JP2014506018A - I2−ii−iv−vi4及びi2−(ii、iv)−iv−vi4半導体フィルムを含む半導体フィルムと、前記半導体フィルムを含む電子デバイスを形成する方法 - Google Patents
I2−ii−iv−vi4及びi2−(ii、iv)−iv−vi4半導体フィルムを含む半導体フィルムと、前記半導体フィルムを含む電子デバイスを形成する方法 Download PDFInfo
- Publication number
- JP2014506018A JP2014506018A JP2013554649A JP2013554649A JP2014506018A JP 2014506018 A JP2014506018 A JP 2014506018A JP 2013554649 A JP2013554649 A JP 2013554649A JP 2013554649 A JP2013554649 A JP 2013554649A JP 2014506018 A JP2014506018 A JP 2014506018A
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- Japan
- Prior art keywords
- semiconductor film
- oxidation state
- solvent
- solution
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000003647 oxidation Effects 0.000 claims abstract description 66
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 66
- 239000002904 solvent Substances 0.000 claims abstract description 62
- 239000002243 precursor Substances 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims description 53
- 239000011135 tin Substances 0.000 claims description 46
- 229910052802 copper Inorganic materials 0.000 claims description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 34
- 229910052718 tin Inorganic materials 0.000 claims description 33
- 239000011669 selenium Substances 0.000 claims description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 16
- 229910052711 selenium Inorganic materials 0.000 claims description 15
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 7
- 239000006184 cosolvent Substances 0.000 claims description 7
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 231100000252 nontoxic Toxicity 0.000 claims description 6
- 230000003000 nontoxic effect Effects 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- -1 and mixing about Substances 0.000 claims description 5
- 239000005361 soda-lime glass Substances 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 150000004662 dithiols Chemical class 0.000 claims description 3
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 3
- ALPIESLRVWNLAX-UHFFFAOYSA-N hexane-1,1-dithiol Chemical compound CCCCCC(S)S ALPIESLRVWNLAX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims 1
- 239000010408 film Substances 0.000 description 117
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 10
- 230000000737 periodic effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000006193 liquid solution Substances 0.000 description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical group [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000003841 chloride salts Chemical class 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000000224 chemical solution deposition Methods 0.000 description 3
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000011787 zinc oxide Substances 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910021480 group 4 element Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical compound S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000334 hepatotoxic Toxicity 0.000 description 1
- 230000003082 hepatotoxic effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
-
- 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
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02491—Conductive materials
-
- 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
- H01L21/02557—Sulfides
-
- 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
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Abstract
【選択図】図1
Description
本明細書は、その全てが参考文献によって本明細書に組み込まれている仮出願明細書である、2011年2月18日に申請された、米国仮出願明細書第61/444,398号明細書の出願日の優先権を主張する。
2Cu(CH3COO)2・H2O+ZnCl2+SnCl2・2H2O+4SC(NH2)2→Cu2ZnSnS4(s)+4HCl(g)+4H2NCN(g)+4CH3COOH (g)+3H2O(g)
半導体フィルムと、電子デバイス製造の例を、本発明の実施形態にしたがって以下で記述し、いくつかの実験結果を表す。材料および方法両方への多くの改変が、本開示物の範囲から逸脱することなしに実行されてよいことが当業者に明らかであろう。
コーティング溶液を、0.8mmolのCu(CH3COO)2・H2O(99.99%、Aldrichより入手)、0.56mmolのZnCl2(99.1%、Mallinckrodt Bakerより入手)、0.55mmolのSnCl2・2H2O(99.95%、Aldrichから入手)および2.64mmolのチオウレア(99%、Aldrichより入手)を、室温にて0.7mL ジメチルスルホキシド(DMSO)(99%、Aldrichより入手)内に溶解することによって、CZTSフィルムを形成するために調製した。CZTSフィルムを、Mo/SLG基質上にコーティング溶液をスピンコーティングし、続いてホットプレート上580℃にてアニーリングすることによって得た。スピンコーティングは、1500rpmにて1分間で実施した。アニーリングは、5ppmより少ないO2およびH2Oで、グローブボックス内部2.5分間実施した。コーティングおよびアニーリング段階を、1.4μmのCZTSフィルムを得るために、7回繰り返した。発生した総反応は以下のようでありうる。
2Cu(CH3COO)2・H2O+ZnCl2+SnCl2・2H2O+4SC(NH2)2→Cu2ZnSnS4(s)+4HCl(g)+4H2NCN(g)+4CH3COOH(g) +3H2O(g)
以上で記述したCZTSフィルムを、流れているAr(10sccm)で、チューブ火炉中、グラファイトボックス内20分間500℃にて、Se蒸気下アニーリングすることによって、セレン化し、Cu2ZnSn(SxSe1−x)4(CZTSSe)吸収材を形成した。Se蒸気は、セレンペレット(99.99%、Aldrichより得た)を用いて提供した。図3(b)は、得られたセレン化半導体フィルムのPXRDパターンを図解している。
Claims (20)
- 半導体フィルムを形成する方法であって、
液体溶媒中、第一元素の供給源、ここで前記第一元素は銅および銀から選択される、第二元素の供給源、ここで前記第二元素は亜鉛およびカドミウムから選択される、第三元素の供給源、ここで前記第三元素は、スズ、ゲルマニウムおよびケイ素から選択される、および第四元素の供給源、ここで前記第4元素はセレン、硫黄およびテルリウムから選択される、を混合して溶液を形成することであって、前記混合することに、前記液体溶媒中の前記第二および前記第三元素を含む、少なくとも1つのハロゲン化金属塩を解離させることが含まれる、混合すること、
前記溶液で、基質の少なくとも一部をコーティングすること、および
前記溶液をアニーリングして、半導体フィルムを形成すること、
を含む方法。 - 前記第四元素が硫黄であり、前記方法がさらに、半導体フィルムをセレン化することを含む、請求項1に記載の方法。
- 前記溶媒が、極性溶媒を含む、請求項1に記載の方法。
- 前記溶媒が、非毒性溶媒を含む、請求項1に記載の方法。
- 前記溶媒が、ジメチルスルホキシド(DMSO)、ジメチルホルムアミド(DMF)、ジクロロメタン、テトラヒドロフラン、酢酸エチル、酢酸プロピルまたは任意の他の酢酸塩、アセトン、メチルエチルケトン、メチルアミルケトン、または任意の他のケトン、アセトニトリル、任意の極性非プロトン性溶媒、エタノール、n−プロパノール、i−プロパノール、テルピネオール、または任意の他のアルコール、エチレングリコール、プロピレングリコール、または任意の他のジオール、フェノール、クレソールまたは任意の他のフェノール性溶媒から選択される、請求項1に記載の方法。
- 前記溶液に、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、ピリジンまたは任意の他のアミン、ヘキサンチオールまたは任意の他のチオール、エタンジチオール、ヘキサンジチオール、または任意の他のジチオール、ジエチルエーテルまたは任意の他のエーテルから選択される共溶媒が含まれる、請求項5に記載の方法。
- 少なくとも1つのハロゲン化金属塩に、塩化Zn(II)および塩化Sn(II)が含まれる、請求項1に記載の方法。
- 前記第一元素は銅であり、前記第二元素は亜鉛であり、前記第三元素はスズであり、前記第四元素は硫黄であり、前記半導体フィルムはCZTSまたはCZTSSeフィルムを含む、請求項1に記載の方法。
- 前記混合することにさらに、液体溶媒中酢酸Cu(II)、塩化Zn(II)、塩化Sn(II)、およびチオ尿素を混合することが含まれる、請求項8に記載の方法。
- 前記第一元素は銅であり、前記混合することに、+2酸化状態での銅を有する前駆体を、溶液内に混合することが含まれ、前記ハロゲン化金属塩に、+2酸化状態での元素が含まれる、請求項1に記載の方法。
- 前記銅は、+1酸化状態にて、半導体フィルム内に存在してよく、前記ハロゲン化金属塩中に含まれる+2酸化状態での前記元素は、+4酸化状態にて、半導体フィルム中に存在する、請求項10に記載の方法。
- 前記ハロゲン化金属塩中に含まれる+2酸化状態での前記元素がスズである、請求項11に記載の方法。
- 前記半導体フィルムに、Cu2(Zn,Sn)SnS4フィルムが含まれる、請求項1に記載の方法。
- 電子デバイスを製造する方法であって、
前記基質の少なくとも一部を、液体溶媒中、銅、亜鉛、スズ、およびセレニウムまたは硫黄いずれか、またはセレニウムおよび硫黄の組み合わせの供給源を含む溶液でコートすることで、前記液体溶媒にジメチルスルホキシドが含まれる、前記基質の少なくとも一部をコートすること、
半導体フィルムを産するために前記溶液をアニーリングすること、および
前記半導体フィルムへの電気接点を提供すること
を含む、前記基質上に半導体フィルムを形成すること、を含む方法。 - 前記混合することに、前記液体溶媒中、前記亜鉛またはスズを含む少なくとも1つのハロゲン化金属塩を解離させることが含まれる、請求項14に記載の方法。
- 前記混合することに、前記液体溶媒中、+2酸化状態の銅を含む第一前駆体と、+2酸化状態のスズを含む第二前駆体を混合することが含まれる、請求項14に記載の方法。
- 前記半導体フィルムに、+1酸化状態の銅と、+4酸化状態のスズが含まれる、請求項16に記載の方法。
- 前記電子デバイスに、太陽電池が含まれ、前記方法にさらに、半導体フィルム上に、透明な導体材料を提供することが含まれ、前記半導体フィルムへの電気接点を提供することに、透明導体材料に、伝導性接点を提供することが含まれる、請求項14に記載の方法。
- 前記基質に、伝導的にコートされた基質が含まれ、前記半導体フィルムに電気接点を提供することに、前記伝導的にコートされた基質上に半導体フィルムを形成することが含まれる、請求項18に記載の方法。
- 前記伝導的にコートされた基質が、モリブデン−コートソーダ石灰ガラスを含む、請求項19に記載の方法。
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CN107871795A (zh) * | 2017-11-17 | 2018-04-03 | 福州大学 | 一种基于柔性钼衬底的镉掺杂铜锌锡硫硒薄膜的带隙梯度的调控方法 |
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WO2014135390A1 (de) | 2013-03-06 | 2014-09-12 | Basf Se | Tintenzusammensetzung zur herstellung halbleitender dünnschicht-filme |
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KR20150112547A (ko) * | 2014-03-28 | 2015-10-07 | 삼성전자주식회사 | ZnO 나노와이어의 제조방법 및 그 방법에 의해 제조된 ZnO 나노와이어 |
KR102208962B1 (ko) | 2014-03-28 | 2021-01-28 | 삼성전자주식회사 | ZnO 나노와이어의 제조방법 및 그 방법에 의해 제조된 ZnO 나노와이어 |
CN107871795A (zh) * | 2017-11-17 | 2018-04-03 | 福州大学 | 一种基于柔性钼衬底的镉掺杂铜锌锡硫硒薄膜的带隙梯度的调控方法 |
Also Published As
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CN103650155A (zh) | 2014-03-19 |
EP2676300A4 (en) | 2017-05-03 |
US20140220728A1 (en) | 2014-08-07 |
JP5774727B2 (ja) | 2015-09-09 |
CN103650155B (zh) | 2016-10-12 |
WO2012112927A3 (en) | 2012-11-08 |
WO2012112927A2 (en) | 2012-08-23 |
EP2676300A2 (en) | 2013-12-25 |
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