1
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
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- C01B19/00—Selenium; Tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
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- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- 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
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- 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
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- 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
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- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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- 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
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- 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
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- 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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a coating solution for forming a light absorbing layer and a method for producing a coating solution for forming a light absorbing layer.
- a chalcopyrite solar cell is a solar cell formed by forming a light absorption layer made of a chalcopyrite (chalcopyrite) material on a substrate.
- chalcopyrite-based materials are copper (Cu), indium (In), gallium (Ga), selenium (Se), sulfur (S), and the like, and typical examples of the light absorption layer include Cu.
- (in, Ga) Se 2 and Cu (in, Ga) (Se , S) 2 include, are abbreviated CIGS, etc. CIGSS respectively.
- CZTS solar cells made of, for example, copper (Cu), zinc (Zn), tin (Sn), selenium (Se), and sulfur (S) that replace indium, which is a rare metal, have been studied.
- Typical examples of the absorption layer include Cu 2 ZnSnSe 4 , Cu 2 ZnSnS 4 , and Cu 2 ZnSn (S, Se) 4 .
- FIG. 1 is a schematic cross-sectional view showing an example of a chalcopyrite solar cell or a CZTS solar cell.
- the chalcopyrite solar cell or CZTS solar cell includes a first electrode 3, a CIGS or CZTS layer (light absorption layer) 4, a buffer layer 5, an i-ZnO layer 6 and The second electrode 7 is schematically configured by being stacked in this order.
- the buffer layer for example, a CdS layer, a ZnS layer, an InS layer, or the like is known.
- Terminals are joined to the first electrode 3 and the second electrode 7, respectively, and wiring is connected to the terminals.
- a chalcopyrite or CZTS solar cell 1 light incident in the direction of arrow A is absorbed by the CIGS or CZTS layer 4 to generate an electromotive force, and current flows in the direction of arrow B.
- the surface of the second electrode 7 is protected by being covered with an antireflection film layer 8 made of, for example, an MgF 2 layer.
- a coating solution is prepared by dissolving elements such as Cu, In, Ga, Se, and S in a specific solvent to prepare a coating solution.
- the CIGS layer is formed by applying and baking.
- a method of preparing a coating solution a method using hydrazine as a solvent and a method of adding amines as a dissolution accelerator instead of using hydrazine are known (see Patent Documents 1 and 2). .
- the coating solution is a metal dispersion coating solution
- the coating apparatus since the coating solution is a metal dispersion coating solution, there is a problem in its storage stability. Furthermore, special consideration is required for the coating apparatus in order to maintain the metal dispersion, and the degree of freedom in selecting the coating apparatus is low.
- the coating solution for forming a light absorbing layer of the present invention is a coating solution used for forming a light absorbing layer of a CZTS solar cell, and includes (A) a hydrazine coordinated Cu chalcogenide complex component and (B) a hydrazine coordinated Sn.
- a chalcogenide complex component and (C) a hydrazine-coordinated Zn chalcogenide complex component are dissolved in dimethyl sulfoxide.
- DMSO dimethyl sulfoxide
- the coating solution for forming a light absorption layer used for forming the light absorption layer of the CZTS solar cell of this embodiment includes (A) a hydrazine coordinated Cu chalcogenide complex component, (B) a hydrazine coordinated Sn chalcogenide complex component, (C) It can be obtained by dissolving a hydrazine-coordinated Zn chalcogenide complex component in dimethyl sulfoxide (DMSO). In addition, it is preferable that an amine solvent does not contain in this coating liquid for light absorption layer formation.
- the hydrazine coordinated Cu chalcogenide complex component (A) can also be obtained by reacting metal Cu and chalcogen in dimethyl sulfoxide in the presence of hydrazine, and concentrating and filtering. Specifically, after stirring for 3 days to 1 week at room temperature in the presence of 2 equivalents of hydrazine to metal Cu in 2 to 4 equivalents of Se and DMSO, residual hydrazine is removed under reduced pressure.
- the hydrazine-coordinated Cu—Se complex / DMSO solution can also be prepared by further concentrating and then filtering the resulting concentrate.
- the chalcogen Se or S can be used, and Se is preferably used.
- Cu copper selenide (Cu 2 Se).
- the poor solvent an alcohol solvent is preferably used, and isopropanol (IPA) is more preferably used.
- the hydrazine coordinated Sn chalcogenide complex component (B) used in this embodiment needs to be generated so as to be dissolved in DMSO.
- DMSO dimethyl methacrylate
- the crude product is extracted with DMSO, and a poor solvent is added to the resulting solution. In addition, it can be obtained by reprecipitation.
- metal Sn and chalcogen are added to hydrazine and stirred at room temperature for about 1 to 3 days. Thereafter, hydrazine is removed from the resulting solution under a nitrogen stream to obtain a crude product. The obtained crude product is extracted with DMSO.
- the extracted liquid from which the crude product has been extracted is filtered through, for example, a 0.2 ⁇ m PTFE filter, and then concentrated. Then, a poor solvent is added to the concentrate for reprecipitation, the supernatant is removed, the precipitate is washed with IPA or the like, and dried to obtain a tan hydrazine coordination Sn chalcogenide complex.
- the hydrazine coordinated Sn chalcogenide complex component (B) can also be prepared by the following method. 3 equivalents of metal Sn in hydrazine (5 ml), stirred at room temperature for 1 to 3 days, then added IPA and stirred to precipitate a yellow product. The supernatant was removed, and the precipitate was washed with IPA. The crude product can be obtained by drying. Next, the hydrazine-coordinated Sn-Se complex / DMSO solution can be prepared by extracting the product from the crude product with DMSO (80 ° C, 1 hr), concentrating, and then filtering the resulting concentrate. it can.
- the chalcogen Se or S can be used, and Se is preferably used.
- Sn as well as metals Sn, for example, may be used selenide Sn (SnSe, SnSe 2).
- SnSe selenide Sn
- SnSe selenide Sn
- IPA IPA
- the hydrazine may be anhydrous hydrazine, but it is preferable to use hydrazine monohydrate or hydrous hydrazine.
- the ratio of the amount of Sn and chalcogen is preferably about 3 mol of chalcogen with respect to 1 mol of Sn.
- the Zn chalcogenide complex used in this embodiment needs to be generated so as to be dissolved in DMSO.
- Zn or ZnSe and chalcogen are mixed in the presence of hydrazine to obtain a crude product, and then obtained by extracting the crude product with dimethyl sulfoxide. be able to.
- hydrazine is added to Zn selenide and chalcogen in DMSO and stirred at room temperature for about 3 to 7 days. Thereafter, hydrazine is removed from the obtained solution under a nitrogen stream to obtain a crude product (reaction intermediate solution). The obtained crude product is extracted with DMSO.
- the extract from which the crude product has been extracted is filtered through, for example, a 0.2 ⁇ m PTFE filter, and then concentrated.
- a hydrazine-coordinated Zn chalcogenide complex can be obtained by filtering the concentrated solution obtained thereafter.
- the formation of the hydrazine coordinated Zn chalcogenide complex as described above is represented by the following formula (3).
- chalcogen Se or S can be used, and Se is preferable.
- Zn not only Zn selenide but also metal Zn, for example, may be used.
- the hydrazine may be anhydrous hydrazine, but it is preferable to use hydrazine monohydrate or hydrous hydrazine. Further, hydrazine can be used as a reaction solvent in place of DMSO.
- the ratio of Zn selenide (ZnSe) to chalcogen is preferably 2 mol or more, more preferably about 3 to 4 mol of chalcogen with respect to 1 mol of Zn selenide.
- a hydrazine coordinated Sb chalcogenide complex in order to enlarge the crystal grains.
- a hydrazine-coordinated Sb chalcogenide complex for example, selenized Sb (Sb 2 Se 3 ) and chalcogen are added to hydrazine to obtain a crude product, and then the crude product is extracted with DMSO. It is obtained by adding a poor solvent to the obtained solution and recrystallizing it.
- selenide Sb and chalcogen are added to hydrazine and stirred at room temperature for about 3 to 7 days. Thereafter, hydrazine is removed from the resulting solution under a nitrogen stream to obtain a crude product. The obtained crude product is extracted with DMSO.
- the extract from which the crude product has been extracted is filtered through, for example, a 0.2 ⁇ m PTFE filter, and a poor solvent is added to the filtrate to cause reprecipitation, thereby obtaining a black hydrazine coordinated Sb chalcogenide complex.
- the production of the hydrazine coordinated Sb chalcogenide complex as described above is represented by the following formula (4).
- the chalcogen Se or S can be used, and Se is preferably used. Moreover, as a poor solvent, it is preferable to use an alcohol solvent, and it is more preferable to use IPA.
- the hydrazine may be anhydrous hydrazine, but it is preferable to use hydrazine monohydrate or hydrous hydrazine.
- the ratio of the amount of selenized Sb (Sb 2 Se 3 ) and chalcogen is preferably 2 mol or more of chalcogen with respect to 1 mol of selenized Sb. In the present embodiment, the selenization Sb has been described.
- the ratio of the amount of antimony (Sb) to the chalcogen is as follows. It is preferable to use 4 mol or more of chalcogen with respect to 1 mol of antimony.
- DMSO is added to the hydrazine coordinated Cu chalcogenide complex described above and stirred at room temperature for about one night to obtain a DMSO solution (first solution) in which the hydrazine coordinated Cu chalcogenide complex is dissolved.
- DMSO is added to the hydrazine-coordinated Sn chalcogenide complex described above and stirred for about 1 hour at a temperature of about 80 to 120 ° C. to obtain a DMSO solution (second solution) in which the hydrazine-coordinated Sn chalcogenide complex is dissolved. .
- DMSO is added to the hydrazine-coordinated Zn chalcogenide complex and stirred for about 1 hour at a temperature of about 80 to 120 ° C. to obtain a DMSO solution (third solution) in which the hydrazine-coordinated Zn chalcogenide complex is dissolved. .
- DMSO is added to the hydrazine coordinated Sb chalcogenide complex described above and stirred overnight at room temperature to obtain a DMSO solution (fourth solution) in which the hydrazine coordinated Sb chalcogenide complex is dissolved.
- Na 2 Se is added to Na 2 Se and stirred in DMSO at room temperature for about 3 to 7 days to obtain a uniform solution.
- the reason why Na is used in this embodiment is to improve the film quality (grain size and crystal quality) of the light absorption layer, and this Na solution may not be used.
- a DMSO solution in which the hydrazine coordinated Cu chalcogenide complex is dissolved, a DMSO solution in which the hydrazine coordinated Sn chalcogenide complex is dissolved, and a DMSO solution in which the hydrazine coordinated Zn chalcogenide complex is dissolved are mixed.
- the light-absorbing layer-forming coating liquid of this embodiment can be produced.
- the fourth solution may be added to the light absorbing layer forming coating solution of the present embodiment.
- the coating solution for forming the light absorption layer of this embodiment uses DMSO as a solvent, and the coating solution itself does not contain hydrazine. Therefore, when forming the light absorption layer, the chemical properties (explosive properties) of hydrazine are used. ) Is no longer a problem and the safety of the manufacturing process is improved.
- the hydrazine coordination metal chalcogenide complex is uniformly dissolved in the solvent, its storage stability is improved and the degree of freedom in selecting the coating apparatus is improved.
- the light absorbing layer forming coating solution of this embodiment does not use amines as a dissolution accelerator.
- amines are used as dissolution promoters, the PV characteristics deteriorate as a result of the amines remaining in the device after film formation.
- the light-absorbing layer-forming coating solution of the present embodiment further contains a miscible additive, for example, an organic solvent for adjusting the viscosity, a film, or the like, as long as the effects of the present invention are not impaired.
- a miscible additive for example, an organic solvent for adjusting the viscosity, a film, or the like, as long as the effects of the present invention are not impaired.
- An additional resin for improving the performance, a surfactant for improving the coating property, a stabilizer, and the like can be appropriately added and contained.
- the method for manufacturing a CZTS solar cell according to the present embodiment includes a step of forming a first electrode on a substrate, a step of forming a light absorption layer on the first electrode, and a buffer layer on the light absorption layer. And a step of forming a second electrode on the buffer layer.
- the step of forming the light absorption layer on the first electrode it may be formed by using a conventionally known appropriate method.
- a Mo layer may be formed by sputtering using nitrogen as a sputtering gas.
- the buffer layer may be formed as a CdS layer, for example, and may be formed using a chemical bath deposition method, for example.
- the transparent electrode may be formed using an appropriate material.
- the above-described coating solution for forming the light absorption layer is applied onto the first electrode (substrate).
- a coating method a spin coating method, a dip coating method, a doctor blade (applicator) method, a curtain / slit casting method, a printing method, a spray method, or the like can be used.
- the application conditions may be set as appropriate according to the desired film thickness, material concentration, and the like.
- the substrate is set on a spin coater and a coating solution is applied.
- the coating conditions at this time may be appropriately set according to the film thickness to be formed.
- the coating can be formed by maintaining the rotation speed at 300 to 3000 rpm for 10 to 60 seconds.
- it can carry out by immersing a base
- substrate you may vacuum-dry.
- Firing conditions can be appropriately set according to the desired film thickness, material type, and the like. For example, it can be a two-stage process in which baking (annealing) is performed in an oven after soft baking (pre-baking) on a hot plate.
- the temperature of the hot plate is set to 100 to 400 ° C. and soft baking is performed for 1 to 30 minutes, and the inside of the oven is raised to 300 to 600 ° C. Annealing is performed by holding for 1 to 180 minutes. Thereby, the light absorption layer is cured.
- the film thickness of the light absorption layer is measured. If the thickness is smaller than the desired thickness, the light absorption layer forming coating solution is again applied on the substrate and baked. By repeating these steps, a light absorption layer having a desired thickness can be obtained.
- the CZTS solar cell of this embodiment can be manufactured. And since the hydrazine is not contained in the coating liquid for light absorption layer formation, the safety
- the hydrazine coordinated Cu chalcogenide complex is obtained by dissolving Cu and chalcogen in DMSO to which hydrazine has been added and recrystallizing the resulting solution by adding a poor solvent.
- the present invention is not limited to this, and any hydrazine coordinated Cu chalcogenide complex may be used.
- Cu and chalcogen are dissolved in DMSO to which hydrazine is added, and then the residual hydrazine is removed. Can be used as is.
- the hydrazine-coordinated Cu chalcogenide complex has very good solubility in DMSO. By using this complex, a coating solution for forming a light absorption layer with higher accuracy than before can be prepared. can do.
- Example 1 In Example 1, a coating solution for forming a light absorption layer was prepared as follows.
- Zinc selenide (ZnSe, 460 mg, 4.02 mmol), 2-6 equivalents of Se (5 equivalents: 1588 mg, 20.11 mmol) and 2-4 equivalents of hydrazine (3 equivalents: to ZnSe) in DMSO (8 ml).
- DMSO dimethyl sulfoxide
- the mixture is stirred at room temperature for 3 days to 1 week, and then residual hydrazine is removed under a nitrogen stream to obtain a reaction intermediate solution.
- the hydrazine coordination Zn precursor solution was prepared by filtering.
- a hydrazine coordinated Cu—Se complex, a hydrazine coordinated Sn—Se complex, and a hydrazine coordinated Zn—Se complex are dissolved in DMSO, respectively, and a hydrazine coordinated Cu—Se complex / DMSO solution (concentration: Cu 2).
- solution A hydrazine coordinated Sn—Se complex / DMSO solution (concentration: 178.2 mg / ml in terms of SnSe 2 )
- solution B hydrazine-coordinated Zn—Se complex / DMSO solution (concentration: 12.4 mg / ml in terms of ZnSe)
- solution C hydrazine-coordinated Zn—Se complex / DMSO solution
- a dipping method was adopted as a coating method for the coating liquid, and the baking conditions were soft baking at 300 ° C. for 1 minute on a hot plate, and then the hot plate was covered and annealed at 540 ° C. for 10 minutes. .
- Example 2 In the same manner as in Example 1, a hydrazine coordinated Cu—Se complex, a hydrazine coordinated Sn—Se complex, and a hydrazine coordinated Zn—Se complex were obtained. Thereafter, a hydrazine coordinated Cu—Se complex, a hydrazine coordinated Sn—Se complex, and a hydrazine coordinated Zn—Se complex are dissolved in DMSO, respectively, and a hydrazine coordinated Cu—Se complex / DMSO solution (concentration: Cu 2).
- solution D Se conversion 76.3 mg / ml)
- solution E hydrazine coordinated Sn—Se complex / DMSO solution
- solution F A hydrazine-coordinated Zn—Se complex / DMSO solution (concentration: 15.9 mg / ml in terms of ZnSe)
- solution D (4.412 ml), solution E (5.00 ml) and solution F (14.084 ml) were mixed to obtain a CZTS / DMSO precursor solution (a) (300 ° C./1 min + 500 ° C./5 min.
- the amount of solid content remaining after baking was 6.95 mg / ml).
- 15 ml of the obtained CZTS / DMSO precursor solution (a) was fractionated, and the solvent was distilled off by distillation to obtain a CZTS solid mixture.
- DMSO (5 ml) was added thereto to obtain a concentrated CZTS / DMSO solution (solid content remaining after baking at 300 ° C./1 min + 500 ° C./5 min 100.40 mg / ml).
- a spin coating method is used as a coating method for the coating solution, and the baking condition is soft baking at 375 ° C. for 1 minute on a hot plate, followed by covering the hot plate and annealing at 540 ° C. for 10 minutes. It was.
- FIG. 3 shows the results of XRD (X-ray diffraction measurement) after film formation.
- 2 ⁇ about 27 °, 45 °, and 53 to 54 °, respectively, and strong corresponding to the (112) plane, (220) / (204) plane, and (312) / (116) plane of CZTS.
- a peak is confirmed.
- These include sputtering (R. A. Wibowo et al., Journal of Physics and Chemistry of Solids, 68, 1908-1913 (2007)) and co-evaporation (G. S. Buba et al. Physics, 41, 205305 (2008) and GS Babu et al, Semiconductor Science and Technology, 23, 085023 (2008)), etc., show good agreement with the results of XRD measurement. Formation of a CZTS film was confirmed.
- FIG. 4 shows a sectional view of the obtained film by an electron microscope (SEM).
- the spin coating method was employ
- the solar cell was manufactured so that the substrate, the Mo layer, the CZTS layer (light absorption layer), the CdS layer, the ZnO layer, the ITO layer, the Ni—Al layer, and the MgF 2 layer were sequentially formed from the substrate. Table 1 shows the results of device evaluation of the solar cell thus manufactured.
- FF refers to a fill factor and indicates a value obtained by dividing the maximum output of the solar cell by (open circuit voltage ⁇ short circuit current).
- Voc refers to the open voltage, which is the voltage obtained when the terminal is opened during light irradiation, and indicates the maximum voltage of the solar cell.
- Jsc indicates a short-circuit current, which is a current obtained when a terminal is short-circuited during light irradiation, and indicates the maximum current of the solar cell.
- Rs indicates a series resistance, and Rsh indicates a parallel resistance. From the result of Table 1, it was confirmed that the solar cell manufactured using the coating liquid of this invention shows a favorable characteristic.
- DMSO dimethyl sulfoxide
- the coating solution for forming the light absorption layer of the present invention improved its storage stability and improved the degree of freedom in selecting the coating apparatus. Therefore, the present invention is extremely useful industrially.
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Abstract
Description
本願は、2011年6月10日に米国に出願された、米国特許出願第13/157,923号に基づき優先権を主張し、その内容をここに援用する。
図1に示すように、カルコパイライト系太陽電池またはCZTS系太陽電池は、基板2上に第1の電極3、CIGSまたはCZTS層(光吸収層)4、バッファ層5、i-ZnO層6及び第2の電極7が、この順序で積層されて概略構成されている。なお、バッファ層としては、例えばCdS層や、ZnS層や、InS層等が知られている。
なお、第2の電極7の表面は、例えばMgF2層からなる反射防止膜層8によって覆われることで保護されている。
そして、塗布液を調製する方法としては、溶剤としてヒドラジンを用いる方法と、ヒドラジンを用いない代わりに、溶解促進剤としてアミン類を添加する方法とが知られている(特許文献1及び2参照)。
本発明の光吸収層形成用塗布液は、CZTS系太陽電池の光吸収層の形成に用いられる塗布液であって、(A)ヒドラジン配位Cuカルコゲニド錯体成分と、(B)ヒドラジン配位Snカルコゲニド錯体成分と、(C)ヒドラジン配位Znカルコゲニド錯体成分とを、ジメチルスルホキシドに溶解させてなることを特徴とする。
本実施形態のCZTS系太陽電池の光吸収層の形成に用いられる光吸収層形成用塗布液は、(A)ヒドラジン配位Cuカルコゲニド錯体成分と、(B)ヒドラジン配位Snカルコゲニド錯体成分と、(C)ヒドラジン配位Znカルコゲニド錯体成分とを、ジメチルスルホキシド(DMSO)に溶解させることで得られる。
なお、この光吸収層形成用塗布液には、アミン系溶媒が含有していないことが好ましい。
具体的には、金属Cuと2~4当量のSeとDMSO中にて金属Cuに対し2当量のヒドラジン存在下、室温で3日~1週間撹拌した後、減圧条件下にて残留ヒドラジンを除去し、さらに濃縮を行い、その後に得た濃縮液をろ過することでもヒドラジン配位Cu-Se錯体/DMSO溶液を調製することができる。
以上のようなヒドラジン配位Cuカルコゲニド錯体の生成を化学式に示すと、下記式(1)の通りとなる。
次いで、粗生成物からDMSOにて生成物を抽出(80゜C,1hr)、濃縮し、その後に得た濃縮液をろ過することでもヒドラジン配位Sn-Se錯体/DMSO溶液を調整することができる。
以上のようなヒドラジン配位Znカルコゲニド錯体の生成を化学式に示すと、下記式(3)の通りとなる。
ヒドラジン配位Sbカルコゲニド錯体を生成する場合は、例えばセレン化Sb(Sb2Se3)とカルコゲンを、ヒドラジンに添加して粗生成物を得た後に、粗生成物をDMSOにて抽出し、得られた溶液に貧溶媒を加えて、再結晶させて得る。
以上のようなヒドラジン配位Sbカルコゲニド錯体の生成を化学式に示すと、下記式(4)の通りとなる。
なお、本実施形態では、セレン化Sbを用いて説明したが、セレン化Sbの代わりに、単体のアンチモンを用いてもよく、その場合には、アンチモン(Sb)とカルコゲンの量の比は、1molのアンチモンに対して、4mol以上のカルコゲンを用いることが好ましい。
まず、上述したヒドラジン配位Cuカルコゲニド錯体に、DMSOを加え、室温にて一晩程度撹拌することで、ヒドラジン配位Cuカルコゲニド錯体が溶解したDMSO溶液(第1溶液)を得る。
なお、本実施形態でNaを用いる理由は、光吸収層の膜質(グレインサイズや結晶品質)の向上のためであり、このNa溶液を用いなくても構わない。
以上のようにして、本実施形態の光吸収層形成用塗布液を製造することができる。
本実施形態の光吸収層形成用塗布液には、前記第4溶液を加えてもよい。また、本実施形態の光吸収層形成用塗布液には、前記Na溶液を加えてもよい。
本実施形態のCZTS系太陽電池の製造方法は、基板上に第1の電極を形成する工程と、第1の電極上に光吸収層を形成する工程と、光吸収層上にバッファ層を形成する工程と、バッファ層上に第2の電極を形成する工程と、から概略構成されている。
塗布条件は、所望の膜厚、材料の濃度などに応じて適宜設定すればよい。
また、ディップ法を用いる場合には、塗布液が入った容器中に、基体を浸漬させることにより行うことができ、浸漬回数は1回でもよいし、複数回行ってもよい。
なお、基体上に光吸収層形成用塗布液を塗布した後に、真空乾燥を行っても構わない。
焼成条件は、所望の膜厚、材料の種類などに応じて適宜設定することができる。例えば、ホットプレート上でソフトベーク(前焼成)を行った後に、オーブン中で焼成(アニーリング)を行う2段階工程とすることができる。
これにより、光吸収層が硬化される。
例えば、上記実施形態では、ヒドラジン配位Cuカルコゲニド錯体は、Cuとカルコゲンを、ヒドラジンが添加されたDMSOに溶解させ、得られた溶液に貧溶媒を加えることで再結晶させて得ているが、これに限定されず、どのようなヒドラジン配位Cuカルコゲニド錯体でも構わない。また、最終的には、ヒドラジン配位Cuカルコゲニド錯体が溶解されたDMSOを準備すれば足りるので、例えばCuとカルコゲンをヒドラジンが添加されたDMSOに溶解させ、その後残留ヒドラジンを除去して得た溶液を、そのまま利用しても構わない。
もっとも、上記実施形態のように、ヒドラジン配位Cuカルコゲニド錯体は、DMSOへの溶解性が非常によいので、この錯体を用いることで、従来よりも精度のよい光吸収層形成用塗布液を調製することができる。
(実施例1)
実施例1では、以下の通りに、光吸収層形成用塗布液を調製した。
ろ過液にIPA(合計20ml)を徐々に加え再結晶させることで黒色のヒドラジン配位Cu-Se錯体(2424mg)を得た。
次いで、溶液A(1.904ml)、溶液B(1.255ml)および溶液C(14.400ml)を混合し、CZTS/DMSO前駆体溶液を調製した。
2θ=約27゜,45゜および53~54゜にそれぞれ、CZTSの(112)面、(220)/(204)面、(312)/(116)面に相当する強いピークが確認された。これらはスパッタ法(R. A. Wibowo et al., Journal of Physics and Chemistry of Solids, 68, 1908-1913 (2007))や同時蒸着法(G. S. Babu et al, Journal of Physics D: Applied Physics, 41, 205305 (2008)およびG. S. Babu et al, Semiconductor Science and Technology, 23, 085023 (2008))などの真空法にて報告されているXRD測定結果と良い一致を示すことから、CZTS膜の生成を確認した。
実施例1と同様の方法で、ヒドラジン配位Cu-Se錯体と、ヒドラジン配位Sn-Se錯体と、ヒドラジン配位Zn-Se錯体を得た。その後、ヒドラジン配位Cu-Se錯体と、ヒドラジン配位Sn-Se錯体と、ヒドラジン配位Zn-Se錯体をそれぞれDMSOに溶解させて、ヒドラジン配位Cu-Se錯体/DMSO溶液(濃度:Cu2Se換算76.3mg/ml)(以下「溶液D」と称する)、ヒドラジン配位Sn-Se錯体/DMSO溶液(濃度:SnSe2換算98.4mg/ml)(以下「溶液E」と称する)およびヒドラジン配位Zn-Se錯体/DMSO溶液(濃度:ZnSe換算15.9mg/ml)(以下「溶液F」と称する)を調製した。
得られたCZTS/DMSO前躯体溶液(a)15mlを分取し、蒸留にて溶媒を留去してCZTS固形混合物を得た。これにDMSO5mlを添加し、濃縮CZTS/DMSO溶液を得た(300℃/1min+500℃/5minにて焼成した後に残留する固形分量100.40mg/ml)。
実施例1と同様、2θ=約27゜,45゜および53~54゜にそれぞれ、CZTSの(112)面、(220)/(204)面、(312)/(116)面に相当する強いピークが確認される。これらはスパッタ法(R. A. Wibowo et al., Journal of Physics and Chemistry of Solids, 68, 1908-1913 (2007))や同時蒸着法(G. S. Babu et al, Journal of Physics D: Applied Physics, 41, 205305 (2008)およびG. S. Babu et al, Semiconductor Science and Technology, 23, 085023 (2008))などの真空法にて報告されているXRD測定結果と良い一致を示すことから、CZTS膜の生成を確認した。
実施例1と同様の方法で、ヒドラジン配位Cu-Se錯体と、ヒドラジン配位Sn-Se錯体と、ヒドラジン配位Zn-Se錯体を得た。その後、ヒドラジン配位Cu-Se錯体と、ヒドラジン配位Sn-Se錯体と、ヒドラジン配位Zn-Se錯体をDMSOに溶解させて、光吸収層形成用塗布液を調製した。
この塗布液は、混合モル比が、Cu/(Zn+Sn)=0.81,Zn/Sn=1.22となるように調製した。
また、基板から順に、基板、Mo層、CZTS層(光吸収層)、CdS層、ZnO層、ITO層、Ni-Al層、MgF2層となるように太陽電池を製造した。
このようにして製造した太陽電池のデバイス評価の結果を表1に示す。
表1の結果より、本発明の塗布液を用いて製造した太陽電池は、良好な特性を示すことが確認された。
2 基板
3 第1の電極
4 CZTS層(光吸収層)
5 バッファ層
6 i-ZnO層
7 第2の電極
Claims (13)
- CZTS系太陽電池の光吸収層の形成に用いられる塗布液であって、
(A)ヒドラジン配位Cuカルコゲニド錯体成分と、(B)ヒドラジン配位Snカルコゲニド錯体成分と、(C)ヒドラジン配位Znカルコゲニド錯体成分とを、ジメチルスルホキシドに溶解させてなる光吸収層形成用塗布液。 - 前記光吸収層形成用塗布液が、アミン系溶媒を含有しない請求項1に記載の光吸収層形成用塗布液。
- 前記(A)ヒドラジン配位Cuカルコゲニド錯体成分が、CuまたはCu2Seとカルコゲンとを、ヒドラジン存在下、ジメチルスルホキシド中で反応させ、得られた溶液に貧溶媒を加えるもしくは濃縮およびろ過することで得られたものであることを特徴とする請求項1または2に記載の光吸収層形成用塗布液。
- 前記(B)ヒドラジン配位Snカルコゲニド錯体成分が、Sn、SnSeおよびSnSe2からなる群より選ばれる少なくとも1種とカルコゲンとを、ヒドラジンに添加して粗生成物を得た後に、該粗生成物をジメチルスルホキシドにて抽出して得られたものである請求項1~3のいずれか一項に記載の光吸収層形成用塗布液。
- 前記(C)ヒドラジン配位Znカルコゲニド錯体成分が、ZnまたはZnSeとカルコゲンとを、ヒドラジンの存在下混合して粗生成物を得た後に、該粗生成物をジメチルスルホキシドにて抽出して得られたものである請求項1~4のいずれか一項に記載の光吸収層形成用塗布液。
- 前記貧溶媒が、アルコール系溶媒である請求項3に記載の光吸収層形成用塗布液。
- 前記カルコゲンが、硫黄またはセレンである請求項3~6のいずれか一項に記載の光吸収層形成用塗布液。
- カルコパイライト系またはCZTS系太陽電池の光吸収層の形成に用いられる塗布液の製造方法であって、
ヒドラジン配位Cuカルコゲニド錯体が溶解されたジメチルスルホキシドからなる第1溶液を準備する工程と、
ヒドラジン配位Snカルコゲニド錯体をジメチルスルホキシドに溶解させて第2溶液を調製する工程と、
ヒドラジン配位Znカルコゲニド錯体をジメチルスルホキシドに溶解させて第3溶液を調製する工程と、
前記第1溶液と、前記第2溶液と、前記第3溶液と、を混合する工程と、を有することを特徴とする光吸収層形成用塗布液の製造方法。 - CuまたはCu2Seとカルコゲンとを、ヒドラジン存在下、ジメチルスルホキシド中で反応させ、得られた溶液に貧溶媒を加えるもしくは濃縮およびろ過することで、ヒドラジン配位Cuカルコゲニド錯体を得る請求項8に記載の光吸収層形成用塗布液の製造方法。
- Sn、SnSeおよびSnSe2からなる群より選ばれる少なくとも1種とカルコゲンとを、ヒドラジンに添加して粗生成物を得た後に、該粗生成物をジメチルスルホキシドにて抽出することで、前記ヒドラジン配位Snカルコゲニド錯体を得る請求項8または9に記載の光吸収層形成用塗布液の製造方法。
- ZnまたはZnSeとカルコゲンとを、ヒドラジンの存在下混合して粗生成物を得た後に、該粗生成物をジメチルスルホキシドにて抽出することで、前記ヒドラジン配位Znカルコゲニド錯体を得る請求項8~10のいずれか一項に記載の光吸収層形成用塗布液の製造方法。
- 前記貧溶媒が、アルコール系溶媒である請求項9に記載の光吸収層形成用塗布液の製造方法。
- 前記カルコゲンが、硫黄またはセレンである請求項9~12のいずれか一項に記載の光吸収層形成用塗布液の製造方法。
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CN201280027751.1A CN103597605A (zh) | 2011-06-10 | 2012-06-08 | 光吸收层形成用涂布液及光吸收层形成用涂布液的制造方法 |
EP12796125.8A EP2706577A4 (en) | 2011-06-10 | 2012-06-08 | A liquid for forming a light-absorbing layer and a process for producing the liquid for forming a light-absorbing layer |
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JP5938486B2 (ja) * | 2013-11-07 | 2016-06-22 | 積水化学工業株式会社 | 半導体形成用塗布液、半導体薄膜、薄膜太陽電池及び薄膜太陽電池の製造方法 |
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US9368660B2 (en) | 2011-08-10 | 2016-06-14 | International Business Machines Corporation | Capping layers for improved crystallization |
CN106098845A (zh) * | 2016-06-29 | 2016-11-09 | 郭舒洋 | 一种高结晶度铜锌锡硫薄膜的制备方法 |
JP2019087745A (ja) * | 2017-11-08 | 2019-06-06 | 東京応化工業株式会社 | 均一系塗布液及びその製造方法 |
CN108588838B (zh) * | 2018-03-23 | 2019-12-06 | 桂林电子科技大学 | 一种制备具有高热电性能的SnSe多晶块体的方法 |
KR102512512B1 (ko) * | 2020-09-03 | 2023-03-22 | 한국과학기술연구원 | 은 원소가 혼입된 찰코파이라이트 화합물계 박막 및 그 제조 방법 |
CN113979468B (zh) * | 2021-12-09 | 2023-05-09 | 山东中鸿新能源科技有限公司 | 一种太阳能电池组件用CZTS(Se)系纳米粉体的制备方法 |
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US20120313044A1 (en) | 2012-12-13 |
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