WO2011146791A1 - Atypical kesterite compositions - Google Patents
Atypical kesterite compositions Download PDFInfo
- Publication number
- WO2011146791A1 WO2011146791A1 PCT/US2011/037265 US2011037265W WO2011146791A1 WO 2011146791 A1 WO2011146791 A1 WO 2011146791A1 US 2011037265 W US2011037265 W US 2011037265W WO 2011146791 A1 WO2011146791 A1 WO 2011146791A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tin
- copper
- zinc
- group
- kesterite
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 36
- 230000001427 coherent effect Effects 0.000 claims abstract description 14
- -1 copper chalcogenides Chemical class 0.000 claims description 98
- 239000010949 copper Substances 0.000 claims description 79
- 239000011701 zinc Substances 0.000 claims description 70
- 239000011669 selenium Substances 0.000 claims description 59
- 239000000758 substrate Substances 0.000 claims description 45
- 239000011135 tin Substances 0.000 claims description 45
- 229910052802 copper Inorganic materials 0.000 claims description 40
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 39
- 229910052718 tin Inorganic materials 0.000 claims description 39
- 229910052725 zinc Inorganic materials 0.000 claims description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 31
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- 229910052711 selenium Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 150000004770 chalcogenides Chemical class 0.000 claims description 16
- 239000013110 organic ligand Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052798 chalcogen Inorganic materials 0.000 claims description 13
- 150000001787 chalcogens Chemical class 0.000 claims description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 150000001786 chalcogen compounds Chemical class 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 150000003346 selenoethers Chemical class 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 150000004703 alkoxides Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 5
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 5
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical class [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 5
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002390 heteroarenes Chemical class 0.000 claims description 3
- MFIWAIVSOUGHLI-UHFFFAOYSA-N selenium;tin Chemical class [Sn]=[Se] MFIWAIVSOUGHLI-UHFFFAOYSA-N 0.000 claims description 3
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical class [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 description 32
- 239000002184 metal Substances 0.000 description 30
- 239000000976 ink Substances 0.000 description 24
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 19
- 238000000576 coating method Methods 0.000 description 17
- 239000010408 film Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000003446 ligand Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- JJPZOIJCDNHCJP-UHFFFAOYSA-N dibutyl(sulfanylidene)tin Chemical compound CCCC[Sn](=S)CCCC JJPZOIJCDNHCJP-UHFFFAOYSA-N 0.000 description 4
- 238000001548 drop coating Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 4
- WSDTWCKXZSLBGW-UHFFFAOYSA-N zinc;2-methoxyethanolate Chemical compound [Zn+2].COCC[O-].COCC[O-] WSDTWCKXZSLBGW-UHFFFAOYSA-N 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 229960005235 piperonyl butoxide Drugs 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052950 sphalerite Inorganic materials 0.000 description 3
- 150000007944 thiolates Chemical class 0.000 description 3
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- 125000002927 2-methoxybenzyl group Chemical group [H]C1=C([H])C([H])=C(C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 description 2
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical compound COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 101150023635 Ctse gene Proteins 0.000 description 2
- 229910018038 Cu2ZnSnSe4 Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- HXAFQWICVBBXMZ-UHFFFAOYSA-N ethylsulfanyl(trimethyl)silane Chemical compound CCS[Si](C)(C)C HXAFQWICVBBXMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000058 selane Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- ASGPFYMRPNHVFW-UHFFFAOYSA-N zinc dibutyl(sulfanylidene)tin ethanol 1-methoxyethanolate Chemical compound COC([O-])C.[Zn+2].C(C)O.C(CCC)[Sn](CCCC)=S.COC([O-])C ASGPFYMRPNHVFW-UHFFFAOYSA-N 0.000 description 2
- QQYNGKGFOZQMHD-UHFFFAOYSA-N (3-methoxyphenyl) acetate Chemical compound COC1=CC=CC(OC(C)=O)=C1 QQYNGKGFOZQMHD-UHFFFAOYSA-N 0.000 description 1
- GKQXPTHQTXCXEV-UHFFFAOYSA-N (4-chlorophenyl)methanethiol Chemical compound SCC1=CC=C(Cl)C=C1 GKQXPTHQTXCXEV-UHFFFAOYSA-N 0.000 description 1
- RKTRHMNWVZRZJQ-UHFFFAOYSA-N (4-fluorophenyl)methanethiol Chemical compound FC1=CC=C(CS)C=C1 RKTRHMNWVZRZJQ-UHFFFAOYSA-N 0.000 description 1
- HGTBAIVLETUVCG-UHFFFAOYSA-M (methylthio)acetate Chemical compound CSCC([O-])=O HGTBAIVLETUVCG-UHFFFAOYSA-M 0.000 description 1
- FBZVZUSVGKOWHG-UHFFFAOYSA-N 1,1-dimethoxy-n,n-dimethylethanamine Chemical compound COC(C)(OC)N(C)C FBZVZUSVGKOWHG-UHFFFAOYSA-N 0.000 description 1
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 1
- OPCJOXGBLDJWRM-UHFFFAOYSA-N 1,2-diamino-2-methylpropane Chemical compound CC(C)(N)CN OPCJOXGBLDJWRM-UHFFFAOYSA-N 0.000 description 1
- ZCCPVTVGEQLONB-UHFFFAOYSA-N 1-(1,3-dioxolan-2-yl)-n-methylmethanamine Chemical compound CNCC1OCCO1 ZCCPVTVGEQLONB-UHFFFAOYSA-N 0.000 description 1
- SXYRTDICSOVQNZ-UHFFFAOYSA-N 1-(2-methoxyethoxy)ethanol Chemical compound COCCOC(C)O SXYRTDICSOVQNZ-UHFFFAOYSA-N 0.000 description 1
- LWSUTSHXGLKYLY-UHFFFAOYSA-N 1-(2-tert-butylsulfanyl-2-methoxy-2-pentylsulfanylethyl)sulfanyl-2-decylsulfanyl-2-dodecylsulfanyl-1-(2-ethoxy-1-heptylsulfanyl-1-hexylsulfanyl-2-nonylsulfanyl-2-octylsulfanylethyl)sulfanylethane-1,2-dithiol Chemical compound CCCCCCCCCCCCSC(C(S)(SCC(OC)(SCCCCC)SC(C)(C)C)SC(C(OCC)(SCCCCCCCC)SCCCCCCCCC)(SCCCCCC)SCCCCCCC)(S)SCCCCCCCCCC LWSUTSHXGLKYLY-UHFFFAOYSA-N 0.000 description 1
- BHUXAQIVYLDUQV-UHFFFAOYSA-N 1-(diethylamino)propan-2-ol Chemical compound CCN(CC)CC(C)O BHUXAQIVYLDUQV-UHFFFAOYSA-N 0.000 description 1
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- ZLTWIJREHQCJJL-UHFFFAOYSA-N 1-trimethylsilylethanol Chemical compound CC(O)[Si](C)(C)C ZLTWIJREHQCJJL-UHFFFAOYSA-N 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-M 2,2,3,3,4,4,4-heptafluorobutanoate Chemical compound [O-]C(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-M 0.000 description 1
- SSFAUOAQOOISRQ-UHFFFAOYSA-N 2,2-diethoxy-n,n-dimethylethanamine Chemical compound CCOC(CN(C)C)OCC SSFAUOAQOOISRQ-UHFFFAOYSA-N 0.000 description 1
- HJKLEAOXCZIMPI-UHFFFAOYSA-N 2,2-diethoxyethanamine Chemical compound CCOC(CN)OCC HJKLEAOXCZIMPI-UHFFFAOYSA-N 0.000 description 1
- HUMIEJNVCICTPJ-UHFFFAOYSA-N 2,2-dimethoxy-n-methylethanamine Chemical compound CNCC(OC)OC HUMIEJNVCICTPJ-UHFFFAOYSA-N 0.000 description 1
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-M 2,4,6-trimethylphenolate Chemical compound CC1=CC(C)=C([O-])C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-M 0.000 description 1
- GCTFDMFLLBCLPF-UHFFFAOYSA-N 2,5-dichloropyridine Chemical compound ClC1=CC=C(Cl)N=C1 GCTFDMFLLBCLPF-UHFFFAOYSA-N 0.000 description 1
- SESUUAOAUZDHHP-UHFFFAOYSA-N 2,5-dimethoxybenzenethiol Chemical compound COC1=CC=C(OC)C(S)=C1 SESUUAOAUZDHHP-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- CLLLODNOQBVIMS-UHFFFAOYSA-N 2-(2-methoxyethoxy)acetic acid Chemical compound COCCOCC(O)=O CLLLODNOQBVIMS-UHFFFAOYSA-N 0.000 description 1
- CDBORKXXLPAUKJ-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanethiol Chemical compound COCCOCCS CDBORKXXLPAUKJ-UHFFFAOYSA-N 0.000 description 1
- XNIOWJUQPMKCIJ-UHFFFAOYSA-N 2-(benzylamino)ethanol Chemical compound OCCNCC1=CC=CC=C1 XNIOWJUQPMKCIJ-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- YBDSNEVSFQMCTL-UHFFFAOYSA-N 2-(diethylamino)ethanethiol Chemical compound CCN(CC)CCS YBDSNEVSFQMCTL-UHFFFAOYSA-N 0.000 description 1
- DENMGZODXQRYAR-UHFFFAOYSA-N 2-(dimethylamino)ethanethiol Chemical compound CN(C)CCS DENMGZODXQRYAR-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- BCLSJHWBDUYDTR-UHFFFAOYSA-N 2-(propylamino)ethanol Chemical compound CCCNCCO BCLSJHWBDUYDTR-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- ULIKDJVNUXNQHS-UHFFFAOYSA-N 2-Propene-1-thiol Chemical compound SCC=C ULIKDJVNUXNQHS-UHFFFAOYSA-N 0.000 description 1
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- KNFXXAGQEUUZAZ-UHFFFAOYSA-N ethyl ethaneperoxoate Chemical compound CCOOC(C)=O KNFXXAGQEUUZAZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-M methoxyacetate Chemical compound COCC([O-])=O RMIODHQZRUFFFF-UHFFFAOYSA-M 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YWTJTYXQYJSKNB-UHFFFAOYSA-N methyl propaneperoxoate Chemical compound CCC(=O)OOC YWTJTYXQYJSKNB-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- CURJNMSGPBXOGK-UHFFFAOYSA-N n',n'-di(propan-2-yl)ethane-1,2-diamine Chemical compound CC(C)N(C(C)C)CCN CURJNMSGPBXOGK-UHFFFAOYSA-N 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- CFNHVUGPXZUTRR-UHFFFAOYSA-N n'-propylethane-1,2-diamine Chemical compound CCCNCCN CFNHVUGPXZUTRR-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 125000004708 n-butylthio group Chemical group C(CCC)S* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- SVEUVITYHIHZQE-UHFFFAOYSA-N n-methylpyridin-2-amine Chemical compound CNC1=CC=CC=N1 SVEUVITYHIHZQE-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- NCYVXEGFNDZQCU-UHFFFAOYSA-N nikethamide Chemical compound CCN(CC)C(=O)C1=CC=CN=C1 NCYVXEGFNDZQCU-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- RARSHUDCJQSEFJ-UHFFFAOYSA-N p-Hydroxypropiophenone Chemical compound CCC(=O)C1=CC=C(O)C=C1 RARSHUDCJQSEFJ-UHFFFAOYSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HDOUGSFASVGDCS-UHFFFAOYSA-N pyridin-3-ylmethanamine Chemical compound NCC1=CC=CN=C1 HDOUGSFASVGDCS-UHFFFAOYSA-N 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- IHLZXPVSSFCZLU-UHFFFAOYSA-N tert-butyl 4-bromo-2-chlorobenzoate Chemical compound CC(C)(C)OC(=O)C1=CC=C(Br)C=C1Cl IHLZXPVSSFCZLU-UHFFFAOYSA-N 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical compound OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- DUYAAUVXQSMXQP-UHFFFAOYSA-M thioacetate Chemical compound CC([S-])=O DUYAAUVXQSMXQP-UHFFFAOYSA-M 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 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
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1283—Control of temperature, e.g. gradual temperature increase, modulation of temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
Abstract
This invention relates to processes for making kesterite compositions with atypical Cu:Zn:Sn:S ratios and/or kesterite compositions with unusually small coherent domain sizes. This invention also relates to these kesterite compositions and their use in preparing CZTS films.
Description
TITLE
ATYPICAL KESTERITE COMPOSITIONS
FIELD OF THE INVENTION
This invention relates to processes for making kesterite
compositions with atypical Cu:Zn:Sn:S ratios and/or kesterite compositions with unusually small coherent domain sizes. This invention also relates to these kesterite compositions and their use in preparing CZTS films. BACKGROUND
Crystalline multinary-metal chalcogenide compositions containing only non-toxic and abundant elements are of particular interest in developing environmentally sustainable processes and devices. Copper tin sulfide (Cu2SnS3 or "CTS") and copper zinc tin sulfide (Cu2ZnSnS4 or "CZTS") are particularly useful examples of this class of materials, and are of interest due to their potential applications as small band-gap
semiconductors, as nonlinear materials, and as suitable candidates for photovoltaic cell materials.
Thin-film photovoltaic cells typically use semiconductors such as CdTe or copper indium gallium sulfide/selenide (CIGS) as an energy absorber material. Due to toxicity of cadmium and the limited availability of indium, alternatives are sought. CZTS possesses a band gap energy of about 1 .5 eV and a large absorption coefficient (approx. 104 cm-1), making it a promising CIGS replacement.
Challenges in making CZTS thin-films are illustrative of the general challenges that must be surmounted in making films of crystalline multinary-metal chalcogenide compositions. Current techniques to make CZTS thin films (e.g., thermal evaporation, sputtering, hybrid sputtering, pulsed laser deposition and electron beam evaporation) require
complicated equipment and therefore tend to be expensive.
Electrochemical deposition is an inexpensive process, but compositional non-uniformity and/or the presence of secondary phases prevents this method from generating high-quality CZTS thin-films. CZTS thin-films can
also be made by the spray pyrolysis of a solution containing metal salts, typically CuCI, ZnC^, and SnCI4, using thiourea as the sulfur source. This method tends to yield films of poor morphology, density and grain size. Photochemical deposition has also been shown to generate p-type CZTS thin films. However, the composition of the product is not well-controlled, and it is difficult to avoid the formation of impurities such as hydroxides. The synthesis of CZTS nanoparticles, which incorporate high-boiling amines as capping agents, has also been disclosed. The presence of capping agents in the nanoparticle layer may contaminate and lower the density of the annealed CZTS film.
A hybrid solution-particle approach to CZTS involving the preparation of a hydrazine-based slurry comprising dissolved Cu-Sn chalcogenides (S or S-Se), Zn-chalcogenide particles, and excess chalcogen has been reported. However, hydrazine is a highly reactive and potentially explosive solvent that is described in the Merck Index as a "violent poison."
Hence, there still exists a need for simple, low-cost, scalable materials and processes with a low number of operations that provide high-quality, crystalline CTS and CZTS films with tunable composition and morphology. There also exists a need for low-temperature routes to these materials using solvents and reagents with relatively low toxicity.
SUMMARY
One aspect of this invention is a composition comprising a compound having a kesterite structure, wherein the Cu/Zn ratio of the kesterite is greater than about 3.1 .
One aspect of this invention is a composition comprising a compound having a kesterite structure, wherein the Cu/Zn ratio of the kesterite is less than about 1 .6.
One aspect of this invention is a composition comprising a compound having a kesterite structure, wherein the coherent domain size of the kesterite is 2 - 30 nm.
Another aspect of this invention is a process comprising:
a) preparing an ink comprising:
i) a copper source selected from the group consisting of copper complexes of nitrogen-, oxygen-, sulfur-, and selenium-based organic ligands, and mixtures thereof;
ii) a tin source selected from the group consisting of tin complexes of nitrogen-, oxygen-, carbon-, sulfur-, and selenium-based organic ligands, tin hydrides, tin sulfides, tin selenides, and mixtures thereof; iii) a zinc source selected from the group consisting of zinc complexes of nitrogen-, oxygen-, sulfur-, and selenium-based organic ligands, and mixtures thereof;
iv) an elemental chalcogen selected from the group consisting of: elemental S, elemental selenium, and mixtures thereof;
v) a solvent;
iv) optionally, a chalcogen compound selected from the group consisting of: R1S-Z, R1Se-Z and mixtures thereof, with each Z
independently selected from the group consisting of: H and SiR5 3; wherein each R1 and R5 is independently selected from the group consisting of: hydrocarbyl and O-, N-, S-, halogen-, and tri(hydrocarbyl)silyl-substituted hydrocarbyl;
b) heating the ink to a temperature of 150 - 300 °C;
b) disposing the ink onto a substrate; and
c) heating the substrate and ink disposed thereon to a temperature of 80 - 350 °C to form a coated substrate comprising CZTS-Se kesterite. DETAILED DESCRIPTION
Herein, the terms "solar cell" and "photovoltaic cell" are
synonymous unless specifically defined otherwise. These terms refer to devices that use semiconductors to convert visible and near-visible light energy into usable electrical energy. The terms "band gap energy", "optical band gap", and "band gap" are synonymous unless specifically defined otherwise. These terms refer to the energy required to generate electron-hole pairs in a semiconductor material, which in general is the minimum energy needed to excite an electron from the valence band to
the conduction band.
Herein, element groups are represented utilizing CAS notation. As used herein, the term "chalcogen" refers to Group VIA elements, and the terms "metal chalcogenides" or "chalcogenides" refer to materials that comprise metals and Group VIA elements. Suitable Group VIA elements include sulfur, selenium and tellurium. Metal chalcogenides are important candidate materials for photovoltaic applications, since many of these compounds have optical band gap values well within the terrestrial solar spectra.
Herein, the term "binary-metal chalcogenide" refers to a
chalcogenide composition comprising one metal. The term "ternary-metal chalcogenide" refers to a chalcogenide composition comprising two metals. The term "quaternary-metal chalcogenide" refers to a
chalcogenide composition comprising three metals. The term "multinary- metal chalcogenide" refers to a chalcogenide composition comprising two or more metals and encompasses ternary and quaternary metal chalcogenide compositions.
Herein, the terms "copper tin sulfide" and "CTS" refer to Cu2SnS3; "copper tin selenide" and "CTSe" refer to Cu2SnSe3; and "copper tin sulfide/selenide" and "CTS-Se" encompass all possible combinations of Cu2Sn(S,Se)3, including Cu2SnS3, Cu2SnSe3, and Cu2SnSxSe3-x, where 0 < x < 3. The terms "copper tin sulfide", "copper tin selenide", "copper tin sulfide/selenide", "CTS", "CTSe" and "CTS-Se" further encompass fractional stoichiometries, e.g., Cu1.80Sn 1.05S3. That is, the stoichiometry of the elements can vary from a strictly 2:1 :3 molar ratio.
Herein, the terms copper zinc tin sulfide and "CZTS" refer to Cu2ZnSnS4; copper zinc tin selenide and "CZTSe" refer to Cu2ZnSnSe4; and copper zinc tin sulfide/selenide and "CZTS-Se" encompass all possible combinations of Cu2ZnSn(S,Se)4, including Cu2ZnSnS4,
Cu2ZnSnSe4, and Cu2ZnSnSxSe4-x, where 0 < x < 4. The terms "CZTS," "CZTSe," and "CZTS-Se" further encompass copper zinc tin
sulfide/selenide semiconductors with fractional stoichiometries, e.g., Cu1.94Zno.63Sn 1.3S4. That is, the stoichiometry of the elements can vary
from a strictly 2:1 :1 :4 molar ratio. Materials designated as CTS-Se and CZTS-Se may also contain small amounts of other elements such as sodium. To date, the highest efficiencies have been measured for copper- poor CZTS-Se solar cells, where by "copper-poor" it is understood that the ratio Cu/(Zn+Sn) is less than 1 .0. For high efficiency devices, a molar ratio of zinc to tin is greater than one is also desirable.
The term "kesterite" is commonly used to refer to materials belonging to the kesterite family of minerals and is also the common name of the mineral CZTS. As used herein, the term "kesterite" refers to crystalline compounds in either the 14- or l4-2m space groups having the nominal formula Cu2ZnSn(S-Se) , and also "atypical kesterites" wherein zinc has replaced a fraction of the copper or copper has replaced a fraction of the zinc to give CucZnzSn(S-Se)4 wherein c is greater than two and z is less than one; or c is less than two and z is greater than one. The term "kesterite structure" refers to the structure of these compounds. X- ray absorption spectroscopy (XAS) reveals spectral features unique to the kesterite form and allows for determination of the ratio of Cu to Zn in the kesterite phase. This allows for the identification of atypical kesterite compositions, which are clearly distinguished from a mixture of separate sulfide phases producing the same elemental ratios in aggregate. Control of stoichiometry in this phase allows for control of electronic properties for improved performance in a photovoltaic device.
As used herein, "coherent domain size" refers to the size of crystalline domains over which a defect-free, coherent structure may exist. The coherency comes from the fact that the three-dimensional ordering is not broken inside of these domains.
Herein, the term "metal salts" refers to compositions wherein metal cations and inorganic anions are joined by ionic bonding. Relevant classes of inorganic anions comprise oxides, sulfides, carbonates, sulfates and halides. Herein, the term "metal complexes" refers to compositions wherein a metal is bonded to a surrounding array of molecules or anions, typically called "ligands" or "complexing agents". The atom within a ligand that is directly bonded to the metal atom or ion is called the "donor atom"
and, herein, often comprises nitrogen, oxygen, selenium, or sulfur.
Herein, ligands are classified according to the "Covalent Bond Classification (CBC) Method" (Green, M. L. H. J. Organomet. Chem. 1995, 500, 127-148). An "X-function ligand" is one which interacts with a metal center via a normal 2-electron covalent bond, composed of 1 electron from the metal and 1 electron from the X ligand. Simple examples of X-type ligands include alkyls and thiolates. Herein, the term "nitrogen-, oxygen-, carbon-, sulfur-, and selenium-based organic ligands" refers specifically to carbon-containing X-function ligands, wherein the donor atom comprises nitrogen, oxygen, carbon, sulfur, or selenium. Herein, the term
"complexes of nitrogen-, oxygen-, carbon-, sulfur-, and selenium-based organic ligands" refers to the metal complexes comprising these ligands. Examples include metal complexes of amidos, alkoxides,
acetylacetonates, acetates, carboxylates, hydrocarbyls, O-, N-, S-, Se-, and halogen-substituted hydrocarbyls, thiolates, selenolates,
thiocarboxylates, selenocarboxylates, dithiocarbamates, and
diselenocarbamates.
As defined herein, a "hydrocarbyl group" is a univalent group containing only carbon and hydrogen. Examples of hydrocarbyl groups include unsubstituted alkyls, cycloalkyls, and aryl groups, including alkyl- subsituted aryl groups. Suitable hydrocarbyl groups and alkyl groups contain 1 to about 30 carbons, or 1 to 25, 1 to 20, 1 to 15, 1 to 10, 1 to 5, 1 to 4, or 1 to 2 carbons. By "heteroatom-substituted hydrocarbyl" is meant a hydrocarbyl group that contains one or more heteroatoms wherein the free valence is located on carbon, not on the heteroatom. Examples include hydroxyethyl and carbomethoxyethyl. Suitable heteroatom substituents include O-, N-, S-, halogen, and tri(hydrocarbyl)silyl. In a substituted hydrocarbyl, all of the hydrogens may be substituted, as in trifluoromethyl. Herein, the term "tri(hydrocarbyl)silyl" encompasses silyl substituents, wherein the substituents on silicon are hydrocarbyls. Herein, by Ό-, N-, S-, and Se-based functional groups" is meant univalent groups other than hydrocarbyl and substituted hydrocarbyl that comprise O-, N-, S-, or Se-heteroatoms, wherein the free valence is located on this
heteroatom. Examples of O-, N-, S-, and Se-based functional groups include alkoxides, amidos, thiolates, and selenolates.
Process for Forming Atypical Kesterites
One aspect of this invention is a process to form kesterite with atypical Cu/Zn ratios and/or small coherent domains.
The process comprises:
a) preparing an ink comprising:
i) a copper source selected from the group consisting of copper complexes of nitrogen-, oxygen-, sulfur-, and selenium-based organic ligands, and mixtures thereof;
ii) a tin source selected from the group consisting of tin complexes of nitrogen-, oxygen-, carbon-, sulfur-, and selenium-based organic ligands, tin hydrides, tin sulfides, tin selenides, and mixtures thereof; iii) a zinc source selected from the group consisting of zinc complexes of nitrogen-, oxygen-, sulfur-, and selenium-based organic ligands, and mixtures thereof;
iv) an elemental chalcogen selected from the group consisting of: elemental S, elemental selenium, and mixtures thereof;
v) a solvent;
iv) optionally, a chalcogen compound selected from the group consisting of: R1S-Z, R1Se-Z and mixtures thereof, with each Z
independently selected from the group consisting of: H and SiR53; wherein each R1 and R5 is independently selected from the group consisting of: hydrocarbyl and O-, N-, S-, halogen-, and tri(hydrocarbyl)silyl-substituted hydrocarbyl;
b) heating the ink to a temperature of 150 - 300 °C;
b) disposing the ink onto a substrate; and
c) heating the substrate and ink disposed thereon to a temperature of 80 - 350 °C to form a coated substrate comprising CZTS-Se kesterite.
In some embodiments, the ratio of the total number of moles of elemental chalcogen, sulfur- and selenium-based organic ligands, and tin- sulfides and selenides to the total number of moles of the copper, tin and zinc complexes is at least about 1 . In some embodiments, a chalcogen
compound is present. In some embodiments, the elemental chalcogen comprises sulfur and the molar ratio of sulfur to tin source is about 0.2 to about 5, or about 0.5 to about 2.5.
In some embodiments, the nitrogen-, oxygen-, carbon-, sulfur-, and selenium-based organic ligands are selected from the group consisting of: amidos; alkoxides; acetylacetonates; carboxylates; hydrocarbyls; O-, N-, S-, halogen- and tri(hydrocarbyl)silyl-substituted hydrocarbyls; thio- and selenolates; thio-, seleno-, and dithiocarboxylates; dithio-, diseleno-, and thioselenocarbamates; and dithioxanthogenates.
Suitable amidos include: bis(trimethylsilyl)amino, dimethylamino, diethylamino, diisopropylamino, N-methyl-f-butylamino, 2-(dimethylamino)- N-methylethylamino, N-methylcyclohexylamino, dicyclohexylamino, N- ethyl-2-methylallylamino, bis(2-methoxyethyl)amino, 2- methylaminomethyl-1 ,3-dioxolane, pyrrolidino, i-butyl-1 - piperazinocarboxylate, N-methylanilino, N-phenylbenzylamino, N-ethyl-o- toluidino, bis(2,2,2-trifluoromethyl)amino, N-f-butylthmethylsilylamino, and mixtures thereof. Some ligands may chelate the metal center, and, in some cases, comprise more than one type of donor atom, e.g., the dianion of N-benzyl-2-aminoethanol is a suitable ligand comprising both amino and alkoxide groups.
Suitable alkoxides include: methoxide, ethoxide, n-propoxide, i- propoxide, n-butoxide, f-butoxide, neopentoxide, ethylene glycol dialkoxide, 1 -methylcyclopentoxide, 2-fluoroethoxide, 2,2,2,- trifluoroethoxide, 2-ethoxyethoxide, 2-methoxyethoxide, 3-methoxy-1 - butoxide, methoxyethoxyethoxide, 3,3-diethoxy-1 -propoxide, 2- dimethylaminoethoxide, 2-diethylaminoethoxide, 3-dimethylamino-1 - propoxide, 3-diethylamino-1 -propoxide, 1 -dimethylamino-2-propoxide, 1 - diethylamino-2-propoxide, 2-(1 -pyrrol idinyl)ethoxide, 1 -ethyl-3- pyrrolidinoxide, 3-acetyl-1 -propoxide, 4-methoxyphenoxide, 4- chlorophenoxide, 4-f-butylphenoxide, 4-cyclopentylphenoxide, 4- ethylphenoxide, 3,5-bis(trifluoromethyl)phenoxide, 3-chloro-5- methoxyphenoxide, 3,5-dimethoxyphenoxide, 2,4,6-trimethylphenoxide, 3,4,5-trimethylphenoxide, 3,4,5-trimethoxyphenoxide, 4-i-butyl-
catecholate(2-) , 4-propanoylphenoxide, 4-(ethoxycarbonyl)phenoxide, 3- (methylthio)-l -propoxide, 2-(ethylthio)-1 -ethoxide, 2-(methylthio)ethoxide,
4- (methylthio)-1 -butoxide, 3-(methylthio)-1 -hexoxide, 2- methoxybenzylalkoxide, 2-(trimethylsilyl)ethoxide,
(trimethylsilyl)nnethoxide, 1 -(trimethylsilyl)ethoxide, 3- (trimethylsilyl)propoxide, 3-methylthio-1 -propoxide, and mixtures thereof.
Herein, the term acetylacetonate refers to the anion of 1 ,3- dicarbonyl compounds, A1C(O)CH(A2)C(O)A1 , wherein each A1 is independently selected from hydrocarbyl, substituted hydrocarbyl, and O-,
5- , and N-based functional groups and each A2 is independently selected from hydrocarbyl, substituted hydrocarbyl, halogen, and O-, S-, and N- based functional groups. Suitable acetylacetonates include: 2,4- pentanedionate, 3-methyl-2-4-pentanedionate, 3-ethyl-2,4- pentanedionate, 3-chloro-2,4-pentanedionate, 1 ,1 ,1 -trifluoro-2,4- pentanedionate, 1 ,1 ,1 ,5,5,5-hexafluoro-2,4-pentanedionate,
1 ,1 ,1 ,5,5,6,6,6,-octafluoro-2,4-hexanedionate, ethyl 4,4,4- trifluoroacetoacetate, 2-methoxyethylacetoacetate, methylacetoacetate, ethylacetoacetate, f-butylacetoacetate, 1 -phenyl-1 ,3-butanedionate, 2,2,6,6-tetramethyl-3,5-heptanedionate,
allyloxyethoxytrifluoroacetoacetate, 4,4,4-trifluoro-1 -phenyl-1 ,3- butanedionate, 1 ,3-diphenyl-1 ,3-propanedionate, 6,6,7,7,8,8,8,- heptafluoro-2-2-dimethyl-3,5-octanedionate, and mixtures thereof.
Suitable carboxylates include: acetate, trifluoroacetate, propionate, butyrates, hexanoate, octanoate, decanoate, stearate, isobutyrate, t- butylacetate, heptafluorobutyrate, methoxyacetate, ethoxyacetate, methoxypropionate, 2-ethylhexanoate, 2-(2-methoxyethoxy)acetate, 2-[2- (2-methoxyethoxy)ethoxy]acetate, (methylthio)acetate, tetrahydro-2- furoate, 4-acetylbutyrate, phenylacetate, 3-methoxyphenylacetate, (trimethylsilyl)acetate, 3-(trimethylsilyl)propionate, maleate, benzoate, acetylenedicarboxylate, and mixtures thereof.
Suitable hydrocarbyls include: methyl, ethyl, n-propyl, /'-propyl, n- butyl, /'-butyl, sec-butyl, f-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, neopentyl, 3-methylbutyl, phenyl, benzyl, 4-f-butylbenzyl, 4-f-butylphenyl,
p-tolyl, 2-methyl-2-phenyl propyl, 2-mesityl, 2-phenylethyl, 2-ethylhexyl, 2- methyl-2-phenyl propyl, 3,7-dimethyloctyl, allyl, vinyl, cyclopentyl, cyclohexyl, and mixtures thereof.
Suitable O-, N-, S-, halogen- and tri(hydrocarbyl)silyl-substituted hydrocarbyls include: 2-methoxyethyl, 2-ethoxyethyl, 4-methoxyphenyl, 2 methoxybenzyl, 3-methoxy-1 -butyl, 1 ,3-dioxan-2-ylethyl, 3- trifluoromethoxyphenyl, 3,4-(methylenedioxy)phenyl, 2,4-dimethoxyphenyl 2,5-dimethoxyphenyl, 3,4-dimethoxyphenyl, 2-methoxybenzyl, 3- methoxybenzyl, 4-methoxy benzyl, 3,5-dimethoxyphenyl, 3,5-dimethyl-4- methoxyphenyl, 3,4,5-thmethoxyphenyl, 4-methoxyphenethyl, 3,5- dimethoxybenzyl, 4-(2-tetrahydro-2H-pyranoxy)phenyl, 4-phenoxyphenyl,
2- benzyloxyphenyl, 3-benzyloxyphenyl, 4-benzyloxyphenyl, 3-fluoro-4- methoxyphenyl, 5-fluoro-2-methoxyphenyl, 2-ethoxyethenyl, 1 -ethoxyvinyl
3- methyl-2-butenyl, 2-furyl, carbomethoxyethyl, 3-dimethylamino-1 -propyl, 3-diethylamino-1 -propyl, 3-[bis(trimethylsilyl)amino]phenyl, 4-(N,N- dimethyl)aniline, [2-(1 -pyrrolidinylmethyl)phenyl], [3-(1 - pyrrolidinylmethyl)phenyl], [4-(1 -pyrrolidinylmethyl)phenyl], [2-(4- morpholinylmethyl)phenyl], [3-(4-morpholinylmethyl)phenyl], [4-(4- morpholinylmethyl)phenyl], (4-(1 -piperidinylmethyl)phenyl), (2-(1 - piperidinylmethyl)phenyl), (3-(1 -piperidinylmethyl)phenyl), 3-(1 ,4-dioxa-8- azaspiro[4,5]dec-8-ylmethyl)phenyl, 1 -methyl-2-pyrrolyl, 2-fluoro-3-pyridyl, 6-methoxy-2-pyrimidyl, 3-pyridyl, 5-bromo-2-pyridyl, 1 -methyl-5-imidazolyl
2- chloro-5-pyrimidyl, 2,6-dichloro-3-pyrazinyl, 2-oxazolyl, 5-pyrimidyl, 2- pyridyl, 2-(ethylthio)ethyl, 2-(methylthio)ethyl, 4-(methylthio)butyl, 3- (methylthio)-l -hexyl, 4-thioanisole, 4-bromo-2-thiazolyl, 2-thiophenyl, chloromethyl, 4-fluorophenyl, 3-fluorophenyl, 4-chlorophenyl, 3- chlorophenyl, 4-fluoro-3-methylphenyl, 4-fluoro-2-methylphenyl, 4-fluoro-
3- methylphenyl, 5-fluoro-2-methylphenyl, 3-fluoro-2-methylphenyl, 4- chloro-2-methylphenyl, 3-fluoro-4-methylphenyl, 3,5-bis(trifluoromethyl)- phenyl, 3,4,5-trifluorophenyl, 3-chloro-4-fluorophenyl, 3-chloro-5- fluorophenyl, 4-chloro-3-fluorophenyl, 3,4-dichlorophenyl, 3,5- dichlorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2-bromobenzyl, 3-
bromobenzyl, 4-fluorobenzyl, perfluoroethyl, 2-(trimethylsilyl)ethyl,
(trimethylsilyl)methyl, 3-(trinnethylsilyl)propyl, and mixtures thereof.
Suitable thio- and selenolates include: 1 -thioglycerol, phenylthio, ethylthio, methylthio, n-propylthio, /-propylthio, n-butylthio, /'-butylthio, t- butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n- decylthio, n-dodecylthio, 2-methoxyethylthio, 2-ethoxyethylthio, 1 ,2- ethanedithiolate, 2-pyridinethiolate, 3,5- bis(trifluoromethyl)benzenethiolate, toluene-3,4-dithiolate, 1 ,2- benzenedithiolate, 2-dimethylaminoethanethiolate, 2- diethylaminoethanethiolate, 2-propene-1 -thiolate, 2-hydroxythiolate, 3- hydroxythiolate, methyl-3-nnercaptopropionate anion, cyclopentanethiolate, 2-(2-methoxyethoxy)ethanethiolate, 2-(trimethylsilyl)ethanethiolate, pentafluorophenylthiolate, 3,5-dichlorobenzenethiolate, phenylthiolate, cyclohexanethiolate, 4-chlorobenzenemethanethiolate, 4- fluorobenzenemethanethiolate, 2-methoxybenzenethiolate, 4- methoxybenzenethiolate, benzylthiolate, 3-methylbenzylthiolate, 3- ethoxybenzenethiolate, 2,5-dimethoxybenzenethiolate, 2- phenylethanethiolate, 4-f-butylbenzenethiolate, 4-f-butylbenzylthiolate, phenylselenolate, methylselenolate, ethylselenolate, n-propylselenolate, /'- propylselenolate, n-butylselenolate, /'-butylselenolate, f-butylselenolate, pentylselenolate, hexylselenolate, octylselenolate, benzylselenolate, and mixtures thereof.
Suitable thio-, seleno-, and dithiocarboxylates include: thioacetate, thiobenzoate, selenobenzoate, dithiobenzoate, and mixtures thereof.
Suitable dithio-, diseleno-, and thioselenocarbamates include:
dimethyldithiocarbamate, diethyldithiocarbamate, dipropyldithiocarbamate, dibutyldithiocarbamate, bis(hydroxyethyl)dithiocarbamate,
dibenzyldithiocarbamate, dimethyldiselenocarbamate,
diethyldiselenocarbamate, dipropyldiselenocarbamate,
dibutyldiselenocarbamate, dibenzyldiselenocarbamate, and mixtures thereof.
Suitable dithioxanthogenates include: methylxanthogenate, ethylxanthogenate, /-propylxanthogenate, and mixtures thereof.
For the chalcogen compounds, suitable R1S- and R1Se- of R1S-Z and R1Se-Z are selected from the above list of suitable thio- and selenolates.
Suitable SiR5 3 include: SiMe3, SiEt3, SiPr3, SiBu3, Si(/'-Pr)3,
SiEtMe2, SiMe2(/'-Pr), Si(f-Bu)Me2, and Si(cyclohexyl)Me2.
Many of these ligands and chalcogen compounds are commercially available or readily synthesized by the addition of an amine, alcohol, or alkyl nucleophile to CS2 or CSe2 or CSSe.
In some embodiments, a solvent is present and the boiling point of the solvent is greater than about 100 °C or 1 10 °C or 120 °C or 130 °C or 140 °C or 150 °C or 160 °C or 170 °C or 180 °C or 190 °C at atmospheric pressure. In some embodiments, the process is conducted at atmospheric pressure. Suitable solvents include: heteroaromatics, amines, and mixtures thereof. Suitable heteroaromatics include pyridine and
substituted pyridines. Suitable amines include compounds of the form R6NH2, wherein each R6 is independently selected from the group consisting of: O-, N-, S-, and Se-substituted hydrocarbyl. In some embodiments, the solvent comprises an amino-substituted pyridine. In some embodiments, the solvent comprises about 95 to about 5 wt%, or 90 to 10 wt%, or 80 to 20 wt%, or 70 to 30 wt%, or 60 to 40 wt% of the ink, based on the total weight of the ink.
Suitable heteroaromatic solvents include: pyridine, 2-picoline, 3- picoline, 3,5-lutidine, 4-f-butylpyridine, 2-aminopyridine, 3-aminopyridine, diethylnicotinamide, 3-cyanopyridine, 3-fluoropyridine, 3-chloropyridine, 2,3-dichloropyridine, 2,5-dichloropyridine, 5,6,7,8-tetrahydroisoquinoline, 6-chloro-2-picoline, 2-methoxypyridine, 3-(aminomethyl)pyridine, 2-amino- 3-picoline, 2-amino-6-picoline, 2-amino-2-chloropyridine, 2,3- diaminopyridine, 3,4-diaminopyridine, 2-(methylamino)pyridine, 2- dimethylaminopyridine, 2-(aminomethyl)pyridine, 2-(2-aminoethyl)pyridine, 2-methoxypyridine, 2-butoxypyridine, and mixtures thereof.
Suitable amine solvents include: butylamine, hexylamine, octylamine, 3-methoxypropylamine, 2-methylbutylamine, isoamylamine, 1 ,2-dimethylpropylamine, hydrazine, ethylenediamine, 1 ,3-
diaminopropane, 1 ,2-diaminopropane, 1 ,2-diamino-2-methylpropane, 1 ,3- diaminopentane, 1 ,1 -dimethylhydrazine, N-ethylmethylamine,
diethylamine, N-methylpropylamine, diisopropylamine, dibutylamine, triethylamine, N-methylethylenediamine, N-ethylethylenediamine, N- propylethylenediamine, N-isopropylethylenediamine, Ν,Ν'- dimethylethylenediannine, Ν,Ν-dimethylethylenediannine, Ν,Ν'- diethylethylenediamine, Ν,Ν-diethylethylenediamine, N,N- diisopropylethylenediamine, Ν,Ν-dibutylethylenediamine, Ν,Ν,Ν'- trimethylethylenediannine, 3-dimethylanninopropylannine, 3- diethylaminopropylannine, diethylenetriamine, cyclohexylamine, bis(2- methoxyethyl)annine, aminoacetaldehyde diethyl acetal,
methylaminoacetaldehyde dimethyl acetal, N,N-dimethylacetamide dimethyl acetal, dimethylaminoacetaldehyde diethyl acetal,
diethylaminoacetaldehyde diethyl acetal, 4-aminobutyraldehyde diethyl acetal, 2-methylaminomethyl-1 ,3-dioxolane, ethanolamine, 3-amino-1 - propanol, 2-hydroxyethylhydrazine, Ν,Ν-diethylhydroxylamine, 4-amino-1 - butanol, 2-(2-aminoethoxy)ethanol, 2-(methylamino)ethanol, 2- (ethylamino)ethanol, 2-(propylamino)ethanol, diethanolamine,
diisopropanolamine, Ν,Ν-dimethylethanolamine, N,N-diethylethanolamine, 2-(dibutylamino)ethanol, 3-dimethylamino-1 -propanol, 3-diethylamino-1 - propanol, 1 -dimethylamino-2-propanol, 1 -diethylamino-2-propanol, N- methyldiethanolamine, N-ethyldiethanolamine, 3-amino-1 ,2-propanediol, and mixtures thereof.
Preparing the ink typically comprises mixing the components (i) - (v) by any conventional method. In some embodiments, the ink is a solution; in other embodiments, the ink is a suspension or dispersion. Typically, the preparation is conducted under an inert atmosphere, taking precautions to protect the reaction mixtures from air and light.
In some embodiments, the ink is prepared at about 20 - 100 °C, e.g., when the reagents are solids or have high boiling points and/or when one or more of the solvents is a solid at room temperature, e.g., 2- aminopyridine or 3-aminopyridine. In some embodiments, all of the ink components are added together at room temperature. In some
embodiments, elemental chalcogen is added last, following the mixing of all the other components for about half an hour at room temperature. In some embodiments, the components are added consecutively. For example, all of the reagents except copper can be mixed and heated at about 100 °C prior to addition of the copper source, or all of the reagents except tin can be mixed and heated at about 100 °C prior to the addition of the tin source.
The ink is heated to a temperature of greater than about 150 C° or 160 °C or 170 °C or 180 °C or 190 °C before coating onto a substrate. Suitable heating methods include conventional heating and micowave heating. In some embodiments, it has been found that this heat- processing step aids the formation of CZTS-Se, with XAS analysis of films formed from heat-processed inks indicating the presence of kesterite upon heating the films at heating temperatures as low as 120 °C. This heat- processing step is typically carried out under an inert atmosphere. The ink produced at this stage can be stored for extended periods (e.g., a couple of months) without any noticeable decrease in efficacy. In some
embodiments, the molar ratio of copper to zinc to tin is about 2:1 :1 in the ink.
The substrate can be rigid or flexible. In one embodiment, the substrate comprises in layered sequence: (i) a base film; and (ii) optionally, an electrically conductive coating. The base film is selected from the group consisting of: glass, metals, and polymeric films. Suitable electrically conductive coatings include: metal conductors, transparent conducting oxides, and organic conductors. Of particular interest are substrates of molybdenum-coated soda-lime glass, molybdenum-coated polyimide films, or molybdenum-coated polyimide films with a thin layer of a sodium compound (e.g., NaF, Na2S, or Na2Se). In one embodiment, the substrate comprises material selected from the group consisting of metal foils, plastics, polymers, metalized plastics, glass, solar glass, low-iron glass, green glass, soda-lime glass, steel, stainless steel, aluminum, ceramics, metal plates, metalized ceramic plates, and metalized polymer plates.
The ink is disposed on a substrate to provide a coated substrate by any of a variety of solution-based coating and printing techniques, including spin-coating, spray-coating, dip-coating, rod-coating, drop-cast coating, roller coating, slot-die coating, draw-down coating, ink-jet printing, contact printing, gravure printing, flexographic printing, and screen printing. The coating can be dried by evaporation, by applying vacuum, by heating, or by combinations thereof. In some embodiments, the substrate and disposed ink are heated at a temperature from 80 - 350 °C, or 100 - 300 °C, or 120 - 250 °C, or 150 -190 °C to remove at least a portion of the solvent, if present, and by-products derived from the ligands and
chalcogen source.
Atypical Kesterite Compositions
Additional aspects of this invention are atypical kesterite
compositions produced by the processes of this invention.
One aspect of this invention is a composition comprising a compound having a kesterite structure, wherein the Cu/Zn ratio of the kesterite is greater than about 3.1 .
In some embodiments, the composition further comprises one or more copper-, tin-, or zinc-containing compounds selected from the group consisting of binary copper chalcogenides, binary copper oxides, binary tin chalcogenides, binary tin oxides, binary zinc chalcogenides, ZnO, and CTS-Se. In some embodiments, a molar ratio of copper to zinc to tin is about 2:1 :1 of the overall composition. In some embodiments, a molar ratio of copper to (zinc plus tin) is less than one, and a molar ratio of zinc to tin is greater than one. In some embodiments, the heated layers comprise CZTS-Se wherein the coherent domain size of the kesterite is 2 - 30 nm.
One aspect of this invention is a composition comprising a compound having a kesterite structure, wherein the Cu/Zn ratio of the kesterite is less than about 1 .6.
In some embodiments, the composition further comprises one or more copper-, tin-, or zinc-containing compounds selected from the group
consisting of binary copper chalcogenides, binary copper oxides, binary tin chalcogenides, binary tin oxides, binary zinc chalcogenides, ZnO, and CTS-Se. In some embodiments, a molar ratio of copper to zinc to tin is about 2:1 :1 of the overall composition. In some embodiments, a molar ratio of copper to (zinc plus tin) is less than one, and a molar ratio of zinc to tin is greater than one. In some embodiments, the heated layers comprise CZTS-Se wherein the coherent domain size of the kesterite is 2 - 30 nm.
One aspect of this invention is a composition comprising a compound having a kesterite structure, wherein the coherent domain size of the kesterite is 2 - 30 nm.
In some embodiments, the composition further comprises one or more copper-, tin-, or zinc-containing compounds selected from the group consisting of binary copper chalcogenides, binary copper oxides, binary tin chalcogenides, binary tin oxides, binary zinc chalcogenides, ZnO, and CTS-Se. In some embodiments, the composition further comprises CuS, CU2S, ZnS, and SnS2. In some embodiments, a molar ratio of copper to zinc to tin is about 2:1 :1 of the overall composition. In some
embodiments, a molar ratio of copper to (zinc plus tin) is less than one, and a molar ratio of zinc to tin is greater than one. In other embodiments, the heated layers comprise CZTS-Se wherein the Cu/Zn ratio of the kesterite is greater than about 3.1 . In yet other embodiments, the heated layers comprise CZTS-Se wherein the Cu/Zn ratio of the kesterite is less than about 1 .6.
The inks described above can be used to form CTS-Se or CZTS-Se layers on a substrate. Typically, the ink is coated onto the substrate by conventional means and then dried by applying a vacuum, by evaporation or by heating at a temperature from 80 - 350 °C. Suitable substrates include metal foils, plastics, polymers, metalized plastics, glass, solar glass, low-iron glass, green glass, soda-lime glass, steel, stainless steel, aluminum, ceramics, metal plates, metalized ceramic plates, and metalized polymer plates.
For some inks, it has been found that CZTS-Se is formed during
this heating step, with XAS analysis indicating the presence of kesterite.
More typically, the dried, coated substrate is annealed by heating the substrate at about 350 °C to about 800 °C. The annealing step can be carried out under an inert atmosphere, provided that the ratio of the total number of moles of the chalcogen, chalcogen compound, sulfur-, and selenium-based organic ligands, and tin-sulfides and selenides to the total number of moles of the copper, tin and zinc complexes is at least about 1 . Alternatively, the annealing step can be carried out in an atmosphere comprising an inert gas and reactive component selected from the group consisting of: selenium vapor, sulfur vapor, hydrogen, hydrogen sulfide, hydrogen selenide, and mixtures thereof. Typically, at least a portion of the chalcogen can be exchanged (e.g., S can be replaced by Se) by conducting the annealing step in the presence of selenium vapor or hydrogen selenide.
It has been found that CTS-Se and /or CZTS-Se can be formed in high yield during the annealing step, as determined by XRD or XAS. In some embodiments, annealed films consist essentially of CTS-Se or CZTS-Se, according to XRD analysis.
CZTS-Se can serve as the absorber layer in a photovoltaic cell. A CZTS-Se-based photovoltaic cell can be made by forming the CZTS-Se layer on a photovoltaic substrate (e.g., Mo-coated SLG) and then depositing a buffer layer, a transparent top contact layer, electrode pads, and an antireflective layer in sequence onto the annealed CZTS layer. Except for the absorber layer, the same materials and processes used to assemble a CIGS-based photovoltaic cell can be used to assemble a CZTS-Se-based photovoltaic cell.
EXAMPLES
General
Materials. All reagents were purchased from Aldrich (Milwaukee,
Wl), Alfa Aesar (Ward Hill, MA), TCI (Portland, OR), or Gelest (Morrisville, PA). Solid reagents were used without further purification. Liquid reagents that were not packaged under an inert atmosphere were
degassed by bubbling argon through the liquid for 1 hr. Anhydrous solvents were used for the preparation of all fornnulations and for all cleaning procedures carried out within the drybox. Solvents were either purchased as anhydrous from Aldrich or Alfa Aesar, or purified by standard methods (e.g., Pangborn, A. G., et. al. Organometallics, 1996, 15, 1518-1520) and then stored in the drybox over activated molecular sieves.
Formulation and Coating Preparations. Substrates (SLG slides) were cleaned sequentially with aqua regia, Miilipore® water and
isopropanol, dried at 1 10 °C, and coated on the non-float surface of the SLG substrate. All formulations and coatings were prepared in a nitrogen- purged drybox. Vials containing formulations were heated and stirred on a magnetic hotplate/stirrer. Coatings were dried in the drybox.
Details of X-ray Analysis.
XAS Analysis. XANES spectroscopy at the Cu, Zn and Sn K-edges were carried out at the Advanced Photon Source at the Argonne National Laboratory. Data were collected in fluorescence geometry at beamline 5BMD, DND-CAT. Thin film samples were presented to the incident x-ray beam as made. An Oxford spectroscopy-grade ion chamber was used to determine the X-ray incident intensity (l0). The l0 detector was filled with 570 Torr of N2 and 20 Torr of Ar. The fluorescence detector was a Lytle Cell filled with Xe installed perpendicular to the beam propagation direction. Data were collected from 8879 eV to 9954 eV for the Cu edge. The high final energy was used in order to capture a portion of the Zn edge in the same data set, to allow edge step ratio determination as an estimate of Cu:Zn ratio in the film. The Zn edge data were collected over the range 9557 eV to 10,404 eV. Sn edge data covered the range of 29,000 eV to 29,750 eV. The data energy scales were calibrated based on data from metal reference foils collected prior to sample data collection. A second order background was subtracted and the spectra were normalized. Data from several Cu, Zn and Sn sulfide and oxide standards (Cu2ZnSnS4, Cu2SnS3, CuS, Cu2S, CuO, Cu2O, ZnS, ZnO, SnS, SnO and SnO2) were obtained under the same conditions. Non-linear least squares
fitting of a linear combination of the appropriate standards to the spectra obtained from the samples yielded the phase distribution for each element. XRD Analysis. Powder X-ray diffraction was used for the identification of crystalline phases. Data were obtained with a Philips X'PERT automated powder diffractometer, Model 3040. The diffractometer was equipped with automatic variable anti-scatter and divergence slits, X'Celerator RTMS detector, and Ni filter. The radiation was CuK(alpha) (45 kV, 40 mA).
Data were collected at room temperature from 4 to 120°. 2-theta; using a continuous scan with an equivalent step size of 0.02°; and a count time of from 80 sec to 240 sec per step in theta-theta geometry. Thin film samples were presented to the X-ray beam as made. MDI/Jade software version 9.1 was used with the International Committee for Diffraction Data database PDF4+ 2008 for phase identification and data analysis.
Identification of CZTS with Small Coherent Domain Size. Comparison of XRD and XAS data can identify films containing nanoscale domains of Cu2ZnSnS , kesterite, in which the coherent domain size (d) is 2 - 30 nm. Detection of kesterite crystalline material at this length scale by x-ray diffraction is difficult due to diffraction peak broadening effects, particularly on the weak lines required to differentiate kesterite from the common impurity phase sphalerite (ZnS). However, x-ray absorption spectroscopy (XAS) is not limited by the size of crystalline domains over which a defect- free, coherent structure may exist. Allowing the interpretation of x-ray diffraction peaks to be guided by the XAS, peak broadening in the diffraction patterns suggests a 30 nm upper limit on domain size. At least two unit cells of kesterite would need to be present in a domain in order for the local environment of at least some of the atoms to resemble that of bulk crystalline kesterite, and so give rise to the appropriate spectrum. This puts a lower limit of 2nm on the domain size.
Identification of CZTS-Se Kesterite with Atypical Stoichiometries. In the case of XAS, one obtains the fraction of Cu atoms and Zn atoms in the kesterite phase. This, along with a knowledge of overall Cu:Zn ratio, which is determined as described above, allows for determination of the ratio of Cu to Zn in the kesterite phase. This is clearly distinguished from
a mixture of separate sulfide phases producing the same elemental ratios in aggregate.
Example 1
Di-n-butyltinsulfide
Zinc diethyldithiocarbamate (0.5919 g, 1 .635 mmol), copper(ll) dimethyldithiocarbamate (0.9930 g, 3.267 mmol), and di-n-butyltinsulfide (0.4506 g, 1 .701 mmol) were placed in a 40 ml_ amber vial equipped with a stir bar. 4-f-Butylpyridine (4.4144 g) was added, and the resulting mixture was stirred well. Next, 0.0520 g (1 .621 mmol) of elemental sulfur was added. The reaction mixture was stirred for -12 hr at room
temperature and then -40 hr at a first heating temperature of 105 °C.
Next, the reaction mixture was stirred for -8 hr at a second heating temperature of 190 °C. SLG coated substrate 1A was produced via drop- coating according to the following procedure: While being maintained at 105 °C with stirring, a small portion of the formulation was drawn into a pipette and then spread uniformly onto the substrate, which was also heated to 105 °C. The coating on the SLG slide was then dried in the drybox by raising the temperature of the hotplate from 105 °C to 170 °C for 0.5 h.
This procedure was repeated with the exception that the coated substrate was dried at 210 °C for 2 hr to produce coated substrate 1 B. This procedure was also repeated with the exceptions that 2- aminopyridine was used as the solvent and a treated SLG slide was used as the substrate to produce coated substrate 1 C.
Analysis of coated substrates 1A, 1 B and 1 C by XAS confirmed
the presence of CZTS with high Cu/Zn for 1A (Cu/Zn in kesterite = 6.45 1A) and low Cu/Zn for 1 B and 1 C (Cu/Zn in kesterite = 1 .06 for 1 B and 1 .27 for 1C).
acetylacetonate trmet y s ane
In the drybox, zinc diethyldithiocarbamate (0.842 mmol), copper(ll) acetate (1 .58 mmol), and tin(ll) acetylacetonate (0.846 mmol) were placed in a 20 ml_ vial equipped with a stir bar. 2-Aminopyridine (1 .0058 g) was added, followed by 5.05 mmol of (ethylthio)trimethylsilane and 0.814 mmol of sulfur. The reaction mixture was stirred for -40 hr at a first heating temperature of 105 °C. Next, the reaction mixture was stirred for ~8 hr at a second heating temperature of 190 °C. A treated glass slide was coated via drop-coating to produce coated substrate 2A in a manner similar to described above in Example 1 , with drying at 170 °C for -0.5 h.
This procedure was repeated with the exception that the 3- aminopyridine was used as the solvent to produce coated substrate 2B. Analysis of coated substrates 2A and 2B by XAS confirmed the presence of CZTS with low Cu/Zn for 2A and 2B (Cu/Zn in kesterite = 1 .06 for 2A and 1 .10 for 2B).
Zinc Methoxyethoxide Copper(l) Acetate
Bu . Bu
+ Sn^S R + 4 H0^^SH
Bu S Bu *
2-Mercapfo-
Di-n-butyltinsulfide ethanol Zinc methoxyethoxide (1 .638 mmol), copper(l) acetate (3.263 mmol), di-n-butyltinsulfide (1 .631 mmol), and 2-mercaptoethanol (6.885 mmol) were placed together in a 40 ml_ amber vial equipped with a stir bar. 4-f-Butylpyridine (1 .857 g) was added, and the resulting mixture was stirred well. Next, 1 .634 mmol of elemental sulfur was added. The reaction mixture was stirred for -12 hr at room temperature and then -40 hr at 105 °C. Next, the reaction mixture was stirred -16 hr at 190 °C. A SLG coated substrate 3A was produced via drop-coating according to the procedure of Example 1 , with drying at 250 °C for 0.5 hr.
This procedure was repeated using 2-aminopyridine as the solvent with the reaction mixture stirring -8 hr at a second heating temperature of 170 °C, to produce coated substrate 3B. This procedure was repeated using 4-f-butylpyridine as the solvent with the reaction mixture stirring -8 hr at a second heating temperature of 160 °C, to produce coated substrate 3C. Coatings 3B and 3C were both dried at at 170 °C for 0.5 hr and then annealed at 550 °C for 0.5 hr.
Analysis of coated substrates 3A, 3B and 3C by XAS confirmed the presence of CZTS with low Cu/Zn for 3A (Cu/Zn in kesterite = 1 .43 for 3A), high Cu/Zn for 3B (Cu/Zn in kesterite = 2.70 for 3B) and low Cu/Zn for 3C (Cu/Zn in kesterite = 1 .45 for 3C).
Example 4
+ 2
O "O
Zinc Methoxyethoxide Copper(ll)
Methoxide
+ (Me3Si)2N— Sn-N(SiMe3)2 8 Me3Si-SEt
Bis[bis(trimethylsilyl)- (Ethylthio)- amino]tin(ll) trimethylsilane
Following the procedure of Example 1 , a formulation was prepared using 0.1768 g (0.820 mmol) of zinc methoxyethoxide, 0.2047 g (1 .630 mmol) of copper(ll) methoxide, 0.4004 g (0.91 1 mmol)
bis[bis(trimethysilyl)amino]tin(ll), 0.8990 g (6.692 mmol) of
ethylthiotrimethylsilane, 0.0259 g (0.808 mmol) of elemental sulfur, and 0.4700 g of 3,5-lutidine with a second heating temperature of 165 °C. The coating was dried in the drybox at 170 °C for 0.5 h. Analysis of the coated substrate by XAS confirmed the presence of CZTS with low Cu/Zn (Cu/Zn in kesterite = 1 .18).
Zinc Methoxyethoxide Copper(l) Acetate
Di-n-butyltinsulfide ethanol Zinc methoxyethoxide (1 .638 mmol), copper(l) acetate (3.263 mmol), di-n-butyltinsulfide (1 .631 mmol), and 2-mercaptoethanol (6.885 mmol) were placed together in a 40 ml_ amber vial equipped with a stir bar. 4-f-Butylpyridine (1 .857 g) was added, and the resulting mixture was stirred well. Next, 1 .634 mmol of elemental sulfur was added. The reaction mixture was stirred for -12 hr at room temperature and then -40 hr at 105 °C. Next, the reaction mixture was stirred -16 hr at 190 °C. A
SLG coated substrate 5A was produced via drop-coating according to the following procedure: While being maintained at 105 °C with stirring, a small portion of the formulation was drawn into a pipette and then spread uniformly onto the substrate, which was also heated to 105 °C. The coating on the SLG slide was then dried in the drybox by raising the temperature of the hotplate from 105 °C to 250 °C for 0.5 h.
This procedure was repeated using 3.714 g of 4-f-butylpyridine with ~9 hr of heating during the second heat at 190 °C to produce coated substrate 5B, and using 3.714 g of 4-f-butylpyridine with -1 1 hr of heating during the second heat at 190 °C to produce coated substrate 5C.
Analysis of coated substrates 5A, 5B and 5C by XRD indicated that CZTS may be present in these samples in at most trace amounts.
However, both Cu and Zn XAS spectra (Table 5-1 ) indicated the presence of significant quantities of CZTS in all three coatings . CuS, CU2S and ZnS comprised the other copper- and zinc-containing species, with only traces of ZnO present. Sn XAS analysis indicated Sn(IV) sulfides (e.g., CZTS and SnS2) as the predominate tin-containing compounds, comprising greater than 89% of all tin-containing compounds in all three coatings. Comparison of the XRD and XAS data indicates that this route produces films containing nanoscale domains of CZTS kesterite, in which the coherent domain size (d) is 2 - 30 nm. The Cu/Zn ratio in kesterite of coating 5A was 1 .43.
Claims
1 . A composition comprising a compound having a kesterite structure, wherein the Cu/Zn ratio of the kesterite is greater than about 3.1 or less than about 1 .6.
2. The composition of claim 1 , further comprising one or more copper-, tin-, or zinc-containing compounds selected from the group consisting of binary copper chalcogenides, binary copper oxides, binary tin
chalcogenides, binary tin oxides, binary zinc chalcogenides, ZnO, and CTS-Se.
3. The composition of claim 2, wherein the molar ratio of copper to zinc to tin is about 2:1 :1 .
4. The composition of claim 2, wherein the molar ratio of copper to (zinc plus tin) is less than one, and the molar ratio of zinc to tin is greater than one.
5. A composition comprising a compound having a kesterite structure, wherein the coherent domain size of the kesterite is 2 - 30 nm.
6. The composition of claim 5, further comprising one or more copper-, tin-, or zinc-containing compounds selected from the group consisting of binary copper chalcogenides, binary copper oxides, binary tin
chalcogenides, binary tin oxides, binary zinc chalcogenides, ZnO, and CTS-Se.
7. The composition of claim 6, wherein the molar ratio of copper to zinc to tin is about 2:1 :1 .
8. The composition of Claim 6, wherein the molar ratio of copper to (zinc plus tin) is less than one, and the molar ratio of zinc to tin is greater than one.
9. The composition of claim 5, wherein the Cu/Zn ratio of the kesterite is greater than about 3.1 .
10. A process comprising:
a) preparing an ink comprising:
i) a copper source selected from the group consisting of copper complexes of nitrogen-, oxygen-, sulfur-, and selenium-based organic ligands, and mixtures thereof;
ii) a tin source selected from the group consisting of tin complexes of nitrogen-, oxygen-, carbon-, sulfur-, and selenium-based organic ligands, tin hydrides, tin sulfides, tin selenides, and mixtures thereof; iii) a zinc source selected from the group consisting of zinc complexes of nitrogen-, oxygen-, sulfur-, and selenium-based organic ligands, and mixtures thereof;
iv) an elemental chalcogen selected from the group consisting of: elemental S, elemental selenium, and mixtures thereof;
v) a solvent;
iv) optionally, a chalcogen compound selected from the group consisting of: R1S-Z, R1Se-Z and mixtures thereof, with each Z
independently selected from the group consisting of: H and SiR53; wherein each R1 and R5 is independently selected from the group consisting of: hydrocarbyl and O-, N-, S-, halogen- and tri(hydrocarbyl)silyl-substituted hydrocarbyl;
b) heating the ink to a temperature of 150 - 300 °C;
b) disposing the ink onto a substrate; and
c) heating the substrate and ink disposed thereon to a temperature of 80 - 350 °C to form a coated substrate comprising CZTS-Se kesterite.
1 1 . The process of claim 10, wherein the ratio of the total number of moles of the chalcogen compound, the sulfur- and selenium-based organic ligands, and the copper-, tin- and zinc-sulfides and selenides to the total number of moles of the copper, tin and zinc complexes is at least about 1 .
12. The process of claim 1 1 , wherein the ink comprises a chalcogen compound.
13. The process of claim 10, wherein the elemental chalcogen comprises sulfur and the molar ratio of elemental chalcogen is about 0.2 to about 5 relative to the tin source.
14. The process of claim 10, wherein the nitrogen-, oxygen-, carbon-, sulfur- and selenium-based organic ligands are selected from the group consisting of: amidos; alkoxides; acetylacetonates; carboxylates;
hydrocarbyls; O-, N-, S-, halogen-, and tri(hydrocarbyl)silyl-substituted hydrocarbyls; thio- and selenolates; thio-, seleno-, and dithiocarboxylates; dithio-, diseleno-, and thioselenocarbamates; and dithioxanthogenates.
15. The process of claim 10, wherein the process is conducted at atmospheric pressure and the boiling point of the solvent is greater than about 150 °C at atmospheric pressure.
16. The process of claim 10, wherein the solvent is selected from the group consisting of heteroaromatics, amines, and mixtures thereof.
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CN102769046A (en) * | 2012-07-31 | 2012-11-07 | 深圳先进技术研究院 | Copper-zinc-tin-sulfide-selenium film and preparation method thereof, as well as copper-zinc-tin-sulfide-selenium film solar cell |
JP2013112584A (en) * | 2011-11-30 | 2013-06-10 | Murata Mfg Co Ltd | Method for producing compound semiconductor ultra-fine particle |
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WO2010138636A2 (en) * | 2009-05-26 | 2010-12-02 | Purdue Research Foundation | Synthesis of multinary chalcogenide nanoparticles comprising cu, zn, sn, s, and se |
US8426241B2 (en) * | 2010-09-09 | 2013-04-23 | International Business Machines Corporation | Structure and method of fabricating a CZTS photovoltaic device by electrodeposition |
US8617915B2 (en) * | 2010-09-20 | 2013-12-31 | International Business Machines Corporation | Annealing thin films |
US8647897B2 (en) | 2011-03-21 | 2014-02-11 | The Board Of Trustees Of The Leland Stanford Junior University | Air-stable ink for scalable, high-throughput layer deposition |
CN102800751A (en) * | 2012-07-29 | 2012-11-28 | 北京工业大学 | Wet chemical preparation method of solar cell absorption layer Cu2ZnSnS4 film |
CN103204540A (en) * | 2013-02-23 | 2013-07-17 | 北京工业大学 | Preparation method of non-hydrazine group solution of Cu2ZnSnS4 solar cell absorbing layer film |
KR101650049B1 (en) * | 2013-09-12 | 2016-08-22 | 주식회사 엘지화학 | Metal Calcogenide Nano Particle for Manufacturing Light Absorbing Layer of Solar Cell and Method for Manufacturing the Same |
WO2015039106A2 (en) * | 2013-09-16 | 2015-03-19 | Wake Forest University | Polycrystalline films comprising copper-zinc-tin-chalcogenide and methods of making the same |
WO2016053016A1 (en) * | 2014-09-29 | 2016-04-07 | 이화여자대학교 산학협력단 | Cztse-based thin film and manufacturing method therefor, and solar cell using cztse-based thin film |
CN105355720B (en) * | 2015-12-03 | 2017-02-01 | 华东师范大学 | Method for preparing copper-tin-sulfur thin film solar cell absorption layer |
WO2019125912A1 (en) * | 2017-12-18 | 2019-06-27 | Colgate-Palmolive Company | Analytical methods |
PL241410B1 (en) * | 2019-02-11 | 2022-09-26 | Akademia Górniczo-Hutnicza im. Stanisława Staszica w Krakowie | Method for producing powder kesterite of Cu₂SnZnS₄ type |
PL241416B1 (en) * | 2019-02-11 | 2022-09-26 | Akademia Górniczo-Hutnicza im. Stanisława Staszica w Krakowie | Method for producing powder kesterite of Cu₂SnZnS₄ type, intended for production of active layers in thin film photovoltaic cells |
CN111554760B (en) * | 2020-05-15 | 2022-06-17 | 南京邮电大学 | Precursor solution of copper-zinc-tin-sulfur thin film solar cell and preparation method and application thereof |
CN112210374B (en) * | 2020-10-16 | 2021-04-20 | 河南大学 | Copper-tin-sulfur and ZnS alloy quantum dot and perovskite battery prepared by using same |
CN114447128B (en) * | 2022-01-29 | 2024-04-23 | 江西理工大学 | Method for preparing zinc yellow tin ore structure thin film solar cell absorption layer based on sulfur-free source precursor |
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Cited By (3)
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JP2013112584A (en) * | 2011-11-30 | 2013-06-10 | Murata Mfg Co Ltd | Method for producing compound semiconductor ultra-fine particle |
CN102769046A (en) * | 2012-07-31 | 2012-11-07 | 深圳先进技术研究院 | Copper-zinc-tin-sulfide-selenium film and preparation method thereof, as well as copper-zinc-tin-sulfide-selenium film solar cell |
CN102769046B (en) * | 2012-07-31 | 2015-04-15 | 深圳先进技术研究院 | Copper-zinc-tin-sulfide-selenium film and preparation method thereof, as well as copper-zinc-tin-sulfide-selenium film solar cell |
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