CN104829521B - A kind of 10,15 diphenyl benzfluorenes and carbazole derivates and its application - Google Patents
A kind of 10,15 diphenyl benzfluorenes and carbazole derivates and its application Download PDFInfo
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Abstract
The invention provides a kind of 10,15 diphenyl benzfluorenes and carbazole derivates, it is characterised in that with such as formula（I）Shown structure：Wherein：Ar1‑Ar4Be independently selected from H, C6~C30 substituted or non-substituted aromatic hydrocarbon group, C6~C30 substituted or non-substituted condensed-nuclei aromatics group, C6~C30 substituted or non-substituted condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle, triarylamine group, aryl oxide group base group, one kind in C1~C12 substituted or non-substituted aliphatic alkyl group；Ar5One kind in the substituted or non-substituted condensed-nuclei aromatics group of substituted or non-substituted aromatic hydrocarbon group, C6~C30 selected from C6~C30, C1~C12 substituted or non-substituted aliphatic alkyl group.Ar6‑Ar7It is independently selected from one kind in H, C6~C30 substituted or non-substituted aromatic hydrocarbon group, C6~C30 substituted or non-substituted condensed-nuclei aromatics group, C1~C12 substituted or non-substituted aliphatic alkyl group.Simultaneously carbazole derivates can be used as hole-injecting material, hole transport layer material, fluorescent host material or luminescent material to this kind of 10,15 diphenyl benzfluorenes in organic electroluminescence device.
Description
Technical field
The present invention relates to a class new organic materials, and its application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
The hole used always in organic electroluminescent device is injected and transmission material is usually an aromatic amino-derivative（Example
Such as light extraction patent：Publication number CN1152607C, publication date 2004,6,2）, it is general to be structurally characterized in that, as injection material,
One arylamine construction unit is at least separated at more than one, and between two N with a phenyl ring in a molecule, sees formula 1；Make
For transmission material, one arylamine construction unit is usually two in a molecule, and is separated between two N with biphenyl, at this
In class material, typical example is NPB, and its structure is shown in formula 2.
In recent years, the research of this kind of material has some new progresses, and one or more thienyls are introduced in the molecule, or
Person introduces one or more benzothienyls, sees formula 3 and formula 4（Light extraction patent：Publication number CN101506191A, publication date 2009,
8,12）, result is the Hole injection capacity for considerably increasing material；As transmission material, when by an arylamine in material
When construction unit carbazole or dibenzofurans substitution, the transmittability of material all has a more substantial increase.See formula 5 and formula 6（Go out
Light patent：Publication number CN102334210A, the applying date 2012,1,25；Publication number：WO2010/114017A1, publication date 2010,
10,7）.
The content of the invention
It is an object of the invention to propose the new benzfluorene of a class and carbazole analog derivative, such compound can be used for
ORGANIC ELECTROLUMINESCENCE DISPLAYS field.Specifically, this kind of compound is in display of organic electroluminescence, as hole-injecting material
Or as hole mobile material, light emitting host material or luminescent material can be also used as in fluorescent device.
Especially, it has been found that in the material of the present invention, if only connecting condensed ring on benzfluorene and carbazole precursor structure
Aromatic hydrocarbons, rather than connection triaryl amine or condensed hetero ring aromatic hydrocarbons, such as carbazole group, dibenzothiophenes group, dibenzofurans group
Deng such material is suitable as light emitting host material, device light emitting efficiency is improved a lot, and device lifetime is longer.And
Triaryl amine or condensed hetero ring aromatic hydrocarbons, such as carbazole group, dibenzothiophenes group, two are connected with benzfluorene and carbazole precursor structure
Benzofuran group etc., such material is suitable as hole mobile material.In a word, the use of material of the present invention, reduces device
The luminous efficiency for opening bright voltage, improving device of part, adds the service life of device.
Therefore, the technical scheme that the present invention takes is：
One kind 10,15- diphenyl benzfluorene and carbazole derivates, with such as formula（I）Shown structure：
Wherein：Ar1-Ar4Be independently selected from H, C6~C30 substituted or non-substituted aromatic hydrocarbon group, C6~C30 substitution or
Non-substituted condensed-nuclei aromatics group, C6~C30 substituted or non-substituted condensed hetero ring group, five yuan, hexa-atomic heterocycle or substitution
One in heterocycle, triarylamine group, aryl oxide group base group, C1~C12 substituted or non-substituted aliphatic alkyl group
Kind；
Ar5The substituted or non-substituted condensed ring virtue of substituted or non-substituted aromatic hydrocarbon group, C6~C30 selected from C6~C30
One kind in hydrocarbon or condensed hetero ring aromatic hydrocarbon group, C1~C12 substituted or non-substituted aliphatic alkyl group.
Ar6-Ar7Be independently selected from H, C6~C30 substituted or non-substituted aromatic hydrocarbon group, C6~C30 it is substituted or non-substituted
Condensed-nuclei aromatics group, one kind in C1~C12 substituted or non-substituted aliphatic alkyl group.
Further, the Ar1、Ar2、Ar6、Ar7It is simultaneously H.
Further, the Ar5Alkyl, phenyl, aminomethyl phenyl, ethylphenyl, methoxyphenyl, connection selected from C1~C6
Phenyl, naphthyl, anthryl, phenanthryl, perylenes base, pyrenyl.
Further, the Ar3Or Ar4Selected from phenyl, phenyl, naphthyl, C1-6Alkyl, one or two kinds of bases in carbazyl
The phenyl of group's substitution, naphthyl, phenyl, naphthyl, C1-6Alkyl, in carbazyl one or two kinds of substituent groups naphthyl, anthryl,
Phenyl, naphthyl, C1-6Alkyl, in carbazyl one or two kinds of substituent groups anthryl, phenanthryl, phenyl, naphthyl, C1-6Alkane
The phenanthryl , perylene bases of one or two kinds of substituent groups, phenyl, naphthyl, C in base, carbazyl1-6Alkyl, it is a kind of in carbazyl or
Two kinds of substituent group perylene bases, pyrenyl, phenyl, naphthyl, C1-6Alkyl, in carbazyl one or two kinds of substituent groups pyrenyl,
Fluoranthene base, phenyl, naphthyl, C1-6Alkyl, in carbazyl one or two kinds of substituent groups fluoranthene base,Base, phenyl, naphthyl,
C1-6Alkyl, one or two kinds of substituent groups in carbazylBase, Sanya phenyl, phenyl, naphthyl, C1-6Alkyl, carbazole
The Sanya phenyl of one or two kinds of substituent groups, carbazyl, phenyl, naphthyl, C in base1-6Alkyl, a kind of in carbazyl or two
Plant the carbazyl of substituent group, triarylamine, phenyl, naphthyl, C1-6Alkyl, one or two kinds of substituent groups in carbazyl
Triarylamine, diaryl-amine base, N- phenyl carbazole bases, N- phenylnaphthalenes amido, dibenzothiophenes base, dibenzofuran group, benzo thiophene
Fen base.
In order to illustrate more clearly of present invention, lower mask body narration the present invention relates to 10,15- diphenyl benzos
Fluorenes and carbazole derivates preferred structure：
The invention provides a kind of 10,15- diphenyl benzfluorene that can be applied in organic electroluminescence device and carbazole
Derivative.
10, the 15- diphenyl benzfluorene and carbazole derivates of the present invention has higher hole migration ability, described
Simultaneously carbazole derivates can be used as hole-injecting material, hole biography to 10,15- diphenyl benzfluorenes in organic electroluminescence device
Defeated material or material of main part.
Present invention also offers a kind of organic electroluminescence device, including substrate, and sequentially form on the substrate
Anode layer, organic luminescence function layer and cathode layer；
The organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer；
The hole mobile material of the hole transmission layer is described 10,15- diphenyl benzfluorene and carbazole derivates.
Present invention also offers a kind of organic electroluminescence device, including substrate, and sequentially form on the substrate
Anode layer, organic luminescence function layer and cathode layer；
Described organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer；
The material of main part of the organic luminous layer contains described 10,15- diphenyl benzfluorene and carbazole derivates.
Embodiment
Basic raw material used in the present invention, bromo- 7,12- diphenyl benzo [k] fluoranthene of 3-, 2,4- bis- bromo nitrobenzenes,
2,5- bis- bromo nitrobenzenes, and bromo carbazole derivative, bromo dibenzofurans, bromo dibenzothiophenes, bromo Chrysene,
Bromo triphenylene, bromo pyrene etc., major industrial chemicals it can be commercially available at home.Close in 5- bromine benzophenanthrenes system this laboratory oneself
Into.
Embodiment
The synthesis of main intermediate 7,12- diphenyl benzo [k] fluoranthene -3- boric acid
By bromo- 7,12- diphenyl benzo [k] fluoranthene of 9.65g 3-（Molecular weight 482,0.02mol）It is dissolved in 120ml dryings
THF in, -80 DEG C be added dropwise normal-butyls reason 9ml（2.5M, 0.0225mol）, 15min is stirred, then triisopropyl borate is added dropwise
20ml.Hydrolysis, regulation pH to neutrality separates out boronic acid derivatives 8.9g, yield intimate 100%.
Embodiment 1
The synthesis of compound 1
（1）The first step,
1000 milliliters of a bite bottles, with magnetic agitation, add 7,12- diphenyl benzo [k] fluoranthene -3- boric acid 18g（Molecular weight
448,0.04mol）, 2,4- bis- bromo nitrobenzene 11.4g（Molecular weight 278,0.041mol）, the usage amount 2.6g of Pd (PPh3) 4（Molecule
Amount 1154,0.00253mol）, sodium carbonate 200ml（2M）, toluene 200ml, ethanol 200ml.After argon gas displacement, TLC is used in backflow
Monitoring reaction, reacts complete, cooling, has separated basic unit, be evaporated, post point is carried out with 1/10 ethyl acetate/petroleum ether after 3 hours
From obtaining 22.3g products, molecular weight 603, yield 92.6%.
（2）Second step,
In a bite bottle, with magnetic agitation, the final product 22.3g of the first step is added（Molecular weight 603,0.037mol）,
Triphenylphosphine 21.3g（Molecular weight 262,0.0814mol）, o-dichlorohenzene 300ml.Mixture is heated to 175 DEG C, and TCL is used in stirring
Board monitoring course of reaction, reacts 15 hours and completes.Cooling, is evaporated in vacuo solvent, washes, and dries, with pillar layer separation, acetic acid second
Ester and petroleum ether mixtures elution, obtain target molecule 18.5g, molecular weight 571, yield 87.8%
（3）3rd step,
500 milliliters of a bite bottles, with magnetic agitation, add second step final product 18.5g（Molecular weight 571,0.032mol）,
Iodobenzene 12.7g（Molecular weight 204,0.05mol）, cuprous iodide 1.0g（Molecular weight 190,0.00526mol）, potassium carbonate 13.8g
（138,0.1mol）, DMPU solvents 180ml.Mixture is heated to 175 DEG C, stirring, with TCL board monitoring courses of reaction, reaction 13
Hour completes.Cooling, is poured into water, filters out, and dries, with pillar layer separation, ethyl acetate and petroleum ether mixtures elution, obtains
Target molecule 17.95g, molecular weight 647, yield 85.4%
（4）4th step,
1000 milliliters of a bite bottles, with magnetic agitation, add above-mentioned 3rd step final product 17.95g（Molecular weight 647,
0.0277mol）, triphenylamine -4- boric acid 9.0g（Molecular weight 289,0.031mol）, Pd (PPh3)4Usage amount 3.0g（Molecular weight
1154,0.0026mol）, sodium carbonate 220ml（2M）, toluene 220ml, ethanol 220ml.After argon gas displacement, backflow is monitored with TLC
Reaction, reacts complete, cooling, product solid is largely separated out, filtering, is purified with recrystallization method after 4 hours（Also may be used if necessary
Use post separation Methods For Purification）, obtain 17.1g products, yield 75.6%.
Product MS（m/e）：812, elementary analysis（C62H40N2）：Theoretical value C：91.60%, H：4.96%, N：3.45%；
Measured value C：91.63%, H：4.93%, N：3.44%.
Embodiment 2
The synthesis of compound 2
Synthesis step is same as the four-step reaction in embodiment 1, and simply in the 4th step, triphenylamine -4- boric acid is changed into 4-
（N- phenyl-N-（1- naphthyls）Amino））Phenyl boric acid, obtains compound 2.
Product MS（m/e）：862, elementary analysis（C66H42N2）：Theoretical value C：91.85%, H：4.91%, N：3.25%；It is real
Measured value C：91.80%, H：4.92%, N：3.28%.
Embodiment 3
The synthesis of compound 3
Synthesis step is same as the four-step reaction in embodiment 1, and simply in the 4th step, triphenylamine -4- boric acid is changed into 4-
（Carbazole -9- bases））Phenyl boric acid, obtains compound 3.
Product MS（m/e）：810, elementary analysis（C62H38N2）：Theoretical value C：91.82%, H：4.72%, N：3.45%；It is real
Measured value C：91.81%, H：4.76%, N：3.43%.
Embodiment 4
The synthesis of compound 4
Synthesis step is same as the four-step reaction in embodiment 1, and simply in the 4th step, triphenylamine -4- boric acid is changed into N-
Phenyl carbazole -3- boric acid, obtains compound 4.
Product MS（m/e）：810, elementary analysis（C62H38N2）：Theoretical value C：91.82%, H：4.72%, N：3.45%；It is real
Measured value C：91.84%, H：4.76%, N：3.40%.
Embodiment 5
The synthesis of compound 5
Synthesis step is same as the four-step reaction in embodiment 1, and simply in the 4th step, triphenylamine -4- boric acid is changed into two
Benzothiophene -2- boric acid, obtains compound 5.
Product MS（m/e）：751, elementary analysis（C56H33NS）：Theoretical value C：89.45%, H：4.42%, N：1.86%,
S：4.26%；Measured value C：89.42%, H：4.44%, N：1.85%, S：4.29%.
Embodiment 6
The synthesis of compound 6
Synthesis step is same as the four-step reaction in embodiment 1, and simply in the 4th step, triphenylamine -4- boric acid is changed into two
Benzothiophene -4- boric acid, obtains compound 6.
Product MS（m/e）：751, elementary analysis（C56H33NS）：Theoretical value C：89.45%, H：4.42%, N：1.86%,
S：4.26%；Measured value C：89.43%, H：4.46%, N：1.83%, S：4.28%.
Embodiment 7
The synthesis of compound 7
Synthesis step is same as the four-step reaction in embodiment 1, and simply in the 4th step, triphenylamine -4- boric acid is changed into two
Benzofuran -2- boric acid, obtains compound 7.
Product MS（m/e）：735, elementary analysis（C56H33NO）：Theoretical value C：91.40%, H：4.52%, N：1.90%,
O：2.17%；Measured value C：91.44%, H：4.51%, N：1.93%, O：2.12%.
Embodiment 8
The synthesis of compound 8
Synthesis step is same as the four-step reaction in embodiment 1, and simply in the 4th step, triphenylamine -4- boric acid is changed into two
Benzofuran -4- boric acid, obtains compound 8.
Product MS（m/e）：735, elementary analysis（C56H33NO）：Theoretical value C：91.40%, H：4.52%, N：1.90%,
O：2.17%；Measured value C：91.42%, H：4.50%, N：1.92%, O：2.16%.
Embodiment 9
The synthesis of compound 9
Synthesis step totally four step, first three step is same as the preceding three-step reaction in embodiment 1, obtains intermediate bromo-derivative.
4th step is reacted as the following formula and step is carried out：
1000 milliliters of a bite bottles, with electric stirring, nitrogen protection adds the 3rd step intermediate bromo-derivative 15.8g（Molecular weight
647,0.0244mol）, N- phenyl-2-naphthylamines 11g（Molecular weight 219,0.05mol）, cuprous iodide 3.0g（Molecular weight 190,
0.0158mol）, potassium carbonate 40g（138,0.1mol）, DMPU solvents 400ml.Mixture is heated to 175 DEG C, and high degree of agitation is used
TCL board monitoring courses of reaction, react 15 hours and complete.Cooling, is poured into water, filters out, and dries, with pillar layer separation, acetic acid second
Ester and petroleum ether mixtures elution, obtain the common 15.1g of compound 9, yield 78.5%.
Product MS（m/e）：786, elementary analysis（C60H38N2）：Theoretical value C：91.57%, H：4.87%, N：3.56%；It is real
Measured value C：91.55%, H：4.86%, N：3.59%.
Embodiment 10
The synthesis of compound 10
Synthesis step is same as the four-step reaction in embodiment 1, simply in the 4th step, triphenylamine -4- boric acid is changed into glimmering
Anthracene -3- boric acid, obtains compound 10.
Product MS（m/e）：769, elementary analysis（C60H35N）：Theoretical value C：93.60%, H：4.58%, N：1.82%；It is real
Measured value C：93.63%, H：4.60%, N：1.77%.
Embodiment 11
The synthesis of compound 11
Synthesis step is same as the four-step reaction in embodiment 1, simply in the 4th step, triphenylamine -4- boric acid is changed into glimmering
Anthracene -3- boric acid, obtains compound 11.
Product MS（m/e）：769, elementary analysis（C60H35N）：Theoretical value C：93.60%, H：4.58%, N：1.82%；It is real
Measured value C：93.62%, H：4.59%, N：1.79%.
Embodiment 12
The synthesis of compound 12
Synthesis step is same as the four-step reaction in embodiment 1, and simply in the 4th step, triphenylamine -4- boric acid is changed into three
Sub- benzene -2- boric acid, obtains compound 12.
Product MS（m/e）：795, elementary analysis（C62H37N）：Theoretical value C：93.55%, H：4.69%, N：1.76%；It is real
Measured value C：93.57%, H：4.66%, N：1.77%.
Embodiment 13
The synthesis of compound 13
Synthesis step is same as the four-step reaction in embodiment 1, and the bromo nitrobenzenes of 2,4- bis- simply are changed into 2 in the first step,
The bromo nitrobenzenes of 5- bis-, obtain compound 13.
Product MS（m/e）：812, elementary analysis（C62H40N2）：Theoretical value C：91.60%, H：4.96%, N：3.45%；It is real
Measured value C：91.62%, H：4.97%, N：3.41%.
Embodiment 14
The synthesis of compound 14
Synthesis step is same as the four-step reaction in embodiment 1, and the bromo nitrobenzenes of 2,4- bis- simply are changed into 2 in the first step,
The bromo nitrobenzenes of 5- bis-；In the 4th step, triphenylamine -4- boric acid is changed into 4-（N- phenyl-N-（1- naphthyls）Amino）Phenyl boric acid, is obtained
To compound 14.
Product MS（m/e）：862, elementary analysis（C66H42N2）：Theoretical value C：91.85%, H：4.91%, N：3.25%；It is real
Measured value C：91.83%, H：4.90%, N：3.27%.
Embodiment 15
The synthesis of compound 15
Synthesis step is same as the four-step reaction in embodiment 1, and the bromo nitrobenzenes of 2,4- bis- simply are changed into 2 in the first step,
The bromo nitrobenzenes of 5- bis-；In the 4th step, triphenylamine -4- boric acid is changed into N- phenyl carbazole -3- boric acid, compound 15 is obtained.
Product MS（m/e）：810, elementary analysis（C62H38N2）：Theoretical value C：91.82%, H：4.72%, N：3.45%；It is real
Measured value C：91.80%, H：4.74%, N：3.46%.
Embodiment 16
The synthesis of compound 16
Synthesis step is same as the four-step reaction in embodiment 1, and the bromo nitrobenzenes of 2,4- bis- simply are changed into 2 in the first step,
The bromo nitrobenzenes of 5- bis-；In the 4th step, triphenylamine -4- boric acid is changed into dibenzothiophenes -2- boric acid, compound 16 is obtained.
Product MS（m/e）：751, elementary analysis（C56H33NS）：Theoretical value C：89.45%, H：4.42%, N：1.86%,
S：4.26%；Measured value C：89.46%, H：4.44%, N：1.83%, S：4.27%.
Embodiment 17
The synthesis of compound 17
Synthesis step is same as the four-step reaction in embodiment 1, and the bromo nitrobenzenes of 2,4- bis- simply are changed into 2 in the first step,
The bromo nitrobenzenes of 5- bis-；In the 4th step, triphenylamine -4- boric acid is changed into dibenzothiophenes -4- boric acid, compound 17 is obtained.
Product MS（m/e）：751, elementary analysis（C56H33NS）：Theoretical value C：89.45%, H：4.42%, N：1.86%,
S：4.26%；Measured value C：89.42%, H：4.43%, N：1.87%, S：4.28%.
Embodiment 18
The synthesis of compound 18
Synthesis step is same as the four-step reaction in embodiment 1, and the bromo nitrobenzenes of 2,4- bis- simply are changed into 2 in the first step,
The bromo nitrobenzenes of 5- bis-；In the 4th step, triphenylamine -4- boric acid is changed into dibenzofurans -4- boric acid, compound 18 is obtained.
Product MS（m/e）：735, elementary analysis（C56H33NO）：Theoretical value C：91.40%, H：4.52%, N：1.90%,
O：2.17%；Measured value C：91.43%, H：4.51%, N：1.92%, O：2.14%.
Embodiment 19
The synthesis of compound 19
Synthesis step is same as the four-step reaction in embodiment 1, and the bromo nitrobenzenes of 2,4- bis- simply are changed into 2 in the first step,
The bromo nitrobenzenes of 5- bis-；In the 4th step, triphenylamine -4- boric acid is changed into dibenzofurans -2- boric acid, compound 19 is obtained.
Product MS（m/e）：735, elementary analysis（C56H33NO）：Theoretical value C：91.40%, H：4.52%, N：1.90%,
O：2.17%；Measured value C：91.41%, H：4.54%, N：1.92%, O：2.13%.
Here is the Application Example of each compound of the invention：
The structure of organic electroluminescence device used is in the present embodiment：Substrate/anode/hole injection layer (HIL)/sky
Cave transport layer（HTL）/ organic luminous layer（EL）/ electron transfer layer (ETL)/negative electrode.
Substrate can be glass substrate, plastics or stainless steel, and the present embodiment uses glass substrate.
Anode layer can be larger for work function（More than 4.0eV）Metal, alloy, electroconductive oxide or its mixture, such as
ITO (tin indium oxide), IZO（Indium zinc oxide）Or ZnO.The present embodiment uses ITO, and thickness is 180nm.
The hole-injecting material used in hole injection layer, the present embodiment is the compound in the present invention.In order to realize more
Good device performance, these materials can be also doped with some oxidants injects effect, such as doping F4-TCNQ there is provided hole,
The two part by weight is 100:4, gross thickness is 150nm.Hole injection layer 3 can be starlike polyamines in comparative example, polyaniline etc.,
Such as m-MTDATA, 2-TNATA, 1-TNATA.This time comparative example uses 1-TNATA doping 2,3,5,6- tetrafluoro Kuis
Bismethane（F4-TCNQ）, the two part by weight is 100:4, gross thickness is 150nm.
Hole transmission layer, can be aromatic amine chemicals, such as N, N '-two-（1- naphthyls）- N, N '-diphenyl -1,1 '-biphenyl
Base -4,4 '-diamines（NPB）.NPB is used in the present embodiment, thickness is 20nm.
Luminescent layer, can be by the way of body-dopant luminescent dye, and luminescent dye can be red, green, blue for transmitting
AND is used to adulterate DSA-ph, ADN in color, yellow, the dyestuff of orange or white etc. any color, the present embodiment
（Title：9,10- bis- (2- naphthyls) anthracene）For material of main part, DSA-ph（Title, 4- bis--（4-N, N- diphenyl）Amino-styrene
Base benzene）For day blue light luminescent dye, doping ratio is 5%（Weight ratio）, i.e. ADN and DSA-ph ratio are 100:5, luminescent layer
Thickness is 30nm.
Electron injecting layer and negative electrode can be relatively low for work function（Less than 4eV）Metal, alloy, electroconductive oxide or it is mixed
The doping of compound, such as Mg and Ag is used as cathode layer, or LiF/Al, or Li2O/Al, or LiQ/Al.Electron injection in the present embodiment
Layer is LiF and Al with cathode layer, and thickness is respectively 0.5nm and 150nm, and Al layers of plating are overlying on described LiF layers.
Embodiment 20
What the present embodiment was enumerated is example of the compound in the present invention as hole injection layer.The device junction of the present embodiment
Structure is：ITO/HIL:F4TCNQ(150nm,4wt%)/NPB(20nm)/AND：DSA-ph（30nm, 5wt%）/Alq3(20nm)/
LiF(0.5nm)/Al(150nm)。
The method for preparing organic electroluminescence device in the present embodiment is as follows：
1. glass substrate is cleaned with the method for ultrasonic detergent and the deionized water ultrasound boiled, and be placed on red
Dried under outer lamp.
2. one layer of ITO is sputtered on glass as anode, thickness is 180nm；
3. the above-mentioned glass substrate with anode ITO is placed in vacuum chamber, is evacuated to 1 × 10-5Pa-1×10-3Pa,
1-TDATA and F4-TCNQ doped layers are deposited on above-mentioned anode tunic as hole injection layer, speed is 0.1nm/s, evaporation film
Thickness is 150nm, as a comparison case；The F4-TCNQ that adulterates respectively of compound 1,2,9,13,14 in the evaporation present invention is used as embodiment
In hole injection layer.
4. continue to be deposited one layer of NPB film as hole transmission layer, speed is 0.1nm/s, evaporation thickness is 20nm；
5. the method steamed altogether using double source again carries out the evaporation doping of luminescent layer, and the material of main part of luminescent layer is ADN, is lighted
Dyestuff is DSA-ph, and doping concentration is 5wt ﹪, and evaporation thickness is 30nm；
6. on luminescent layer, continue that one layer of electron transfer layer Alq is deposited3, its evaporation rate is 0.1nm/s, and total film is deposited
Thickness is 20nm；
7. it is last, LiF layers and the Al layers of electron injecting layer and negative electrode as device are deposited successively on above-mentioned luminescent layer
Layer, wherein LiF layers of evaporation rate is 0.01~0.02nm/s, and thickness is 0.5nm, and Al layers of evaporation rate is 1nm/s, thickness
For 150nm.
Organic electroluminescence device performance in the embodiment 20 of table 1
As can be seen from the above embodiments, noted using the compound 1,2,9,13,14 in the present invention as the hole of device
Enter layer, it is possible to achieve the efficiency higher than comparative example and lower voltage.It should be noted that the compound conduct in the present invention
During hole injection layer, can also be undoped F4TCNQ, and more preferable effect can be reached after the F4TCNQ that only adulterates.
Embodiment 21
What the present embodiment was enumerated is example of the compound in the present invention as hole transmission layer.The device junction of the present embodiment
Structure is：ITO/1-TNATA:Compound (20nm)/AND in F4TCNQ (150nm, 4wt%)/present invention：DSA-ph（30nm,
5wt%）/Alq3(20nm)/LiF(0.5nm)/Al(150nm).Its preparation method is with reference to embodiment 20, and difference is device
Hole injection layer in structure is adulterated F4-TCNQ using 1-TNATA, hole transmission layer using the compound 3 in the present invention, 4,5,
6th, 7,8,15,16,17,18,19, remaining all same.
Organic electroluminescence device performance in the embodiment 21 of table 2
As can be seen from the above embodiments, made using the compound 3,4,5,6,7,8,15,16,17,18,19 in the present invention
For the hole transmission layer of device, it is possible to achieve the efficiency higher than comparative example and lower voltage.
Embodiment 22
What the present embodiment was enumerated is example of the compound in the present invention as main body.The device architecture of the present embodiment be and
The difference of preparation method and embodiment 21 is that the hole transmission layer in device architecture uses NPB, luminescent layer material of main part
Compound 10,11,12 in the present invention, remaining all same.
Organic electroluminescence device performance in the embodiment 22 of table 3
As can be seen from the above embodiments, using material of main part of the compound 10,11,12 in the present invention as device,
The efficiency higher than comparative example and lower voltage can be realized.
Result above shows that new organic materials of the invention are used for organic electroluminescence device, can effectively reduce
Landing voltage, improves current efficiency, is hole-injecting material of good performance and light emitting host material.
Although the present invention is described in conjunction with the embodiments, the invention is not limited in above-described embodiment, it should manage
Solution, under the guiding of present inventive concept, those skilled in the art can carry out various modifications and improvements, and appended claims are summarised
The scope of the present invention.
Claims (5)
1. one kind 10,15- diphenyl benzfluorene and carbazole derivates, as hole-injecting material, it is characterised in that the chemical combination
Thing is selected from following structural formula：
2. one kind 10,15- diphenyl benzfluorene and carbazole derivates, as hole mobile material, it is characterised in that the chemical combination
Thing is selected from following structural formula：
3. the 10,15- diphenyl benzfluorene and carbazole derivates described in a kind of claim 1 or 2 are in organic electroluminescence device
In application.
4. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate
Functional layer and cathode layer；The organic luminescence function layer includes hole injection layer, hole transmission layer, organic luminous layer and electronics
Transport layer, it is characterised in that：The hole-injecting material of the hole injection layer is the 10,15- diphenyl benzenes described in claim 1
And fluorenes and carbazole derivates.
5. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate
Functional layer and cathode layer；The organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, and it is special
Levy and be：The hole mobile material of the hole transmission layer is the 10,15- diphenyl benzfluorene and carbazole described in claim 2
Derivative.
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| CN108129332B (en) * | 2016-12-01 | 2021-12-17 | 北京鼎材科技有限公司 | Fluorene substituted derivative and application thereof |
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| KR20200068352A (en) * | 2018-12-05 | 2020-06-15 | 엘지디스플레이 주식회사 | Organic compounds, organic light emitting diode and organic light emitting device having the compounds |
| KR20200073601A (en) * | 2018-12-14 | 2020-06-24 | 엘지디스플레이 주식회사 | Organic compound, and Organic light emitting diode and Organic light emitting display device including the same |
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| US20080124455A1 (en) * | 2006-11-24 | 2008-05-29 | Samsung Electronics Co., Ltd. | Organic light emitting compound, organic light emitting device comprising the same, and method of manufacturing the organic light emitting device |
| CN101515632A (en) * | 2008-02-14 | 2009-08-26 | 财团法人山形县产业技术振兴机构 | Organic light-emitting element |
| CN102001989A (en) * | 2009-08-28 | 2011-04-06 | 三星移动显示器株式会社 | Heteroarylamine compounds, organic light-emitting devices and panel display devices |
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| CN101133098A (en) * | 2005-03-04 | 2008-02-27 | 住友化学株式会社 | Biscarbazol-9-yl-substituted triarylamine-containing polymers and electronic devices |
| US20080124455A1 (en) * | 2006-11-24 | 2008-05-29 | Samsung Electronics Co., Ltd. | Organic light emitting compound, organic light emitting device comprising the same, and method of manufacturing the organic light emitting device |
| CN101515632A (en) * | 2008-02-14 | 2009-08-26 | 财团法人山形县产业技术振兴机构 | Organic light-emitting element |
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