WO2012114803A1 - Cadmium telluride powder for solar cells, cadmium telluride film for solar cells, and solar cell - Google Patents
Cadmium telluride powder for solar cells, cadmium telluride film for solar cells, and solar cell Download PDFInfo
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- WO2012114803A1 WO2012114803A1 PCT/JP2012/051245 JP2012051245W WO2012114803A1 WO 2012114803 A1 WO2012114803 A1 WO 2012114803A1 JP 2012051245 W JP2012051245 W JP 2012051245W WO 2012114803 A1 WO2012114803 A1 WO 2012114803A1
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- cdte
- solar cell
- film
- powder
- cadmium telluride
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- 239000000843 powder Substances 0.000 title claims abstract description 90
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title claims description 184
- 239000012535 impurity Substances 0.000 claims abstract description 52
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 15
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 11
- 229910004613 CdTe Inorganic materials 0.000 claims abstract 4
- 238000004519 manufacturing process Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 150000002902 organometallic compounds Chemical class 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 claims description 7
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 239000004065 semiconductor Substances 0.000 abstract description 25
- 239000010408 film Substances 0.000 description 87
- 239000010410 layer Substances 0.000 description 41
- 239000000758 substrate Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229910052976 metal sulfide Inorganic materials 0.000 description 12
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- MRPWWVMHWSDJEH-UHFFFAOYSA-N antimony telluride Chemical compound [SbH3+3].[SbH3+3].[TeH2-2].[TeH2-2].[TeH2-2] MRPWWVMHWSDJEH-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- RYCMMAQVUSKGFZ-UHFFFAOYSA-L cadmium(2+);n,n-dibutylcarbamodithioate Chemical compound [Cd+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC RYCMMAQVUSKGFZ-UHFFFAOYSA-L 0.000 description 1
- HCXZJUCLTQLEBI-UHFFFAOYSA-L cadmium(2+);n,n-dimethylcarbamodithioate Chemical compound [Cd+2].CN(C)C([S-])=S.CN(C)C([S-])=S HCXZJUCLTQLEBI-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- GNFABDZKXNKQKN-UHFFFAOYSA-N tris(prop-2-enyl)phosphane Chemical compound C=CCP(CC=C)CC=C GNFABDZKXNKQKN-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- 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
- H01L21/02551—Group 12/16 materials
- H01L21/02562—Tellurides
-
- 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
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
- H01L21/02579—P-type
-
- 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
- H01L21/02587—Structure
- H01L21/0259—Microstructure
- H01L21/02601—Nanoparticles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
-
- 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
- Y02E10/543—Solar cells from Group II-VI materials
-
- 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 CdTe powder used as a raw material for forming a cadmium telluride (CdTe) film, a cadmium telluride (CdTe) film for a solar cell using the CdTe powder, and a solar cell.
- CdTe cadmium telluride
- CdTe cadmium telluride
- Solar power generation is power generation using solar cells, and solar cells directly convert light energy from the sun into electricity. Therefore, solar power generation is expected as an alternative energy source for fossil energy, and is attracting more attention as an energy source for dealing with global environmental problems. In order to put solar cells into practical use in the future, it is necessary to increase the light conversion efficiency by which the solar cells convert light energy into electrical energy, and to further improve efficiency.
- Solar cells include at least one pair of semiconductor films having p-type and n-type characteristics, and those using semiconductors such as silicon (Si) and compound are in practical use.
- CdTe has a forbidden band width (band gap) of about 1.5 eV, and has high consistency with the spectrum of sunlight. Therefore, CdTe can be said to be an optimum material for absorbing solar light energy. Therefore, CdTe is used as an effective material for forming a photoelectric conversion layer for solar cells having high light conversion efficiency.
- the CdTe film is mainly formed using a close sublimation (CSS) method or a vapor transport deposition (VTD) method. Is done. At this time, the CdTe raw material is used as a raw material for forming the CdTe film.
- CCS close sublimation
- VTD vapor transport deposition
- These film forming methods are methods in which a raw material powder containing CdTe as a main component is heated and vaporized and supplied to a substrate, and CdTe is formed on a thin film forming substrate.
- CdTe exhibits p-type conductivity even when no impurity is added (doping).
- the carrier concentration is low, when a non-doped film is used as the p-type semiconductor of the solar cell, The light conversion efficiency was quite low.
- a powder or raw material in which a compound containing a group I and / or group V element or an organometallic compound is mixed as an additive to a powder containing CdTe as a main component is added to a powder or a paste by adding a solvent or a binder.
- a method for producing a CdTe film is proposed in which a CdTe film is produced by using a material coated on a support (CdTe paste) as a raw material for the CSS method, and the carrier concentration is increased (see, for example, Patent Document 1).
- the present invention has been made in view of the above, and an object thereof is to provide a CdTe powder for a solar cell, a CdTe film for a solar cell, and a solar cell capable of producing a CdTe film containing an acceptor impurity.
- CdTe powder for solar cells CdTe films for solar cells, and solar cells.
- a CdTe film obtained by using a raw material powder containing a predetermined amount of acceptor impurities and containing CdTe as a main component is used as a p-type semiconductor of a solar cell.
- the relationship between the solar cell and the light conversion efficiency was clarified.
- the CdTe powder for solar cells of the present invention is characterized by containing cadmium, tellurium, and acceptor impurities, and having an impurity concentration of 1 ⁇ 10 16 cm ⁇ 3 or more and 1 ⁇ 10 20 cm ⁇ 3 or less.
- the acceptor impurity is at least one element selected from the group consisting of antimony, arsenic, bismuth, phosphorus, nitrogen, lithium, potassium, sodium, rubidium, copper, silver, gold, and at least one of the groups It is preferably a metal compound containing one element or at least one of an organometallic compound containing at least one element of the group.
- the CdTe film for solar cells of the present invention is characterized in that it contains cadmium, tellurium, and acceptor impurities, and has an impurity concentration of 1 ⁇ 10 16 cm ⁇ 3 or more and 1 ⁇ 10 20 cm ⁇ 3 or less.
- the acceptor impurity is at least one element selected from the group consisting of antimony, arsenic, bismuth, phosphorus, nitrogen, lithium, potassium, sodium, rubidium, copper, silver, gold, and at least one of the groups It is preferably a metal compound containing one element or at least one of an organometallic compound containing at least one element of the group.
- the solar cell of the present invention includes the CdTe film for solar cell described above.
- the method for producing a CdTe film for a solar cell of the present invention uses a cadmium telluride powder containing acceptor impurities and having an impurity concentration of 1 ⁇ 10 16 cm ⁇ 3 or more and 1 ⁇ 10 20 cm ⁇ 3 or less as a raw material. It is characterized by producing.
- the CdTe powder has at least one element selected from the group consisting of antimony, arsenic, bismuth, phosphorus, nitrogen, lithium, potassium, sodium, rubidium, copper, silver, and gold as the acceptor impurity. It is preferable to use at least one of a metal compound containing at least one element of the group, or an organometallic compound containing at least one element of the group.
- the present invention it is possible to produce a CdTe film containing acceptor impurities. As a result, a CdTe film having a high carrier concentration can be obtained. Therefore, when the CdTe film is used as a p-type semiconductor of a solar cell, the light conversion efficiency of the solar cell can be further improved.
- FIG. 1 is a cross-sectional view showing an example of a reaction apparatus used for producing a CdTe film for a solar cell.
- FIG. 2 is a schematic cross-sectional view showing an example of a solar cell.
- the CdTe powder for solar cell according to this embodiment contains cadmium (Cd), tellurium (Te), and acceptor impurities, and has an impurity concentration of 1 ⁇ 10 16 cm ⁇ 3 or more and 1 ⁇ 10 20 cm ⁇ 3 or less.
- the solar cell CdTe powder according to the present embodiment contains Cd and Te as main components.
- the solar cell CdTe powder according to this embodiment is obtained by mixing acceptor impurities in advance with a CdTe single crystal powder.
- the acceptor impurity is an impurity element contained in the solar cell CdTe powder according to the present embodiment other than Cd and Te.
- an impurity is an element added for the purpose of controlling the polarity (p-type, n-type) and carrier density of a semiconductor.
- An acceptor impurity refers to an additive substance that can form holes in a p-type semiconductor (a state in which electrons are insufficient).
- Acceptor impurities include, for example, antimony (Sb), arsenic (As), bismuth (Bi), phosphorus (P), nitrogen (N), lithium (Li), potassium (K), sodium (Na), and rubidium (Rb).
- At least one element selected from the group consisting of copper (Cu), silver (Ag), and gold (Au), a metal compound containing at least one element of the group, or an organic metal containing at least one element of the group At least one such as a compound is shown.
- An example of the metal compound is antimony telluride.
- the organometallic compound is, for example, at least one selected from the group consisting of triphenylantimony, antimony octylate, triphenylbismuth, triphenylphosphine, triphenyl phosphate, triphenyl phosphite, triallylphosphine, and triallylamine.
- the acceptor impurity is preferably P, N, or Sb, and particularly preferably Sb.
- acceptor impurities generally emit electrons or generate holes.
- the acceptor impurity in the present embodiment generates holes and takes charge of electrical conduction in the p-type semiconductor.
- the solar cell CdTe powder according to the present embodiment contains acceptor impurities, and when a CdTe film is formed using the solar cell CdTe powder according to the present embodiment, holes in the CdTe polycrystal containing the acceptor impurity are formed. Many carriers can be formed. As a result, a p-type semiconductor with a high carrier concentration can be manufactured.
- the impurity concentration of the solar cell CdTe powder according to this embodiment is 1 ⁇ 10 16 cm ⁇ 3 or more and 1 ⁇ 10 20 cm ⁇ 3 or less.
- the impurity concentration is more preferably 1 ⁇ 10 17 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3 , and still more preferably 1 ⁇ 10 18 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3 .
- a higher carrier concentration is preferable, but since there is a correlation with the n-type carrier concentration of the pn junction partner, a carrier concentration in the above range is preferable in this embodiment.
- a CdTe film containing acceptor impurities can be obtained by including a predetermined amount of acceptor impurities in CdTe, as will be described later.
- a CdTe film having a high carrier concentration is obtained. Therefore, when the CdTe film produced from the CdTe powder for solar cell according to this embodiment is used as a p-type semiconductor layer of the solar cell, the light conversion efficiency of the solar cell is increased. Further improvement can be achieved. Further, by adjusting the amount of acceptor impurities added to CdTe, the carrier concentration of CdTe powder can be increased and the carrier concentration can be adjusted.
- a powder or raw material obtained by mixing a powder mainly composed of CdTe and an additive is added to a solvent or a binder to form a liquid or a paste, which is applied on a support (CdTe
- CdTe In the case of producing a CdTe film using a paste), it is necessary to print the CdTe paste on a support, apply it, and then fire it, so that the number of steps required to produce the CdTe film increases and the cost increases.
- the CdTe film can be formed by directly heating the CdTe powder in a powder state.
- a process such as applying a paste as a raw material of the CdTe film on the support becomes unnecessary. Since the CdTe powder can be used as a raw material for forming the CdTe film in a powder state, the cost required for producing the CdTe film can be reduced.
- the solar cell CdTe film is produced using the solar cell CdTe powder according to the present embodiment as a raw material. Since the CdTe powder for solar cells according to this embodiment is a CdTe polycrystal containing a predetermined amount of acceptor impurities in CdTe as described above, many holes are generated in the CdTe from the acceptor impurities. Therefore, the CdTe film for solar cells formed using the CdTe powder for solar cells according to this embodiment has a high carrier concentration. For this reason, as will be described later, the solar cell CdTe film using the solar cell CdTe film as a photoelectric conversion layer can be a solar cell having high light conversion efficiency.
- FIG. 1 is a cross-sectional view showing an example of a reaction apparatus used for producing a CdTe film for a solar cell.
- the reaction apparatus 10 includes a chamber 11, a pair of susceptors 12 and 13, and a heater 14.
- the chamber 11 is a tube made of, for example, quartz.
- the pair of susceptors 12 and 13 are provided in the chamber 11 and are made of carbon or the like.
- the heater 14 is not particularly limited as long as the inside of the chamber 11 can be heated, and examples thereof include an infrared lamp heater.
- a pair of susceptors 12 and 13 are disposed in the chamber 11, and the CdTe powder for solar cells according to the present embodiment is disposed on the susceptor 12 as the semiconductor material 15.
- the semiconductor material 15 As the semiconductor material 15, the CdTe powder for solar cell according to the present embodiment is used.
- Spacers 16 are provided at both ends of the susceptor 12.
- the substrate 17 is arranged close to the semiconductor material 15 and the substrate 17 with a gap of about 0.1 mm to several mm through the spacer 16.
- the surface of the substrate 17 opposite to the semiconductor material 15 side is covered with the susceptor 13.
- An inert gas 18 is supplied into the chamber 11, and air or the inert gas 18 in the chamber 11 is sucked by a rotary pump 19 to form a vacuum state.
- the inert gas 18 include argon gas and nitrogen gas.
- the atmosphere in the chamber 11 is replaced with an inert gas 18 to keep the inside of the chamber 11 at about 133.32 Pa to 2666.44 Pa.
- the susceptors 12 and 13 are heated to a temperature range of about 400 ° C. to 800 ° C. by the heater 14, and the temperature of the semiconductor material 15 is set higher than that of the substrate 17 and is held for a certain time.
- CdTe When the semiconductor material 15 is heated in the inert gas 18, CdTe is vaporized into Cd + 1 / 2Te 2 vapor and scattered from the semiconductor material 15 on the susceptor 12, and CdTe is formed on the substrate 17. Similarly, acceptor impurities contained in the CdTe powder are also vaporized and scattered from the semiconductor material 15 on the susceptor 12, and a carrier substance is formed on the substrate 17. Thereby, a CdTe film for a solar cell containing acceptor impurities and CdTe is formed on the surface of the substrate 17.
- a CdTe powder for a solar cell is produced using a CSS method using CdTe powder as a raw material.
- the present embodiment is not limited to this and uses a VTD method or the like.
- a CdTe film for a solar cell may be produced.
- FIG. 2 is a schematic cross-sectional view showing an example of a solar cell.
- the solar cell 20 includes a translucent heat-resistant substrate 21, a translucent conductive film 22, a metal sulfide layer 23, a CdTe layer 24, an ohmic electrode 25, a metal electrode (collector). Electrode) 26.
- the translucent heat-resistant substrate 21 has a property of transmitting light having a wavelength that can contribute to photoelectric conversion in the semiconductor layer.
- a substrate having translucency and strength is used, and examples thereof include borosilicate glass and soda lime glass.
- the translucent conductive film 22 is provided on the translucent heat-resistant substrate 21.
- the light-transmitting conductive film 22 include a film made of a tin oxide such as a tin oxide film and an indium tin oxide film, and a zinc oxide film. Among these, a tin oxide film is particularly preferable.
- the film thickness of the translucent conductive film 22 is preferably, for example, 100 nm or more and 1000 nm or less from the viewpoint of achieving both light transmittance and conductivity.
- the metal sulfide layer 23 is laminated on the translucent conductive film 22.
- the metal sulfide layer 23 is a layer containing a metal sulfide and functions as an n-type semiconductor layer.
- the metal sulfide include cadmium sulfide and zinc sulfide. These may be used alone or in combination. Of these, cadmium sulfide and a mixture of cadmium sulfide and zinc sulfide are preferable.
- the film thickness of the metal sulfide layer is preferably, for example, 50 nm or more and 500 nm or less.
- the CdTe layer 24 is laminated on the metal sulfide layer 23.
- the CdTe layer 24 is formed using a solar cell CdTe film formed by including the solar cell CdTe powder according to this embodiment, and functions as a p-type semiconductor layer.
- the thickness of the CdTe layer 24 is preferably, for example, 1 ⁇ m or more and 10 ⁇ m or less from the viewpoint of achieving both light absorption efficiency and conductivity.
- the ohmic electrode 25 is an electrode provided in the CdTe layer 24 and in ohmic contact with the CdTe layer 24.
- the ohmic electrode 25 is formed of a material such as carbon or nickel, for example.
- the metal electrode 26 is provided on the electrode 25 and the exposed translucent conductive film 22.
- the metal electrode 26 is formed of, for example, a mixture containing one or more of aluminum (Al), silver (Ag), and indium (In).
- the translucent heat-resistant substrate 21 is set to a predetermined dimension (for example, 100 mm ⁇ 100 mm ⁇ 1 mm), and then the translucent conductive film having a predetermined film thickness (for example, 600 nm) is formed on the translucent heat-resistant substrate 21.
- a film 22 is provided.
- a metal having a predetermined film thickness (for example, 50 nm) is formed on the translucent conductive film 22 by inducing a gas generated by heating cadmium dimethyldithiocarbamate to about 280 ° C. on the translucent conductive film 22 for 60 seconds.
- a sulfide layer 23 is formed.
- a CdTe layer 24 having a predetermined film thickness (for example, 5 ⁇ m) is formed on the metal sulfide layer 23.
- the substrate 17 shown in FIG. The CdTe layer 24 is formed using the translucent heat-resistant substrate 21 on which the physical layer 23 is formed.
- the metal sulfide layer 23 and the CdTe layer 24 around the portion that becomes the light receiving surface are peeled off by using, for example, laser scribe (wavelength 1.05 ⁇ m), and the translucent conductive film 22 is exposed.
- An ohmic electrode 25 is formed on the CdTe layer 24, and a metal electrode 26 is formed on the ohmic electrode 25 and the exposed translucent conductive film 22. Thereby, the solar cell 20 is obtained.
- the solar cell 20 uses a solar cell CdTe film formed using the solar cell CdTe powder according to the present embodiment for the CdTe layer 24. For this reason, since the carrier concentration in the CdTe layer 24 is high, the open-circuit voltage and the fill factor of the solar cell 20 are improved, and the light conversion efficiency can be improved.
- the CdTe layer 24 has a single-layer structure, but the solar cell 20 is not limited to the single-layer structure CdTe layer 24, and may have a multilayer structure.
- the solar cell CdTe powder according to the present embodiment can be used as a photoelectric conversion layer of a solar cell by forming a CdTe film, but the present embodiment is not particularly limited to this, The present invention can also be suitably used for manufacturing integrated circuits using various semiconductor materials.
- Example 1> (Preparation of CdTe powder containing Sb) 6N-Cd: 716 g, 6N-Te: 813 g, Sb 2 Te 3 : 4 mg were put into a PBN boat, respectively, and then the PBN boat was placed in a quartz ampule, and the inside of the quartz ampule was vacuumed by the rotary pump 19. Then, nitrogen gas was introduced into the quartz ampule to keep it at 1 ⁇ 10 ⁇ 4 Pa to 5 ⁇ 10 ⁇ 4 Pa, and then sealed with a hydrogen burner. This quartz ampoule was raised to about 1200 ° C. with a heater to produce CdTe polycrystal.
- the produced polycrystalline CdTe was pulverized to obtain a CdTe powder.
- the Sb concentration of the obtained CdTe powder was about 1 ⁇ 10 16 cm ⁇ 3 .
- generated CdTe powder was measured using the glow discharge mass spectrometry (Glow Discharge Mass Spectrometry: GDMS).
- An organic solvent solution of dimethyltin dichloride was sprayed on a glass substrate made of borosilicate glass.
- a glass substrate coated by spraying an organic solvent solution of dimethyltin dichloride is thermally decomposed on the glass substrate in a muffle furnace heated to 450 ° C. in an air atmosphere to form SnO having a thickness of about 500 nm.
- a transparent conductive film consisting of 2 was prepared.
- an organic solvent solution of cadmium dibutyldithiocarbamate was sprayed on a transparent conductive film on a glass substrate and applied.
- a CdS film having a thickness of about 100 nm was formed on the transparent conductive film by pyrolysis.
- a CdTe film having a thickness of about 5 ⁇ m was formed on the CdS film.
- the method for producing the CdTe layer on the CdS film was performed in the same manner as in the case of producing the CdTe layer 24 on the metal sulfide layer 23 shown in FIG.
- a carbon film that was an ohmic electrode for the CdTe film was formed, and an Ag electrode was formed on the carbon film.
- an Ag electrode was formed as a current collector on the CdS film side. This produced the solar cell element.
- Example 2 (Preparation of CdTe powder containing Sb) Example 1 except that the amount of Cd, Te, Sb 2 Te 3 blended when producing CdTe powder was changed to 6N-Cd: 716 g, 6N-Te: 813 g, Sb 2 Te 3 : 40 mg I went there.
- the Sd concentration of the CdTe powder produced in this example was about 1 ⁇ 10 17 cm ⁇ 3 .
- Example 3 (Preparation of CdTe powder containing Sb) Example 1 except that the blending amounts of Cd, Te, Sb 2 Te 3 in preparing CdTe powder were changed to 6N-Cd: 716 g, 6N-Te: 813 g, and Sb 2 Te 3 : 0.14 g. And performed in the same manner.
- the Sd concentration of the CdTe powder produced in this example was about 1 ⁇ 10 18 cm ⁇ 3 .
- a solar cell element was produced in the same manner as in Example 1.
- Example 4 (Preparation of CdTe powder containing Sb) Example 1 except that the blending amounts of Cd, Te, and Sb 2 Te 3 at the time of preparing the CdTe powder were changed to 6N—Cd: 716 g, 6N—Te: 813 g, and Sb 2 Te 3 : 4.17 g. And performed in the same manner.
- the Sd concentration of the CdTe powder produced in this example was about 1 ⁇ 10 19 cm ⁇ 3 .
- a solar cell element was produced in the same manner as in Example 1.
- Example 5 (Preparation of CdTe powder containing Sb) Example 1 except that the blending amounts of Cd, Te, and Sb 2 Te 3 in preparing CdTe powder were changed to 6N—Cd: 716 g, 6N—Te: 813 g, and Sb 2 Te 3 : 41.7 g. And performed in the same manner.
- the Sb concentration of the CdTe powder produced in this example was about 1 ⁇ 10 20 cm ⁇ 3 .
- a solar cell element was produced in the same manner as in Example 1.
- Example 2 (Preparation of CdTe powder containing Sb) Example 1 except that the blending amounts of Cd, Te, and Sb 2 Te 3 in preparing CdTe powder were changed to 6N-Cd: 716 g, 6N-Te: 813 g, and Sb 2 Te 3 : 162.2 g. And performed in the same manner.
- the Sb concentration of the produced CdTe powder was about 1 ⁇ 10 21 cm ⁇ 3 .
- a solar cell element was produced in the same manner as in Example 1.
- Table 1 shows the measurement results of the Sb concentration and the film thickness d of the CdTe film in Examples 1 to 5 and Comparative Examples 1 and 2.
- the light conversion efficiency of the solar cell element obtained using the CdTe powder having an Sb concentration of 1 ⁇ 10 16 cm ⁇ 3 was about 14% (see Example 1). Moreover, the light conversion efficiency of the solar cell element obtained using the CdTe powder having an Sb concentration of 1 ⁇ 10 17 cm ⁇ 3 was about 15% (see Example 2). Moreover, the light conversion efficiency of the solar cell element obtained using the CdTe powder having an Sb concentration of 1 ⁇ 10 18 cm ⁇ 3 was about 16% (see Example 3). Moreover, the light conversion efficiency of the solar cell element obtained using the CdTe powder having an Sb concentration of 1 ⁇ 10 19 cm ⁇ 3 was about 15% (see Example 4).
- the light conversion efficiency of the solar cell element obtained using the CdTe powder having an Sb concentration of 1 ⁇ 10 20 cm ⁇ 3 was about 13% (see Example 5). Therefore, it was confirmed that the light conversion efficiency of the solar cell element obtained using the CdTe powder decreases as the Sb concentration contained in CdTe increases. This is considered to be due to the fact that the light conversion efficiency was lowered by Sb in which no hole was formed from Sb.
- the light conversion efficiency of the solar cell element obtained using the Sb concentration of 1 ⁇ 10 15 cm ⁇ 3 or 1 ⁇ 10 21 cm ⁇ 3 CdTe powder was about 5% (see Comparative Examples 1 and 2). ). Therefore, it can be said that the light conversion efficiency of the solar cell obtained using the CdTe powder can be increased by setting the Sb concentration contained in the CdTe powder within an appropriate predetermined range.
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Abstract
A CdTe powder for solar cells of the present invention contains Cd, Te and an acceptor impurity, and the impurity concentration is from 1 × 1016 cm-3 to 1 × 1020 cm-3 (inclusive). Consequently, a CdTe film into which an acceptor impurity is added can be produced, so that the light conversion efficiency of a solar cell can be further improved when the CdTe film is used as a p-type semiconductor layer of the solar cell.
Description
本発明は、テルル化カドミウム（ＣｄＴｅ）膜を形成するための原料として用いるＣｄＴｅ粉末、そのＣｄＴｅ粉末を用いた太陽電池用テルル化カドミウム（ＣｄＴｅ）膜および太陽電池に関する。
The present invention relates to a CdTe powder used as a raw material for forming a cadmium telluride (CdTe) film, a cadmium telluride (CdTe) film for a solar cell using the CdTe powder, and a solar cell.
太陽光発電は太陽電池を使った発電であり、太陽電池は、太陽からの光エネルギーを直接電気に変換する。そのため、太陽光発電は化石エネルギーの代替エネルギー源として期待されており、地球環境問題への対応エネルギー源としてさらに注目されている。今後、太陽電池を本格的に実用化するためには、太陽電池が光エネルギーを電気エネルギーに変換する光変換効率を高め、更なる効率化を図る必要がある。
Solar power generation is power generation using solar cells, and solar cells directly convert light energy from the sun into electricity. Therefore, solar power generation is expected as an alternative energy source for fossil energy, and is attracting more attention as an energy source for dealing with global environmental problems. In order to put solar cells into practical use in the future, it is necessary to increase the light conversion efficiency by which the solar cells convert light energy into electrical energy, and to further improve efficiency.
太陽電池は、ｐ型およびｎ型の特性を持った少なくとも１対の半導体膜を備え、シリコン（Ｓｉ）系、化合物系などの半導体を用いたものが実用化されている。ＣｄＴｅの禁制帯幅（バンドギャップ）は約１．５ｅＶであり、太陽光のスペクトルとの整合性が高いため、ＣｄＴｅは太陽の光エネルギーを吸収するためには最適な材料といえる。そのため、ＣｄＴｅは高い光変換効率を有する太陽電池用の光電変換層を形成するための有力な材料として用いられている。
Solar cells include at least one pair of semiconductor films having p-type and n-type characteristics, and those using semiconductors such as silicon (Si) and compound are in practical use. CdTe has a forbidden band width (band gap) of about 1.5 eV, and has high consistency with the spectrum of sunlight. Therefore, CdTe can be said to be an optimum material for absorbing solar light energy. Therefore, CdTe is used as an effective material for forming a photoelectric conversion layer for solar cells having high light conversion efficiency.
ＣｄＴｅを含むＣｄＴｅ膜で太陽電池用の光電変換層を形成する場合、ＣｄＴｅ膜は主として近接昇華（Close Spaced Sublimation：ＣＳＳ）法あるいは気相輸送堆積（Vapor Transport Deposition：ＶＴＤ）法を用いて成膜される。このとき、ＣｄＴｅ原料がＣｄＴｅ膜の成膜用の原料として用いられる。これらの成膜方法は、ＣｄＴｅを主成分として含む原料粉末を加熱して蒸気にして基板に供給し、薄膜形成用基板上にＣｄＴｅを成膜する方法である。
When a photoelectric conversion layer for a solar cell is formed using a CdTe film containing CdTe, the CdTe film is mainly formed using a close sublimation (CSS) method or a vapor transport deposition (VTD) method. Is done. At this time, the CdTe raw material is used as a raw material for forming the CdTe film. These film forming methods are methods in which a raw material powder containing CdTe as a main component is heated and vaporized and supplied to a substrate, and CdTe is formed on a thin film forming substrate.
ＣｄＴｅは、特に、不純物添加（ドーピング）をしない場合であっても、ｐ型の電導性を示すが、キャリア濃度が低いため、ドーピングしない膜を太陽電池のｐ型半導体として用いると、太陽電池の光変換効率はかなり低いものであった。
In particular, CdTe exhibits p-type conductivity even when no impurity is added (doping). However, since the carrier concentration is low, when a non-doped film is used as the p-type semiconductor of the solar cell, The light conversion efficiency was quite low.
従来は、ＣｄＴｅを主成分とする粉末にＩ族および／あるいはＶ族元素を含む化合物または有機金属化合物を添加剤として混入した粉末原料に、溶媒もしくは粘結剤を加えて液状またはペースト状にし、支持体上に塗布したもの（ＣｄＴｅペースト）をＣＳＳ法の原料として用いてＣｄＴｅ膜を製造し、キャリア濃度を高めるＣｄＴｅ膜の製造方法が提案されている（例えば、特許文献１参照）。
Conventionally, a powder or raw material in which a compound containing a group I and / or group V element or an organometallic compound is mixed as an additive to a powder containing CdTe as a main component is added to a powder or a paste by adding a solvent or a binder. A method for producing a CdTe film is proposed in which a CdTe film is produced by using a material coated on a support (CdTe paste) as a raw material for the CSS method, and the carrier concentration is increased (see, for example, Patent Document 1).
しかしながら、ＣｄＴｅペーストを耐熱性基板上に印刷法により作製する方法は工程が多く、手間と費用が掛かり、膜の厚さによって成長可能時間が制約されるため、長時間の連続成長が困難である、という問題があった。
However, a method for producing a CdTe paste on a heat-resistant substrate by a printing method involves many steps, is time-consuming and expensive, and the growth time is limited by the thickness of the film, so that long-term continuous growth is difficult. There was a problem.
本発明は、上記に鑑みてなされたものであって、アクセプタ不純物を含むＣｄＴｅ膜を製造することができる太陽電池用ＣｄＴｅ粉末、太陽電池用ＣｄＴｅ膜および太陽電池を提供することを目的とする。
The present invention has been made in view of the above, and an object thereof is to provide a CdTe powder for a solar cell, a CdTe film for a solar cell, and a solar cell capable of producing a CdTe film containing an acceptor impurity.
上述した課題を解決し、目的を達成するために、本発明者らは太陽電池用ＣｄＴｅ粉末、太陽電池用ＣｄＴｅ膜および太陽電池について鋭意研究をした。その結果、アクセプタ不純物を含むＣｄＴｅ多結晶の不純物濃度に着目し、所定量のアクセプタ不純物を含み、ＣｄＴｅを主成分とする原料粉末を使用して得たＣｄＴｅ膜を太陽電池のｐ型半導体として用いた際の太陽電池の光変換効率との関係について解明した。この得られた知見に基づいて、所定量のアクセプタ不純物を含むＣｄＴｅを用いてＣｄＴｅ膜を作製することで、得られるＣｄＴｅ膜を太陽電池のｐ型半導体として用いた際に太陽電池の光変換効率を向上させることができることを見出した。本発明は、係る知見に基づいて完成されたものである。
In order to solve the above-described problems and achieve the object, the present inventors have conducted intensive research on CdTe powder for solar cells, CdTe films for solar cells, and solar cells. As a result, paying attention to the impurity concentration of CdTe polycrystal containing acceptor impurities, a CdTe film obtained by using a raw material powder containing a predetermined amount of acceptor impurities and containing CdTe as a main component is used as a p-type semiconductor of a solar cell. The relationship between the solar cell and the light conversion efficiency was clarified. Based on the obtained knowledge, by producing a CdTe film using CdTe containing a predetermined amount of acceptor impurities, the light conversion efficiency of the solar cell when the resulting CdTe film is used as a p-type semiconductor of the solar cell. It was found that can be improved. The present invention has been completed based on such knowledge.
本発明の太陽電池用ＣｄＴｅ粉末は、カドミウムとテルルとアクセプタ不純物とを含み、不純物濃度が１×１０16ｃｍ-3以上１×１０20ｃｍ-3以下であることを特徴とする。
The CdTe powder for solar cells of the present invention is characterized by containing cadmium, tellurium, and acceptor impurities, and having an impurity concentration of 1 × 10 16 cm −3 or more and 1 × 10 20 cm −3 or less.
本発明の好ましい態様として、前記アクセプタ不純物が、アンチモン、砒素、ビスマス、リン、窒素、リチウム、カリウム、ナトリウム、ルビジウム、銅、銀、金からなる群から選ばれる少なくとも１つの元素、前記群の少なくとも１つの元素を含む金属化合物、または前記群の少なくとも１つの元素を含む有機金属化合物の少なくとも１つであることが好ましい。
As a preferred embodiment of the present invention, the acceptor impurity is at least one element selected from the group consisting of antimony, arsenic, bismuth, phosphorus, nitrogen, lithium, potassium, sodium, rubidium, copper, silver, gold, and at least one of the groups It is preferably a metal compound containing one element or at least one of an organometallic compound containing at least one element of the group.
本発明の太陽電池用ＣｄＴｅ膜は、カドミウムとテルルとアクセプタ不純物とを含み、不純物濃度が１×１０16ｃｍ-3以上１×１０20ｃｍ-3以下であることを特徴とする。
The CdTe film for solar cells of the present invention is characterized in that it contains cadmium, tellurium, and acceptor impurities, and has an impurity concentration of 1 × 10 16 cm −3 or more and 1 × 10 20 cm −3 or less.
本発明の好ましい態様として、前記アクセプタ不純物が、アンチモン、砒素、ビスマス、リン、窒素、リチウム、カリウム、ナトリウム、ルビジウム、銅、銀、金からなる群から選ばれる少なくとも１つの元素、前記群の少なくとも１つの元素を含む金属化合物、または前記群の少なくとも１つの元素を含む有機金属化合物の少なくとも１つであることが好ましい。
As a preferred embodiment of the present invention, the acceptor impurity is at least one element selected from the group consisting of antimony, arsenic, bismuth, phosphorus, nitrogen, lithium, potassium, sodium, rubidium, copper, silver, gold, and at least one of the groups It is preferably a metal compound containing one element or at least one of an organometallic compound containing at least one element of the group.
本発明の太陽電池は、上記に記載の太陽電池用ＣｄＴｅ膜を含むことを特徴とする。
The solar cell of the present invention includes the CdTe film for solar cell described above.
本発明の太陽電池用ＣｄＴｅ膜の製造方法は、アクセプタ不純物を含み、不純物濃度が１×１０16ｃｍ-3以上１×１０20ｃｍ-3以下であるテルル化カドミウム粉末を原料として用い、ＣｄＴｅ膜を作製することを特徴とする。
The method for producing a CdTe film for a solar cell of the present invention uses a cadmium telluride powder containing acceptor impurities and having an impurity concentration of 1 × 10 16 cm −3 or more and 1 × 10 20 cm −3 or less as a raw material. It is characterized by producing.
本発明の好ましい態様として、前記ＣｄＴｅ粉末が、前記アクセプタ不純物として、アンチモン、砒素、ビスマス、リン、窒素、リチウム、カリウム、ナトリウム、ルビジウム、銅、銀、金からなる群から選ばれる少なくとも１つの元素、前記群の少なくとも１つの元素を含む金属化合物、または前記群の少なくとも１つの元素を含む有機金属化合物の少なくとも１つを用いることが好ましい。
As a preferred embodiment of the present invention, the CdTe powder has at least one element selected from the group consisting of antimony, arsenic, bismuth, phosphorus, nitrogen, lithium, potassium, sodium, rubidium, copper, silver, and gold as the acceptor impurity. It is preferable to use at least one of a metal compound containing at least one element of the group, or an organometallic compound containing at least one element of the group.
本発明によれば、アクセプタ不純物を含むＣｄＴｅ膜を製造することができる、という効果を奏する。これにより、キャリア濃度が高いＣｄＴｅ膜が得られるため、ＣｄＴｅ膜を太陽電池のｐ型半導体として用いた際、太陽電池の光変換効率を更に向上させることができる。
According to the present invention, it is possible to produce a CdTe film containing acceptor impurities. As a result, a CdTe film having a high carrier concentration can be obtained. Therefore, when the CdTe film is used as a p-type semiconductor of a solar cell, the light conversion efficiency of the solar cell can be further improved.
以下、本発明を好適に実施するための形態（以下、実施形態という。）につき、詳細に説明する。尚、本発明は以下の実施形態および実施例に記載した内容により限定されるものではない。また、以下に記載した実施形態および実施例における構成要素には、当業者が容易に想定できるもの、実質的に同一のもの、いわゆる均等の範囲のものが含まれる。更に、以下に記載した実施形態および実施例で開示した構成要素は適宜組み合わせてもよいし、適宜選択して用いてもよい。
Hereinafter, modes for suitably carrying out the present invention (hereinafter referred to as embodiments) will be described in detail. In addition, this invention is not limited by the content described in the following embodiment and an Example. In addition, constituent elements in the embodiments and examples described below include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the embodiments and examples described below may be appropriately combined or may be appropriately selected and used.
＜太陽電池用ＣｄＴｅ粉末＞
本実施形態に係る太陽電池用ＣｄＴｅ粉末は、カドミウム（Ｃｄ）とテルル（Ｔｅ）とアクセプタ不純物とを含み、不純物濃度が１×１０16ｃｍ-3以上１×１０20ｃｍ-3以下である。 <CdTe powder for solar cell>
The CdTe powder for solar cell according to this embodiment contains cadmium (Cd), tellurium (Te), and acceptor impurities, and has an impurity concentration of 1 × 10 16 cm −3 or more and 1 × 10 20 cm −3 or less.
本実施形態に係る太陽電池用ＣｄＴｅ粉末は、カドミウム（Ｃｄ）とテルル（Ｔｅ）とアクセプタ不純物とを含み、不純物濃度が１×１０16ｃｍ-3以上１×１０20ｃｍ-3以下である。 <CdTe powder for solar cell>
The CdTe powder for solar cell according to this embodiment contains cadmium (Cd), tellurium (Te), and acceptor impurities, and has an impurity concentration of 1 × 10 16 cm −3 or more and 1 × 10 20 cm −3 or less.
本実施形態に係る太陽電池用ＣｄＴｅ粉末は、ＣｄとＴｅとを主成分として含むものである。本実施形態に係る太陽電池用ＣｄＴｅ粉末は、ＣｄＴｅ単結晶の粉末に予めアクセプタ不純物を混合して得られる。
The solar cell CdTe powder according to the present embodiment contains Cd and Te as main components. The solar cell CdTe powder according to this embodiment is obtained by mixing acceptor impurities in advance with a CdTe single crystal powder.
アクセプタ不純物は、本実施形態に係る太陽電池用ＣｄＴｅ粉末にＣｄおよびＴｅ以外に含まれる不純物元素である。一般に、不純物（ドーパント）は、半導体の極性（ｐ型、ｎ型）やキャリア密度を制御する目的で添加される元素である。アクセプタ不純物とは、ｐ型半導体のホールを作る(電子が足りない状態)ことができる添加物質をいう。アクセプタ不純物は、例えば、アンチモン（Ｓｂ）、砒素（Ａｓ）、ビスマス（Ｂｉ）、リン（Ｐ）、窒素（Ｎ）、リチウム（Ｌｉ）、カリウム（Ｋ）、ナトリウム（Ｎａ）、ルビジウム（Ｒｂ）、銅（Ｃｕ）、銀（Ａｇ）、金（Ａｕ）からなる群から選ばれる少なくとも１つの元素、前記群の少なくとも１つの元素を含む金属化合物、または前記群の少なくとも１つの元素を含む有機金属化合物などの少なくとも１つを示す。金属化合物は、例えば、テルル化アンチモンなどである。また、有機金属化合物は、例えば、トリフェニルアンチモン、オクチル酸アンチモン、トリフェニルビスマス、トリフェニルホスフィン、リン酸トリフェニル、亜リン酸トリフェニル、トリアリルホスフィン、トリアリルアミンからなる群より選ばれる少なくとも１つである。本実施形態においては、アクセプタ不純物としては、これらの中では、Ｐ、Ｎ、Ｓｂが好ましく、Ｓｂが特に好ましい。
The acceptor impurity is an impurity element contained in the solar cell CdTe powder according to the present embodiment other than Cd and Te. In general, an impurity (dopant) is an element added for the purpose of controlling the polarity (p-type, n-type) and carrier density of a semiconductor. An acceptor impurity refers to an additive substance that can form holes in a p-type semiconductor (a state in which electrons are insufficient). Acceptor impurities include, for example, antimony (Sb), arsenic (As), bismuth (Bi), phosphorus (P), nitrogen (N), lithium (Li), potassium (K), sodium (Na), and rubidium (Rb). , At least one element selected from the group consisting of copper (Cu), silver (Ag), and gold (Au), a metal compound containing at least one element of the group, or an organic metal containing at least one element of the group At least one such as a compound is shown. An example of the metal compound is antimony telluride. The organometallic compound is, for example, at least one selected from the group consisting of triphenylantimony, antimony octylate, triphenylbismuth, triphenylphosphine, triphenyl phosphate, triphenyl phosphite, triallylphosphine, and triallylamine. One. In the present embodiment, the acceptor impurity is preferably P, N, or Sb, and particularly preferably Sb.
アクセプタ不純物は、上述の通り、一般には電子を放出し、又は正孔（ホール）を発生するものである。本実施形態におけるアクセプタ不純物は、正孔（ホール）を発生し、ｐ型半導体内で電気伝導を担う。本実施形態に係る太陽電池用ＣｄＴｅ粉末はアクセプタ不純物を含むことで、本実施形態に係る太陽電池用ＣｄＴｅ粉末を用いてＣｄＴｅ膜を形成した際、アクセプタ不純物を含むＣｄＴｅ多結晶中に正孔のキャリアが多く形成できる。その結果、キャリア濃度が高いｐ型半導体を作製することが可能となる。
As described above, acceptor impurities generally emit electrons or generate holes. The acceptor impurity in the present embodiment generates holes and takes charge of electrical conduction in the p-type semiconductor. The solar cell CdTe powder according to the present embodiment contains acceptor impurities, and when a CdTe film is formed using the solar cell CdTe powder according to the present embodiment, holes in the CdTe polycrystal containing the acceptor impurity are formed. Many carriers can be formed. As a result, a p-type semiconductor with a high carrier concentration can be manufactured.
本実施形態に係る太陽電池用ＣｄＴｅ粉末の不純物濃度は、１×１０16ｃｍ-3以上１×１０20ｃｍ-3以下となる。不純物濃度は、より好ましくは１×１０17ｃｍ-3以上１×１０19ｃｍ-3以下であり、更に好ましくは１×１０18ｃｍ-3以上１×１０19ｃｍ-3以下である。キャリア濃度は原則として高い方が好ましいが、ｐｎ接合の相手方のｎ型キャリア濃度との相関もあるために、本実施形態では、上記範囲のキャリア濃度が好ましい。
The impurity concentration of the solar cell CdTe powder according to this embodiment is 1 × 10 16 cm −3 or more and 1 × 10 20 cm −3 or less. The impurity concentration is more preferably 1 × 10 17 cm −3 to 1 × 10 19 cm −3 , and still more preferably 1 × 10 18 cm −3 to 1 × 10 19 cm −3 . In principle, a higher carrier concentration is preferable, but since there is a correlation with the n-type carrier concentration of the pn junction partner, a carrier concentration in the above range is preferable in this embodiment.
よって、本実施形態に係る太陽電池用ＣｄＴｅ粉末によれば、ＣｄＴｅ中にアクセプタ不純物を所定量含めることで、後述するように、アクセプタ不純物を含むＣｄＴｅ膜が得られる。これにより、キャリア濃度が高いＣｄＴｅ膜が得られるため、本実施形態に係る太陽電池用ＣｄＴｅ粉末により作製されたＣｄＴｅ膜を太陽電池のｐ型半導体層として用いた際、太陽電池の光変換効率を更に向上させることができる。また、ＣｄＴｅに含めるアクセプタ不純物の添加量を調整することで、ＣｄＴｅ粉末のキャリア濃度を高めることができると共に、キャリア濃度を調整することができる。
Therefore, according to the CdTe powder for solar cells according to this embodiment, a CdTe film containing acceptor impurities can be obtained by including a predetermined amount of acceptor impurities in CdTe, as will be described later. As a result, a CdTe film having a high carrier concentration is obtained. Therefore, when the CdTe film produced from the CdTe powder for solar cell according to this embodiment is used as a p-type semiconductor layer of the solar cell, the light conversion efficiency of the solar cell is increased. Further improvement can be achieved. Further, by adjusting the amount of acceptor impurities added to CdTe, the carrier concentration of CdTe powder can be increased and the carrier concentration can be adjusted.
更に、太陽電池を作製する際、ＣｄＴｅを主成分とする粉末と添加剤とを混合した粉末原料に、溶媒または粘結剤を加えて液状またはペースト状にし、支持体上に塗布したもの（ＣｄＴｅペースト）を用いてＣｄＴｅ膜を作製する場合、ＣｄＴｅペーストを支持体上に印刷して塗布してから焼成する必要があるため、ＣｄＴｅ膜を作製するに要する工程が多くなり、費用が高くなる。これに対し、ＣｄＴｅ粉末を用いてＣＳＳ法によりＣｄＴｅ膜を作製する場合、ＣｄＴｅ粉末を粉末状態のまま、直接加熱してＣｄＴｅ膜を形成することができる。このため、本実施形態に係る太陽電池用ＣｄＴｅ粉末を用いてＣＳＳ法によりＣｄＴｅ膜を作製する場合、支持体上にＣｄＴｅ膜の原料となるペーストなどを塗布しておくなどの工程が不要となり、ＣｄＴｅ粉末を粉末状態のままＣｄＴｅ膜を形成するための原料として用いることができるため、ＣｄＴｅ膜の作製に要する費用を軽減することができる。
Further, when a solar cell is produced, a powder or raw material obtained by mixing a powder mainly composed of CdTe and an additive is added to a solvent or a binder to form a liquid or a paste, which is applied on a support (CdTe In the case of producing a CdTe film using a paste), it is necessary to print the CdTe paste on a support, apply it, and then fire it, so that the number of steps required to produce the CdTe film increases and the cost increases. On the other hand, when a CdTe film is produced by the CSS method using CdTe powder, the CdTe film can be formed by directly heating the CdTe powder in a powder state. For this reason, when a CdTe film is produced by the CSS method using the CdTe powder for solar cells according to the present embodiment, a process such as applying a paste as a raw material of the CdTe film on the support becomes unnecessary. Since the CdTe powder can be used as a raw material for forming the CdTe film in a powder state, the cost required for producing the CdTe film can be reduced.
＜太陽電池用ＣｄＴｅ膜＞
太陽電池用ＣｄＴｅ膜は、上記の本実施形態に係る太陽電池用ＣｄＴｅ粉末を原料として生成されるものである。本実施形態に係る太陽電池用ＣｄＴｅ粉末は、上述の通り、ＣｄＴｅにアクセプタ不純物を所定量含んだＣｄＴｅ多結晶であるため、アクセプタ不純物からＣｄＴｅ中に正孔が多く発生している。よって、本実施形態に係る太陽電池用ＣｄＴｅ粉末を用いて形成された太陽電池用ＣｄＴｅ膜は、高いキャリア濃度を有する。このため、後述するように、前記太陽電池用ＣｄＴｅ膜を光電変換層として用いた太陽電池用ＣｄＴｅ膜は、高い光変換効率を有する太陽電池とすることができる。 <CdTe film for solar cell>
The solar cell CdTe film is produced using the solar cell CdTe powder according to the present embodiment as a raw material. Since the CdTe powder for solar cells according to this embodiment is a CdTe polycrystal containing a predetermined amount of acceptor impurities in CdTe as described above, many holes are generated in the CdTe from the acceptor impurities. Therefore, the CdTe film for solar cells formed using the CdTe powder for solar cells according to this embodiment has a high carrier concentration. For this reason, as will be described later, the solar cell CdTe film using the solar cell CdTe film as a photoelectric conversion layer can be a solar cell having high light conversion efficiency.
太陽電池用ＣｄＴｅ膜は、上記の本実施形態に係る太陽電池用ＣｄＴｅ粉末を原料として生成されるものである。本実施形態に係る太陽電池用ＣｄＴｅ粉末は、上述の通り、ＣｄＴｅにアクセプタ不純物を所定量含んだＣｄＴｅ多結晶であるため、アクセプタ不純物からＣｄＴｅ中に正孔が多く発生している。よって、本実施形態に係る太陽電池用ＣｄＴｅ粉末を用いて形成された太陽電池用ＣｄＴｅ膜は、高いキャリア濃度を有する。このため、後述するように、前記太陽電池用ＣｄＴｅ膜を光電変換層として用いた太陽電池用ＣｄＴｅ膜は、高い光変換効率を有する太陽電池とすることができる。 <CdTe film for solar cell>
The solar cell CdTe film is produced using the solar cell CdTe powder according to the present embodiment as a raw material. Since the CdTe powder for solar cells according to this embodiment is a CdTe polycrystal containing a predetermined amount of acceptor impurities in CdTe as described above, many holes are generated in the CdTe from the acceptor impurities. Therefore, the CdTe film for solar cells formed using the CdTe powder for solar cells according to this embodiment has a high carrier concentration. For this reason, as will be described later, the solar cell CdTe film using the solar cell CdTe film as a photoelectric conversion layer can be a solar cell having high light conversion efficiency.
（太陽電池用ＣｄＴｅ膜の作製方法）
太陽電池用ＣｄＴｅ膜は、ＣｄＴｅ粉末を原料として用いてＣＳＳ法などによって作製される。図１は、太陽電池用ＣｄＴｅ膜の作製に用いられる反応装置の一例を示す断面図である。図１に示すように、反応装置１０は、チャンバー１１と一対のサセプター１２、１３と、加熱器１４とを有するものである。チャンバー１１は、例えば石英などを材料として作製される管である。一対のサセプター１２、１３は、チャンバー１１内に設けられ、カーボンなどで作製されるものである。加熱器１４は、チャンバー１１内を加熱できるものであれば特に限定されるものではなく、例えば、赤外線ランプヒーターなどが挙げられる。 (Method for producing CdTe film for solar cell)
The solar cell CdTe film is produced by a CSS method using CdTe powder as a raw material. FIG. 1 is a cross-sectional view showing an example of a reaction apparatus used for producing a CdTe film for a solar cell. As shown in FIG. 1, thereaction apparatus 10 includes a chamber 11, a pair of susceptors 12 and 13, and a heater 14. The chamber 11 is a tube made of, for example, quartz. The pair of susceptors 12 and 13 are provided in the chamber 11 and are made of carbon or the like. The heater 14 is not particularly limited as long as the inside of the chamber 11 can be heated, and examples thereof include an infrared lamp heater.
太陽電池用ＣｄＴｅ膜は、ＣｄＴｅ粉末を原料として用いてＣＳＳ法などによって作製される。図１は、太陽電池用ＣｄＴｅ膜の作製に用いられる反応装置の一例を示す断面図である。図１に示すように、反応装置１０は、チャンバー１１と一対のサセプター１２、１３と、加熱器１４とを有するものである。チャンバー１１は、例えば石英などを材料として作製される管である。一対のサセプター１２、１３は、チャンバー１１内に設けられ、カーボンなどで作製されるものである。加熱器１４は、チャンバー１１内を加熱できるものであれば特に限定されるものではなく、例えば、赤外線ランプヒーターなどが挙げられる。 (Method for producing CdTe film for solar cell)
The solar cell CdTe film is produced by a CSS method using CdTe powder as a raw material. FIG. 1 is a cross-sectional view showing an example of a reaction apparatus used for producing a CdTe film for a solar cell. As shown in FIG. 1, the
チャンバー１１内に一対のサセプター１２、１３を配置し、サセプター１２上に本実施形態に係る太陽電池用ＣｄＴｅ粉末を半導体材料１５として配置する。半導体材料１５は、上記の本実施形態に係る太陽電池用ＣｄＴｅ粉末が用いられる。サセプター１２の両端にはスペーサ１６が設けられる。基板１７をスペーサ１６を介して半導体材料１５と基板１７とを０．１ｍｍ～数ｍｍ程度の隙間を有するように近接して配置する。基板１７の半導体材料１５側とは反対側の面をサセプター１３で覆う。
A pair of susceptors 12 and 13 are disposed in the chamber 11, and the CdTe powder for solar cells according to the present embodiment is disposed on the susceptor 12 as the semiconductor material 15. As the semiconductor material 15, the CdTe powder for solar cell according to the present embodiment is used. Spacers 16 are provided at both ends of the susceptor 12. The substrate 17 is arranged close to the semiconductor material 15 and the substrate 17 with a gap of about 0.1 mm to several mm through the spacer 16. The surface of the substrate 17 opposite to the semiconductor material 15 side is covered with the susceptor 13.
チャンバー１１内に不活性ガス１８を供給し、チャンバー１１内の空気や不活性ガス１８をロータリーポンプ１９により吸引し、真空状態を形成する。不活性ガス１８としては、例えば、アルゴンガス、窒素ガスなどが挙げられる。チャンバー１１内の雰囲気を不活性ガス１８に置換して、チャンバー１１内を１３３．３２Ｐａ～２６６６．４４Ｐａ程度に保つ。加熱器１４によりサセプター１２、１３を４００℃～８００℃程度の温度範囲に加熱し、半導体材料１５の温度を基板１７よりも高温にして一定時間保持する。半導体材料１５を不活性ガス１８中で加熱すると、ＣｄＴｅは気化してＣｄ＋１／２Ｔｅ2の蒸気となり、サセプター１２上の半導体材料１５から飛散し、基板１７上にＣｄＴｅが成膜される。また、ＣｄＴｅ粉末に含まれるアクセプタ不純物も同様に、蒸気となり、サセプター１２上の半導体材料１５から飛散し、基板１７上にキャリア物質が成膜される。これにより、基板１７の表面にアクセプタ不純物とＣｄＴｅとを含む太陽電池用ＣｄＴｅ膜が成膜される。
An inert gas 18 is supplied into the chamber 11, and air or the inert gas 18 in the chamber 11 is sucked by a rotary pump 19 to form a vacuum state. Examples of the inert gas 18 include argon gas and nitrogen gas. The atmosphere in the chamber 11 is replaced with an inert gas 18 to keep the inside of the chamber 11 at about 133.32 Pa to 2666.44 Pa. The susceptors 12 and 13 are heated to a temperature range of about 400 ° C. to 800 ° C. by the heater 14, and the temperature of the semiconductor material 15 is set higher than that of the substrate 17 and is held for a certain time. When the semiconductor material 15 is heated in the inert gas 18, CdTe is vaporized into Cd + 1 / 2Te 2 vapor and scattered from the semiconductor material 15 on the susceptor 12, and CdTe is formed on the substrate 17. Similarly, acceptor impurities contained in the CdTe powder are also vaporized and scattered from the semiconductor material 15 on the susceptor 12, and a carrier substance is formed on the substrate 17. Thereby, a CdTe film for a solar cell containing acceptor impurities and CdTe is formed on the surface of the substrate 17.
本実施形態においては、ＣｄＴｅ粉末を原料とし、ＣＳＳ法を用いて太陽電池用ＣｄＴｅ膜を作製する場合について説明したが、本実施形態は、これに限定されるものではなく、ＶＴＤ法などを用いて太陽電池用ＣｄＴｅ膜を作製するようにしてもよい。
In the present embodiment, the case where a CdTe powder for a solar cell is produced using a CSS method using CdTe powder as a raw material has been described. However, the present embodiment is not limited to this and uses a VTD method or the like. Thus, a CdTe film for a solar cell may be produced.
＜太陽電池＞
太陽電池用ＣｄＴｅ膜は、太陽電池の光電変換層として好適に用いることができる。図２は、太陽電池の一例を示す概略断面図である。図２に示すように、太陽電池２０は、透光性耐熱性基板２１と、透光性導電膜２２と、金属硫化物層２３と、ＣｄＴｅ層２４と、オーミック電極２５と、金属電極（集電極）２６とを有する。 <Solar cell>
The CdTe film for solar cells can be suitably used as a photoelectric conversion layer for solar cells. FIG. 2 is a schematic cross-sectional view showing an example of a solar cell. As shown in FIG. 2, thesolar cell 20 includes a translucent heat-resistant substrate 21, a translucent conductive film 22, a metal sulfide layer 23, a CdTe layer 24, an ohmic electrode 25, a metal electrode (collector). Electrode) 26.
太陽電池用ＣｄＴｅ膜は、太陽電池の光電変換層として好適に用いることができる。図２は、太陽電池の一例を示す概略断面図である。図２に示すように、太陽電池２０は、透光性耐熱性基板２１と、透光性導電膜２２と、金属硫化物層２３と、ＣｄＴｅ層２４と、オーミック電極２５と、金属電極（集電極）２６とを有する。 <Solar cell>
The CdTe film for solar cells can be suitably used as a photoelectric conversion layer for solar cells. FIG. 2 is a schematic cross-sectional view showing an example of a solar cell. As shown in FIG. 2, the
透光性耐熱性基板２１は、半導体層で光電変換に寄与し得る波長の光を透過させる性質を有する。透光性耐熱性基板２１としては、透光性と強度を有するものが用いられ、例えば、ホウ珪酸ガラス、ソーダライムガラスなどが挙げられる。
The translucent heat-resistant substrate 21 has a property of transmitting light having a wavelength that can contribute to photoelectric conversion in the semiconductor layer. As the translucent heat-resistant substrate 21, a substrate having translucency and strength is used, and examples thereof include borosilicate glass and soda lime glass.
透光性導電膜２２は、透光性耐熱性基板２１上に設けられている。透光性導電膜２２としては、例えば、酸化スズ膜、酸化インジウムスズ膜などのスズ酸化物からなる膜、酸化亜鉛膜などが挙げられる。これらの中でも、特に、酸化スズ膜が好ましい。透光性導電膜２２の膜厚は、光の透過率と導電性との両立を図る観点から、例えば、１００ｎｍ以上１０００ｎｍ以下であることが好ましい。
The translucent conductive film 22 is provided on the translucent heat-resistant substrate 21. Examples of the light-transmitting conductive film 22 include a film made of a tin oxide such as a tin oxide film and an indium tin oxide film, and a zinc oxide film. Among these, a tin oxide film is particularly preferable. The film thickness of the translucent conductive film 22 is preferably, for example, 100 nm or more and 1000 nm or less from the viewpoint of achieving both light transmittance and conductivity.
金属硫化物層２３は、透光性導電膜２２の上に積層される。金属硫化物層２３は、金属硫化物を含む層であり、ｎ型半導体層として機能する。金属硫化物としては、例えば、硫化カドミウム、硫化亜鉛などが挙げられる。これらは単独で用いてもよく、組み合わせて用いてもよい。これらのうちでは、硫化カドミウム、硫化カドミウムと硫化亜鉛との混合物が好ましい。金属硫化物層の膜厚は、例えば、５０ｎｍ以上５００ｎｍ以下であることが好ましい。
The metal sulfide layer 23 is laminated on the translucent conductive film 22. The metal sulfide layer 23 is a layer containing a metal sulfide and functions as an n-type semiconductor layer. Examples of the metal sulfide include cadmium sulfide and zinc sulfide. These may be used alone or in combination. Of these, cadmium sulfide and a mixture of cadmium sulfide and zinc sulfide are preferable. The film thickness of the metal sulfide layer is preferably, for example, 50 nm or more and 500 nm or less.
ＣｄＴｅ層２４は、金属硫化物層２３の上に積層される。ＣｄＴｅ層２４は、本実施形態に係る太陽電池用ＣｄＴｅ粉末を含んで形成される太陽電池用ＣｄＴｅ膜を用いて形成され、ｐ型半導体層として機能する。ＣｄＴｅ層２４の膜厚は、光の吸収効率と導電性との両立を図る観点から、例えば、１μｍ以上１０μｍ以下であることが好ましい。
The CdTe layer 24 is laminated on the metal sulfide layer 23. The CdTe layer 24 is formed using a solar cell CdTe film formed by including the solar cell CdTe powder according to this embodiment, and functions as a p-type semiconductor layer. The thickness of the CdTe layer 24 is preferably, for example, 1 μm or more and 10 μm or less from the viewpoint of achieving both light absorption efficiency and conductivity.
オーミック電極２５は、ＣｄＴｅ層２４に設けられ、ＣｄＴｅ層２４にオーミック接触させた電極である。オーミック電極２５は、例えば、カーボン、ニッケルなどの材料で形成される。
The ohmic electrode 25 is an electrode provided in the CdTe layer 24 and in ohmic contact with the CdTe layer 24. The ohmic electrode 25 is formed of a material such as carbon or nickel, for example.
金属電極２６は、電極２５上および露出させた透光性導電膜２２上に設けられている。金属電極２６は、例えば、アルミニウム（Ａｌ）、銀（Ａｇ）、インジウム（Ｉｎ）の１つ以上を含む混合物などで形成される。
The metal electrode 26 is provided on the electrode 25 and the exposed translucent conductive film 22. The metal electrode 26 is formed of, for example, a mixture containing one or more of aluminum (Al), silver (Ag), and indium (In).
太陽電池２０の作製方法の一例について説明する。まず、透光性耐熱性基板２１を所定の寸法（例えば、１００ｍｍ×１００ｍｍ×１ｍｍ）にした後、この透光性耐熱性基板２１上に所定の膜厚（例えば、６００ｎｍ）の透光性導電膜２２を設ける。この透光性導電膜２２上にジメチルジチオカルバミン酸カドミウムを２８０℃程度に加熱して発生するガスを６０秒間誘導することによって透光性導電膜２２上に所定の膜厚（例えば、５０ｎｍ）の金属硫化物層２３を形成する。金属硫化物層２３上に所定の膜厚（例えば、５μｍ）のＣｄＴｅ層２４を形成する。このとき、金属硫化物層２３上へのＣｄＴｅ層２４の作製方法については、上述の太陽電池用ＣｄＴｅ膜の製造方法のように、図１に示す基板１７を透光性導電膜２２と金属硫化物層２３とが形成された透光性耐熱性基板２１として用い、ＣｄＴｅ層２４の成形を行う。その後、受光面となる部分の周囲の金属硫化物層２３、ＣｄＴｅ層２４を、例えばレーザースクライブ（波長１．０５μｍ）を用いて剥離し、透光性導電膜２２を露出させる。ＣｄＴｅ層２４上にオーミック電極２５を形成し、オーミック電極２５上および露出させた透光性導電膜２２上に金属電極２６を各々形成する。これにより、太陽電池２０が得られる。
An example of a method for manufacturing the solar cell 20 will be described. First, the translucent heat-resistant substrate 21 is set to a predetermined dimension (for example, 100 mm × 100 mm × 1 mm), and then the translucent conductive film having a predetermined film thickness (for example, 600 nm) is formed on the translucent heat-resistant substrate 21. A film 22 is provided. A metal having a predetermined film thickness (for example, 50 nm) is formed on the translucent conductive film 22 by inducing a gas generated by heating cadmium dimethyldithiocarbamate to about 280 ° C. on the translucent conductive film 22 for 60 seconds. A sulfide layer 23 is formed. A CdTe layer 24 having a predetermined film thickness (for example, 5 μm) is formed on the metal sulfide layer 23. At this time, with respect to the method for producing the CdTe layer 24 on the metal sulfide layer 23, the substrate 17 shown in FIG. The CdTe layer 24 is formed using the translucent heat-resistant substrate 21 on which the physical layer 23 is formed. Thereafter, the metal sulfide layer 23 and the CdTe layer 24 around the portion that becomes the light receiving surface are peeled off by using, for example, laser scribe (wavelength 1.05 μm), and the translucent conductive film 22 is exposed. An ohmic electrode 25 is formed on the CdTe layer 24, and a metal electrode 26 is formed on the ohmic electrode 25 and the exposed translucent conductive film 22. Thereby, the solar cell 20 is obtained.
太陽電池２０は、ＣｄＴｅ層２４に本実施形態に係る太陽電池用ＣｄＴｅ粉末を用いて形成される太陽電池用ＣｄＴｅ膜を用いている。このため、ＣｄＴｅ層２４中のキャリア濃度は高いため、太陽電池２０の開放電圧および曲線因子は向上し、良好な光変換効率を有することができる。
The solar cell 20 uses a solar cell CdTe film formed using the solar cell CdTe powder according to the present embodiment for the CdTe layer 24. For this reason, since the carrier concentration in the CdTe layer 24 is high, the open-circuit voltage and the fill factor of the solar cell 20 are improved, and the light conversion efficiency can be improved.
本実施形態では、ＣｄＴｅ層２４は１層構造としているが、太陽電池２０は１層構造のＣｄＴｅ層２４に限定されるものではなく、多層構造としてもよい。
In this embodiment, the CdTe layer 24 has a single-layer structure, but the solar cell 20 is not limited to the single-layer structure CdTe layer 24, and may have a multilayer structure.
本実施形態に係る太陽電池用ＣｄＴｅ粉末は、ＣｄＴｅ膜とすることで、太陽電池の光電変換層として用いることができるが、本実施形態は特にこれに限定されるものではなく、赤外線受光素子や種々の半導体材料を用いた集積回路等の製造にも好適に用いることができる。
The solar cell CdTe powder according to the present embodiment can be used as a photoelectric conversion layer of a solar cell by forming a CdTe film, but the present embodiment is not particularly limited to this, The present invention can also be suitably used for manufacturing integrated circuits using various semiconductor materials.
本発明の内容を実施例及び比較例を用いて以下に詳細に説明するが、本発明は以下の実施例に限定されるものではない。
The content of the present invention will be described in detail below using examples and comparative examples, but the present invention is not limited to the following examples.
＜実施例１＞
（Ｓｂを含むＣｄＴｅ粉末の作製）
６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ2Ｔｅ3：４ｍｇを各々ＰＢＮ製ボートに入れた後、ＰＢＮ製ボートを石英製アンプル内に設置し、ロータリーポンプ１９で石英製アンプル内を真空に引き、石英製アンプル内に窒素ガスを導入して１×１０-4Ｐａ～５×１０-4Ｐａに保った後、水素バーナーを用いて封止した。この石英製アンプルをヒータにより１２００℃程度にまで上昇させ、ＣｄＴｅ多結晶を生成した。この生成された多結晶のＣｄＴｅを粉砕して粉末にし、ＣｄＴｅ粉末を得た。本実施例において、得られたＣｄＴｅ粉末のＳｂ濃度は、１×１０16ｃｍ-3程度であった。なお、生成されたＣｄＴｅ粉末のＳｂ濃度は、グロー放電質量分析法（Glow Discharge Mass Spectrometry：ＧＤＭＳ）を用いて測定した。 <Example 1>
(Preparation of CdTe powder containing Sb)
6N-Cd: 716 g, 6N-Te: 813 g, Sb 2 Te 3 : 4 mg were put into a PBN boat, respectively, and then the PBN boat was placed in a quartz ampule, and the inside of the quartz ampule was vacuumed by therotary pump 19. Then, nitrogen gas was introduced into the quartz ampule to keep it at 1 × 10 −4 Pa to 5 × 10 −4 Pa, and then sealed with a hydrogen burner. This quartz ampoule was raised to about 1200 ° C. with a heater to produce CdTe polycrystal. The produced polycrystalline CdTe was pulverized to obtain a CdTe powder. In this example, the Sb concentration of the obtained CdTe powder was about 1 × 10 16 cm −3 . In addition, Sb density | concentration of the produced | generated CdTe powder was measured using the glow discharge mass spectrometry (Glow Discharge Mass Spectrometry: GDMS).
（Ｓｂを含むＣｄＴｅ粉末の作製）
６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ2Ｔｅ3：４ｍｇを各々ＰＢＮ製ボートに入れた後、ＰＢＮ製ボートを石英製アンプル内に設置し、ロータリーポンプ１９で石英製アンプル内を真空に引き、石英製アンプル内に窒素ガスを導入して１×１０-4Ｐａ～５×１０-4Ｐａに保った後、水素バーナーを用いて封止した。この石英製アンプルをヒータにより１２００℃程度にまで上昇させ、ＣｄＴｅ多結晶を生成した。この生成された多結晶のＣｄＴｅを粉砕して粉末にし、ＣｄＴｅ粉末を得た。本実施例において、得られたＣｄＴｅ粉末のＳｂ濃度は、１×１０16ｃｍ-3程度であった。なお、生成されたＣｄＴｅ粉末のＳｂ濃度は、グロー放電質量分析法（Glow Discharge Mass Spectrometry：ＧＤＭＳ）を用いて測定した。 <Example 1>
(Preparation of CdTe powder containing Sb)
6N-Cd: 716 g, 6N-Te: 813 g, Sb 2 Te 3 : 4 mg were put into a PBN boat, respectively, and then the PBN boat was placed in a quartz ampule, and the inside of the quartz ampule was vacuumed by the
（太陽電池素子の作製）
ホウ珪酸ガラス製のガラス基板上に二塩化ジメチルスズの有機溶媒溶液を噴霧して塗布した。二塩化ジメチルスズの有機溶媒溶液を噴霧して塗布したガラス基板を、４５０℃に加熱された空気雰囲気のマッフル炉内で、ガラス基板上で二塩化ジメチルスズを熱分解して、膜厚５００ｎｍ程度のＳｎＯ2からなる透明導電膜を作成した。その後、ジブチルジチオカルバミン酸カドミウムの有機溶媒溶液をガラス基板上の透明導電膜に噴霧して塗布し、酸素を若干量含む窒素雰囲気の４３０℃程度に加熱されたマッフル炉内で、ジブチルジチオカルバミン酸カドミウムを熱分解させて透明導電膜上に膜厚１００ｎｍ程度のＣｄＳ膜を作成した。その後、ＣｄＳ膜上には膜厚が５μｍ程度のＣｄＴｅ膜を形成した。このとき、ＣｄＳ膜上へのＣｄＴｅ層の作製方法については、上述のように、図２に示す金属硫化物層２３上にＣｄＴｅ層２４を作製する場合と同様に行った。ＣｄＳ膜上にＣｄＴｅ層を形成した後、ＣｄＴｅ膜に対するオーミック電極であるカーボン膜を形成し、カーボン膜上にＡｇ電極を形成した。また、ＣｄＳ膜側の集電体としてＡｇ電極を形成した。これにより、太陽電池素子を作製した。 (Production of solar cell element)
An organic solvent solution of dimethyltin dichloride was sprayed on a glass substrate made of borosilicate glass. A glass substrate coated by spraying an organic solvent solution of dimethyltin dichloride is thermally decomposed on the glass substrate in a muffle furnace heated to 450 ° C. in an air atmosphere to form SnO having a thickness of about 500 nm. A transparent conductive film consisting of 2 was prepared. After that, an organic solvent solution of cadmium dibutyldithiocarbamate was sprayed on a transparent conductive film on a glass substrate and applied. A CdS film having a thickness of about 100 nm was formed on the transparent conductive film by pyrolysis. Thereafter, a CdTe film having a thickness of about 5 μm was formed on the CdS film. At this time, the method for producing the CdTe layer on the CdS film was performed in the same manner as in the case of producing theCdTe layer 24 on the metal sulfide layer 23 shown in FIG. After the CdTe layer was formed on the CdS film, a carbon film that was an ohmic electrode for the CdTe film was formed, and an Ag electrode was formed on the carbon film. In addition, an Ag electrode was formed as a current collector on the CdS film side. This produced the solar cell element.
ホウ珪酸ガラス製のガラス基板上に二塩化ジメチルスズの有機溶媒溶液を噴霧して塗布した。二塩化ジメチルスズの有機溶媒溶液を噴霧して塗布したガラス基板を、４５０℃に加熱された空気雰囲気のマッフル炉内で、ガラス基板上で二塩化ジメチルスズを熱分解して、膜厚５００ｎｍ程度のＳｎＯ2からなる透明導電膜を作成した。その後、ジブチルジチオカルバミン酸カドミウムの有機溶媒溶液をガラス基板上の透明導電膜に噴霧して塗布し、酸素を若干量含む窒素雰囲気の４３０℃程度に加熱されたマッフル炉内で、ジブチルジチオカルバミン酸カドミウムを熱分解させて透明導電膜上に膜厚１００ｎｍ程度のＣｄＳ膜を作成した。その後、ＣｄＳ膜上には膜厚が５μｍ程度のＣｄＴｅ膜を形成した。このとき、ＣｄＳ膜上へのＣｄＴｅ層の作製方法については、上述のように、図２に示す金属硫化物層２３上にＣｄＴｅ層２４を作製する場合と同様に行った。ＣｄＳ膜上にＣｄＴｅ層を形成した後、ＣｄＴｅ膜に対するオーミック電極であるカーボン膜を形成し、カーボン膜上にＡｇ電極を形成した。また、ＣｄＳ膜側の集電体としてＡｇ電極を形成した。これにより、太陽電池素子を作製した。 (Production of solar cell element)
An organic solvent solution of dimethyltin dichloride was sprayed on a glass substrate made of borosilicate glass. A glass substrate coated by spraying an organic solvent solution of dimethyltin dichloride is thermally decomposed on the glass substrate in a muffle furnace heated to 450 ° C. in an air atmosphere to form SnO having a thickness of about 500 nm. A transparent conductive film consisting of 2 was prepared. After that, an organic solvent solution of cadmium dibutyldithiocarbamate was sprayed on a transparent conductive film on a glass substrate and applied. A CdS film having a thickness of about 100 nm was formed on the transparent conductive film by pyrolysis. Thereafter, a CdTe film having a thickness of about 5 μm was formed on the CdS film. At this time, the method for producing the CdTe layer on the CdS film was performed in the same manner as in the case of producing the
＜実施例２＞
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ2Ｔｅ3：４０ｍｇに変更したこと以外は、実施例１と同様にして行った。本実施例において生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０17ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Example 2>
(Preparation of CdTe powder containing Sb)
Example 1 except that the amount of Cd, Te, Sb 2 Te 3 blended when producing CdTe powder was changed to 6N-Cd: 716 g, 6N-Te: 813 g, Sb 2 Te 3 : 40 mg I went there. The Sd concentration of the CdTe powder produced in this example was about 1 × 10 17 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ2Ｔｅ3：４０ｍｇに変更したこと以外は、実施例１と同様にして行った。本実施例において生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０17ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Example 2>
(Preparation of CdTe powder containing Sb)
Example 1 except that the amount of Cd, Te, Sb 2 Te 3 blended when producing CdTe powder was changed to 6N-Cd: 716 g, 6N-Te: 813 g, Sb 2 Te 3 : 40 mg I went there. The Sd concentration of the CdTe powder produced in this example was about 1 × 10 17 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
＜実施例３＞
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇとＳｂ2Ｔｅ3：０．１４ｇに変更したこと以外は、実施例１と同様にして行った。本実施例において生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０18ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Example 3>
(Preparation of CdTe powder containing Sb)
Example 1 except that the blending amounts of Cd, Te, Sb 2 Te 3 in preparing CdTe powder were changed to 6N-Cd: 716 g, 6N-Te: 813 g, and Sb 2 Te 3 : 0.14 g. And performed in the same manner. The Sd concentration of the CdTe powder produced in this example was about 1 × 10 18 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇとＳｂ2Ｔｅ3：０．１４ｇに変更したこと以外は、実施例１と同様にして行った。本実施例において生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０18ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Example 3>
(Preparation of CdTe powder containing Sb)
Example 1 except that the blending amounts of Cd, Te, Sb 2 Te 3 in preparing CdTe powder were changed to 6N-Cd: 716 g, 6N-Te: 813 g, and Sb 2 Te 3 : 0.14 g. And performed in the same manner. The Sd concentration of the CdTe powder produced in this example was about 1 × 10 18 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
＜実施例４＞
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ2Ｔｅ3：４．１７ｇに変更したこと以外は、実施例１と同様にして行った。本実施例において生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０19ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Example 4>
(Preparation of CdTe powder containing Sb)
Example 1 except that the blending amounts of Cd, Te, and Sb 2 Te 3 at the time of preparing the CdTe powder were changed to 6N—Cd: 716 g, 6N—Te: 813 g, and Sb 2 Te 3 : 4.17 g. And performed in the same manner. The Sd concentration of the CdTe powder produced in this example was about 1 × 10 19 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ2Ｔｅ3：４．１７ｇに変更したこと以外は、実施例１と同様にして行った。本実施例において生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０19ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Example 4>
(Preparation of CdTe powder containing Sb)
Example 1 except that the blending amounts of Cd, Te, and Sb 2 Te 3 at the time of preparing the CdTe powder were changed to 6N—Cd: 716 g, 6N—Te: 813 g, and Sb 2 Te 3 : 4.17 g. And performed in the same manner. The Sd concentration of the CdTe powder produced in this example was about 1 × 10 19 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
＜実施例５＞
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ2Ｔｅ3：４１．７ｇに変更したこと以外は、実施例１と同様にして行った。本実施例において生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０20ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Example 5>
(Preparation of CdTe powder containing Sb)
Example 1 except that the blending amounts of Cd, Te, and Sb 2 Te 3 in preparing CdTe powder were changed to 6N—Cd: 716 g, 6N—Te: 813 g, and Sb 2 Te 3 : 41.7 g. And performed in the same manner. The Sb concentration of the CdTe powder produced in this example was about 1 × 10 20 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ2Ｔｅ3：４１．７ｇに変更したこと以外は、実施例１と同様にして行った。本実施例において生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０20ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Example 5>
(Preparation of CdTe powder containing Sb)
Example 1 except that the blending amounts of Cd, Te, and Sb 2 Te 3 in preparing CdTe powder were changed to 6N—Cd: 716 g, 6N—Te: 813 g, and Sb 2 Te 3 : 41.7 g. And performed in the same manner. The Sb concentration of the CdTe powder produced in this example was about 1 × 10 20 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
＜比較例１＞
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ濃度が１×１０18ｃｍ-3のＣｄＴｅ粉末を１．５ｇに変更したこと以外は、実施例１と同様にして行った。生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０15ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Comparative Example 1>
(Preparation of CdTe powder containing Sb)
The blending amount of Cd, Te, Sb 2 Te 3 in preparing CdTe powder is 6N-Cd: 716 g, 6N-Te: 813 g, and CdTe powder with Sb concentration of 1 × 10 18 cm −3 is 1.5 g. The procedure was the same as in Example 1 except that the change was made. The Sb concentration of the produced CdTe powder was about 1 × 10 15 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ濃度が１×１０18ｃｍ-3のＣｄＴｅ粉末を１．５ｇに変更したこと以外は、実施例１と同様にして行った。生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０15ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Comparative Example 1>
(Preparation of CdTe powder containing Sb)
The blending amount of Cd, Te, Sb 2 Te 3 in preparing CdTe powder is 6N-Cd: 716 g, 6N-Te: 813 g, and CdTe powder with Sb concentration of 1 × 10 18 cm −3 is 1.5 g. The procedure was the same as in Example 1 except that the change was made. The Sb concentration of the produced CdTe powder was about 1 × 10 15 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
＜比較例２＞
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ2Ｔｅ3：１６２．２ｇに変更したこと以外は、実施例１と同様にして行った。生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０21ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Comparative Example 2>
(Preparation of CdTe powder containing Sb)
Example 1 except that the blending amounts of Cd, Te, and Sb 2 Te 3 in preparing CdTe powder were changed to 6N-Cd: 716 g, 6N-Te: 813 g, and Sb 2 Te 3 : 162.2 g. And performed in the same manner. The Sb concentration of the produced CdTe powder was about 1 × 10 21 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
（Ｓｂを含むＣｄＴｅ粉末の作製）
ＣｄＴｅ粉末を作製する際のＣｄ、Ｔｅ、Ｓｂ2Ｔｅ3の配合量を、６Ｎ－Ｃｄ：７１６ｇ、６Ｎ－Ｔｅ：８１３ｇ、Ｓｂ2Ｔｅ3：１６２．２ｇに変更したこと以外は、実施例１と同様にして行った。生成されたＣｄＴｅ粉末のＳｂ濃度は、１×１０21ｃｍ-3程度であった。
（太陽電池素子の作製）
この生成されたＣｄＴｅ粉末を用いて実施例１と同様にして太陽電池素子を作製した。 <Comparative Example 2>
(Preparation of CdTe powder containing Sb)
Example 1 except that the blending amounts of Cd, Te, and Sb 2 Te 3 in preparing CdTe powder were changed to 6N-Cd: 716 g, 6N-Te: 813 g, and Sb 2 Te 3 : 162.2 g. And performed in the same manner. The Sb concentration of the produced CdTe powder was about 1 × 10 21 cm −3 .
(Production of solar cell element)
Using this produced CdTe powder, a solar cell element was produced in the same manner as in Example 1.
実施例１～５、比較例１、２におけるＳｂ濃度、ＣｄＴｅ膜の膜厚ｄの測定結果を表１に示す。
Table 1 shows the measurement results of the Sb concentration and the film thickness d of the CdTe film in Examples 1 to 5 and Comparative Examples 1 and 2.
＜光変換効率の評価＞
実施例１～５、比較例１、２の各々において得られた太陽電池素子の光の変換効率を測定した。光変換効率は、ＪＩＣ Ｃ ８９１３に従って測定を行った。このときの変換効率の測定結果を表１に示す。 <Evaluation of light conversion efficiency>
The light conversion efficiencies of the solar cell elements obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were measured. The light conversion efficiency was measured according to JIS C 8913. Table 1 shows the measurement results of the conversion efficiency at this time.
実施例１～５、比較例１、２の各々において得られた太陽電池素子の光の変換効率を測定した。光変換効率は、ＪＩＣ Ｃ ８９１３に従って測定を行った。このときの変換効率の測定結果を表１に示す。 <Evaluation of light conversion efficiency>
The light conversion efficiencies of the solar cell elements obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were measured. The light conversion efficiency was measured according to JIS C 8913. Table 1 shows the measurement results of the conversion efficiency at this time.
表１に示すように、Ｓｂ濃度が１×１０16ｃｍ-3のＣｄＴｅ粉末を用いて得られた太陽電池素子の光変換効率は、１４％程度であった（実施例１参照）。また、Ｓｂ濃度が１×１０17ｃｍ-3のＣｄＴｅ粉末を用いて得られた太陽電池素子の光変換効率は、１５％程度であった（実施例２参照）。また、Ｓｂ濃度が１×１０18ｃｍ-3のＣｄＴｅ粉末を用いて得られた太陽電池素子の光変換効率は、１６％程度であった（実施例３参照）。また、Ｓｂ濃度が１×１０19ｃｍ-3のＣｄＴｅ粉末を用いて得られた太陽電池素子の光変換効率は、１５％程度であった（実施例４参照）。また、Ｓｂ濃度が１×１０20ｃｍ-3のＣｄＴｅ粉末を用いて得られた太陽電池素子の光変換効率は、１３％程度であった（実施例５参照）。よって、ＣｄＴｅに含まれるＳｂ濃度が高くなるにしたがってＣｄＴｅ粉末を用いて得られた太陽電池素子の光変換効率は小さくなることが確認された。これは、Ｓｂからホールが形成されていないＳｂによって光変換効率が低下したことによるものと考えられる。一方、Ｓｂ濃度が１×１０15ｃｍ-3や１×１０21ｃｍ-3ＣｄＴｅ粉末を用いて得られた太陽電池素子の光変換効率は、５％程度であった（比較例１、２参照）。よって、ＣｄＴｅ粉末に含まれるＳｂ濃度を適正な所定範囲とすることで、ＣｄＴｅ粉末を用いて得られる太陽電池の光変換効率を高くすることができるといえる。
As shown in Table 1, the light conversion efficiency of the solar cell element obtained using the CdTe powder having an Sb concentration of 1 × 10 16 cm −3 was about 14% (see Example 1). Moreover, the light conversion efficiency of the solar cell element obtained using the CdTe powder having an Sb concentration of 1 × 10 17 cm −3 was about 15% (see Example 2). Moreover, the light conversion efficiency of the solar cell element obtained using the CdTe powder having an Sb concentration of 1 × 10 18 cm −3 was about 16% (see Example 3). Moreover, the light conversion efficiency of the solar cell element obtained using the CdTe powder having an Sb concentration of 1 × 10 19 cm −3 was about 15% (see Example 4). Moreover, the light conversion efficiency of the solar cell element obtained using the CdTe powder having an Sb concentration of 1 × 10 20 cm −3 was about 13% (see Example 5). Therefore, it was confirmed that the light conversion efficiency of the solar cell element obtained using the CdTe powder decreases as the Sb concentration contained in CdTe increases. This is considered to be due to the fact that the light conversion efficiency was lowered by Sb in which no hole was formed from Sb. On the other hand, the light conversion efficiency of the solar cell element obtained using the Sb concentration of 1 × 10 15 cm −3 or 1 × 10 21 cm −3 CdTe powder was about 5% (see Comparative Examples 1 and 2). ). Therefore, it can be said that the light conversion efficiency of the solar cell obtained using the CdTe powder can be increased by setting the Sb concentration contained in the CdTe powder within an appropriate predetermined range.
したがって、ＣｄＴｅ粉末に含まれるＳｂ濃度を適正な所定範囲とすることで、ＣｄＴｅ粉末を用いて得られる太陽電池の光変換効率は高くできるため、太陽電池として好適に用いることができることが判明した。
Therefore, it has been found that by setting the Sb concentration contained in the CdTe powder to an appropriate predetermined range, the light conversion efficiency of the solar cell obtained using the CdTe powder can be increased, so that it can be suitably used as a solar cell.
また、本実施例では、アクセプタ不純物としてＳｂを用いた場合の試験結果について示すが、Ｓｂ以外の他のアクセプタ不純物についても同様の傾向を示すといえる。
In addition, in this example, the test result when Sb is used as the acceptor impurity is shown, but it can be said that the acceptor impurity other than Sb shows the same tendency.
１０ 反応装置
１１ チャンバー
１２、１３ サセプター
１４ 加熱器
１５ 半導体材料
１６ スペーサ
１７ 基板
１８ 不活性ガス
１９ ロータリーポンプ
２０ 太陽電池
２１ 透光性耐熱性基板
２２ 透光性導電膜
２３ 金属硫化物層
２４ ＣｄＴｅ層
２５ オーミック電極
２６ 金属電極（集電極） DESCRIPTION OFSYMBOLS 10 Reaction apparatus 11 Chamber 12, 13 Susceptor 14 Heater 15 Semiconductor material 16 Spacer 17 Substrate 18 Inert gas 19 Rotary pump 20 Solar cell 21 Translucent heat-resistant substrate 22 Translucent conductive film 23 Metal sulfide layer 24 CdTe layer 25 Ohmic electrode 26 Metal electrode (collector electrode)
１１ チャンバー
１２、１３ サセプター
１４ 加熱器
１５ 半導体材料
１６ スペーサ
１７ 基板
１８ 不活性ガス
１９ ロータリーポンプ
２０ 太陽電池
２１ 透光性耐熱性基板
２２ 透光性導電膜
２３ 金属硫化物層
２４ ＣｄＴｅ層
２５ オーミック電極
２６ 金属電極（集電極） DESCRIPTION OF
Claims (7)
- カドミウムとテルルとアクセプタ不純物とを含み、
不純物濃度が１×１０16ｃｍ-3以上１×１０20ｃｍ-3以下であることを特徴とする太陽電池用テルル化カドミウム粉末。 Including cadmium, tellurium and acceptor impurities,
Cadmium telluride powder for solar cells, wherein the impurity concentration is 1 × 10 16 cm −3 or more and 1 × 10 20 cm −3 or less. - 請求項１において、
前記アクセプタ不純物が、アンチモン、砒素、ビスマス、リン、窒素、リチウム、カリウム、ナトリウム、ルビジウム、銅、銀、金からなる群から選ばれる少なくとも１つの元素、前記群の少なくとも１つの元素を含む金属化合物、または前記群の少なくとも１つの元素を含む有機金属化合物の少なくとも１つである太陽電池用テルル化カドミウム粉末。 In claim 1,
The acceptor impurity is at least one element selected from the group consisting of antimony, arsenic, bismuth, phosphorus, nitrogen, lithium, potassium, sodium, rubidium, copper, silver, gold, and a metal compound containing at least one element of the group Or a cadmium telluride powder for solar cells, which is at least one of an organometallic compound containing at least one element of the group. - カドミウムとテルルとアクセプタ不純物とを含み、
不純物濃度が１×１０16ｃｍ-3以上１×１０20ｃｍ-3以下であることを特徴とする太陽電池用テルル化カドミウム膜。 Including cadmium, tellurium and acceptor impurities,
A cadmium telluride film for solar cells, wherein the impurity concentration is 1 × 10 16 cm −3 or more and 1 × 10 20 cm −3 or less. - 請求項３において、
前記アクセプタ不純物が、アンチモン、砒素、ビスマス、リン、窒素、リチウム、カリウム、ナトリウム、ルビジウム、銅、銀、金からなる群から選ばれる少なくとも１つの元素、前記群の少なくとも１つの元素を含む金属化合物、または前記群の少なくとも１つの元素を含む有機金属化合物の少なくとも１つである太陽電池用テルル化カドミウム膜。 In claim 3,
The acceptor impurity is at least one element selected from the group consisting of antimony, arsenic, bismuth, phosphorus, nitrogen, lithium, potassium, sodium, rubidium, copper, silver, gold, and a metal compound containing at least one element of the group Or a cadmium telluride film for solar cells, which is at least one of an organometallic compound containing at least one element of the group. - 請求項３または４に記載の太陽電池用テルル化カドミウム膜を含むことを特徴とする太陽電池。 A solar cell comprising the cadmium telluride film for a solar cell according to claim 3 or 4.
- アクセプタ不純物を含み、不純物濃度が１×１０16ｃｍ-3以上１×１０20ｃｍ-3以下であるテルル化カドミウム粉末を原料として用い、ＣｄＴｅ膜を作製することを特徴とする太陽電池用テルル化カドミウム膜の製造方法。 Tellurization for solar cells characterized in that a CdTe film is produced using cadmium telluride powder containing acceptor impurities and having an impurity concentration of 1 × 10 16 cm −3 or more and 1 × 10 20 cm −3 or less as a raw material. A method for producing a cadmium film.
- 請求項６において、
前記テルル化カドミウム粉末が、前記アクセプタ不純物として、アンチモン、砒素、ビスマス、リン、窒素、リチウム、カリウム、ナトリウム、ルビジウム、銅、銀、金からなる群から選ばれる少なくとも１つの元素、前記群の少なくとも１つの元素を含む金属化合物、または前記群の少なくとも１つの元素を含む有機金属化合物の少なくとも１つを用いる太陽電池用テルル化カドミウム膜の製造方法。 In claim 6,
The cadmium telluride powder has at least one element selected from the group consisting of antimony, arsenic, bismuth, phosphorus, nitrogen, lithium, potassium, sodium, rubidium, copper, silver, gold as the acceptor impurity, at least of the group A method for producing a cadmium telluride film for a solar cell, using at least one of a metal compound containing one element or an organometallic compound containing at least one element of the group.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-039061 | 2011-02-24 | ||
| JP2011039061 | 2011-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012114803A1 true WO2012114803A1 (en) | 2012-08-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2012/051245 WO2012114803A1 (en) | 2011-02-24 | 2012-01-20 | Cadmium telluride powder for solar cells, cadmium telluride film for solar cells, and solar cell |
Country Status (2)
| Country | Link |
|---|---|
| TW (1) | TW201240911A (en) |
| WO (1) | WO2012114803A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014156597A1 (en) | 2013-03-29 | 2014-10-02 | Jx日鉱日石金属株式会社 | Compound semiconductor single crystals for photoelectric conversion elements, photoelectric conversion element, and production method for compound semiconductor single crystals for photoelectric conversion elements |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1187749A (en) * | 1997-09-02 | 1999-03-30 | Matsushita Denchi Kogyo Kk | Solar cell and formation method for semiconductor film thereof |
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2012
- 2012-01-20 WO PCT/JP2012/051245 patent/WO2012114803A1/en active Application Filing
- 2012-02-17 TW TW101105222A patent/TW201240911A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1187749A (en) * | 1997-09-02 | 1999-03-30 | Matsushita Denchi Kogyo Kk | Solar cell and formation method for semiconductor film thereof |
Non-Patent Citations (2)
| Title |
|---|
| O.VIGIL-GALAN ET AL.: "Physical properties of Bi doped CdTe thin films grown by the CSVT method", SOLAR ENERGY MATERIALS & SOLAR CELLS, vol. 90, 11 May 2006 (2006-05-11), pages 2228 - 2234 * |
| T.L.CHU: "THIN FILM CADMIUM TELLURIDE SOLAR CELLS BY TWO CHEMICAL VAPOR DEPOSITION TECHNIQUES", SOLAR CELLS, vol. 23, 1988, pages 31 - 48 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014156597A1 (en) | 2013-03-29 | 2014-10-02 | Jx日鉱日石金属株式会社 | Compound semiconductor single crystals for photoelectric conversion elements, photoelectric conversion element, and production method for compound semiconductor single crystals for photoelectric conversion elements |
| US9362431B2 (en) | 2013-03-29 | 2016-06-07 | Jx Nippon Mining & Metals Corporation | Compound semiconductor single crystal ingot for photoelectric conversion devices, photoelectric conversion device, and production method for compound semiconductor single crystal ingot for photoelectric conversion devices |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201240911A (en) | 2012-10-16 |
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