CN104538488B - 一种铜铟镓硒薄膜及其制备方法 - Google Patents
一种铜铟镓硒薄膜及其制备方法 Download PDFInfo
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- CN104538488B CN104538488B CN201410692724.7A CN201410692724A CN104538488B CN 104538488 B CN104538488 B CN 104538488B CN 201410692724 A CN201410692724 A CN 201410692724A CN 104538488 B CN104538488 B CN 104538488B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title abstract 9
- 239000010949 copper Substances 0.000 claims abstract description 112
- 229910052802 copper Inorganic materials 0.000 claims abstract description 90
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000004070 electrodeposition Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- 239000011733 molybdenum Substances 0.000 claims abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 14
- 238000007747 plating Methods 0.000 claims abstract description 10
- 239000010409 thin film Substances 0.000 claims description 46
- 239000011669 selenium Substances 0.000 claims description 43
- 229910052733 gallium Inorganic materials 0.000 claims description 30
- 229910052738 indium Inorganic materials 0.000 claims description 29
- 229910052711 selenium Inorganic materials 0.000 claims description 29
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 28
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 27
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 229910005267 GaCl3 Inorganic materials 0.000 claims description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- 229910003597 H2SeO3 Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 235000019263 trisodium citrate Nutrition 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 15
- 238000005530 etching Methods 0.000 abstract description 12
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000005240 physical vapour deposition Methods 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract 2
- 239000010408 film Substances 0.000 description 45
- 235000011649 selenium Nutrition 0.000 description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005137 deposition process Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910018162 SeO2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000017168 chlorine Nutrition 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 235000011083 sodium citrates Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- -1 gallium ions Chemical class 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- LNBXMNQCXXEHFT-UHFFFAOYSA-N selenium tetrachloride Chemical compound Cl[Se](Cl)(Cl)Cl LNBXMNQCXXEHFT-UHFFFAOYSA-N 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
本发明公开一种铜铟镓硒薄膜及其制备方法,所述方法包括S1、在钼基底上镀一层厚度为10~1000nm的铜;S2、在电解液体系中,采用电化学沉积法在经步骤S1镀铜处理的钼基底上沉积形成贫铜的铜铟镓硒薄膜。采用该方法制备太阳电池用的光吸收层材料CIGS薄膜,不仅能避免采用PVD法或CVD法存在的工艺和设备复杂、成本高昂、难以大规模生产等不足,也能有效克服传统电化学沉积法必须使用剧毒的刻蚀剂的问题,实现铜铟镓硒薄膜大面积连续沉积、免刻蚀制备,有利于其大规模工业推广与应用,得到与传统电化学沉积KCN刻蚀富铜薄膜质量相当的免刻蚀贫铜CIGS薄膜。
Description
技术领域
本发明涉及太阳电池的光吸收层,具体涉及一种作为太阳电池光吸收层的铜铟镓硒薄膜及其制备方法。
背景技术
目前CuInSe2(CIS)薄膜太阳电池已成为最重要和最具发展前景的太阳电池之一,CuInSe2薄膜是直接能隙半导体材料,能隙为1.05eV,而且可以通过掺杂Ga形成铜铟镓硒Cu(In,Ga)Se2(CIGS)使能隙宽度在1.05~1.67eV内连续调整,适合于太阳光的光电转换要求;铜铟镓硒Cu(In,Ga)Se2薄膜具有较高光吸收系数(达105cm-1),且性能稳定,不存在光衰效应,因此受到光伏界广泛关注。
目前制备铜铟镓硒(CIGS)薄膜的方法有真空和非真空之分。真空法能够较精密地控制膜层的组分,获得高质量的CIGS薄膜,但由于真空法制备薄膜必须在高真空下进行,需要昂贵的真空设备和高纯度的原料,同时还存在着原料利用率不高、工艺复杂、难以实现膜层的大面积和连续沉积等问题,这些缺陷限制了CIGS薄膜电池的大规模生产和应用;非真空方法中,最常见的是电化学沉积法,该方法可在低温和非真空条件下进行大面积、多元组分、持续的薄膜沉积,具有设备和工艺简单、成本低廉、界面结合好、材料利用率高(超过95%)等优点。因此采用电化学沉积法制备太阳电池的CIGS薄膜成为降低真空法成本、获得大面积高质量薄膜的主要研究方向之一。
在电化学沉积制备CIGS薄膜的方法中,由于铜元素在铜铟镓硒生长过程中起到了非常重要的作用,尤其是促进了铜铟镓硒薄膜结晶性能的改善及晶粒的长大,故传统电化学沉积工艺中一般沉积富铜的铜、铟、镓、硒并退火,以保证薄膜质量。但是部分富铜相以Cu2-xSe的形态存在于薄膜表面,由于该物相导电性能良好,在后续电池制备中容易导致电池的短路,为此,大多数研究机构采用的办法是用氰化钾(KCN)刻蚀薄膜表面的Cu2-xSe,此方法保证了薄膜的结晶质量并有效避免了因Cu2-xSe引起的电池短路。但是,又产生了新的技术矛盾:KCN作为一种有剧毒的化学物质,极大程度限制了电化学沉积工艺制备铜铟镓硒的大规模应用及生产。
发明内容
为了解决上述技术矛盾,本发明提出一种电化学沉积免刻蚀制备铜铟镓硒薄膜的方法,以及由此方法制备得到的铜铟镓硒薄膜。
本发明提出的铜铟镓硒薄膜的制备方法如下:
一种铜铟镓硒薄膜的制备方法,包括以下步骤:
S1、镀铜:在钼基底上镀一层厚度为10~1000nm的铜;
S2、沉积:在电解液体系中,采用电化学沉积法在经步骤S1镀铜处理的钼基底上沉积贫铜的铜、铟、镓和硒;
S3、退火:将经过步骤S2沉积贫铜的铜、铟、镓和硒后的钼基底置于含硒的真空、空气、氩气或氮气中,在250~550℃下热处理0.1~5.5小时,再冷却,形成含有CuxInaGabSec的铜铟镓硒薄膜,其中,x<a+b,0<a≤2,0<b≤2,0<c≤5。
采用上述制备方法制备太阳电池用铜铟镓硒薄膜,由于事先在钼基底上镀10~1000nm厚的铜,在采用电化学沉积法沉积铜、铟、镓、硒时,可以沉积贫铜的铜、铟、镓、硒,这样一来,在退火时,熔融态的铜硒相能够促进In和Ga元素的迁移形成铜铟镓硒化合物,同时镀铜层的铜促进薄膜结晶的生长,从而形成与传统富铜沉积法制备的薄膜质量(质量指标为:结晶性能和形貌)相当的薄膜。如果镀铜层厚度小于10nm则由于镀铜太少而无法进行步骤S2的贫铜成分沉积,如果厚度大于1000nm则会因为镀铜层太厚导致形成的薄膜难以附着、极易脱落。由于事先在钼基底上镀铜,故可以采用贫铜(即铜的量少于铟和镓的总量)的铜、铟、镓和硒进行沉积,因此,薄膜表面不会有针状的Cu2-xSe存在,不需要再对薄膜进行KCN(氰化钾)刻蚀处理,可见,通过该制备方法能够获得与传统的电化学沉积采用富铜的铜、铟、镓和硒制备的薄膜质量相当的铜铟镓硒薄膜,实现了电化学沉积贫铜铜、铟、镓和硒且免刻蚀制备铜铟镓硒薄膜。
优选地,所述电解液体系选自水溶液体系、有机溶液体系及离子液体体系中的一种或几种,并且,所述电解液体系中:0<铜离子摩尔浓度≤0.15mol/L,0<铟离子摩尔浓度≤0.30mol/L,0<镓离子摩尔浓度≤0.50mol/L,0<硒离子摩尔浓度≤0.30mol/L。
优选地,所述电解液体系中含有络合剂,所述络合剂选自柠檬酸钠、硫氰化钾、焦磷酸酸钾、柠檬酸、乙二胺四乙酸、氨三乙酸、羟基亚乙基二膦酸、酒石酸、氨基磺酸、氰化钾、氟化氨和乙二胺中的一种或几种,任意一种的摩尔浓度为0.01~1mol/L。
优选地,在步骤S2的沉积过程中,所述电解液体系的温度为20~150℃,沉积10~150分钟。
优选地,所述电解液体系中含有支持电解质,用于提高所述电解液体系的导电性和消除反应离子电迁移。
优选地,所述支持电解质选自氯化钠、硫酸钠、硝酸钠、氯化钾、硫酸钾、硝酸钾、氯化铵、氯化锂、硫酸锂、硝酸锂的一种或几种。
优选地,步骤S1中镀铜采用电化学沉积、蒸发或溅射工艺。
优选地,步骤S2中的电化学沉积为一步沉积或分步沉积。
本发明提供的铜铟镓硒薄膜的技术方案如下:
一种铜铟镓硒薄膜,用于太阳电池的光吸收层,通过前述的制备方法制备而成。
优选地,所述CuInaGabSec中的b、c分别为:0<b≤1,0<c≤4。
优选地,所述CuInaGabSec中的a、b、c分别为:1≤a≤2,0<b≤1,1≤c≤4。
优选地,所述铜铟镓硒薄膜厚度为0.01~5μm。
通过本发明的上述制备方法制备得到的上述贫铜的铜铟镓硒薄膜,退火后获得了与刻蚀富铜薄膜形貌及结晶性能相当的铜铟镓硒薄膜。
综上,本发明提供的制备方法不仅能避免采用PVD(物理气相沉积)法或CVD(化学气相沉积)法存在的工艺和设备复杂、成本高昂、难以大规模生产等不足,也能有效克服传统电化学沉积法必须使用剧毒的刻蚀剂的问题,实现大面积连续沉积、免刻蚀制备铜铟镓硒薄膜,有利于其大规模工业推广与应用。采用本发明的免刻蚀贫铜电化学沉积工艺制备的铜铟镓硒薄膜具有薄膜形貌好、结晶性能好、成分可控、膜层附着力强、低成本、高效率、高质量和易于实现大面积沉积等优势,由该薄膜形成的太阳电池光吸收层吸收和转换效率高,是推广大规模工业化生产高质量太阳电池用铜铟镓硒半导体薄膜的有效手段。
附图说明
图1是直接在Mo基底上电化学沉积贫铜的铜、铟、镓和硒形成的CIGS薄膜在SEM下的形貌;
图2是直接在Mo基底上电化学沉积富铜的铜、铟、镓和硒形成的CIGS薄膜在SEM下的形貌;
图3是在镀铜的Mo基底上电化学沉积贫铜的铜、铟、镓和硒形成的CIGS薄膜在SEM下的形貌。
具体实施方式
下面结合优选的实施方式对本发明作进一步说明。
本发明的具体实施方式提供一种制备太阳电池光吸收材料—铜铟镓硒薄膜的方法,该方法包括:
S1、在钼基底上镀一层厚度为10~1000nm的铜层。具体地,可以采用电化学沉积、蒸发或者溅射等工艺在钼基底上镀制一层例如10nm、20nm、50nm、100nm、500nm或者1000nm厚的铜层。
S2、在镀有铜层的钼基底上电化学沉积贫铜的铜、铟、镓和硒;
S3、将经过步骤S2沉积贫铜的铜、铟、镓和硒后的钼基底置于含硒的真空、空气、氩气或氮气中,在250~550℃下热处理0.1~5.5小时,再冷却,形成含CuxInaGabSec的铜铟镓硒薄膜,其中x<a+b,而a、b、c的取值分别为0<a≤2,0<b≤2,0<c≤5。
在具体实施时,步骤S2电化学沉积所用的电解液体系可以是水溶液体系、有机溶液体系及离子液体体系中的一种几种,在电解液体系中铜、铟、镓、硒四种的离子浓度分别为:0~0.15mol/L,0~0.3mol/L,0~0.5mol/L,0~0.3mol/L,但是均不包含0。在步骤S2电化学沉积时,可以采用一步沉积(即共沉积)或者分步沉积。采用共沉积时,可以加入适当浓度的络合剂和支持电解质。络合剂例如可以是柠檬酸钠、硫氰化钾、焦磷酸酸钾、柠檬酸、乙二胺四乙酸、氨三乙酸、羟基亚乙基二膦酸、酒石酸、氨基磺酸、氰化钾、氟化氨和乙二胺中的一种或几种,且加入的每种络合剂的摩尔浓度为0.01~1mol/L;所述支持电解质是用于提高所述电解液体系的导电性和消除反应离子电迁移,可以是氯化钠、硫酸钠、硝酸钠、氯化钾、硫酸钾、硝酸钾、氯化铵、氯化锂、硫酸锂、硝酸锂的一种或几种。在具体的实施例中,步骤S2进行电化学沉积时,电解液体系的温度为20~150℃,PH为0.3~13,沉积10~150分钟。
实施例1
采用溅射工艺,在Mo(钼)玻璃基底上镀制50nm厚的Cu(铜)。在溶质组成为0.15mol/L Cu(NO3)2,0.30mol/L InCl3,0.5mol/L GaCl3,0.30mol/L H2SeO3,1mol/L氯化钾,1mol/L柠檬酸三钠的500ml水溶液中,用稀盐酸将其pH调整至0.3,形成步骤S2所需的电解液体系;以镀Cu的Mo玻璃为工作电极,大面积Pt网为对电极,饱和甘汞电极(SCE)为参比电极;设置工作电极电位0.5V(与SCE之间),电解液体系温度为80℃,在工作电极即镀铜的钼基底上进行电化学沉积(沉积时间10分钟)贫铜的铜、铟、镓、硒,再将沉积处理过的钼基底置于含Se的氩气中,在250℃温度下热处理5.5小时,形成3~5μm厚的含CuIn1~2Ga0~1Se1~4(0不含)的CIGS薄膜。本例中,在其他条件相同的情况下,对比了传统富铜电化学沉积与本方法的免刻蚀贫铜电化学沉积形成的CIGS薄膜(该薄膜包含CuIn1~2Ga0~1Se1~4(0不含))的形貌,如图1所示,显示的是直接在Mo基底上电化学沉积贫铜的铜、铟、镓、硒形成的贫铜CIGS薄膜;图2所示为直接在Mo基底上电化学沉积富铜的铜、铟、镓、硒形成的富铜CIGS薄膜;图3所示为在镀Cu的Mo基底上电化学沉积贫铜的铜、铟、镓、硒形成的贫铜CIGS薄膜。有以下发现:
通过SEM(扫描式电子显微镜)进行薄膜形貌观察,图1中的贫铜CIGS薄膜形貌较差,疏松多孔,颗粒大小均匀;图2中的富铜CIGS薄膜由于经过KCN刻蚀获得的薄膜形貌较图1中的薄膜有了大幅改善,表面变得致密平整且结晶颗粒均有所长大,符合高效率光吸收和光转换的要求,这得益于Cu在铜铟镓硒薄膜生长过程中所起到的促进作用;而图3的贫铜CIGS薄膜获得了与图2中经过KCN刻蚀的富铜CIGS薄膜相当的形貌,这说明在Mo基底上镀制一层Cu亦促进了薄膜的生长。此外,由图3的样品表面形貌可知,由于采用了整体贫铜的成分进行电化学沉积,故薄膜表面并未有针状的Cu2-xSe的存在,不需要再对薄膜进行KCN刻蚀处理,这说明本发明提供的制备方法不但能够获得与传统电化学沉积工艺制备的薄膜质量相当的铜铟镓硒薄膜,而且实现了贫铜薄膜免KCN刻蚀。
实施例2
在本实施例中,采用电化学沉积工艺在Mo玻璃基底上镀制105nm厚度的Cu层。在溶质组成为0.02mol/L CuSO4,0.04mol/L In2(SO4)3,0.1mol/L Ga2(SO4)3,0.04mol/L SeO2,1mol/L硫酸钠的500ml二甲基亚砜(DMSO)与水混合体系中,用氢氧化钠将其pH调整至13,形成步骤S2所需的电解液体系;以镀Cu的Mo玻璃为工作电极,大面积Pt网为对电极,双盐桥系统连接的饱和甘汞电极(SCE)为参比电极。调整工作电极电位-2.5V(与SCE),电解液体系温度为80℃,在工作电极基底上进行电化学沉积(沉积时间90分钟)贫铜的铜、铟、镓、硒,再将沉积处理过的钼基底置于含Se的真空中,在400℃温度下热处理3.1小时,冷却形成3~5微米厚的含CuInaGabSec(0<a≤2,0<b≤1,0<c≤4)的贫铜CIGS薄膜。通过SEM(扫描式电子显微镜)进行薄膜形貌观察,发现本实施例制备而得的CIGS薄膜表面致密平整、结晶颗粒比如图1所示的薄膜的结晶颗粒大且大小均匀。
实施例3
用二甲基甲酰胺(DMF)代替实施例2中的二甲基亚砜(DMSO)和水,其他工艺参数与实施例2相同,最终可制备出贫铜的铜铟镓硒半导体薄膜材料。通过SEM(扫描式电子显微镜)进行薄膜形貌观察,发现本实施例制备而得的CIGS薄膜结晶颗粒比如图1所示的薄膜的结晶颗粒大。
实施例4
采用蒸发工艺,在Mo玻璃基底上镀制210nm厚度的Cu层。在500ml的氯化胆碱(C5H14ONCl)和尿素((NH2)2CO)混合成的离子液体中溶解0.04mol CuCl2,0.04mol InCl3,0.02mol GaCl3,0.06M SeCl4(均为无水氯化物),并以此为电解液体系,用稀盐酸将其pH调整至4,形成步骤S2所需的电解液体系;以镀Cu的Mo为工作电极,大面积Pt网为对电极,Pt丝为参比电极;调整工作电极电位-0.8V(相对于SCE),电解液体系温度为150℃,在工作电极基底上进行电化学沉积(沉积10分钟)贫铜的铜、铟、镓、硒,再将沉积处理过的钼基底置于含Se的氮气或氩气(含水量为1ppm以下)中,在550℃温度下热处理0.1小时,冷却形成0.01~1微米厚的含CuInaGabSec(1≤a≤2,0<b≤1,1≤c≤4)的贫铜CIGS薄膜。通过SEM(扫描式电子显微镜)进行薄膜形貌观察,发现本实施例制备而得的CIGS薄膜表面致密平整、结晶颗粒比如图1所示的薄膜的结晶颗粒大,形貌上与图2中的薄膜类似,说明本实施例制备的CIGS薄膜与图2中薄膜质量相当。
实施例5
采用电化学沉积工艺在Mo玻璃基底上镀制10nm厚度的Cu层。在溶质组成为0.05mol/L CuSO4,0.04mol/L In2(SO4)3,0.3mol/L Ga2(SO4)3,0.06mol/L SeO2,1mol/L硫酸钠的500ml二甲基亚砜(DMSO)与水混合体系中,用稀盐酸将其pH调整至5,形成步骤S2所需的电解液体系;以镀Cu的Mo玻璃为工作电极,大面积Pt网为对电极,双盐桥系统连接的饱和甘汞电极(SCE)为参比电极。调整工作电极电位-5V(与SCE),电解液体系温度为150℃,在工作电极基底上进行电化学沉积(沉积时间10分钟)贫铜的铜、铟、镓、硒,再将沉积处理过的钼基底置于含Se的空气中,在300℃温度下热处理5.5小时,冷却形成5微米厚的含CuInaGabSec(1<a≤2,0<b≤1,0<c≤4)的贫铜CIGS薄膜。通过SEM(扫描式电子显微镜)进行薄膜形貌观察,发现本实施例制备而得的CIGS薄膜表面平整、结晶颗粒比如图1所示的薄膜的结晶颗粒大且大小均匀。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的技术人员来说,在不脱离本发明构思的前提下,还可以做出若干等同替代或明显变型,而且性能或用途相同,都应当视为属于本发明的保护范围。
Claims (1)
1.一种铜铟镓硒薄膜的制备方法,其特征在于,包括以下步骤:
S1、镀铜:在钼基底上镀一层厚度为10~1000nm的铜;
S2、沉积:在电解液体系中,采用电化学沉积法在经步骤S1镀铜处理的钼基底上沉积贫铜的铜、铟、镓和硒;其中,沉积时间为10分钟,电解液体系温度为80℃;
S3、退火:将经过步骤S2沉积贫铜的铜、铟、镓和硒后的钼基底置于含硒的氩气中,在250℃下热处理5.5小时,再冷却,形成3~5μm厚的含有CuxInaGabSec的铜铟镓硒薄膜,其中,x<a+b,0<a≤2,0<b≤2,0<c≤5;
其中,在溶质组成为0.15mol/L Cu(NO3)2,0.30mol/L InCl3,0.5mol/L GaCl3,0.30mol/L H2SeO3,1mol/L氯化钾,1mol/L柠檬酸三钠的500ml水溶液中,用稀盐酸将其pH调整至0.3,形成步骤S2所需的电解液体系。
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