CN104205311A - 硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池 - Google Patents
硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池 Download PDFInfo
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- CN104205311A CN104205311A CN201380016074.8A CN201380016074A CN104205311A CN 104205311 A CN104205311 A CN 104205311A CN 201380016074 A CN201380016074 A CN 201380016074A CN 104205311 A CN104205311 A CN 104205311A
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- Prior art keywords
- sulfide semiconductor
- coating fluid
- sulfide
- semiconductor
- film
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 140
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- 238000000576 coating method Methods 0.000 title claims abstract description 67
- 239000010409 thin film Substances 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000000737 periodic effect Effects 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000010408 film Substances 0.000 claims description 61
- 239000012530 fluid Substances 0.000 claims description 61
- 150000001875 compounds Chemical class 0.000 claims description 59
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 239000005864 Sulphur Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 description 38
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical class NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 15
- 229910052787 antimony Inorganic materials 0.000 description 13
- 238000004566 IR spectroscopy Methods 0.000 description 11
- 229940007424 antimony trisulfide Drugs 0.000 description 11
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- -1 salt compound Chemical class 0.000 description 8
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 7
- 238000012795 verification Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 150000004763 sulfides Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000012990 dithiocarbamate Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 3
- 229940116357 potassium thiocyanate Drugs 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 3
- 239000012991 xanthate Substances 0.000 description 3
- MHIITNFQDPFSES-UHFFFAOYSA-N 25,26,27,28-tetrazahexacyclo[16.6.1.13,6.18,11.113,16.019,24]octacosa-1(25),2,4,6,8(27),9,11,13,15,17,19,21,23-tridecaene Chemical class N1C(C=C2C3=CC=CC=C3C(C=C3NC(=C4)C=C3)=N2)=CC=C1C=C1C=CC4=N1 MHIITNFQDPFSES-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 description 2
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- IHBMMJGTJFPEQY-UHFFFAOYSA-N sulfanylidene(sulfanylidenestibanylsulfanyl)stibane Chemical group S=[Sb]S[Sb]=S IHBMMJGTJFPEQY-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- POEOLRMDMUNLPY-UHFFFAOYSA-N 2,3-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC2=CC=C(C=CC=N3)C3=C2N=C1C1=CC=CC=C1 POEOLRMDMUNLPY-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GUYCALWXEFWWKA-UHFFFAOYSA-N C(N)(S)=S.[Sb] Chemical compound C(N)(S)=S.[Sb] GUYCALWXEFWWKA-UHFFFAOYSA-N 0.000 description 1
- NJHJOTDYNWFYHV-UHFFFAOYSA-N COC1=CC=CC=C1[Bi] Chemical compound COC1=CC=CC=C1[Bi] NJHJOTDYNWFYHV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- VEFUFOVCKKFFCH-UHFFFAOYSA-N NC(=S)N.[Bi] Chemical compound NC(=S)N.[Bi] VEFUFOVCKKFFCH-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BSGDBOGFFJULBB-UHFFFAOYSA-N S(O)(O)(=S)=O.[Bi] Chemical compound S(O)(O)(=S)=O.[Bi] BSGDBOGFFJULBB-UHFFFAOYSA-N 0.000 description 1
- LAPHGSZCSIEJPZ-UHFFFAOYSA-N S(O)(O)(=S)=O.[Sb] Chemical compound S(O)(O)(=S)=O.[Sb] LAPHGSZCSIEJPZ-UHFFFAOYSA-N 0.000 description 1
- 241001249696 Senna alexandrina Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 1
- ISWQCIVKKSOKNN-UHFFFAOYSA-L Tiron Chemical compound [Na+].[Na+].OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O ISWQCIVKKSOKNN-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- CAAQLIZHFQVUIY-UHFFFAOYSA-N [Sb].NC(N)=S Chemical compound [Sb].NC(N)=S CAAQLIZHFQVUIY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
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- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- PEQMCTODPDZUDG-UHFFFAOYSA-N antimony;ethanol Chemical compound [Sb].CCO PEQMCTODPDZUDG-UHFFFAOYSA-N 0.000 description 1
- ZAYSUZKWSFEDME-UHFFFAOYSA-N antimony;thiocyanic acid Chemical compound [Sb].SC#N ZAYSUZKWSFEDME-UHFFFAOYSA-N 0.000 description 1
- IKIBSPLDJGAHPX-UHFFFAOYSA-N arsenic triiodide Chemical compound I[As](I)I IKIBSPLDJGAHPX-UHFFFAOYSA-N 0.000 description 1
- SYRRNDDIEBJFIC-UHFFFAOYSA-N arsenic;ethanol Chemical compound [As].CCO SYRRNDDIEBJFIC-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- WOCXOAVNOAMFFP-UHFFFAOYSA-K bismuth nitric acid trihydroxide Chemical compound [OH-].[Bi+3].[N+](=O)(O)[O-].[OH-].[OH-] WOCXOAVNOAMFFP-UHFFFAOYSA-K 0.000 description 1
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 description 1
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 1
- SDYQNIINLMLUTA-UHFFFAOYSA-N bismuth;thiocyanic acid Chemical compound [Bi].SC#N SDYQNIINLMLUTA-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明的目的在于提供一种硫化物半导体形成用涂布液,其能够大面积且简易地形成作为光电转换材料的半导体材料而言有用的硫化物半导体。另外,本发明的目的在于提供一种使用该硫化物半导体形成用涂布液所制造的硫化物半导体薄膜和薄膜太阳能电池。本发明为一种硫化物半导体形成用涂布液,其含有下述络合物,所述络合物包含元素周期表第15族的金属元素和硫。
Description
技术领域
本发明涉及适合作为太阳能电池等光电转换元件用的半导体材料的、硫化物半导体形成用涂布液。另外,本发明涉及使用该硫化物半导体形成用涂布液所制造的硫化物半导体薄膜和薄膜太阳能电池。
背景技术
关于硫化锑(Sb2S3)、硫化铋(Bi2S3)等硫化物半导体,由于其带隙为1.0~2.5eV,因此在可见光区域显示出高光吸收特性。因此,这样的硫化物半导体有望被视为太阳能电池等的光电转换材料、可见光应答型光催化剂材料。另外,关于这样的硫化物半导体,由于其红外区域中的高透射性,因此也在尽力研究将其作为红外线传感器,另外,由于其电导率因光照射而发生变化,因此作为光电导材料也受到关注。
一直以来,这样的硫化物半导体的薄膜通过真空蒸镀法、溅射法、气相反应法(CVD)等方法进行制造。例如非专利文献1中报告了利用溅射法的硫化锑薄膜的制作方法。这样的方法中,刚刚成膜后的膜呈无定形(带隙2.24eV),通过在400℃、硫气氛下进行烧成,从而得到结晶膜(带隙1.73eV)。
另外,非专利文献2中也公开了使用了电化学沉积法的硫化物薄膜的制作方法。这样的方法中,可得到带隙分别为1.58eV(Sb2S3)、1.74eV(Bi2S3)的薄膜。
但是,真空蒸镀法、溅射法等方法存在如下的问题:不仅装置昂贵而在成本方面不利,而且难以大面积地成膜。另外,电化学沉积法虽然不需要真空设备,能够在常温下成膜,但存在仅能够在导电性的基板上进行成膜的问题。
现有技术文献
非专利文献
非专利文献1:Matthieu Y.Versavel and Joel A.Haber,Thin Solid Films,515(18),7171-7176(2007)
非专利文献2:N.S.Yesugade,et al.,Thin Solid Films,263(2),145-149(1995)
发明内容
发明所要解决的课题
鉴于上述现状,本发明的目的在于提供一种硫化物半导体形成用涂布液,所述硫化物半导体形成用涂布液能够大面积且简易地形成作为光电转换材料的半导体材料而言有用的硫化物半导体。另外,本发明的目的在于提供一种使用该硫化物半导体形成用涂布液所制造的硫化物半导体薄膜和薄膜太阳能电池。
用于解决课题的手段
本发明为一种硫化物半导体形成用涂布液,其含有络合物,所述络合物包含元素周期表第15族的金属元素和硫。以下,对本发明进行详细说明。
本发明人认为,通过使用含有含金属化合物和含硫化合物的硫化物半导体形成用涂布液(即,硫化物半导体的前体溶液),能够采用印刷法大面积且简易地形成硫化物半导体。但是,由于将含金属化合物、含硫化合物、和用于将它们溶解的溶剂组合,而容易在硫化物半导体的膜表面产生不光滑,其结果,有时电特性和半导体特性降低。另外,这样的方法难以实现重现性高的成膜。
本发明人等经过广泛深入的研究,结果发现,通过在含有含金属化合物和含硫化合物的硫化物半导体形成用涂布液中,使用可在有机溶剂中形成包含金属元素和硫的络合物这样的含金属化合物和含硫化合物,由此可得到稳定的涂布液,涂布后通过简易的处理而能够制作出期望的硫化物半导体,从而完成了本发明。
本发明的硫化物半导体形成用涂布液含有络合物,所述络合物包含元素周期表第15族的金属元素和硫。
通过形成这样的络合物,可得到稳定的涂布液。其结果,不仅可形成均匀优质的硫化物半导体,而且其电特性和半导体特性也提高。需要说明的是,包含元素周期表第15族的金属元素和硫的络合物可以利用红外吸收光谱且通过测定来自金属元素硫间的键的吸收峰而加以确认。
作为上述元素周期表第15族的金属元素,优选锑、铋。其中,由于可形成电特性和半导体特性更优异的硫化物半导体,因此更优选锑。
上述包含元素周期表第15族的金属元素和硫的络合物优选在上述元素周期表第15族的金属元素与含硫化合物之间形成。含硫化合物中的硫元素由于具有不参与化学键合的孤立电子对,因此易于在与上述元素周期表第15族的金属元素的空的电子轨道(d轨道或f轨道)之间形成配位键。
为了形成这样的络合物,本发明的硫化物半导体形成用涂布液优选为至少由含有元素周期表第15族的金属元素的含金属化合物、含硫化合物和有机溶剂制得的涂布液。
上述含有元素周期表第15族的金属元素的含金属化合物,根据所使用的含硫化合物和有机溶剂,以能够形成络合物的方式进行适当选择。作为上述含有元素周期表第15族的金属元素的含金属化合物,可举出上述元素周期表第15族的金属元素的金属盐、有机金属化合物等。
作为上述金属盐,可举出例如:上述元素周期表第15族的金属元素的氯化物、氧氯化物、硝酸盐、碳酸盐、硫酸盐、铵盐、硼酸盐、硅酸盐、磷酸盐、氢氧化物、过氧化物等。另外,也包括上述金属盐的水合物。
作为上述有机金属化合物,可举出例如:上述元素周期表第15族的金属元素的羧酸、二羧酸、低聚羧酸、聚羧酸的盐化合物。更具体而言,可举出:上述元素周期表第15族的金属元素的乙酸、甲酸、丙酸、辛酸、硬脂酸、草酸、柠檬酸、乳酸等的盐化合物等。
作为上述含有元素周期表第15族的金属元素的含金属化合物,具体而言,可举出例如:氯化锑、乙酸锑、溴化锑、氟化锑、醇酸锑、三乙醇锑、三丙醇锑、硝酸铋、氯化铋、硝酸氢氧化铋、三(2-甲氧基苯基)铋、碳酸铋、碳酸氧铋、磷酸铋、溴化铋、三乙醇铋、三异丙醇锑、碘化砷、三乙醇砷等。这些含有元素周期表第15族的金属元素的含金属化合物可以单独使用,也可以并用2种以上。
本发明的硫化物半导体形成用涂布液中含有元素周期表第15族的金属元素的含金属化合物的添加量没有特别限定,但优选的下限为0.5重量%、优选的上限为70重量%。若上述添加量为0.5重量%以上,则能够容易地制作出优质的硫化物半导体。若上述添加量为70重量%以下,则能够容易地得到稳定的涂布液。
上述含硫化合物根据所使用的含有元素周期表第15族的金属元素的含金属化合物和有机溶剂,以能够形成络合物的方式适当加以选择。
作为上述含硫化合物,可举出例如:硫脲、硫脲的衍生物、硫代乙酰胺、硫代乙酰胺的衍生物、二硫代氨基甲酸盐(Dithiocarbamate)、黄原酸盐(Xanthate)、二硫代磷酸盐(Dithiophosphate)、硫代硫酸盐、硫代氰酸盐等。
作为上述硫脲的衍生物,可举出:1-乙酰基-2-硫脲、亚乙基硫脲、1,3-二乙基-2-硫脲、1,3-二甲基硫脲、四甲基硫脲、N-甲基硫脲、1-苯基-2-硫脲等。作为上述二硫代氨基甲酸盐,可举出:二甲基二硫代氨基甲酸钠、二乙基二硫代氨基甲酸钠、二甲基二硫代氨基甲酸钾、二乙基二硫代氨基甲酸钾等。作为上述黄原酸盐,可举出:乙基黄原酸钠(sodium ethylxanthate)、乙基黄原酸钾、异丙基黄原酸钠、异丙基黄原酸钾等。作为上述硫代硫酸盐,可举出:硫代硫酸钠、硫代硫酸钾、硫代硫酸铵等。作为上述硫代氰酸盐,可举出:硫代氰酸钾、硫代氰酸钾、硫代氰酸铵等。这些含硫化合物可以单独使用,也可以并用2种以上。
本发明的硫化物半导体形成用涂布液中含硫化合物的添加量,相对于上述含有元素周期表第15族的金属元素的含金属化合物的摩尔数,优选为1~30倍。更优选为2~20倍。若上述添加量为1倍以上,则容易得到化学计量比的硫化物半导体。若上述添加量为30倍以下,则涂布液的稳定性进一步提高。
上述有机溶剂根据所使用的含有元素周期表第15族的金属元素的含金属化合物和含硫化合物,以能够形成络合物的方式适当加以选择。
作为上述有机溶剂,可举出例如:甲醇、乙醇、N,N-二甲基甲酰胺、二甲基亚砜、丙酮、二噁烷、四氢呋喃、异丙醇、正丙醇、氯仿、氯苯、吡啶、甲苯等,其中,特别优选甲醇、乙醇、丙酮。这些有机溶剂可以单独使用,也可以并用2种以上。其中,由于可以形成电特性和半导体特性更优异的硫化物半导体,因此优选N,N-二甲基甲酰胺。
另外,本发明的硫化物半导体形成用涂布液在不损害本发明的效果的范围内可以还含有水等非有机溶剂成分。
作为上述包含元素周期表第15族的金属元素和硫的络合物,具体而言,可举出例如:铋-硫脲络合物、铋-硫代硫酸络合物、铋-硫代氰酸络合物、锑-硫脲络合物、锑-硫代硫酸络合物、锑-硫代氰酸络合物、锑-二硫代氨基甲酸络合物、锑-黄原酸络合物等。
另外,通过在基板上涂布本发明的硫化物半导体形成用涂布液而制造的硫化物半导体薄膜也是本发明之一。这样得到的硫化物半导体的薄膜作为太阳能电池用材料、光催化剂材料或光电导材料而有用。
涂布本发明的硫化物半导体形成用涂布液的方法没有特别限定,可举出例如旋涂法、辊对辊等印刷法。通过使用本发明的硫化物半导体形成用涂布液,能够采用印刷法,均匀且平滑地形成硫化物半导体薄膜,由此,能够使硫化物半导体薄膜的电特性和半导体特性提高,也能够削减形成成本。
另外,将使用本发明的硫化物半导体形成用涂布液得到的硫化物半导体用作光电转换层的薄膜太阳能电池也是本发明之一。
上述光电转换层优选还包含与硫化物半导体邻接的有机半导体。此时,上述光电转换层中的硫化物半导体与有机半导体的位置关系可以是两者相互邻接,也可以是包含硫化物半导体层和有机半导体层的层叠体,也可以是将硫化物半导体和有机半导体混合而复合成的复合膜。
作为上述包含硫化物半导体层和有机半导体层的层叠体的制造方法,可以利用在使用本发明的硫化物半导体形成用涂布液而得到的硫化物半导体薄膜层上层叠有机半导体薄膜层的方法,相反,也可以在有机半导体薄膜层上层叠硫化物半导体薄膜层。
作为上述将硫化物半导体和有机半导体混合而复合成的复合膜的制作方法,可举出将本发明的硫化物半导体形成用涂布液与有机半导体的混合液涂布到基板上的方法。
作为上述有机半导体,没有特别限定,可举出例如:聚(3-烷基噻吩)等噻吩衍生物等。另外,作为上述有机半导体,还可举出例如:聚对苯乙炔衍生物、聚乙烯基咔唑衍生物、聚苯胺衍生物、聚乙炔衍生物等导电性高分子等。另外,作为上述有机半导体,还可举出例如:酞菁衍生物、萘酞菁衍生物、并五苯衍生物、苯并卟啉衍生物等卟啉衍生物等。其中,由于耐久性较高,因此优选噻吩衍生物、酞菁衍生物、萘菁衍生物、苯并卟啉衍生物。
本发明的薄膜太阳能电池除上述光电转换层以外,还可以具有基板、空穴输送层、电子输送层等。上述基板没有特别限定,可举出例如:钠钙玻璃、无碱玻璃等透明玻璃基板、陶瓷基板、透明塑料基板等。
上述空穴输送层的材料没有特别限定,可举出例如:P型导电性高分子、P型低分子有机半导体、P型金属氧化物、P型金属硫化物、表面活性剂等,具体而言,可举出例如:聚乙撑二氧噻吩的聚苯乙烯磺酸加成物、含羧基聚噻吩、酞菁、卟啉、含氟基膦酸、含羰基膦酸、氧化钼、氧化钒、氧化钨、氧化镍、氧化铜、氧化锡、硫化钼、硫化钨、硫化铜、硫化锡等。
上述电子输送层的材料没有特别限定,可举出例如:N型导电性高分子、N型低分子有机半导体、N型金属氧化物、N型金属硫化物、卤化碱金属、碱金属、表面活性剂等,具体而言,可举出例如:含氰基聚苯乙炔、含硼聚合物、浴铜灵、二苯基菲绕啉、羟基喹啉铝、噁二唑化合物、苯并咪唑化合物、萘四羧酸化合物、苝衍生物、氧化膦化合物、硫化膦化合物、含氟基酞菁、氧化钛、氧化锌、氧化铟、氧化锡、氧化镓、硫化锡、硫化铟、硫化锌等。
发明效果
就本发明而言,能够提供一种硫化物半导体形成用涂布液,该涂布液能够大面积且简易地形成作为光电转换材料的半导体材料而言有用的硫化物半导体。另外,本发明中,能够提供使用该硫化物半导体形成用涂布液所制造的硫化物半导体薄膜和薄膜太阳能电池。
具体实施方式
以下列举出实施例来更详细地说明本发明,但本发明并不仅限定于这些实施例。
(实施例1)
(硫化物半导体形成用涂布液的制作)
在100重量份甲醇中添加氯化锑(III)20重量份后,通过搅拌进行溶解。接着,边搅拌边将硫脲(CS(NH2)2)13.5重量份缓慢地添加到所得到的氯化锑(III)的甲醇溶液中。此时,溶液由混合前的无色透明变为黄色透明。添加结束后进一步搅拌30分钟,由此制作出硫化锑形成用涂布液。
对硫化锑形成用涂布液测定红外吸收光谱,结果来自-NH2伸缩振动(Stretching vibration)的3个吸收峰的位置(3370cm-1、3290cm-1、3148cm-1)与硫脲单一成分的来自-NH2的吸收峰的位置相同。另一方面,相对于在硫脲单一成分中为1个峰(1413cm-1),来自C=S键的吸收峰在硫化锑形成用涂布液中分为2个。另外,来自C-N的伸缩振动的吸收峰从1474cm-1迁移至1511cm-1。
从这些结果可知,在硫化锑形成用涂布液中,在锑与硫脲之间形成络合物,该络合物的形成并不是在锑原子与硫脲中的氮原子之间形成的,而是在锑原子与硫脲中的硫原子之间形成的。
(硫化物半导体薄膜的形成)
在转速3000rpm的条件下在ITO玻璃基板(ITO膜的厚度:240nm)上通过旋涂来涂布硫化锑形成用涂布液。涂布后,在室温下放置10分钟后,在70℃下干燥5分钟。此时的膜几乎为无色透明。然后,将样品投入真空炉,边抽真空,边在260℃下烧成10分钟,由此得到硫化锑的薄膜。从真空炉中取出的膜为黑色。将烧成后的膜用甲醇进行超声波洗涤5分钟,然后进行膜的物性评价。
首先,用膜厚计(KLA-TENCOR、P-16+)测定平均膜厚,结果为120nm。然后,用分光光度计(日立高科公司制、U-4100)测定膜的吸收光谱,从该吸收光谱估算带隙,结果带隙为1.7eV。然后,进行薄膜X射线衍射分析(装置:RINT-Ultima III),结果,所得到的膜是具有辉锑矿结构(Stibnite)的结晶膜。另外,用光学显微镜和激光显微镜来确认膜表面的形状,结果为平滑且均匀的形状。
(薄膜太阳能电池的制作)
通过旋涂法在所得到的硫化锑薄膜的表面将聚(3-烷基噻吩)(P3HT)进行成膜(膜厚:100nm)而作为P型半导体层。然后,通过旋涂法将聚(3,4-亚乙二氧基噻吩):聚(苯乙烯磺酸)(PEDOT:PSS)成膜为100nm的厚度来作为空穴输送层。接着,通过真空蒸镀法在其表面将厚度80nm的金电极进行成膜,由此制作出薄膜太阳能电池。
(实施例2)
将氯化锑(III)变更为乙酸锑(III),除此以外,通过与实施例1同样的方法制作出硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池。另外,对于硫化物半导体薄膜的物性,也通过与实施例1同样的方法进行评价。
需要说明的是,对所得到的硫化物半导体形成用涂布液测定红外吸收光谱,结果确认出在锑与硫脲之间形成了络合物。
(实施例3)
将硫脲变更为硫代硫酸钠,除此以外,通过与实施例1同样的方法制作出硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池。另外,对于硫化物半导体薄膜的物性,也通过与实施例1同样的方法进行评价。
需要说明的是,对所得到的硫化物半导体形成用涂布液测定红外吸收光谱,结果确认出在锑与硫代硫酸之间形成了络合物。
(实施例4)
将硫脲变更为硫代氰酸钾,除此以外,通过与实施例1同样的方法制作出硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池。另外,对于硫化物半导体薄膜的物性,也通过与实施例1同样的方法进行评价。
需要说明的是,对所得到的硫化物半导体形成用涂布液测定红外吸收光谱,结果确认出在锑与硫代氰酸之间形成了络合物。
(实施例5)
将溶剂从甲醇变更为异丙醇,除此以外,通过与实施例1同样的方法制作出硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池。另外,对于硫化物半导体薄膜的物性,也通过与实施例1同样的方法进行评价。
需要说明的是,对所得到的硫化物半导体形成用涂布液测定红外吸收光谱,结果确认出在锑与硫脲之间形成了络合物。
(实施例6)
将溶剂从甲醇变更为N,N-二甲基甲酰胺,除此以外,通过与实施例1同样的方法制作出硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池。另外,对于硫化物半导体薄膜的物性,也通过与实施例1同样的方法进行评价。
需要说明的是,对所得到的硫化物半导体形成用涂布液测定红外吸收光谱,结果确认出在锑与硫脲之间形成了络合物。
(实施例7)
将氯化锑(III)变更为硝酸铋(III),除此以外,通过与实施例1同样的方法制作出硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池。另外,对于硫化物半导体薄膜的物性,也通过与实施例1同样的方法进行评价。
需要说明的是,对所得到的硫化物半导体形成用涂布液测定红外吸收光谱,结果确认出在铋与硫脲之间形成了络合物。
(实施例8)
将硫脲变更为乙基黄原酸钾、将溶剂从甲醇变更为甲苯、将烧成温度从260℃变更为200℃,除此以外,通过与实施例1同样的方法制作出硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池。另外,对于硫化物半导体薄膜的物性,也通过与实施例1同样的方法进行评价。
需要说明的是,对所得到的硫化物半导体形成用涂布液测定红外吸收光谱,结果确认出在锑与乙基黄原酸之间形成了络合物。
(比较例1)
将硫脲变更为硫化钠,除此以外,通过与实施例1同样的方法制作出硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池。另外,对于硫化物半导体薄膜的物性,也通过与实施例1同样的方法进行评价。
需要说明的是,所得到的硫化物半导体形成用涂布液不是透明的,而是容易发生沉淀的黄色混浊液。对于该黄色混浊成分,用红外吸收光谱和荧光X射线进行测定,结果可知为硫化锑。因此可以确认出,在使用硫化钠的情况下,在硫化物半导体形成用涂布液中没有形成络合物,而是氯化锑与硫化钠直接反应而形成了硫化锑。
(比较例2)
将溶剂从甲醇变更为水,除此以外,通过与实施例1同样的方法制作出硫化物半导体形成用涂布液、硫化物半导体薄膜和薄膜太阳能电池。另外,对于硫化物半导体薄膜的物性,也通过与实施例1同样的方法进行评价。
需要说明的是,所得到的硫化物半导体形成用涂布液不是透明的,而是白色的混浊液。对于该白色混浊液成分,用红外吸收光谱和荧光X射线进行测定,结果可知为氧化锑。可认为这是由于作为原料的氯化锑在水中容易发生水解而造成的。
(评价)
对所得到的薄膜太阳能电池进行以下的评价。
(太阳能电池特性评价)
在实施例和比较例中得到的薄膜太阳能电池的电极间连接电源(KEITHLEY公司制、236型),使用强度100mW/cm2的阳光模拟器(山下电装公司制)来测定太阳能电池的能量转换效率。需要说明的是,将比较例1中得到的太阳能电池的能量转换效率设为1.0而作为标准。结果如表1所示。
[表1]
产业上的可利用性
根据本发明,能够提供一种硫化物半导体形成用涂布液,该涂布液能够大面积且简易地形成作为光电转换材料的半导体材料而言有用的硫化物半导体。另外,根据本发明,能够提供一种使用该硫化物半导体形成用涂布液所制造的硫化物半导体薄膜和薄膜太阳能电池。
Claims (5)
1.一种硫化物半导体形成用涂布液,其特征在于,
含有络合物,所述络合物包含元素周期表第15族的金属元素和硫。
2.根据权利要求1所述的硫化物半导体形成用涂布液,其特征在于,
所述硫化物半导体形成用涂布液至少由含有元素周期表第15族的金属元素的含金属化合物、含硫化合物和有机溶剂制得。
3.一种硫化物半导体薄膜,其特征在于,
所述硫化物半导体薄膜是通过在基板上涂布权利要求1或2所述的硫化物半导体形成用涂布液而制造的。
4.一种薄膜太阳能电池,其特征在于,
将使用权利要求1或2所述的硫化物半导体形成用涂布液而制得的硫化物半导体用作光电转换层。
5.根据权利要求4所述的薄膜太阳能电池,其特征在于,
光电转换层还包含与硫化物半导体邻接的有机半导体。
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PCT/JP2013/062028 WO2013168567A1 (ja) | 2012-05-07 | 2013-04-24 | 硫化物半導体形成用塗布液、硫化物半導体薄膜及び薄膜太陽電池 |
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US20160226009A1 (en) * | 2013-09-25 | 2016-08-04 | Sekisui Chemical Co., Ltd. | Thin film solar cell, semiconductor thin film and coating liquid for forming semiconductor |
WO2015068683A1 (ja) * | 2013-11-07 | 2015-05-14 | 積水化学工業株式会社 | 半導体形成用塗布液、半導体薄膜、薄膜太陽電池及び薄膜太陽電池の製造方法 |
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US20050009229A1 (en) * | 2003-07-10 | 2005-01-13 | International Business Machines Corporation | Solution deposition of chalcogenide films |
WO2011102673A2 (ko) * | 2010-02-18 | 2011-08-25 | 한국화학연구원 | 전고체상 이종 접합 태양전지 |
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