CN105355681B - 一种溅射靶材及用该溅射靶材制作的cigs基薄膜太阳能电池 - Google Patents
一种溅射靶材及用该溅射靶材制作的cigs基薄膜太阳能电池 Download PDFInfo
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- CN105355681B CN105355681B CN201510711517.6A CN201510711517A CN105355681B CN 105355681 B CN105355681 B CN 105355681B CN 201510711517 A CN201510711517 A CN 201510711517A CN 105355681 B CN105355681 B CN 105355681B
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- 239000010409 thin film Substances 0.000 title claims abstract description 36
- 238000005477 sputtering target Methods 0.000 title abstract description 38
- 239000013077 target material Substances 0.000 title abstract description 35
- 239000010408 film Substances 0.000 claims abstract description 150
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000004544 sputter deposition Methods 0.000 claims abstract description 28
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 25
- 238000004062 sedimentation Methods 0.000 claims abstract description 19
- 229910052738 indium Inorganic materials 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 78
- 239000011787 zinc oxide Substances 0.000 claims description 39
- 229960001296 zinc oxide Drugs 0.000 claims description 22
- 239000002019 doping agent Substances 0.000 claims description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 14
- 210000001142 back Anatomy 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000928 Yellow copper Inorganic materials 0.000 claims description 4
- MOAPOQQDYQRCET-UHFFFAOYSA-N [Cu].[In].[Se]=S Chemical compound [Cu].[In].[Se]=S MOAPOQQDYQRCET-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 238000003780 insertion Methods 0.000 claims description 4
- 230000037431 insertion Effects 0.000 claims description 4
- -1 aluminium selenium sulphur Chemical compound 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
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- 239000002184 metal Substances 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-UHFFFAOYSA-N 0.000 claims description 2
- DWGQLIHNAWNSTB-UHFFFAOYSA-N [AlH3].[Se] Chemical compound [AlH3].[Se] DWGQLIHNAWNSTB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical group [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 claims 1
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- 229910052793 cadmium Inorganic materials 0.000 abstract description 11
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000001552 radio frequency sputter deposition Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 28
- 238000000034 method Methods 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 11
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000005361 soda-lime glass Substances 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
- C23C14/0623—Sulfides, selenides or tellurides
- C23C14/0629—Sulfides, selenides or tellurides of zinc, cadmium or mercury
-
- 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
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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Abstract
本发明提供了一种溅射靶材及用该溅射靶材制作的CIGS基薄膜太阳能电池，通过在硒化锌材料中掺入一定量的B、Al、Ga、In元素来制作硒化锌溅射靶材，并用该硒化锌溅射靶来制作无镉的薄膜太阳能电池，本发明的硒化锌溅射靶材可使用DC溅射沉积或AC溅射沉积，可避免使用复杂的RF溅射设备沉积硒化锌膜层，可降低薄膜电池的制造成本。
Description
技术领域
本发明涉及薄膜太阳能电池技术领域，更具体的，本发明提供一种溅射靶材及用该溅射靶材制作CIGS基薄膜太阳能电池。
背景技术
随着全球气候变暖、生态环境恶化和常规能源的短缺，越来越多的国家开始大力发展太阳能利用技术。太阳能光伏发电是零排放的清洁能源，具有安全可靠、无噪音、无污染、资源取之不尽、建设周期短、使用寿命长等优势，因而备受关注。铜铟镓硒(CIGS)是一种直接带隙的P型半导体材料，其吸收系数高达105/cm，2um厚的铜铟镓硒薄膜就可吸收90％以上的太阳光。CIGS薄膜的带隙从1.04eV到1.67eV范围内连续可调，可实现与太阳光谱的最佳匹配。铜铟镓硒薄膜太阳电池作为新一代的薄膜电池具有成本低、性能稳定、抗辐射能力强、弱光也能发电等优点，其转换效率在薄膜太阳能电池中是最高的，已超过20％的转化率，因此日本、德国、美国等国家都投入巨资进行研究和产业化。
在CIGS基薄膜太阳能电池中，最经常的是采用化学水浴法沉积CdS膜层作为电池的缓冲层。但是采用湿化学方式来沉积CdS膜层具有如下的缺点：1)化学水浴工艺不能很好的适应于大规模的CIGS基薄膜太阳能电池的生产工艺过程，其沉积的膜层厚度均匀性较差；2)CdS膜层中的Cd是重金属元素，电池生产过程中含镉废水的处理将增加电池的制造成本，在薄膜电池的使用过程中可能因为自然条件及其他因素作用，会存在镉泄漏到环境中去的危险，导致生态环境遭受破坏，同时由于镉的存在，这种电池的回收处理也比较困难。
CdS是具有大致2.4eV的禁带宽度，入射光在CdS膜层厚度为几十纳米的情况下就已经被吸收，使得更少的入射光达到光吸收层，这将使薄膜电池的短路电流减少，而ZnS的禁带宽度比CdS大得多，用ZnS取代CdS作为薄膜电池的缓冲层不仅可以提高薄膜电池的短路电流，还有利于薄膜电池获得蓝光区的光谱响应，而且其晶格参数与光吸收层更匹配。
因此，近年来人们一直致力于无镉缓冲层的开发，使用化学水浴法沉积硫化锌、硒化锌、硫化铟等无镉材料作为薄膜电池的缓冲层。也有人使用纯的硫化锌、硒化锌溅射靶材来制作缓冲层，由于纯的硫化锌、硒化锌靶材不能导电，所以其只能采用RF溅射设备进行沉积膜层。用RF溅射设备沉积缓冲层，由于设备比较复杂，且实现大面积沉积难度较大，一般都是较小尺寸的沉积，沉积膜层速度慢，因此制造成本较高。
中国专利CN103025916公开了一种用化学水浴法沉积ZnS膜层，用其替代CdS膜层作为电池的缓冲层，已到达生产无镉薄膜太阳能电池的目的。但是使用化学水浴法沉积薄膜难以实现在大面积条件下的良好沉积，生产效率较低，而且生产也会造成较多的废水排放，这些都将增大电池的制造成本。
发明内容
本发明的目的在于克服现有技术之不足，提供一种溅射靶材及用该溅射靶材制作CIGS基薄膜太阳能电池，通过在硒化锌材料中掺入一定量的B、Al、Ga、In元素来制作硒化锌溅射靶材，该溅射靶材可使用DC溅射沉积或AC溅射沉积，其生产工艺与CIGS基薄膜太阳能电池的生产工艺相匹配，同时可避免使用复杂的RF溅射设备沉积硒化锌膜层，因而可实现高效生产，降低薄膜电池的生产成本。用本发明的硒化锌溅射靶来制作薄膜太阳能电池的缓冲层替代传统的硫化镉膜层，实现薄膜电池的无镉生产，同时可避免缓冲层的制作过程产生大量的有毒废水，避免重金属镉对环境的污染。
本发明解决其技术问题所采用的技术方案是：提供一种溅射靶材，其特征在于：所述溅射靶材包含硒化锌材料，和至少包含一种掺杂剂材料；所述掺杂剂材料选自B、Al、Ga或In元素中的至少一种，所述溅射靶材中掺杂剂材料的含量为100ppm至4000ppm。所述溅射靶材中掺杂剂材料的含量优选为500ppm至2500ppm。
当硒化锌溅射靶材中掺杂剂材料的含量小于100ppm时，靶材的导电性很差，因此不能使用DC或AC溅射沉积；当硒化锌溅射靶材中掺杂剂的含量大于4000ppm时，溅射沉积的硒化锌膜层的电阻率不够高，这将会恶化其作为缓冲层的性能，进而导致薄膜电池性能下降。所述硒化锌溅射靶材中硒与锌的原子比可为大于1、等于1或者小于1。
所述溅射靶材采用冷等静压成型、热等静压成型或烧结成型。所述溅射靶材具有导电性，可用DC溅射沉积镀膜或AC溅射沉积镀膜。
本发明提供一种CIGS基薄膜太阳能电池，其特征在于：包括，提供一衬底，覆盖衬底表面的背电极层，覆盖背电极层的p型光吸收层，覆盖p型光吸收层的n型半导体层，覆盖n型半导体层的掺杂硒化锌膜层，覆盖掺杂硒化锌膜层的透明导电层；所述掺杂硒化锌膜层是使用具有导电性的硒化锌靶材通过DC或AC溅射沉积的，所述掺杂硒化锌膜层的掺杂剂选自B、Al、Ga或In元素中的至少一种，所述掺杂剂的含量为100ppm至4000ppm，所述掺杂剂的含量优选为500ppm至2500ppm。所述掺杂硒化锌膜层的溅射沉积过程可通入适量的含有硫族元素的气体。
所述背电极层为钼电极层、钛电极层、铬电极层或AZO透明导电层；所述背电极层中可含有一定量的氧和/或氮元素；所述背电极层中可含有一定量的碱金属元素。
所述p型光吸收层为具有黄铜矿结构的p型铜铟镓硒膜层、p型铜铟镓硫膜层、p型铜铟镓硒硫膜层、p型铜铟硒膜层、p型铜铟硫膜层或p型铜铟硒硫膜层；所述p型光吸收层中含有碱金属元素，所述p型光吸收层中优选含有钠；所述p型光吸收层中还可含有锑或铋元素。所述p型光吸收层可由先溅射预制层后硒化法、共蒸法沉积或反应溅射法沉积获得。
所述n型半导体层为具有黄铜矿结构的n型铜铟镓硒膜层、n型铜铟镓硫膜层、n型铜铟镓硒硫膜层、n型铜铟镓铝硒膜层、n型铜铟镓铝硫膜层、n型铜铟镓铝硒硫膜层、n型铜铟硒膜层、n型铜铟硫膜层或n型铜铟硒硫膜层。所述n型半导体层中含有碱金属元素，所述n型半导体层中优选含有钠；所述n型半导体层中还可含有锑或铋元素。所述n型半导体层可由热扩散法、共蒸法沉积或反应溅射法沉积获得。
所述透明导电层选用银基透明导电膜、氧化铟掺杂锡、氧化锌掺杂铝、氧化锌掺杂镓、氧化锌掺杂铟、氧化锡掺杂氟、氧化锡掺杂碘、氧化锡掺杂锑或石墨烯中的一种或两种以上透明导电膜。
所述衬底为钠钙玻璃衬底、不锈钢薄板、聚酰亚胺板、铝薄板或钛薄板。
在衬底与背电极层之间可插入一层电介质材料层。所述电介质材料层由氧化硅、氮化硅、氮氧化硅、氮化钛、氧化钛、氮氧化钛、氮氧化锆、氧化锆、氮化锆、氮化铝、氧化铝、氧化硅铝、氮化硅铝、氮氧化硅铝、锌锡氧化物或它们的混合物组成；所述电介质材料层或由硅、锆和钛中的至少一种元素与钼组成的至少两种元素的氧化物、氮化物或氮氧化物组成；当衬底为玻璃基板时，所述电介质材料层可由一含有Li、K中至少一种元素的碱过滤层替代，该碱过滤层包含Li、K中的至少一种元素和Si、Al、O三种元素。
在所述掺杂硒化锌膜层与透明导电层之间插入一层本征氧化锌膜层，或者插入一层具有高电阻率的掺杂氧化锌膜层，或者插入一层本征氧化锌膜层和一层具有高电阻率的掺杂氧化锌膜层；所述掺杂氧化锌膜层电阻率不小于0.08Ωcm，同时不大于95Ωcm，所述掺杂氧化锌膜层的掺杂剂可选自B、Al、Ga或In元素中的至少一种。
进一步的，还包括减反射膜层，所述减反射膜层覆盖所述透明导电层。
所述减反射膜可由一层或多层组成；减反射膜层可由一层氟化镁组成，或由折射率大于1.80的第一材料层和折射率小于1.70的第二材料层组成，或者由其他适用于减反射膜层的材料组成。
一种CIGS基薄膜太阳能电池的制备方法，所述的电池包括一衬底，覆盖衬底表面的背电极层，覆盖背电极层的p型光吸收层，覆盖p型光吸收层的n型半导体层，覆盖n型半导体层的掺杂硒化锌膜层，覆盖掺杂硒化锌膜层的透明导电层；其特征在于：所述掺杂硒化锌膜层使用具有导电性的硒化锌靶材通过DC或AC溅射沉积，所述掺杂硒化锌膜层的掺杂剂选自B、Al、Ga或In元素中的至少一种，所述掺杂剂的含量为100ppm至4000ppm。
与现有技术相比本发明具有以下优点：
1、与传统采用化学水浴法沉积缓冲层相比，使用本发明的溅射靶材溅射沉积掺杂硒化锌膜层作为CIGS基薄膜太阳能电池的缓冲层，可避免有毒废水的产生及重金属镉对环境的污染。
2、与传统采用化学水浴法沉积缓冲层或采用RF溅射法沉积缓冲层相比，本发明的溅射靶材可用DC或AC来溅射沉积膜层，因而可实现大面积均匀成膜，且可实现高的沉积速率。
3、与传统采用化学水浴法沉积缓冲层或采用RF溅射法沉积缓冲层相比，本发明的溅射靶材可用DC或AC来溅射沉积膜层，其生产膜层的工艺相对简单，又与CIGS基薄膜太阳能电池的生产工艺相匹配，可实现大规模连续清洁生产，提高生产效率，降低制造成本。
附图说明
图1为本发明CIGS基薄膜太阳能电池的一种结构示意图；
图2为本发明CIGS基薄膜太阳能电池的另一种结构示意图；
图3为本发明CIGS基薄膜太阳能电池的又一种结构示意图；
图4为本发明CIGS基薄膜太阳能电池的再一种结构示意图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。
在此先说明，本发明中DC溅射指的是直流溅射，AC溅射指的是交流溅射，RF溅射指的是射频溅射，硫族元素指的是硫元素和硒元素，在本发明的整个说明书及权利要求中都是如此。
本发明通过提供一种溅射靶材，所述溅射靶材包含硒化锌材料，和至少包含一种掺杂剂材料；所述掺杂剂材料选自B、Al、Ga或In元素中的至少一种，所述溅射靶材中掺杂剂材料的含量为100ppm至4000ppm。本发明的硒化锌溅射靶材具有一定的导电性，因此可使用DC或AC来溅射沉积膜层，DC或AC溅射沉积速率快，可实现大面积均匀成膜，且溅射设备构造较为简单。用本发明的硒化锌溅射靶材来制作CIGS基薄膜太阳能电池的缓冲层，可实现薄膜太阳能电池的无镉化生产，避免重金属镉对环境的污染，其生产膜层的工艺与CIGS基薄膜太阳能电池的生产工艺相匹配，可实现大规模连续清洁生产，提高生产效率，降低制造成本。
以下通过几个具体实施例来说明本发明的一种溅射靶材及用该溅射靶材制作CIGS基薄膜太阳能电池。以下涉及的实施例，均是在干净的衬底表面上依次沉积上各膜层。
实施例1
在一钠钙玻璃表面上采用磁控溅射沉积500nm的钼电极层；接着在钼电极层上形成1.9um的p型铜铟镓硒光吸收层；接着在p型铜铟镓硒光吸收层上形成50nm的n型铜铟镓硒膜层；接着在n型铜铟镓硒膜层上使用Al掺杂的硒化锌靶材，采用DC磁控溅射沉积50nm的掺杂硒化锌膜层，掺杂硒化锌膜层中Al的含量为500ppm；接着在掺杂硒化锌膜层上采用磁控溅射沉积800nm的AZO(Al掺杂ZnO)膜层作为透明导电层。本实施例的薄膜电池的结构如图1所示。
实施例2
在一钠钙玻璃表面上采用磁控溅射沉积550nm的钼电极层；接着在钼电极层上形成1.8um的p型铜铟镓硒光吸收层；接着在p型铜铟镓硒光吸收层上形成45nm的n型铜铟镓硒膜层；接着在n型铜铟镓硒膜层上使用Al掺杂的硒化锌靶材，采用AC磁控溅射沉积40nm的掺杂硒化锌膜层，掺杂硒化锌膜层中Al的含量为800ppm；接着在掺杂硒化锌膜层上采用磁控溅射沉积40nm的掺杂氧化锌膜层，掺杂氧化锌膜层的电阻率为45Ωcm；接着在掺杂氧化锌膜层上采用磁控溅射沉积600nm的AZO(Al掺杂ZnO)膜层作为透明导电层。本实施例的薄膜电池的结构如图2所示。
实施例3
在一钠钙玻璃表面上采用磁控溅射沉积500nm的金属钼电极层；接着在钼电极层上形成1.9um的p型铜铟镓硒光吸收层；接着在p型铜铟镓硒光吸收层上形成35nm的n型铜铟镓硒膜层；接着在n型铜铟镓硒膜层上使用Al掺杂的硒化锌靶材，采用DC磁控溅射沉积50nm的掺杂硒化锌膜层，掺杂硒化锌膜层中Al的含量为1300ppm；接着在掺杂硒化锌膜层上采用磁控溅射沉积40nm的本征ZnO膜层；接着在本征ZnO膜层上采用采用磁控溅射沉积800nm的AZO(Al掺杂ZnO)膜层作为透明导电层。本实施例的薄膜电池的结构如图3所示。
实施例4
在一钠钙玻璃表面上采用磁控溅射沉积500nm的钼电极层；接着在钼电极层上形成2.0um的p型铜铟镓硒光吸收层；接着在p型铜铟镓硒光吸收层上形成30nm的n型铜铟镓硒膜层；接着在n型铜铟镓硒膜层上使用Al掺杂的硒化锌靶材，采用AC磁控溅射沉积30nm的掺杂硒化锌膜层，掺杂硒化锌膜层中Al的含量为600ppm；接着在掺杂硒化锌膜层上采用磁控溅射沉积40nm的本征ZnO膜层；接着在本征ZnO膜层上采用磁控溅射沉积30nm的掺杂氧化锌膜层，掺杂氧化锌膜层的电阻率为35Ωcm；接着在掺杂氧化锌膜层上采用采用磁控溅射沉积600nm的AZO(Al掺杂ZnO)膜层作为透明导电层。本实施例的薄膜电池的结构如图4所示。
实施例5
在一不锈钢薄板上采用磁控溅射沉积50nm的氮氧化硅膜层；接着在氮氧化硅膜层上采用磁控溅射沉积500nm的钼电极层；接着在钼电极层上形成2.1um的p型铜铟镓硒硫光吸收层；接着在p型铜铟镓硒硫光吸收层上形成20nm的n型铜铟镓硒硫膜层；接着在n型铜铟镓硒硫膜层上使用B掺杂的硒化锌靶材，采用DC磁控溅射沉积40nm的掺杂硒化锌膜层，掺杂硒化锌膜层中B的含量为1200ppm；接着在掺杂硒化锌膜层上采用磁控溅射沉积40nm的本征ZnO膜层；接着在本征ZnO膜层上采用采用磁控溅射沉积800nm的AZO(Al掺杂ZnO)膜层作为透明导电层。
实施例6
在一不锈钢薄板上采用磁控溅射沉积50nm的氧化硅膜层；接着在氧化硅膜层上采用磁控溅射沉积500nm的钼电极层；接着在钼电极层上形成2.0um的p型铜铟镓硫光吸收层；接着在p型铜铟镓硫光吸收层上形成35nm的n型铜铟镓硫膜层；接着在n型铜铟镓硫膜层上使用Ga掺杂的硒化锌靶材，采用DC磁控溅射沉积40nm的掺杂硒化锌膜层，掺杂硒化锌膜层中Ga的含量为600ppm；接着在掺杂硒化锌膜层上采用磁控溅射沉积40nm的本征ZnO膜层；接着在本征ZnO膜层上采用采用磁控溅射沉积800nm的AZO(Al掺杂ZnO)膜层作为透明导电层。
实施例7
在一不锈钢薄板上采用磁控溅射沉积50nm的氮化硅膜层；接着在氮化硅膜层上采用磁控溅射沉积500nm的钼电极层；接着在钼电极层上形成1.8um的p型铜铟镓硒光吸收层；接着在p型铜铟镓硒光吸收层上形成25nm的n型铜铟镓硒膜层；接着在n型铜铟镓硒膜层上使用In掺杂的硒化锌靶材，采用DC磁控溅射沉积40nm的掺杂硒化锌膜层，掺杂硒化锌膜层中In的含量为1800ppm；接着在掺杂硒化锌膜层上采用磁控溅射沉积40nm的本征ZnO膜层；接着在本征ZnO膜层上采用采用磁控溅射沉积800nm的AZO(Al掺杂ZnO)膜层作为透明导电层。
上述实施例仅用来进一步说明本发明的一种溅射靶材及用该溅射靶材制作CIGS基薄膜太阳能电池，但本发明并不局限于实施例，凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均落入本发明技术方案的保护范围内。
Claims (8)
1.一种CIGS基薄膜太阳能电池，其特征在于：包括一衬底，覆盖衬底表面的背电极层，覆盖背电极层的p型光吸收层，覆盖p型光吸收层的n型半导体层，覆盖n型半导体层的掺杂硒化锌膜层，覆盖掺杂硒化锌膜层的透明导电层；所述掺杂硒化锌膜层是使用具有导电性的硒化锌靶材通过DC或AC溅射沉积的，所述掺杂硒化锌膜层的掺杂剂选自B、Al、Ga或In元素中的至少一种，所述掺杂剂的含量为100ppm至4000ppm。
2.根据权利要求1所述的一种CIGS基薄膜太阳能电池，其特征在于：所述衬底为钠钙玻璃衬底、不锈钢薄板、聚酰亚胺板、铝薄板或钛薄板。
3.根据权利要求1所述的一种CIGS基薄膜太阳能电池，其特征在于：所述背电极层为钼电极层、钛电极层、铬电极层或AZO透明导电层。
4.根据权利要求1所述的一种CIGS基薄膜太阳能电池，其特征在于：所述p型光吸收层为具有黄铜矿结构的p型铜铟镓硒膜层、p型铜铟镓硫膜层、p型铜铟镓硒硫膜层、p型铜铟硒膜层、p型铜铟硫膜层或p型铜铟硒硫膜层。
5.根据权利要求1所述的一种CIGS基薄膜太阳能电池，其特征在于：所述n型半导体层为具有黄铜矿结构的n型铜铟镓硒膜层、n型铜铟镓硫膜层、n型铜铟镓硒硫膜层、n型铜铟镓铝硒膜层、n型铜铟镓铝硫膜层、n型铜铟镓铝硒硫膜层、n型铜铟硒膜层、n型铜铟硫膜层或n型铜铟硒硫膜层。
6.根据权利要求1所述的一种CIGS基薄膜太阳能电池，其特征在于：所述透明导电层选用银基透明导电膜、氧化铟掺杂锡、氧化锌掺杂铝、氧化锌掺杂镓、氧化锌掺杂铟、氧化锡掺杂氟、氧化锡掺杂碘、氧化锡掺杂锑或石墨烯中的一种或两种以上透明导电膜。
7.根据权利要求1所述的一种CIGS基薄膜太阳能电池，其特征在于：在所述掺杂硒化锌膜层与透明导电层之间插入一层本征氧化锌膜层，或者插入一层具有高电阻率的掺杂氧化锌膜层，或者插入一层本征氧化锌膜层和一层具有高电阻率的掺杂氧化锌膜层；所述掺杂氧化锌膜层电阻率不小于0.08Ωcm，同时不大于95Ωcm。
8.一种CIGS基薄膜太阳能电池的制备方法，所述的电池包括一衬底，覆盖衬底表面的背电极层，覆盖背电极层的p型光吸收层，覆盖p型光吸收层的n型半导体层，覆盖n型半导体层的掺杂硒化锌膜层，覆盖掺杂硒化锌膜层的透明导电层；其特征在于：所述掺杂硒化锌膜层使用具有导电性的硒化锌靶材通过DC或AC溅射沉积，所述掺杂硒化锌膜层的掺杂剂选自B、Al、Ga或In元素中的至少一种，所述掺杂剂的含量为100ppm至4000ppm。
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