CN108794494A - One kind three and carbazole-aromatic amine derivant hole mobile material and the preparation method and application thereof - Google Patents
One kind three and carbazole-aromatic amine derivant hole mobile material and the preparation method and application thereof Download PDFInfo
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- CN108794494A CN108794494A CN201810625829.9A CN201810625829A CN108794494A CN 108794494 A CN108794494 A CN 108794494A CN 201810625829 A CN201810625829 A CN 201810625829A CN 108794494 A CN108794494 A CN 108794494A
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- carbazole
- aromatic amine
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- mobile material
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 241001597008 Nomeidae Species 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000005429 oxyalkyl group Chemical group 0.000 claims abstract description 7
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 6
- 230000005525 hole transport Effects 0.000 claims abstract description 6
- 238000005401 electroluminescence Methods 0.000 claims abstract description 4
- 230000005669 field effect Effects 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 238000004440 column chromatography Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 11
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [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 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 61
- 238000003756 stirring Methods 0.000 description 16
- 239000012074 organic phase Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- -1 carbazole Chemical class 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 239000005457 ice water Substances 0.000 description 12
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- 238000002242 deionisation method Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 6
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000003446 ligand 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
- 238000000967 suction filtration Methods 0.000 description 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 4
- MAWGHOPSCKCTPA-UHFFFAOYSA-N 6-bromo-1h-indole Chemical compound BrC1=CC=C2C=CNC2=C1 MAWGHOPSCKCTPA-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000001246 bromo group Chemical class Br* 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- FGFUBBNNYLNVLJ-UHFFFAOYSA-N indolone Natural products C1=CC=C2C(=O)C=NC2=C1 FGFUBBNNYLNVLJ-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- QEZYDNSACGFLIC-UHFFFAOYSA-N CN.[I] Chemical compound CN.[I] QEZYDNSACGFLIC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940054051 antipsychotic indole derivative Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/14—Ortho-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- 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
-
- 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)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention discloses one kind three and carbazole-aromatic amine derivant hole mobile material and the preparation method and application thereof, the material be using three and carbazole as core, aromatic amine derivative as the starlike micromolecular compound of modification group, general formula structure is as shown in following formula 1：.Wherein, one kind in R is C1-C30 straight chain, branched alkyl or oxyalkyl chain.The materials synthesis route of the present invention is brief, and reaction raw materials are cheap, and reaction process is easy to control, and is easily isolated, purity is high, yield is high；And the material has higher hole mobility, good dissolubility.Particularly, excellent photoelectric conversion efficiency is obtained when being applied to perovskite solar cell as hole mobile material.It is this kind of to have excellent performance and low-cost novel hole transport material can be widely applied in organic electroluminescence device, organic solar batteries, perovskite solar cell or organic field effect tube device, there is important application potential.
Description
Technical field
The invention belongs to optoelectronic materials technologies, and in particular to one kind three and carbazole-aromatic amine derivant hole transport material
Material and the preparation method and application thereof.
Background technology
Efficient hole mobile material is in the efficiency that can not only increase substantially organic electro-optic device, additionally it is possible to ensure device
Part works steadily in the long term.For example, in perovskite area of solar cell, hole mobile material plays transporting holes and blocking
The double action of electronics, can be to avoid photo-generate electron-hole to compound in inside battery；Meanwhile organic hole transport material is dredged
The characteristic of water can be to avoid perovskite by moisture attack, to greatly improve the stability of device.2,2', 7,7'- tetra-
It is most commonly used that two fluorenes of [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells is that perovskite area of solar cell is applied
Efficient hole mobile material.However, spiral shell two it is fluorene structured synthesis step it is cumbersome, cause its cost to be up to ten times of gold, it is high
Cost limit the large-scale commercial application of perovskite solar cell, therefore develop a kind of efficient and cheap novel
Hole mobile material is particularly important.
It is developed currently, having various new small molecule hole transport material and is applied to hole mobile material neck
Domain, such as benzene, biphenyl, pyrene, triazine, three and indenes etc., however it is that nuclear design is developed that these materials, which are based on electron neutral group, is made
Can not only electronics have been transmitted but also can reduce the hole mobility of material to a certain extent with transporting holes by obtaining these materials.It adopts
Electron neutral group is substituted with electron rich group and designs hole mobile material as core, is the approach for obtaining higher mobility
One of.
Indole derivatives (such as carbazole, three and carbazole) have stronger electron, higher hole mobility, preferably
Dissolubility, unformed film forming, excellent photostability and thermal stability, and cause the extensive concern of people.Simultaneously with three
For carbazole, three and carbazole be a kind of electron rich group of big plane, the molecular structure of C3h symmetry is conducive to intermolecular have
Sequence arranges, to realize efficient electric charge transfer, therefore three and carbazole derivates there is higher hole mobility.Not only such as
This, three and carbazole can be synthesized by brief easily-controllable reaction by cheap starting material.These unique photoelectric properties make
It obtains three and carbazole has prodigious potentiality in terms of developing efficient hole mobile material cheap and easy to get.Nazeeruddin etc.
[Rakstys K；Abate A；Dar M I,et al.Triazatruxene-Based Hole Transporting
Materials for Highly Efficient Perovskite Solar Cells[J].J Am Chem Soc,2015,
137(51):16172-16178.] report a series of three and carbazole derivative synthetic method, and the material is applied to
The hole transmission layer of perovskite solar cell achieves the photoelectric conversion efficiency of highest 18.3%.However their method needs
Want four steps that could obtain final product, the cost for reducing organic electro-optic device is unfavorable.
We are based on three and carbazole is core, with the derivative of aromatic amine carries out end group modification construct it is a kind of it is simple and easy to get newly
Type hole mobile material can be obtained final product by the reaction simple and easy to control of two to three steps.Three and carbazole electron rich plane
Structure makes the intermolecular π-π that could be formed with effect stack, to be conducive to the transmission in hole；Aromatic amine as modification group not
Only can be with the photoelectric property of controlled material, and the distorted-structure of aromatic amine can seriously be accumulated to avoid material, so as to improve material
The film forming of material.
Invention content
The object of the present invention is to provide one kind three and carbazole-aromatic amine derivant hole mobile material and preparation method thereof with
Using to solve the problems, such as that hole mobile material preparation is complicated, with high costs or performance is poor.
To achieve the above object, the technical solution adopted by the present invention is：
One kind three and carbazole-aromatic amine derivant hole mobile material, the material be using three and carbazole as core, fragrance
Starlike micromolecular compound of the derivative of amine as modification group, general formula structure is as shown in following formula 1：
In formula 1, Ar is one of group shown in the following Expression 2：
Wherein, one kind in R, R1 and R2 are C1-C30 straight chain, branched alkyl or oxyalkyl chain；* it is link position.
Preferably, in the Formula 1, three and 2,7,12- s of carbazole and modification group by-C-C- keys or
Person's-C-N- keys link；Described R, R1 and R2 are one kind of the straight chain of C1-C12, branched alkyl or oxyalkyl chain.
A kind of three and carbazole-aromatic amine derivant hole mobile material preparation method, include the following steps：
The preparation of compound I：In nitrogen protection and under the conditions of be protected from light, by compound II, palladium catalyst, any one Ar1-
The single boric acid or secondary amine of Ar6 is dissolved in toluene with alkali, is reacted, and reaction terminates to purify to obtain compound I through column chromatography；
Wherein, the structure of compound II is as shown in Equation 3：
Preferably, the molar ratio of single boric acid of the compound II and any one Ar1-Ar6 or secondary amine is 1:3~1:6.
Preferably, the palladium catalyst is the one of which of tetra-triphenylphosphine palladium or tris(dibenzylideneacetone) dipalladium,
Molar ratio with compound II is 0.09:1~0.15:1.
Preferably, the alkali is the one of which of wet chemical or potassium tert-butoxide, is with compound II molar ratios
4:1~6:1.
Preferably, the mass volume ratio of the compound II and toluene is：Toluene solvant 15 is added per 500mg compounds II
~25mL.
Preferably, the reaction condition is：60~120 DEG C of 8~72h of reaction of temperature control.
Three and the carbazole-aromatic amine derivant hole mobile material of the present invention can be used as hole extraction material, hole to pass
Defeated material or electron-blocking materials are applied to organic electroluminescence device, organic solar batteries, perovskite solar cell
Or in organic field effect tube.Particularly, hole mobile material can be used as to be applied to prepare efficient perovskite solar-electricity
Pond device.
Advantageous effect：Three and the carbazole-aromatic amine derivant hole mobile material synthetic route of the present invention is brief, and reaction is former
Material is cheap, and reaction process is easy to control, and product is easily isolated, purity is high, yield is high；And with higher hole mobility and
Good dissolubility.Particularly, which is applied to perovskite solar cell as hole mobile material, obtains excellent
Device performance.This kind of efficient and cheap material is in organic electroluminescence device, organic solar batteries, perovskite solar energy
Battery or organic field effect tube etc. have important application potential.
Description of the drawings
Fig. 1 is the MALDI-TOF spectrograms of T1；
Fig. 2 is the 1H NMR spectras of T1；
Fig. 3 is the MALDI-TOF spectrograms of T2；
Fig. 4 is the 1H NMR spectras of T2；
Fig. 5 is T1 and T2 ultraviolet-ray visible absorbing emission spectrum；
Fig. 6 is the spin coating fluorescence spectrum of the perovskite thin film of T1 and T2；
Fig. 7 is the structural schematic diagram of perovskite solar cell；
Fig. 8 is the J-V curves of T1, T2 and Sprio-OMeTAD as the perovskite solar cell of hole transmission layer.
Specific implementation mode
The present invention one kind three and carbazole-aromatic amine derivant hole mobile material, the material be using three simultaneously carbazole as
Starlike micromolecular compound of the derivative as modification group of core, aromatic amine, general formula structure is as shown in following formula 1：
In formula 1, Ar is one of group shown in the following Expression 2：
Wherein, one kind in R, R1 and R2 are C1-C30 straight chain, branched alkyl or oxyalkyl chain；* it is link position；N
It is nitrogen-atoms, S is sulphur atom.
Preferably, in Formula 1, three and 2,7,12- s of carbazole and modification group pass through-C-C- keys or-C-
N- keys link；Described R, R1 and R2 are one kind of the straight chain of C1-C12, branched alkyl or oxyalkyl chain.
The preparation method of a kind of three and carbazole-aromatic amine derivant hole mobile material of the invention, includes the following steps：
The preparation of compound I：In nitrogen protection and under the conditions of be protected from light, by compound II, palladium catalyst, any one Ar1-
The single boric acid or secondary amine of Ar6 is dissolved in toluene with alkali, and in 60~120 DEG C of 8~72h of reaction of temperature, reaction terminates pure through column chromatography
Change to obtain compound I；
Wherein, the structure of compound II is as shown in Equation 3：
Wherein, the molar ratio of single boric acid of compound II and any one Ar1-Ar6 or secondary amine is 1:3~1:6；Palladium chtalyst
Agent is the one of which of tetra-triphenylphosphine palladium or tris(dibenzylideneacetone) dipalladium, and the molar ratio with compound II is 0.09:1
~0.15:1；Alkali is the one of which of wet chemical or potassium tert-butoxide, is 4 with compound II molar ratios:1~6:1；Change
The mass volume ratio for closing object II and toluene is：15~25mL of toluene solvant is added per 500mg compounds II.
In above-mentioned preparation method, 6- bromo indole ketone first passes through alkylation and is prepared 1- hexyl -6- bromo indole ketone, 1- oneself
Compound II is prepared in the cyclization under phosphorus oxychloride catalysis of base -6- bromo indoles ketone, then compound II and different aromatic aminos
Compound I is prepared by Suzuki coupling reactions or Buchwald-Hartwig coupling reactions in group Ar：
Below by way of several embodiments, the present invention will be further described, according to following embodiments, can be better understood from
The present invention.However, as it will be easily appreciated by one skilled in the art that specific material proportion, process conditions described in embodiment and
Its result is merely to illustrate the present invention, without that should will not limit the present invention described in detail in claims.
Embodiment 1：
Reaction condition one：Under nitrogen protection, by 6- bromo indole -2- ketone (212.0mg, 1.0mmol), potassium carbonate
(276mg, 2mmol), tetrabutylammonium bromide (33mg, 0.1mmol) are placed in twoport reaction bulb.Reaction unit is sealed, substitutes nitrogen
Gas three times, plugs nitrogen ball.Inject 22mL tetrahydrofurans, stir 30min under the conditions of 85 DEG C, be then slowly injected into 2mL bromines oneself
Alkane keeps stirring 8h at 80 DEG C.It pours into ice water and is quenched after reaction is slowly cooled to room temperature, extracted with dichloromethane organic
Phase, after deionization washing three times, organic phase is dried with anhydrous magnesium sulfate.Organic phase is slightly produced through vacuum-concentrcted after suction filtration
Object, using column chromatography technology, (leacheate is dichloromethane (DCM)/petroleum ether (PE)=1:1) it purifies, obtains white waxy solid
The compound bromo- indolones of 1- hexyls -6- (167mg), yield 56.3%.
Reaction condition two：Under nitrogen protection, by 6- bromo indole -2- ketone (212.0mg, 1.0mmol), potassium carbonate
(552mg, 4mmol), tetrabutylammonium bromide (66mg, 0.2mmol) are placed in twoport reaction bulb.Reaction unit is sealed, substitutes nitrogen
Gas three times, plugs nitrogen ball.Inject 22mL tetrahydrofurans, stir 30min under the conditions of 85 DEG C, be then slowly injected into 2mL bromines oneself
Alkane keeps stirring 8h at 80 DEG C.It pours into ice water and is quenched after reaction is slowly cooled to room temperature, extracted with dichloromethane organic
Phase, after deionization washing three times, organic phase is dried with anhydrous magnesium sulfate.Organic phase is slightly produced through vacuum-concentrcted after suction filtration
Object uses column chromatography technology (leacheate DCM/PE=1:1) it purifies, it is bromo- to obtain white waxy solid compound 1- hexyls -6-
Indolone (164mg), yield 55.4%.
Reaction condition three：Under nitrogen protection, by 6- bromo indole -2- ketone (212.0mg, 1.0mmol), potassium carbonate
(276mg, 2mmol), tetrabutylammonium bromide (33mg, 0.1mmol) are placed in twoport reaction bulb.Reaction unit is sealed, substitutes nitrogen
Gas three times, plugs nitrogen ball.Inject 22mL tetrahydrofurans, stir 30min under the conditions of 85 DEG C, be then slowly injected into 3mL bromines oneself
Alkane keeps stirring 8h at 85 DEG C.It pours into ice water and is quenched after reaction is slowly cooled to room temperature, extracted with dichloromethane organic
Phase, after deionization washing three times, organic phase is dried with anhydrous magnesium sulfate.Organic phase is slightly produced through vacuum-concentrcted after suction filtration
Object uses column chromatography technology (leacheate DCM/PE=1:1) it purifies, it is bromo- to obtain white waxy solid compound 1- hexyls -6-
Indolone (172mg), yield 58.1%.
1H NMR(400MHz,CDCl3,ppm):δ 7.07-6.99 (m, 2H), 6.88 (d, J=0.8Hz, 1H), 3.60-
3.55 (m, 2H), 3.37 (s, 2H), 1.57 (s, 2H), 1.25 (t, J=9.2Hz, 6H), 0.81 (t, J=6.9Hz, 3H)；13C
NMR(100MHz,CDCl3,ppm):δ174.68,146.05,125.64,124.81,123.47,121.32,111.68,
40.18,35.36,31.43,27.30,26.59,22.54,14.01；GC-MS(m/z):calcd for C14H18BrNO,
Molecular Weight:296.21；Found:295.06(M+).Anal.Calcd for C14H18BrNO:C 56.77,
H6.13,N 4.73.
Embodiment 2：
Reaction condition one：The compound bromo- indolones of 1- hexyls -6- (10g, 33mmol) are placed in twoport reaction bulb, are sealed
Good reaction unit injects 40mL phosphorus oxychloride, keeps stirring 8h at 100 DEG C.Ice water is poured into after reaction is slowly cooled to room temperature
In be quenched, adjust Ph to neutrality, it is right that suction filtration obtains solid crude product.Use column chromatography technology (leacheate DCM/PE=1:10)
Purifying, obtains compound as white solid II (1.86mg), yield 20.3%.
Reaction condition two：The compound bromo- indolones of 1- hexyls -6- (10g, 33mmol) are placed in twoport reaction bulb, are sealed
Good reaction unit injects 80mL phosphorus oxychloride, keeps stirring 8h at 100 DEG C.Ice water is poured into after reaction is slowly cooled to room temperature
In be quenched, adjust Ph to neutrality, it is right that suction filtration obtains solid crude product.Use column chromatography technology (leacheate DCM/PE=1:10)
Purifying, obtains compound as white solid II (3.54mg), yield 38.6%.
Reaction condition three：The compound bromo- indolones of 1- hexyls -6- (10g, 33mmol) are placed in twoport reaction bulb, are sealed
Good reaction unit injects 60mL phosphorus oxychloride, keeps stirring 8h at 100 DEG C.Ice water is poured into after reaction is slowly cooled to room temperature
In be quenched, adjust Ph to neutrality, it is right that suction filtration obtains solid crude product.Use column chromatography technology (leacheate DCM/PE=1:10)
Purifying, obtains compound as white solid II (3.33mg), yield 36.0%.
1H NMR(400MHz,CDCl3):δ 8.02 (d, J=8.6Hz, 3H), 7.71 (d, J=1.7Hz, 3H), 7.42 (dd,
J=8.6,1.7Hz, 3H), 4.78-4.71 (m, 6H), 1.89 (s, 6H), 1.23 (d, J=2.2Hz, 18H), 0.80 (t, J=
7.0Hz,9H).13C NMR(101MHz,CDCl3):δ141.85,138.66,122.84,122.50,121.97,116.57,
113.46,102.98,77.03,47.00,31.33,29.67,26.24,22.45,13.89.MALDI-TOF-MS(m/z):
calcd for C42H48Br3N3,Molecular Weight:834.58；Found:831.14(M+).
Embodiment 3：
Reaction condition one：In N2It protects and is protected from light down, by compound II (834.0mg, 1.0mmol), N, N '-dimethyl two
Aniline (1183.6mg, 6mmol), potassium tert-butoxide (660.0mg, 6.0mmol) rapidly join catalyst Pd2(dba)3(137.4mg,
0.15mmol), ligand tri-tert-butylphosphine (60.0mg, 0.30mmol) is in two mouth flask.Reaction unit is sealed, substitutes N2Three
It is secondary, plug balloon.Toluene (45mL) solvent of injection through bubbling deoxygenation, 100 DEG C of stirring 48h.Reaction is quenched in ice water, uses dichloromethane
Alkane extracts organic phase, and after deionization washing two or three times, anhydrous magnesium sulfate drying filters.Vacuum-concentrcted crude product, column chromatography
(leacheate DCM/PE=1:3) it purifies, obtains the solid chemical compound T1 (796mg) of yellow, yield 67.3%.
Reaction condition two：In N2It protects and is protected from light down, by compound II (834.0mg, 1.0mmol), N, N '-dimethyl two
Aniline (1183.6mg, 6mmol), potassium tert-butoxide (660.0mg, 6.0mmol) rapidly join catalyst Pd2(dba)3(91.6mg,
0.1mmol), ligand tri-tert-butylphosphine (40.0mg, 0.20mmol) is in two mouth flask.Reaction unit is sealed, substitutes N2Three
It is secondary, plug balloon.Toluene (45mL) solvent of injection through bubbling deoxygenation, 100 DEG C of stirring 48h.Reaction is quenched in ice water, uses dichloromethane
Alkane extracts organic phase, and after deionization washing two or three times, anhydrous magnesium sulfate drying filters.Vacuum-concentrcted crude product, column chromatography
(leacheate DCM/PE=1:3) it purifies, obtains the solid chemical compound T1 (758mg) of yellow, yield 64.1%.
Reaction condition three：In N2It protects and is protected from light down, by compound II (834.0mg, 1.0mmol), N, N '-dimethyl two
Aniline (789.6mg, 4mmol), potassium tert-butoxide (495.0mg, 4.5mmol) rapidly join catalyst Pd2(dba)3(91.6mg,
0.1mmol), ligand tri-tert-butylphosphine (40.0mg, 0.20mmol) is in two mouth flask.Reaction unit is sealed, substitutes N2Three
It is secondary, plug balloon.Toluene (45mL) solvent of injection through bubbling deoxygenation, 100 DEG C of stirring 48h.Reaction is quenched in ice water, uses dichloromethane
Alkane extracts organic phase, and after deionization washing two or three times, anhydrous magnesium sulfate drying filters.Vacuum-concentrcted crude product, column chromatography
(leacheate DCM/PE=1:3) it purifies, obtains the solid chemical compound T1 (692mg) of yellow, yield 58.5%.
1H NMR(400MHz,C7D8):δ 8.19 (d, J=8.7Hz, 3H), 7.50 (d, J=1.6Hz, 3H), 7.42-
7.26 (m, 15H), 6.98 (d, J=8.0Hz, 12H), 4.54 (t, J=7.5Hz, 6H), 2.17 (s, 18H), 1.71 (s, 6H),
1.00-0.87 (m, 18H), 0.71 (t, J=7.0Hz, 9H) .MALDI-TOF-MS (m/z):calcd for C84H90N6,
Molecular Weight:1183.69；Found:1182.72(M+).
Embodiment 4：
Reaction condition one：In N2It protects and is protected from light down, by compound II (834.0mg, 1.0mmol), N, N '-dimethyl two
Aniline (1375.6mg, 6mmol), potassium tert-butoxide (660.0mg, 6.0mmol) rapidly join catalyst Pd2(dba)3(137.4mg,
0.15mmol), ligand tri-tert-butylphosphine (60.0mg, 0.30mmol) is in two mouth flask.Reaction unit is sealed, substitutes N2Three
It is secondary, plug balloon.Toluene (45mL) solvent of injection through bubbling deoxygenation, 100 DEG C of stirring 48h.Reaction is quenched in ice water, uses dichloromethane
Alkane extracts organic phase, and after deionization washing two or three times, anhydrous magnesium sulfate drying filters.Vacuum-concentrcted crude product, column chromatography
(leacheate DCM/PE=1:6) it purifies, obtains the solid chemical compound T2 (845mg) of yellow, yield 66.1%.
Reaction condition two：In N2It protects and is protected from light down, by compound II (834.0mg, 1.0mmol), N, N '-dimethyl two
Aniline (1375.6mg, 6mmol), potassium tert-butoxide (660.0mg, 6.0mmol) rapidly join catalyst Pd2(dba)3(91.6mg,
0.1mmol), ligand tri-tert-butylphosphine (40.0mg, 0.20mmol) is in two mouth flask.Reaction unit is sealed, substitutes N2Three
It is secondary, plug balloon.Toluene (45mL) solvent of injection through bubbling deoxygenation, 100 DEG C of stirring 48h.Reaction is quenched in ice water, uses dichloromethane
Alkane extracts organic phase, and after deionization washing two or three times, anhydrous magnesium sulfate drying filters.Vacuum-concentrcted crude product, column chromatography
(leacheate DCM/PE=1:6) it purifies, obtains the solid chemical compound T2 (817mg) of yellow, yield 63.9%.
Reaction condition three：In N2It protects and is protected from light down, by compound II (834.0mg, 1.0mmol), N, N '-dimethyl two
Aniline (1031.7mg, 4.5mmol), potassium tert-butoxide (495.0mg, 4.5mmol) rapidly join catalyst Pd2(dba)3
(91.6mg, 0.1mmol), ligand tri-tert-butylphosphine (40.0mg, 0.20mmol) is in two mouth flask.Reaction unit is sealed,
Substitute N2Three times, balloon is plugged.Toluene (45mL) solvent of injection through bubbling deoxygenation, 100 DEG C of stirring 48h.Reaction is quenched in ice water,
Organic phase is extracted with dichloromethane, after deionization washing two or three times, anhydrous magnesium sulfate drying filters.Vacuum-concentrcted slightly produces
Object, column chromatography (leacheate DCM/PE=1:6) it purifies, obtains the solid chemical compound T2 (775mg) of yellow, yield 60.6%.
1H NMR(400MHz,C7D8):δ 8.21 (d, J=8.7Hz, 3H), 7.45 (d, J=1.8Hz, 3H), 7.35-
7.26 (m, 15H), 6.78 (d, J=9.0Hz, 12H), 4.53 (m, 6H), 3.38 (s, 18H), 1.76 (s, 6H), 1.01-0.93
(m, 1H), 0.72 (t, J=6.9Hz, 9H) .MALDI-TOF-MS (m/z):calcd for C84H90N6O6,Molecular
Weight:1279.68；Found:1278.69(M+).
The structural schematic diagram for the perovskite solar cell device that the present invention designs is as shown in Fig. 7, and preparation process is as follows：
1) FTO (fluorine doped tin indium oxide) electro-conductive glass is placed under ozone environment, through ultraviolet irradiation 15 minutes, then successively
With deionized water/cleanser, acetone and isopropanol be cleaned by ultrasonic 20 minutes it is spare；
2) control condition (2000rmp, 60s) is by titanium dioxide (TiO2) solution is spin-coated on FTO (fluorine doped tin indium oxide) and leads
On electric glass, to prepare the TiO of about 30nm thickness2As electron transfer layer, then anneal 2 hours on 200 DEG C of hot plate；
3) the dissolving lead iodide (PbI in N,N-dimethylformamide (DMF)2) it is prepared into perovskite presoma, and make
With being preceding heated to stirring 10 minutes at 100 DEG C；
4) substrate is heated to 100 DEG C, control condition, with rotating speed 4000rmp, time 60s is by PbI2Solution is spin-coated on heat
Substrate on, substrate is transferred on hot plate anneals 5 minutes to remove extra DMF solvent immediately after；
5) after substrate is cooled to room temperature, control condition, with rotating speed 4000rmp, time 60s is different by methylamine iodine (MAI)
Propanol solution is spun to the PbI prepared before2On film, substrate is then placed in the dust free room that relative humidity is about 30-40%
In, it anneals 1 hour on 100 DEG C of hot plate；
6) T1 of 60.3mg (or T2 of 65.1mg) is dissolved in 1mL chlorobenzenes, the 4- of 28.8mL is then added thereto
Tert .-butylpyridine (TPB) and bis- (trifyl) imide li (Li-TFSI) solution of 17.5mL are (per 520mg LI-TSFI/
1mL acetonitrile solutions) solution of hole transmission layer is prepared, hole mobile material is spin-coated on by control condition (4000rmp, 60s)
On calcium titanium ore bed, then in drier (humidity<15%) it in, is placed 12 hours in the case of dark.
7) gold for depositing about 80nm on the hole transport layer by the method for vacuum evaporation is used as to electrode.
Three and the electric current of perovskite solar cell devices for preparing as hole transmission layer of carbazole-aromatic amine derivant and
Voltage relationship figure is as shown in Fig. 8, and the detail parameters of device are summarized in table 1：
Table 1
From the parameter in Fig. 8 and table 1 as it can be seen that three and carbazole-aromatic amine derivant as hole transmission layer when, perovskite
Open-circuit voltage (the V of solar cell deviceOC), short circuit current (JSC) and fill factor (FF) can approach be based on Sprio-
The level of device prepared by OMeTAD.And pass through us and calculate, the cost of T1 and T2 are respectively 35 $ g-1With 39 $ g-1, much low
In manufacturing cost (the 598 $ g of Sprio-OMeTAD-1).Three and carbazole-aromatic amine derivant perovskite solar cell quotient
There are prodigious potentiality in industryization application.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. one kind three and carbazole-aromatic amine derivant hole mobile material, it is characterised in that：The material be using three and carbazole as
Starlike micromolecular compound of the derivative as modification group of core, aromatic amine, general formula structure is as shown in following formula 1：
In formula 1, Ar is one of group shown in the following Expression 2：
Wherein, one kind in R, R1 and R2 are C1-C30 straight chain, branched alkyl or oxyalkyl chain；* it is link position.
2. according to claim 1 three and carbazole-aromatic amine derivant hole mobile material, it is characterised in that：It is described logical
In formula structural formula 1, three and 2,7,12- of carbazole linked by-C-C- keys or-C-N- keys with modification group；Described R, R1
With one kind of straight chain, branched alkyl or oxyalkyl chain that R2 is C1-C12.
3. a kind of described in claim 1 three and carbazole-aromatic amine derivant hole mobile material preparation method, feature exists
In：Include the following steps：
The preparation of compound I：In nitrogen protection and under the conditions of be protected from light, by compound II, palladium catalyst, any one Ar1-Ar6
Single boric acid or secondary amine and alkali be dissolved in toluene, reacted, reaction terminates to purify to obtain compound I through column chromatography；
Wherein, the structure of compound II is as shown in Equation 3：
4. according to claim 3 three and carbazole-aromatic amine derivant hole mobile material preparation method, feature exists
In：Single boric acid of the compound II and any one Ar1-Ar6 or the molar ratio of secondary amine are 1:3~1:6.
5. according to claim 3 three and carbazole-aromatic amine derivant hole mobile material preparation method, feature exists
In：The palladium catalyst is the one of which of tetra-triphenylphosphine palladium or tris(dibenzylideneacetone) dipalladium, with compound II's
Molar ratio is 0.09:1~0.15:1.
6. according to claim 3 three and carbazole-aromatic amine derivant hole mobile material preparation method, feature exists
In：The alkali is the one of which of wet chemical or potassium tert-butoxide, is 4 with compound II molar ratios:1~6:1.
7. according to claim 3 three and carbazole-aromatic amine derivant hole mobile material preparation method, feature exists
In：The mass volume ratio of the compound II and toluene is：15~25mL of toluene solvant is added per 500mg compounds II.
8. according to claim 3 three and carbazole-aromatic amine derivant hole mobile material preparation method, feature exists
In：The reaction condition is：In 60~120 DEG C of 8~72h of reaction of temperature.
9. one kind as described in claim 1 three and carbazole-aromatic amine derivant hole mobile material as hole extract material,
Hole mobile material or electron-blocking materials are applied to organic electroluminescence device, organic solar batteries, the perovskite sun
Application in energy battery or organic field effect tube.
10. application according to claim 9, it is characterised in that：Described three and carbazole-aromatic amine derivant hole transport material
Material is applied to perovskite solar cell device as hole mobile material.
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| CN112079849B (en) * | 2020-08-14 | 2023-06-27 | 浙江工业大学 | Indole derivative-proEDOT compound and preparation and application thereof |
| WO2024031919A1 (en) * | 2022-08-12 | 2024-02-15 | 苏州大学 | Carbazole fused boron-nitrogen derivative, preparation method therefor, and use thereof |
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Application publication date: 20181113 |