CN108948026A - One kind three and carbazole-phenyl hole mobile material and the preparation method and application thereof - Google Patents
One kind three and carbazole-phenyl hole mobile material and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses one kind three and carbazole-phenyl hole mobile materials and the preparation method and application thereof.The material be using three and carbazole as core, benzene derivate as modification group starlike small molecule compound.Materials synthesis route of the invention is simple, it is low in cost, reaction process is easily controllable, it is easily isolated, high income, and the material has suitable HOMO energy level, good dissolubility, excellent hole mobility, excellent thermal stability and amorphous character, and the noncrystal membrane of high quality can be prepared by solwution method.There is potential commercial application value in fields such as organic electroluminescence device, organic solar batteries device, perovskite solar cell device or organic field effect tube devices.
Description
Technical field
The invention belongs to optoelectronic materials technologies, and in particular to one kind three and carbazole-phenyl hole mobile material and its
Preparation method and application.
Background technique
Hole mobile material plays indispensable role in terms of the efficiency and stability for promoting organic electro-optic device.
In perovskite area of solar cell, high-performance hole mobile material most widely used at present be 2,2', 7,7'- tetra- [N,
N- bis- (4- methoxyphenyl) amino] two fluorenes (Sprio-OMeTAD) of -9,9'- spiral shell.But Sprio-OMeTAD cumbersome synthesis
Step and high preparation cost limit the large-scale production and application of perovskite solar battery.Develop the new of Cheap highly effective
Type hole mobile material is one of the important channel for promoting the commercialization process of perovskite solar battery.
Three and carbazole be a kind of group with the pi-conjugated system of two dimension, hole mobility with higher, excellent heat are steady
Qualitative, strong electron donation and the unique property such as cheap and easy to get, and its synthetic route is simple, is easy to purify, and is easy to modify,
Alkyl chain and modification group can be changed easily to regulate and control its aggregation extent and photoelectric property.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 carbazoles hole mobile material synthetic method, be applied to calcium titanium
The efficiency of highest 18.3% is achieved when mine solar battery.Revive into brave class group [Su P Y；Huang L B；Liu J M,et
al.A multifunctional poly-N-vinylcarbazole interlayer in perovskite solar
cells for high stability and efficiency:a test with new triazatruxene-based
Hole transporting materials [J] .J.Mater.Chem.A, 2017,5 (5): 1913-1918.] report two
Three and carbazoles hole mobile material synthetic method, applied to the photoelectricity for achieving highest 15.5% in the device of conventional structure
Transfer efficiency.The hole mobile material that they report is both needed to obtain final product by four-step reaction, is unfavorable for reducing material
Preparation cost simplifies preparation process.
, based on three and core of the carbazole as molecule, devising a series of simply react by three steps can be prepared by for we
Hole mobile material, change intramolecular alkyl chain length and type can with the aggregation extent of controlled material, thus obtain compared with
High hole mobility and excellent film morphology.It is designed to provide the sky that one kind is cheap, preparation is simple, has excellent performance
Hole transport materials and preparation method thereof.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the present invention provides one kind three and carbazole-phenyl hole
Transmission material and the preparation method and application thereof, the material only need the simple controllable reaction of three steps that can prepare, and reaction raw materials are honest and clean
Valence, product is easily isolated, purity is high, yield are high, and the material has lower HOMO energy level and higher hole mobility,
When being used as the hole transmission layer of organic electro-optic device as hole mobile material with excellent performance.Solves hole transport
Cumbersome, the with high costs or poor performance problem of material preparation route.
Technical solution: to achieve the above object, the technical solution adopted by the present invention are as follows:
The present invention provides one kind three and carbazole-phenyl hole mobile materials.The material is using three and carbazole is core, benzene
Starlike small molecule compound of the derivative as modification group, general formula structure is as shown in following formula I:
Ar in Formulas I is one of following group:
Wherein, R, R1、R2And R3For C1-C30One of straight chain, branched alkyl or oxyalkyl chain；It * is link position；N
It is nitrogen-atoms.
Further, in the structural formula I, three and the position 1- of 2,7,12- s of carbazole and Ar group pass through-C-C- key
Link.
Further, described R, R1、R2And R3For C1-C12Straight chain, branched alkyl or oxyalkyl chain one kind.
Meanwhile the present invention provides described in one kind three and carbazole-phenyl hole mobile material preparation method, including following
Step:
The preparation of chemical compounds I:, will be any in compound ii, palladium catalyst, I formula in nitrogen protection and under the conditions of be protected from light
One of which and the alkali of single boric acid of Ar1-Ar6 are dissolved in suitable toluene solution, 60~120 DEG C of 8~72h of reaction of temperature control, instead
It should terminate to purify to obtain compound I through column chromatography.
Wherein, R C1-C30One of straight chain, branched alkyl or oxyalkyl chain.
The II formula and any one Ar1-Ar6Single boric acid molar ratio be 1:3~1:9；Palladium catalyst is four triphenyls
Phosphine palladium is 0.09:1~0.15:1 with compound II molar ratio；Alkali is potassium carbonate, is 3:1~9:1 with compound II molar ratio；
15~25mL of toluene is added in every 500mg compound II, and 7.5~12.5mL of water is added.
Of the present invention a kind of three and carbazole-phenyl hole mobile material can be used as hole extract material, hole pass
Defeated material or electron-blocking materials are applied to organic electroluminescence device, organic solar batteries, perovskite solar battery
Or in organic field effect tube.Particularly, it can be used as hole mobile material to be applied to prepare efficient perovskite solar-electricity
Pond device.
The utility model has the advantages that provided by the invention a kind of three and carbazole-phenyl hole mobile material and the preparation method and application thereof,
Compared with prior art, it has the advantage that
Simultaneously carbazole-phenyl hole mobile material synthetic route is brief by the present invention three, and reaction raw materials are cheap, and reaction process is easy
Control, product is easily isolated, purity is high, yield are high, and the material has lower HOMO energy level and higher hole migration
Rate.Particularly, performance can match in excellence or beauty Sprio- under similarity condition when hole transmission layer as perovskite solar battery
The level of OMeTAD.It is this kind of to have excellent performance and low-cost novel hole transport material can be widely applied to organic electroluminescence
In luminescent device, organic solar batteries, perovskite solar cell device or organic field effect tube device, have important
Application potential.
Detailed description of the invention
Fig. 1 is the MALDI-TOF spectrogram of TAT-Ph-OMe；
Fig. 2 is TAT-Ph-OMe's1H NMR spectra；
Fig. 3 is TAT-Ph-OMe's13C NMR spectra；
Fig. 4 is TAT-Ph-OMe ultraviolet-ray visible absorbing emission spectrum；
Fig. 5 is the relationship between energy levels figure in TAT-Ph-OMe and perovskite solar battery between each material；
Fig. 6 is the spin coating fluorescence spectrum of the perovskite thin film of TAT-Ph-OMe；
Fig. 7 is the structural schematic diagram of perovskite solar cell device；
Fig. 8 is J-V curve of the TAT-Ph-OMe as the perovskite solar battery of hole transmission layer.
Specific embodiment
The present invention provides one kind three and carbazole-phenyl hole mobile materials.The material is using three and carbazole is core, benzene
Starlike small molecule compound of the derivative as modification group, general formula structure is as shown in following formula I:
Ar in Formulas I is one of following group:
Wherein, R, R1、R2And R3For C1-C30One of straight chain, branched alkyl or oxyalkyl chain；It * is link position；N
It is nitrogen-atoms.
In the structural formula I, three and the position 1- of 2,7,12- s of carbazole and Ar group pass through-C-C- key and link；It is described
R, R1And R2For C1-C12Straight chain, branched alkyl or oxyalkyl chain one kind.
Three and carbazole-phenyl hole mobile material preparation method, comprising the following steps: 6- bromo indole ketone first passes through
It crosses alkylation and 1- hexyl -6- bromo indole ketone is prepared, the cyclization under phosphorus oxychloride catalysis of 1- hexyl -6- bromo indole ketone is prepared
Compound II, then compound II is prepared from different benzene derivate modification group Ar by Suzuki coupling reaction
Compound I:
The present invention will be further explained with reference to the accompanying drawings and examples.
Embodiment
According to following embodiments, the present invention can be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies specific material proportion, process conditions and its result described in example and is merely to illustrate the present invention, without that should will not limit
The present invention described in detail in claims processed.
Below by way of several embodiments, the present invention will be further described, but embodiment does not limit and of the invention covers model
It encloses.
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 flask.Reaction unit is sealed, substitutes nitrogen
Gas three times, plugs nitrogen ball.Inject 22mL tetrahydrofuran, stir 30min under the conditions of 85 DEG C, be then slowly injected into 2mL bromine oneself
Alkane keeps stirring 8h at 80 DEG C.It pours into ice water and is quenched after reacting and being slowly cooled to room temperature, extracted with methylene chloride (DCM)
Organic phase, after deionization washing three times, organic phase is dry with anhydrous magnesium sulfate.Organic phase is obtained through vacuum-concentrcted after suction filtration
Crude product, use column chromatography technology (leacheate for methylene chloride (DCM) and petroleum ether (PE) mixed liquor, ratio 1:1) purifying,
Obtain the white waxy solid compound bromo- indolone of 1- hexyl -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 flask.Reaction unit is sealed, substitutes nitrogen
Gas three times, plugs nitrogen ball.Inject 22mL tetrahydrofuran, stir 30min under the conditions of 85 DEG C, be then slowly injected into 2mL bromine oneself
Alkane keeps stirring 8h at 80 DEG C.It pours into ice water and is quenched after reacting and being slowly cooled to room temperature, be extracted with dichloromethane organic
Phase, after deionization washing three times, organic phase is dry 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) to purify, it is bromo- to obtain white waxy solid compound 1- hexyl -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 flask.Reaction unit is sealed, substitutes nitrogen
Gas three times, plugs nitrogen ball.Inject 22mL tetrahydrofuran, stir 30min under the conditions of 85 DEG C, be then slowly injected into 3mL bromine oneself
Alkane keeps stirring 8h at 85 DEG C.It pours into ice water and is quenched after reacting and being slowly cooled to room temperature, be extracted with dichloromethane organic
Phase, after deionization washing three times, organic phase is dry 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) to purify, it is bromo- to obtain white waxy solid compound 1- hexyl -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；Target product molecular formula are as follows: C14H18BrNO, molecular weight
Are as follows: 296.21；Mass spectral results are as follows: 295.06 (M+).
Embodiment 2:
Reaction condition one: being placed in twoport reaction flask for the compound bromo- indolone of 1- hexyl -6- (10g, 33mmol), sealing
Good reaction unit injects 40mL phosphorus oxychloride, keeps stirring 8h at 100 DEG C.Ice water is poured into after reacting and being 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: being placed in twoport reaction flask for the compound bromo- indolone of 1- hexyl -6- (10g, 33mmol), sealing
Good reaction unit injects 80mL phosphorus oxychloride, keeps stirring 8h at 100 DEG C.Ice water is poured into after reacting and being 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: being placed in twoport reaction flask for the compound bromo- indolone of 1- hexyl -6- (10g, 33mmol), sealing
Good reaction unit injects 60mL phosphorus oxychloride, keeps stirring 8h at 100 DEG C.Ice water is poured into after reacting and being 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. target product molecular formula are as follows:
C42H48Br3N3, molecular weight are as follows: 834.58；Mass spectral results are as follows: 831.14 (M+).
Embodiment 3:
Reaction condition one: in nitrogen protection and under being protected from light, by compound II (834.0mg, 1.0mmol), 2,4- dimethoxy
Base phenyl boric acid (1091.8mg, 6mmol), catalyst Pd (PPh3)4(173.3mg, 0.15mmol), the phase transfer catalyst tetrabutyl
Ammonium bromide (TBAB) (32.2mg, 0.1mmol) is placed in two mouth flask.Reaction unit is sealed, substitutes nitrogen three times, plugs nitrogen
Balloon.Toluene (40mL) solvent and wet chemical (20mL, 2M) that injection is steamed purification again, is bubbled deoxygenation, in 85 DEG C of items
It is stirred for 24 hours under part.It pours into ice water and is quenched after reacting and being slowly cooled to room temperature, organic phase, deionization is extracted with dichloromethane
After washing three times, organic phase is dry with anhydrous magnesium sulfate.Organic phase obtains crude product through vacuum-concentrcted after suction filtration, using column
Chromatographic technique (leacheate DCM/PE=1:3) purifying, obtains compound as white solid TAT-Ph-OMe (787mg), yield
78.3%.
Reaction condition two: in nitrogen protection and under being protected from light, by compound II (834.0mg, 1.0mmol), 2,4- dimethoxy
Base phenyl boric acid (818.9mg, 4.5mmol), catalyst Pd (PPh3)4(173.3mg, 0.15mmol), phase transfer catalyst TBAB
(32.2mg, 0.1mmol) is placed in two mouth flask.Reaction unit is sealed, substitutes nitrogen three times, plugs nitrogen ball.Injection warp
Tetrahydrofuran (40mL) solvent and wet chemical (20mL, 2M) for steaming purification again, being bubbled deoxygenation, are stirred under the conditions of 85 DEG C
24h.It pours into ice water and is quenched after reacting and being slowly cooled to room temperature, organic phase is extracted with dichloromethane, deionization is washed three times
Afterwards, organic phase is dry with anhydrous magnesium sulfate.Organic phase obtains crude product through vacuum-concentrcted after suction filtration, using column chromatography technology
(leacheate DCM/PE=1:3) purifying, obtains compound as white solid TAT-Ph-OMe (772mg), yield 76.7%.
Reaction condition three: in nitrogen protection and under being protected from light, by compound II (834.0mg, 1.0mmol), 2,4- dimethoxy
Base phenyl boric acid (727.9mg, 4mmol), catalyst Pd (PPh3)4(103.9mg, 0.09mmol), phase transfer catalyst TBAB
(32.2mg, 0.1mmol) is placed in two mouth flask.Reaction unit is sealed, substitutes nitrogen three times, plugs nitrogen ball.Injection warp
Tetrahydrofuran (40mL) solvent and wet chemical (20mL, 2M) for steaming purification again, being bubbled deoxygenation, are stirred under the conditions of 85 DEG C
24h.It pours into ice water and is quenched after reacting and being slowly cooled to room temperature, organic phase is extracted with dichloromethane, deionization is washed three times
Afterwards, organic phase is dry with anhydrous magnesium sulfate.Organic phase obtains crude product through vacuum-concentrcted after suction filtration, using column chromatography technology
(leacheate DCM/PE=1:3) purifying, obtains compound as white solid TAT-Ph-OMe (747mg), yield 74.3%.
We confirmed the structure of target product, data by mass spectrum (attached drawing 1), hydrogen spectrum (attached drawing 2) and carbon spectrum (attached drawing 3)
As a result as follows:1H NMR(400MHz,C6D6): δ 8.49 (d, J=8.3Hz, 2H), 8.03 (d, J=11.1Hz, 2H), 7.83 (d,
J=8.2Hz, 3H), 7.66-7.54 (m, 3H), 6.73-6.51 (m, 6H), 4.84 (dd, J=18.4,11.3Hz, 6H), 3.45
(dt, J=21.2,5.8Hz, 18H), 1.91 (d, J=6.6Hz, 6H), 1.03 (dd, J=29.9,5.2Hz, 18H), 0.70
(dd, J=13.1,6.9Hz, 9H)13C NMR(101MHz,C6D6):δ160.44,158.04,141.58,139.36,
133.50,131.79,122.55,121.88,121.35,112.09,104.81,103.83,99.61,54.54,46.88,
(31.41,29.92,26.32,22.44,13.77.MALDI-TOF-MS m/z): target product molecular formula are as follows: C66H75N3O6；Point
Son amount are as follows: 1006.34；Mass spectral results are as follows: 1005.57 (M+).
Embodiment 4:
The structural schematic diagram for the perovskite solar cell device that we design is as shown in Fig. 7, and preparation step is as follows:
1) FTO electro-conductive glass is placed under ozone environment, through ultraviolet irradiation 15 minutes, then successively with deionized water/go
Dirty powder, acetone and isopropanol ultrasonic cleaning 20 minutes are spare；
2) control condition (2000rmp, 60s) is by titanium dioxide (TiO2) solution is spin-coated on ITO electro-conductive glass, with preparation
The TiO of about 30nm thickness2As electron transfer layer, then anneal 2 hours on 200 DEG C of hot plate；
3) PbI is dissolved in N,N-dimethylformamide (DMF)2It is prepared into perovskite presoma, and is using preceding heating
It is stirred 10 minutes to 100 DEG C；
4) substrate is heated to 100 DEG C, control condition (4000rmp, 60s) is by PbI2Solution is spin-coated on the substrate of heat,
Substrate is transferred on hot plate immediately after and anneals 5 minutes to remove extra DMF solvent；
5) after substrate is cooled to room temperature, before the aqueous isopropanol of MAI is spun to by control condition (4000rmp, 60s)
The PbI of preparation2On film, then substrate is placed in the dust free room that relative humidity is about 30-40%, on 100 DEG C of hot plate
Annealing 1 hour；
6) TAT-Ph-OMe of 51.2mg is dissolved in 1mL chlorobenzene, the 4- tert-butyl of 28.8mL is then added thereto
Pyridine (TPB) and bis- (trifyl) imide li (Li-TFSI) solution (the every 520mgLI-TSFI/1mL acetonitriles of 17.5mL
Solution) solution of hole transmission layer is prepared, hole mobile material is spin-coated on calcium titanium ore bed by control condition (4000rmp, 60s)
On, then in drier (humidity < 15%), placed 12 hours in the case where dark.
7) gold of about 80nm is deposited as to electrode by the method for vacuum evaporation on the hole transport layer.
The ultraviolet-ray visible absorbing emission spectrum of TAT-Ph-OMe is as shown in Fig. 4, and the material absorption spectrum is in ultra-violet (UV) band
Domain will not influence perovskite material and absorb incident light.By relationship between energy levels figure (attached drawing 5) it can be seen that TAT-Ph-OMe have with
The energy level that perovskite material matches, this is conducive to hole and is injected into the material from perovskite material.Pass through perovskite thin film
Very strong quenching has occurred in the perovskite thin film fluorescence that fluorescence spectrum (attached drawing 6) can be seen that spin coating TAT-Ph-OMe, this says
Bright hole has efficiently extracted TAT-Ph-OMe from perovskite.
The electric current and voltage relationship figure for the perovskite solar cell device that TAT-Ph-OMe is prepared as hole transmission layer
As shown in Fig. 8, the detail parameters of device are summarized in following table:
From the parameter in Fig. 8 and upper table as it can be seen that when TAT-Ph-OMe is as hole transmission layer, perovskite solar battery
Open-circuit voltage (the V of deviceOC), short circuit current (JSC) and fill factor (FF) can reach with based on Sprio-OMeTAD system
The level that standby device compares favourably, and the device based on TAT-Ph-OMe preparation has higher photoelectric conversion efficiency (PCE).
Importantly, the cost for being computed the TAT-Ph-OMe of the route preparation designed by us is about $ 32g-1, less than Sprio-
/ 10th (598g of OMeTAD preparation cost-1)。
Materials synthesis route of the invention is simple, and low in cost, reaction process is easily controllable, is easily isolated, high income, and
And the material has suitable HOMO energy level, good dissolubility, excellent hole mobility, excellent thermal stability and non-
Crystalline state characteristic can prepare the noncrystal membrane of high quality by solwution method.In organic electroluminescence device, organic solar batteries
The fields such as device, perovskite solar cell device or organic field effect tube device have potential commercial application value.
The above is only a preferred embodiment of the present invention, it should be pointed out 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-phenyl hole mobile material, it is characterised in that: the material is using three and carbazole is core, with benzene
Starlike small molecule compound of the derivative as modification group.
2. according to claim 1 a kind of three and carbazole-phenyl hole mobile material, which is characterized in that the knot of the material
Structure general formula is as shown in following formula I:
Ar is one of following group:
Wherein, R, R1、R2And R3For C1-C30One of straight chain, branched alkyl or oxyalkyl chain.
3. according to claim 1 a kind of three and carbazole-phenyl hole mobile material, which is characterized in that described three are simultaneously
The position 2,7,12- of carbazole and the position 1- of Ar group are linked by-C-C- key.
4. according to claim 1 a kind of three and carbazole-phenyl hole mobile material, which is characterized in that described R, the R1、
R2And R3For C1-C12Straight chain, branched alkyl or oxyalkyl chain one kind.
5. according to any one of claims 1 to 4 three and carbazole-phenyl hole mobile material preparation method, feature exist
In, comprising the following steps:
In nitrogen protection and under the conditions of be protected from light, by any Ar in compound II, palladium catalyst, I formula1-Ar6Single boric acid wherein
One kind being dissolved in toluene aqueous solution with alkali, and phase transfer catalyst, 60~120 DEG C of 8~72h of reaction of temperature control is added, and reaction terminates warp
Column chromatography purifies to obtain compound I；
The general structure of the compound II are as follows:
Wherein, R C1-C30One of straight chain, branched alkyl or oxyalkyl chain.
6. according to claim 5 a kind of three and carbazole-phenyl hole mobile material preparation method, which is characterized in that
The II formula and any one Ar1-Ar6Single boric acid molar ratio be 1:3~1:9.
7. according to claim 5 a kind of three and carbazole-phenyl hole mobile material preparation method, which is characterized in that
Palladium catalyst is tetra-triphenylphosphine palladium, is 0.09:1~0.15:1 with compound II molar ratio；The phase transfer catalyst is four
Butylammonium bromide is 0.1:1~0.3:1 with compound II molar ratio.
8. according to claim 5 a kind of three and carbazole-phenyl hole mobile material preparation method, which is characterized in that
Alkali is potassium carbonate, is 3:1~9:1 with compound II molar ratio.
9. according to claim 5 three and carbazole-phenyl hole mobile material preparation method, it is characterised in that: every
15~25mL of toluene is added in 500mg compound II, and 7.5~12.5mL of water is added.
10. according to any one of claims 1 to 4 three and the application of carbazole-phenyl hole mobile material, which is characterized in that
The material is applied to organic electroluminescence device as hole extraction material, hole mobile material or electron-blocking materials, has
In machine solar battery, perovskite solar cell device or organic field effect tube.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020119503A1 (en) * | 2018-12-10 | 2020-06-18 | 广州华睿光电材料有限公司 | Organic electroluminescent device comprising light extraction layer, heteroatom polyaromatic ring compound, and composition |
| CN112079840A (en) * | 2020-08-03 | 2020-12-15 | 浙江工业大学 | Indole derivative-thiophene compound and preparation and application thereof |
| CN112079849A (en) * | 2020-08-14 | 2020-12-15 | 浙江工业大学 | Indole derivative-proEDOT compound and preparation and application thereof |
| CN112094282A (en) * | 2020-08-03 | 2020-12-18 | 浙江工业大学 | Indole derivative-EDOT compound and preparation and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023148A (en) * | 2004-09-20 | 2007-08-22 | Lg化学株式会社 | Carbazole derivative and organic light emitting device using same |
| CN103421012A (en) * | 2012-05-24 | 2013-12-04 | 南京工业大学 | Method for preparing tricarbazole materials from aryl oxindole in one step |
| CN103524511A (en) * | 2013-10-21 | 2014-01-22 | 南京邮电大学 | Preparation method of 2,7,12-tribromo-5,10,15-trialkyltricarbazole |
| CN103664950A (en) * | 2012-09-04 | 2014-03-26 | 北京师范大学 | Novel trimerization carbazole based narrow band gap conjugated micromolecule material and preparation method thereof |
| WO2016083655A1 (en) * | 2014-11-28 | 2016-06-02 | Abengoa Research, S.L. | Novel compound and use thereof as a hole-transport material |
-
2018
- 2018-06-15 CN CN201810617494.6A patent/CN108948026A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023148A (en) * | 2004-09-20 | 2007-08-22 | Lg化学株式会社 | Carbazole derivative and organic light emitting device using same |
| CN103421012A (en) * | 2012-05-24 | 2013-12-04 | 南京工业大学 | Method for preparing tricarbazole materials from aryl oxindole in one step |
| CN103664950A (en) * | 2012-09-04 | 2014-03-26 | 北京师范大学 | Novel trimerization carbazole based narrow band gap conjugated micromolecule material and preparation method thereof |
| CN103524511A (en) * | 2013-10-21 | 2014-01-22 | 南京邮电大学 | Preparation method of 2,7,12-tribromo-5,10,15-trialkyltricarbazole |
| WO2016083655A1 (en) * | 2014-11-28 | 2016-06-02 | Abengoa Research, S.L. | Novel compound and use thereof as a hole-transport material |
Non-Patent Citations (4)
| Title |
|---|
| KASPARAS RAKSTYS ET AL.: ""Triazatruxene-Based Hole Transporting Materials for Highly Efficient Perovskite Solar Cells"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| KUN-HAN LIN ET AL.: ""A Rising Star: Truxene as a Promising Hole Transport Material in Perovskite Solar Cells"", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| PEI-YANG SU ET AL.: ""A multifunctional poly-N-vinylcarbazole interlayer in perovskite solar cells for high stability and efficiency: a test with new triazatruxene-based hole transporting materials"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| TIANHAO ZHU ET AL.: ""The synthesis, photophysical and electrochemical properties of a series of novel 3,8,13-substituted triindole derivatives"", 《DYES AND PIGMENTS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020119503A1 (en) * | 2018-12-10 | 2020-06-18 | 广州华睿光电材料有限公司 | Organic electroluminescent device comprising light extraction layer, heteroatom polyaromatic ring compound, and composition |
| CN112079840A (en) * | 2020-08-03 | 2020-12-15 | 浙江工业大学 | Indole derivative-thiophene compound and preparation and application thereof |
| CN112094282A (en) * | 2020-08-03 | 2020-12-18 | 浙江工业大学 | Indole derivative-EDOT compound and preparation and application thereof |
| CN112094282B (en) * | 2020-08-03 | 2023-06-09 | 浙江工业大学 | Indole derivative-EDOT compound and preparation and application thereof |
| CN112079840B (en) * | 2020-08-03 | 2023-06-27 | 浙江工业大学 | Indole derivative-thiophene compound and preparation and application thereof |
| CN112079849A (en) * | 2020-08-14 | 2020-12-15 | 浙江工业大学 | Indole derivative-proEDOT compound and preparation and application thereof |
| CN112079849B (en) * | 2020-08-14 | 2023-06-27 | 浙江工业大学 | Indole derivative-proEDOT compound and preparation and application thereof |
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