JP6307327B2 - Method for producing metal chalcogenide compound using crystal growth accelerator - Google Patents
Method for producing metal chalcogenide compound using crystal growth accelerator Download PDFInfo
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- JP6307327B2 JP6307327B2 JP2014073399A JP2014073399A JP6307327B2 JP 6307327 B2 JP6307327 B2 JP 6307327B2 JP 2014073399 A JP2014073399 A JP 2014073399A JP 2014073399 A JP2014073399 A JP 2014073399A JP 6307327 B2 JP6307327 B2 JP 6307327B2
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- JP
- Japan
- Prior art keywords
- crystal growth
- metal chalcogenide
- chalcogenide compound
- copper
- growth accelerator
- Prior art date
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- 239000013078 crystal Substances 0.000 title claims description 161
- -1 chalcogenide compound Chemical class 0.000 title claims description 142
- 229910052751 metal Inorganic materials 0.000 title claims description 125
- 239000002184 metal Substances 0.000 title claims description 125
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000010949 copper Substances 0.000 claims description 64
- 239000000758 substrate Substances 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 39
- 229910052802 copper Inorganic materials 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 37
- 239000011669 selenium Substances 0.000 claims description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 21
- 239000007952 growth promoter Substances 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 20
- 229910052711 selenium Inorganic materials 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 229910052798 chalcogen Inorganic materials 0.000 claims description 16
- 150000001787 chalcogens Chemical class 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 239000011147 inorganic material Substances 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims 1
- 150000002366 halogen compounds Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 description 26
- 230000005496 eutectics Effects 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000004065 semiconductor Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 11
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000001737 promoting effect Effects 0.000 description 8
- 230000004907 flux Effects 0.000 description 7
- 229910052733 gallium Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 150000004770 chalcogenides Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000004771 selenides Chemical class 0.000 description 4
- 239000005361 soda-lime glass Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 2
- 229910016001 MoSe Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910005642 SnTe Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 description 2
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000004772 tellurides Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910004813 CaTe Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910016509 CuF 2 Inorganic materials 0.000 description 1
- 229910002531 CuTe Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017680 MgTe Inorganic materials 0.000 description 1
- 229910005913 NiTe Inorganic materials 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910004411 SrTe Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- DWRNSCDYNYYYHT-UHFFFAOYSA-K gallium(iii) iodide Chemical compound I[Ga](I)I DWRNSCDYNYYYHT-UHFFFAOYSA-K 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- RMUKCGUDVKEQPL-UHFFFAOYSA-K triiodoindigane Chemical compound I[In](I)I RMUKCGUDVKEQPL-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Photovoltaic Devices (AREA)
Description
本発明は、結晶成長促進剤を用いた金属カルコゲナイド化合物の製造方法に関し、より詳細には、硫黄、セレンから選択されるカルコゲン元素と、銅とを含有する金属カルコゲナイド化合物の結晶成長に供される結晶成長促進剤を用いた金属カルコゲナイド化合物の製造方法に関する。 The present invention relates to a method of manufacturing a crystal growth promoter metal chalcogenide compound used, more particularly, is subjected sulfur, a chalcogen element selected from selenium, the crystal growth of the metal chalcogenide compound containing a copper the method for producing a metal chalcogenide compound using crystal growth promoter.
従来から硫黄及び／又はセレンを含有する金属カルコゲナイド化合物は、その優れた光物性や半導体物性のため、蛍光体や太陽電池に代表される光電変換素子の分野で広く利用されている。
とりわけ、銅を含有する金属カルコゲナイド化合物は、優れた光吸収特性と優れた半導体特性を有するために、光電変換素子の分野での利用が拡大している。
Conventionally, metal chalcogenide compounds containing sulfur and / or selenium have been widely used in the field of photoelectric conversion elements typified by phosphors and solar cells because of their excellent optical properties and semiconductor properties.
In particular, a metal chalcogenide compound containing copper has been used in the field of photoelectric conversion elements because it has excellent light absorption characteristics and excellent semiconductor characteristics.
このような、優れた光物性や半導体特性を得るためには、金属カルコゲナイド化合物結晶中における電子の移動が重要であるため、高い結晶性や用途に応じた適切な結晶サイズが必要になる。
無機材料の結晶性向上や結晶サイズの制御のために、合成時の焼成温度で融解する融剤（フラックス）が用いられ、例えば、特許文献１には、セシウム、ルビジウム、バリウム及びランタンを融剤として含有する第四級カルコゲナイド化合物の製造方法が開示されている。また、特許文献２には、金属カルコゲナイド化合物が広く利用される、ＣＩＧＳ太陽電池の光吸収層材料に対し、リチウム化合物やカリウム化合物を用いてＣＩＧＳの結晶成長を促進する技術が開示されている。
In order to obtain such excellent optical properties and semiconductor characteristics, the movement of electrons in the metal chalcogenide compound crystal is important, so that high crystallinity and an appropriate crystal size according to the application are required.
In order to improve the crystallinity of inorganic materials and control the crystal size, a flux (flux) that melts at the firing temperature at the time of synthesis is used. For example, Patent Document 1 discloses cesium, rubidium, barium, and lanthanum as fluxes. A method for producing a quaternary chalcogenide compound is disclosed. Patent Document 2 discloses a technique for promoting CIGS crystal growth using a lithium compound or a potassium compound with respect to a light absorbing layer material of a CIGS solar cell in which a metal chalcogenide compound is widely used.
しかしながら、この技術は、融剤と金属カルコゲナイド化合物が異なる元素で構成されているため相互の親和性が乏しく、結晶成長が十分に起こらない場合や、結晶成長を促すためには、高温で長時間の焼成を必要とするなど生産性が劣る場合があった。
また、例えば、特許文献３には、ＣＩＧＳ太陽電池の光吸収層材料の１種であるＣｕＩｎＳｅ２の単結晶を合成する際に、ＣｕＳｅやＳｅの溶融状態を利用してＣｕＩｎＳｅ２の結晶成長を促進する技術が開示されている。
However, this technique has a low affinity for the flux and the metal chalcogenide compound because they are composed of different elements, and when crystal growth does not occur sufficiently or to promote crystal growth, In some cases, the productivity was inferior, for example, requiring baking.
Further, for example, in Patent Document 3, when a single crystal of CuInSe 2 which is one kind of light absorption layer material of a CIGS solar cell is synthesized, the crystal growth of CuInSe 2 is performed using the molten state of CuSe or Se. Techniques for promoting are disclosed.
また、例えば、特許文献４には、その結晶成長を促進する技術を、真空蒸着を用いた製法に応用した例として、インジウムとガリウムとセレンとを含む層上に、銅とセレンとを含む層を蒸着し、銅とセレンを含む層を加熱溶融して拡散させてＣＩＧＳ膜を製造する方法が開示されている。この方法は、不純物を含有させない点において優れた技術であるが、金属カルコゲナイド化合物がセレン化物である場合のみに限定的に使用できる技術であり、更には、光吸収層に変換する物質そのもので結晶成長促進を行うため、精緻な制御が必要になり、生産性に劣る場合があった。 Further, for example, in Patent Document 4, as an example in which a technique for promoting crystal growth is applied to a manufacturing method using vacuum deposition, a layer containing copper and selenium is formed on a layer containing indium, gallium, and selenium. A method for producing a CIGS film is disclosed in which a layer containing copper and selenium is heated and melted and diffused. This method is an excellent technique in that it does not contain impurities, but it can be used only when the metal chalcogenide compound is a selenide, and further, the substance itself that is converted into the light absorption layer is crystallized. In order to promote growth, precise control is required, and productivity may be inferior.
さらに、例えば、特許文献５には、各種複合材料だけでなく、光センサや太陽電池などの高効率光電変換材料、発光素子などの半導体素子に利用することのできる金属カルコゲナイド化合物超格子の製造方法が開示されている。
一方、フラックスを用いて酸化物を合成する技術については、例えば、特許文献６には、フラックスを用いてコバルト酸リチウムを合成する技術が開示され、特許文献７には、フラックスを用いて基材上に酸化物ナノ無機結晶を形成した積層体が開示されている。
Furthermore, for example, Patent Document 5 discloses a method for producing a metal chalcogenide compound superlattice that can be used not only for various composite materials but also for high-efficiency photoelectric conversion materials such as optical sensors and solar cells, and semiconductor devices such as light-emitting elements. Is disclosed.
On the other hand, as for the technology for synthesizing an oxide using a flux, for example, Patent Literature 6 discloses a technology for synthesizing lithium cobalt oxide using a flux, and Patent Literature 7 discloses a base material using a flux. A laminate having oxide nano-inorganic crystals formed thereon is disclosed.
しかしながら、上述したように、太陽電池に代表される光電変換素子の分野で広く利用されている硫黄及び／又はセレンから選択されるカルコゲン元素と銅とを含有する金属カルコゲナイド化合物は知られているものの、本発明のような結晶成長促進剤及びそれを用いた金属カルコゲナイド化合物の製造方法については何ら開示されていない。
本発明は、このような問題に鑑みてなされたもので、その目的とするところは、硫黄、セレンから選択されるカルコゲン元素と、銅とを含有する金属カルコゲナイド化合物の結晶成長に供される結晶成長促進剤を用いた金属カルコゲナイド化合物の製造方法を提供することにある。
However, as described above, metal chalcogenide compounds containing a chalcogen element and copper selected from sulfur and / or selenium widely used in the field of photoelectric conversion elements typified by solar cells are known. There is no disclosure of a crystal growth promoter as in the present invention and a method for producing a metal chalcogenide compound using the same.
The present invention has been made in view of such problems. The object of the present invention is to provide a crystal that is used for crystal growth of a metal chalcogenide compound containing a chalcogen element selected from sulfur and selenium and copper. It is to provide a method for producing a metal chalcogenide compound using growth promoter.
本発明は、このような目的を達成するためになされたもので、請求項１に記載の発明は、硫黄、セレンから選択されるカルコゲン元素と、銅とを含有する金属カルコゲナイド化合物の結晶成長に供される無機材料の結晶成長促進剤を用いた金属カルコゲナイド化合物の製造方法であって、前記金属カルコゲナイド化合物を構成する元素を１種以上の化合物にすべて含む金属カルコゲナイド化合物原料と、１種以上の銅のハロゲン化物を含有する前記結晶成長促進剤とを接触させて、前記金属カルコゲナイド化合物に対して、同一金属種である銅のハロゲン化物を含有し、前記金属カルコゲナイド化合物原料として使用する前記結晶成長促進剤を作用させることで、前記金属カルコゲナイド化合物の結晶成長を促進させ、前記ハロゲン化合物の銅を前記金属カルコゲナイド化合物の銅として取り込むために、前記結晶成長促進剤の融解温度以上に加熱することを特徴とする。
また、請求項２に記載の発明は、請求項１に記載の発明において、前記金属カルコゲナイド化合物原料と結晶成長促進剤との接触を基板上で行うことを特徴とする。
The present invention has been made to achieve such an object, and the invention according to claim 1 is directed to crystal growth of a metal chalcogenide compound containing a chalcogen element selected from sulfur and selenium and copper. A method for producing a metal chalcogenide compound using a crystal growth accelerator of an inorganic material to be provided, the metal chalcogenide compound raw material including all the elements constituting the metal chalcogenide compound in one or more compounds, and one or more kinds Contacting the crystal growth accelerator containing a copper halide, the crystal growth containing a copper halide of the same metal type as the metal chalcogenide compound and used as the metal chalcogenide compound raw material By causing the accelerator to act, the crystal growth of the metal chalcogenide compound is promoted, and To capture as copper of the metal chalcogenide compound, characterized in that heating above the melting temperature of the crystal growth promoters.
The invention according to claim 2 is characterized in that, in the invention according to claim 1 , the metal chalcogenide compound raw material and the crystal growth accelerator are contacted on a substrate.
本発明によれば、硫黄、セレンから選択されるカルコゲン元素と、銅とを含有する金属カルコゲナイド化合物の結晶成長を、１種以上の銅のハロゲン化物を少なくとも含有する結晶成長促進剤を用いることで促進し、低温で高結晶性の結晶面の発達した結晶を得ることができる。 According to the present invention, crystal growth of a metal chalcogenide compound containing a chalcogen element selected from sulfur and selenium and copper is performed using a crystal growth accelerator containing at least one or more types of copper halides. It is possible to obtain a crystal having a high crystallinity developed at a low temperature.
以下、本発明の実施の形態について説明する。
本発明者らは、上述した課題を解決するために鋭意検討した結果、硫黄、セレンから選択されるカルコゲン元素と、銅とを含有する金属カルコゲナイド化合物の結晶成長に、１種以上の銅のハロゲン化物を含有する結晶成長促進剤が高い効果を示すこと、また、結晶成長促進剤の融解温度以上に加熱することで、結晶成長の優れた金属カルコゲナイド化合物が製造できることを見出し本発明に至った。
Embodiments of the present invention will be described below.
As a result of intensive studies to solve the above-described problems, the present inventors have found that one or more types of copper halogen atoms are used for crystal growth of a metal chalcogenide compound containing a chalcogen element selected from sulfur and selenium and copper. The present inventors have found that a crystal growth accelerator containing a compound exhibits a high effect and that a metal chalcogenide compound having excellent crystal growth can be produced by heating to a temperature higher than the melting temperature of the crystal growth accelerator.
本発明の結晶成長促進剤は、金属カルコゲナイド化合物の結晶成長に供される無機材料の結晶成長促進剤である。また、金属カルコゲナイド化合物は、硫黄、セレンから選択されるカルコゲン元素と、銅とを含有し、結晶成長促進剤は、１種以上の銅のハロゲン化物を含有する。
また、結晶成長促進剤が含有する１種以上の銅のハロゲン化物が、塩化第一銅及び／又は塩化第二銅である。
The crystal growth promoter of the present invention is an inorganic material crystal growth promoter used for crystal growth of a metal chalcogenide compound. The metal chalcogenide compound contains a chalcogen element selected from sulfur and selenium and copper, and the crystal growth accelerator contains one or more types of copper halides.
Moreover, the 1 or more types of copper halide which a crystal growth promoter contains is cuprous chloride and / or cupric chloride.
また、本発明の結晶成長促進剤を用いた金属カルコゲナイド化合物の製造方法は、金属カルコゲナイド化合物の結晶成長に供される無機材料の結晶成長促進剤を用いた金属カルコゲナイド化合物の製造方法である。金属カルコゲナイド化合物を構成する元素を１種以上の化合物にすべて含む金属カルコゲナイド化合物原料と、１種以上の銅のハロゲン化物を含有する結晶成長促進剤とを接触させて加熱する。 The method for producing a metal chalcogenide compound using the crystal growth accelerator of the present invention is a method for producing a metal chalcogenide compound using an inorganic material crystal growth accelerator used for crystal growth of the metal chalcogenide compound. A metal chalcogenide compound raw material containing all of the elements constituting the metal chalcogenide compound in one or more compounds and a crystal growth accelerator containing one or more copper halides are brought into contact with each other and heated.
また、加熱温度が、結晶成長促進剤の融解温度以上である。また、金属カルコゲナイド化合物原料と結晶成長促進剤との接触を基板上で行う。つまり、本発明の結晶成長促進剤は、硫黄、セレンから選択されるカルコゲン元素と、銅とを含有する金属カルコゲナイド化合物の結晶成長に供される。
そこで、まず、カルコゲナイド化合物について以下に説明する。
The heating temperature is equal to or higher than the melting temperature of the crystal growth accelerator. Further, the metal chalcogenide compound raw material and the crystal growth accelerator are contacted on the substrate. That is, the crystal growth accelerator of the present invention is used for crystal growth of a metal chalcogenide compound containing a chalcogen element selected from sulfur and selenium and copper.
First, the chalcogenide compound will be described below.
本発明において、金属カルコゲナイド化合物は、硫黄、セレンから選択されるカルコゲン元素と、銅を含有する金属カルコゲナイド化合物であれば特に限定されないが、例えば、銅の硫化物、セレン化物の他に、これらの化合物とマグネシウム、カルシウム、ストロンチウム、バリウム、亜鉛、カドミウム、鉄、ニッケル、モリブデン、銀、アルミニウム、ガリウム、インジウム、錫、鉛、アンチモン、ビスマスなどの金属の酸化物、硫化物、セレン化物、テルル化物が混晶した混晶化合物などが例示できる。 In the present invention, the metal chalcogenide compound is not particularly limited as long as it is a chalcogen element selected from sulfur and selenium and a metal chalcogenide compound containing copper, for example, in addition to copper sulfide and selenide, Compounds and oxides, sulfides, selenides, tellurides of magnesium, calcium, strontium, barium, zinc, cadmium, iron, nickel, molybdenum, silver, aluminum, gallium, indium, tin, lead, antimony, bismuth and other metals Examples thereof include mixed crystal compounds in which are mixed crystals.
具体的には、ＣｕＳ、Ｃｕ２Ｓの硫化銅、ＣｕＳｅ、Ｃｕ２Ｓｅのセレン化銅やこれらの硫化銅、セレン化銅と、例えば、ＣｕＯ、Ｃｕ２Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＺｎＯ、ＣｄＯ、ＦｅＯ、Ｆｅ２Ｏ３、ＮｉＯ、ＭｏＯ、ＭｏＯ２、Ａｇ２Ｏ、Ａｌ２Ｏ、Ｇａ２Ｏ３、Ｉｎ２Ｏ３、ＳｎＯ、ＳｎＯ２、ＰｂＯ、Ｓｂ２Ｏ３、Ｂｉ２Ｏ３などの各種金属酸化物類、ＭｇＳ、ＣａＳ、ＳｒＳ、ＺｎＳ、ＣｄＳ、ＦｅＳ、Ｆｅ２Ｓ３、ＦｅＳ２、ＮｉＳ、ＭｏＳ、ＭｏＳ２、Ａｇ２Ｓ、Ａｌ２Ｓ、Ｇａ２Ｓ３、Ｉｎ２Ｓ３、ＳｎＳ、ＳｎＳ２、ＰｂＳ、Ｓｂ２Ｓ３、Ｂｉ２Ｓ３などの各種金属硫化物類、ＭｇＳｅ、ＣａＳｅ、ＳｒＳｅ、ＺｎＳｅ、ＣｄＳｅ、ＦｅＳｅ、Ｆｅ２Ｓｅ３、ＦｅＳｅ２、ＮｉＳｅ、ＭｏＳｅ、ＭｏＳｅ２、Ａｇ２Ｓｅ、Ａｌ２Ｓｅ３、Ｇａ２Ｓｅ３、Ｉｎ２Ｓｅ３、ＳｎＳｅ、ＳｎＳｅ２、ＰｂＳｅ、Ｓｂ２Ｓｅ３、Ｂｉ２Ｓｅ３などの各種金属セレン化物類、ＣｕＴｅ，Ｃｕ２Ｔｅ、ＭｇＴｅ、ＣａＴｅ、ＳｒＴｅ、ＺｎＴｅ、ＣｄＴｅ、ＦｅＴｅ、Ｆｅ２Ｔｅ３、ＦｅＴｅ２、ＮｉＴｅ、ＭｏＴｅ、ＭｏＴｅ２、Ａｇ２Ｔｅ、Ａｌ２Ｔｅ３、Ｇａ２Ｔｅ３、Ｉｎ２Ｔｅ３、ＳｎＴｅ、ＳｎＴｅ２、ＰｂＴｅ、Ｓｂ２Ｔｅ３、Ｂｉ２Ｔｅ３などの各種金属テルル化物との混晶化合物が例示できる。 Specifically, CuS, Cu 2 S copper sulfide, CuSe, Cu 2 Se of copper selenide and these copper sulfide, and copper selenide, e.g., CuO, Cu 2 O, MgO , CaO, SrO, ZnO, CdO, FeO, Fe 2 O 3 , NiO, MoO, MoO 2, Ag 2 O, Al 2 O, Ga 2 O 3, In 2 O 3, SnO, SnO 2, PbO, Sb 2 O 3, Bi 2 O 3 Various metal oxides such as MgS, CaS, SrS, ZnS, CdS, FeS, Fe 2 S 3 , FeS 2 , NiS, MoS, MoS 2 , Ag 2 S, Al 2 S, Ga 2 S 3 , In 2 S 3, SnS, SnS 2, PbS, Sb 2 S 3, Bi 2 various metal sulfides such as S 3, MgSe, CaSe, SrSe , ZnSe, CdSe, FeSe, Fe 2 Se 3, FeS 2, NiSe, MoSe, MoSe 2 , Ag 2 Se, Al 2 Se 3, Ga 2 Se 3, In 2 Se 3, SnSe, SnSe 2, PbSe, various metal selenides, such as Sb 2 Se 3, Bi 2 Se 3 CuTe, Cu 2 Te, MgTe, CaTe, SrTe, ZnTe, CdTe, FeTe, Fe 2 Te 3 , FeTe 2 , NiTe, MoTe, MoTe 2 , Ag 2 Te, Al 2 Te 3 , Ga 2 Te 3 , In Examples thereof include mixed crystal compounds with various metal tellurides such as 2 Te 3 , SnTe, SnTe 2 , PbTe, Sb 2 Te 3 , Bi 2 Te 3 .
より具体的には、ＣｕＩｎＳ２、ＣｕＧａＳ２、ＣｕＩｎＳｅ２、ＣｕＧａＳｅ２などの三元系金属カルコゲナイド化合物類、Ｃｕ（Ｉｎ（１−ｘ），Ｇａｘ）Ｓ２（０＜ｘ＜１）やＣｕ（Ｉｎ（１−ｘ），Ｇａｘ）（Ｓ（１−ｙ），Ｓｅｙ）２（０＜ｘ，ｙ＜１）の如くの三元系金属カルコゲナイド化合物類の一部元素が置換された混晶化合物類、Ｃｕ２ＺｎＳｎＳ４、Ｃｕ２ＺｎＧｅＳ４、Ｃｕ２ＺｎＳｎＳｅ４、Ｃｕ２ＺｎＧｅＳｅ４などの四元系金属カルコゲナイド化合物類、（Ｃｕ（１−ｘ），Ａｇｘ）ＺｎＳｎＳ４（０＜ｘ＜１）、Ｃｕ２ＺｎＳｎ（Ｓ（１−ｘ），Ｓｅｘ）４（０＜ｘ＜１）、（Ｃｕ（１−ｘ），Ａｇｘ）ＺｎＳｎ（Ｓ（１−ｙ），Ｓｅｙ）４（０＜ｘ，ｙ＜１）の如くの四元系金属カルコゲナイド化合物類の一部元素が置換された混晶化合物類などが例示できる。 More specifically, ternary metal chalcogenide compounds such as CuInS 2 , CuGaS 2 , CuInSe 2 and CuGaSe 2 , Cu (In (1-x) , Ga x ) S 2 (0 <x <1) and Cu Partial elements of ternary metal chalcogenide compounds such as (In (1-x) , Ga x ) (S (1-y) , Se y ) 2 (0 <x, y <1) were substituted Mixed crystal compounds, quaternary metal chalcogenide compounds such as Cu 2 ZnSnS 4 , Cu 2 ZnGeS 4 , Cu 2 ZnSnSe 4 , Cu 2 ZnGeSe 4 , (Cu (1-x) , Ag x ) ZnSnS 4 (0 < x <1), Cu 2 ZnSn (S (1-x) , Se x ) 4 (0 <x <1), (Cu (1-x) , Ag x ) ZnSn (S (1-y) , Se y ) 4 (0 <x, y <1) Such as a mixed crystal compounds in which a part element of the four-component metal chalcogenide compounds have been substituted as can be exemplified.
なお、蛍光体における賦活剤（発光中心）や、半導体におけるドーパント類などの成分を含有する金属カルコゲナイド化合物や、Ｃｕ含有のｐ型半導体におけるＣｕの欠損に代表される組成比が化学量論からずれた金属カルコゲナイド化合物も本発明の金属カルコゲナイド化合物に含まれる。
本発明の、結晶成長促進剤は、金属カルコゲナイド化合物の結晶成長を促進し、結晶性を向上し、結晶面の発達した高品質の結晶を形成する機能を有する。そのため、結晶粒内の結晶性や結晶接合面の接合状態といった結晶品質を求められる、光機能や電子機能を有する金属カルコゲナイド化合物の結晶成長に供されるとその効果が顕著に現れる。
In addition, the composition ratio represented by the defect | deletion of Cu in the metal chalcogenide compound containing components, such as the activator (emission center) in a fluorescent substance, dopants in a semiconductor, and a p-type semiconductor containing Cu shifts from stoichiometry. Metal chalcogenide compounds are also included in the metal chalcogenide compounds of the present invention.
The crystal growth promoter of the present invention has a function of promoting crystal growth of a metal chalcogenide compound, improving crystallinity, and forming a high-quality crystal with a developed crystal plane. For this reason, when it is used for crystal growth of a metal chalcogenide compound having an optical function and an electronic function, which requires crystal quality such as crystallinity in crystal grains and a bonding state of a crystal bonding surface, the effect becomes remarkable.
とりわけ、太陽電池に代表される光電変換素子のｐｎ接合を担う半導体のような電子が流れる電子機能を有するカルコゲナイド化合物に対しては、結晶品質が高くなることで特性が大幅に改善されるため効果的であり、ＣｕＳ、Ｃｕ２Ｓ、ＣｕＳｅ、Ｃｕ２Ｓｅ、ＣｕＩｎＳ２、ＣｕＧａＳ２、ＣｕＩｎＳｅ２、ＣｕＧａＳｅ２、Ｃｕ２ＺｎＳｎＳ４、Ｃｕ２ＺｎＧｅＳ４、Ｃｕ２ＺｎＳｎＳｅ４、Ｃｕ２ＺｎＧｅＳｅ４並びにこれらの混晶化合物といったＣｕを含有するｐ型半導体に有効に作用する。 In particular, for chalcogenide compounds having an electronic function in which electrons flow, such as a semiconductor that bears the pn junction of a photoelectric conversion element typified by a solar cell, the characteristics are greatly improved due to the high crystal quality, which is effective. CuS, Cu 2 S, CuSe, Cu 2 Se, CuInS 2 , CuGaS 2 , CuInSe 2 , CuGaSe 2 , Cu 2 ZnSnS 4 , Cu 2 ZnGeS 4 , Cu 2 ZnSnSe 4 , Cu 2 ZnGeSe 4 and these It effectively acts on a p-type semiconductor containing Cu such as a mixed crystal compound.
即ち、銅を含有するカルコゲナイド化合物は、銅とカルコゲン元素の軌道の混成によってｐ型半導体になりやすく、このような銅を含有するｐ型半導体では、電子遷移によって発生したキャリアの拡散がｎ型半導体に比べて遅いため、カルコゲナイド化合物の結晶品質がより重要になるためである。従って、本発明のカルコゲナイド化合物が、銅を金属元素として含有し、かつ、硫黄及び又はセレンをカルコゲン元素として含有するカルコゲナイド化合物である場合、本発明の結晶成長促進剤を用いた結晶成長の効果が、実用上大きな効果をもたらし、好ましい。 That is, a chalcogenide compound containing copper is likely to become a p-type semiconductor due to the hybrid of orbits of copper and chalcogen elements. In such a p-type semiconductor containing copper, diffusion of carriers generated by electronic transition is an n-type semiconductor. This is because the crystal quality of the chalcogenide compound becomes more important because it is slower than the above. Therefore, when the chalcogenide compound of the present invention is a chalcogenide compound containing copper as a metal element and sulfur and / or selenium as a chalcogen element, the effect of crystal growth using the crystal growth accelerator of the present invention is obtained. This is preferable because it brings about a large practical effect.
とりわけ、太陽電池に代表される受光素子の分野において、高いエネルギー変換効率を実現でき、高い結晶品質が求められる、ＣｕＩｎＳ２、ＣｕＧａＳ２、ＣｕＩｎＳｅ２、ＣｕＧａＳｅ２並びにこれらの混晶化合物といったインジウム及び／又はガリウムを含有する化合物の場合に、本発明の結晶成長促進剤は優れた効果を示す。即ち、本発明のカルコゲナイド化合物が、銅に加えて、インジウム及び／又はガリウムから選択される元素を金属元素として含有し、かつ、硫黄及び又はセレンをカルコゲン元素として含有するカルコゲナイド化合物である場合、本発明の結晶成長促進剤を用いた結晶成長の効果が、実用上、更に大きくなるので、より好ましい。 In particular, in the field of a light receiving element typified by a solar cell, indium and / or CuInS 2 , CuGaS 2 , CuInSe 2 , CuGaSe 2 , and mixed crystal compounds thereof that can achieve high energy conversion efficiency and require high crystal quality. Alternatively, in the case of a compound containing gallium, the crystal growth promoter of the present invention exhibits an excellent effect. That is, when the chalcogenide compound of the present invention is a chalcogenide compound containing, in addition to copper, an element selected from indium and / or gallium as a metal element and sulfur and / or selenium as a chalcogen element, Since the effect of crystal growth using the crystal growth accelerator of the invention is further increased in practical use, it is more preferable.
次に、本発明の結晶成長促進剤について以下に説明する。
本発明の結晶成長促進剤は、１種以上の銅のハロゲン化物を含有する無機材料であることが必要である。即ち、本発明の銅を含有する金属カルコゲナイド化合物に対し、同一金属種である銅を有する、銅のハロゲン化物を含有する結晶成長促進剤を作用させることで、金属カルコゲナイドと結晶成長促進剤の親和性が高まり、結晶成長が促進される。
Next, the crystal growth promoter of the present invention will be described below.
The crystal growth promoter of the present invention is required to be an inorganic material containing one or more types of copper halides. That is, by applying a crystal growth accelerator containing copper halide having the same metal species to the metal chalcogenide compound containing copper according to the present invention, the affinity between the metal chalcogenide and the crystal growth accelerator is increased. And the crystal growth is promoted.
そのような銅のハロゲン化物としては、ＣｕＦ、ＣｕＦ２のフッ化銅、ＣｕＣｌ、ＣｕＣｌ２の塩化銅、ＣｕＢｒ、ＣｕＢｒ２の臭化銅、ＣｕＩ、ＣｕＩ２のヨウ化銅やこれらの混合物が例示できる。
また、本発明の結晶成長促進剤は、これらの銅のハロゲン化物を含有していればよく、他の化合物と混合して用いることも可能である。
Examples of such copper halides include CuF, CuF 2 copper fluoride, CuCl, CuCl 2 copper chloride, CuBr, CuBr 2 copper bromide, CuI, CuI 2 copper iodide, and mixtures thereof. it can.
Further, the crystal growth accelerator of the present invention only needs to contain these copper halides, and can be used by mixing with other compounds.
このような本発明の結晶成長促進剤と混合して用いられる化合物としては、本発明の結晶成長促進剤と共晶点を有する化合物が好ましい。即ち、結晶成長促進剤と共晶点を有する化合物を使用することによって、低い温度で結晶成長促進剤と、結晶成長促進剤と共晶点を有する化合物の混合物は融解して融液状態となるため、物質の拡散等が促進され、カルコゲナイド化合物の結晶成長が促進されるためである。とりわけ、本発明のカルコゲナイド化合物が複数の化合物から製造される場合に、この融液状態での反応促進が顕著になるため、本発明の結晶成長促進剤とともに、結晶成長促進剤と共晶点を有する化合物を組み合わせて好ましく用いられる。 As a compound used by mixing with the crystal growth accelerator of the present invention, a compound having a eutectic point with the crystal growth accelerator of the present invention is preferable. That is, by using a compound having a crystal growth accelerator and a eutectic point, the mixture of the crystal growth accelerator and the crystal growth accelerator and the compound having a eutectic point melts into a molten state at a low temperature. Therefore, the diffusion of the substance is promoted, and the crystal growth of the chalcogenide compound is promoted. In particular, when the chalcogenide compound of the present invention is produced from a plurality of compounds, the acceleration of the reaction in the melt state becomes remarkable. Therefore, together with the crystal growth accelerator of the present invention, the crystal growth accelerator and the eutectic point are set. It is preferably used in combination with the compound having.
本発明の結晶成長促進剤とともに、共晶点を有する化合物を用いる場合の融解温度（融点）は特に限定されず、結晶成長を促進したいカルコゲナイド化合物やカルコゲナイド化合物原料の種類に応じて適宜選択できるが、常温において融解すると秤量が困難になるなど生産性が劣る場合があるので、好ましくは４０℃以上であり、より好ましくは８０℃以上である。上限に関しては特に制約されないが、１７００℃より高温になると、加熱の際に使用可能な装置に制約が発生して生産性が劣る場合があるので、好ましくは１７００℃以下、より好ましくは１５００℃以下であり、更に好ましくは１２００℃以下、最も好ましくは１０００℃以下である。 The melting temperature (melting point) when using a compound having a eutectic point together with the crystal growth accelerator of the present invention is not particularly limited, and can be appropriately selected according to the type of chalcogenide compound or chalcogenide compound raw material for which crystal growth is desired to be promoted. When the product is melted at room temperature, productivity may be inferior, for example, weighing becomes difficult. The upper limit is not particularly limited, but if the temperature is higher than 1700 ° C., the apparatus that can be used in heating may be restricted and productivity may be inferior. More preferably, it is 1200 degrees C or less, Most preferably, it is 1000 degrees C or less.
また、後述の好ましい製造方法である基板上で本発明の結晶成長促進剤を使用する場合や、そのような製造形態を意図して結晶成長促進剤を選択する場合は、基板の耐熱温度が上限になり、例えば、石英ガラスの基板を用いる場合は、１０００℃以下が好ましく、ソーダライムガラスの基板を用いる場合は、６００℃以下が好ましく、ポリイミド基板を用いる場合は、４５０℃以下が好ましい。 In addition, when the crystal growth accelerator of the present invention is used on a substrate, which is a preferable production method described later, or when a crystal growth accelerator is selected with the intention of such a production form, the heat-resistant temperature of the substrate is the upper limit. For example, when a quartz glass substrate is used, it is preferably 1000 ° C. or lower, when a soda lime glass substrate is used, 600 ° C. or lower is preferable, and when a polyimide substrate is used, 450 ° C. or lower is preferable.
本発明の結晶成長促進剤と、共晶点を有する化合物の混合比は特に限定されず、目的に応じて適宜選択できる。即ち、共晶点を有する２種以上の化合物を混合した場合、それらの化合物の組合せによって特定の比率で共晶点が得られ、融解温度が最も下がるが、このような組合せの材料では、混合比に応じた液相線があるのが一般的であり、共晶点からずれた混合比でも融解温度の低下が観測されるためである。 The mixing ratio of the crystal growth accelerator of the present invention and the compound having a eutectic point is not particularly limited, and can be appropriately selected according to the purpose. That is, when two or more kinds of compounds having eutectic points are mixed, eutectic points are obtained at a specific ratio depending on the combination of these compounds, and the melting temperature is the lowest. This is because there is generally a liquidus line corresponding to the ratio, and a decrease in melting temperature is observed even at a mixing ratio deviated from the eutectic point.
なお、本発明の結晶成長促進剤は、本発明の金属カルコゲナイド化合物原料であったりすることも可能であるが、このような場合は、反応の制御を精緻に行うことが必要になる場合がある。
本発明において、結晶成長促進剤は、ＣｕＣｌ（塩化第一銅）及び／又はＣｕＣｌ２（塩化第二銅）であることが好ましい。
The crystal growth accelerator of the present invention can be the metal chalcogenide compound raw material of the present invention. In such a case, it may be necessary to precisely control the reaction. .
In the present invention, the crystal growth accelerator is preferably CuCl (cuprous chloride) and / or CuCl 2 (cupric chloride).
即ち、本発明において、結晶成長促進剤は、本発明の金属カルコゲナイドの結晶成長場において、融解し、結晶成長を促進したり、或いは、２種以上の金属カルコゲナイド原料の反応を促進したりするのに有効であるため、好ましい温度領域で融解することが望まれ、イオン結合性が強すぎない方が望ましく、また、金属カルコゲナイド化合物の製造後に、結晶成長促進剤を取り除く必要がある場合があり、そのような場合は、水やアルカリ性水溶液などへの溶解性が高い方が好ましいため、程よいイオン結合性を有する、塩化第一銅及び／又は塩化第二銅から選択される塩化銅が好ましく用いられる。 That is, in the present invention, the crystal growth accelerator melts in the crystal growth field of the metal chalcogenide of the present invention and promotes crystal growth or promotes the reaction of two or more metal chalcogenide raw materials. Therefore, it is desirable to melt in a preferable temperature range, it is desirable that the ionic bond is not too strong, and it may be necessary to remove the crystal growth promoter after the production of the metal chalcogenide compound, In such a case, since it is preferable that the solubility in water or an alkaline aqueous solution is high, copper chloride selected from cuprous chloride and / or cupric chloride having moderate ion binding properties is preferably used. .
また、上述したように、本発明の結晶成長促進剤は、共晶点を有する他の化合物と組み合わせて好ましく用いられる。本発明の結晶成長促進剤と共晶点を有する化合物は、共晶点があればその組合せは特に限定されないが、共晶点を有する化合物類は、陰イオンを共有する場合に共晶温度の低下が観測されやすく、塩化銅に対しては、塩化物類、臭化銅に対しては臭化物類、ヨウ化銅に対してはヨウ化物類が好ましく用いられる。 Further, as described above, the crystal growth promoter of the present invention is preferably used in combination with other compounds having a eutectic point. The combination of the crystal growth accelerator of the present invention and the compound having a eutectic point is not particularly limited as long as it has a eutectic point. However, compounds having a eutectic point have a eutectic temperature when they share an anion. A decrease is easily observed, and chlorides are preferably used for copper chloride, bromides for copper bromide, and iodides for copper iodide.
より具体的には、塩化銅に対しては、塩化リチウム、塩化ナトリウム、塩化カリウム、塩化ルビジウム、塩化セシウム、塩化アンモニウム、塩化アルミニウム、塩化ガリウム、塩化インジウムなどの各種金属塩化物類が例示でき、臭化銅に対しては、臭化ナトリウム、臭化カリウムなどの各種金属臭化物類が例示でき、ヨウ化銅に対しては、ヨウ化カリウム、ヨウ化ルビジウム、ヨウ化ガリウム、ヨウ化インジウムなどの各種金属ヨウ化物類が例示できる。 More specifically, for copper chloride, various metal chlorides such as lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, ammonium chloride, aluminum chloride, gallium chloride, indium chloride can be exemplified, Examples of copper bromide include various metal bromides such as sodium bromide and potassium bromide. Examples of copper iodide include potassium iodide, rubidium iodide, gallium iodide, and indium iodide. Various metal iodides can be exemplified.
また、フッ化銅、塩化銅、臭化銅、ヨウ化銅は銅イオンを共有しているために共晶温度の低下が観測されるため、これらを相互に組み合わせて使用することも好ましい。
また、アルカリ金属ハロゲン化物は、取り扱いが容易なために工業生産性に優れ、本発明の結晶成長促進剤と共晶点を有する化合物として好ましく選択される。
また、金属カルコゲナイド化合物原料と結晶成長促進剤が共晶点を有して、結晶成長促進剤の融解温度を下げることも可能である。そのような場合は、結晶成長促進剤の融解温度が低下することによって、本発明の金属カルコゲナイド化合物原料の反応を促進するのみならず、金属カルコゲナイド化合物原料の一部、又は全部が融解し、融液状態で反応するので、反応が一層促進される。
Further, since copper fluoride, copper chloride, copper bromide, and copper iodide share a copper ion, a decrease in the eutectic temperature is observed. Therefore, it is also preferable to use these in combination with each other.
Alkali metal halides are excellent in industrial productivity because they are easy to handle, and are preferably selected as compounds having a eutectic point with the crystal growth accelerator of the present invention.
In addition, the metal chalcogenide compound raw material and the crystal growth accelerator have a eutectic point, and the melting temperature of the crystal growth accelerator can be lowered. In such a case, the melting temperature of the crystal growth accelerator is lowered, thereby not only promoting the reaction of the metal chalcogenide compound raw material of the present invention but also melting or melting part or all of the metal chalcogenide compound raw material. Since it reacts in a liquid state, the reaction is further promoted.
次に、本発明の結晶成長促進剤を用いた、金属カルコゲナイド化合物の製造方法について説明する。
本発明の結晶成長促進剤は、金属カルコゲナイド化合物の結晶成長に有効なので、金属カルコゲナイド化合物、或いは、その製造に必要な金属カルコゲナイド原料、即ち、１種以上の化合物に金属カルコゲナイド化合物を構成する元素をすべて含む金属カルコゲナイド化合物原料と結晶成長促進剤を接触させて加熱することによって、金属カルコゲナイド化合物の結晶成長を促進する。
Next, a method for producing a metal chalcogenide compound using the crystal growth accelerator of the present invention will be described.
Since the crystal growth accelerator of the present invention is effective for crystal growth of a metal chalcogenide compound, the metal chalcogenide compound or a metal chalcogenide raw material necessary for the production thereof, that is, one or more compounds constituting the metal chalcogenide compound is added. Crystal growth of the metal chalcogenide compound is promoted by bringing the metal chalcogenide compound raw material and the crystal growth promoter into contact with each other and heating.
とりわけ、本発明の結晶成長促進剤は、融解状態で、反応場を形成して反応を促進する効果が高いので、金属カルコゲナイド化合物原料が２種以上の化合物である場合により結晶成長や反応促進の効果を発揮する。
加熱温度は、結晶成長促進剤の融解温度以上であれば特に限定されず、結晶成長促進剤の融解温度（融点）や、共晶化合物と共に結晶成長促進剤を用いる場合は、共晶化によって低温化された融解温度（共晶点）によって、適宜選択できる。上限については特に限定されないが、本発明の金属カルコゲナイド化合物の分解温度以下の温度が好ましい。
In particular, the crystal growth promoter of the present invention has a high effect of promoting reaction by forming a reaction field in a molten state. Therefore, when the metal chalcogenide compound raw material is two or more kinds of compounds, the crystal growth or reaction promotion is promoted. Demonstrate the effect.
The heating temperature is not particularly limited as long as it is equal to or higher than the melting temperature of the crystal growth accelerator. The melting temperature (melting point) of the crystal growth accelerator, and when using a crystal growth accelerator together with the eutectic compound, the heating temperature is lowered by eutecticization. The temperature can be appropriately selected depending on the melting temperature (eutectic point). The upper limit is not particularly limited, but a temperature equal to or lower than the decomposition temperature of the metal chalcogenide compound of the present invention is preferable.
また、加熱温度が１７００℃より高温になると、加熱の際に使用可能な装置に制約が発生して生産性が劣る場合があるので、好ましくは１７００℃以下、より好ましくは１５００℃以下であり、更に好ましくは１２００℃以下、最も好ましくは１０００℃以下である。
一方、好ましい製造方法である基板上で本発明の結晶成長促進剤と金属カルコゲナイド化合物原料を接触させて使用する場合や、そのような製造形態を意図して結晶成長促進剤を選択する場合は、基板の耐熱温度が上限になり、例えば石英ガラスの基板を用いる場合は、１０００℃以下が好ましく、ソーダライムガラスの基板を用いる場合は６００℃以下が好ましく、ポリイミド基板を用いる場合は、４５０℃以下が好ましい。
In addition, when the heating temperature is higher than 1700 ° C., there is a case where the apparatus that can be used for heating is restricted and the productivity may be inferior, so that it is preferably 1700 ° C. or less, more preferably 1500 ° C. or less, More preferably, it is 1200 degrees C or less, Most preferably, it is 1000 degrees C or less.
On the other hand, when the crystal growth accelerator of the present invention and the metal chalcogenide compound raw material are used in contact with each other on a substrate which is a preferred production method, or when a crystal growth accelerator is selected with the intention of such production form, The upper temperature limit of the substrate is the upper limit. For example, when a quartz glass substrate is used, it is preferably 1000 ° C. or lower, when a soda lime glass substrate is used, 600 ° C. or lower is preferable, and when a polyimide substrate is used, 450 ° C. or lower. Is preferred.
本発明において金属カルコゲナイド化合物原料と結晶成長促進剤の比率は特に限定されないが、金属カルコゲナイド化合物のモル分率が小さいと結晶成長に供される結晶成長促進剤の廃棄物が増えたり、結晶成長促進剤の洗浄が煩雑になるなどして生産性が低下する場合があるので、５％以上、より好ましくは１０％以上である。上限に関しては、結晶成長促進剤の割合が小さいと、結晶成長促進効果が小さくなる場合があるため、カルコゲナイド化合物のモル分率は、好ましくは９８％以下、より好ましくは９５％以下、更に好ましくは９０％以下である。 In the present invention, the ratio between the metal chalcogenide compound raw material and the crystal growth accelerator is not particularly limited. However, if the molar fraction of the metal chalcogenide compound is small, the crystal growth accelerator waste used for crystal growth increases or the crystal growth acceleration. Since the productivity may be lowered due to complicated cleaning of the agent, it is 5% or more, more preferably 10% or more. Regarding the upper limit, since the crystal growth promoting effect may be reduced if the proportion of the crystal growth accelerator is small, the molar fraction of the chalcogenide compound is preferably 98% or less, more preferably 95% or less, and still more preferably. 90% or less.
また、金属カルコゲナイド化合物原料と結晶成長促進剤の共晶点を活用して、低温反応を実現しようとするときは、それらの共晶組成比が好ましい混合比である。
なお、金属カルコゲナイド化合物原料が２種以上の化合物で構成される場合、即ち、２種以上の金属カルコゲナイド化合物原料から製造する場合は、製造しようとする金属カルコゲナイド化合物のモル分率を用いて同様に計算し、金属カルコゲナイド化合物と結晶成長促進剤の比率を求める。
Moreover, when it is going to implement | achieve a low temperature reaction using the eutectic point of a metal chalcogenide compound raw material and a crystal growth promoter, those eutectic composition ratios are a preferable mixing ratio.
In addition, when the metal chalcogenide compound raw material is composed of two or more kinds of compounds, that is, when the metal chalcogenide compound raw material is produced from two or more kinds of metal chalcogenide compound raw materials, the molar fraction of the metal chalcogenide compound to be produced is similarly used. Calculate the ratio of the metal chalcogenide compound to the crystal growth accelerator.
本発明において、結晶成長促進剤と金属カルコゲナイド化合物原料の混合法は、特に限定されず、結晶成長促進剤と金属カルコゲナイド化合物原料が接触して存在すればよい。具体的には、坩堝に代表される１つの容器の中に一緒に存在させたり、あるいは、基板上に一緒に存在させたりする方法が例示できる。
坩堝（るつぼ；ｃｒｕｃｉｂｌｅ、ｍｅｌｔｉｎｇ ｐｏｔ）に代表される容器中で接触させる場合は、結晶成長促進剤と金属カルコゲナイド化合物原料を重ねて投入してもよいし、予め混合して投入してもよいが、予め混合して投入して接触させる方が、結晶成長促進剤と金属カルコゲナイド化合物原料の接触面積が増大し、結晶成長促進効果が向上するので好ましい。予め混合する方法は、特に限定されないが、乳鉢に代表される粉砕しながら混合する方法が、同様の理由で好ましい。また、混合前に、ボールミル、ビーズミル、ジェットミルなどの粉砕機で予め結晶成長促進剤や金属カルコゲナイド化合物原料を粉砕しておくと、接触面積が増大し、結晶成長促進効果が向上するので好ましい。
In the present invention, the method for mixing the crystal growth accelerator and the metal chalcogenide compound raw material is not particularly limited, as long as the crystal growth accelerator and the metal chalcogenide compound raw material are in contact with each other. Specifically, there can be exemplified a method of existing together in one container represented by a crucible, or existing together on a substrate.
When contacting in a vessel typified by a crucible (crucible, melting pot), the crystal growth accelerator and the metal chalcogenide compound material may be added in layers, or may be mixed and added in advance. It is preferable to add them in advance and contact them because the contact area between the crystal growth promoter and the metal chalcogenide compound raw material is increased and the crystal growth promotion effect is improved. A method of mixing in advance is not particularly limited, but a method of mixing while pulverizing as represented by a mortar is preferable for the same reason. In addition, it is preferable to pulverize the crystal growth promoter and the metal chalcogenide compound raw material in advance with a pulverizer such as a ball mill, a bead mill, or a jet mill before mixing because the contact area increases and the crystal growth promoting effect is improved.
また、金属カルコゲナイド化合物原料や結晶成長促進剤が、水に代表される溶媒に溶解する化合物を含む場合は、予め溶解する化合物をその溶媒に溶解して混合する方法も結晶成長促進剤や金属カルコゲナイド化合物原料の接触面積を増大させる手法として好ましく用いられる。
本発明において、金属カルコゲナイド化合物の製造に供される２種以上の化合物に本発明のカルコゲナイド化合物を構成する元素をすべて含むカルコゲナイド化合物原料としては、特に限定されず、複数種の材料が反応して、目的の化合物が形成されればよい。
In addition, when the metal chalcogenide compound raw material or crystal growth accelerator contains a compound that dissolves in a solvent typified by water, the method of dissolving and mixing the compound that dissolves in advance in the solvent can also be used as the crystal growth accelerator or metal chalcogenide. It is preferably used as a method for increasing the contact area of the compound raw material.
In the present invention, the chalcogenide compound raw material containing all the elements constituting the chalcogenide compound of the present invention in two or more compounds used for the production of the metal chalcogenide compound is not particularly limited, and a plurality of types of materials react with each other. The target compound may be formed.
具体的には、金属カルコゲナイド化合物を複数種反応させる方法、少なくとも１種の金属カルコゲナイド化合物と、金属元素を含有する化合物のところで例示した金属塩類等やその金属塩に含有される金属、硫黄及び／又はセレンから選択されるカルコゲン元素を加えて反応させる方法、２種の上記金属、金属塩類等に硫黄及び／又はセレンから選択されるカルコゲン元素を加えて反応させる方法などが例示できる。また、硫黄及び／又はセレンの供給方法は、それぞれの単体を用いてもよいし、硫化水素やセレン化水素といったガス状の物質を用いても構わないが、それぞれの単体元素を用いる方が、簡便で生産性に優れるので好ましい。 Specifically, a method of reacting a plurality of metal chalcogenide compounds, at least one metal chalcogenide compound, metal salts exemplified in the compound containing a metal element, etc., metals contained in the metal salts, sulfur and / or Alternatively, a method of reacting by adding a chalcogen element selected from selenium, a method of adding and reacting a chalcogen element selected from sulfur and / or selenium, etc. to the above two metals, metal salts and the like can be exemplified. In addition, as a method for supplying sulfur and / or selenium, each simple substance may be used, or a gaseous substance such as hydrogen sulfide or hydrogen selenide may be used. It is preferable because it is simple and excellent in productivity.
このような反応は、上述したように、容器の中で行ってもよいし、基板上で行ってもよいが、本発明の金属カルコゲナイド化合物の薄膜を形成する場合は、基板上で行うのが好ましい。即ち、基板上で反応を行うことによって、容易に緻密な膜を形成できるためである。また、基板上で反応をする場合、基板の耐熱温度が加熱の上限になるが、本発明の結晶成長促進剤を用いて金属カルコゲナイド化合物を製造する場合、結晶成長促進剤を用いずに加熱する場合に比べて、低温で結晶成長が進むので、結晶性や粒子サイズの優れた金属カルコゲナイド化合物膜が形成されるためである。 As described above, such a reaction may be performed in a container or on a substrate. However, when a thin film of the metal chalcogenide compound of the present invention is formed, it may be performed on a substrate. preferable. That is, a dense film can be easily formed by performing a reaction on the substrate. In addition, when the reaction is carried out on the substrate, the heat-resistant temperature of the substrate becomes the upper limit of heating, but when the metal chalcogenide compound is produced using the crystal growth accelerator of the present invention, heating is performed without using the crystal growth accelerator. This is because crystal growth proceeds at a low temperature as compared with the case, so that a metal chalcogenide compound film having excellent crystallinity and particle size is formed.
このように、基板上で反応を進行させる場合、本発明の金属カルコゲナイド化合物原料と本発明の結晶成長促進剤を混合して基板上に付着させて反応させてもよいし、積層して付着させて反応させてもよい。また、本発明の金属カルコゲナイド化合物原料の１つの成分を予め基板上に付着し、その表面に少なくとも他の１つの金属カルコゲナイド化合物の原料と結晶成長促進剤を付着させて反応させることも可能であり、均一な膜を製造する場合には、この方法が好ましく用いられる。 Thus, when the reaction is allowed to proceed on the substrate, the metal chalcogenide compound raw material of the present invention and the crystal growth accelerator of the present invention may be mixed and deposited on the substrate for reaction, or stacked and deposited. May be reacted. It is also possible to cause one component of the metal chalcogenide compound raw material of the present invention to adhere to the substrate in advance, and to cause at least one other metal chalcogenide compound raw material and a crystal growth accelerator to react with each other. In the case of producing a uniform film, this method is preferably used.
また、基板上に本発明の金属カルコゲナイド化合物や結晶成長促進剤を付着させる方法は特に限定されず、バーコーターやブレードコーターといったコーティング装置を用いて塗布する方法や、スパッタリング法や真空蒸着法といった真空成膜法を用いて成膜する方法が例示でき、これらを組み合わせて使用することも可能である。
本発明において、本発明の金属カルコゲナイド化合物を基板上で製造する際に用いられる基板は特に限定されず、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリイミドなどの各種樹脂基板、ソーダライムガラス、無アルカリガラス、石英ガラスなどの各種ガラス基板、酸化亜鉛、サファイア、ジルコニウムなどの各種セラミックス基板、シリコン、ガリウム砒素などの各種半導体基板や、これらの基板上に、酸化シリコン、窒化シリコン、酸化アルミニウム、酸化ハフニウムなどの絶縁層を設置した基板や、金、銀、銅、白金、アルミニウム、鉄、チタン、モリブデン、タングステン、タンタル、ニオブ、ニッケルなどの各種金属層を設置した基板、アルミニウムをドープした酸化亜鉛（ＡＺＯ）、ガリウムをドープした酸化亜鉛（ＧＺＯ）、インジウムとガリウムをドープした酸化亜鉛（ＩＧＺＯ）、錫をドープした酸化インジウム（ＩＴＯ）、フッ素をドープした酸化錫（ＦＴＯ）、アンチモンをドープした酸化錫（ＡＴＯ）、燐をドープした酸化錫（ＰＴＯ）などの透明導電層を設置した基板など、本発明のカルコゲナイド化合物膜の用途に応じて適宜選択できる。
Further, the method for adhering the metal chalcogenide compound or crystal growth accelerator of the present invention on the substrate is not particularly limited, and a coating method such as a bar coater or a blade coater, a vacuum such as a sputtering method or a vacuum deposition method. A method of forming a film using a film forming method can be exemplified, and these can be used in combination.
In the present invention, the substrate used for producing the metal chalcogenide compound of the present invention on the substrate is not particularly limited, and various resin substrates such as polyethylene terephthalate, polyethylene naphthalate, polyimide, soda lime glass, alkali-free glass, quartz Various glass substrates such as glass, various ceramic substrates such as zinc oxide, sapphire, and zirconium, various semiconductor substrates such as silicon and gallium arsenide, and insulation such as silicon oxide, silicon nitride, aluminum oxide, and hafnium oxide on these substrates A substrate provided with a layer, a substrate provided with various metal layers such as gold, silver, copper, platinum, aluminum, iron, titanium, molybdenum, tungsten, tantalum, niobium, nickel, zinc oxide doped with aluminum (AZO), Gallium doped acid Zinc (GZO), zinc oxide doped with indium and gallium (IGZO), indium oxide doped with tin (ITO), tin oxide doped with fluorine (FTO), tin oxide doped with antimony (ATO), doped with phosphorus A substrate provided with a transparent conductive layer such as tin oxide (PTO) can be appropriately selected according to the application of the chalcogenide compound film of the present invention.
本発明の金属カルコゲナイド化合物を太陽電池に代表される受発光素子の光吸収／発光層として使用するときは、金属層や透明導電層を設置して導電性を付与した、各種樹脂基板や各種ガラス基板が好適に用いられる。
また、このような場合は、例えば、極性の異なる半導体層や、バッファ層、更には、基板と対極を為す電極層などを設置して、デバイス化して用いることも可能である。
When the metal chalcogenide compound of the present invention is used as a light absorption / light emitting layer of a light emitting / receiving element typified by a solar cell, various resin substrates and various glasses provided with conductivity by installing a metal layer or a transparent conductive layer. A substrate is preferably used.
In such a case, for example, a semiconductor layer having a different polarity, a buffer layer, and an electrode layer that counters the substrate may be installed and used as a device.
そのような場合は、本発明の基板と対極を為す電極層のいずれか片方が光を透過する透明導電層であることが好ましい。また、極性の異なる半導体層やバッファ層は、ＣｄＳ、ＺｎＳ、Ｉｎ２Ｓ３、ＺｎＯ、（Ｚｎｘ，Ｍｇ（１−ｘ））Ｏといった各種材料を、化学バス堆積法に代表される溶液法や、スパッタリング法、真空蒸着法といった真空成膜法を用いて設置できる。 In such a case, it is preferable that any one of the electrode layers which make a counter electrode with the board | substrate of this invention is a transparent conductive layer which permeate | transmits light. In addition, for semiconductor layers and buffer layers having different polarities, various materials such as CdS, ZnS, In 2 S 3 , ZnO, (Zn x , Mg (1-x) ) O are used as a solution method represented by a chemical bath deposition method. Alternatively, it can be installed by using a vacuum film formation method such as a sputtering method or a vacuum evaporation method.
以上のように、本発明の結晶成長促進剤を用いれば、硫黄、セレンから選択されるカルコゲン元素と、銅とを含有する金属カルコゲナイド化合物の結晶成長が促進される。その結果、高い結晶性を有したり、粒子サイズが大きな結晶が得られる。また、本発明の結晶成長促進剤を用いれば、結晶面の明確な高結晶性の粒子が得られることも特徴であり、電子物性を要求される、触媒や半導体の分野で優れた性能を発揮する。 As described above, when the crystal growth accelerator of the present invention is used, crystal growth of a metal chalcogenide compound containing a chalcogen element selected from sulfur and selenium and copper is promoted. As a result, a crystal having high crystallinity or a large particle size can be obtained. In addition, if the crystal growth accelerator of the present invention is used, highly crystalline particles with a clear crystal plane can be obtained, and it exhibits excellent performance in the field of catalysts and semiconductors that require electronic properties. To do.
また、本発明の結晶成長促進剤を用いれば、低温で結晶成長や反応が促進されるので、本発明の好ましい製造方法である、基板上で金属カルコゲナイド化合物を製造する際には、樹脂基板やソーダライムガラス基板のような耐熱性が低い基板上でも優れた金属カルコゲナイド化合物の結晶を得ることができる。
以下、本発明を実施例と比較例を用いて具体的に説明するが、本発明はこれらの技術的範囲に限定されない。
In addition, when the crystal growth accelerator of the present invention is used, crystal growth and reaction are promoted at a low temperature. Therefore, when a metal chalcogenide compound is produced on a substrate, which is a preferred production method of the present invention, a resin substrate or An excellent metal chalcogenide compound crystal can be obtained even on a substrate having low heat resistance such as a soda lime glass substrate.
EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited to these technical scopes.
本発明で用いられる測定法は、以下のとおりである。
＜結晶構造＞
（実施例１、比較例１）
粉末を粉末試料ホルダーに詰めて固定し、基板測定時は、株式会社リガク製Ｘ線回折装置ＵｌｔｉｍａIV型を用い、ターゲットとしてＣｕを用い、励起電圧４０ｋＶ、励起電流４０ｍＡとし、操作軸は２θ／θとして測定した。検出器には、高速１次元Ｘ線検出器Ｄ／ｔｅＸ Ｕｌｔｒａを用いた。
（実施例２、比較例２）
基板を粘土でホルダーに固定し、株式会社リガク製Ｘ線回折装置ＭｉｎｉＦｌｅｘIIを用い、ターゲットとしてＣｕを用い、励起電圧３０ｋＶ、励起電流１５ｍＡとし、操作軸は２θ／θとして測定した。検出器には、株式会社リガク製高速一次元検出器Ｄ／ｔｅＸ Ｕｌｔｒａを用いた。
The measuring method used in the present invention is as follows.
<Crystal structure>
(Example 1, Comparative Example 1)
The powder is packed and fixed in a powder sample holder, and at the time of substrate measurement, an Rigaku X-ray diffractometer Ultimate IV type is used, Cu is used as a target, an excitation voltage is 40 kV, an excitation current is 40 mA, and an operation axis is 2θ / θ. As measured. A high-speed one-dimensional X-ray detector D / teX Ultra was used as the detector.
(Example 2, comparative example 2)
The substrate was fixed to a holder with clay, an X-ray diffractometer MiniFlexII manufactured by Rigaku Corporation was used, Cu was used as the target, the excitation voltage was 30 kV, the excitation current was 15 mA, and the operation axis was 2θ / θ. A high-speed one-dimensional detector D / teX Ultra manufactured by Rigaku Corporation was used as the detector.
＜結晶性＞
結晶構造の測定と同様の測定を行い、ＣｕＩｎＳ２の１１２面のピークの半値幅を評価した。
＜融解温度の測定＞
株式会社リガク製示差熱天秤Ｔｈｅｒｍｏ ｐｌｕｓ ＥＶＯ ＴＧ８１２０型を用い、白金製の容器に試料を投入して、高純度窒素雰囲気下、１０℃／分の昇温速度で６００℃まで加熱して測定した。
<Crystallinity>
The same measurement as the measurement of the crystal structure was performed, and the half width of the peak of the 112 face of CuInS 2 was evaluated.
<Measurement of melting temperature>
Using a differential thermal balance Thermo plus EVO TG8120 manufactured by Rigaku Corporation, the sample was put into a platinum container and measured by heating to 600 ° C. at a heating rate of 10 ° C./min in a high purity nitrogen atmosphere.
金属カルコゲナイド化合物の原料として、Ｃｕ２Ｓを０．１５９ｇとＩｎ２Ｓ３を０．３２６ｇを秤量し、結晶成長促進剤としてＣｕＣｌを０．４２２ｇ秤量し、乳鉢を用いて１５分間混合した。得られた混合粉を、アルミナ製の坩堝に入れて、アルミナ製の横型管状炉内で、窒素雰囲気下、内温４００℃で１時間焼成し、黒色の粉末Ａを得た。粉末ＡをＸ回折装置を用いて構造解析を行ったところ、粉末ＡはＣｕＩｎＳ２であり、その１１２面に起因する回折線の半値幅は０．１４１ｄｅｇあることが確認された。 As raw materials for the metal chalcogenide compound, 0.159 g of Cu 2 S and 0.326 g of In 2 S 3 were weighed, 0.422 g of CuCl was weighed as a crystal growth accelerator, and mixed for 15 minutes using a mortar. The obtained mixed powder was put in an alumina crucible and fired in an alumina horizontal tubular furnace for 1 hour at an internal temperature of 400 ° C. in a nitrogen atmosphere to obtain black powder A. When structural analysis was performed on the powder A using an X diffractometer, it was confirmed that the powder A was CuInS 2 and the half width of the diffraction line caused by the 112 plane was 0.141 deg.
別に、この組成を熱重量・示唆熱分析装置を用いて、窒素雰囲気下で評価したところ、Ｃｕ２ＳとＣｕＣｌの共晶点が観測され、結晶成長促進剤の融解温度が３８９℃であった。 Separately, when this composition was evaluated using a thermogravimetric / suggested thermal analyzer in a nitrogen atmosphere, a eutectic point of Cu 2 S and CuCl was observed, and the melting temperature of the crystal growth accelerator was 389 ° C. .
無アルカリガラス上に６００ｎｍ厚のＭｏと５０ｎｍ厚のＩｎをこの順で真空成膜法を用いて積層し、基板とした。
金属カルコゲナイド化合物の原料として、Ｃｕ２Ｓを０．１３８４ｇとＩｎ２Ｓ３を０．２８３３ｇを秤量し、結晶成長促進剤としてＣｕＣｌ２を０．０５０８ｇ、結晶成長促進剤と共晶点を有する化合物としてＮａＣｌを０．０２２１ｇ秤量し、乳鉢を用いて１５分間混合した後、蒸留水２００μＬを加えてペースト化し、前記基板上にバーコーター（＃９）を用いて塗布した。
600 nm thick Mo and 50 nm thick In were laminated in this order on a non-alkali glass by using a vacuum film forming method to obtain a substrate.
As a raw material for the metal chalcogenide compound, 0.1384 g of Cu 2 S and 0.2833 g of In 2 S 3 are weighed, 0.0508 g of CuCl 2 as a crystal growth accelerator, and a compound having a eutectic point with a crystal growth accelerator As a sample, 0.0221 g of NaCl was weighed and mixed for 15 minutes using a mortar, and then 200 μL of distilled water was added to form a paste, which was applied onto the substrate using a bar coater (# 9).
次いで、アルミナ製の横型管状炉内で、窒素雰囲気下、内温５５０℃で１時間焼成し、黒色の粉末Ｂが基板上に堆積されていることを確認した。この粉末ＢをＸ回折装置を用いて構造解析を行ったところ、粉末ＢはＣｕＩｎＳ２であり、その１１２面に起因する回折線の半値幅は０．１３０ｄｅｇあることが確認された。
別に、この組成比で混合した結晶成長促進剤と共晶点を有する化合物の混合物を、熱重量・示唆熱分析装置を用いて、窒素雰囲気下で評価したところ、融解温度が３７１℃であった。
Subsequently, it was baked for 1 hour at an internal temperature of 550 ° C. in a nitrogen atmosphere in a horizontal tubular furnace made of alumina, and it was confirmed that black powder B was deposited on the substrate. When this powder B was subjected to a structural analysis using an X diffraction device, it was confirmed that the powder B was CuInS 2 and the half-width of the diffraction line caused by its 112 plane was 0.130 deg.
Separately, a mixture of a crystal growth accelerator and a compound having a eutectic point mixed at this composition ratio was evaluated under a nitrogen atmosphere using a thermogravimetric / suggested thermal analyzer, and the melting temperature was 371 ° C. .
［比較例１］
結晶成長促進剤を添加しなかった以外は、実施例１と同様にして焼成したところ、茶褐色の粉末Ｚを得た。粉末Ｚを実施例１と同様にして評価したところ、粉末Ｚ中には、ＣｕＩｎＳ２が生成していたが、原料のＩｎ２Ｓ３が残存し、反応が十分に進行していないことが分かった。
[Comparative Example 1]
When baked in the same manner as in Example 1 except that the crystal growth accelerator was not added, a brown powder Z was obtained. When the powder Z was evaluated in the same manner as in Example 1, CuInS 2 was produced in the powder Z, but it was found that the raw material In 2 S 3 remained and the reaction did not proceed sufficiently. It was.
［比較例２］
結晶成長促進剤を添加しなかった以外は、実施例２と同様にして焼成したところ、黒色の粉末Ｙが基板上に堆積されていることを確認した。この粉末Ｚを実施例２と同様にして評価したところ、粉末Ｚ中には、ＣｕＩｎＳ２が生成していたが、原料のＩｎ２Ｓ３が残存し、反応が十分に進行していないことが分かった。
[Comparative Example 2]
When baked in the same manner as in Example 2 except that the crystal growth accelerator was not added, it was confirmed that black powder Y was deposited on the substrate. When this powder Z was evaluated in the same manner as in Example 2, CuInS 2 was produced in the powder Z, but the raw material In 2 S 3 remained and the reaction did not proceed sufficiently. I understood.
本発明の結晶成長促進剤は、カルコゲナイド化合物の結晶成長に有効であり、粒子サイズや結晶性を向上できる。 The crystal growth accelerator of the present invention is effective for crystal growth of chalcogenide compounds, and can improve the particle size and crystallinity.
Claims (2)
前記金属カルコゲナイド化合物を構成する元素を１種以上の化合物にすべて含む金属カルコゲナイド化合物原料と、１種以上の銅のハロゲン化物を含有する前記結晶成長促進剤とを接触させて、
前記金属カルコゲナイド化合物に対して、同一金属種である銅のハロゲン化物を含有し、前記金属カルコゲナイド化合物原料として使用する前記結晶成長促進剤を作用させることで、前記金属カルコゲナイド化合物の結晶成長を促進させ、
前記ハロゲン化合物の銅を前記金属カルコゲナイド化合物の銅として取り込むために、前記結晶成長促進剤の融解温度以上に加熱することを特徴とする結晶成長促進剤を用いた金属カルコゲナイド化合物の製造方法。 A method for producing a metal chalcogenide compound using an inorganic material crystal growth accelerator provided for crystal growth of a metal chalcogenide compound containing a chalcogen element selected from sulfur and selenium and copper,
Contacting a metal chalcogenide compound raw material containing all of the elements constituting the metal chalcogenide compound in one or more compounds with the crystal growth promoter containing one or more copper halides;
The metal chalcogenide compound contains a halide of copper which is the same metal species, and the crystal growth accelerator used as the metal chalcogenide compound raw material is allowed to act to promote crystal growth of the metal chalcogenide compound. ,
In order to take in copper of the halogen compound as copper of the metal chalcogenide compound, a method for producing a metal chalcogenide compound using a crystal growth accelerator , wherein heating is performed at a temperature equal to or higher than a melting temperature of the crystal growth accelerator .
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