CN116655581A - Organic hole transport material and preparation method and application thereof - Google Patents
Organic hole transport material and preparation method and application thereof Download PDFInfo
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- CN116655581A CN116655581A CN202310626170.XA CN202310626170A CN116655581A CN 116655581 A CN116655581 A CN 116655581A CN 202310626170 A CN202310626170 A CN 202310626170A CN 116655581 A CN116655581 A CN 116655581A
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- hole transport
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- solar cell
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- 239000000463 material Substances 0.000 title claims abstract description 135
- 230000005525 hole transport Effects 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- SDXUIOOHCIQXRP-UHFFFAOYSA-N 1,2,4,5-tetrafluorobenzene Chemical compound FC1=CC(F)=C(F)C=C1F SDXUIOOHCIQXRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000004528 spin coating Methods 0.000 claims description 26
- 150000003732 xanthenes Chemical class 0.000 claims description 18
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- QFUPJXCUNNWZJQ-UHFFFAOYSA-N 2-bromofluoren-1-one Chemical compound C1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 QFUPJXCUNNWZJQ-UHFFFAOYSA-N 0.000 claims description 8
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 8
- -1 di-tert-butyl methyl phosphine tetrafluoroborate Chemical compound 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- SJTBRFHBXDZMPS-UHFFFAOYSA-N 3-fluorophenol Chemical compound OC1=CC=CC(F)=C1 SJTBRFHBXDZMPS-UHFFFAOYSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000011160 research Methods 0.000 abstract description 4
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 52
- 239000000243 solution Substances 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 239000011521 glass Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000021615 conjugation Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- LNUIUONEPHRXHM-UHFFFAOYSA-L disodium acetic acid ethane-1,2-diamine diacetate Chemical class [Na+].[Na+].CC(O)=O.CC(O)=O.CC([O-])=O.CC([O-])=O.NCCN LNUIUONEPHRXHM-UHFFFAOYSA-L 0.000 description 3
- JURBTQKVGNFPRJ-UHFFFAOYSA-N ditert-butyl(methyl)phosphane Chemical class CC(C)(C)P(C)C(C)(C)C JURBTQKVGNFPRJ-UHFFFAOYSA-N 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- OOBPIWAAJBRELM-UHFFFAOYSA-N imidazol-1-yl-(2-methylfuran-3-yl)methanone Chemical compound O1C=CC(C(=O)N2C=NC=C2)=C1C OOBPIWAAJBRELM-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001894 space-charge-limited current method Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MNBDZJINQUZDFP-UHFFFAOYSA-N 2-bromospiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=C(Br)C=C21 MNBDZJINQUZDFP-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical group FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to the field of organic battery materials, and particularly discloses an organic hole transport material, a preparation method and application thereof. The organic hole transport material is synthesized by taking 1,2,4, 5-tetrafluorobenzene as a central unit and spirofluorene xanthene as a two-side structure through a coupling reaction. The organic hole transport material has good solubility, higher quantum efficiency and higher hole mobility, can be used as a hole transport layer to be applied to a perovskite solar cell, can effectively improve the photoelectric conversion efficiency and stability of the solar cell, and provides good reference significance for the research of high-performance hole transport materials.
Description
Technical Field
The invention relates to the field of organic battery materials, and particularly discloses an organic hole transport material, a preparation method and application thereof.
Background
In recent years, organic-inorganic hybrid Perovskite Solar Cells (PSCs) become a research hot spot of a new generation of solar cells due to the advantages of wide material sources, simple preparation process, high efficiency and the like. The hole transport material in the perovskite solar cell has the effects of extracting and transporting holes, inhibiting charge recombination, preventing the perovskite light capturing layer from being corroded by moisture and the like, is an indispensable part of the perovskite solar cell, and has become a research hot spot.
Spirofluorene xanthene (SFX), a classical spiro compound, is composed of two parts of a fluorene ring and a xanthene ring, forming a spiro atom at the bridging atom of the fluorene ring. SFX has the following basic characteristics: the cross geometry, steric hindrance effect and the conjugation of the spiro atom are broken. The unique aggregation configuration and the intrinsic steric hindrance are beneficial to inhibiting the accumulation of molecules, the spiro conjugation effect caused by conjugation interruption can reduce the conjugation degree of the whole molecule, the structure is suitable for designing wide-bandgap molecules, and the spiro structure can improve the rigidity of the molecules and increase the thermal stability of the molecules, so that the service life of the perovskite solar cell is prolonged.
In the prior art, the hole transport material used for the perovskite solar cell is complex in synthesis, difficult to purify, poor in solubility, unstable in performance and not provided with high hole mobility, and the high hole transport rate material such as a Spiro-OMeTAD material has the problems of high synthesis difficulty, multiple synthesis steps, high purification difficulty, low yield and the like, so that the research and development of the hole transport material which is simple and convenient in synthesis, has high hole mobility and has a proper energy level structure is of great significance to the development of the perovskite solar cell.
Disclosure of Invention
Aiming at the technical problems that a hole transport material used in a perovskite solar cell is complex in synthesis, difficult to purify, poor in solubility, unstable in performance and not provided with high hole mobility and influencing the use effect of a cell device in the prior art, the invention provides an organic hole transport material, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the first aspect of the present invention provides an organic hole transport material comprising at least the steps of: the structure of the organic hole transport material is shown as formula 1:
R 1 、R 2 and R is 3 Selected from H or F, wherein R 1 、R 2 And R is 3 At least two hydrogen atoms.
Compared with the prior art, the novel organic hole transport material provided by the invention takes 1,2,4, 5-tetrafluorobenzene and spirofluorene xanthene derivatives as main raw materials, and based on a spirofluorene xanthene skeleton with high steric hindrance and high hole mobility, 1,2,4, 5-tetrafluorobenzene is introduced as an intermediate bridging unit through coupling reaction, a donor-acceptor-donor (D-A-D) type conjugated system is formed by coupling a fluorene end or a xanthene end of spirofluorene with 1,2,4, 5-tetrafluorobenzene, and the introduction of fluorine atoms can regulate and control the material energy level and band gap, so that a compound has deeper HOMO energy level, thereby improving the device efficiency.
Preferably, the organic hole transport material has the structure of
Any one of the following.
The second aspect of the present invention provides a method for preparing the organic hole transport material, which at least comprises the following steps: under inert atmosphere, carrying out Suzuki coupling reaction on 1,2,4, 5-tetrafluorobenzene, a spirofluorene xanthene derivative shown in a formula 2, an acid binding agent, a palladium catalyst and a phosphorus-containing ligand in an organic solvent to obtain the organic hole transport material;
wherein the structure of formula 2 is as follows:
R 1 and R is 2 Selected from H or F, wherein R 1 And R is 2 At least one hydrogen atom.
Preferably, the spirofluorene xanthene derivative is
Any one of the following.
Preferably, the phosphorus-containing ligand is any one of di-tert-butyl methyl phosphine tetrafluoroborate, 2-dicyclohexylphosphine-2 ',4',6' -triisopropyl biphenyl, tri-tert-butyl phosphine, 1' -binaphthyl-2, 2' -bisdiphenyl phosphine, tri (o-methylphenyl) phosphine or 4, 5-bisdiphenyl phosphine-9, 9-dimethyl xanthene.
Preferably, the acid binding agent is any one of calcium carbonate, cesium carbonate, sodium carbonate, potassium phosphate, potassium tert-butoxide or sodium tert-butoxide.
Preferably, the palladium catalyst is any one of tetrakis (triphenylphosphine) palladium, [1, 1-bis (diphenylphosphine) ferrocene ] palladium dichloride or palladium acetate.
Preferably, the molar ratio of the spirofluorene xanthene derivative to 1,2,4, 5-tetrafluorobenzene is 1:1-1.2.
Preferably, the molar ratio of the spirofluorene xanthene derivative to palladium catalyst is 5-50:1.
Preferably, the molar ratio of the spirofluorene xanthene derivative to the acid binding agent is 1:2-1.
Preferably, the molar ratio of the spirofluorene xanthene derivative to the phosphorus-containing ligand is 1:5-10.
Preferably, the temperature of the Suzuki coupling reaction is 80-120 ℃ and the reaction time is 12-48 h.
Preferably, after the Suzuki coupling reaction is finished, the system is quenched, extracted, dried and separated by column chromatography to obtain the organic hole transport material.
Preferably, the quencher is a saturated disodium edetate solution having a pH of 7.5-8.
Preferably, the extracting agent for extraction is dichloromethane.
Preferably, the drying is performed using anhydrous sodium sulfate.
Preferably, the eluent for column chromatography separation is petroleum ether and ethyl acetate with the volume ratio of 18-22:1.
Preferably, the preparation method of the spirofluorene xanthene derivative comprises the following steps:
under inert atmosphere, uniformly mixing 2-bromofluorenone, methane sulfonic acid and phenolic ligand, and then carrying out dehydration condensation reaction in an organic solvent to obtain the spirofluorene xanthene derivative.
Preferably, the phenolic ligand is any one of phenol, 4-fluorophenol or 3-fluorophenol.
Preferably, the molar ratio of the 2-bromofluorenone, the methane sulfonic acid and the phenolic ligand is 1-1.1:4-5:10-12.
Preferably, the dehydration condensation reaction temperature is 145-155 ℃ and the reaction time is 45-50 h.
Preferably, after the dehydration condensation reaction is finished, the reaction system is poured into absolute methanol, filtered and washed to obtain the spirofluorene xanthene derivative.
Preferably, the mass ratio of the anhydrous methanol to the total mass of the mixture of 2-bromofluorenone, methane sulfonic acid and phenolic ligand is 10 to 15:1.
A third aspect of the present invention provides a hole transport layer comprising the organic hole transport material.
A fourth aspect of the invention provides a perovskite solar cell comprising the hole transport layer.
Preferably, the perovskite solar cell sequentially comprises a conductive glass substrate layer, a titanium dioxide layer, a perovskite layer, a hole transport layer and a metal electrode.
Preferably, the preparation method of the hole transport layer comprises the following steps: the preparation method of the hole transport layer comprises the following steps: and dissolving the organic hole transport material in chlorobenzene to obtain an organic hole transport material solution, adding 4-tert-butylpyridine and lithium bistrifluoromethane sulfonyl imide into the organic hole transport material solution, uniformly mixing, and spin-coating the mixture to a perovskite layer to obtain a hole transport layer.
Preferably, the mass ratio of the organic hole transport material, the 4-tertiary butyl pyridine and the lithium bis (trifluoromethanesulfonyl) imide is 1-2:1.5-3.5:1.2-3.
Preferably, the concentration of the organic hole transport material solution is 30mg/mL-60mg/mL.
Preferably, the spin coating speed is 4000rpm-4100rpm, and the spin coating time is 22s-27s.
Preferably, the preparation method of the conductive glass substrate layer comprises the following steps: and (3) airing clean conductive glass, immersing the cleaned conductive glass in ultrapure water, acetone and isopropanol in sequence, carrying out ultrasonic cleaning, and carrying out ultraviolet-ozone treatment after blow-drying to obtain the conductive glass substrate layer.
Preferably, the ultrasonic cleaning time is 25min-35min.
Preferably, the drying is performed by adopting nitrogen, and the gas flow rate is 0.03L/min-0.05L/min.
Preferably, the ultraviolet-ozone treatment time is 20min-35min.
Preferably, the preparation method of the titanium dioxide layer comprises the following steps: and placing the titanium tetrachloride solution in the conductive glass substrate layer, drying, flushing, drying, and annealing to obtain the titanium dioxide layer.
Preferably, the drying temperature is 70-75 ℃ and the drying time is 1-2 h.
Preferably, the drying is performed by adopting nitrogen, and the gas flow is 0.03L/min-0.05L/min.
Preferably, the annealing temperature is 170-190 ℃ and the annealing time is 25-35 min.
Preferably, the thickness of the titanium dioxide layer is 35nm-45nm.
Preferably, the preparation method of the perovskite layer comprises the following steps: and carrying out ultraviolet-ozone treatment on the conductive glass base on which the titanium dioxide layer is deposited, coating the precursor solution on the titanium dioxide layer by using a spin coating method, and annealing after spin coating is finished to obtain the perovskite layer.
Preferably, the preparation method of the precursor solution comprises the following steps: uniformly mixing lead iodide, 1H-imidazole-1-yl (2-methyl-3-furyl) ketone and methyl iodized amine, and then dissolving the mixture in a mixed solution of anhydrous N, N-dimethylformamide and anhydrous dimethyl sulfoxide in a volume ratio of 3.8-4:1.
Preferably, the lead iodide is used in an amount of 1g to 5g
Preferably, the mass ratio of the lead iodide, the 1H-imidazole-1-yl (2-methyl-3-furyl) ketone and the methyl iodized amine is 20-25:15-17:3-4.
Preferably, the mass concentration of the precursor solution is 0.05g/mL-1mg/mL.
Preferably, the spin coating is performed by spin-coating the precursor at a speed of 1000rpm-1100rpm for 3s-6s, adjusting the spin-coating speed to 3800rpm-4200rpm, spin-coating for 8s-12s, dripping 130mL-170mL of chlorobenzene, and spin-coating for 30s to obtain the spin-coated perovskite layer.
Preferably, the annealing treatment temperature is 140-160 ℃ and the treatment time is 25-35 min.
Preferably, the preparation method of the metal electrode comprises the following steps: gold is deposited on the surface of the hole transport layer by thermal evaporation deposition to a thickness of 90nm to 110nm.
The organic hole transport material provided by the invention is applied to a perovskite solar cell, is simple and convenient to synthesize, has good solubility, stable performance, high quantum efficiency and high hole mobility, can effectively improve the photoelectric conversion efficiency and stability of the perovskite solar cell, and provides good reference significance for the research of high-performance hole transport materials.
Drawings
FIG. 1 is a diagram of the product of example 1 1 H NMR spectrum (500 MHz, CDCl) 3 ，ppm)；
FIG. 2 is a diagram of the product of example 1 13 C NMR spectrum (400 MHz, CDCl) 3 ，ppm)；
FIG. 3 is a diagram of the product of example 2 1 H NMR spectrum (500 MHz, CDCl) 3 ，ppm)；
FIG. 4 is a diagram of the product of example 2 13 C NMR spectrum (400 MHz, CDCl) 3 ，ppm)；
FIG. 5 is a thermogravimetric analysis and DSC test of the product of example 2;
FIG. 6 is a graph showing hole transport property test of the product of example 2;
FIG. 7 is an electrochemical cyclic voltammogram of the product of example 2;
FIG. 8 is a graph of J-V characteristics of the perovskite solar cell prepared as test example 4;
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides an organic hole transport material, which is prepared by the following specific process:
step one, under inert atmosphere, uniformly mixing 1g (3.86 mmol) of dry 2-bromofluorenone, 1mL (15.44 mmol) of methane sulfonic acid and 3.6g (38.6 mmol) of phenol, reacting for 48 hours at 150 ℃, adding 100mL of anhydrous methanol after the reaction is finished, filtering after ultrasonic treatment for 10min, washing a solid filter material with methanol, and drying to obtain 2-bromo-spiro [ fluorene-9, 9' -xanthene ];
step two, under inert atmosphere, 0.15g (1 mmol) of dried 1,2,4, 5-tetrafluorobenzene, 0.41g (1 mmol) of dried 2-bromo-spiro [ fluorene-9, 9' -xanthene ] and 0.28g (2 mmol) of potassium carbonate, 0.01g (0.05 mmol) of palladium acetate and 0.02g (0.1 mmol) of tetrafluoroboric acid di-tert-butyl methyl phosphonium salt are dissolved in 5mL of dried N, N-dimethylacetamide, after being uniformly mixed, the mixture is reacted for 24 hours at 105 ℃, after the reaction is finished, the system is poured into a saturated ethylenediamine tetraacetic acid disodium salt solution with the pH of 8 for quenching, dichloromethane is adopted for multiple extraction, 45mL of dichloromethane is taken each time, the organic phases are combined, the obtained organic phases are dried for 24 hours by using anhydrous sodium sulfate, the solvent is removed through filtration and column chromatography, petroleum ether and ethyl acetate with the volume ratio of 19:1 are taken as eluent, and the organic hole transport material is obtained, and the structure is as follows:
the yield thereof was found to be 77.9%.
Example 2
The embodiment provides an organic hole transport material, which is prepared by the following specific process:
step one, under inert atmosphere, uniformly mixing 1g (3.86 mmol) of dry 2-bromofluorenone, 1mL (15.44 mmol) of methane sulfonic acid and 4.33g (38.6 mmol) of 4-fluorophenol, reacting for 48 hours at 150 ℃, adding 100mL of anhydrous methanol after the reaction is finished, filtering after ultrasonic treatment for 10min, washing a solid filter material with methanol, and drying to obtain 2-bromo-3 ',6' -difluorospiro [ fluorene-9, 9' -xanthene ];
step two, under inert atmosphere, 0.15g (1 mmol) of dried 1,2,4, 5-tetrafluorobenzene, 0.45g (1 mmol) of dried 2-bromo-3 ',6' -difluorospiro [ fluorene-9, 9' -xanthene ], 0.28g (2 mmol) of potassium carbonate, 0.01g (0.05 mmol) of palladium acetate and 0.02g (0.1 mmol) of tetrafluoroboric acid di-tert-butyl methyl phosphonium salt are dissolved in 5mL of dried N, N-dimethylacetamide, after being uniformly mixed, the mixture is reacted for 24 hours at 105 ℃, after the reaction is finished, the system is poured into a saturated ethylenediamine tetraacetic acid disodium salt solution with the pH of 7.5 for quenching, dichloromethane is adopted for multiple extraction, 45mL of dichloromethane is taken each time, the organic phases are combined, the obtained organic phases are dried for 24 hours by anhydrous sodium sulfate, the filtration, the solvent is removed by reduced pressure distillation, the column chromatography is separated, petroleum ether and ethyl acetate with the volume ratio of 18:1 are taken as eluent, and the organic hole transport material is obtained, and the structure is as follows:
the yield thereof was found to be 62.5%.
Example 3
The embodiment provides an organic hole transport material, which is prepared by the following specific process:
step one, under inert atmosphere, uniformly mixing 1g (3.86 mmol) of dry 2-bromofluorenone, 1mL (15.44 mmol) of methane sulfonic acid and 4.33g (38.6 mmol) of 3-fluorophenol, reacting for 48 hours at 150 ℃, adding 100mL of anhydrous methanol after the reaction is finished, filtering after ultrasonic treatment for 10min, washing a solid filter material with methanol, and drying to obtain 2-bromo-2 ',7' -difluorospiro [ fluorene-9, 9' -xanthene ];
step two, under inert atmosphere, 0.15g (1 mmol) of dried 1,2,4, 5-tetrafluorobenzene, 0.45g (1 mmol) of dried 2-bromo-2 ',7' -difluorospiro [ fluorene-9, 9' -xanthene ], 0.28g (2 mmol) of potassium carbonate, 0.01g (0.05 mmol) of palladium acetate and 0.02g (0.1 mmol) of tetrafluoroboric acid di-tert-butyl methyl phosphonium salt are dissolved in 5mL of dried N, N-dimethylacetamide, after being uniformly mixed, the mixture is reacted for 24 hours at 105 ℃, after the reaction is finished, the system is poured into a 100mL of saturated ethylenediamine tetraacetic acid disodium salt solution with the pH of 8 for quenching, dichloromethane is adopted for multiple extraction, 45mL of dichloromethane is taken each time, the organic phases are combined, the obtained organic phases are dried for 24 hours by using anhydrous sodium sulfate, the solvent is filtered, the solvent is distilled off under reduced pressure, the volume ratio of 21:1 petroleum ether and ethyl acetate are taken as eluent, and the organic hole transport material is obtained, and the structure is as follows:
the yield thereof was found to be 53.4%.
Example 4
The embodiment provides an organic hole transport material, which is prepared by the following specific process:
compared with the embodiment 2, the embodiment replaces 4-fluorophenol with 2-fluorophenol to obtain the organic hole transport material, and the structure is as follows:
yield thereof was found to be 51.7%
Comparative example 1
The difference between this comparative example and example 1 is that 1,2,4, 5-tetrafluorobenzene is replaced with an equal amount of 9, 10-dibromoanthracene, and the other components and preparation process are unchanged, so that an organic hole transport material is obtained, and the structure is as follows:
the yield thereof was found to be 47.9%.
Test example 1
The perovskite solar cell was prepared by using the organic hole transport material obtained in example 1, and the specific contents are as follows:
s1, airing clean conductive glass, immersing the clean conductive glass in ultrapure water, acetone and isopropanol in sequence, respectively adopting an ultrasonic cleaning mode to clean the clean conductive glass for 30min, adopting nitrogen with the gas flow of 0.04L/min to blow-dry the clean conductive glass, and carrying out ultraviolet-ozone treatment for 25min after blow-drying to obtain a conductive glass substrate layer;
s2, placing titanium tetrachloride solution in the conductive glass substrate layer, drying for 1.5 hours at 70 ℃, flushing with ultrapure water, drying with nitrogen with the gas flow of 0.05L/min, and annealing for 30 minutes at 180 ℃ after drying to obtain a titanium dioxide layer with the thickness of 40 nm;
s3, carrying out ultraviolet-ozone treatment on the conductive glass substrate on which the titanium dioxide layer is deposited for 15min, uniformly mixing 2g of lead iodide, 1.5g of 1H-imidazol-1-yl (2-methyl-3-furyl) ketone and 0.4g of methyl iodized amine, and then dissolving the mixture in 50mL of a mixed solution of anhydrous N, N-dimethylformamide and anhydrous dimethyl sulfoxide in a volume ratio of 4:1 to obtain a precursor solution. Uniformly dripping 50mL of precursor solution on the prepared compact titanium dioxide layer, spin-coating at 1000rpm for 5s, adjusting to 4000rpm, spin-coating for 10s, rapidly dripping 150mL of chlorobenzene solution on the surface, and spin-coating for 30s again; after spin coating is completed, placing the conductive glass substrate on a heating plate, and annealing for 30min at the set temperature of 150 ℃ to obtain a perovskite layer;
s4, dissolving 0.3g of organic hole transport material in 10mL of chlorobenzene, adding 0.45g of 4-tert-butylpyridine and 0.4g of lithium bistrifluoromethane sulfonyl imide into the solution, uniformly mixing, and coating the solution on a perovskite layer at a spin coating speed of 4000rpm to form a hole transport layer, wherein the concentration of the organic hole transport material solution is 30mg/mL;
and S5, depositing gold on the surface of the hole transport layer through thermal evaporation deposition, wherein the thickness is 100nm, and obtaining the perovskite solar cell.
Test example 2
Preparing a perovskite solar cell by using the organic hole transport material obtained in example 1, wherein S4, 0.45g of the organic hole transport material is dissolved in 10mL of chlorobenzene, 0.7g of 4-tertiary butyl pyridine and 0.5g of lithium bistrifluoromethane sulfonyl imide are added into the solution, the solution is uniformly mixed and then coated on a perovskite layer at a spin coating speed of 4000rpm, and the hole transport layer is formed, wherein the concentration of the organic hole transport material solution in example 1 is 45mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 3
Preparing a perovskite solar cell by using the organic hole transport material obtained in example 1, wherein S4, 0.6g of the organic hole transport material is dissolved in 10mL of chlorobenzene, 0.9g of 4-tertiary butyl pyridine and 1g of lithium bistrifluoromethane sulfonyl imide are added into the solution, the solution is uniformly mixed and then coated on a perovskite layer at a spin coating speed of 4000rpm, and the solution of the organic hole transport material in example 1 has a concentration of 60mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 4
The organic hole transport material obtained in example 2 was used to replace the organic hole transport material obtained in test example 1, in the preparation of perovskite solar cell, wherein the concentration of the organic hole transport material solution in example 2 was 30mg/mL, and the specific preparation process was the same as that in test example 1, and will not be described here again.
Test example 5
The organic hole transport material obtained in example 2 was used in place of the organic hole transport material obtained in test example 1 to prepare a perovskite solar cell, wherein S4, 0.45g of the organic hole transport material was dissolved in 10mL of chlorobenzene, 0.7g of 4-t-butylpyridine and 0.5g of lithium bistrifluoromethylsulfonylimide were added thereto, and after mixing uniformly, the mixture was applied to a perovskite layer at a spin coating speed of 4000rpm, to form a hole transport layer, wherein the concentration of the organic hole transport material solution of example 2 was 45mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 6
The organic hole transport material obtained in example 2 was used to replace the organic hole transport material obtained in test example 1 for preparing a perovskite solar cell, wherein S4, 0.6g of the organic hole transport material was dissolved in 10mL of chlorobenzene, 0.9g of 4-tert-butylpyridine and 1g of lithium bistrifluoromethylsulfonylimide were added thereto, and after being uniformly mixed, the mixture was coated on a perovskite layer at a spin coating speed of 4000rpm, and the hole transport layer was formed, wherein the concentration of the organic hole transport material solution in example 2 was 60mg/mL, and other preparation processes were the same as in test example 1 and will not be repeated here.
Test example 7
The organic hole transport material obtained in example 3 was used to replace the organic hole transport material obtained in test example 1, in the preparation of perovskite solar cell, wherein the concentration of the organic hole transport material solution in example 3 was 30mg/mL, and the specific preparation process was the same as that in test example 1, and will not be repeated here.
Test example 8
The organic hole transport material obtained in example 3 was used to replace the organic hole transport material obtained in test example 1 for preparing a perovskite solar cell, wherein S4, 0.45g of the organic hole transport material was dissolved in 10mL of chlorobenzene, 0.7g of 4-tert-butylpyridine and 0.5g of lithium bistrifluoromethylsulfonylimide were added thereto, and after being uniformly mixed, the mixture was coated on a perovskite layer at a spin coating speed of 4000rpm, and the concentration of the organic hole transport material solution of example 3 was 45mg/mL, and the specific preparation process was the same as in test example 1 and will not be repeated here.
Test example 9
The organic hole-transporting material obtained in example 3 was used to prepare a perovskite solar cell instead of the organic hole-transporting material obtained in test example 1, wherein S4, 0.6g of the organic hole-transporting material was dissolved in 10mL of chlorobenzene, 0.9g of 4-t-butylpyridine and 1g of lithium bistrifluoromethylsulfonylimide were added thereto, and after mixing uniformly, the mixture was applied to a perovskite layer at a spin coating speed of 4000rpm, and the hole-transporting layer was formed, wherein the concentration of the organic hole-transporting material solution of example 3 was 60mg/mL, and the specific preparation process was the same as that of test example 1 and will not be repeated here.
Test example 10
The organic hole transport material obtained in example 4 was used to replace the organic hole transport material obtained in test example 1, in the preparation of perovskite solar cell, wherein the concentration of the organic hole transport material solution in example 4 was 30mg/mL, and the specific preparation process was the same as that in test example 1, and will not be repeated here.
Test example 11
The organic hole transport material obtained in example 4 was used to replace the organic hole transport material obtained in test example 1 for preparing a perovskite solar cell, wherein S4, 0.45g of the organic hole transport material was dissolved in 10mL of chlorobenzene, 0.7g of 4-tert-butylpyridine and 0.5g of lithium bistrifluoromethylsulfonylimide were added thereto, and after being uniformly mixed, the mixture was coated on a perovskite layer at a spin coating speed of 4000rpm, and the concentration of the organic hole transport material solution of example 4 was 45mg/mL, and the specific preparation process was the same as in test example 1 and will not be repeated here.
Test example 12
The organic hole-transporting material obtained in example 4 was used to prepare a perovskite solar cell instead of the organic hole-transporting material obtained in test example 1, wherein S4, 0.6g of the organic hole-transporting material was dissolved in 10mL of chlorobenzene, 0.9g of 4-t-butylpyridine and 1g of lithium bistrifluoromethylsulfonylimide were added thereto, and after mixing uniformly, the mixture was applied to a perovskite layer at a spin coating speed of 4000rpm, and the hole-transporting layer was formed, wherein the concentration of the organic hole-transporting material solution of example 4 was 60mg/mL, and the specific preparation process was the same as that of test example 1 and will not be repeated here.
Test example 13
The perovskite solar cell was prepared by using commercially available Spiro-ome tad as a hole transporting material instead of the sample obtained in example 1, and the specific preparation process was the same as that of test example 1, and will not be repeated here.
Test example 14
The organic hole transport material obtained in comparative example 1 was used to replace the organic hole transport material obtained in test example 1, in the preparation of perovskite solar cell, wherein the concentration of the organic hole transport material solution in comparative example 1 was 30mg/mL, and the specific preparation process was the same as that in test example 1, and will not be described here again.
Test example 15
The organic hole-transporting material obtained in comparative example 1 was used in place of the organic hole-transporting material obtained in test example 1 to prepare a perovskite solar cell, wherein S4, 0.45g of the organic hole-transporting material was dissolved in 10mL of chlorobenzene, 0.7g of 4-t-butylpyridine and 0.5g of lithium bistrifluoromethylsulfonylimide were added thereto, and after being uniformly mixed, the mixture was coated on a perovskite layer at a spin coating speed of 4000rpm, and a hole-transporting layer was formed, wherein the concentration of the organic hole-transporting material solution of comparative example 1 was 45mg/mL, and the specific preparation process was the same as that of test example 1 and will not be repeated here.
Test example 16
The organic hole-transporting material obtained in comparative example 1 was used in place of the organic hole-transporting material obtained in test example 1 to prepare a perovskite solar cell, wherein S4, 0.6g of the organic hole-transporting material was dissolved in 10mL of chlorobenzene, 0.9g of 4-t-butylpyridine and 1g of lithium bistrifluoromethylsulfonylimide were added thereto, and after mixing uniformly, the mixture was applied to a perovskite layer at a spin coating speed of 4000rpm, to form a hole-transporting layer, wherein the concentration of the organic hole-transporting material solution of comparative example 1 was 60mg/mL, and the specific preparation process was the same as that of test example 1 and will not be repeated here.
Test results
The battery performance data of each test example is shown in table 1.
Table 1 table of performance data for perovskite solar cell preparation for each test example
As can be seen from Table 1, the organic hole transport material provided by the invention can show the photoelectric properties which are relatively similar to those obtained by the Sprio-OMeTAD material, especially the battery device obtained in test example 5, and the performance of the battery device prepared by the Sprio-OMeTAD material is the closest. However, compared with Sprio-OMeTAD materials, the organic hole transport material prepared by the method has the advantages of low raw material price, simpler synthesis mode, fewer synthesis steps, easier purification and the like, can meet the commercial application, and shows larger cost advantage in large-scale production.
As can be seen from fig. 3 and 4, the thermal decomposition temperature of the organic hole transport material obtained in example 2 at the state of 5% weight loss is 416 ℃, and also exceeds 400 ℃, which indicates that the material has good thermal stability and can well meet the basic requirement as a hole transport material. It is worth mentioning that the organic hole transport material obtained in example 2 has no obvious endothermic or exothermic process within 100 ℃, which indicates that the material has good crystallization resistance, higher than the glass transition temperature of common hole transport materials, and good thermal stability.
Using table 1 and the energy level calculation formula (E HOMO = - (eox+4.4) eV, eox is the starting potential), the HOMO level of the organic hole transporting material obtained in example 2 is-5.27 eV, the lumo level is-2.31 eV, the energy level is very close to the perovskite layer, not only holes can be transported, but also electrons can be effectively blocked from passing through, indicating that introduction of fluorine atoms having electron withdrawing properties into the molecular structure can indeed lower the HOMO level of the compound. Reducing the energy gap between the HOMO level of the hole transporting material and the maximum value of the perovskite valence band is advantageous for increasing the open circuit voltage and extraction of holes, so that a higher open circuit voltage may be obtained for the fluorinated product. And further higher device efficiency can be obtained.
Test example 4 the device was tested by means of space charge limited current method after fabrication of the device, the hole mobility of the compound was tested by means of space charge limited current method (SCLC), the hole mobility test was indicative of the hole transporting ability of the compound, the higher the hole mobility, the better the hole transporting ability, the hole mobility of the organic hole transporting material obtained in example 2 was calculated to be 2.31X10 -4 cm 2 V -1 S -1 。
In conclusion, the invention designs and synthesizes an organic hole transport material, adopts a simple and convenient synthesis mode of direct arylation, and adopts a simple and convenient column chromatography mode to directly purify and obtain a product with higher purity, wherein the central carbon atom of the spirofluorene molecule is sp 3 The hybridization, so that the spirofluorene molecular space structure presents a non-planar state, thereby reducing the formation of material aggregates to a certain extent, avoiding the quenching of the luminescence of the material, and simultaneously reducing the molecular accumulation to ensure that the material has good solubility, thus obtaining better film forming propertyThe good hole transport layer reduces a plurality of defects of fluorene materials, and simultaneously can improve the thermal stability of the hole transport material, thereby improving the stability of the device. The fluorene structure and the fluorobenzene structure have good thermodynamic property, stable spectral property and good stability, and finally the hole transport material with excellent device performance is obtained.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. An organic hole transport material characterized by: the structure of the organic hole transport material is shown as formula 1:
R 1 、R 2 、R 3 selected from H or F, wherein R 1 、R 2 、R 3 At least two hydrogen atoms.
2. The organic hole transport material of claim 1, wherein: the organic hole transport material has the structure that
Any one of the following.
3. A method for producing the organic hole transport material according to claim 1, characterized in that: at least comprises the following steps: under inert atmosphere, carrying out Suzuki coupling reaction on 1,2,4, 5-tetrafluorobenzene, a spirofluorene xanthene derivative shown in a formula 2, an acid binding agent, a palladium catalyst and a phosphorus-containing ligand in an organic solvent to obtain the organic hole transport material;
wherein the structure of formula 2 is as follows:
R 1 and R is 2 Selected from H or F, wherein R 1 And R is 2 At least one hydrogen atom.
4. The method for producing an organic hole transport material according to claim 3, wherein: the spirofluorene xanthene derivative is
Any one of them; and/or
The phosphorus-containing ligand is any one of di-tert-butyl methyl phosphine tetrafluoroborate, 2-dicyclohexylphosphine-2 ',4',6' -triisopropyl biphenyl, tri-tert-butyl phosphine, 1' -binaphthyl-2, 2' -bisdiphenylphosphine, tri (o-methylphenyl) phosphine or 4, 5-bisdiphenylphosphine-9, 9-dimethyl xanthene; and/or
The acid binding agent is any one of calcium carbonate, cesium carbonate, sodium carbonate, potassium phosphate, potassium tert-butoxide or sodium tert-butoxide; and/or
The palladium catalyst is any one of tetra (triphenylphosphine) palladium, [1, 1-bis (diphenylphosphine) ferrocene ] palladium dichloride or palladium acetate; and/or
The molar ratio of the spirofluorene xanthene derivative to the 1,2,4, 5-tetrafluorobenzene is 1:1-1.2; and/or
The molar ratio of the spirofluorene xanthene derivative to the palladium catalyst is 5-50:1; and/or
The molar ratio of the spirofluorene xanthene derivative to the acid binding agent is 1:2-10; and/or
The molar ratio of the spirofluorene xanthene derivative to the phosphorus-containing ligand is 1:5-10.
5. The method for producing an organic hole transport material according to any one of claims 3 or 4, wherein: the preparation method of the spirofluorene xanthene derivative comprises the following steps:
under inert atmosphere, uniformly mixing 2-bromofluorenone, methane sulfonic acid and phenolic ligand, and then carrying out dehydration condensation reaction in an organic solvent to obtain the spirofluorene xanthene derivative.
6. The method for producing an organic hole transport material according to claim 5, wherein: the phenolic ligand is any one of phenol, 4-fluorophenol or 3-fluorophenol; and/or
The molar ratio of the 2-bromofluorenone to the methane sulfonic acid to the phenolic ligand is 1-1.1:4-5:10-12.
7. A hole transport layer characterized by: comprising the organic hole transport material according to any one of claims 1 or 2.
8. A perovskite solar cell, characterized by: comprising the hole transport layer of claim 7.
9. The perovskite solar cell of claim 8, wherein: the preparation method of the hole transport layer comprises the following steps: and dissolving the organic hole transport material in chlorobenzene to obtain an organic hole transport material solution, adding 4-tert-butylpyridine and lithium bistrifluoromethane sulfonyl imide into the organic hole transport material solution, uniformly mixing, and spin-coating the mixture to a perovskite layer to obtain a hole transport layer.
10. The perovskite solar cell of claim 9, wherein: the mass ratio of the organic hole transport material to the 4-tert-butylpyridine to the lithium bis (trifluoromethanesulfonyl) imide is 1-2:1.5-3.5:1.2-3; and/or
The concentration of the organic hole transport material solution is 30mg/mL-60mg/mL.
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