TWI644444B - 金屬摻雜之Cu(In,Ga)(S,Se)<sub>2</sub>奈米顆粒 - Google Patents
金屬摻雜之Cu(In,Ga)(S,Se)<sub>2</sub>奈米顆粒 Download PDFInfo
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- TWI644444B TWI644444B TW106133116A TW106133116A TWI644444B TW I644444 B TWI644444 B TW I644444B TW 106133116 A TW106133116 A TW 106133116A TW 106133116 A TW106133116 A TW 106133116A TW I644444 B TWI644444 B TW I644444B
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- Prior art keywords
- nanoparticle
- sodium
- antimony
- salt
- formate
- Prior art date
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- 239000002105 nanoparticle Substances 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000011734 sodium Substances 0.000 claims abstract description 45
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 43
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 37
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 35
- 229910052738 indium Inorganic materials 0.000 claims abstract description 35
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 23
- 229910052787 antimony Inorganic materials 0.000 claims description 19
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 15
- 150000003573 thiols Chemical class 0.000 claims description 8
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 7
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical group CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 6
- -1 sodium methylhexyldithioaminoformate Chemical group 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 3
- ZFTULLWQVJWSCE-UHFFFAOYSA-K antimony(3+);n,n-diethylcarbamodithioate Chemical group [Sb+3].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S.CCN(CC)C([S-])=S ZFTULLWQVJWSCE-UHFFFAOYSA-K 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 4
- 150000004675 formic acid derivatives Chemical class 0.000 claims 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims 1
- 239000004280 Sodium formate Substances 0.000 claims 1
- NJGBSFDVMQSDTF-UHFFFAOYSA-K antimony(3+);triformate Chemical compound [Sb+3].[O-]C=O.[O-]C=O.[O-]C=O NJGBSFDVMQSDTF-UHFFFAOYSA-K 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims 1
- 235000019254 sodium formate Nutrition 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 9
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 abstract description 4
- 235000017281 sodium acetate Nutrition 0.000 abstract description 4
- 239000001632 sodium acetate Substances 0.000 abstract description 4
- 125000004436 sodium atom Chemical group 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000011669 selenium Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 235000013339 cereals Nutrition 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000976 ink Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 7
- 238000010348 incorporation Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 5
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 5
- 238000004993 emission spectroscopy Methods 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 150000001462 antimony Chemical class 0.000 description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000005361 soda-lime glass Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 3
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000013341 scale-up Methods 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
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZIPRMPRBQSJVJY-UHFFFAOYSA-N C(C(=O)C)(=O)O.C(C)(=N)N Chemical compound C(C(=O)C)(=O)O.C(C)(=N)N ZIPRMPRBQSJVJY-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- NHIBZEPCEGVOKM-UHFFFAOYSA-K [Sb+3].C(C)N(C([S-])=S)CCCCCC.C(C)N(C([S-])=S)CCCCCC.C(C)N(C([S-])=S)CCCCCC Chemical compound [Sb+3].C(C)N(C([S-])=S)CCCCCC.C(C)N(C([S-])=S)CCCCCC.C(C)N(C([S-])=S)CCCCCC NHIBZEPCEGVOKM-UHFFFAOYSA-K 0.000 description 1
- GKCFCBKQXBLKMI-UHFFFAOYSA-K [Sb+3].CN(C([S-])=S)CCCCCC.CN(C([S-])=S)CCCCCC.CN(C([S-])=S)CCCCCC Chemical compound [Sb+3].CN(C([S-])=S)CCCCCC.CN(C([S-])=S)CCCCCC.CN(C([S-])=S)CCCCCC GKCFCBKQXBLKMI-UHFFFAOYSA-K 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- ILXXJSPHTMOLID-UHFFFAOYSA-K antimony(3+);n,n-dimethylcarbamodithioate Chemical compound [Sb+3].CN(C)C([S-])=S.CN(C)C([S-])=S.CN(C)C([S-])=S ILXXJSPHTMOLID-UHFFFAOYSA-K 0.000 description 1
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 1
- KWQLUUQBTAXYCB-UHFFFAOYSA-K antimony(3+);triiodide Chemical compound I[Sb](I)I KWQLUUQBTAXYCB-UHFFFAOYSA-K 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 150000007942 carboxylates Chemical group 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- WMMYFRXVXJPWDI-UHFFFAOYSA-N dimethylaminoantimony Chemical compound CN(C)[Sb] WMMYFRXVXJPWDI-UHFFFAOYSA-N 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000011234 nano-particulate material Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- MRPLDNNCIMEROJ-UHFFFAOYSA-M sodium N-ethyl-N-hexylcarbamodithioate Chemical compound C(C)N(C([S-])=S)CCCCCC.[Na+] MRPLDNNCIMEROJ-UHFFFAOYSA-M 0.000 description 1
- HJCKMSFBKHYZQX-UHFFFAOYSA-M sodium N-hexyl-N-methylcarbamodithioate Chemical compound CN(C([S-])=S)CCCCCC.[Na+] HJCKMSFBKHYZQX-UHFFFAOYSA-M 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- WWGXHTXOZKVJDN-UHFFFAOYSA-M sodium;n,n-diethylcarbamodithioate;trihydrate Chemical compound O.O.O.[Na+].CCN(CC)C([S-])=S WWGXHTXOZKVJDN-UHFFFAOYSA-M 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
- H01L21/02579—P-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02587—Structure
- H01L21/0259—Microstructure
- H01L21/02601—Nanoparticles
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Abstract
使用各種方法以當CIGS層沈積於光伏打裝置上時在含CIGS油墨中提供所要之摻雜金屬濃度。當該摻雜金屬係鈉時,其可藉由以下步驟併入:在Cu(In,Ga)(S,Se)2
奈米顆粒之合成反應開始時,將例如乙酸鈉之鈉鹽與含銅、銦及/或鎵之試劑一起添加;合成Cu(In,Ga)(S,Se)2
奈米顆粒並將鈉鹽添加至反應溶液,隨後在分離該等奈米顆粒之前溫和加熱以幫助鈉擴散;及/或,使用能夠利用其分子鏈之一端將該等Cu(In,Ga)(S,Se)2
奈米顆粒封端且利用其鏈之另一端結合至鈉原子之配位子。
Description
本發明大體係關於光伏打裝置。更特定而言,其係關於基於銅銦鎵二硒化物/二硫化物薄膜光伏打裝置。
如銅銦鎵二硒化物及硫化物(Cu(In,Ga)(S,Se)2
,在本文中稱為「CIGS」)之半導體材料係強光吸收劑且具有與光伏打(PV)應用之最佳光譜範圍匹配良好之帶隙。此外,由於此等材料具有強吸收係數,因此太陽能電池中之作用層僅需要為幾微米厚。 銅銦二硒化物(CuInSe2
)由於其獨特結構及電性質而係用於薄膜PV應用之最有前景之候選者中之一者。其1.0 eV之帶隙與太陽能光譜良好匹配。CuInSe2
太陽能電池可藉由CuInS2
膜之硒化製成,此乃因在硒化過程期間,Se替代S且取代作用產生體積膨脹,此減少空隙空間且可重現地形成高品質緻密CuInSe2
吸收劑層。[Q. Guo、G.M. Ford、H.W. Hillhouse及R. Agrawal,Nano Lett.
, 2009,9
, 3060]假定S由Se完全替代,所得之晶格體積膨脹係約14.6%,此係基於黃銅礦(正方晶系) CuInS2
(a
= 5.52 Å,c
= 11.12 Å)及CuInSe2
(a
= 5.78 Å,c
= 11.62 Å)之晶格參數來計算。此意味著CuInS2
奈米晶體膜可藉由在富硒氣氛中使該膜退火容易地轉化成主要地硒化物材料。因此,CuInS2
係用於生產CuInSe2
或CuIn(S,Se)2
吸收劑層之有前景替代前體。 吸收劑材料之理論最佳帶隙係在1.2 eV至1.4 eV之範圍內。藉由將鎵併入至CuIn(S,Se)2
薄膜中,可操控帶隙使得在硒化之後形成具有針對太陽能吸收之最佳帶隙之Cux
Iny
Gaz
Sa
Seb
吸收劑層。 習用地,昂貴地氣相或蒸發技術(例如,有機金屬化學氣相沈積(MO-CVD)、射頻(RF)濺鍍及急驟蒸發)已用於在基板上沈積CIGS膜。儘管此等技術提供高品質膜,但其難以按比例擴大至較大面積沈積及較高製程生產量且此係昂貴的。因此,已開發CIGS材料之溶液處理。一種此類方法涉及沈積CIGS奈米顆粒,該等CIGS奈米顆粒可經熱處理以形成結晶CIGS層。 使用CIGS之奈米顆粒之一個主要優點係其可分散於介質中以形成可以類似於報紙類製程中之油墨的方式印刷於基板上之油墨。可使用諸如旋轉塗佈、狹縫塗佈及刮刀塗佈等低成本印刷技術沈積奈米顆粒油墨或膏糊。可印刷太陽能電池可替代太陽能電池製造之標準習用真空沈積方法,此乃因印刷製程尤其當於捲輪式薄膜輸送處理框架中實施時達成高得多的生產量。 迄今為止所開發之合成方法提供對顆粒形態之有限控制,且顆粒溶解性通常較差,此使得油墨調配係困難的。 挑戰係生產總體係小的、具有低熔融點、窄大小分佈且併入揮發性封端劑之奈米顆粒,以使得該等奈米顆粒可分散於介質中且封端劑在膜烘烤製程期間可容易地去除。另一挑戰係避免納入來自合成前體或有機配位子之可能危害最終裝置之總體效率之雜質。 美國公開案第2009/0139574號[Preparation of Nanoparticle Material,於2009年6月4日公開](其全部內容以引用方式併入至本文中)闡述膠狀CIGS奈米顆粒之合成,該等奈米顆粒具有單分散大小分佈且利用能夠溶液處理且可在熱處理期間在相對低之溫度下移除之有機配位子封端。 與基於奈米顆粒之CIGS沈積方法相關聯之挑戰中之一者係在熱處理之後達成大晶粒。大約膜厚之晶粒大小係所要的,此乃因晶粒邊界充當電子-電洞重組中心。已報告諸如鈉[R. Kimura、T. Mouri、N. Takuhai、T. Nakada、S. Niki、A. Yamada、P. Fons、T. Matsuzawa、K. Takahashi及A. Kunioka,Jpn. J. Appl. Phys.
, 1999,38
, L899]及銻[M. Yuan、D.B. Mitzi、W. Liu、A.J. Kellock、S.J. Chey及V.R. Deline,Chem. Mater.
, 2010,22
, 285]等元素摻雜劑,以改良CIGS膜之晶粒大小且因此改良所得裝置之電力轉換效率(PCE)。 鈉併入至CIGS中係用於增加最大光伏打電池效率之眾所周知方法。認為鈉之作用係增加淨載流子濃度及膜導電性且可能地增強晶粒生長。鈉通常以介於0.1重量%至1.0重量%之間的範圍內之濃度添加。 用以併入鈉之常見方法係藉由自鈉鈣玻璃(SLG)基板穿過鉬背接觸層擴散至毗鄰CIGS層中。目前尚未充分瞭解限制或使得鈉能夠在晶體生長期間自SLG擴散之過程。此方法之一個缺點係不易於控制鈉之擴散。 其他已知併入方法包括自沈積於CIGS吸收劑層下面或上面之含鈉薄前體層之擴散、鈉化合物在CIGS生長期間之共蒸發或將CIGS膜浸泡於鈉鹽溶液中。舉例而言,Guo等人藉由在硒化之前將由CIGS奈米顆粒製備之膜浸泡在1 M氯化鈉水溶液中來將鈉併入至該等膜中。[Q. Guo、G.M. Ford、R. Agrawal及H. Hillhouse,Prog. Photovolt. Res. Appl.
, 2013,21
, 64] 此等方法需要無鈉基板或鹼金屬擴散障壁(諸如,Al2
O3
或極緻密鉬)。否則,在使用SLG基板之情況下,可能將太多鈉併入至CIGS中。 通常用於上文述及之方法中之鈉化合物之實例包括氟化鈉(NaF)、硒化鈉(Na2
Se)及硫化鈉(Na2
S)。 此等併入方法涉及其中在生長吸收劑層之前或之後在單獨階段處生產含鈉化合物之多步驟製程。此係藉由使用昂貴真空沈積技術達成且無法應用於藉由以捲輪式薄膜輸送方法在撓性基板上印刷CIGS油墨生產之可印刷光伏打裝置。 在鈉鹽溶液中浸泡係簡單方法,但不清楚使用此方法可在何種程度上調整鈉之併入。 在先前技術中,在已藉由濺鍍Cu-In-Ga前體、隨後硒化來製備CIGS膜之情形中,鈉摻雜儘管促進CuInSe2
層內之晶粒生長,但可造成CuInSe2
與CuGaSe2
之相隔離。[F. Hergert、S. Jost, R. Hock、M. Purwins及J. Palm,Thin Solid Films
, 2007,515
, 5843]因此,其中四元CIGS相固有的在奈米顆粒內之基於奈米顆粒之方法可在無相隔離之情況下使能夠鈉增強晶粒生長。 用鈉摻雜Cu2
ZnSnS4
(CZTS)奈米顆粒之方法先前已由Zhou等人闡述。[H. Zhou、T.-B. Song、W.-C. Hsu、S. Luo、S. Ye、H.-S. Duan、C.J. Hsu、W. Yang及Y. Yang,J. Am. Chem. Soc.
, 2013,135
, 15998]經鈉摻雜CZTS奈米顆粒係藉由「熱注射」方法製備,藉以將硫前體注射於在高溫下溶於油胺中之銅、鋅及錫前體鹽之溶液中。在退火之時段之後,將三氟乙酸鈉(CF3
COONa)於油酸中之溶液注射於CZTS奈米顆粒溶液中,然後退火達另一時間段。Na/(Cu + Zn + Sn)之比率可自0.5%至10%調整,且表徵表明鈉分佈於奈米顆粒表面上,而非均勻地分佈於整個奈米顆粒中。迄今為止,尚未報告適用於製備經鈉摻雜CIGS奈米顆粒之方法。 Mitzi及其合作者已探尋將銻併入至使用基於肼溶液沈積方法形成之CIGS裝置中。使用於肼中之Sb2
S3
/S觀察到顯著晶粒生長,其中PCE自未經摻雜膜之10.3%改良至摻雜有0.2莫耳% Sb之膜之12.3%。[M. Yuan、D.B. Mitzi、W. Liu、A.J. Kellock、S.J. Chey及V.R. Deline,Chem. Mater.
, 2010,22
, 285]以1.2莫耳%,可在低溫(<400℃)下退火之膜中觀察到晶粒生長。[M. Yuan、D.B. Mitzi、O. Gunawan、A.J. Kellock、S.J. Chey及V.R. Deline,Thin Solid Films
, 2010,519
, 852]儘管利用銻摻雜具有晶粒大小及PCE之改良,但沈積方法由於肼之有毒及不穩定性質而帶有顯著風險。另外,安全地處置肼所需之防範措施在按比例擴大該方法時形成顯著挑戰。 Carrate等人闡述配位子交換方法以經由雙相系統利用銻鹽(SbCl3
)取代CZTS奈米顆粒表面上之有機配位子來將其替代。[A. Carrate、A. Shavel、X. Fontané、J. Montserrat、J. Fan、M. Ibáñez、E. Saucedo、A. Pérez-Rodríguez及A. Cabot,J. Am. Chem. Soc.
, 2013,135
, 15982] CZTS-SbCl3
奈米顆粒在溶液中保持穩定達足以允許噴射沈積之時間。 儘管由Carrate等人製作之奈米顆粒可藉由噴射塗佈進行沈積,但奈米顆粒表面上缺少有機配位子可致使材料難以使用其他塗佈技術進行處理,此乃因油墨調配物之有機組分對其塗料性質係關鍵的。 先前技術中未報告銻塗佈之CIGS奈米顆粒之製備。 亦報告在用2重量%鎘或鉍摻雜CuInSe2
助熔劑、隨後使用電子束進行局部化脈衝式退火時CuInSe2
薄膜中之晶粒生長。[R.J. Gupta、D. Bhattacharya及O.N. Sullivan,J. Cryst. Growth
, 1988,87
, 151]藉由透射電子顯微術(transition electron microscopy, TEM)觀察到高達10 μm之晶粒大小。然而,脈衝式退火會是不易於按比例擴大之方法。另外,用有毒鎘摻雜會是不利的。 因此,使用基於奈米顆粒之沈積方法形成經摻雜CIGS膜之方法將係有益的。
本文所述之方法直接在CIGS奈米顆粒生長期間併入金屬摻雜劑而無需多步驟製程或昂貴真空技術。 可將金屬摻雜之奈米顆粒分散於溶劑中以形成油墨,將該油墨印刷並燒結以藉由熔融或熔合奈米顆粒前體材料以形成薄膜,使得奈米顆粒聚結以形成大晶粒薄膜。圖1係概述用於自CIGS奈米顆粒形成CIGS膜且隨後製作PV裝置之製備程序之流程圖。 當CIGS層沈積於光伏打裝置上時,該方法在含CIGS油墨中提供所要之摻雜金屬濃度。 當摻雜金屬係鈉時,其可藉由以下步驟併入: • 在Cu(In,Ga)(S,Se)2
奈米顆粒之合成反應開始時,將例如乙酸鈉之鈉鹽與含銅、銦及/或鎵之試劑一起添加; • 合成Cu(In,Ga)(S,Se)2
奈米顆粒並將鈉鹽添加至反應溶液,隨後在分離奈米顆粒之前溫和加熱以幫助鈉擴散;及/或, • 使用能夠利用其分子鏈之一端將該等Cu(In,Ga)(S,Se)2
奈米顆粒封端且利用其鏈之另一端結合至鈉原子之配位子。 當摻雜金屬係銻時,其可藉由以下步驟併入: • 在Cu(In,Ga)(S,Se)2
奈米顆粒之合成反應開始時,將例如乙酸銻之銻鹽與含銅、銦及/或鎵之試劑一起添加; • 合成Cu(In,Ga)(S,Se)2
奈米顆粒並將銻鹽添加至反應溶液,隨後在分離奈米顆粒之前溫和加熱以幫助銻擴散;及/或, • 使用能夠利用其分子鏈之一端將該等Cu(In,Ga)(S,Se)2
奈米顆粒封端且利用其鏈之另一端結合至銻原子之配位子。
相關申請案之交叉參考
本申請案主張於2014年1月30日提出申請之美國臨時申請案第61/933,616號的權益。 本發明涉及一種將諸如鈉及/或銻之金屬可控制地併入至CIGS奈米顆粒中之方法。可經由不同印刷方法沈積金屬摻雜之CIGS奈米顆粒以形成適宜厚度之膜。 以下係將(例如)鈉併入至CIGS奈米顆粒中之不同方法: 在第一實施例中,在Cu(In,Ga)(S,Se)2
奈米顆粒之合成反應開始時,將例如乙酸鈉之鈉鹽與含銅、銦及/或鎵之試劑一起添加(例如,在美國專利公開案第2009/0139574號中所揭示)。除乙酸鈉之外的適合鈉鹽包括(但不限於)無機鹽,諸如氯化鈉、氟化鈉、溴化鈉,以及其他有機鹽,諸如油酸鈉及烷基二硫胺基甲酸鈉鹽(諸如二乙基二硫胺基甲酸鈉、二甲基二硫胺基甲酸鈉、甲基己基二硫胺基甲酸鈉及乙基己基二硫胺基甲酸鈉)。 在第二實施例中,合成Cu(In,Ga)(S,Se)2
奈米顆粒且隨後將鈉鹽添加至反應溶液,隨後在分離奈米顆粒之前溫和加熱以幫助鈉擴散。此方法准許在無需在CIGS奈米顆粒之整個合成過程中提供鈉鹽之情況下併入鈉。此方法當鈉鹽在合成期間之某一階段可形成干擾時係尤其有用的。此方法亦可在分離奈米顆粒之後作為單獨步驟執行,如在圖2中圖解說明,其中「TOP」係三辛基膦且「NC」係奈米晶體。在一些實施例中,在室溫下併入鈉。在替代實施例中,將鈉鹽添加至CIGS奈米顆粒之分散液,隨後例如在200℃下加熱。 在第三實施例中,使用能夠利用其分子鏈之一端將Cu(In,Ga)(S,Se)2
奈米顆粒封端且利用該鏈之另一端結合至鈉原子之含鈉配位子。此類型之配位子之實例係在另一端具有能夠結合鈉之羧酸根基團之硫醇配位子,如在圖3中圖解說明。 此方法可延伸至用例如銻(Sb)之其他金屬摻雜CIGS奈米顆粒。適合銻鹽包括(但不限於)乙酸銻、三苯基銻及參(二甲基胺基)銻、鹵化銻(諸如,氯化銻、氟化銻、溴化銻及碘化銻),以及二烷基二硫胺基甲酸銻(諸如,二乙基二硫胺基甲酸銻、二甲基二硫胺基甲酸銻、甲基己基二硫胺基甲酸銻及乙基己基二硫胺基甲酸銻)。 該方法允許將金屬直接併入於奈米顆粒前體中而不使用真空技術。 上述方法允許在合成奈米顆粒前體的同時併入金屬,藉此消除對用以包括金屬之額外步驟的需要。由於合成方法能夠控制引入之金屬量,因此可精確調整所併入金屬之含量。有可能在燒結製程期間保留金屬分佈以產生金屬摻雜之CIGS膜。 用於生產併入選自週期表之13族[Al, Ga, In]、16族[S, Se, Te]及11族[Ce, Ag, Au]或12族[Zn, Cd]之離子的奈米顆粒之製程在Nigel Pickett及James Harris之美國公開案第2009/0139574號中揭示,其全部內容據此以引用方式併入本文中。在一個實施例中,所揭示之製程包括在硒醇化合物之存在下實現包含13族、16族及11族或12族離子之奈米顆粒前體組合物至奈米顆粒材料之轉化。其他實施例包括用於製作包括併入選自週期表之13族、16族及11族或12族之離子之奈米顆粒之薄膜的方法以及用於生產包括奈米顆粒之可印刷油墨調配物之方法。 儘管已顯示並闡述特定實施例,但其並不意欲限制本專利涵蓋之範疇。熟習此項技術者將理解可做出各種改變及修改。 各個實施例藉由以下實例加以說明。 實例1:使用二乙基二硫胺基甲酸鈉製備鈉摻雜之CuInS2
奈米顆粒 用乙酸銅(I) (2.928 g,23.88 mmol)、乙酸銦(III) (9.706 g,33.25 mmol)及苄基醚(50 mL)裝載烘箱乾燥之250 mL圓底燒瓶。燒瓶配備有Liebig冷凝器及收集器,且在100℃下將混合物脫氣1小時。然後用氮回填充燒瓶。將經脫氣1-辛硫醇(40 mL,230 mmol)添加至混合物,隨後將其加熱至200℃並保持2小時。添加二乙基二硫胺基甲酸鈉三水合物(1.390 g,6.169 mmol)於苄基醚(18 mL)/油胺(2 mL)中之懸浮液,且用少量甲醇沖洗殘餘物。將溫度進一步在200℃下維持30分鐘,然後使其冷卻至160℃並攪拌約18小時。然後將混合物冷卻至室溫。 在有氧條件下使用異丙醇、甲苯、甲醇及二氯甲烷經由離心作用分離奈米顆粒,然後在真空下進行乾燥。 藉由感應耦合電漿有機發射光譜法(ICP-OES)之表徵給出按質量計之以下元素組成:13.04% Cu;30.70% In;0.628% Na;20.48% S。此等同於CuIn1.30
Na0.13
S3.11
之化學計量,即相對於銅之莫耳數,13%鈉。有機硫醇配位子貢獻總硫含量。 實例2:使用油酸鈉製備鈉摻雜之CuInS2
奈米顆粒 用乙酸銅(I) (2.928 g,23.88 mmol)、乙酸銦(III) (9.707 g,33.25 mmol)及苄基醚(50 mL)裝載烘箱乾燥之250 mL圓底燒瓶。燒瓶配備有Liebig冷凝器及收集器,且在100℃下將混合物脫氣1小時。然後用氮回填充燒瓶。將經脫氣1-辛硫醇(40 mL,230 mmol)添加至混合物,隨後將其加熱至200℃並保持2小時。添加油酸鈉(1.879 g, 6.172 mmol)於苄基醚(20 mL)中之懸浮液,且用少量甲醇沖洗殘餘物。將溫度進一步在200℃下維持30分鐘,然後使其冷卻至160℃並攪拌約18小時。然後將混合物冷卻至室溫。 在有氧條件下使用異丙醇、甲苯、甲醇及二氯甲烷經由離心作用分離奈米顆粒,然後在真空下進行乾燥。 藉由感應耦合電漿有機發射光譜法(ICP-OES)之表徵給出按質量計之以下元素組成:13.04% Cu;28.31% In;0.784% Na;19.86% S。此等同於CuIn1.20
Na0.17
S3.02
之化學計量,即與銅之莫耳數相比,17%鈉。有機硫醇配位子貢獻總硫含量。 實例3:使用油酸鈉製備鈉摻雜之CuInS2
奈米顆粒 用乙酸銅(I) (2.928 g,23.88 mmol)、乙酸銦(III) (9.705 g,33.24 mmol)、油酸鈉(0.743 g,2.44 mmol)及苄基醚(50 mL)裝載烘箱乾燥之250 mL圓底燒瓶。燒瓶配備有Liebig冷凝器及收集器,且在100℃下將混合物脫氣1小時。然後用氮回填充燒瓶。將經脫氣1-辛硫醇(40 mL,230 mmol)添加至混合物,隨後將其加熱至200℃並保持2小時,然後使其冷卻至160℃並退火約18小時。然後將混合物冷卻至室溫。 在有氧條件下使用異丙醇、甲苯、甲醇、二氯甲烷及丙酮經由離心作用分離奈米顆粒,然後在真空下進行乾燥。 藉由感應耦合電漿有機發射光譜法(ICP-OES)之表徵給出按質量計之以下元素組成:13.43% Cu;28.56% In;0.96% Na;20.19% S。此等同於CuIn1.18
Na0.20
S2.98
之化學計量,即與銅之莫耳數相比,20%鈉。有機硫醇配位子貢獻總硫含量。 實例4:使用三苯基銻製備銻摻雜之Cu(In,Ga)S2
奈米顆粒 用乙酸銅(I) (0.369 g,3.01 mmol)、乙酸銦(III) (0.7711 g,2.641 mmol)、乙醯丙酮酸鎵(III) (0.4356 g,1.187 mmol)、三苯基銻(0.055 g,160 μmol)、苄基醚(6 mL)及1 M硫於油胺中之溶液(9 mL,9 mmol)裝載100 mL圓底燒瓶。在100℃下將混合物脫氣1小時,然後用氮回填充燒瓶。將1-辛硫醇(4.8 mL,28 mmol)注射至燒瓶中,隨後將其加熱至200℃並保持2小時。將溫度降至160℃並保持過夜。然後將混合物冷卻至室溫。 在有氧條件下使用甲苯及甲醇經由離心作用分離奈米顆粒。 藉由感應耦合電漿有機發射光譜法(ICP-OES)之表徵給出按質量計之以下元素組成:15.47% Cu;26.09% In;6.41% Ga;0.25% Sb;20.67% S。此等同於CuIn0.93
Ga0.38
Sb0.01
S2.65
之化學計量,即與銅之莫耳數相比,1%銻。有機硫醇配位子貢獻總硫含量。 實例5:使用乙酸銻製備銻摻雜之Cu(In,Ga)S2
奈米顆粒 用乙酸銅(I) (0.369 g,3.01 mmol)、乙酸銦(III) (0.7711 g,2.641 mmol)、乙醯丙酮酸鎵(III) (0.4356 g,1.187 mmol)、乙酸銻(III) (0.047 g,160 μmol)、苄基醚(6 mL)及1 M硫於油胺中之溶液(9 mL,9 mmol)裝載100 mL圓底燒瓶。在100℃下將混合物脫氣1小時,然後用氮回填充燒瓶。將1-辛硫醇(4.8 mL,28 mmol)注射至燒瓶中,隨後將其加熱至200℃並保持2小時。將溫度降至160℃並保持過夜。然後將混合物冷卻至室溫。 在有氧條件下使用甲苯及甲醇經由離心作用分離奈米顆粒。 藉由感應耦合電漿有機發射光譜法(ICP-OES)之表徵給出按質量計之以下元素組成:15.39% Cu;26.02% In;6.17% Ga;0.92% Sb;21.20% S。此等同於CuIn0.94
Ga0.37
Sb0.03
S2.73
之化學計量,即與銅之莫耳數相比,3%銻。有機硫醇配位子貢獻總硫含量。 儘管已顯示並闡述本發明之特定實施例,但其並不意欲限制本專利涵蓋之範疇。熟習此項技術者將理解,可在不背離如以下申請專利範圍字面上及等效地涵蓋之本發明範疇之情況下做出各種改變及修改。
無
圖1係繪示用於調配基於CIGS奈米顆粒之油墨之方法的流程圖,該油墨可經處理以形成薄膜且然後製作併入此膜之光伏打裝置。 圖2係用於將金屬併入至CIGS奈米顆粒中之製程之示意性繪示。 圖3係根據本發明之經配位子封端之奈米顆粒之示意性繪示。
Claims (20)
- 一種鈉摻雜之奈米顆粒,其包含:Cu(In,Ga)(S,Se)2奈米顆粒;及併入該Cu(In,Ga)(S,Se)2奈米顆粒中的鈉,其中該奈米粒顆粒係藉由包含在Cu(In,Ga)(S,Se)2奈米顆粒之合成反應開始時向含銅、銦及鎵的試劑的混合物中添加烷基二硫胺基甲酸鈉鹽的方法製備。
- 如請求項1之奈米顆粒,其中該Cu(In,Ga)(S,Se)2奈米顆粒中的該鈉含量為0.62至0.96質量%。
- 如請求項1之奈米顆粒,其進一步包含與該奈米顆粒的表面結合的封端配位子。
- 如請求項3之奈米顆粒,其中該封端配位子係有機胺、有機硫醇及三辛基膦中的任一者。
- 如請求項4之奈米顆粒,其中該有機胺係油胺。
- 如請求項4之奈米顆粒,其中該有機硫醇係1-辛硫醇。
- 一種銻摻雜之奈米顆粒,其包含:Cu(In,Ga)(S,Se)2奈米顆粒;及併入該Cu(In,Ga)(S,Se)2奈米顆粒中的銻,其中該奈米粒顆粒係藉由包含在Cu(In,Ga)(S,Se)2奈米顆粒之合成反應開始時向含銅、銦及鎵的試劑的混合物中添加烷基二硫胺基甲酸銻鹽的方法製備。
- 如請求項7之奈米顆粒,其中該Cu(In,Ga)(S,Se)2奈米顆粒中的該銻含量為0.25至0.92質量%。
- 如請求項7之奈米顆粒,其進一步包含與該奈米顆粒的表面結合的封端配位子。
- 如請求項9之奈米顆粒,其中該封端配位子係有機胺、有機硫醇及三辛基膦中的任一者。
- 如請求項10之奈米顆粒,其中該有機胺係油胺。
- 如請求項10之奈米顆粒,其中該有機硫醇係1-辛硫醇。
- 如請求項1之奈米顆粒,其中該烷基二硫胺基甲酸鈉鹽係二乙基二硫胺基甲酸鈉。
- 如請求項1之奈米顆粒,其中該烷基二硫胺基甲酸鈉鹽係二甲基二硫胺基甲酸鈉。
- 如請求項1之奈米顆粒,其中該烷基二硫胺基甲酸鈉鹽係甲基己基二硫胺基甲酸鈉。
- 如請求項1之奈米顆粒,其中該烷基二硫胺基甲酸鈉鹽係乙基己基二硫胺基甲酸鈉。
- 如請求項7之奈米顆粒,其中該烷基二硫胺基甲酸銻鹽係二乙基二硫胺基甲酸銻。
- 如請求項7之奈米顆粒,其中該烷基二硫胺基甲酸銻鹽係二甲基二硫胺基甲酸銻。
- 如請求項7之奈米顆粒,其中該烷基二硫胺基甲酸銻鹽係甲基己基二硫胺基甲酸銻。
- 如請求項7之奈米顆粒,其中該烷基二硫胺基甲酸銻鹽係乙基己基二硫胺基甲酸銻。
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US20090320916A1 (en) * | 2008-05-09 | 2009-12-31 | International Business Machines Corporation | Techniques for Enhancing Performance of Photovoltaic Devices |
US20120282730A1 (en) * | 2011-05-06 | 2012-11-08 | Yueh-Chun Liao | Ink composition, Chalcogenide Semiconductor Film, Photovoltaic Device and Methods for Forming the same |
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US10170651B2 (en) | 2019-01-01 |
JP2017511784A (ja) | 2017-04-27 |
KR20160101174A (ko) | 2016-08-24 |
TW201537761A (zh) | 2015-10-01 |
US20150214400A1 (en) | 2015-07-30 |
US20180366599A1 (en) | 2018-12-20 |
TWI610452B (zh) | 2018-01-01 |
EP3100305A1 (en) | 2016-12-07 |
KR20180041246A (ko) | 2018-04-23 |
WO2015114346A1 (en) | 2015-08-06 |
JP6330051B2 (ja) | 2018-05-23 |
CN105940501A (zh) | 2016-09-14 |
JP6688832B2 (ja) | 2020-04-28 |
KR102010251B1 (ko) | 2019-08-13 |
CN105940501B (zh) | 2018-01-05 |
CN107919289A (zh) | 2018-04-17 |
TW201743460A (zh) | 2017-12-16 |
JP2018140934A (ja) | 2018-09-13 |
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