JP6121791B2 - Aqueous composition, metal sulfide thin film, metal sulfide particles, and photoelectric conversion element - Google Patents
Aqueous composition, metal sulfide thin film, metal sulfide particles, and photoelectric conversion element Download PDFInfo
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- JP6121791B2 JP6121791B2 JP2013098679A JP2013098679A JP6121791B2 JP 6121791 B2 JP6121791 B2 JP 6121791B2 JP 2013098679 A JP2013098679 A JP 2013098679A JP 2013098679 A JP2013098679 A JP 2013098679A JP 6121791 B2 JP6121791 B2 JP 6121791B2
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- sulfide
- aqueous solution
- solution composition
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- thin film
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- 229910052976 metal sulfide Inorganic materials 0.000 title claims description 120
- 238000006243 chemical reaction Methods 0.000 title claims description 112
- 239000000203 mixture Substances 0.000 title claims description 103
- 239000010409 thin film Substances 0.000 title claims description 81
- 239000002245 particle Substances 0.000 title description 35
- 239000007864 aqueous solution Substances 0.000 claims description 112
- 239000010419 fine particle Substances 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 51
- 238000010521 absorption reaction Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- -1 carboxylate ion Chemical class 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 27
- 229910021645 metal ion Inorganic materials 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- OKGXJRGLYVRVNE-UHFFFAOYSA-N diaminomethylidenethiourea Chemical compound NC(N)=NC(N)=S OKGXJRGLYVRVNE-UHFFFAOYSA-N 0.000 claims description 21
- 238000000862 absorption spectrum Methods 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 11
- 229910052793 cadmium Inorganic materials 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001722 carbon compounds Chemical class 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
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- 239000002184 metal Substances 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 description 78
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 54
- 239000000758 substrate Substances 0.000 description 31
- 150000003585 thioureas Chemical class 0.000 description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 29
- 239000012535 impurity Substances 0.000 description 28
- 239000010408 film Substances 0.000 description 24
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 23
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 23
- 238000005755 formation reaction Methods 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000000224 chemical solution deposition Methods 0.000 description 21
- 229910052717 sulfur Inorganic materials 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 17
- 239000013078 crystal Substances 0.000 description 13
- 230000006866 deterioration Effects 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052745 lead Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 3
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- GMEHFXXZSWDEDB-UHFFFAOYSA-N N-ethylthiourea Chemical compound CCNC(N)=S GMEHFXXZSWDEDB-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- SNWNLRQYQRTOBP-UHFFFAOYSA-N [O--].[S--].[Zn++].[Zn++] Chemical compound [O--].[S--].[Zn++].[Zn++] SNWNLRQYQRTOBP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- RMUFSRMRRDOUHH-UHFFFAOYSA-N hydrazinylmethylidenethiourea Chemical compound NN=CNC(N)=S RMUFSRMRRDOUHH-UHFFFAOYSA-N 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- POXAIQSXNOEQGM-UHFFFAOYSA-N propan-2-ylthiourea Chemical compound CC(C)NC(N)=S POXAIQSXNOEQGM-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 2
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
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- KREOCUNMMFZOOS-UHFFFAOYSA-N 1,3-di(propan-2-yl)thiourea Chemical compound CC(C)NC(S)=NC(C)C KREOCUNMMFZOOS-UHFFFAOYSA-N 0.000 description 1
- KAJICSGLHKRDLN-UHFFFAOYSA-N 1,3-dicyclohexylthiourea Chemical compound C1CCCCC1NC(=S)NC1CCCCC1 KAJICSGLHKRDLN-UHFFFAOYSA-N 0.000 description 1
- ALVBWLGHXVFVEL-UHFFFAOYSA-N 1-(diaminomethylidene)-3-ethylthiourea Chemical compound CCNC(=S)N=C(N)N ALVBWLGHXVFVEL-UHFFFAOYSA-N 0.000 description 1
- SPLJCDGYZTYQQY-UHFFFAOYSA-N 1-(diaminomethylidene)-3-methylthiourea Chemical compound CNC(=S)NC(N)=N SPLJCDGYZTYQQY-UHFFFAOYSA-N 0.000 description 1
- IKGVILAOZDBXSV-UHFFFAOYSA-N 1-(diaminomethylidene)-3-phenylthiourea Chemical compound NC(N)=NC(=S)NC1=CC=CC=C1 IKGVILAOZDBXSV-UHFFFAOYSA-N 0.000 description 1
- GCZZOZBWAZHCAN-UHFFFAOYSA-N 1-phenyl-3-(1,3-thiazol-2-yl)thiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=NC=CS1 GCZZOZBWAZHCAN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- NASZHXNNWDSNKO-UHFFFAOYSA-N C(N)(=N)NC(NC(N)=N)=S Chemical compound C(N)(=N)NC(NC(N)=N)=S NASZHXNNWDSNKO-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UYIDDRHLIYTWGH-UHFFFAOYSA-N [Bi]=S.[Cu]=S Chemical compound [Bi]=S.[Cu]=S UYIDDRHLIYTWGH-UHFFFAOYSA-N 0.000 description 1
- SGXFXOOVJIJTEQ-UHFFFAOYSA-M [OH-].[Zn+2].[S-2].[Zn+2].[O-2].[Zn+2] Chemical compound [OH-].[Zn+2].[S-2].[Zn+2].[O-2].[Zn+2] SGXFXOOVJIJTEQ-UHFFFAOYSA-M 0.000 description 1
- GNAFETLWJDXDLJ-UHFFFAOYSA-N [Pb]=S.[Hg]=S Chemical compound [Pb]=S.[Hg]=S GNAFETLWJDXDLJ-UHFFFAOYSA-N 0.000 description 1
- JKBPYWPYERJPGX-UHFFFAOYSA-N [Pb]=S.[S-2].[Cd+2] Chemical compound [Pb]=S.[S-2].[Cd+2] JKBPYWPYERJPGX-UHFFFAOYSA-N 0.000 description 1
- FJSLXIFSVWITDH-UHFFFAOYSA-N [S].[Cu].[Pb].[S] Chemical compound [S].[Cu].[Pb].[S] FJSLXIFSVWITDH-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- BCWCBZFRNZWLAR-UHFFFAOYSA-N cadmium(2+) sulfanylidenemercury sulfide Chemical compound [Hg]=S.[S-2].[Cd+2] BCWCBZFRNZWLAR-UHFFFAOYSA-N 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
- 239000004202 carbamide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
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- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
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- XPDICGYEJXYUDW-UHFFFAOYSA-N tetraarsenic tetrasulfide Chemical compound S1[As]2S[As]3[As]1S[As]2S3 XPDICGYEJXYUDW-UHFFFAOYSA-N 0.000 description 1
- BXJGLLKRUQQYTC-UHFFFAOYSA-N thallium(1+);sulfide Chemical compound [S-2].[Tl+].[Tl+] BXJGLLKRUQQYTC-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Description
本発明は、溶液析出法によって不純物の少ない金属硫化物を生成できる水溶液組成物、ならびに、不純物の少ない金属硫化物薄膜および金属硫化物粒子、不純物の少ないバッファ層を有する光電変換素子に関する。 The present invention relates to an aqueous solution composition capable of producing a metal sulfide with few impurities by a solution deposition method, and a photoelectric conversion element having a metal sulfide thin film and metal sulfide particles with few impurities, and a buffer layer with few impurities.
特許文献１等に示されるように、太陽電池等の光電変換素子においては、光電変換層に隣接して、バッファ層が設けられる。このバッファ層は、光生成キャリアの再結合の防止、バンド不連続の整合、格子整合、および、光電変換層の表面凹凸のカバレッジ等を目的とするものである。
このようなバッファ層としては、一例として、硫化カドミウムや硫化亜鉛等の金属硫化物が用いられている。
As shown in Patent Document 1 and the like, in a photoelectric conversion element such as a solar cell, a buffer layer is provided adjacent to the photoelectric conversion layer. This buffer layer is intended to prevent recombination of photogenerated carriers, band discontinuous matching, lattice matching, coverage of surface irregularities of the photoelectric conversion layer, and the like.
As such a buffer layer, metal sulfides such as cadmium sulfide and zinc sulfide are used as an example.
硫化カドミウムや硫化亜鉛の粉末を生成する方法が、非特許文献１や非特許文献２に記載されている。
これらの文献に記載される方法では、チオ尿素誘導体であるアルキルチオ尿素と、金属塩化物とを原料として、還流状態の有機溶媒中で反応することで、硫化カドミウムや硫化亜鉛を生成している。
Non-patent document 1 and non-patent document 2 describe a method for producing a powder of cadmium sulfide or zinc sulfide.
In the methods described in these documents, cadmium sulfide and zinc sulfide are generated by reacting alkylthiourea, which is a thiourea derivative, and a metal chloride as raw materials in a refluxing organic solvent.
具体的には、非特許文献１には、Ｎ−メチルチオ尿素あるいはＮ−エチルチオ尿素と塩化カドミウムとをエタノールに投入し、還流状態で１〜２時間程度反応することで前躯体となる錯体を生成し、この錯体をＴＯＰＯ(tri-octylphosphine oxide)やＴＯＰ(tri-octylphosphine)を用いて処理することにより、硫化カドミウムの粉末を生成する方法が記載されている。
また、非特許文献２には、Ｎ，Ｎ’−ジシクロヘキシルチオ尿素あるいはＮ，Ｎ’−ジイソプロピルチオ尿素と塩化亜鉛とをエタノールに投入し、還流状態で１時間程度反応することで、前躯体となる錯体を生成し、この錯体をＴＯＰを用いて処理することにより、硫化亜鉛の粉末を生成する方法が記載されている。
Specifically, in Non-Patent Document 1, N-methylthiourea or N-ethylthiourea and cadmium chloride are added to ethanol and reacted for about 1 to 2 hours under reflux to produce a complex that becomes a precursor. In addition, a method is described in which a cadmium sulfide powder is produced by treating this complex with TOPO (tri-octylphosphine oxide) or TOP (tri-octylphosphine).
In Non-Patent Document 2, N, N′-dicyclohexylthiourea or N, N′-diisopropylthiourea and zinc chloride are added to ethanol and reacted for about 1 hour in a reflux state. Is produced, and the complex is treated with TOP to produce a zinc sulfide powder.
この方法は、有機溶媒を用い、しかも、還流状態での反応が必要であるため、手間がかかり、かつ、環境的にも不利である。これに対し、有機溶媒を用いない、簡便で安全な金属硫化物の生成方法として、溶液析出法が知られている。
溶液析出法による金属硫化物の生成は、一般的に、金属イオンと硫黄源とを含む水溶液を用いて、水溶液中で金属硫化物を生成して析出することにより行われる。また、硫黄源としては、一般的に、チオ尿素が用いられる。
また、溶液析出法は、液相からの析出反応であるため、金属硫化物等の目的物を、基板等の被着体上に膜状に析出させることも可能である。この方法は、一般的に、化学浴析出法（ＣＢＤ(chemical bath deposition)法）や化学溶液析出法と言われている。
Since this method uses an organic solvent and requires a reaction in a reflux state, it takes time and is also environmentally disadvantageous. On the other hand, a solution precipitation method is known as a simple and safe method for producing a metal sulfide without using an organic solvent.
The production of metal sulfides by the solution precipitation method is generally performed by producing and depositing metal sulfides in an aqueous solution using an aqueous solution containing metal ions and a sulfur source. Moreover, thiourea is generally used as the sulfur source.
In addition, since the solution precipitation method is a precipitation reaction from a liquid phase, it is possible to deposit a target object such as a metal sulfide in a film form on an adherend such as a substrate. This method is generally referred to as chemical bath deposition (CBD) or chemical solution deposition.
例えば、前述の特許文献１には、チオ尿素、亜鉛イオン、クエン酸の金属塩およびアンモニアを含む水溶液（反応液）を調製して、この水溶液を用いる化学浴析出法によって、光電変換素子のバッファ層として、硫化亜鉛（Ｚｎ（Ｓ，Ｏ）および／またはＺｎ（Ｓ，Ｏ）を主成分とする亜鉛化合物）からなる層を形成することが記載されている。 For example, in Patent Document 1 described above, an aqueous solution (reaction solution) containing thiourea, zinc ions, a metal salt of citric acid and ammonia is prepared, and a buffer of a photoelectric conversion element is obtained by a chemical bath deposition method using this aqueous solution. It is described that a layer made of zinc sulfide (a zinc compound containing Zn (S, O) and / or Zn (S, O) as a main component) is formed as the layer.
チオ尿素を用いた溶液析出法による金属硫化物の生成反応機構は、非特許文献３に記されている。この反応では、チオ尿素が水溶液中で加水分解を起こし、Ｃ＝Ｓ結合が切断されてＳＨ-イオンやＳ2-イオンが生成する。一般的に、塩基性領域では、金属硫化物の溶解度が低い。そのため、生成したＳＨ-イオンやＳ2-イオンは、直ちに金属イオンと結合し、金属硫化物を形成する。この際、ＯＨ-イオンや水分子も同時に化合物中に取り込まれるため、得られる化合物は、金属硫化物を含む化合物となる。
さらに詳細な反応機構として、例えば非特許文献４には、金属イオンが硫黄原子に求電子的に結合する機構が提案されている。
Non-patent document 3 describes the reaction mechanism of metal sulfide formation by solution precipitation using thiourea. In this reaction, thiourea undergoes hydrolysis in an aqueous solution, and the C = S bond is cleaved to generate SH - ions and S 2- ions. In general, the solubility of metal sulfides is low in the basic region. Therefore, the generated SH - ions and S 2- ions are immediately bonded to metal ions to form metal sulfides. At this time, since OH - ions and water molecules are simultaneously taken into the compound, the resulting compound is a compound containing a metal sulfide.
As a more detailed reaction mechanism, for example, Non-Patent Document 4 proposes a mechanism in which a metal ion is electrophilically bound to a sulfur atom.
これらの文献にも示されるように、溶液析出法による金属硫化物の生成は、硫黄源として、チオ尿素を用いることが一般的である。
しかしながら、非特許文献５や非特許文献６には、チオ尿素を用いる溶液析出法による金属硫化物の生成では、チオ尿素の分解物であるグアニジンやチオシアン酸イオンが、不純物として不可避的に薄膜や粒子内に取り込まれる場合が有ることが記載されている。
As shown in these documents, thiourea is generally used as a sulfur source in the production of metal sulfide by the solution precipitation method.
However, in Non-Patent Document 5 and Non-Patent Document 6, in the production of metal sulfides by the solution precipitation method using thiourea, guanidine and thiocyanate ions, which are decomposition products of thiourea, are inevitably formed as thin films and impurities. It is described that it may be incorporated into the particles.
一方で、特許文献２には、チオ尿素に代えて、チオ尿素誘導体であるＮ−モノアルキルチオ尿素（メチルチオ尿素、エチルチオ尿素、イソプロピルチオ尿素）を用いるＣＢＤ法によって、金属硫化物の膜を形成することが記載されている。
この方法によれば、反応水溶液中におけるコロイドの発生、すなわち微粒子形成を抑制し、薄膜形成を優先的に進行させることができる。また、特許文献２には、硫黄源としてＮ−モノアルキルチオ尿素を用いることで、形成された金属硫化物薄膜中のＣ元素やＮ元素を、チオ尿素を用いた場合より少なくできることも、示されている。
On the other hand, in Patent Document 2, a metal sulfide film is formed by a CBD method using N-monoalkylthiourea (methylthiourea, ethylthiourea, isopropylthiourea) which is a thiourea derivative instead of thiourea. It is described.
According to this method, generation of colloid in the reaction aqueous solution, that is, formation of fine particles can be suppressed, and thin film formation can be preferentially advanced. Patent Document 2 also shows that by using N-monoalkylthiourea as a sulfur source, the number of C elements and N elements in the formed metal sulfide thin film can be reduced as compared with the case of using thiourea. ing.
しかしながら、硫黄源としてＮ−モノアルキルチオ尿素を用いても、溶液析出法で生成した金属硫化物中に混入する不純物は、十分に抑制できているとは言えない。また、従来の溶液析出法による金属硫化物の生成は、反応速度が遅い。加えて、従来の溶液析出法による金属硫化物の生成では、７０℃以上の高温で反応しなければ、反応が適正に進行しない場合が有り、さらに、金属硫化物中の不純物も多くなってしまう場合も有る。
そのため、溶液析出法によって、さらに不純物の少ない金属硫化物を、より速い反応速度で、かつ、低い反応温度（水溶液温度）で生成する方法の出現が望まれている。
However, even if N-monoalkylthiourea is used as the sulfur source, it cannot be said that impurities mixed in the metal sulfide produced by the solution precipitation method can be sufficiently suppressed. Moreover, the reaction rate of the production of metal sulfide by the conventional solution precipitation method is slow. In addition, in the production of metal sulfides by the conventional solution precipitation method, the reaction may not proceed properly unless it is reacted at a high temperature of 70 ° C. or higher, and the impurities in the metal sulfide increase. There are cases.
Therefore, the appearance of a method for producing a metal sulfide with fewer impurities at a higher reaction rate and at a lower reaction temperature (aqueous solution temperature) by the solution precipitation method is desired.
本発明の目的は、このような従来技術の問題点を解決することにあり、化学浴析出法等の溶液析出法による金属硫化物の生成において、不純物が少ない金属硫化物を、速い反応速度で生成でき、しかも、低い反応温度（水溶液温度）でも、適正に反応を進行できる水溶液組成物、ならびに、不純物の少ない金属硫化物薄膜および金属硫化物微粒子、および、不純物の少ないバッファ層を有する光電変換素子を提供することにある。 An object of the present invention is to solve such problems of the prior art. In the production of metal sulfides by solution deposition methods such as chemical bath deposition, metal sulfides with less impurities can be produced at a high reaction rate. An aqueous solution composition that can be produced and that can proceed properly even at a low reaction temperature (aqueous solution temperature), and a photoelectric conversion having a metal sulfide thin film and metal sulfide fine particles with few impurities and a buffer layer with few impurities It is to provide an element.
この目的を達成するために、本発明の水溶液組成物は、溶液析出法による金属硫化物の生成に用いる水溶液組成物であって、
下記の一般式［Ｉ］
Ｒ1，Ｒ2−Ｎ−Ｃ（＝Ｓ）−Ｎ−Ｒ3，Ｒ4 ・・・ 一般式［Ｉ］
（一般式［Ｉ］において、Ｒ1〜Ｒ4は、それぞれ、水素原子またはヘテロ原子を有してもよい炭化水素基である）
で示され、かつ、Ｒ1〜Ｒ4の少なくとも１つが水素原子以外で、さらに、Ｒ1〜Ｒ4の少なくとも１つが窒素原子を含むチオ尿素誘導体と、難溶性硫化物を形成できる金属イオンとを含むことを特徴とする水溶液組成物を提供する。
In order to achieve this object, the aqueous solution composition of the present invention is an aqueous solution composition used for producing a metal sulfide by a solution precipitation method,
The following general formula [I]
R 1 , R 2 —N—C (═S) —N—R 3 , R 4 ... General formula [I]
(In the general formula [I], R 1 to R 4 are each a hydrocarbon group which may have a hydrogen atom or a hetero atom)
In shown, and, in addition at least one hydrogen atom of R 1 to R 4, further comprising a thiourea derivative containing at least one nitrogen atom of R 1 to R 4, a metal ion capable of forming a sparingly soluble sulfides The aqueous solution composition characterized by including this is provided.
このような本発明の水溶液組成物において、チオ尿素誘導体のＲ1〜Ｒ4の少なくとも１つがグアニル基であるのが好ましい。
また、チオ尿素誘導体の少なくともＲ2およびＲ4が水素原子であるのが好ましい。
また、チオ尿素誘導体がグアニルチオ尿素であるのが好ましい。
また、アンモニアを含むのが好ましい。
また、カルボン酸イオンを含むのが好ましい。
さらに、金属イオンが、カドミウム、亜鉛、インジウムおよびスズから選択される少なくとも１種の金属のイオンであるのが好ましい。
In such an aqueous solution composition of the present invention, at least one of R 1 to R 4 of the thiourea derivative is preferably a guanyl group.
Moreover, it is preferable that at least R 2 and R 4 of the thiourea derivative are hydrogen atoms.
The thiourea derivative is preferably guanylthiourea.
Moreover, it is preferable that ammonia is included.
Further, it preferably contains a carboxylate ion.
Furthermore, the metal ions are preferably ions of at least one metal selected from cadmium, zinc, indium and tin.
また、本発明の金属硫化物薄膜は、赤外吸収スペクトルにおける、２０００〜２１００ｃｍ-1の最大吸収強度ＩＲ−１、１０００〜１２００ｃｍ-1の最大吸収強度ＩＲ−２、および、１５００〜１７００ｃｍ-1の最大吸収強度ＩＲ−３の強度比が、ＩＲ−１／ＩＲ−２＜０．５、および、ＩＲ−１／ＩＲ−３＜０．５を満たすことを特徴とする金属硫化物薄膜を提供する。
また、本発明の金属硫化物微粒子は、赤外吸収スペクトルにおける、２０００〜２１００ｃｍ-1の最大吸収強度ＩＲ−１、１０００〜１２００ｃｍ-1の最大吸収強度ＩＲ−２、および、１５００〜１７００ｃｍ-1の最大吸収強度ＩＲ−３の強度比が、ＩＲ−１／ＩＲ−２＜０．５、および、ＩＲ−１／ＩＲ−３＜０．５を満たすことを特徴とする金属硫化物微粒子を提供する。
In addition, the metal sulfide thin film of the present invention has a maximum absorption intensity IR- 1 of 2000 to 2100 cm −1, a maximum absorption intensity IR-2 of 1000 to 1200 cm −1 , and 1500 to 1700 cm −1 in the infrared absorption spectrum. Provided is a metal sulfide thin film characterized in that the maximum absorption intensity IR-3 intensity ratio satisfies IR-1 / IR-2 <0.5 and IR-1 / IR-3 <0.5 To do.
In addition, the metal sulfide fine particles of the present invention have a maximum absorption intensity IR- 1 of 2000 to 2100 cm −1, a maximum absorption intensity IR-2 of 1000 to 1200 cm −1 , and 1500 to 1700 cm −1 in the infrared absorption spectrum. Provided is a metal sulfide fine particle characterized in that the intensity ratio of the maximum absorption intensity IR-3 satisfies IR-1 / IR-2 <0.5 and IR-1 / IR-3 <0.5 To do.
このような本発明の金属硫化物薄膜および金属硫化物微粒子において、カルボニル結合を有する炭素化合物を含有するのが好ましい。 Such a metal sulfide thin film and metal sulfide fine particles of the present invention preferably contain a carbon compound having a carbonyl bond.
また、本発明の光電変換素子は、赤外吸収スペクトルにおける、２０００〜２１００ｃｍ-1の最大吸収強度ＩＲ−１、１０００〜１２００ｃｍ-1の最大吸収強度ＩＲ−２、および、１５００〜１７００ｃｍ-1の最大吸収強度ＩＲ−３の強度比が、ＩＲ−１／ＩＲ−２＜０．５、および、ＩＲ−１／ＩＲ−３＜０．５を満たす金属硫化物からなる薄膜を、バッファ層として有することを特徴とする光電変換素子を提供する。 The photoelectric conversion element of the present invention, in the infrared absorption spectrum, the maximum absorption intensity IR-2 of the maximum absorption intensity IR-1,1000~1200cm -1 of 2000～2100Cm -1, and, of 1500～1700Cm -1 As a buffer layer, a thin film made of a metal sulfide satisfying IR-1 / IR-2 <0.5 and IR-1 / IR-3 <0.5 in the intensity ratio of maximum absorption intensity IR-3 The photoelectric conversion element characterized by the above is provided.
このような本発明の光電変換素子において、金属硫化物からなる薄膜が、カルボニル結合を有する炭素化合物を含有するのが好ましい。 In such a photoelectric conversion element of the present invention, the thin film made of a metal sulfide preferably contains a carbon compound having a carbonyl bond.
このような本発明の水溶液組成物によれば、化学浴析出法などの溶液析出法によって、不純物の少ない金属硫化物を、速い反応速度で生成でき、さらに、低い反応温度（低温の水溶液組成物）でも、適正な金属硫化物を生成できる。
また、本発明の金属硫化物薄膜および金属硫化物微粒子は、不純物が少ない高品質な金属硫化物薄膜および金属硫化物微粒子であり、さらに、本発明の光電変換素子は、不純物が少ないバッファ層を有し、バッファ層の不純物に起因する特性低下や経時劣化が少ない、高品質な光電変換素子である。
According to such an aqueous solution composition of the present invention, a metal sulfide with less impurities can be generated at a high reaction rate by a solution precipitation method such as a chemical bath precipitation method, and a low reaction temperature (low temperature aqueous solution composition). ) But can produce the proper metal sulfide.
The metal sulfide thin film and metal sulfide fine particles of the present invention are high-quality metal sulfide thin films and metal sulfide fine particles with few impurities, and the photoelectric conversion element of the present invention has a buffer layer with few impurities. It is a high-quality photoelectric conversion element that has little deterioration in characteristics and deterioration with time due to impurities in the buffer layer.
以下、本発明の水溶液組成物、金属硫化物薄膜、金属硫化物微粒子および光電変換素子について、添付の図面に示される好適実施例を基に、詳細に説明する。 Hereinafter, the aqueous solution composition, metal sulfide thin film, metal sulfide fine particles and photoelectric conversion element of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
本発明の水溶液組成物は、化学浴析出法（ＣＢＤ(chemical bath deposition)法）や化学溶液析出法等の溶液析出法（液相析出法）による金属硫化物の生成に用いられる水溶液組成物である。
なお、本発明の水溶液組成物は、ＣＢＤ法等による金属硫化物薄膜の形成（生成）のみならず、金属硫化物微粒子の形成にも利用される。水溶液から液相析出によって目的物の微粒子や薄膜を生成する手法においては、過飽和度（溶存種の濃度と、固体物質の飽和状態での溶存種との濃度の差）によって、系内で均一核生成、すなわち微粒子形成が支配的になるか、不均一核生成、すなわち薄膜形成が支配的になるかが決まる。従って、微粒子形成に用いる水溶液組成物と、薄膜形成に用いる水溶液組成物は、組成、濃度、液温等は同一ではないものの、類似の水溶液組成物として定められる。ただし、微粒子形成と薄膜形成のいずれか一方のみを進行させることは難しい。
The aqueous solution composition of the present invention is an aqueous solution composition used for the production of metal sulfides by a solution deposition method (liquid phase deposition method) such as a chemical bath deposition method (CBD (chemical bath deposition) method) or a chemical solution deposition method. is there.
The aqueous solution composition of the present invention is used not only for the formation (generation) of a metal sulfide thin film by the CBD method or the like, but also for the formation of metal sulfide fine particles. In the method of producing fine particles or thin films of the target product by liquid phase precipitation from an aqueous solution, uniform nuclei are generated in the system depending on the degree of supersaturation (the difference between the concentration of dissolved species and the dissolved species in the saturated state of the solid substance). It is determined whether the generation, that is, the formation of fine particles becomes dominant, or the generation of non-uniform nucleation, that is, the formation of thin film becomes dominant. Accordingly, the aqueous solution composition used for forming the fine particles and the aqueous solution composition used for forming the thin film are defined as similar aqueous solution compositions although the composition, concentration, liquid temperature, and the like are not the same. However, it is difficult to advance only one of fine particle formation and thin film formation.
本発明の水溶液組成物は、一般式［Ｉ］
Ｒ1，Ｒ2−Ｎ−Ｃ（＝Ｓ）−Ｎ−Ｒ3，Ｒ4 ・・・ 一般式［Ｉ］
（一般式［Ｉ］において、Ｒ1〜Ｒ4は、それぞれ、水素原子またはヘテロ原子を有してもよい炭化水素基である）
で示され、かつ、Ｒ1〜Ｒ4の少なくとも１つが水素原子以外で、さらに、Ｒ1〜Ｒ4の少なくとも１つが窒素原子を含むチオ尿素誘導体（以下、このチオ尿素誘導体を『所定のチオ尿素誘導体』とも言う）と、難溶性の硫化物を形成できる金属イオンとを含む水溶液組成物である。
The aqueous solution composition of the present invention has the general formula [I].
R 1 , R 2 —N—C (═S) —N—R 3 , R 4 ... General formula [I]
(In the general formula [I], R 1 to R 4 are each a hydrocarbon group which may have a hydrogen atom or a hetero atom)
And at least one of R 1 to R 4 is other than a hydrogen atom, and at least one of R 1 to R 4 contains a nitrogen atom (hereinafter, this thiourea derivative is referred to as a “predetermined thiourea”). It is also referred to as “urea derivative”) and a metal ion capable of forming a sparingly soluble sulfide.
前述のように、ＣＢＤ法等の溶液析出法による金属硫化物の生成においては、硫黄源としてチオ尿素を用いるのが通常である。これに対して、本発明の水溶液組成物においては、溶液析出法による金属硫化物の生成において、所定のチオ尿素誘導体を用いる。
本発明においては、この所定のチオ尿素誘導体を用いることにより、不純物が少ない、高品質な金属硫化物（薄膜および／または微粒子）を生成することを可能にしている。加えて、本発明の水溶液組成物は、所定のチオ尿素誘導体を用いることにより、金属硫化物生成の反応速度（生成速度）を向上し、さらに、金属硫化物の反応温度（反応中の水溶液組成物の温度）を低下させることを可能にしている。
As described above, in the production of metal sulfides by solution precipitation methods such as the CBD method, it is usual to use thiourea as a sulfur source. On the other hand, in the aqueous solution composition of the present invention, a predetermined thiourea derivative is used in the production of metal sulfide by the solution precipitation method.
In the present invention, by using this predetermined thiourea derivative, it is possible to produce a high-quality metal sulfide (thin film and / or fine particles) with few impurities. In addition, the aqueous solution composition of the present invention improves the reaction rate (production rate) of metal sulfide formation by using a predetermined thiourea derivative, and further, the reaction temperature of the metal sulfide (the aqueous solution composition during the reaction). The temperature of the object) can be lowered.
前述のように、硫黄源としてチオ尿素を用いるＣＢＤ法等の溶液析出法で生成した金属硫化物（金属硫化物を含む化合物）には、不純物としてチオシアン酸イオンを含む場合があることが知られている。チオシアン酸イオンは、チオ尿素の分解に伴い生成する。
本発明の水溶液組成物は、チオ尿素に代えて所定のチオ尿素誘導体を用いることによって、チオシアン酸イオンの生成を抑制でき、金属硫化物中への取り込みが少なくなったものと推定される。このことによって、不純物の少ない高品質な金属硫化物（金属硫化物薄膜、金属硫化物微粒子）を生成することが可能になり、例えば、光電変換素子のバッファ層など、半導体素子等に用いた場合の性能低下、経時劣化の抑制が可能になる。
As described above, it is known that metal sulfides (compounds containing metal sulfides) produced by a solution precipitation method such as CBD method using thiourea as a sulfur source may contain thiocyanate ions as impurities. ing. Thiocyanate ions are generated with the decomposition of thiourea.
In the aqueous solution composition of the present invention, it is presumed that by using a predetermined thiourea derivative instead of thiourea, the generation of thiocyanate ions can be suppressed and the incorporation into the metal sulfide is reduced. This makes it possible to produce high-quality metal sulfides (metal sulfide thin films, metal sulfide fine particles) with few impurities. For example, when used for semiconductor elements such as buffer layers of photoelectric conversion elements It is possible to suppress degradation of performance and deterioration with time.
また、従来のチオ尿素を用いる水溶液組成物による溶液析出法でも、反応速度は、水溶液の濃度の上昇や、ｐＨの調整によって、ある程度であれば向上させることができる。
しかしながら、本発明は、チオ尿素に代わって、所定のチオ尿素誘導体を用いることにより、同じ濃度領域において劇的な反応速度の向上を達成しており、効果が著しい。
また、成膜温度については、硫黄含有化合物の分解反応の反応エネルギーに関わる因子であることから、同一の硫黄含有化合物を用いる限り、劇的な低減は困難である。これに対し、本発明では、チオ尿素に代わって、所定のチオ尿素誘導体を用いるため、分解反応が大幅に促進され、反応温度を低下させることが可能になる。
In addition, even in the conventional solution precipitation method using an aqueous solution composition using thiourea, the reaction rate can be improved to some extent by increasing the concentration of the aqueous solution or adjusting the pH.
However, the present invention achieves a dramatic improvement in the reaction rate in the same concentration range by using a predetermined thiourea derivative instead of thiourea, and the effect is remarkable.
Further, since the film forming temperature is a factor related to the reaction energy of the decomposition reaction of the sulfur-containing compound, it is difficult to drastically reduce it as long as the same sulfur-containing compound is used. On the other hand, in the present invention, since a predetermined thiourea derivative is used instead of thiourea, the decomposition reaction is greatly accelerated and the reaction temperature can be lowered.
この所定のチオ尿素誘導体が効果を示す作用機序は必ずしも明らかではない。
しかしながら、本発明者の検討によれば、チオ尿素が水溶液中で加水分解を起こし、Ｃ＝Ｓ結合が切断されることを考えると、窒素原子に結合する水素原子の少なくとも１つを、窒素原子を含む他の官能基で置換することによって、Ｃ＝Ｓ近傍の電子密度が変化するなどして、反応性が高まることが考えられる。一般的には、硫黄原子の近傍に電子をより局在化させることにより、結合のイオン性が高まり、結合の切断反応の反応性が向上すると考えられる。本発明で用いる所定のチオ尿素誘導体においても、同様の機構が働いているものと推定される。
The mechanism of action of this predetermined thiourea derivative is not always clear.
However, according to the study by the present inventor, considering that thiourea is hydrolyzed in an aqueous solution and the C═S bond is cleaved, at least one hydrogen atom bonded to the nitrogen atom is replaced with a nitrogen atom. By substituting with another functional group containing, the electron density in the vicinity of C = S may change, and the reactivity may be increased. In general, it is considered that by making electrons more localized in the vicinity of a sulfur atom, the ionicity of the bond is increased and the reactivity of the bond breaking reaction is improved. It is presumed that the same mechanism works in the predetermined thiourea derivative used in the present invention.
所定のチオ尿素誘導体において、一般式［Ｉ］のＲ1〜Ｒ4としては、水素原子、メチル基、エチル基、フェニル基、アリル基、フェニル基、チアゾリル基、ジメチルフェニル基、アミノイミノメチル基等、水素原子、および、チオ尿素の水素原子に置換可能な各種の官能基が、各種、例示される。 In the predetermined thiourea derivative, R 1 to R 4 in the general formula [I] include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an allyl group, a phenyl group, a thiazolyl group, a dimethylphenyl group, and an aminoiminomethyl group. And various functional groups that can be substituted with hydrogen atoms and hydrogen atoms of thiourea.
ここで、本発明の水溶液組成物においては、所定のチオ尿素誘導体は、前述のように、一般式［Ｉ］で示され、かつ、Ｒ1〜Ｒ4の少なくとも１つが水素原子以外で、さらに、Ｒ1〜Ｒ4の少なくとも１つが窒素原子を含むチオ尿素誘導体である。
本発明においては、この条件に当てはまるものであれば、各種のチオ尿素誘導体が利用可能である。
具体的には、１−フェニル−３−（２−チアゾリル）チオ尿素、グアニルチオ尿素等が例示される。
Here, in the aqueous solution composition of the present invention, the predetermined thiourea derivative is represented by the general formula [I] as described above, and at least one of R 1 to R 4 is other than a hydrogen atom, , R 1 to R 4 are thiourea derivatives containing a nitrogen atom.
In the present invention, various thiourea derivatives can be used as long as this condition is met.
Specific examples include 1-phenyl-3- (2-thiazolyl) thiourea and guanylthiourea.
中でも、少なくともＲ1がアミノイミノメチル基（−Ｃ（＝ＮＨ）ＮＨ2）であるチオ尿素誘導体が好ましい。この場合、少なくともＲ2およびＲ4が水素原子であるのが好ましく、特に、Ｒ2、Ｒ3およびＲ4がすべてＨであるグアニルチオ尿素が最も好ましい。
なお、グアニルチオ尿素は、１−（アミノイミノメチル）チオ尿素； グチミン； グアニルチオウレア； アミジノチオ尿素； チオジシアノジアミジン； １−アミジノチオ尿素； １−（アミノイミノメチル）イソチオ尿素； アミジノチオウレア； 等の別名でも呼称される。
Among them, a thiourea derivative in which at least R 1 is an aminoiminomethyl group (—C (═NH) NH 2 ) is preferable. In this case, it is preferable that at least R 2 and R 4 are hydrogen atoms, and guanylthiourea in which R 2 , R 3 and R 4 are all H is most preferable.
Guanylthiourea is 1- (aminoiminomethyl) thiourea; Gutimine; Guanylthiourea; Amidinothiourea; Thiodicyanodiamidine; 1-Amidinothiourea; 1- (Aminoiminomethyl) isothiourea; Amidinothiourea; But it is also called.
また、Ｒ1がアミノイミノメチル基で、Ｒ2、Ｒ3およびＲ4の全てが水素原子ではない化合物すなわちグアニルチオ尿素の誘導体としては、１，３−ビス−グアニルチオ尿素、１−メチル−３−グアニルチオ尿素、１−エチル−３−グアニルチオ尿素、１−フェニル−３−グアニルチオ尿素、１−［Ｎ１−（３，４−ジクロロフェニル）アミジノ］チオ尿素、１−ブチル−３−［Ｎ１−（３，４−ジクロロフェニル）アミジノ］チオ尿素、１−エチル−３−［Ｎ１−（３，４−ジクロロフェニル）アミジノ］チオ尿素等が例示される。 Further, compounds in which R 1 is an aminoiminomethyl group and all of R 2 , R 3 and R 4 are not hydrogen atoms, that is, derivatives of guanylthiourea include 1,3-bis-guanylthiourea, 1-methyl-3- Guanylthiourea, 1-ethyl-3-guanylthiourea, 1-phenyl-3-guanylthiourea, 1- [N1- (3,4-dichlorophenyl) amidino] thiourea, 1-butyl-3- [N1- (3 Examples include 4-dichlorophenyl) amidino] thiourea and 1-ethyl-3- [N1- (3,4-dichlorophenyl) amidino] thiourea.
本発明の水溶液組成物において、グアニルチオ尿素およびグアニルチオ尿素の誘導体、中でも特にグアニルチオ尿素が、とりわけ顕著な効果を示す作用機序も必ずしも明らかではない。
本発明者の検討によれば、アミノイミノメチル基の窒素原子には非共有電子対が存在しており、これらが金属イオンに配位して、グアニルチオ尿素−金属イオンの錯体を形成するため、金属イオンとグアニルチオ尿素との反応が促進されるものと推定される。
この点を考慮すると、本発明の水溶液組成物において、所定のチオ尿素誘導体のＲ1〜Ｒ4のうち、窒素原子を含むものは、非共有電子対が存在する窒素を含むのが好ましい。
In the aqueous solution composition of the present invention, the mechanism of action of guanylthiourea and derivatives of guanylthiourea, particularly guanylthiourea, among others, is particularly not clear.
According to the study of the present inventor, an unshared electron pair exists in the nitrogen atom of the aminoiminomethyl group, and these coordinate to a metal ion to form a guanylthiourea-metal ion complex. It is presumed that the reaction between metal ions and guanylthiourea is promoted.
Considering this point, in the aqueous solution composition of the present invention, among the R 1 to R 4 of the predetermined thiourea derivative, those containing a nitrogen atom preferably contain nitrogen in which an unshared electron pair exists.
本発明の水溶液組成物において、一般式［Ｉ］で示される所定のチオ尿素誘導体の含有量（濃度）は、目的とする反応速度（成膜速度）や、目的とする金属硫化物の大きさ（厚さや粒径等）等に応じて、適宜、設定すればよい。
本発明者の検討によれば、本発明の水溶液組成物において、一般式［Ｉ］で示される所定のチオ尿素誘導体の含有量は、０．００１〜０．５ｍｏｌ／Ｌ（リットル）が好ましく、０．００５〜０．１ｍｏｌ／Ｌがより好ましい。
一般式［Ｉ］で示される所定のチオ尿素誘導体の含有量を、上記範囲とすることにより、反応速度や反応率等の点で好ましい結果を得ることができる。
In the aqueous solution composition of the present invention, the content (concentration) of the predetermined thiourea derivative represented by the general formula [I] depends on the target reaction rate (film formation rate) and the size of the target metal sulfide. What is necessary is just to set suitably according to (thickness, a particle size, etc.) etc.
According to the study of the present inventor, the content of the predetermined thiourea derivative represented by the general formula [I] in the aqueous solution composition of the present invention is preferably 0.001 to 0.5 mol / L (liter), 0.005-0.1 mol / L is more preferable.
By setting the content of the predetermined thiourea derivative represented by the general formula [I] within the above range, favorable results can be obtained in terms of reaction rate, reaction rate, and the like.
本発明の水溶液組成物は、所定のチオ尿素誘導体に加え、難溶性の硫化物を形成できる金属イオンを含む。
なお、難溶性とは、具体的には、常圧（大気圧）における２５℃の水に対する、硫化物として溶解度積が、［Ｍn+］［Ｓ2-］＝１０-5ｍｏｌ2／Ｌ2以下（Ｍはｎ価の金属イオン）であることを示す。
The aqueous solution composition of the present invention contains a metal ion capable of forming a hardly soluble sulfide in addition to a predetermined thiourea derivative.
Note that the poor solubility specifically means that the solubility product as a sulfide with respect to water at 25 ° C. under normal pressure (atmospheric pressure) is [M n + ] [S 2− ] = 10 −5 mol 2 / L 2. It is shown below (M is an n-valent metal ion).
金属イオンとしては、難溶性の硫化物を形成できる金属イオンが、各種、例示される。
具体的には、カドミウム、亜鉛、インジウム、および、スズ等の１以上の金属のイオンが好適に例示される。中でも、カドミウムおよび／または亜鉛のイオンが好ましく例示される。
Examples of metal ions include various metal ions that can form a sparingly soluble sulfide.
Specifically, ions of one or more metals such as cadmium, zinc, indium, and tin are preferably exemplified. Of these, cadmium and / or zinc ions are preferably exemplified.
本発明の水溶液組成物において、金属イオンの含有量も、目的とする反応速度や、目的とする金属硫化物の大きさ等に応じて、適宜、設定すればよいが、０．０００５〜０．５ｍｏｌ／Ｌが好ましく、０．００１〜０．１ｍｏｌ／Ｌがより好ましい。
金属イオンの含有量を、上記範囲とすることにより、反応速度や反応率等の点で好ましい結果を得ることができる。
In the aqueous solution composition of the present invention, the content of metal ions may be appropriately set according to the target reaction rate, the size of the target metal sulfide, and the like. 5 mol / L is preferable, and 0.001 to 0.1 mol / L is more preferable.
By setting the content of metal ions in the above range, preferable results can be obtained in terms of reaction rate, reaction rate, and the like.
このような金属イオンは、硫酸亜鉛、酢酸亜鉛、硝酸亜鉛、塩化亜鉛や、硫酸カドミウム、酢酸カドミウム、硝酸カドミウム、塩化カドミウムなどの金属塩等によって、本発明の水溶液組成物に添加すればよい。 Such metal ions may be added to the aqueous solution composition of the present invention by a metal salt such as zinc sulfate, zinc acetate, zinc nitrate, zinc chloride, cadmium sulfate, cadmium acetate, cadmium nitrate, cadmium chloride or the like.
本発明の水溶液組成物は、所定のチオ尿素誘導体および金属イオンに加えて、アンモニアを含有するのが好ましい。
アンモニアを含有することにより、金属硫化物の生成が促進される、緩衝作用によって反応時のｐＨ等の条件が安定に保たれる等の点で好ましい。
The aqueous solution composition of the present invention preferably contains ammonia in addition to the predetermined thiourea derivative and metal ions.
By containing ammonia, production of metal sulfide is promoted, and conditions such as pH during the reaction are stably maintained by a buffering action.
本発明の水溶液組成物において、アンモニアの含有量も、目的とする反応速度や、目的とする金属硫化物の大きさ等に応じて、適宜、設定すればよいが、０．０１〜２ｍｏｌ／Ｌが好ましく、０．１〜２ｍｏｌ／Ｌがより好ましい。
アンモニアの含有量を、上記範囲とすることにより、塩基性条件となって反応が進みやすい、反応中のアンモニア揮発が減るため、条件が安定に保たれる等の点で好ましい結果を得ることができる。
In the aqueous solution composition of the present invention, the ammonia content may be appropriately set according to the target reaction rate, the size of the target metal sulfide, etc., but is 0.01 to 2 mol / L. Is preferable, and 0.1 to 2 mol / L is more preferable.
By setting the ammonia content in the above-mentioned range, it is possible to obtain favorable results in that the reaction tends to proceed under basic conditions, the ammonia volatilization during the reaction is reduced, and the conditions are kept stable. it can.
本発明の水溶液組成物は、さらに、カルボン酸イオンを含有するのが好ましい。
カルボン酸イオンを含有することにより、金属硫化物の生成が促進される、高ｐＨでも溶液の安定性が高まる等の点で好ましい。
It is preferable that the aqueous solution composition of the present invention further contains a carboxylate ion.
By containing a carboxylate ion, the production of metal sulfide is promoted, and the stability of the solution is increased even at high pH.
本発明の水溶液組成物において、カルボン酸イオンの含有量も、目的とする反応速度や、目的とする金属硫化物の大きさ等に応じて、適宜、設定すればよいが、金属イオンと同等程度が好ましい。すなわち、０．０００５〜０．５ｍｏｌ／Ｌが好ましく、０．００１〜０．１ｍｏｌ／Ｌがより好ましい。
カルボン酸イオンの含有量を、上記範囲とすることにより、高ｐＨ条件においても反応溶液中で金属イオンが安定に存在できる等の点で好ましい結果を得ることができる。
なお、カルボン酸イオンは、各種の有機酸や有機酸塩等によって、本発明の水溶液組成物に添加すればよい。中でも、クエン酸、および、クエン酸三ナトリウム等のクエン酸塩は、好適に利用される。
In the aqueous solution composition of the present invention, the content of carboxylate ions may be set as appropriate according to the target reaction rate, the size of the target metal sulfide, etc. Is preferred. That is, 0.0005 to 0.5 mol / L is preferable, and 0.001 to 0.1 mol / L is more preferable.
By setting the carboxylate ion content in the above range, preferable results can be obtained in that metal ions can be stably present in the reaction solution even under high pH conditions.
In addition, what is necessary is just to add carboxylate ion to the aqueous solution composition of this invention by various organic acids, organic acid salt, etc. Of these, citric acid and citrate salts such as trisodium citrate are preferably used.
また、本発明の水溶液組成物には、これらの成分以外にも、ＣＢＤ法等の溶液析出法にる金属硫化物の生成に用いられる、各種の添加剤を、適宜、含有してもよい。 In addition to these components, the aqueous solution composition of the present invention may appropriately contain various additives used for the production of metal sulfides by a solution precipitation method such as the CBD method.
本発明の水溶液組成物は、ｐＨが９．０〜１２．５であるのが好ましく、９．５〜１２．０であるのがより好ましい。
水溶液組成物のｐＨを上記範囲とすることにより、反応溶液中で金属イオンが安定に存在できる等の点で好ましい結果を得ることができる。
The aqueous solution composition of the present invention preferably has a pH of 9.0 to 12.5, and more preferably 9.5 to 12.0.
By setting the pH of the aqueous solution composition to the above range, a preferable result can be obtained in that metal ions can be stably present in the reaction solution.
本発明の水溶液組成物は、ＣＢＤ法等の溶液析出法に用いられる公知の水溶液組成物と、同様に調製すればよい。
例えば、水（純水、イオン交換水）に、所定のチオ尿素誘導体、硫酸塩などの金属イオン源、アンモニア、クエン酸塩等のカルボン酸源を、投入して、本発明の水溶液組成物を調製すればよい。あるいは、各成分を含有する水溶液を、別々に調製して、調製した水溶液を混合することにより、本発明の水溶液組成物を調製してもよい。
What is necessary is just to prepare the aqueous solution composition of this invention similarly to the well-known aqueous solution composition used for solution precipitation methods, such as CBD method.
For example, a predetermined thiourea derivative, a metal ion source such as sulfate, or a carboxylic acid source such as ammonia or citrate is added to water (pure water or ion-exchanged water), and the aqueous solution composition of the present invention is used. What is necessary is just to prepare. Or you may prepare the aqueous solution composition of this invention by preparing the aqueous solution containing each component separately, and mixing the prepared aqueous solution.
ここで、本発明の水溶液組成物は、含有する成分によっては、自動的に金属硫化物の生成反応が進行してしまう場合が有る。
このような場合には、例えば、アンモニアを含有するＡ液と、アンモニアを含有しないＢ液のように、水溶液組成物を２つ（複数）に分けておき、金属硫化物を生成する際に、２つの水溶液を混合すればよい。なお、この際においては、所定のチオ尿素誘導体と金属イオンとを含有する液体は、本発明の水溶液組成物の一種であるとも言える。
あるいは、全ての成分を含有する水溶液組成物を調製した後、反応が進まない程度の低温で保管する等の方法で、本発明の水溶液組成物における金属硫化物の生成反応を停止した状態としておき、金属硫化物を生成する際に、加熱等の方法で反応を開始するようにしてもよい。
Here, depending on the components contained in the aqueous solution composition of the present invention, the metal sulfide formation reaction may automatically proceed.
In such a case, for example, when the aqueous solution composition is divided into two (plurality) like the liquid A containing ammonia and the liquid B not containing ammonia, when producing the metal sulfide, What is necessary is just to mix two aqueous solution. In this case, it can be said that the liquid containing the predetermined thiourea derivative and the metal ion is a kind of the aqueous solution composition of the present invention.
Alternatively, after preparing an aqueous solution composition containing all the components, the production reaction of the metal sulfide in the aqueous solution composition of the present invention is stopped by a method such as storing at a low temperature at which the reaction does not proceed. When producing the metal sulfide, the reaction may be started by a method such as heating.
本発明の水溶液組成物は、溶液析出法による金属硫化物の生成に用いられる。
ここで、本発明の水溶液組成物を用いる金属硫化物の生成は、ＣＢＤ法による一般的な金属硫化物薄膜の形成など、公知の水溶液組成物を用いる一般的な溶液析出法による金属硫化物の生成と同様に行えばよい。
The aqueous solution composition of the present invention is used for the production of metal sulfides by a solution precipitation method.
Here, the formation of the metal sulfide using the aqueous solution composition of the present invention is the formation of the metal sulfide by a general solution precipitation method using a known aqueous solution composition, such as formation of a general metal sulfide thin film by the CBD method. It may be performed in the same manner as the generation.
なお、前述のように、本発明の水溶液組成物によれば、金属硫化物の反応温度（水溶液組成の温度）を低減しても、金属硫化物の生成反応（合成反応）を適正に進行して、かつ、不純物の少ない金属硫化物を生成できる。例えば、本発明の水溶液組成物によれば、従来のチオ尿素やモノアルキルチオ尿素を用いた溶液析出法では困難であった低い温度での反応でも、金属硫化物を適正に生成できる。
従って、本発明の水溶液組成物を用いた金属硫化物の生成において、反応温度は、要求される反応速度、生成する金属硫化物の種類、生産設備や環境等に応じて、適宜、設定すればよい。
As described above, according to the aqueous solution composition of the present invention, even if the reaction temperature of the metal sulfide (temperature of the aqueous solution composition) is reduced, the formation reaction (synthesis reaction) of the metal sulfide proceeds properly. In addition, metal sulfides with less impurities can be produced. For example, according to the aqueous solution composition of the present invention, a metal sulfide can be appropriately generated even in a reaction at a low temperature, which has been difficult by the conventional solution precipitation method using thiourea or monoalkylthiourea.
Therefore, in the production of metal sulfide using the aqueous solution composition of the present invention, the reaction temperature may be appropriately set according to the required reaction rate, the type of metal sulfide to be produced, production equipment, environment, etc. Good.
ここで、本発明者の検討によれば、本発明の水溶液組成物を用いた金属硫化物の生成において、反応温度は、２０〜９０℃、特に、４０〜８０℃とするのが好ましい。
反応温度を上記範囲とすることにより、反応の制御が容易で、再現性に優れる、反応容器の耐熱性が不要である等の点で好ましい結果を得ることができる。
Here, according to examination of this inventor, in the production | generation of the metal sulfide using the aqueous solution composition of this invention, it is preferable that reaction temperature shall be 20-90 degreeC, especially 40-80 degreeC.
By setting the reaction temperature within the above range, preferable results can be obtained in that the reaction is easily controlled, the reproducibility is excellent, and the heat resistance of the reaction vessel is unnecessary.
このような本発明の水溶液組成物は、各種の金属硫化物の生成に利用可能である。
ここで、本発明の水溶液組成物を用いて生成する金属硫化物（後述する本発明の金属硫化物薄膜、金属硫化物微粉末、光電変換素子のバッファ層）には、不可避的に混入する各種の化合物が含まれてもよい。
すなわち、本発明の水溶液組成物を用いて生成する金属硫化物は、不可避的に混入される化合物を含む、金属硫化物を含む化合物であってもよい。例えば、硫化亜鉛であれば、Ｚｎ（Ｏ，Ｓ）で示される硫化亜鉛−酸化亜鉛混晶体でもよく、あるいはさらに、クエン酸等に起因するカルボニ結合を有する炭素化合物など、水溶液組成物に含まれる成分に起因する化合物が含まれてもよい。
Such an aqueous solution composition of the present invention can be used to produce various metal sulfides.
Here, various types of metal sulfides inevitably mixed in the metal sulfide (metal sulfide thin film, metal sulfide fine powder, buffer layer of the photoelectric conversion element described later) formed using the aqueous solution composition of the present invention. These compounds may be included.
That is, the metal sulfide produced | generated using the aqueous solution composition of this invention may be a compound containing a metal sulfide containing the compound mixed unavoidable. For example, in the case of zinc sulfide, it may be a zinc sulfide-zinc oxide mixed crystal represented by Zn (O, S), or further included in an aqueous solution composition such as a carbon compound having a carboni bond derived from citric acid or the like. Compounds resulting from the components may be included.
本発明の水溶液組成物を用いて生成できる金属硫化物としては、一例として、硫化カドミウム、硫化亜鉛、硫化水銀、硫化鉛、硫化アンチモン、硫化砒素、硫化ビスマス、硫化コバルト（ＣｏＳ、Ｃｏ3Ｓ4）、硫化銅（ＣｕＳ、Ｃｕ2Ｓ）、硫化インジウム、硫化ガリウム、硫化鉄、硫化マンガン、硫化モリブデン、硫化ニッケル、硫化銀、硫化タリウム、硫化スズ（ＳｎＳ2、Ｓｎ2Ｓ3）、硫化亜鉛−酸化亜鉛混晶体（Ｚｎ（Ｓ，Ｏ））、硫化亜鉛−酸化亜鉛−水酸化亜鉛混晶体（Ｚｎ（Ｓ，Ｏ，ＯＨ））、硫化カドミウム−硫化亜鉛混晶体（（Ｃｄ，Ｚｎ）Ｓ）、硫化カドミウム−硫化水銀混晶体（（Ｃｄ，Ｈｇ）Ｓ）、硫化カドミウム−硫化鉛混晶体（（Ｃｄ，Ｐｂ）Ｓ）、硫化水銀−硫化鉛混晶体（（Ｈｇ，Ｐｂ）Ｓ）、硫化カドミウム−硫化ビスマス混晶体（（Ｃｄ，Ｂｉ）Ｓ）、硫化銅−硫化鉛混晶体（（Ｃｕ，Ｐｂ）Ｓ）、 硫化銅−硫化ビスマス混晶体（（Ｃｕ，Ｂｉ）Ｓ）、硫化鉛−硫化スズ混晶体（（Ｐｂ，Ｓｎ）Ｓ）、硫化鉛−硫化ビスマス混晶体（（Ｐｂ，Ｂｉ）Ｓ）、硫化インジウム銅（ＣｕＩｎＳ2、ＣｕＩｎ5Ｓ8）、および、硫化ガリウム銅等が例示される。
中でも、硫化カドミウム、硫化亜鉛、硫化インジウム等の金属硫化物は、好適である。
Examples of metal sulfides that can be produced using the aqueous solution composition of the present invention include cadmium sulfide, zinc sulfide, mercury sulfide, lead sulfide, antimony sulfide, arsenic sulfide, bismuth sulfide, and cobalt sulfide (CoS, Co 3 S 4). ), Copper sulfide (CuS, Cu 2 S), indium sulfide, gallium sulfide, iron sulfide, manganese sulfide, molybdenum sulfide, nickel sulfide, silver sulfide, thallium sulfide, tin sulfide (SnS 2 , Sn 2 S 3 ), zinc sulfide -Zinc oxide mixed crystal (Zn (S, O)), zinc sulfide-zinc oxide-zinc hydroxide mixed crystal (Zn (S, O, OH)), cadmium sulfide-zinc sulfide mixed crystal ((Cd, Zn) S) ), Cadmium sulfide-mercury sulfide mixed crystal ((Cd, Hg) S), cadmium sulfide-lead sulfide mixed crystal ((Cd, Pb) S), mercury sulfide-lead sulfide mixed crystal ((Hg, Pb) S), Potassium sulfide Medium-bismuth sulfide mixed crystal ((Cd, Bi) S), copper sulfide-lead sulfide mixed crystal ((Cu, Pb) S), copper sulfide-bismuth sulfide mixed crystal ((Cu, Bi) S), lead sulfide- Examples are tin sulfide mixed crystal ((Pb, Sn) S), lead sulfide-bismuth sulfide mixed crystal ((Pb, Bi) S), indium copper sulfide (CuInS 2 , CuIn 5 S 8 ), and gallium copper sulfide. Is done.
Among these, metal sulfides such as cadmium sulfide, zinc sulfide, and indium sulfide are preferable.
本発明の金属硫化物薄膜および金属硫化物微粒子、ならびに、本発明の光電変換素子におけるバッファ層（以下、『本発明の素子のバッファ層』とも言う）は、いずれも、２０００〜２１００ｃｍ-1の最大吸収強度ＩＲ−１、１０００〜１２００ｃｍ-1の最大吸収強度ＩＲ−２、および、１５００〜１７００ｃｍ-1の最大吸収強度ＩＲ−３の強度比が、ＩＲ−１／ＩＲ−２＜０．５、および、ＩＲ−１／ＩＲ−３＜０．５を満たすものである。 The metal sulfide thin film and metal sulfide fine particles of the present invention, and the buffer layer in the photoelectric conversion device of the present invention (hereinafter also referred to as “buffer layer of the device of the present invention”) are all 2000-2100 cm −1 . The intensity ratio of the maximum absorption intensity IR- 1, the maximum absorption intensity IR-2 of 1000 to 1200 cm -1 and the maximum absorption intensity IR-3 of 1500 to 1700 cm -1 is IR-1 / IR-2 <0.5. And IR-1 / IR-3 <0.5.
このような、本発明の金属硫化物薄膜および金属硫化物微粒子、ならびに、本発明の素子のバッファ層は、前述の本発明の水溶液組成物を用いて、溶液析出法で形成することができる。また、本発明の水溶液組成物は、好ましくは、カルボン酸イオンを含有する。 Such a metal sulfide thin film and metal sulfide fine particles of the present invention and the buffer layer of the element of the present invention can be formed by the solution deposition method using the aqueous solution composition of the present invention described above. Moreover, the aqueous solution composition of the present invention preferably contains a carboxylate ion.
所定のチオ尿素誘導体を含有する水溶液組成物を用いる溶液析出法で形成された金属硫化物において、２０００〜２１００ｃｍ-1における最大吸収は、所定のチオ尿素誘導体の分解によって生じたチオシアン酸イオンの吸収ピークである。また、１０００〜１２００ｃｍ-1の最大吸収は、水酸基の吸収ピーク、１５００〜１７００ｃｍ-1の最大吸収は、カルボン酸イオンの吸収ピークである。
ここで、前述のように、本発明の水溶液組成物によれば、不純物の少ない金属硫化物を生成できる。
すなわち、２０００〜２１００ｃｍ-1の最大吸収強度ＩＲ−１、１０００〜１２００ｃｍ-1の最大吸収強度ＩＲ−２、および、１５００〜１７００ｃｍ-1の最大吸収強度ＩＲ−３において、ＩＲ−１とＩＲ−２との強度比であるＩＲ−１／ＩＲ−２が０．５未満であり、さらに、ＩＲ−１とＩＲ−３との強度比であるＩＲ−１／ＩＲ−３が０．５未満であるということは、金属硫化物内に不可避的に取り込まれる水酸基およびカルボン酸イオンに比して、所定のチオ尿素誘導体の分解によって生じたチオシアン酸イオンの混入が、極めて少ないことを示す。
In a metal sulfide formed by a solution precipitation method using an aqueous solution composition containing a predetermined thiourea derivative, the maximum absorption at 2000 to 2100 cm −1 is the absorption of thiocyanate ions generated by the decomposition of the predetermined thiourea derivative. It is a peak. The maximum absorption of the 1000 to 1200 -1, the absorption peak of hydroxyl groups, the maximum absorption of 1500～1700Cm -1 is the absorption peak of carboxylate ion.
Here, as described above, according to the aqueous solution composition of the present invention, a metal sulfide with few impurities can be generated.
That is, the maximum absorption intensity IR-2 of the maximum absorption intensity IR-1,1000~1200cm -1 of 2000～2100Cm -1, and, at the maximum absorption intensity IR-3 of 1500~1700cm -1, IR-1 and IR- IR-1 / IR-2, which is an intensity ratio with 2, is less than 0.5, and IR-1 / IR-3, which is an intensity ratio between IR-1 and IR-3, is less than 0.5. The fact that there is very little contamination of thiocyanate ions generated by the decomposition of a given thiourea derivative, as compared with hydroxyl groups and carboxylate ions inevitably incorporated into the metal sulfide.
すなわち、本発明の金属硫化物薄膜および金属硫化物微粒子は、不純物の少ない、高品質な物であり、例えば、半導体素子等に利用した際に、不純物に起因する性能低下や経時劣化が抑制できる。
また、本発明の光電変換素子は、不純物の少ないバッファ層を有するので、バッファ層の性能低下や経時劣化に起因する特性の低下等の無い、高品質な光電変換素子である。
That is, the metal sulfide thin film and metal sulfide fine particles of the present invention are high-quality products with few impurities, and can suppress performance degradation and deterioration with time due to impurities when used in, for example, semiconductor devices. .
In addition, since the photoelectric conversion element of the present invention has a buffer layer with few impurities, it is a high-quality photoelectric conversion element that has no deterioration in performance due to deterioration of the buffer layer performance or deterioration with time.
本発明の金属硫化物薄膜および金属硫化物微粒子、ならびに、本発明の素子のバッファ層において、ＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３のいすれか一方でも０．５以上であると、金属硫化物中の不純物が多く、不純物に起因する性能劣化や経時劣化が大きくなる等の不都合を生じる。
この点を考慮すると、ＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３は、共に、０．２未満が好ましい。
In the metal sulfide thin film and metal sulfide fine particles of the present invention and the buffer layer of the device of the present invention, either IR-1 / IR-2 or IR-1 / IR-3 is 0.5 or more. If so, there are many impurities in the metal sulfide, which causes inconveniences such as performance deterioration and deterioration with time due to the impurities.
Considering this point, both IR-1 / IR-2 and IR-1 / IR-3 are preferably less than 0.2.
また、金属硫化物に含まれる不純物量の指標となるＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３は、小さい方が好ましく、すなわち、下限に限定は無い。
しかしながら、これらの強度比を０にするのは、極めて困難であり、コストや生産性等を考慮すると、非現実的である。そのため、ＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３は、共に、０．０１以上であるのが好ましい。
Further, IR-1 / IR-2 and IR-1 / IR-3, which are indicators of the amount of impurities contained in the metal sulfide, are preferably smaller, that is, there is no limitation on the lower limit.
However, it is extremely difficult to set these intensity ratios to 0, and it is impractical in view of cost, productivity, and the like. Therefore, both IR-1 / IR-2 and IR-1 / IR-3 are preferably 0.01 or more.
また、本発明の金属硫化物薄膜および金属硫化物微粒子、ならびに、本発明の素子のバッファ層は、好ましくは、カルボン酸イオンを含有する。
カルボン酸イオンを含有することにより、例えばＣＩＧＳ太陽電池のバッファ層として用いる場合に、光電変換効率の面内均一性が高い光電変換素子を作成できる等の点で好ましい結果を得ることができる。
The metal sulfide thin film and metal sulfide fine particles of the present invention and the buffer layer of the device of the present invention preferably contain carboxylate ions.
By containing a carboxylate ion, for example, when used as a buffer layer of a CIGS solar cell, a preferable result can be obtained in that a photoelectric conversion element having high in-plane uniformity of photoelectric conversion efficiency can be created.
このような本発明の金属硫化物薄膜および本発明の素子のバッファ層は、前述のように、本発明の水溶液組成物を用いて、一般的なＣＢＤ法と同様に成膜を行うことで、形成できる。また、この際に、本発明の金属硫化物微粒子も形成されるので、水溶液の濾別等によって微粒子を得ればよい。
あるいは、被成膜基板を用いずにＣＢＤ法と同様の操作を行うことで、本発明の金属硫化物微粒子を形成して、濾別等によって微粒子を得てもよい。
As described above, the metal sulfide thin film of the present invention and the buffer layer of the element of the present invention are formed by using the aqueous solution composition of the present invention in the same manner as the general CBD method, Can be formed. At this time, since the metal sulfide fine particles of the present invention are also formed, the fine particles may be obtained by filtering the aqueous solution.
Alternatively, the metal sulfide fine particles of the present invention may be formed by performing the same operation as in the CBD method without using a film formation substrate, and fine particles may be obtained by filtration or the like.
このような本発明の金属硫化物薄膜は、一例として、光電変換素子に用いられるＣＩＧＳ層やＣｄＴｅ層のバッファ層、蛍光体、エレクトロクロミックデバイス、光学薄膜、光学素子、電界効果トランジスタ、各種のセンサ、各種の変換器等に、好適に利用される。
また、本発明の金属硫化物微粒子は、一例として、触媒、光触媒、蛍光体、光電気化学セルの半導体層（微粒子塗布による形成）、光学素子、電界効果トランジスタ、各種のセンサ、各種の変換器等に、好適に利用される。
Such metal sulfide thin films of the present invention include, for example, CIGS layers and buffer layers for CdTe layers used in photoelectric conversion elements, phosphors, electrochromic devices, optical thin films, optical elements, field effect transistors, and various sensors. It is suitably used for various converters.
In addition, the metal sulfide fine particles of the present invention include, for example, a catalyst, a photocatalyst, a phosphor, a semiconductor layer of a photoelectrochemical cell (formation by applying fine particles), an optical element, a field effect transistor, various sensors, and various converters. Etc. are suitably used.
前述のように、本発明の光電変換素子は、前述のバッファ層を有する光電変換素子である。なお、本発明の光電変換素子は、バッファ層が前述のバッファ層である以外は、基本的に、公知の光電変換素子と同様のものである。 As described above, the photoelectric conversion element of the present invention is a photoelectric conversion element having the buffer layer described above. The photoelectric conversion element of the present invention is basically the same as a known photoelectric conversion element except that the buffer layer is the aforementioned buffer layer.
図１に、本発明の光電変換素子の一例を概念的に示す。
図１に示すように、光電変換素子１０は、基板１２上に、下部電極（裏面電極）１４と、Iｂ族元素とIIIｂ族元素とVIｂ族元素とからなる少なくとも１種のカルコパイライト構造の化合物半導体を主成分とする光電変換層（光電変換半導体層）１６と、バッファ層１８と、窓層２０と、透光性導電層（透明電極）２４と、上部電極（グリッド電極）２６とが、順次、積層された素子である。
FIG. 1 conceptually shows an example of the photoelectric conversion element of the present invention.
As shown in FIG. 1, the photoelectric conversion element 10 includes a substrate 12, a lower electrode (back electrode) 14, and at least one compound having a chalcopyrite structure composed of a group Ib element, a group IIIb element, and a group VIb element. A photoelectric conversion layer (photoelectric conversion semiconductor layer) 16 having a semiconductor as a main component, a buffer layer 18, a window layer 20, a translucent conductive layer (transparent electrode) 24, and an upper electrode (grid electrode) 26, The devices are sequentially stacked.
（基板）
基板１２は、公知の光電変換素子に利用される公知のものである。
具体的には、ガラス基板、表面に絶縁膜が成膜されたステンレス等の金属基板、Ａｌを主成分とするＡｌ基材の少なくとも一方の面側にＡｌ2Ｏ3を主成分とする陽極酸化膜が形成された陽極酸化基板、Ｆｅを主成分とするＦｅ材の少なくとも一方の面側にＡｌを主成分とするＡｌ材が複合された複合基材の少なくとも一方の面側にＡｌ2Ｏ3を主成分とする陽極酸化膜が形成された陽極酸化基板、Ｆｅを主成分とするＦｅ材の少なくとも一方の面側にＡｌを主成分とするＡｌ膜が成膜された基材の少なくとも一方の面側にＡｌ2Ｏ3を主成分とする陽極酸化膜が形成された陽極酸化基板、およびポリイミド等の樹脂基板等が挙げられる。
(substrate)
The board | substrate 12 is a well-known thing utilized for a well-known photoelectric conversion element.
Specifically, a glass substrate, a metal substrate such as stainless steel with an insulating film formed on the surface, an anodic oxidation mainly comprising Al 2 O 3 on at least one surface side of an Al base material mainly comprising Al. An anodized substrate having a film formed thereon, Al 2 O 3 on at least one surface side of a composite base material in which an Al material containing Al as a main component is composited on at least one surface side of an Fe material containing Fe as a main component An anodized substrate having an anodic oxide film mainly composed of Fe, and at least one of a base material having an Al film mainly composed of Al formed on at least one surface side of an Fe material mainly composed of Fe Examples thereof include an anodized substrate having an anodized film mainly composed of Al 2 O 3 on the surface side, and a resin substrate such as polyimide.
（下部電極）
下部電極（裏面電極）１４は、一例として、Ｍｏ、Ｃｒ、Ｗ、および、これらの組合わせ等を主成分とするものが好ましく例示され、Ｍｏ等が特に好ましい。
下部電極１４の膜厚は、２００〜１０００ｎｍ程度が好ましい。
(Lower electrode)
As an example, the lower electrode (back electrode) 14 preferably has Mo, Cr, W, and a combination thereof as a main component, and Mo is particularly preferable.
The film thickness of the lower electrode 14 is preferably about 200 to 1000 nm.
（光電変換層）
光電変換層１６の主成分は、公知の光電変換素子に用いられている各種の材料が利用可能であるが、少なくとも１種のカルコパイライト構造の化合物半導体であることが好ましく、Iｂ族元素とIIIｂ族元素とVIｂ族元素とからなる少なくとも１種の化合物半導体であることがより好ましい。
光電変換層１６の主成分としては、ＣｕおよびＡｇからなる群より選択された少なくとも１種のIｂ族元素と、Ａｌ，ＧａおよびＩｎからなる群より選択された少なくとも１種のIIIｂ族元素と、Ｓ，Ｓｅ，およびＴｅからなる群から選択された少なくとも１種のVIｂ族元素とからなる少なくとも１種の化合物半導体であることが好ましい。
(Photoelectric conversion layer)
As the main component of the photoelectric conversion layer 16, various materials used in known photoelectric conversion elements can be used, but at least one compound semiconductor having a chalcopyrite structure is preferable. More preferably, it is at least one compound semiconductor composed of a group element and a group VIb element.
As a main component of the photoelectric conversion layer 16, at least one type Ib group element selected from the group consisting of Cu and Ag, and at least one type IIIb group element selected from the group consisting of Al, Ga, and In, It is preferably at least one compound semiconductor comprising at least one VIb group element selected from the group consisting of S, Se, and Te.
このような化合物半導体としては、ＣｕＡｌＳ2、ＣｕＧａＳ2、ＣｕＩｎＳ2、ＣｕＡｌＳｅ2、ＣｕＧａＳｅ2、ＡｇＡｌＳ2、ＡｇＧａＳ2、ＡｇＩｎＳ2、ＡｇＡｌＳｅ2、ＡｇＧａＳｅ2、ＡｇＩｎＳｅ2、ＡｇＡｌＴｅ2、ＡｇＧａＴｅ2、ＡｇＩｎＴｅ2、Ｃｕ（Ｉｎ，Ａｌ）Ｓｅ2、Ｃｕ（Ｉｎ，Ｇａ）（Ｓ，Ｓｅ）2、Ｃｕ1-zＩｎ1-xＧａxＳｅ2-yＳy（式中、０≦ｘ≦１、０≦ｙ≦２、０≦ｚ≦１）（ＣＩ（Ｇ）Ｓ）、Ａｇ（Ｉｎ，Ｇａ）Ｓｅ2、およびＡｇ（Ｉｎ，Ｇａ）（Ｓ，Ｓｅ）2等が挙げられる。 Examples of such compound semiconductors include CuAlS 2 , CuGaS 2 , CuInS 2 , CuAlSe 2 , CuGaSe 2 , AgAlS 2 , AgGaS 2 , AgInS 2 , AgAlSe 2 , AgGaSe 2 , AgInSe 2 , AgAlTe 2 , AgAlTe 2 , AgGaTe 2 , AgGaTe 2 Cu (in, Al) Se 2 , Cu (in, Ga) (S, Se) 2, Cu in 1-z in 1-x Ga x Se 2-y S y ( wherein, 0 ≦ x ≦ 1,0 ≦ y ≦ 2, 0 ≦ z ≦ 1) (CI (G) S), Ag (In, Ga) Se 2 , Ag (In, Ga) (S, Se) 2 and the like.
光電変換層１６の膜厚は、１．０〜３．０μｍが好ましく、１．５〜２．０μｍが特に好ましい。 1.0-3.0 micrometers is preferable and, as for the film thickness of the photoelectric converting layer 16, 1.5-2.0 micrometers is especially preferable.
（バッファ層）
バッファ層１８は、光生成キャリアの再結合の防止、バンド不連続の整合、格子整合、および、光電変換層の表面凹凸のカバレッジ等を目的として、設けられる層である。
ここで、前述のように、本発明の光電変換素子１０において、バッファ層１８は、２０００〜２１００ｃｍ-1の最大吸収強度ＩＲ−１、１０００〜１２００ｃｍ-1の最大吸収強度ＩＲ−２、および、１５００〜１７００ｃｍ-1の最大吸収強度ＩＲ−３の強度比が、ＩＲ−１／ＩＲ−２＜０．５、および、ＩＲ−１／ＩＲ−３＜０．５を満たす、不純物の少ないものである。また、好ましくは、カルボン酸イオンを含有する。
(Buffer layer)
The buffer layer 18 is a layer provided for the purpose of preventing recombination of photogenerated carriers, band discontinuous matching, lattice matching, coverage of surface irregularities of the photoelectric conversion layer, and the like.
Here, as described above, in the photoelectric conversion element 10 of the present invention, the buffer layer 18, the maximum absorption intensity IR-2 of the maximum absorption intensity IR-1,1000~1200cm -1 of 2000～2100Cm -1, and, Intensity ratio of maximum absorption intensity IR-3 of 1500-1700 cm -1 satisfies IR-1 / IR-2 <0.5 and IR-1 / IR-3 <0.5, and has few impurities is there. Moreover, Preferably, carboxylate ion is contained.
このようなバッファ層１８は、前述の本発明の水溶液組成物を用いたＣＢＤ法等で形成できるのは、前述の通りである。 As described above, the buffer layer 18 can be formed by the CBD method using the aqueous solution composition of the present invention.
バッファ層１８の主成分としては、硫化カドミウム、硫化亜鉛、硫化インジウム等が例示される。また、バッファ層１８は、例えば硫化亜鉛であれば酸化亜鉛との混晶体（Ｚｎ（Ｓ，Ｏ））等、不可避的に混入される化合物を含有しても良いのは、前述のとおりである。
また、バッファ層１８の膜厚は、１〜２０００ｎｍが好ましく、１５〜２００ｎｍがより好ましい。
Examples of the main component of the buffer layer 18 include cadmium sulfide, zinc sulfide, and indium sulfide. In addition, as described above, the buffer layer 18 may contain a compound inevitably mixed, such as a mixed crystal with ZnO (Zn (S, O)) in the case of zinc sulfide. .
Moreover, the film thickness of the buffer layer 18 is preferably 1 to 2000 nm, and more preferably 15 to 200 nm.
（窓層）
窓層２０は、光を取り込む中間層である。なお、窓層２０は必須ではなく、窓層２０のない光電変換素子もある。
窓層２０は、ｉ−ＺｎＯ等の各種の光電変換素子の窓層に用いられる公知の物で形成すればよい。窓層２０の膜厚は、１０〜２０００ｎｍが好ましく、１５〜２００ｎｍがより好ましい。
(Window layer)
The window layer 20 is an intermediate layer that captures light. Note that the window layer 20 is not essential, and some photoelectric conversion elements do not have the window layer 20.
What is necessary is just to form the window layer 20 with the well-known thing used for the window layer of various photoelectric conversion elements, such as i-ZnO. 10-2000 nm is preferable and, as for the film thickness of the window layer 20, 15-200 nm is more preferable.
（透光性導電層）
透光性導電層（透明電極）２４は、光を取り込むと共に、下部電極１４と対になって、光電変換層１６で生成された電流が流れる電極として機能する層である。
透光性導電層２４の組成としては、ＺｎＯ：Ａｌ等のｎ−ＺｎＯ等が好ましい。また、透光性導電層２４の膜厚は、５０〜２０００ｎｍが好ましい。
透光性導電層２４は、例えば、スパッタリング等の気相法で形成してもよいし、液相法により形成してもよい。
(Translucent conductive layer)
The translucent conductive layer (transparent electrode) 24 is a layer that captures light and functions as an electrode through which a current generated by the photoelectric conversion layer 16 flows in a pair with the lower electrode 14.
As a composition of the translucent conductive layer 24, n-ZnO such as ZnO: Al is preferable. Moreover, the film thickness of the translucent conductive layer 24 is preferably 50 to 2000 nm.
The translucent conductive layer 24 may be formed by, for example, a vapor phase method such as sputtering, or may be formed by a liquid phase method.
（上部電極）
上部電極（グリッド電極）２６は、公知の光電変換素子と同様、アルミニウム等を主成分とする上部電極が例示される。
また、上部電極２６の膜厚は、０．１〜３μｍが好ましい。
(Upper electrode)
The upper electrode (grid electrode) 26 is exemplified by an upper electrode mainly composed of aluminum or the like, similarly to a known photoelectric conversion element.
The film thickness of the upper electrode 26 is preferably 0.1 to 3 μm.
このような本発明の光電変換素子１０は、前述のように、バッファ層１８に混入している不純物が少ないので、バッファ層の性能低下や経時劣化に起因する特性の低下等の無い、高品質な光電変換素子である。
このような本発明の光電変換素子１０は、例えば、太陽電池等に好ましく使用することができる。また、光電変換素子１０には、必要に応じて、カバーガラス、保護フィルム等を取り付けて、太陽電池とすることができる。
As described above, the photoelectric conversion element 10 according to the present invention has a high quality in which there are few impurities mixed in the buffer layer 18 and thus there is no deterioration in performance due to deterioration in buffer layer performance or deterioration with time. This is a photoelectric conversion element.
Such a photoelectric conversion element 10 of the present invention can be preferably used for, for example, a solar cell. Moreover, a cover glass, a protective film, etc. can be attached to the photoelectric conversion element 10 as needed, and it can be set as a solar cell.
以上、本発明の水溶液組成物、金属硫化物薄膜、金属硫化物粒子および光電変換素子について詳細に説明したが、本発明は、上述の例に限定はされず、本発明の要旨を逸脱しない範囲において、各種の改良や変更を行ってもよいのは、勿論である。 As described above, the aqueous solution composition, metal sulfide thin film, metal sulfide particles, and photoelectric conversion element of the present invention have been described in detail. However, the present invention is not limited to the above-described examples, and does not depart from the gist of the present invention. Of course, various improvements and changes may be made.
以下、本発明の具体的実施例を挙げ、本発明について、より詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.
［実施例１］
グアニルチオ尿酸の濃度が０．０５ｍｏｌ／Ｌ、硫酸亜鉛の濃度が０．０３ｍｏｌ／Ｌ、アンモニアの濃度が０．１５ｍｏｌ／Ｌ、クエン酸三ナトリウムの濃度が０．０３ｍｏｌ／Ｌの水溶液組成物を調製して、ＣＢＤ法による成膜を行うための反応槽に投入した。なお、アンモニアは、混合水溶液を反応槽に投入する直前に混合した。この点に関しては、他の例も同様である。
この水溶液組成物の２０℃におけるｐＨは１０．２であった。
[Example 1]
Prepare an aqueous solution composition having a guanylthiouric acid concentration of 0.05 mol / L, a zinc sulfate concentration of 0.03 mol / L, an ammonia concentration of 0.15 mol / L, and a trisodium citrate concentration of 0.03 mol / L. Then, it was put into a reaction vessel for film formation by the CBD method. Ammonia was mixed immediately before the mixed aqueous solution was put into the reaction vessel. In this regard, the other examples are the same.
This aqueous composition had a pH of 10.2 at 20 ° C.
この反応槽に、成膜を行われる基板としてステンレス板を投入して、ＣＢＤ法によって、基板の表面に硫化亜鉛（Ｚｎ（Ｓ，Ｏ））の薄膜を形成し、かつ、硫化亜鉛微粒子を形成した。反応温度（水溶液組成物の温度）は、８０℃とした。 A stainless steel plate is placed in the reaction vessel as a substrate for film formation, and a zinc sulfide (Zn (S, O)) thin film is formed on the surface of the substrate by the CBD method, and zinc sulfide fine particles are formed. did. The reaction temperature (temperature of the aqueous solution composition) was 80 ° C.
基板を反応槽に投入して３０分経過した時点で、基板を反応槽から取り出して、表面を純水で洗浄した。
さらに、６０分経過した時点で、水溶液組成物を汲み出し、濾過して、微粒子を分離した。得られた微粒子は、純水で洗浄して、乾燥した。
基板の表面に形成された薄膜および微粒子を、走査型電子顕微鏡で観察し、ＥＤＸ装置で元素分析したところ、共に、硫化亜鉛が主成分であることが確認された。
When 30 minutes had passed since the substrate was put into the reaction vessel, the substrate was taken out of the reaction vessel and the surface was washed with pure water.
Furthermore, when 60 minutes passed, the aqueous solution composition was pumped out and filtered to separate the fine particles. The obtained fine particles were washed with pure water and dried.
When the thin film and fine particles formed on the surface of the substrate were observed with a scanning electron microscope and subjected to elemental analysis with an EDX apparatus, it was confirmed that zinc sulfide was the main component.
基板の断面を走査型電子顕微鏡で観察することにより、形成された硫化亜鉛膜の膜厚を測定した。その結果、膜厚は、３８ｎｍであった。
また、得られた硫化亜鉛粒子を電子顕微鏡で観察して、粒径を測定した。その結果、硫化亜鉛粒子の平均粒径は、０．５μｍであった。
さらに、ＦＴＩＲ−ＡＴＲ法によって、基板に形成された硫化亜鉛膜の赤外吸収スペクトルを測定した。その結果、２０００〜２１００ｃｍ-1の最大吸収強度ＩＲ−１、１０００〜１２００ｃｍ-1の最大吸収強度ＩＲ−２、および、１５００〜１７００ｃｍ-1の最大吸収強度ＩＲ−３の強度比、ＩＲ−１／ＩＲ−２、および、ＩＲ−１／ＩＲ−３は、共に、０．５未満であった。
The thickness of the formed zinc sulfide film was measured by observing a cross section of the substrate with a scanning electron microscope. As a result, the film thickness was 38 nm.
Moreover, the obtained zinc sulfide particles were observed with an electron microscope, and the particle size was measured. As a result, the average particle diameter of the zinc sulfide particles was 0.5 μm.
Furthermore, the infrared absorption spectrum of the zinc sulfide film formed on the substrate was measured by the FTIR-ATR method. As a result, the maximum absorption intensity IR-2 of the maximum absorption intensity IR-1,1000~1200cm -1 of 2000～2100Cm -1, and the intensity ratio of the maximum absorption intensity IR-3 of 1500~1700cm -1, IR-1 / IR-2 and IR-1 / IR-3 were both less than 0.5.
［実施例２］
反応温度を５０℃とした以外は、実施例１と同様に硫化亜鉛薄膜および硫化亜鉛粒子の形成を行い、３０分経過した時点で基板を取り出し、また、６０分経過した時点で、硫化亜鉛微粒子を分離し、洗浄、乾燥した。形成された薄膜および微粒子を実施例１と同様に分析したところ、共に、硫化亜鉛が主成分であることが確認された。
実施例１と同様に、形成された硫化亜鉛薄膜の膜厚、硫化亜鉛微粒子の粒径、および、硫化亜鉛薄膜の赤外吸収スペクトルを測定した。
その結果、硫化亜鉛薄膜の膜厚は２３ｎｍ、硫化亜鉛微粒子の平均粒径は０．５μｍ、ＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３は、共に、０．５未満であった。
[Example 2]
A zinc sulfide thin film and zinc sulfide particles were formed in the same manner as in Example 1 except that the reaction temperature was 50 ° C., and the substrate was taken out when 30 minutes passed, and the zinc sulfide fine particles were passed when 60 minutes passed. Was separated, washed and dried. When the formed thin film and fine particles were analyzed in the same manner as in Example 1, it was confirmed that zinc sulfide was the main component.
In the same manner as in Example 1, the thickness of the formed zinc sulfide thin film, the particle diameter of the zinc sulfide fine particles, and the infrared absorption spectrum of the zinc sulfide thin film were measured.
As a result, the film thickness of the zinc sulfide thin film was 23 nm, the average particle diameter of the zinc sulfide fine particles was 0.5 μm, and IR-1 / IR-2 and IR-1 / IR-3 were both less than 0.5. .
［実施例３］
反応温度を２０℃にした以外は、実施例１と同様に硫化亜鉛薄膜および硫化亜鉛粒子の形成を行い、３０分経過した時点で基板を取り出し、また、６０分経過した時点で、硫化亜鉛微粒子を分離し、洗浄、乾燥した。形成された薄膜および微粒子を実施例１と同様に分析したところ、共に、硫化亜鉛が主成分であることが確認された。
実施例１と同様に、形成された硫化亜鉛薄膜の膜厚、硫化亜鉛微粒子の粒径、および、硫化亜鉛薄膜の赤外吸収スペクトルを測定した。
その結果、硫化亜鉛薄膜の膜厚は２ｎｍ、硫化亜鉛微粒子の平均粒径は０．１μｍ、ＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３は、共に、０．５未満であった。
[Example 3]
A zinc sulfide thin film and zinc sulfide particles were formed in the same manner as in Example 1 except that the reaction temperature was changed to 20 ° C., and the substrate was taken out after 30 minutes. Was separated, washed and dried. When the formed thin film and fine particles were analyzed in the same manner as in Example 1, it was confirmed that zinc sulfide was the main component.
In the same manner as in Example 1, the thickness of the formed zinc sulfide thin film, the particle diameter of the zinc sulfide fine particles, and the infrared absorption spectrum of the zinc sulfide thin film were measured.
As a result, the thickness of the zinc sulfide thin film was 2 nm, the average particle size of the zinc sulfide fine particles was 0.1 μm, and IR-1 / IR-2 and IR-1 / IR-3 were both less than 0.5. .
［実施例４］
グアニルチオ尿酸の濃度が０．００７５ｍｏｌ／Ｌ、硫酸カドミウムの濃度が０．００１４ｍｏｌ／Ｌ、アンモニアの濃度が１．５ｍｏｌ／Ｌである水溶液組成物を調製した。
この水溶液組成物のｐＨは１２であった。
[Example 4]
An aqueous solution composition having a guanylthiouric acid concentration of 0.0075 mol / L, a cadmium sulfate concentration of 0.0014 mol / L, and an ammonia concentration of 1.5 mol / L was prepared.
The pH of this aqueous solution composition was 12.
この水溶液組成物を用い、反応温度を２０℃にした以外は、実施例１と同様にして、硫化カドミウム薄膜および硫化カドミウム微粒子の形成を行い、３０分経過した時点で基板を取り出し、また、６０分経過した時点で、硫化カドミウム微粒子を分離し、洗浄、乾燥した。形成された薄膜および微粒子を実施例１と同様に分析したところ、共に、硫化カドミウムが主成分であることが確認された。
実施例１と同様に、形成された硫化カドミウム薄膜の膜厚、硫化カドミウム粒子の粒径、および、硫化カドミウム薄膜の赤外吸収スペクトルを測定した。
その結果、硫化カドミウム薄膜の膜厚は２３ｎｍ、硫化カドミウム微粒子の平均粒径は０．２μｍ、ＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３は、共に、０．５未満であった。
Using this aqueous solution composition, a cadmium sulfide thin film and cadmium sulfide fine particles were formed in the same manner as in Example 1 except that the reaction temperature was 20 ° C., and the substrate was taken out after 30 minutes. At the point of time, cadmium sulfide fine particles were separated, washed and dried. When the formed thin film and fine particles were analyzed in the same manner as in Example 1, it was confirmed that cadmium sulfide was the main component.
In the same manner as in Example 1, the thickness of the formed cadmium sulfide thin film, the particle size of the cadmium sulfide particles, and the infrared absorption spectrum of the cadmium sulfide thin film were measured.
As a result, the thickness of the cadmium sulfide thin film was 23 nm, the average particle size of the cadmium sulfide fine particles was 0.2 μm, and IR-1 / IR-2 and IR-1 / IR-3 were both less than 0.5. .
［比較例１］
グアニルチオ尿素に代えて、濃度０．０５ｍｏｌ／Ｌのチオ尿素を含有する以外、実施例１の水溶液組成物と同様の組成を有する水溶液組成物を調製した。
この水溶液組成物のｐＨは１０．２であった。
この水溶液組成物を用いた以外は、実施例１と同様に硫化亜鉛薄膜および硫化亜鉛粒子の形成を行い、３０分経過した時点で基板を取り出し、また、６０分経過した時点で、硫化亜鉛微粒子を分離し、洗浄、乾燥した。形成された薄膜および微粒子を実施例１と同様に分析したところ、共に、硫化亜鉛が主成分であることが確認された。
[Comparative Example 1]
Instead of guanylthiourea, an aqueous solution composition having the same composition as the aqueous solution composition of Example 1 was prepared except that thiourea having a concentration of 0.05 mol / L was contained.
The pH of this aqueous solution composition was 10.2.
Except for using this aqueous solution composition, a zinc sulfide thin film and zinc sulfide particles were formed in the same manner as in Example 1, and the substrate was taken out after 30 minutes. When 60 minutes had passed, zinc sulfide fine particles were formed. Was separated, washed and dried. When the formed thin film and fine particles were analyzed in the same manner as in Example 1, it was confirmed that zinc sulfide was the main component.
実施例１と同様に、形成された硫化亜鉛薄膜の膜厚、硫化亜鉛微粒子の粒径、および、硫化亜鉛薄膜の赤外吸収スペクトルを測定した。
その結果、硫化亜鉛薄膜の膜厚は１５ｎｍ、硫化亜鉛微粒子の平均粒径は０．４μｍ、ＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３は、共に、０．５を超えていた。
In the same manner as in Example 1, the thickness of the formed zinc sulfide thin film, the particle diameter of the zinc sulfide fine particles, and the infrared absorption spectrum of the zinc sulfide thin film were measured.
As a result, the thickness of the zinc sulfide thin film was 15 nm, the average particle diameter of the zinc sulfide fine particles was 0.4 μm, and IR-1 / IR-2 and IR-1 / IR-3 both exceeded 0.5. .
［比較例２］
反応温度を５０℃にした以外は、比較例１と同様に硫化亜鉛薄膜および硫化亜鉛粒子の形成を行い、３０分経過した時点で基板を取り出し、また、６０分経過した時点で、硫化亜鉛微粒子を分離し、洗浄、乾燥した。
形成された微粒子を実施例１と同様に分析したところ、硫化亜鉛が主成分であることが確認された。なお、基板の表面には、薄膜は形成されていなかった。
実施例１と同様に、硫化亜鉛微粒子の粒径を測定した。その結果、硫化亜鉛微粒子の平均粒径は０．１μｍであった。
[Comparative Example 2]
A zinc sulfide thin film and zinc sulfide particles were formed in the same manner as in Comparative Example 1 except that the reaction temperature was changed to 50 ° C., and the substrate was taken out after 30 minutes, and after 60 minutes, the zinc sulfide fine particles Was separated, washed and dried.
When the formed fine particles were analyzed in the same manner as in Example 1, it was confirmed that zinc sulfide was the main component. Note that no thin film was formed on the surface of the substrate.
In the same manner as in Example 1, the particle size of the zinc sulfide fine particles was measured. As a result, the average particle diameter of the zinc sulfide fine particles was 0.1 μm.
［比較例３］
反応温度を２０℃にした以外は、比較例１と同様に硫化亜鉛薄膜および硫化亜鉛粒子の形成を行い、３０分経過した時点で基板を取り出し、また、６０分経過した時点で、硫化亜鉛微粒子を分離し、洗浄、乾燥した。
しかしながら、基板の表面に薄膜は成膜されておらず、また、硫化亜鉛微粒子も形成されていなかった。
[Comparative Example 3]
Except that the reaction temperature was 20 ° C., the zinc sulfide thin film and the zinc sulfide particles were formed in the same manner as in Comparative Example 1, and the substrate was taken out after 30 minutes, and after 60 minutes, the zinc sulfide fine particles Was separated, washed and dried.
However, no thin film was formed on the surface of the substrate, and no zinc sulfide fine particles were formed.
［比較例４］
グアニルチオ尿素に代えて、濃度０．００７５ｍｏｌ／Ｌのチオ尿素を含有する以外、実施例４の水溶液組成物と同様の組成を有する水溶液組成物を調製した。
この水溶液組成物のｐＨは１２であった。
[Comparative Example 4]
An aqueous solution composition having the same composition as the aqueous solution composition of Example 4 was prepared except that thiourea having a concentration of 0.0075 mol / L was contained instead of guanylthiourea.
The pH of this aqueous solution composition was 12.
この水溶液組成物を用いた以外は、実施例４と同様にして硫化カドミウム薄膜および硫化カドミウム粒子の形成を行い、３０分経過した時点で基板を取り出し、また、６０分経過した時点で、硫化カドミウム微粒子を分離し、洗浄、乾燥した。形成された微粒子を実施例１と同様に分析したところ、硫化カドミウムが主成分であることが確認された。なお、基板の表面には、薄膜は形成されていなかった。
実施例１と同様に、硫化カドミウム微粒子の粒径を測定した。硫化カドミウム微粒子の平均粒径は０．１μｍであった。
A cadmium sulfide thin film and cadmium sulfide particles were formed in the same manner as in Example 4 except that this aqueous solution composition was used, and the substrate was taken out when 30 minutes passed, and cadmium sulfide was passed when 60 minutes passed. The fine particles were separated, washed and dried. When the formed fine particles were analyzed in the same manner as in Example 1, it was confirmed that cadmium sulfide was the main component. Note that no thin film was formed on the surface of the substrate.
In the same manner as in Example 1, the particle size of the cadmium sulfide fine particles was measured. The average particle diameter of the cadmium sulfide fine particles was 0.1 μm.
［比較例５］
グアニルチオ尿素に代えて、濃度０．０５ｍｏｌ／Ｌのメチルチオ尿素を含有する以外、実施例１の水溶液組成物と同様の組成を有する水溶液組成物を調製した。
この水溶液組成物のｐＨは１０．２であった。
[Comparative Example 5]
Instead of guanylthiourea, an aqueous solution composition having the same composition as the aqueous solution composition of Example 1 was prepared except that it contained methylthiourea at a concentration of 0.05 mol / L.
The pH of this aqueous solution composition was 10.2.
この水溶液組成物を用いた以外は、実施例１と同様に硫化亜鉛薄膜および硫化亜鉛粒子の形成を行い、３０分経過した時点で基板を取り出し、また、６０分経過した時点で、硫化亜鉛微粒子を分離し、洗浄、乾燥した。形成された薄膜および微粒子を実施例１と同様に分析したところ、共に、硫化亜鉛が主成分であることが確認された。 Except for using this aqueous solution composition, a zinc sulfide thin film and zinc sulfide particles were formed in the same manner as in Example 1, and the substrate was taken out after 30 minutes. When 60 minutes had passed, zinc sulfide fine particles were formed. Was separated, washed and dried. When the formed thin film and fine particles were analyzed in the same manner as in Example 1, it was confirmed that zinc sulfide was the main component.
実施例１と同様に、形成された硫化亜鉛薄膜の膜厚、硫化亜鉛微粒子の粒径、および、硫化亜鉛薄膜の赤外吸収スペクトルを測定した。
その結果、硫化亜鉛薄膜の膜厚は６ｎｍ、硫化亜鉛微粒子の平均粒径は０．１μｍ、ＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３は、共に、０．５を超えていた。
In the same manner as in Example 1, the thickness of the formed zinc sulfide thin film, the particle diameter of the zinc sulfide fine particles, and the infrared absorption spectrum of the zinc sulfide thin film were measured.
As a result, the thickness of the zinc sulfide thin film was 6 nm, the average particle diameter of the zinc sulfide fine particles was 0.1 μm, and IR-1 / IR-2 and IR-1 / IR-3 both exceeded 0.5. .
［比較例６］
反応温度を２０℃にした以外は、比較例５と同様に硫化亜鉛薄膜および硫化亜鉛粒子の形成を行い、３０分経過した時点で基板を取り出し、また、６０分経過した時点で、硫化亜鉛微粒子を分離を行った。
しかしながら、反応が進んでおらず、薄膜および微粒子共に得られなかった。
[Comparative Example 6]
A zinc sulfide thin film and zinc sulfide particles were formed in the same manner as in Comparative Example 5 except that the reaction temperature was 20 ° C., and the substrate was taken out after 30 minutes. Separated.
However, the reaction did not proceed, and neither a thin film nor fine particles were obtained.
下記表に、以上の結果をまとめて示す。
また、図２に、実施例１（実線）および比較例１（破線）で測定した赤外吸収スペクトルを、図３（Ａ）に、実施例２で形成した硫化亜鉛粒子の顕微鏡写真を処理して出力した画像を、図３（Ｂ）に、実施例２で形成した硫化亜鉛粒子の顕微鏡写真を処理して出力した画像を、それぞれ示す。
The following table summarizes the above results.
FIG. 2 shows the infrared absorption spectrum measured in Example 1 (solid line) and Comparative Example 1 (dashed line), and FIG. 3A shows a micrograph of the zinc sulfide particles formed in Example 2. FIG. 3B shows images output by processing the micrographs of the zinc sulfide particles formed in Example 2, respectively.
実施例１、比較例１および比較例５を比較すると、グアニルチオ尿素を用いる本発明の水溶液組成物では、チオ尿素やモノアルキルチオ尿素（メチルチオ尿素）を用いる従来の水溶液組成物に比して、速い成膜速度および形成速度で、硫化亜鉛薄膜および硫化亜鉛微粒子が形成されている。 Comparing Example 1, Comparative Example 1 and Comparative Example 5, the aqueous solution composition of the present invention using guanylthiourea is faster than the conventional aqueous solution composition using thiourea or monoalkylthiourea (methylthiourea). The zinc sulfide thin film and the zinc sulfide fine particles are formed at the film formation rate and the formation rate.
また、実施例２および比較例２、ならびに、実施例３、比較例３および比較例６を比較すると、グアニルチオ尿素を用いる本発明の水溶液組成物は、５０℃および２０℃でも、硫化亜鉛薄膜および硫化亜鉛微粒子が形成されている。
これに対し、チオ尿素やモノアルキルチオ尿素を用いる従来の水溶液組成物では、５０℃では硫化亜鉛薄膜が形成されず、２０℃では硫化亜鉛薄膜および硫化亜鉛微粒子が共に形成されなかった。なお、図３にも示されるように、比較例２でも、硫化亜鉛微粒子は形成できているものの、その粒径は、実施例２に比して小さい。
すなわち、本発明によれば、従来は不可能であった低温でも、溶液析出法による金属硫化物の薄膜および微粒子の形成が可能である。
また、実施例４および比較例４を比較すると、この結果は、硫化カドミウムの薄膜および微粒子の形成でも同様であることが分かる。
Further, when Example 2 and Comparative Example 2, and Example 3, Comparative Example 3 and Comparative Example 6 are compared, the aqueous solution composition of the present invention using guanylthiourea has a zinc sulfide thin film and Zinc sulfide fine particles are formed.
On the other hand, in a conventional aqueous solution composition using thiourea or monoalkylthiourea, a zinc sulfide thin film was not formed at 50 ° C., and neither a zinc sulfide thin film nor zinc sulfide fine particles were formed at 20 ° C. As shown in FIG. 3, even in Comparative Example 2, although the zinc sulfide fine particles can be formed, the particle size thereof is smaller than that of Example 2.
That is, according to the present invention, it is possible to form a metal sulfide thin film and fine particles by a solution precipitation method even at a low temperature, which was not possible conventionally.
Further, when Example 4 and Comparative Example 4 are compared, it can be seen that this result is the same for the formation of cadmium sulfide thin films and fine particles.
さらに、図２もに示されるように、実施例１〜４の硫化亜鉛薄膜は、２０５０ｃｍ-1付近の吸収ピークがほとんど見られず、ＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３が、共に０．５未満であり、チオシアン酸イオンの取り込みがほとんど確認されなかった。すなわち、不純物の少ない、本発明の硫化亜鉛薄膜（金属硫化物薄膜）が形成されていた。
これに対し、比較例１で形成された硫化亜鉛薄膜は、２０５０ｃｍ-1付近に大きなピークが見られ、また、ＩＲ−１／ＩＲ−２およびＩＲ−１／ＩＲ−３が、いずれも０．５を超えていた。
以上の結果より、本発明の効果は明らかである。
Further, as shown in FIG. 2, in the zinc sulfide thin films of Examples 1 to 4, almost no absorption peak in the vicinity of 2050 cm −1 was observed, and IR-1 / IR-2 and IR-1 / IR-3 were observed. However, both were less than 0.5, and uptake of thiocyanate ions was hardly confirmed. That is, the zinc sulfide thin film (metal sulfide thin film) of the present invention with few impurities was formed.
On the other hand, the zinc sulfide thin film formed in Comparative Example 1 has a large peak in the vicinity of 2050 cm −1 , and IR-1 / IR-2 and IR-1 / IR-3 are both 0. It was over 5.
From the above results, the effects of the present invention are clear.
光電変換素子のバッファ層等に、好適に利用される。 It is suitably used for a buffer layer of a photoelectric conversion element.
１０ 光電変換素子
１２ 基板
１４ 下部電極（裏面電極）
１６ 光電変換層
１８ バッファ層
２０ 窓層
２４ 透光性導電層（透明電極）
２６ 上部電極（グリッド電極）
10 Photoelectric conversion element 12 Substrate 14 Lower electrode (back electrode)
16 Photoelectric conversion layer 18 Buffer layer 20 Window layer 24 Translucent conductive layer (transparent electrode)
26 Upper electrode (grid electrode)
Claims (10)
グアニルチオ尿素と、
難溶性硫化物を形成できる金属イオンとを含むことを特徴とする水溶液組成物。 An aqueous solution composition used for the production of metal sulfides by a solution precipitation method,
Guanylthiourea ,
An aqueous solution composition comprising a metal ion capable of forming a hardly soluble sulfide.
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