CN117050069A - Organic hole transport material and preparation method and application thereof - Google Patents
Organic hole transport material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117050069A CN117050069A CN202311019055.2A CN202311019055A CN117050069A CN 117050069 A CN117050069 A CN 117050069A CN 202311019055 A CN202311019055 A CN 202311019055A CN 117050069 A CN117050069 A CN 117050069A
- Authority
- CN
- China
- Prior art keywords
- hole transport
- transport material
- dibromo
- organic hole
- acid
- Prior art date
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- Pending
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- 239000000463 material Substances 0.000 title claims abstract description 148
- 230000005525 hole transport Effects 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims abstract description 6
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 48
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- CWGRCRZFJOXQFV-UHFFFAOYSA-N 2,7-dibromofluoren-9-one Chemical compound C1=C(Br)C=C2C(=O)C3=CC(Br)=CC=C3C2=C1 CWGRCRZFJOXQFV-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- UPJLZKCEPFAKSH-UHFFFAOYSA-N 2',7'-dibromo-9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC(Br)=CC=C1C1=CC=C(Br)C=C12 UPJLZKCEPFAKSH-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 238000004528 spin coating Methods 0.000 claims description 21
- CYGGERDBQBUNDY-UHFFFAOYSA-N 2,7-dibromospiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC(Br)=CC=C2C2=CC=C(Br)C=C21 CYGGERDBQBUNDY-UHFFFAOYSA-N 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical group [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- -1 tri-tert-butyl phosphine tetrafluoroborate Chemical group 0.000 claims description 9
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 8
- KLECYOQFQXJYBC-UHFFFAOYSA-N 1-fluoro-2-phenylbenzene Chemical group FC1=CC=CC=C1C1=CC=CC=C1 KLECYOQFQXJYBC-UHFFFAOYSA-N 0.000 claims description 7
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical group [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 5
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229940000207 selenious acid Drugs 0.000 claims description 3
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 claims 1
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 abstract description 7
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 abstract description 7
- 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 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 74
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 26
- 239000011521 glass Substances 0.000 description 24
- 239000011799 hole material Substances 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 16
- 238000000137 annealing Methods 0.000 description 14
- 238000004440 column chromatography Methods 0.000 description 14
- 239000012266 salt solution Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000012043 crude product Substances 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 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
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 8
- 238000004770 highest occupied molecular orbital Methods 0.000 description 7
- 229910017053 inorganic salt Inorganic materials 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 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 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- 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 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 125000003003 spiro group Chemical group 0.000 description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- HRURXKIZWNSHQB-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;cobalt(2+) Chemical compound [Co+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HRURXKIZWNSHQB-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000008151 electrolyte solution Substances 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
- 150000003949 imides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- YFGHCGITMMYXAQ-UHFFFAOYSA-N 2-[(diphenylmethyl)sulfinyl]acetamide Chemical compound C=1C=CC=CC=1C(S(=O)CC(=O)N)C1=CC=CC=C1 YFGHCGITMMYXAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229960001165 modafinil Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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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 takes spirobifluorene and spirofluorene xanthene as skeletons, carbazolyl is respectively introduced on the spirobifluorene as a terminal group, phenoxazinyl is introduced on the spirofluorene xanthene as a terminal group, two types of compounds are formed, pi-conjugated structures can be formed, wherein the carbazolyl and the phenoxazinyl are respectively used as the terminal groups to regulate and control the energy level and band gap of the spirobifluorene or spirofluorene xanthene, and the device efficiency is improved; furthermore, the organic hole transport material provided by the invention is applied to perovskite solar cell devices, so that not only can the hole mobility of the devices be improved, but also the devices have excellent long-term stability, the synthesis is simple and convenient, the product solubility is good, and more ideas are provided for the preparation of perovskite solar cells.
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
The device composition of Perovskite Solar Cells (PSCs) mainly comprises: the transparent conductive substrate, the electron transport layer, the perovskite light absorption layer, the hole transport layer and the metal back electrode, wherein the hole transport layer plays a key role in extracting and transporting photo-generated holes from perovskite to the contact electrode and inhibiting carrier recombination. Although perovskite battery devices without a hole transport layer have been proposed by researchers, their photoelectric conversion efficiency is low, and thus hole transport materials are still essential for efficient perovskite solar cells.
Currently, the most widely used efficient hole transport material in the perovskite solar field is 2,2', 7' tetrakis [ N, N bis (4 methoxyphenyl) amino ]9,9' spirobifluorene (spiratad). However, the preparation cost of the Spiro ome tad molecule is high, and the perovskite solar cell prepared from the Spiro ome tad molecule is poor in stability and low in photoelectric conversion efficiency, so that the commercialization of the Spiro ome tad molecule is limited in wide application range. Therefore, based on molecular engineering, it is important to develop a novel hole transport material which is efficient, stable and low in cost and can replace Spiro OMeTA D.
Disclosure of Invention
In view of the above, the invention provides an organic hole transport material, and a preparation method and application thereof. The organic hole transport material provided by the invention is applied to perovskite solar cell devices, not only can the hole mobility of the devices be improved, but also the devices have excellent long-term stability, the synthesis is simple and convenient, the product solubility is good, and more ideas are provided for the preparation of perovskite solar cells.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the invention provides an organic hole transport material, the structure of which is shown as formula 1 or formula 2:
wherein R is 1 Is carbazolyl, R 2 Is a phenoxazinyl group.
Compared with the prior art, the organic hole transport material provided by the invention has the advantages that spirobifluorene and spirofluorene xanthene are taken as skeletons, carbazolyl is respectively introduced on spirobifluorene as a terminal group, phenoxazinyl is introduced on spirofluorene xanthene as a terminal group, compounds shown in formula 1 and formula 2 are formed, pi-conjugated structures can be formed, wherein the carbazolyl and the phenoxazinyl can be used as the terminal groups to respectively regulate and control the energy level and band gap of spirobifluorene or spirofluorene xanthene, and the device efficiency is improved; furthermore, the organic hole transport material of the formula 1 or the formula 2 provided by the invention can be applied to perovskite solar cell devices, so that not only can the hole mobility of the devices be improved, but also the devices have excellent long-term stability, the synthesis is simple and convenient, the product solubility is better, and more ideas are provided for the preparation of perovskite solar cells.
Preferably, the organic hole transport material is
Preferably, the organic hole transport material is
The invention provides a preparation method of the organic hole transport material, which comprises the following steps:
step 1, uniformly mixing 2, 7-dibromo-9-fluorenone, 2-fluorobiphenyl and a catalyst in a solvent under inert atmosphere, performing a first reaction at 38-40 ℃, adding inorganic acid for quenching reaction, separating an organic phase, performing reduced pressure distillation on the organic phase, adding the obtained first product into acetic acid, performing a second reaction at 110-130 ℃, filtering, and purifying to obtain 2, 7-dibromo-9, 9' -spirobifluorene;
and 2, uniformly mixing carbazole, a copper catalyst, an acid binding agent, 18-crown ether-6 and a solvent in an inert atmosphere, then adding the 2, 7-dibromo-9, 9' -spirobifluorene, reacting at 150-170 ℃, adding water for quenching, filtering, drying and purifying to obtain the compound shown in the formula 1.
Preferably, in step 1, the catalyst is lithium metal.
Preferably, in step 1, the solvent is tetrahydrofuran.
Preferably, in step 1, the inorganic acid is at least one of sulfuric acid, hydrochloric acid, nitric acid or carbonic acid.
Preferably, in step 1, the time of the first reaction is 20h-26h.
Preferably, in step 1, the time of the second reaction is 20h-26h.
Preferably, in the step 1, the molar ratio of the 2, 7-dibromo-9-fluorenone to the 2-fluorobiphenyl is 1 (1-3).
Preferably, in the step 1, the molar ratio of the 2, 7-dibromo-9-fluorenone to the catalyst is 1 (1-3).
Preferably, in the step 1, the mass volume ratio of the 2, 7-dibromo-9-fluorenone to the solvent is 1g (5-6) mL.
Preferably, in the step 1, the molar ratio of the 2, 7-dibromo-9-fluorenone to the inorganic acid is 1 (15-25).
Preferably, in step 1, the mass to volume ratio of the first product to acetic acid is 1g (5-6) mL.
Preferably, in step 2, the copper catalyst is at least one of copper iodide, copper sulfate, copper carbonate or copper hydroxide.
Preferably, in step 2, the acid binding agent is at least one of potassium carbonate, cesium carbonate, sodium carbonate, potassium tert-butoxide, sodium tert-butoxide or potassium phosphate.
Preferably, in step 2, the solvent is dimethylacetamide.
Preferably, in the step 2, the molar ratio of the 2, 7-dibromo-9, 9' -spirobifluorene to carbazole is 1 (1-3).
Preferably, in step 2, the molar ratio of the 2, 7-dibromo-9, 9' -spirobifluorene to the copper catalyst is (15-20): 1.
Preferably, in the step 2, the molar ratio of the 2, 7-dibromo-9, 9' -spirobifluorene to the acid-binding agent is 1 (1-4).
Preferably, in step 2, the molar ratio of 2, 7-dibromo-9, 9' -spirobifluorene to 18-crown-6 is 1 (0.1-0.5).
Preferably, in the step 2, the mass volume ratio of the 2, 7-dibromo-9, 9' -spirobifluorene and the solvent is 1g (5-6) mL.
Preferably, in the step 2, the mass volume ratio of the 2, 7-dibromo-9, 9' -spirobifluorene to the water is 1g (5-11) mL.
Preferably, in step 2, the reaction time is 20h-26h.
Preferably, the preparation method of the compound shown in the formula 2 comprises the following steps:
step a, under inert atmosphere, phenol is dissolved in 2, 7-dibromo-9-fluorenone, then acid solution is added for reaction at 130-160 ℃, organic alcohol is added into reaction liquid for ultrasonic reaction after the reaction is completed, and the reaction liquid is filtered and washed to obtain 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ];
and b, adding the 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ], phenoxazine, an acid binding agent, a palladium catalyst and borate into a solvent in an inert atmosphere, reacting at 150-170 ℃, filtering, washing and purifying to obtain the compound shown in the formula 2.
Preferably, in the step a, the acid solution is at least one of sulfuric acid, selenious acid, methylsulfonic acid or oxalic acid.
Preferably, in step a, the organic alcohol is anhydrous methanol.
Preferably, in the step a, the molar ratio of the 2, 7-dibromo-9-fluorenone to the phenol is 1 (8-10).
Preferably, in the step a, the molar ratio of the 2, 7-dibromo-9-fluorenone to the acid solution is 1 (4-5).
Preferably, in step a, the molar ratio of 2, 7-dibromo-9-fluorenone to organic alcohol is 1 (148-149).
Preferably, in step a, the reaction time is 12h-48h.
Preferably, in the step a, the temperature of the ultrasonic reaction is 20-30 ℃, and the time of the ultrasonic reaction is 8-10 min.
Preferably, in the step b, the acid binding agent is sodium tert-butoxide.
Preferably, in step b, the palladium catalyst is tris (dibenzylideneacetone) dipalladium.
Preferably, in step b, the borate is tri-tert-butylphosphine tetrafluoroborate.
Preferably, in step b, the solvent is toluene.
Preferably, in step b, the molar ratio of 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] to phenoxazine is 1 (4-7).
Preferably, in the step b, the molar ratio of the 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] to the acid binding agent is 1 (5-10).
Preferably, in step b, the molar ratio of the 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] to the palladium catalyst is 1 (0.0012-0.0015).
Preferably, in step b, the molar ratio of 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] to borate is 1 (0.0085-0.0088).
Preferably, in the step b, the mass-volume ratio of the 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] to the solvent is 1g (20-21) mL.
Preferably, in step b, the reaction time is 12h-48h.
The invention provides a hole transport layer comprising the organic hole transport material.
The invention also provides a perovskite solar cell, which comprises the hole transport layer.
Preferably, the perovskite solar cell sequentially comprises a conductive glass substrate layer, a tin dioxide layer, a perovskite layer, a passivation layer, a hole transport layer and a metal electrode.
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 nitrogen.
Preferably, the ultraviolet-ozone treatment time is 25min-35min.
The preparation method of the tin dioxide layer comprises the following steps: and (3) placing the tin dioxide solution on the conductive glass substrate layer, annealing, and then carrying out ultraviolet-ozone treatment and annealing treatment to obtain the tin dioxide layer.
Preferably, the annealing temperature is 115-125 ℃ and the annealing time is 30-40 min.
Preferably, the thickness of the tin dioxide layer is 50nm-100nm.
Preferably, the preparation method of the perovskite layer comprises the following steps: and carrying out ultraviolet-ozone treatment on the conductive glass substrate on which the tin dioxide layer is deposited, spin-coating an inorganic salt solution on the tin dioxide layer, annealing, spin-coating an organic salt solution, and annealing to obtain the perovskite layer.
Preferably, the preparation method of the inorganic salt solution comprises the following steps: and dissolving lead iodide in the mixed solution of anhydrous N, N-dimethylformamide and anhydrous dimethyl sulfoxide in the volume ratio of (8.8-9.2): 1.
Preferably, the mass volume ratio of the lead iodide to the mixed solution is (6-8) g/1 mL.
Preferably, the preparation method of the organic salt solution comprises the following steps: the formamidine hydroiodic acid salt, methyl amine chloride and methyl amine iodide are dissolved in isopropanol to obtain the product.
Preferably, the mass volume ratio of the formamidine hydroiodidate, the methyl amine chloride, the methyl amine iodide and the isopropanol is 1g (0.2-0.3 g) (0.05-0.1 g) (20-25 mL).
Preferably, the conditions for spin coating the inorganic salt solution are as follows: spin coating at 1400rpm-1600rpm for 25s-30s.
Preferably, the inorganic salt solution is spin-coated on the tin dioxide layer, the annealing temperature is 65-75 ℃, and the annealing time is 0.5-1.5 min.
Preferably, when the organic salt solution is spin-coated, the spin-coating conditions are as follows: spin coating at 1750rpm-1850rpm for 25s-35s.
Preferably, the organic salt solution is spin-coated, and annealing is performed when the air humidity is controlled to be 35% -45%, wherein the annealing temperature is 145 ℃ -155 ℃, and the annealing time is 10min-20min.
Preferably, the preparation method of the passivation layer comprises the following steps: and (3) dissolving phenethyl iodized amine in isopropanol, and then spin-coating the solution on a conductive glass substrate containing a tin dioxide layer and a perovskite layer to obtain a passivation layer.
Preferably, the mass volume ratio of the phenethyl iodinated amine and the isopropanol is 1g (400-650) mL.
Preferably, the spin coating conditions are as follows: spin coating at 4500rpm-5500rpm for 25s-35s.
The preparation method of the hole transport layer provided by the invention comprises the following steps: dissolving the organic hole transport material in chlorobenzene to obtain an organic hole transport material solution, adding 4-tert-butylpyridine, acetonitrile solution containing lithium bistrifluoromethylsulfonyl imide and acetonitrile solution containing cobalt bistrifluoromethylsulfonyl imide into the organic hole transport material solution, uniformly mixing, and spin-coating to a perovskite layer to obtain a hole transport layer;
Wherein the concentration of the organic hole transport material solution is 10mg/mL-30mg/mL;
the concentration of the acetonitrile solution containing the lithium bis (trifluoromethanesulfonyl) imide is 510mg/mL-530mg/mL;
the concentration of the acetonitrile solution containing cobalt bistrifluoromethylsulfonylimide is 290mg/mL-310mg/mL;
wherein the cobalt bistrifluoromethylsulfonylimide is Co-TFSI.
The volume ratio of the organic hole transport material solution, 4-tert-butylpyridine, acetonitrile solution containing lithium bis (trifluoromethanesulfonyl) imide and acetonitrile solution containing cobalt bis (trifluoromethanesulfonyl) imide is 1 (51-59): 32-38): 10-15.
Preferably, the spin coating conditions are as follows: spin-coating at 3950rpm-4050rpm for 28s-32s.
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 110nm to 130nm.
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 and stable performance, has 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 cyclic voltammogram of SBF-KZ prepared in example 1;
FIG. 2 is a differential scanning calorimetry plot of SBF-KZ prepared in example 1;
FIG. 3 is a thermogravimetric analysis graph of SBF-KZ prepared in example 1;
FIG. 4 is a graph of hole mobility for SBF-KZ prepared in example 1;
FIG. 5 is a schematic view showing the water contact angle of SBF-KZ prepared in example 1;
FIG. 6 is a graph of current density versus voltage for perovskite batteries prepared by test examples 1-3;
FIG. 7 is a graph of current density versus voltage for the perovskite cell prepared by test example 2 under forward reverse bias;
FIG. 8 is an EQE graph of SBF-KZ prepared in example 1;
FIG. 9 is a graph of the steady state output power of SBF-KZ prepared in example 1;
FIG. 10 is a graph of stability testing of perovskite batteries prepared by test example 2;
FIG. 11 is a cyclic voltammogram of SFX-FEQ prepared in example 4;
FIG. 12 is a differential scanning calorimetry plot of SFX-FEQ prepared in example 4;
FIG. 13 is a thermogravimetric analysis plot of SFX-FEQ prepared in example 4;
FIG. 14 is a hole mobility graph of SFX-FEQ prepared in example 4;
FIG. 15 is a schematic view of water contact angle of SFX-FEQ prepared in example 4;
FIG. 16 is a graph of current density versus voltage for perovskite batteries prepared by test examples 10-12;
FIG. 17 is a graph of current density versus voltage obtained in forward reverse bias for the perovskite cell prepared by test example 11;
FIG. 18 is an EQE graph of SFX-FEQ prepared in example 4;
FIG. 19 is a steady state output power plot of SFX-FEQ prepared in example 4;
FIG. 20 is an electrochemical impedance plot of perovskite batteries prepared by test example 2 and test example 11;
fig. 21 is a device stability test chart of the perovskite battery prepared in example 2;
fig. 22 is a graph of performance tests of the perovskite battery prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment provides an organic hole transport material, which is prepared by the following specific process:
step 1, uniformly mixing 2, 7-dibromo-9-fluorenone (5 mmol,1.69 g) and 2-fluorobiphenyl (5.5 mmol,0.95 g) in tetrahydrofuran (8.45 mL) under inert atmosphere, then adding a lithium metal catalyst (5 mmol,0.04 g) for 3 times, continuously stirring and starting heating, reacting for 26 hours at 40 ℃, closing a heater for standing after the reaction is finished, adding sulfuric acid (75 mmol,7.36 g) for quenching reaction after the system is completely cooled, fully mixing, standing for separating an organic phase, removing redundant solvent by using a rotary evaporator, dissolving the obtained first product in acetic acid for reacting for 20 hours at 130 ℃, filtering, and preparing the solution with the volume ratio of 10:1, as a column chromatography eluent, separating by column chromatography to obtain 2, 7-dibromo-9, 9' -spirobifluorene with the yield of 87.2%; wherein the mass to volume ratio of the first product to acetic acid is 1g to 5ml;
Step 2, carbazole (1 mol,167.21 g), copper iodide (0.07 mol,13.40 g), potassium carbonate (4 mol,552.82 g), 18-crown ether-6 (0.1 mol,26.43 g) and dimethylacetamide (2370.95 mL) are uniformly mixed in an inert atmosphere, a nitrogen gas is pumped for three times, a system is closed, the mixture is placed in an oil bath kettle and stirred at a constant speed, heating and refluxing are carried out for 2 hours, 2, 7-dibromo-9, 9' -spirobifluorene (1 mol,474.19 g) is added, reaction is carried out for 20 hours at 170 ℃, heating is closed after the reaction is finished, water quenching is carried out after the system is fully cooled, filtration and drying are carried out, a mixed solution of dichloromethane and n-hexane with a volume ratio of 1:4 is prepared as a column chromatography eluent, the column chromatography is separated to obtain a crude product, and the crude product is subjected to recrystallization and purification to obtain an organic hole transport material (SBF-KZ), the yield is 88.7%, and the structure is as follows.
1 H NMR(500MHz,Chloroform-d)δ8.11(d,J＝8.1Hz, 2 H),8.06(dt,J＝7.8,1.0Hz, 4 H),7.75(dt,J＝7.7,0.9Hz, 2 H),7.64(dd,J＝8.0,1.9Hz, 2 H),7.38-7.27(m, 6 H),7.24-7.16(m, 10 H),7.02-6.96(m, 4 H).
13 C NMR(126MHz,Chloroform-d)δ128.18(d,J＝18.3Hz),125.93,120.37(d,J＝13.7Hz),119.97,109.71.
Example 2
The embodiment provides an organic hole transport material, which is prepared by the following specific process:
step 1, uniformly mixing 2, 7-dibromo-9-fluorenone (5 mmol,1.69 g) and 2-fluorobiphenyl (5 mmol,0.86 g) in tetrahydrofuran (10.14 mL) under an inert atmosphere, then adding a lithium metal catalyst (15 mmol,0.10 g) for 3 times, continuously stirring and starting heating, reacting for 20h at 38 ℃, closing a heater for standing after the reaction is finished, adding hydrochloric acid (125 mmol,4.56 g) for quenching reaction after the system is completely cooled, fully mixing, standing for separating an organic phase, removing redundant solvent by using a rotary evaporator, dissolving the obtained first product in acetic acid for reacting for 26h at 110 ℃, filtering, and configuring the volume ratio as 10:1, using a mixed solvent of petroleum ether and ethyl acetate as a column chromatography eluent, and separating by column chromatography to obtain 2, 7-dibromo-9, 9' -spirobifluorene with the yield of 86.5%; wherein the mass to volume ratio of the first product to acetic acid is 1g to 6ml;
Step 2, carbazole (3 mol,501.62 g), copper sulfate (0.05 mol,7.98 g), sodium carbonate (1 mol,105.99 g), 18-crown ether-6 (0.5 mol,132.16 g) and dimethylacetamide (2845.14 mL) are uniformly mixed in an inert atmosphere, a nitrogen gas is pumped for three times, the system is closed, the mixture is placed in an oil bath for uniform stirring, the mixture is heated and refluxed for 2 hours, the 2, 7-dibromo-9, 9' -spirobifluorene (1 mol,474.19 g) is added, the mixture is reacted for 26 hours at 150 ℃, the heating is closed after the reaction is finished, the mixture is sufficiently cooled, then water quenching is added, filtering and drying are carried out, a mixed solution of dichloromethane and n-hexane with the volume ratio of 1:4 is prepared as a column chromatography eluent, the column chromatography is separated to obtain a crude product, the crude product is subjected to recrystallization and purification, and the organic hole transport material (SBF-KZ) has the yield of 86.9 percent.
Example 3
The embodiment provides an organic hole transport material, which is prepared by the following specific process:
step 1, uniformly mixing 2, 7-dibromo-9-fluorenone (5 mmol,1.69 g) and 2-fluorobiphenyl (15 mmol,2.58 g) in tetrahydrofuran (9.30 mL) under inert atmosphere, then adding a lithium metal catalyst (10 mmol,0.07 g) for 3 times, continuously stirring and starting heating, reacting for 24 hours at 39 ℃, closing a heater for standing after the reaction is finished, adding nitric acid (100 mmol,6.3 g) for quenching reaction after the system is completely cooled, standing for separating an organic phase after fully mixing, removing redundant solvent by using a rotary evaporator, dissolving the obtained first product in acetic acid for reacting for 25 hours at 120 ℃, filtering, and configuring the volume ratio as 10:1, as a column chromatography eluent, separating by column chromatography to obtain 2, 7-dibromo-9, 9' -spirobifluorene with the yield of 87.1 percent; wherein the mass to volume ratio of the first product to acetic acid is 1g to 5.5ml;
Step 2, carbazole (1.5 mol,250.81 g), copper carbonate (0.06 mol,7.41 g), cesium carbonate (3 mol,977.46 g), 18-crown ether-6 (0.3 mol,79.30 g) and dimethylacetamide (2569 mL) are uniformly mixed in an inert atmosphere, a closed system is obtained after nitrogen is pumped for three times, the mixture is placed in an oil bath kettle and stirred at a constant speed, heated and refluxed for 2 hours, 2, 7-dibromo-9, 9' -spirobifluorene (1 mol,474.19 g) is added, the mixture is reacted for 23 hours at 160 ℃, the heating is closed after the reaction is finished, the mixture is sufficiently cooled, then water quenching is added, filtration and drying are carried out, a mixed solution of dichloromethane and n-hexane with the volume ratio of 1:4 is used as a column chromatography eluent, the crude product is obtained after column chromatography separation, and the crude product is subjected to recrystallization and purification again, so that the organic hole transport material (SBF-KZ) is obtained, and the yield is 87.6%, and the structure is as follows.
Example 4
The embodiment provides an organic hole transport material, which is prepared by the following specific process:
step a, uniformly mixing 2, 7-dibromo-9-fluorenone (5 mmol,1.69 g) and phenol (50 mmol,4.71 g) under inert atmosphere, heating to 50 ℃ to dissolve the phenol, then adding methanesulfonic acid (20 mmol,1.92 g), reacting at 130 ℃ for 48h, adding anhydrous methanol (740 mmol,23.71 g) into the reaction solution after the reaction is finished, carrying out ultrasonic reaction at 30 ℃ for 8min to obtain milky suspension, filtering and flushing with a large amount of anhydrous methanol to obtain 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ], wherein the yield is 82.1%;
Step b, 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] (4 mmol,1.96 g), phenoxazine (28 mmol,5.13 g), sodium tert-butoxide (40 mmol,3.85 g) were added to dry toluene (39.2 mL) under inert atmosphere, then tris (dibenzylideneacetone) dipalladium (0.0048 mmol,4 mg) and tri-tert-butylphosphine tetrafluoroborate (0.034 mmol,9.9 mg) were added, stirring was slowly started, and the system was placed in an oil bath to slowly warm to 150 ℃ for reaction for 12h, after the reaction was completed, the heating was turned off and stirring was continued, the system was filtered after complete cooling, and the cake was rinsed with toluene for a plurality of times, the cake was heated to reflux state in toluene, filtered again while hot, the obtained cake was collected and combined, the solid crude product was obtained by concentrating under reduced pressure, and a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 10:1 was prepared as eluent, and an organic hole transport material (X-FEQ) was obtained in the following structure, yield was as follows.
1 H NMR 1 H NMR(500MHz,DMSO-d6)δ8.02(d,J＝8.2Hz, 1 H),7.65(dd,J＝8.2,1.8Hz, 1 H),7.35-7.27(m, 2 H),7.23(d,J＝1.8Hz, 1 H),6.90(ddd,J＝8.0,5.6,2.7Hz, 1 H),6.31(d,J＝7.9Hz, 1 H).
13 C NMR(126MHz,Chloroform-d)δ156.65,151.17,137.64,131.43,129.12,128.76,127.86,123.60,123.11,122.47,121.45,117.19,54.29,1.08.
Example 5
The embodiment provides an organic hole transport material, which is prepared by the following specific process:
step a, uniformly mixing 2, 7-dibromo-9-fluorenone (5 mmol,1.69 g) and phenol (40 mmol,3.76 g) under inert atmosphere, heating to 55 ℃ to dissolve the phenol, then adding sulfuric acid (25 mmol,2.45 g), reacting for 12h at 160 ℃, adding anhydrous methanol (745 mmol,23.86 g) into the reaction solution after the reaction is finished, carrying out ultrasonic reaction for 10min at 20 ℃ to obtain a milky suspension, filtering and flushing with a large amount of anhydrous methanol to obtain 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ], wherein the yield is 81.6%;
Step b, adding 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] (4 mmol,1.96 g), phenoxazine (16 mmol,2.93 g) and sodium tert-butoxide (20 mmol,1.92 g) to dry toluene (41.16 mL) under inert atmosphere, then adding tris (dibenzylideneacetone) dipalladium (0.006mmol, 5 mg) and tri-tert-butylphosphine tetrafluoroborate (0.035 mmol,10.1 mg), slowly starting stirring, placing the system in an oil bath pot, slowly heating to 170 ℃ for 48h, after the reaction, turning off the heating and continuously maintaining stirring, filtering after the system is completely cooled, eluting the filter cake with toluene for a plurality of times, heating the filter cake in toluene to a reflux state, filtering again while hot, collecting and merging the obtained filter cakes, concentrating under reduced pressure to obtain a solid crude product, preparing a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 10:1 as eluent, and performing column chromatography separation to obtain an organic hole transport material (SFX-FEQ) with the following structure of 77.3%.
Example 6
The embodiment provides an organic hole transport material, which is prepared by the following specific process:
step a, uniformly mixing 2, 7-dibromo-9-fluorenone (5 mmol,1.69 g) and phenol (45 mmol,4.23 g) under inert atmosphere, heating to 52 ℃ to dissolve the phenol, then adding selenious acid (23 mmol,2.92 g), reacting at 140 ℃ for 36h, adding absolute methanol (742 mmol,23.77 g) into the reaction solution after the reaction is finished, carrying out ultrasonic reaction at 20 ℃ for 10min to obtain milky suspension, filtering and flushing with a large amount of absolute methanol to obtain 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] with the yield of 80.4%;
Step b, adding 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] (4 mmol,1.96 g), phenoxazine (20 mmol,3.66 g), sodium tert-butoxide (30 mmol,2.88 g) to dry toluene under inert atmosphere, then adding tris (dibenzylideneacetone) dipalladium (0.0055 mmol,5 mg) and tri-tert-butylphosphine tetrafluoroborate (0.035 mmol,10.1 mg), slowly starting stirring, placing the system in an oil bath kettle, slowly heating to 160 ℃ for reaction for 36h, after the reaction is finished, turning off the heating and keeping stirring, filtering after the system is completely cooled, leaching the filter cake with toluene for a plurality of times, heating the filter cake to a reflux state in toluene, filtering again while hot, collecting and combining the obtained filter cakes, concentrating under reduced pressure to obtain a solid crude product, preparing a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 10:1 as eluent, and carrying out column chromatography to obtain an organic hole transport material (SFX-Q) with a yield of 78.3 percent structure as follows.
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 conductive glass for 30min, adopting nitrogen to blow-dry the conductive glass, and carrying out ultraviolet-ozone treatment for 30min after blow-drying to obtain a conductive glass substrate layer;
S2, mixing tin dioxide with ammonia water to prepare a tin dioxide solution, dripping the tin dioxide solution on a glass sheet, setting the temperature of a heat table to 120 ℃, and continuously annealing for 35min to obtain a titanium dioxide layer with the thickness of 50 nm;
s3, dissolving lead iodide in a mixed solution of anhydrous N, N-dimethylformamide and anhydrous dimethyl sulfoxide in a volume ratio of 9:1 to obtain an inorganic salt solution; wherein the mass volume ratio of the lead iodide to the mixed solution is (6-8) g to 1mL;
dissolving formamidine hydroiodic acid salt, methyl amine chloride and methyl amine iodide in isopropanol to obtain an organic salt solution; wherein the mass volume ratio of the formamidine hydroiodidate, the methyl amine chloride, the methyl amine iodide and the isopropanol is 1g to 0.3g to 0.1g to 20mL;
carrying out ultraviolet-ozone treatment on the conductive glass substrate deposited with the titanium dioxide layer, spin-coating an inorganic salt solution at 1400rpm for 30 seconds, and then annealing at 70 ℃ for 1min on a heating table; then, dripping the prepared organic salt solution on a glass sheet obtained by spin coating of an inorganic salt solution, spin coating for 30s at 1800rpm, and annealing for 15min at 150 ℃ on a heating table when the air humidity is ensured to be 35% -45%, so as to obtain a perovskite layer;
s4, dissolving 5g of phenethyl iodized amine in 500mL of isopropanol, and spin-coating the solution on a conductive glass substrate containing a tin dioxide layer and a perovskite layer at 5000rpm for 30S to obtain a passivation layer;
S5, dissolving the organic hole transport material prepared in the example 1 in chlorobenzene, then adding 4-tert-butylpyridine, acetonitrile solution containing lithium bistrifluoro-methylsulfonylmemide and acetonitrile solution containing cobalt bistrifluoro-methylsulfonylmemide, uniformly mixing, and coating for 30 seconds at a spin coating speed of 4000rpm to obtain a hole transport layer; wherein the concentration of the organic hole transport material solution is 30mg/mL, the concentration of the acetonitrile solution containing lithium bis (trifluoromethanesulfonyl) imide is 520mg/mL, the concentration of the acetonitrile solution containing cobalt bis (trifluoromethanesulfonyl) imide is 300mg/mL, and the volume ratio of the organic hole transport material solution, 4-tert-butylpyridine, the acetonitrile solution containing lithium bis (trifluoromethanesulfonyl) imide and the acetonitrile solution containing cobalt bis (trifluoromethanesulfonyl) imide is 1:55:34:13;
and S6, depositing gold on the surface of the hole transport layer through thermal evaporation deposition, wherein the thickness is 120nm, and obtaining the perovskite solar cell.
Test example 2
Preparing a perovskite solar cell using the organic hole transport material obtained in example 1, wherein in S5, the concentration of the organic hole transport material solution is 20mg/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 using the organic hole transport material obtained in example 1, wherein in S5, the concentration of the organic hole transport material solution is 10mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 4
Preparing a perovskite solar cell using the organic hole transport material obtained in example 2 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 30mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 5
Preparing a perovskite solar cell using the organic hole transport material obtained in example 2 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 20mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 6
Preparing a perovskite solar cell using the organic hole transport material obtained in example 2 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 10mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 7
Preparing a perovskite solar cell using the organic hole transport material obtained in example 3 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 30mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 8
Preparing a perovskite solar cell using the organic hole transport material obtained in example 3 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 20mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 9
Preparing a perovskite solar cell using the organic hole transport material obtained in example 3 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 10mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 10
Preparing a perovskite solar cell using the organic hole transport material obtained in example 4 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 30mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 11
Preparing a perovskite solar cell using the organic hole transport material obtained in example 4 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 20mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 12
Preparing a perovskite solar cell using the organic hole transport material obtained in example 4 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 10mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 13
Preparing a perovskite solar cell using the organic hole transport material obtained in example 5 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 30mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 14
Preparing a perovskite solar cell using the organic hole transport material obtained in example 5 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 20mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 15
Preparing a perovskite solar cell using the organic hole transport material obtained in example 5 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 10mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 16
Preparing a perovskite solar cell using the organic hole transport material obtained in example 6 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 30mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 17
Preparing a perovskite solar cell using the organic hole transport material obtained in example 6 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 20mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Test example 18
Preparing a perovskite solar cell using the organic hole transport material obtained in example 6 instead of the organic hole transport material obtained in test example 1, wherein in S5, the concentration of the organic hole transport material solution is 10mg/mL; other preparation processes are the same as in test example 1, and are not described here again.
Analysis of results
A methylene chloride solution of 0.1M tetrabutylammonium hexafluorophosphate was prepared as an electrolyte solution, and SBF-KZ was then added to prepare a 1X 10 concentration -4 M, performing repeated cyclic scanning on the dichloromethane solution in the electrode system to obtain a cyclic voltammogram; according to the cyclic voltammogram of SBF-KZ, as shown in FIG. 1, the oxidation potential of SBF-KZ is 0.616V, the reduction potential is 0.501V, and the oxidation-reduction peak potential separation value DeltaEp of SBF-KZ is 0.108V, which indicates that SBF-KZ has better oxidation-reduction property. Meter with a meter body The HOMO energy level of SBF-KZ is-5.35 eV, the LUMO energy level is-2.303 eV, and is basically consistent with the energy level calculated by a density functional theory, according to the table 1, the HOMO energy level of the material is high in proximity to the energy level valence band of the perovskite material, so that the material is favorable for efficiently receiving holes from a perovskite layer, meanwhile, the higher HOMO energy level of the material is favorable for obtaining better Voc, the LUMO energy level is higher than the conduction band of the perovskite material and has a higher energy level barrier, electrons from the perovskite material can be effectively blocked by the higher energy level barrier, and loss of carriers and charge recombination are reduced.
TABLE 1
| E g (eV) | E ox (eV) | E ox (eV) | E ox (eV) | |
| SBF-KZ | 3.047 | 0.616 | -5.35 | -2.303 |
As can be seen from the thermogravimetric and DSC diagrams of SBF-KZ, i.e., FIG. 2 and FIG. 3, T of SBF-KZ d The temperature is 405.8 ℃, which shows that the material has good thermal stability, can bear the temperature condition in the preparation process of the device, and canThe hole layer is prepared well and used in devices. T of such materials g The temperature is 185.5 ℃, which shows that the material has almost no obvious crystallization trend before the temperature, and is beneficial to improving the stability of the device.
Hole mobility related parameters were tested under dark state conditions and the hole mobility relative to the hole material was estimated by the law of modafinil and calculated as j=9με 0 ε r V 2 /8d 3 Wherein μ is the hole mobility, ε, which is the desired value 0 And epsilon r Represents the vacuum dielectric constant and the average dielectric constant of the film, d represents the thickness of the film, and V represents the applied bias voltage, respectively; as a result, as shown in FIG. 4, the hole mobility of SBF-KZ was 4.24X10 -5 cm 2 ·V -1 ·S -1 。
In order to determine the hydrophobicity of SBF-KZ, SBF-KZ is prepared into a corresponding chlorobenzene solution with the concentration of 30mg/mL, an ultrasonic cleaning method is used, FTO transparent conductive glass is sequentially and respectively ultrasonically treated with deionized water, acetone and ethanol solution for 15min to obtain clean FTO glass, HTM films are prepared on the FTO glass by spin coating at the spin coating speed of 1000rpm for 60s, the water contact angle test result is shown in figure 5, the water contact angle of the compared Spiro-OMeTAD material is known to be 79 degrees according to figure 5, the water contact angle of the SBF-KZ is known to be 91 degrees, the contact angle of the material is larger than that of the Spiro-OMeTAD material, the SBF-KZ has better hydrophobicity according to the water contact angle, a good protection effect on a perovskite layer can be achieved, the service life of a device is prolonged, and the working time of the device is prolonged.
To investigate the effect of SBF-KZ as an organic hole transport material on device performance for the devices of test examples 1-3, hole transport layer films of different thicknesses were obtained by improving the organic hole transport material, and the PCE of SBF-KZ-based devices reached 18.69% by device current density-voltage (J-V) measured under standard am1.5g (100 mW/cm) solar light irradiation, as seen in fig. 6 and 7, at a concentration of 20mg/mL organic hole transport material.
According to the invention, the influence of SBF-KZ as a hole layer interface on the stability of a PSCs device is explored, the short-circuit current in the device is tested by measuring the External Quantum Efficiency (EQE) of the device, according to the data in fig. 8 and 9, the spectrum data of the SBF-KZ show a very wide frequency band, the EQE value of the SBF-KZ is more than 80% in the range from 400nm to 750nm, the whole visible light area can be well covered, in order to test the performance stability of the PSCs device based on the SBF-KZ as an organic hole transport material, the stable power output of the device is tested by continuously applying the constant voltage of 0.92V and 0.88V for 300s at the maximum power output point (MPP), and the result proves that the device based on the SBF-KZ as the hole layer can reach the stable output efficiency of 18.32%, and the stable output efficiency of the device can still respectively keep 98.87% after 300s time, so that the PSCs based on the SBF-KZ as the organic hole transport material can keep high and stable output for a long time.
As shown in fig. 10, the device still can maintain 70% of the initial efficiency after being placed for 500 hours under the unpackaged condition, and it can be known that the perovskite battery modified by SBF-KZ can well isolate the corrosion of moisture and oxygen in the environment, and PSCs devices can show better device stability.
The perovskite solar cell prepared in test examples 1 to 3 was tested for current-voltage curves to obtain various performance parameters of the solar cell, and the parameters are shown in table 2:
TABLE 2
| Jsc(mA/cm 2 ) | Voc(V) | FF(％) | PCE(％) | |
| Test example 1 | 24.58 | 1.06 | 65.60 | 17.09 |
| Test example 2 | 24.48 | 1.09 | 70.04 | 18.69 |
| Test example 3 | 23.84 | 1.03 | 67.50 | 16.58 |
A methylene chloride solution of 0.1M tetrabutylammonium hexafluorophosphate was prepared as an electrolyte solution, and SFX-FEQ was then added to prepare a 1X 10 concentration -4 M, performing repeated cyclic scanning on the dichloromethane solution in the electrode system to obtain a cyclic voltammogram; according to the cyclic voltammogram of SFX-FEQ, as shown in FIG. 11, the oxidation potential of SFX-FEQ is 0.62V, the reduction potential is 0.501V, and the separation value DeltaEp of the oxidation-reduction peak potential of SFX-FEQ is 0.114V, which indicates that SFX-FEQ has better oxidation-reduction property. The HOMO energy level of SFX-FEQ is-5.36 eV, the LUMO energy level is-2.298 eV, and is basically consistent with the energy level calculated by the density functional theory, according to the table 3, it can be seen that the HOMO energy level of the material is close to the energy level valence band of the perovskite material, so that the material is favorable for efficiently receiving holes from a perovskite layer, and meanwhile, the deeper HOMO energy level of the material is favorable for obtaining better Voc, and the LUMO energy level is higher than the conduction band of the perovskite material and has higher energy level potential The barrier, the higher energy level barrier can effectively block electrons from perovskite materials, and loss of carriers and charge recombination are reduced.
TABLE 3 Table 3
| E g (eV) | E ox (eV) | E ox (eV) | E ox (eV) | |
| SFX-FEQ | 3.062 | 0.621 | -5.36 | -2.298 |
According to the thermogravimetric graph and the DSC graph of the compound SFX-FEQ, namely, the graph in FIG. 12 and the graph in FIG. 13, the Td temperature of the SFX-FEQ can be directly seen to be 410.8 ℃, which shows that the material has good thermal stability, can bear the temperature condition in the preparation process of the device, and can be well prepared into a hole layer for the device. The Tg temperature of the material is 145.2 ℃, which shows that the material has almost no obvious crystallization trend before the Tg temperature, and is beneficial to improving the stability of the device.
The hole mobility-related parameters were tested under dark state conditions and the result is estimated by the Moire's Law to obtain the hole mobility relative to the hole material as shown in FIG. 14From the corresponding data we calculated the hole mobility of SFX-FEQ to be 1.21×10 -4 cm 2 ·V -1 ·S -1 。
In order to determine the hydrophobicity of SFX-FEQ, the SFX-FEQ is prepared into a corresponding chlorobenzene solution with the concentration of 30mg/mL, an ultrasonic cleaning method is used, the FTO transparent conductive glass is sequentially and respectively ultrasonically treated with deionized water, acetone and ethanol solution for 15min to obtain clean FTO glass, the FTO glass is spin-coated on the FTO glass at the spin-coating speed of 1000rpm for 60s to prepare an HTM film, the water contact angle test result is shown in FIG. 15, the hydrophobic angle of the Spiro-OMeTAD material is 79 degrees, the water contact angle of the SBF-KZ is 94 degrees, the contact angle of the material is larger than that of the Spiro-OMeTAD material, the SFX-FEQ has better hydrophobicity according to the water contact angle, the perovskite layer can be well protected, the service life of the device is prolonged, and the working time of the device is prolonged.
To investigate the effect of SFX-FEQ as an organic hole transport material on device performance for the devices of test examples 10-12, hole transport layer films of different thicknesses were obtained by improving the organic hole transport material, and then the PCE of the SFX-FEQ-based device reached 20.71% by measuring the device current density-voltage (J-V) under standard AM1.5G (100 mW/cm) solar light irradiation, as shown in FIGS. 16 and 17, at a concentration of 20mg/mL of the organic hole transport material.
According to the invention, the effect of SFX-FEQ on the stability of PSCs devices after being used as a hole layer interface is explored, short-circuit current in the devices is tested by measuring External Quantum Efficiency (EQE) of the devices, and according to data in fig. 18 and 19, the spectral data of the SFX-FEQ show a very wide frequency band, the EQE value of the SFX-FEQ is more than 80% in the range from 400nm to 750nm, the whole visible light area can be well covered, in order to test the performance stability of the PSCs devices based on the SFX-FEQ as organic hole transport materials, the stable power output of the devices is tested by continuously applying constant voltage of 0.92V and 0.88V for 300s at the maximum power output point (MPP), and the result proves that the devices based on the SFX-FEQ as the hole layer can reach the stable output efficiency of 20.09%, and the stable output efficiency of the devices can still be respectively kept 98.69% after 300s, so that the stable power output of the PSCs based on the SFX-FEQ as the organic hole transport materials can be kept for a long time.
As can be seen from fig. 20, the PSCs device using SFX-FEQ as the organic hole transport material has high complex resistance, and the electron-hole recombination degree in the circuit is lower, which suppresses the accumulation and recombination of charges at the interface, and is beneficial to obtain higher device performance.
As can be seen from fig. 21, the device still maintains more than 70% of the initial efficiency after being placed for 500 hours under the unpackaged condition, and it can be seen that the perovskite battery modified by SFX-FEQ can well isolate the corrosion of moisture and oxygen in the environment, and PSCs devices can exhibit better device stability.
The perovskite solar cell prepared in test examples 1 to 3 was tested for current-voltage curves to obtain various performance parameters of the solar cell, as shown in table 4 in detail:
TABLE 4 Table 4
| Jsc(mA/cm 2 ) | Voc(V) | FF(％) | PCE(％) | |
| Test example 10 | 24.42 | 1.11 | 72.10 | 19.55 |
| Test example 11 | 24.39 | 1.10 | 77.14 | 20.71 |
| Test example 12 | 23.49 | 1.06 | 67.30 | 17.48 |
When the perovskite solar cells of test example 2 and test example 11 of the present invention were tested, as shown in fig. 22, 20 PSCs were repeatedly prepared using SBF-KZ and SFX-FEQ as organic hole transport materials, respectively, and the test performance showed that the perovskite solar cells were concentrated in performance parameters, exhibited good stability and repeatability, had high average photoelectric conversion efficiency, and exhibited good device stability.
According to the invention, the spirobifluorene and spirofluorene xanthene-based hole transport material is designed and synthesized, carbazole and phenoxazine are used as terminal group substituents to reduce the LUMO energy level of the material, the HOMO energy level of the material is improved, the electron withdrawing group capable of improving the conductivity is reasonably selected according to the characteristics of the substituent groups, the energy level matching degree of the spirofluorene material and the perovskite material can be further improved through reasonable molecular design, and the potential of the material applied to PSCs is further improved.
So long as the examples prepared within the scope of the present invention all achieve the effects comparable to those of examples 1 and 4. 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 in that the structure of the organic hole transport material is represented by formula 1 or formula 2:
wherein R is 1 Is carbazolyl, R 2 Is a phenoxazinyl group.
2. The organic hole transport material of claim 1, wherein the organic hole transport material isOr (b)
The organic hole transport material is
3. A method for preparing the organic hole transport material according to claim 1, wherein the method for preparing the compound represented by formula 1 comprises the steps of:
step 1, uniformly mixing 2, 7-dibromo-9-fluorenone, 2-fluorobiphenyl and a catalyst in a solvent under inert atmosphere, performing a first reaction at 38-40 ℃, adding inorganic acid for quenching reaction, separating an organic phase, performing reduced pressure distillation on the organic phase, adding the obtained first product into acetic acid, performing a second reaction at 110-130 ℃, filtering, and purifying to obtain 2, 7-dibromo-9, 9' -spirobifluorene;
step 2, uniformly mixing carbazole, a copper catalyst, an acid binding agent, 18-crown ether-6 and a solvent in an inert atmosphere, then adding the 2, 7-dibromo-9, 9' -spirobifluorene, reacting at 150-170 ℃, adding water for quenching, filtering, drying and purifying to obtain a compound shown in a formula 1;
the preparation method of the compound shown in the formula 2 comprises the following steps:
step a, under inert atmosphere, phenol is dissolved in 2, 7-dibromo-9-fluorenone, then acid solution is added for reaction at 130-160 ℃, organic alcohol is added into reaction liquid for ultrasonic reaction after the reaction is completed, and the reaction liquid is filtered and washed to obtain 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ];
And b, adding the 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ], phenoxazine, an acid binding agent, a palladium catalyst and borate into a solvent in an inert atmosphere, reacting at 150-170 ℃, filtering, washing and purifying to obtain the compound shown in the formula 2.
4. The method for producing an organic hole transport material according to claim 3, wherein in step 1, the catalyst is lithium metal; and/or
In the step 1, the solvent is tetrahydrofuran; and/or
In the step 1, the inorganic acid is at least one of sulfuric acid, hydrochloric acid, nitric acid or carbonic acid; and/or
In the step 1, the time of the first reaction is 20-26 h; and/or
In the step 1, the time of the second reaction is 20-26 h; and/or
In the step 1, the molar ratio of the 2, 7-dibromo-9-fluorenone to the 2-fluorobiphenyl is 1 (1-3); and/or
In the step 1, the molar ratio of the 2, 7-dibromo-9-fluorenone to the catalyst is 1 (1-3); and/or
In the step 1, the mass volume ratio of the 2, 7-dibromo-9-fluorenone to the solvent is 1g (5-6) mL; and/or
In the step 1, the molar ratio of the 2, 7-dibromo-9-fluorenone to the inorganic acid is 1 (15-25); and/or
In the step 1, the mass volume ratio of the first product to the acetic acid is 1g (5-6) mL.
5. The method for producing an organic hole transport material according to claim 3, wherein in step 2, the copper catalyst is at least one of copper iodide, copper sulfate, copper carbonate, and copper hydroxide; and/or
In the step 2, the solvent is dimethylacetamide; and/or
In the step 2, the molar ratio of the 2, 7-dibromo-9, 9' -spirobifluorene to carbazole is 1 (1-3); and/or
In the step 2, the molar ratio of the 2, 7-dibromo-9, 9' -spirobifluorene to the copper catalyst is (15-20): 1; and/or
In the step 2, the molar ratio of the 2, 7-dibromo-9, 9' -spirobifluorene to the acid binding agent is 1: (1-4); and/or
In the step 2, the molar ratio of the 2, 7-dibromo-9, 9' -spirobifluorene to the 18-crown ether-6 is 1 (0.1-0.5); and/or
In the step 2, the mass volume ratio of the 2, 7-dibromo-9, 9' -spirobifluorene to the solvent is 1g (5-6) mL;
in the step 2, the mass volume ratio of the 2, 7-dibromo-9, 9' -spirobifluorene to the water is 1g (5-11) mL; and/or
In the step 2, the reaction time is 20-26 h.
6. The method for preparing an organic hole transport material according to claim 3, wherein in the step a, the acid solution is at least one of sulfuric acid, selenious acid, methylsulfonic acid, or oxalic acid; and/or
In the step a, the organic alcohol is anhydrous methanol; and/or
In the step a, the molar ratio of the 2, 7-dibromo-9-fluorenone to the phenol is 1 (8-10); and/or
In the step a, the molar ratio of the 2, 7-dibromo-9-fluorenone to the acid solution is 1 (4-5); and/or
In the step a, the molar ratio of the 2, 7-dibromo-9-fluorenone to the organic alcohol is 1 (148-149); and/or
In the step a, the reaction time is 12-48 h; and/or
In the step a, the temperature of the ultrasonic reaction is 20-30 ℃, and the time of the ultrasonic reaction is 8-10 min.
7. The method for preparing an organic hole transport material according to claim 3, wherein in the step b, the acid-binding agent is sodium t-butoxide; and/or
In the step b, the palladium catalyst is tris (dibenzylideneacetone) dipalladium; and/or
In the step b, the borate is tri-tert-butyl phosphine tetrafluoroborate; and/or
In the step b, the solvent is toluene; and/or
In the step b, the molar ratio of the 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] to the phenoxazine is 1 (4-7); and/or
In the step b, the molar ratio of the 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] to the acid binding agent is 1 (5-10); and/or
In the step b, the molar ratio of the 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] to the palladium catalyst is 1 (0.0012-0.0015); and/or
In the step b, the molar ratio of the 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] to the borate is 1 (0.0085-0.0088); and/or
In the step b, the mass-volume ratio of the 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] to the solvent is 1g (20-21) mL; and/or
In the step b, the reaction time is 12-48 h.
8. A hole transport layer comprising the organic hole transport material of claim 1 or 2.
9. A method of preparing the hole transport layer of claim 8, comprising the steps of: and dissolving the organic hole transport material in chlorobenzene to obtain an organic hole transport material solution, adding 4-tert-butylpyridine, acetonitrile solution containing lithium bistrifluoro methylsulfonylmethylamide and acetonitrile solution containing cobalt bistrifluoro methylsulfonylmethylamide into the organic hole transport material solution, uniformly mixing, and spin-coating the mixture to a perovskite layer to obtain the hole transport layer.
10. A perovskite solar cell comprising the hole transport layer of claim 8.
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