EP4268291A1 - Manufacturing of organic-inorganic complex halide films - Google Patents
Manufacturing of organic-inorganic complex halide filmsInfo
- Publication number
- EP4268291A1 EP4268291A1 EP21856940.8A EP21856940A EP4268291A1 EP 4268291 A1 EP4268291 A1 EP 4268291A1 EP 21856940 A EP21856940 A EP 21856940A EP 4268291 A1 EP4268291 A1 EP 4268291A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- organic
- solution
- reagent
- film
- reagents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000004820 halides Chemical class 0.000 title claims abstract description 62
- 229910021432 inorganic complex Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 68
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 59
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 150000002367 halogens Chemical class 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 229910001502 inorganic halide Inorganic materials 0.000 claims abstract description 4
- 230000003993 interaction Effects 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 34
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- -1 by vacuum Chemical class 0.000 claims description 19
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 8
- 150000002892 organic cations Chemical class 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 150000001767 cationic compounds Chemical class 0.000 claims description 7
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 4
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910016553 CuOx Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000004770 chalcogenides Chemical class 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000002897 diene group Chemical group 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- 239000007789 gas Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims 1
- MXIRHCBUSWBUKI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCC[CH2+] MXIRHCBUSWBUKI-UHFFFAOYSA-N 0.000 claims 1
- 238000011534 incubation Methods 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 72
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 239000002178 crystalline material Substances 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract description 4
- 239000011358 absorbing material Substances 0.000 abstract description 3
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- 230000003746 surface roughness Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- 239000002243 precursor Substances 0.000 description 16
- 238000013459 approach Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 229910006854 SnOx Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 238000007764 slot die coating Methods 0.000 description 3
- 101100328536 Mus musculus Cntd1 gene Proteins 0.000 description 2
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 2
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- FZHSXDYFFIMBIB-UHFFFAOYSA-L diiodolead;methanamine Chemical compound NC.I[Pb]I FZHSXDYFFIMBIB-UHFFFAOYSA-L 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001198704 Aurivillius Species 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- NUBZVMBAPAMWME-UHFFFAOYSA-N NC.CN(C)C=O Chemical compound NC.CN(C)C=O NUBZVMBAPAMWME-UHFFFAOYSA-N 0.000 description 1
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical compound CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000012042 active reagent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007787 electrohydrodynamic spraying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001017 electron-beam sputter deposition Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3447—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a halide
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- 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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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Definitions
- the claimed invention relates to the field of materials science, namely, to methods of manufacturing for films made of crystalline materials.
- the crystalline material film obtained by the claimed method can be used, for example, for production of semiconductor applications, in particular, solar cells.
- Organic-inorganic complex halides and, in particular, perovskite-like lead halides are advanced materials for use in semiconductor devices, for example, as a light-absorbing material in solar cells, photodetectors, LEDs, etc. Thin films of these compounds are used to create planar semiconductor devices, such as solar cells.
- semiconductor devices for example, as a light-absorbing material in solar cells, photodetectors, LEDs, etc.
- Thin films of these compounds are used to create planar semiconductor devices, such as solar cells.
- the review paper (Park, Nam-Gyu, and Kai Zhu.
- this synthesis scheme is implemented in one stage (crystallization from the precursor solution applied to the substrate, simultaneous gas-phase deposition of precursors) or two stages (two-stage methods, in which each of the precursors is applied to the substrate separately, for example, using the solution or gas-phase approaches and then conditions for a complete chemical reaction between the compounds are to be created).
- Alternative precursors can be metallic lead films and reactive polyhalide melts (RPMs). Their application was first described in WO2018124938A1.
- films of semiconductor materials are produced, for example, by depositing RPM of mixture AX-X2 onto a Pb (or its compounds) film, where AX is an organic or inorganic halide and B2 is a halogen.
- This method has a number of advantages over classical approaches because it does not require the use of lead salt solutions and allows using a metal as the initial precursor.
- Metallic films are potentially more technologically advanced precursors as there is a number of proven industrial approaches for their application, such as vacuum magnetron sputtering.
- a disadvantage of the known method is the technical complexity of homogeneous applying of stoichiometric amount of RPM onto the surface of the metal (metal-containing precursor) to provide the target functional properties of the final film.
- a potential disadvantage of these methods is the fundamental necessity of dosing the liquid containing AX and X2 onto the metal or metal-containing precursor, which complicates the synthesis procedure.
- the film of metallic lead or tin is immersed into a solution of organic halide (AX) and iodine (X2) in an alcohol, whereby the metal is oxidized to form a hybrid halide film with a perovskite-like structure.
- a disadvantage of these approaches is the choice of the solvent system based on isopropyl alcohol to implement this experimental scheme, which leads to the production of films with non-optimal morphology and non-optimal functional properties. As a result, the power conversion efficiency of perovskite solar cells produced by these methods does not exceed 5%.
- the technical problem to be solved by means of the claimed invention is the necessity to overcome the disadvantages inherent in analogues and prototypes at the expense of creation of a more simple and economic method for producing films of crystalline materials and, in particular, films of organic-inorganic complex halides, characterized by improved functional characteristics of the materials produced, in particular, by increase in the efficiency of the solar cells produced using the claimed method up to 13% and more.
- the technical result achieved by using this invention consists of increasing the homogeneity of the obtained films of organic-inorganic complex halides by reducing the number of pinholes and reducing the surface roughness of the film, which contributes to improving the efficiency of the films when they are used as a light-absorbing material in thin- film solar cells.
- the advantages of the claimed method are also the simplicity of synthesis implementation: chemical reaction occurs when a film of the metal-containing precursor is immersed into the reaction solution without necessity of dosed solution applying onto the surface of the metalcontaining precursor film, which provides higher controllability and reproducibility of the synthesis procedure with increase in the size of the film produced (as compared to RU 2712151 and RU 2685296).
- the solar cell based on the film produced by the claimed method is characterized by an increased efficiency (13% and higher) as compared to the prototype.
- the claimed technical result is achieved by the fact that the method of producing a film of organic-inorganic complex halide with perovskite-like structure includes the following stages:
- the layer of reagent B or B' is a film that is formed on the top layer of the carrier substrate made of a material that is inert with respect to reagents B or B', AX and X2.
- the substrate top layer material is selected from among transparent conductive oxide materials, namely ITO, FTO, IZO, IO:H, NiO, or other alloyed oxide materials based on oxides of nickel, tin, indium and zirconium or other conductive materials, Ceo, PCBM, PEIE, TaTm, NPD, Cui, CuO x , CU2O, PTAA, Spiro-TTB, CuGaO2 or their mixtures.
- transparent conductive oxide materials namely ITO, FTO, IZO, IO:H, NiO, or other alloyed oxide materials based on oxides of nickel, tin, indium and zirconium or other conductive materials, Ceo, PCBM, PEIE, TaTm, NPD, Cui, CuO
- Reagent B is a halide, chalcogenide, nitrate or carbonate of B.
- the thickness of layer B or B' is selected in the range from 10 to 1000 nm.
- Reagent B(B') is applied using the application methods relevant to the listed classes of compounds, namely, by vacuum, gas or solution methods.
- a reagent X2 one of the halogens I2, Br2, Ch or their mixture is selected.
- Anions of halogens (T, Br , Cl”), SCN’ or their mixtures are used as component X in reagent AX.
- Inorganic and organic cations as well as their mixtures are used as component A in reagent AX.
- Li + , Na + , K + , Rb + , Cs + , NH 4 + , CU + , Pd + , Pt + , Ag + , Au + , Rh + , Ru + or their mixtures are used as inorganic cation A.
- the solvent belonging to the number of inert or weak ones with respect to the organic-inorganic complex halides characterized by the following parameters: (DN (Donor number) ⁇ 20 kCal/mol, p (Dipole moment) ⁇ 2.5 D, 6HB (Hansen parameter) ⁇ 10 (MPa) 1/2 ) is used.
- the solvent further comprises the addition of a solvent that is not inert or weak with respect to the organic-inorganic complex halides, namely, isopropyl alcohol, ethyl alcohol or butyl alcohol in an amount not exceeding 10 vol.%.
- concentration of AX in the solution is from 0.001 mg/ml to 500 mg/ml
- concentration of X2 in the solution is from 1 to 500 mg/ml.
- the substrate and solution temperatures are maintained between -20 °C and 200 °C.
- the substrate is treated with the solution for a time ranging from 1 second to 48 hours.
- the film after treating with the solution is additionally subjected to posttreatment, which consists of washing the substrate in organic solvents, heat treatment at a temperature from 30 to 400°C for 1 to 7200 seconds or treatment in vacuum, in an atmosphere of inert gas, dry air, humid air, methylamine dimethylformamide (DMF) vapours, dimethylsulphoxide (DMSO), halogen vapours, or irradiation with visible, UV or IR light, or treatment with a solution solvent or a combination of the above-listed post-treatment types.
- posttreatment which consists of washing the substrate in organic solvents, heat treatment at a temperature from 30 to 400°C for 1 to 7200 seconds or treatment in vacuum, in an atmosphere of inert gas, dry air, humid air, methylamine dimethylformamide (DMF) vapours, dimethylsulphoxide (DMSO), halogen vapours, or irradiation with visible, UV or IR light, or treatment with a solution solvent or a combination of the above-listed post-treatment
- the organic solvent for the reagents AX and X2 is an organic solvent belonging to the number of inert or weak ones with respect to the organic-inorganic complex halides.
- Such solvents are characterized by the following parameters: DN (Donor Number) ⁇ 20 kCal/mol, p (Dipole moment) ⁇ 2.5 D, 6HB (Hansen Parameter) ⁇ 10 (MPa) 1/2 ).
- this type of solvents include chloroform, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-xylene, toluene, dichloromethane, benzene, diethyl ether, anisole, iodobenzene, phenethole, decane, hexane, m-xylene, dibenzyl ether, bromobenzene, mesitylene, styrene, ethylbenzene, heptane, diethylcarbonate, 1,2-dichloroethane, ethylbenzene, ethyl acetate, tetrahydro furan, dioxane, etc., as well as their mixtures.
- Fig.l on the left shows a microphotograph of the film of hybrid halide with a perovskitelike structure CH3NH3PM3 (MAPbh) produced by the claimed method.
- the diffractogram of this film is shown on the right (reflections relating to MAPbh are denoted with '*').
- An expert will evidently recognize a relatively large crystallite size in the film (which confirms the improvement of the functional properties of the film) and the absence of impurities of unreacted components of reaction, such as metallic Pb.
- Fig.2 on the left shows the IV-curve of a perovskite solar cell with FTO / TiO2 / SnO2 / MAPbh / Spiro-OMeTAD / Au architecture, in which the MAPbh film has been produced by the claimed method.
- Time dependence of the power conversion efficiency of the given solar cell is shown on the right, which is obtained by tracing the maximum power point. The resulting power conversion efficiency is substantially higher than that achieved in the closest counterparts, WO2017195191, CN104250723B.
- the diffractogram of this film is shown on the right (reflexes relating to MA x FAi- x PbIyBr3-y are denoted by '*').
- An expert will evidently recognize a relatively large crystallite size in the film (which confirms the improvement of the functional properties of the film) and the absence of impurities of unreacted components of reaction, such as metallic Pb.
- Fig.4 shows a photograph of the film MA x FAi- x PbI y Br3- y with the area of about 30 cm 2 produced by the claimed method.
- the visual homogeneity of the film indicates the potential for further scaling of this synthesis method.
- Perovskite-like structure both the perovskite structure itself and structures derived from the perovskite structural type.
- the term 'perovskite-like compounds' or 'perovskite-like phases' for the purposes of this application refers to compounds and phases with a perovskite-like structure.
- the structure of halide perovskites consists of a three-dimensional framework of corner-connected octahedrons [BXe] or distorted octahedrons consisting of a central atom - component B (cation B n+ ) and six atoms X (anions X').
- phases of the so-called layered perovskites, whose formula differs from ABX3 are implied.
- Such compounds contain layers of corner-connected octahedrons or distorted octahedrons of [BXe] composition (perovskite layers) in at least one plane alternating with some other layers (for example, Aurivillius phases, Ruddlesden-Popper phases, Dion- Jacobson phases).
- OICH can have a perovskite-like structure.
- the term 'stabilized efficiency of a solar cell' in this application means the solar cell efficiency obtained by tracing the maximum power point with evaluating the power conversion efficiency value ⁇ 120 seconds later after the beginning of efficiency tracing.
- This efficiency measurement approach is disclosed, for example, in patent US8963368B2 and in the paper by Wenger, Bernard, et al. 'Towards unification of perovskite stability and photovoltaic performance assessment.' arXiv preprint arXiv:2004.11590 (2020).
- Vacuum sputtering techniques to be used in certain variations of the claimed invention e.g. resistive thermal sputtering, magnetron sputtering, electron beam (“e-beam”) sputtering are disclosed, for example, in
- solution application methods to be used in certain variations of the claimed invention are disclosed, for example, in
- the slot-die coating method is a method of applying a solution onto a moving substrate by extruding the solution through a slit die in close proximity to the substrate.
- Stage I forming a layer of reagent B (B') (hereinafter, the notation B (B') refers to reagent B or B', which is an oxide or salt of B) on the top layer of the carrier substrate;
- Stage II immersion of the film obtained at stage I into the solution of the mixture of reagents AX and X2;
- Stage III taking out the film from the solution and its post -treatment.
- the post-treatment stage is additional.
- the claimed invention can be implemented using known means and methods, including those in the conditions of industrial production.
- the carrier substrate may be glass, polymeric film (e.g., polyethylene terephthalate, polydimethylsiloxane, polymethyl methacrylate, polyimides, etc.) or any other optoelectronic device, such as a solar cell.
- polymeric film e.g., polyethylene terephthalate, polydimethylsiloxane, polymethyl methacrylate, polyimides, etc.
- any other optoelectronic device such as a solar cell.
- the transparent conducting oxide materials ITO, FTO, IZO, IO:H, including other alloyed oxide materials based on nickel, tin, indium and zirconium), other electron conducting materials (TiO2, SnO2, Ceo, PCBM), hole conducting oxide materials (Cui, CuO x , CU2O, CuGaO2, NiO, etc.) and their combinations are used as a top layer of the substrate.
- any materials with sufficient chemical inertness towards the reagents to be used in the synthesis can be used as a top layer of the substrate.
- Metals can be used as reagent B.
- the most preferred are: Pb, Sn, Bi, Cu or their mixtures.
- reagent B may contain additives as which ( ⁇ 20 wt%) Eu, Sb, Cd, Ge, Ni, Mn, Fe, Co, Yb, Pd or other elements may be used.
- the wide range of metals that can be used as a reagent in the implementation of this invention is caused by the similar chemical nature of their interaction with a number of polyhalides (AX + X2): each of the indicated metals can be oxidized by polyhalide to form the corresponding metal halide or complex metal halide.
- reagent B' which includes component B, halides, chalcogenides, nitrates, carbonates and other salts of the above metals and their mixtures can be used.
- the most preferred reagents B and B' are: Pb, Sn, Pbh, Sub, PbBr2, PbCh, PbCOa and their mixtures.
- reagent B films with a thickness of 10 to 1000 nm are used.
- films of Pbh with a thickness of 100 to 500 nm or metallic Pb with a thickness of 10 to 200 nm are used as reagent B.
- Reagent B can be applied using methods relevant to the listed compound classes, e.g. vacuum (resistive thermal evaporation, magnetron sputtering, e-beam sputtering), gas (CVD and similar approaches) or solution methods (spin coating, ink jet printing, screen printing, air jet printing, dip coating, blade coating, slot die coating, aerosol spraying including electrostatic spraying and ultrasonic spraying).
- vacuum resistive thermal evaporation, magnetron sputtering, e-beam sputtering
- gas CVD and similar approaches
- solution methods spin coating, ink jet printing, screen printing, air jet printing, dip coating, blade coating, slot die coating, aerosol spraying including electrostatic spraying and ultrasonic spraying.
- halogens h, Br2, Ch or their mixtures can be used. The most preferred is .
- Anions of halogens (F, Br , Cl”), SCN’ or their mixtures can be used as component X in reagent AX.
- reagent AX compounds containing component X and cation A can be used, with inorganic and organic cations as well as their mixtures being used as cation A.
- Cs + is the most preferred in the role of inorganic cation A.
- Li + , Na + , K + , Rb + and their mixtures, including Cs + mixtures, can be used in the role of inorganic cation A.
- Single charged substituted ammonium cations (NR 1 R 2 R 3 R 4 ) + with different organic substituents (R) can be used as organic cation A in most practical variations of the proposed method; the above-mentioned organic substituents, in turn, can contain different functional groups, such as aromatic fragments, diene groups, functional groups containing oxygen (hydroxyl, carbonyl, carboxyl), nitrogen (amino group, cyano group, etc.), sulphur (thiol, sulphoxide, etc.) or represent H atom.
- functional groups such as aromatic fragments, diene groups, functional groups containing oxygen (hydroxyl, carbonyl, carboxyl), nitrogen (amino group, cyano group, etc.), sulphur (thiol, sulphoxide, etc.) or represent H atom.
- An organic solvent belonging to the number of inert or weak ones with respect to the organic-inorganic complex halides is used as a solvent for reagents A and X2.
- Such solvents are characterized by the following parameters: DN (Donor Number) ⁇ 20 kCal/mol, p (Dipole moment) ⁇ 2.5 D, 6HB (Hansen parameter) ⁇ 10 (MPa) 1/2 ).
- this type of solvents include chloroform, chlorobenzene, o -dichlorobenzene, m-dichlorobenzene, p-xylene, toluene, dichloromethane, benzene, diethyl ether, anisole, iodobenzene, phenethole, decane, hexane, m- xylene, dibenzyl ether, bromobenzene, mesitylene, styrene, ethylbenzene, heptane, diethylcarbonate, 1,2-dichloroethane, ethylbenzene, ethyl acetate, tetrahydrofuran, dioxane, etc., as well as their mixtures.
- the solvent may contain additives ( ⁇ 10 vol. %) of solvents that are neither inert nor weak in respect to the organic-inorganic complex halides, such as an additive of isopropyl alcohol, ethyl alcohol, butyl alcohol.
- a solution of reagents AX and X2 can be prepared by adding the required amounts of powders AX and X2 to an appropriate solvent or mixture of solvents. The solvent/reagent mixture is then stored in a sealed vessel for as long as necessary to achieve the required concentration of the solution as to reagents AX and X2.
- the concentration of AX in the solution can be from 0.001 mg/ml to 500 mg/ml, the concentration of X2 in the solution can be from 0.1 to 500 mg/ml.
- the temperature influence within the range from -20°C to +200°C can additionally be used.
- B7B is either B', a substance that contains component B, or directly a pure substance B
- Y' is the by-product of the reaction, which is obtained when an oxide or salt (B') was used as the precursor of component B.
- film B (B') is treated with AX + X2 solution for a period from 1 s to 48 h, with the temperature of the substrate and solution being maintained between -20 °C and 200 °C; then the substrate is taken out from the solution.
- the film can be further posttreated stage III), using a thermal treatment at a temperature from 30°C to 400°C for 1 to 7200 seconds or stored in an inert gas atmosphere, dry air, humid air, solvent vapour (e.g. DMF, DMSO, methylamine, etc.), halogen vapours, or exposure to visible, UV or IR light, or solvent treatment, or a combination of the above post-treatment types.
- a thermal treatment at a temperature from 30°C to 400°C for 1 to 7200 seconds or stored in an inert gas atmosphere, dry air, humid air, solvent vapour (e.g. DMF, DMSO, methylamine, etc.), halogen vapours, or exposure to visible, UV or IR light, or solvent treatment, or a combination of the above post-treatment types.
- a layer of fluorine-doped tin oxide (resistance ⁇ 7 Q/n) was applied onto cleaned glass substrates (substrate carrier), followed by successive layers of TiCh ( ⁇ 20 nm, spray pyrolysis) and SnO x ( ⁇ 7 nm, chemical deposition from solution) (top substrate layer).
- a 62 nm thick layer of metallic lead (reagent B) was applied onto the top layer of the substrate using vacuum thermoresistive evaporation. The temperatures of the substrates and the quartz thickness gauge were maintained at ⁇ 10 °C during sputtering. After evaporation, the substrates were transferred to an argon-filled glove box.
- stage II the substrate Pb / SnO x / TiCh / FTO / glass was immersed in the solution of MAI + I2 in toluene in a sealed container and was stored during 20 minutes at room temperature. Then (stage III) the substrate was extracted from the solution and successively washed with toluene and anhydrous isopropyl alcohol. Thereafter, the substrate was moved to the glove box (rel. humidity ⁇ 5%) and annealed at 100°C for 30 minutes.
- Table 1 shows the materials obtained using the claimed synthesis method.
- the tables provide, respectively, the selected reagents B(B'), AX and X2, their amounts, solvent, solution temperature at stage 2 and treatment time at stage 2.
- the final composition of the films was established by X-ray diffraction phase analysis (XRD).
- XRD X-ray diffraction phase analysis
- Case 4 Table 2 provides the options for producing materials using the claimed approach on different substrates with different top layers.
- Table 3 below provides the options for obtaining materials based on the claimed method using different options for post-treatment (stage III) of the halide films with a perovskite-like structure produced.
- Halide films with perovskite-like structure MAPbk were obtained on the SnO x / TiCh / FTO substrate as follows: by vacuum thermal evaporation of the metallic lead films of about 62 nm thick were applied onto the SnO x / TiCh / FTO substrates, after which the substrates were immersed in the MAI (1 mg/ml) + h solution (20 mg/ml) in toluene and stored in the solution for 40 min at room temperature. Then the substrates obtained were subjected to one of the seven types of post-treatment shown in Table 3. For example, as part of post-treatment No.4, the substrate was successively washed in toluene, then in anhydrous isopropyl alcohol, after that dried in an argon stream and annealed at 100°C for 30 min
- the substrates obtained were then examined by X-ray diffraction phase analysis (XRD) and test solar cells with the FTO / TiO2 / SnO x / MAPbI 3 / Spiro-OMeTAD / Au architecture were assembled from the substrates.
- XRD X-ray diffraction phase analysis
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Abstract
The claimed invention relates to the field of materials science, namely, to methods of manufacturing of films made of crystalline materials. The crystalline material film obtained by the claimed method can be used, for example, in optoelectronic devices based on semiconductors, in particular, in solar cells. The technical result achieved by using this invention is improvement of homogeneity of the obtained films of organic-inorganic complex halides by reducing the number of pinholes and reduction of the surface roughness of the film, which contributes to improvement of overall quality of the films as a light-absorbing material in thin-film solar cells. The claimed technical result is achieved via the improved method of producing the film of organic-inorganic complex halide with a perovskite-like structure which include the following stages: (I) formation a layer of reagent B or B' on the carrier substrate; II) bringing the layer of reagent B or B' into interaction with reagents AX and X2; III) providing the reactive conversion course of the applied reagents; therefore in order to implement stage II, the film, obtained at stage I, is immersed into a solution of the mixture of reagents AX and X2 in an organic solvent, and is kept in the solution until the reactive conversion is completed to ensure the correct course of reaction B'/B + AX + X2 → AnBX(nz+k) + Y', where B is representing the metal, B' is representing the oxide or salt of B, AX is representing organic or inorganic halide, X2 is representing molecular halogen, AnBX(nz+k) is representing organic-inorganic complex halide (OICH), Y' is a reaction side-product, z = 1, 2; k = 2, 3, 4; n = 0÷4, including 19 claims, 3 tables, 4 figures.
Description
MANUFACTURING OF ORGANIC-INORGANIC COMPUEX HAUIDE FIEMS
Field of the invention
The claimed invention relates to the field of materials science, namely, to methods of manufacturing for films made of crystalline materials. The crystalline material film obtained by the claimed method can be used, for example, for production of semiconductor applications, in particular, solar cells.
Background
Organic-inorganic complex halides and, in particular, perovskite-like lead halides are advanced materials for use in semiconductor devices, for example, as a light-absorbing material in solar cells, photodetectors, LEDs, etc. Thin films of these compounds are used to create planar semiconductor devices, such as solar cells. At the moment, there is a wide range of methods for obtaining hybrid lead halide films with a perovskite-like structure to create solar cells based thereon - the so-called Perovskite solar cells. The review paper (Park, Nam-Gyu, and Kai Zhu. 'Scalable fabrication and coating methods for perovskite solar cells and solar modules.' Nature Reviews Materials (2020): 1-18.) discloses main scalable approaches for the synthesis of hybrid lead halide films for the moment. Most often, the production of such compounds can be regarded as a binary reaction between a lead salt and an organic halide, e.g., for so called 3D perovskitelike lead halides and the most common model compound MAPbk (MA = CfLNHL) Pbb + MAI — MAPbE. In the vast majority of cases, this synthesis scheme is implemented in one stage (crystallization from the precursor solution applied to the substrate, simultaneous gas-phase deposition of precursors) or two stages (two-stage methods, in which each of the precursors is applied to the substrate separately, for example, using the solution or gas-phase approaches and then conditions for a complete chemical reaction between the compounds are to be created).
Alternative precursors can be metallic lead films and reactive polyhalide melts (RPMs). Their application was first described in WO2018124938A1.
In this case, films of semiconductor materials are produced, for example, by depositing RPM of mixture AX-X2 onto a Pb (or its compounds) film, where AX is an organic or inorganic halide and B2 is a halogen. This method has a number of advantages over classical approaches because it does not require the use of lead salt solutions and allows using a metal as the initial precursor. Metallic films are potentially more technologically advanced precursors as there is a number of proven industrial approaches for their application, such as vacuum magnetron sputtering.
A disadvantage of the known method is the technical complexity of homogeneous applying of stoichiometric amount of RPM onto the surface of the metal (metal-containing precursor) to provide the target functional properties of the final film.
The problem of difficulty in achieving homogeneous application of RPM over the surface of the precursor film is partially solved when using RPM solutions instead of pure reactive polyhalides (similar solutions are disclosed in the publications RU 2712151 and RU 2685296). This approach is also described in [Belich, N. A., Petrov, A. A., Rudnev, P. O., Stepanov, N. M., Turkevych, I., Goodilin, E. A., & Tarasov, A. B. (2020). From metallic lead films to perovskite solar cells through lead conversion with polyhalides solutions. ACS Applied Materials & Interfaces]. These publications disclose a method based on applying of the AX-X2 mixture with a solvent or inhibitor of their reaction with a metal-containing precursor onto a film of the metal-containing precursor.
A potential disadvantage of these methods is the fundamental necessity of dosing the liquid containing AX and X2 onto the metal or metal-containing precursor, which complicates the synthesis procedure.
The closest by the technical essence to the claimed invention is the method described in publications WO2017195191, CN104250723B, as well as in papers [Rakita, Yevgeny, et al. "Metal to halide perovskite (HaP): an alternative route to HaP coating, directly from Pb (0) or Sn (0) films." Chemistry of Materials 29.20 (17): 8620-8629] n [He, Yingying, et al. "Using elemental Pb surface as a precursor to fabricate large area CH3NH3PbI3 perovskite solar cells." Applied Surface Science 389 (2016): 540-546]. Within the framework of the approach described in these publications, the film of metallic lead or tin is immersed into a solution of organic halide (AX) and iodine (X2) in an alcohol, whereby the metal is oxidized to form a hybrid halide film with a perovskite-like structure. A disadvantage of these approaches is the choice of the solvent system based on isopropyl alcohol to implement this experimental scheme, which leads to the production of films with non-optimal morphology and non-optimal functional properties. As a result, the power conversion efficiency of perovskite solar cells produced by these methods does not exceed 5%.
The technical problem to be solved by means of the claimed invention is the necessity to overcome the disadvantages inherent in analogues and prototypes at the expense of creation of a more simple and economic method for producing films of crystalline materials and, in particular, films of organic-inorganic complex halides, characterized by improved functional characteristics of the materials produced, in particular, by increase in the efficiency of the solar cells produced using the claimed method up to 13% and more.
Disclosure of invention
The technical result achieved by using this invention consists of increasing the homogeneity of the obtained films of organic-inorganic complex halides by reducing the number of pinholes and reducing the surface roughness of the film, which contributes to improving the efficiency of the films when they are used as a light-absorbing material in thin- film solar cells.
The advantages of the claimed method are also the simplicity of synthesis implementation: chemical reaction occurs when a film of the metal-containing precursor is immersed into the reaction solution without necessity of dosed solution applying onto the surface of the metalcontaining precursor film, which provides higher controllability and reproducibility of the synthesis procedure with increase in the size of the film produced (as compared to RU 2712151 and RU 2685296). The solar cell based on the film produced by the claimed method is characterized by an increased efficiency (13% and higher) as compared to the prototype.
The claimed technical result is achieved by the fact that the method of producing a film of organic-inorganic complex halide with perovskite-like structure includes the following stages:
I) forming a layer of reagent B or B' on the carrier substrate;
II) bringing the layer surface of reagent B or B' into interaction with reagents AX and X2;
III) providing the reactive conversion course of the applied reagents; therefore in order to implement stage II the film, obtained at stage I, is immersed into a solution of the mixture of reagents AX and X2 into an organic solvent, and is keeping until completion of the reactive conversion to ensure the correct course of reaction B7B + AX + X2 — ► AnBX(nz+k) + ¥', where B represents the metal, B' represents the oxide or salt of B, AX represents organic or inorganic halide, X2 represents molecular halogen, AnBX(nz+k) represents organic-inorganic complex halide (OICH), Y' is a reaction by-product, z = 1, 2; k = 2, 3, 4; n = 0 -4, including noninteger values of n. The layer of reagent B or B' is a film that is formed on the top layer of the carrier substrate made of a material that is inert with respect to reagents B or B', AX and X2. The substrate top layer material is selected from among transparent conductive oxide materials, namely ITO, FTO, IZO, IO:H, NiO, or other alloyed oxide materials based on oxides of nickel, tin, indium and zirconium or other conductive materials, Ceo, PCBM, PEIE, TaTm, NPD, Cui, CuOx, CU2O, PTAA, Spiro-TTB, CuGaO2 or their mixtures. One of the following metals or their mixture is used as reagent B: Pb, Sn, Bi, Cu, Eu, Sb, Cd, Ge, Ni, Mn, Fe, Co, Yb, Pd. Reagent B' is a halide, chalcogenide, nitrate or carbonate of B. The thickness of layer B or B' is selected in the range from 10 to 1000 nm. Reagent B(B') is applied using the application methods relevant to the listed classes of compounds, namely, by vacuum, gas or solution methods. As a reagent X2, one of the halogens I2, Br2, Ch or their mixture is selected. Anions of
halogens (T, Br , Cl"), SCN’ or their mixtures are used as component X in reagent AX. Inorganic and organic cations as well as their mixtures are used as component A in reagent AX. Li+, Na+, K+, Rb+, Cs+, NH4 +, CU+, Pd+, Pt+, Ag+, Au+, Rh+, Ru+ or their mixtures are used as inorganic cation A. Single charge substituted ammonium cations (NR1R2R3R4)+ with various organic substituents (R) containing the following functional groups such as aromatic fragments, diene groups, functional groups containing oxygen (hydroxyl, carbonyl, carboxyl), nitrogen (amino group, cyano group, etc.), sulphur (thiols, sulphoxides, etc.) or H atom are used as an organic cation A. As an organic solvent for reagents AX and X2, the solvent belonging to the number of inert or weak ones with respect to the organic-inorganic complex halides, characterized by the following parameters: (DN (Donor number) < 20 kCal/mol, p (Dipole moment) < 2.5 D, 6HB (Hansen parameter) < 10 (MPa)1/2) is used. Chloroform, chlorobenzene, o- dichlorobenzene, m-dichlorobenzene, p-xylene, toluene, dichloromethane, benzene, diethyl ether, anisole, iodobenzene, phenethole, decane, hexane, m-xylene, dibenzyl ether, bromobenzene, mesitylene, styrene, ethylbenzene, heptane, diethylcarbonate, 1,2-dichloroethane, ethylbenzene, ethyl acetate, tetrahydro furan, dioxane, etc., as well as their mixtures are used as the organic solvent. The solvent further comprises the addition of a solvent that is not inert or weak with respect to the organic-inorganic complex halides, namely, isopropyl alcohol, ethyl alcohol or butyl alcohol in an amount not exceeding 10 vol.%. The concentration of AX in the solution is from 0.001 mg/ml to 500 mg/ml, the concentration of X2 in the solution is from 1 to 500 mg/ml. At stage II, the substrate and solution temperatures are maintained between -20 °C and 200 °C. At stage II, the substrate is treated with the solution for a time ranging from 1 second to 48 hours. The film after treating with the solution is additionally subjected to posttreatment, which consists of washing the substrate in organic solvents, heat treatment at a temperature from 30 to 400°C for 1 to 7200 seconds or treatment in vacuum, in an atmosphere of inert gas, dry air, humid air, methylamine dimethylformamide (DMF) vapours, dimethylsulphoxide (DMSO), halogen vapours, or irradiation with visible, UV or IR light, or treatment with a solution solvent or a combination of the above-listed post-treatment types.
The key feature of the claimed approach is that the organic solvent for the reagents AX and X2 is an organic solvent belonging to the number of inert or weak ones with respect to the organic-inorganic complex halides. Such solvents are characterized by the following parameters: DN (Donor Number) < 20 kCal/mol, p (Dipole moment) < 2.5 D, 6HB (Hansen Parameter) < 10 (MPa)1/2). In particular, this type of solvents include chloroform, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-xylene, toluene, dichloromethane, benzene, diethyl ether, anisole, iodobenzene, phenethole, decane, hexane, m-xylene, dibenzyl ether, bromobenzene, mesitylene, styrene, ethylbenzene, heptane, diethylcarbonate, 1,2-dichloroethane,
ethylbenzene, ethyl acetate, tetrahydro furan, dioxane, etc., as well as their mixtures. A more detailed description of this classification type of organic solvents is given in the publication [Tutantsev, Andrei Sergeevich, Natalia N. Udalova, Sergey A. Fateev, Andrey A. Petrov, Wang Chengyuan, Eugene G. Maksimov, Eugene A. Goodilin, and Alexey B. Tarasov. 'New Pigeonholing Approach for Selection of Solvents Relevant to Lead Halide Perovskites Processing.' The Journal of Physical Chemistry C (2020)].
The use of this solvent type avoids deterioration of the target film morphology, which may occur, in particular, in alcohol solvents which were used in the solutions being the closest as to the technical essence (WO2017195191, CN104250723B). The classical alcohols do not fit the criteria for the selection of optimal solvents described within the scope of this invention, as, for example, isopropanol, ethanol, methanol and butanol have 6HB > 15.
The recrystallization processes of hybrid perovskite films in alcohol solvents and deterioration of their morphology caused thereby are described, for example, in publication [Hsieh, Tsung-Yu, et al. "Crystal growth and dissolution of methylammonium lead iodide perovskite in sequential deposition: correlation between morphology evolution and photovoltaic performance." ACS Applied Materials & Interfaces 9,10 (2017): 8623-8633.]. According to the authors of this paper, the partial dissolution of lead compounds with the formation of [PbE]2' ions occurs in alcohol solvents containing organic iodides, which leads to a change in the film morphology and formation of pinholes therein. In solvents, which are inert or weak with respect to organic-inorganic complex halides, such effects of dissolution-recrystallization of lead- containing compounds are less pronounced. As a result, when hybrid perovskites are incubated in solvents of this type, no film recrystallization with the formation of pinholes is observed.
The claimed invention is explained by the following illustrations:
Fig.l on the left shows a microphotograph of the film of hybrid halide with a perovskitelike structure CH3NH3PM3 (MAPbh) produced by the claimed method. The diffractogram of this film is shown on the right (reflections relating to MAPbh are denoted with '*'). An expert will evidently recognize a relatively large crystallite size in the film (which confirms the improvement of the functional properties of the film) and the absence of impurities of unreacted components of reaction, such as metallic Pb.
Fig.2 on the left shows the IV-curve of a perovskite solar cell with FTO / TiO2 / SnO2 / MAPbh / Spiro-OMeTAD / Au architecture, in which the MAPbh film has been produced by the claimed method. Time dependence of the power conversion efficiency of the given solar cell is shown on the right, which is obtained by tracing the maximum power point. The resulting power conversion efficiency is substantially higher than that achieved in the closest counterparts, WO2017195191, CN104250723B.
Fig.3 on the left shows a microphotograph of the film of hybrid halide with a perovskitelike structure MAxFAi-xPbIyBr3-y (MA = CH3NH3+, FA =(NH2)2CH+) produced by the claimed method. The diffractogram of this film is shown on the right (reflexes relating to MAxFAi- xPbIyBr3-y are denoted by '*'). An expert will evidently recognize a relatively large crystallite size in the film (which confirms the improvement of the functional properties of the film) and the absence of impurities of unreacted components of reaction, such as metallic Pb.
Fig.4 shows a photograph of the film MAxFAi-xPbIyBr3-y with the area of about 30 cm2 produced by the claimed method. The visual homogeneity of the film indicates the potential for further scaling of this synthesis method.
Terminology used
The following are selected terms and definitions used within the description of the claimed invention for the best understanding of its essence.
Perovskite-like structure, both the perovskite structure itself and structures derived from the perovskite structural type. The term 'perovskite-like compounds' or 'perovskite-like phases' for the purposes of this application refers to compounds and phases with a perovskite-like structure.
Halide with a perovskite-like structure or halide perovskite compounds with the ABX3 formula having a cubic crystal system or any other lower crystal system (for example, tetragonal, rhombical) as well as mixtures of various phases of halide perovskites. The structure of halide perovskites consists of a three-dimensional framework of corner-connected octahedrons [BXe] or distorted octahedrons consisting of a central atom - component B (cation Bn+) and six atoms X (anions X'). In particular, phases of the so-called layered perovskites, whose formula differs from ABX3 are implied. Such compounds contain layers of corner-connected octahedrons or distorted octahedrons of [BXe] composition (perovskite layers) in at least one plane alternating with some other layers (for example, Aurivillius phases, Ruddlesden-Popper phases, Dion- Jacobson phases).
Organic-inorganic complex halide (OICH) refers to compounds, whose composition can be described as AnBX(nz+k) containing a single charged or double charged organic cation A z+ (z = 1, 2), as well as a polyvalent metal cation Bk+ (k = 2, 3, 4) and a halide or pseudohalide ion X', at that the ratio A/B = n can take values in the range from 0 to 4 (including non- integer values of n) depending on the coordination number and valence of Bk+ and the crystal structure motif. In particular cases, OICH can have a perovskite-like structure.
Inert or weak solvent for organic-inorganic complex halides is an organic solvent with characteristics that satisfy the following parameters:
DN (Donor number) < 20 kCal/mol,
p (Dipole moment) < 2.5 D
6HB (Hansen parameter) < 10 (MPa) 1/2
A more detailed description of this classification type of organic solvents is given in the publication [Tutantsev, Andrei Sergeevich, Natalia N. Udalova, Sergey A. Fateev, Andrey A. Petrov, Wang Chengyuan, Eugene G. Maksimov, Eugene A. Goodilin, and Alexey B. Tarasov. 'New Pigeonholing Approach for Selection of Solvents Relevant to Lead Halide Perovskites Processing.' The Journal of Physical Chemistry C (2020)]
The term 'stabilized efficiency of a solar cell' in this application means the solar cell efficiency obtained by tracing the maximum power point with evaluating the power conversion efficiency value ~ 120 seconds later after the beginning of efficiency tracing. This efficiency measurement approach is disclosed, for example, in patent US8963368B2 and in the paper by Wenger, Bernard, et al. 'Towards unification of perovskite stability and photovoltaic performance assessment.' arXiv preprint arXiv:2004.11590 (2020).
The spin coating method to be used in certain variations of implementation of the claimed invention is disclosed, for example, in the thesis paper (http://konf.x-pdf.ru/18fizika/632895-l-fotovoltaicheskie-strukturi- osnove-organicheskih-poluprovodnikov-kvantovih-tochek-cdse.php );
- GOST R ISO 27911-2015 'National Uniform Measurement Assurance System (NMS). Chemical analysis of the surface. Scanning probe microscopy. Determining and calibrating the lateral resolution of a near-field optical microscope' (http ://doc s . cntd .ru/document/ 1200119068);
po luchen i ya-pero vs kitnykh- so I nec hn ykh- ach eek . ht ml .
Vacuum sputtering techniques to be used in certain variations of the claimed invention (e.g. resistive thermal sputtering, magnetron sputtering, electron beam ("e-beam") sputtering are disclosed, for example, in
- the lecture (https://mipt.ru/upload/medialibrary/17b/skol_partl_pvd_dorozhkin.pdf);
- the book (Mattox, Donald M. Handbook of physical vapor deposition (PVD) processing. William Andrew, 2010, Chapters 6, 7).
The solution application methods to be used in certain variations of the claimed invention (ink-jet printing, screen printing, substrate immersion in a precursor solution (dip-coating), blade-coating, slot-die coating, aerosol spraying, ultrasonic spraying) are disclosed, for example, in
- the paper (Park, Nam-Gyu, and Kai Zhu. 'c.' Nature Reviews Materials (2020): 1-18.)
In particular, the slot-die coating method is a method of applying a solution onto a moving substrate by extruding the solution through a slit die in close proximity to the substrate.
The electro spraying method to be used in certain variations of the claimed invention is disclosed, for example, in
- the paper Han, Sunghoon, et al. 'Efficient Planar-Heterojunction Perovskite Solar Cells Fabricated by High-Throughput Sheath-Gas-Assisted Electrospray.' ACS Applied Materials & Interfaces 10, 8 (2018): 7281-7288.
The screen printing method to be used in certain variations of the claimed invention is disclosed, for example, in
- GOST 13.2.004-89. Reprography. Copywriting. Screen printing devices (stencil duplicators). General technical requirements, (http://docs.cntd.ru/document/gost-13-2-004-89)
The aerosol jet printing method to be used in certain variations of the claimed invention is disclosed, for example, in
- the paper Yang, Chunhe, et al. 'Preparation of active layers in polymer solar cells by aerosol jet printing.' ACS applied materials & interfaces 3, 10 (2011): 4053-4058.
- the paper Bag, Santanu, James R. Deneault, and Michael F. Durstock. 'Aerosol-Jet-Assisted Thin-Film Growth of CH3NH3PbI3 Perovskites — A Means to Achieve High Quality, Defect-Free Films for Efficient Solar Cells.' Advanced Energy Materials 7, 20 (2017): 1701151.
Implementation of invention
In the implementation of the claimed method the following main stages of the process for producing films of crystalline materials can be highlighted:
Stage I: forming a layer of reagent B (B') (hereinafter, the notation B (B') refers to reagent B or B', which is an oxide or salt of B) on the top layer of the carrier substrate;
Stage II: immersion of the film obtained at stage I into the solution of the mixture of reagents AX and X2;
Stage III: taking out the film from the solution and its post -treatment. The post-treatment stage is additional.
The claimed invention can be implemented using known means and methods, including those in the conditions of industrial production.
It has been experimentally shown that physical and chemical processes occurring at all basic stages of the proposed process do not depend on the nature of the substrate material or the upper layer of the substrate if this material is selected from among those being inert in relation to reagents B(B'), AX and X2, as well as to the solvents to be used in the synthesis process under the experimental conditions (pressure, temperature, irradiation, etc.). The term 'top
layer' of the carrier substrate for the purposes of the present description refers to that part of the substrate, to which reagent B (B') is applied at stage I.
The carrier substrate may be glass, polymeric film (e.g., polyethylene terephthalate, polydimethylsiloxane, polymethyl methacrylate, polyimides, etc.) or any other optoelectronic device, such as a solar cell.
In the most significant practical applications the transparent conducting oxide materials (ITO, FTO, IZO, IO:H, including other alloyed oxide materials based on nickel, tin, indium and zirconium), other electron conducting materials (TiO2, SnO2, Ceo, PCBM), hole conducting oxide materials (Cui, CuOx, CU2O, CuGaO2, NiO, etc.) and their combinations are used as a top layer of the substrate. Potentially, any materials with sufficient chemical inertness towards the reagents to be used in the synthesis (the most chemically active reagents in the claimed scheme are halogens and mixtures of halogens with organic halides and organic solvents) can be used as a top layer of the substrate.
Metals can be used as reagent B. The most preferred are: Pb, Sn, Bi, Cu or their mixtures. Also, reagent B may contain additives as which (<20 wt%) Eu, Sb, Cd, Ge, Ni, Mn, Fe, Co, Yb, Pd or other elements may be used. The wide range of metals that can be used as a reagent in the implementation of this invention is caused by the similar chemical nature of their interaction with a number of polyhalides (AX + X2): each of the indicated metals can be oxidized by polyhalide to form the corresponding metal halide or complex metal halide. The reactive capacity of polyhalides is described, in particular, in the paper [Petrov, Andrey A., and Alexey B. Tarasov. 'Methylammonium polyiodides in perovskite photovoltaics: from fundamentals to applications.' Frontiers in Chemistry 8 (2020): 418.].
As reagent B', which includes component B, halides, chalcogenides, nitrates, carbonates and other salts of the above metals and their mixtures can be used. The most preferred reagents B and B' are: Pb, Sn, Pbh, Sub, PbBr2, PbCh, PbCOa and their mixtures.
In most practical applications, reagent B films with a thickness of 10 to 1000 nm are used. In the best case, films of Pbh with a thickness of 100 to 500 nm or metallic Pb with a thickness of 10 to 200 nm are used as reagent B.
Reagent B (B') can be applied using methods relevant to the listed compound classes, e.g. vacuum (resistive thermal evaporation, magnetron sputtering, e-beam sputtering), gas (CVD and similar approaches) or solution methods (spin coating, ink jet printing, screen printing, air jet printing, dip coating, blade coating, slot die coating, aerosol spraying including electrostatic spraying and ultrasonic spraying).
As reagent X2, halogens h, Br2, Ch or their mixtures can be used. The most preferred is .
Anions of halogens (F, Br , Cl"), SCN’ or their mixtures can be used as component X in reagent AX.
As reagent AX, compounds containing component X and cation A can be used, with inorganic and organic cations as well as their mixtures being used as cation A. For example, Cs+ is the most preferred in the role of inorganic cation A. Also, Li+, Na+, K+, Rb+ and their mixtures, including Cs+ mixtures, can be used in the role of inorganic cation A. Single charged substituted ammonium cations (NR1R2R3R4)+ with different organic substituents (R) can be used as organic cation A in most practical variations of the proposed method; the above-mentioned organic substituents, in turn, can contain different functional groups, such as aromatic fragments, diene groups, functional groups containing oxygen (hydroxyl, carbonyl, carboxyl), nitrogen (amino group, cyano group, etc.), sulphur (thiol, sulphoxide, etc.) or represent H atom. Most often in practically significant implementations the following cations are used in the role of organic cation: Cs+, Rb+, K+, CH3NH3+, (NH2)2CH+, C(NH2)3+, CH3(CH2)nNH3 + (n=l-15 including their isomers), phenylethylammonium cations, substituted phenylethylammonium cations and their mixtures.
An organic solvent belonging to the number of inert or weak ones with respect to the organic-inorganic complex halides is used as a solvent for reagents A and X2. Such solvents are characterized by the following parameters: DN (Donor Number) < 20 kCal/mol, p (Dipole moment) < 2.5 D, 6HB (Hansen parameter) < 10 (MPa)1/2). In particular, this type of solvents include chloroform, chlorobenzene, o -dichlorobenzene, m-dichlorobenzene, p-xylene, toluene, dichloromethane, benzene, diethyl ether, anisole, iodobenzene, phenethole, decane, hexane, m- xylene, dibenzyl ether, bromobenzene, mesitylene, styrene, ethylbenzene, heptane, diethylcarbonate, 1,2-dichloroethane, ethylbenzene, ethyl acetate, tetrahydrofuran, dioxane, etc., as well as their mixtures. A more detailed description of this classification type of organic solvents is given in the publication [Tutantsev, Andrei Sergeevich, Natalia N. Udalova, Sergey A. Fateev, Andrey A. Petrov, Wang Chengyuan, Eugene G. Maksimov, Eugene A. Goodilin, and Alexey B. Tarasov. 'New Pigeonholing Approach for Selection of Solvents Relevant to Lead Halide Perovskites Processing.' The Journal of Physical Chemistry C (2020)]. In particular, this publication describes how solvents with different combinations of values of the listed parameters (DN, p, 6HB) interact with organic-inorganic lead halide complexes. It is experimentally shown that the so-called "inert or weak solvents with respect to organic- inorganic complex halides" are characterized by weak solubility to lead halide components with a perovskite-like structure. The use of this type of solvents is a prerequisite for the successful implementation of the claimed invention, as it provides a low rate of perovskite film recrystallization, for example, according to the mechanism described in the paper [Hsieh, Tsung-
Yu, et al. "Crystal growth and dissolution of methylammonium lead iodide perovskite in sequential deposition: correlation between morphology evolution and photovoltaic performance." ACS Applied Materials & Interfaces 9, 10 (2017): 8623-8633.].
In some implementations of the method, the solvent may contain additives (<10 vol. %) of solvents that are neither inert nor weak in respect to the organic-inorganic complex halides, such as an additive of isopropyl alcohol, ethyl alcohol, butyl alcohol.
A solution of reagents AX and X2 can be prepared by adding the required amounts of powders AX and X2 to an appropriate solvent or mixture of solvents. The solvent/reagent mixture is then stored in a sealed vessel for as long as necessary to achieve the required concentration of the solution as to reagents AX and X2.
To implement the invention, the concentration of AX in the solution can be from 0.001 mg/ml to 500 mg/ml, the concentration of X2 in the solution can be from 0.1 to 500 mg/ml.
In the course of solution preparation, the temperature influence (temperature maintenance) within the range from -20°C to +200°C can additionally be used.
In the process of implementing the claimed invention, the following chemical reaction scheme is carried out:
B + AX + X2 * AnBX(nz+k) or
B' + AX + X2 * AnBX(nz+k)+ Y', where B7B is either B', a substance that contains component B, or directly a pure substance B, Y' is the by-product of the reaction, which is obtained when an oxide or salt (B') was used as the precursor of component B. z = 1, 2; k = 2, 3, 4; n = 0 -4, including non- integer values of n rather than a pure substance B.
At Stage II, film B (B') is treated with AX + X2 solution for a period from 1 s to 48 h, with the temperature of the substrate and solution being maintained between -20 °C and 200 °C; then the substrate is taken out from the solution.
After completing the above mentioned stage, the film can be further posttreated stage III), using a thermal treatment at a temperature from 30°C to 400°C for 1 to 7200 seconds or stored in an inert gas atmosphere, dry air, humid air, solvent vapour (e.g. DMF, DMSO, methylamine, etc.), halogen vapours, or exposure to visible, UV or IR light, or solvent treatment, or a combination of the above post-treatment types.
Particular implementation cases
Case 1
To form the substrate, a layer of fluorine-doped tin oxide (resistance ~7 Q/n) was applied onto cleaned glass substrates (substrate carrier), followed by successive layers of TiCh (~20 nm, spray pyrolysis) and SnOx (~7 nm, chemical deposition from solution) (top substrate layer).
To implement the stage II, a 62 nm thick layer of metallic lead (reagent B) was applied onto the top layer of the substrate using vacuum thermoresistive evaporation. The temperatures of the substrates and the quartz thickness gauge were maintained at ~10 °C during sputtering. After evaporation, the substrates were transferred to an argon-filled glove box.
10 mg of methylammonium iodide (MAI) and 200 mg of I2 (reagents AX and X2) was added to 10 ml of toluene, after which this mixture was stirred for 8 hours at room temperature in an enclosed container. Upon expiry of 8 hours, the closed container accommodated a solution containing MAI and h in toluene and polyhalide MAIX distributed over the walls and bottom of the container. A dosed volume of MAI and I2 solution without MAIX inclusions was taken to perform the synthesis.
Then (stage II) the substrate Pb / SnOx / TiCh / FTO / glass was immersed in the solution of MAI + I2 in toluene in a sealed container and was stored during 20 minutes at room temperature. Then (stage III) the substrate was extracted from the solution and successively washed with toluene and anhydrous isopropyl alcohol. Thereafter, the substrate was moved to the glove box (rel. humidity <5%) and annealed at 100°C for 30 minutes.
Next, a layer of p-conducting Spiro-OMeTAD material was applied onto the substrates and an electrode (Au) was sputtered. The stabilized power conversion efficiency of the perovskite solar cell, which was obtained by tracking the maximum power point, was equal to 13%, which demonstrates the potential significance of the proposed solution for further practical applications.
The results of scanning electron microscopy and X-ray diffraction phase analysis for M APbh films obtained by the claimed method are shown in Fig. 1.
The IV-curve and the time behavior of the efficiency for solar cells assembled on the basis of these films are shown in Fig. 2.
Case 2
100 mg of formamidinium iodide (FAI), 17 mg of methylammonium bromide (MABr) and 2 g of I2 was added to 100 ml of toluene, after which this mixture was stirred for 12 hours at room temperature in a closed container. Next, 5 mL of the resulting solution was transferred to a separate container, in which the Pb@SnO2@TiO2@FTO substrate was then immersed. The container was heated to 50°C and stored for 35 minutes, after which the substrate was taken out from the container (stage III) and washed successively with toluene and anhydrous isopropanol.
The results of scanning electron microscopy and X-ray phase analysis for MAxFAi-xPbIyBr3-y films obtained by the claimed method are shown in Fig. 3.
A film of the composition MAxFAi-xPbIyBr3-y of larger size (6 x 5 cm) was obtained by a similar method, a photograph of this film is shown in Fig. 4.
Case 3
Table 1 below shows the materials obtained using the claimed synthesis method. The tables provide, respectively, the selected reagents B(B'), AX and X2, their amounts, solvent, solution temperature at stage 2 and treatment time at stage 2. The final composition of the films was established by X-ray diffraction phase analysis (XRD). This list demonstrates a fundamental possibility to obtain films of different classes of crystalline materials using the claimed method, in particular, halides and hybrid halides of transition metals (e.g., Cui and MACU2I3), halide perovskites (so called 3D perovskites with the general formula of ABX3) and organic-inorganic complex halides (2D perovskites such as BA2MAPb2l?).
Table 1
Case 4
Table 2 provides the options for producing materials using the claimed approach on different substrates with different top layers.
Table 2
These results demonstrate that the claimed approach is potentially feasible to obtain organic-inorganic complex halide films on any flat substrates having sufficient chemical inertness with respect to the reagents to be used in the course of synthesis (in particular, many oxides and iodides possess such inertness).
Case 5
Table 3 below provides the options for obtaining materials based on the claimed method using different options for post-treatment (stage III) of the halide films with a perovskite-like structure produced. Halide films with perovskite-like structure MAPbk were obtained on the SnOx / TiCh / FTO substrate as follows: by vacuum thermal evaporation of the metallic lead films of about 62 nm thick were applied onto the SnOx / TiCh / FTO substrates, after which the substrates were immersed in the MAI (1 mg/ml) + h solution (20 mg/ml) in toluene and stored in the solution for 40 min at room temperature. Then the substrates obtained were subjected to one of the seven types of post-treatment shown in Table 3. For example, as part of post-treatment No.4, the substrate was successively washed in toluene, then in anhydrous isopropyl alcohol, after that dried in an argon stream and annealed at 100°C for 30 min.
The substrates obtained were then examined by X-ray diffraction phase analysis (XRD) and test solar cells with the FTO / TiO2 / SnOx / MAPbI3 / Spiro-OMeTAD / Au architecture were assembled from the substrates. The values of typical power conversion efficienies for the solar cells produced are shown in Table 3.
Table 3
Claims
CLAIMS A manufacturing method of organic-inorganic complex halide with a perovskite-like structure is including the following stages:
I) forming a layer of reagent B or B' on the carrier substrate;
II) bringing the layer of reagent B or B' into interaction with reagents AX and X2;
III) providing the reactive conversion of the applied reagents, characterized in that to implement stage II, the film obtained at stage I is immersed into the solution of the mixture of reagents AX and X2 in an organic solvent and kept in the solution until the reactive conversion is completed according to the reaction B'/B + AX + X2 — > AnBX(nz+k) + Y', where B is a metal, B' is an oxide or salt of B, AX is an organic or inorganic halide, X2 is a molecular halogen, AnBX(nz+k) is organic-inorganic complex halide (OICH), Y' is reaction side -product, z = 1, 2; k = 2, 3, 4; n = 0 -4, including non- integer values of n. The method of claim 1, wherein the layer of reagent B or B' is a film which is formed on the top layer of the carrier substrate made of a material that is inert towards to reagents B or B', AX and X2. The method according to claim 2, wherein the substrate top layer material is selected among transparent conductive oxide materials, namely ITO, FTO, IZO, InO:H, NiO, or other alloyed oxide materials based on oxides of nickel, tin, indium and zirconium or other conductive materials, C6o, PCBM, PEIE, TaTm, NPD, Cui, CuOx, Cu2O, PTAA, Spiro-TTB, CuGaO2 or their mixtures. The method according to claim 1 , wherein one of the following metals or their mixture is used as reagent B: Pb, Sn, Bi, Cu, Eu, Sb, Cd, Ge, Ni, Mn, Fe, Co, Yb, Pd. The method according to claim 1, wherein reagent B' is a halide, chalcogenide, nitrate or carbonate of B. The method according to claim 1, wherein the thickness of layer B or B' is selected within a range from 10 to 1000 nm. The method according to claim 1, wherein reagent B(B') is applied using methods relevant to the listed classes of compounds, namely by vacuum, gas or solution methods. The method according to claim 1, wherein one of the following halogens or their mixture is selected as reagent X2: 12, Br2, CI2.
The method according to claim 1, wherein anions of halogens (T, Br , Cl ), SCN or their mixtures are used as component X in reagent AX. The method according to claim 1, wherein inorganic and organic cations, as well as their mixtures, are used as component A in reagent AX. The method according to claim 10, wherein Li+, Na+, K+, Rb+, Cs+, NHC, Cu+, Pd+, Pt+, Ag+, Au+, Rh+, Ru+ or their mixtures are used as inorganic cation A. The method according to claim 10, wherein single charge substituted ammonium cations NR1R2R3R4)+ with various organic substituents (R) containing the following functional groups such as aromatic fragments, diene groups, functional groups are used as organic cation A: containing oxygen (hydroxyl, carbonyl, carboxyl), nitrogen (amino group, cyano group, etc.), sulphur (thiols, sulphoxides, etc.) or H atom. The method according to claim 1, wherein the organic solvent for the reagents AX and X2 is chosen amongst solvents belonging to the inert or weak ones with respect to the organic- inorganic complex halides, characterized by the following parameters: (DN (Donor number) < 20 kCal/mol, p (Dipole moment) < 2.5 D, 5HB (Hansen parameter) < 10 (MPa)1/2) is used . The method according to claim 13, wherein chloroform, chlorobenzene, o-dichlorobenzene, m- dichlorobenzene, p-xylene, toluene, dichloromethane, benzene, diethyl ether, anisole, iodobenzene, phenethole, decane, hexane, m- xylene, dibenzyl ether, bromobenzene, mesitylene, styrene, ethylbenzene, heptane, diethylcarbonate, 1,2-dichloroethane, ethylbenzene, ethyl acetate, tetrahydrofuran, dioxane, etc., as well as their mixtures, are used as the organic solvent. The method according to claim 13, wherein the solution of AX and X2 comprises the additive of a solvent that is not inert or weak with respect to the organic-inorganic complex halides, namely isopropyl alcohol, ethyl alcohol or butyl alcohol in an amount not exceeding 10 vol.%. The method according to claim 1, wherein the concentration of AX in the solution is from 0.001 mg/ml to 500 mg/ml, the concentration of X2 in the solution is from 1 to 500 mg/ml. The method according to claim 1, wherein, at stage II, the temperature of the substrate and the solution is maintained between -20 °C and 200 °C. The method according to claim 1, wherein, at stage II, the substrate is immersed into the solution for a period of time from 1 second to 48 hours. The method according to claim 1, wherein the film after being immersed into the solution is additionally post-treated, which consists of washing the substrate in organic solvents, annealing at a temperature from 30 to 400°C for 1 to 7200 seconds or incubation in vacuum, in an atmosphere of inert gas, dry air, humid air, methylamine vapour, dimethylformamide (DMF)
18 vapour, dimethylsulphoxide (DMSO) vapour, halogen vapors, or irradiation with visible, UV or IR light, or treatment with a solution or a solvent or a combination of the above-listed posttreatment types.
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