CN106892903A - Organic electroluminescent compounds and its luminescent device based on phenol piperazine and carbazole - Google Patents

Organic electroluminescent compounds and its luminescent device based on phenol piperazine and carbazole Download PDF

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CN106892903A
CN106892903A CN201710147312.9A CN201710147312A CN106892903A CN 106892903 A CN106892903 A CN 106892903A CN 201710147312 A CN201710147312 A CN 201710147312A CN 106892903 A CN106892903 A CN 106892903A
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compound
organic
carbazole
electroluminescence device
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CN106892903B (en
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黄锦海
苏建华
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Shanghai Hundred Biological Polytron Technologies Inc
Shanghai Taoe Chemical Technology Co Ltd
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Shanghai Hundred Biological Polytron Technologies Inc
Shanghai Taoe Chemical Technology Co Ltd
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Abstract

The invention provides a kind of organic electroluminescent compounds based on phenol piperazine and carbazole, the compound has preferable heat endurance, high-luminous-efficiency, luminance purity high, can be used for making organic electroluminescence device, be applied to organic solar batteries, OTFT or organophotoreceptorswith field.Present invention also offers a kind of organic electroluminescence device, it includes anode, negative electrode and organic layer, organic layer includes at least one of which in luminescent layer, hole injection layer, hole transmission layer, exciton barrier-layer, electron transfer layer, and at least one of which includes the compound just like structural formula I in organic layer.

Description

Organic electroluminescent compounds and its luminescent device based on phenol piperazine and carbazole
Technical field
The present invention relates to field of organic electroluminescent materials, and in particular to a kind of organic electroluminescence hair based on phenol piperazine and carbazole Optical compounds and its organic electroluminescence device, belong to organic electroluminescence device display technology field.
Background technology
Organic electroluminescence device (OLEDs) is to deposit one by spin coating or vacuum evaporation between two metal electrodes The device that layer organic material is prepared from, the three of classics layers of organic electroluminescence device include hole transmission layer, luminescent layer And electron transfer layer.The hole produced by anode through hole transmission layer with the electronics that is produced by negative electrode through combined with electron transfer layer Luminescent layer forms exciton, then lights.Organic electroluminescence device can be adjusted as desired by the material for changing luminescent layer The light of the various needs of section transmitting.
Organic electroluminescence device as a kind of new Display Technique, with self-luminous, wide viewing angle, low energy consumption, efficiency High, thin, rich color, fast response time, Applicable temperature scope are wide, low driving voltage, can make flexible with it is transparent Display panel and the particular advantages such as environment-friendly, can apply on flat-panel monitor and a new generation's illumination, it is also possible to as The backlight of LCD.
Since invention at the bottom of the eighties in 20th century, organic electroluminescence device has industrially been applied, such as Used as screens such as camera and mobile phones, but current OLED is low due to efficiency, and it is wider that the factor such as service life is short restricts it General application, particularly large screen display, it is therefore desirable to improve the efficiency of device.And restrict one of key factor just It is the performance of the electroluminescent organic material in organic electroluminescence device.Run in applied voltage additionally, due to OLED When, Joule heat can be produced so that organic material is susceptible to crystallization, have impact on life-span and the efficiency of device, therefore, it is also desirable to Develop the electroluminescent organic material of stability and high efficiency.
In organic electroluminescence device, the introducing of hole mobile material and injection material can be effectively reduced positive electricity Lotus is transferred to the ability of luminescent layer from positive pole, improves the efficiency of device and thermally-stabilised.Traditional hole-injecting material, such as copper Phthalocyanine (CuPc), degraded is slow, prepares power consumption height, is unfavorable for environmental protection, and it can absorb light, influence device Efficiency.NPB etc. original hole mobile material, heat endurance is poor, also largely influences device lifetime.Thus, need Develop the electroluminescent organic material of efficient stable.
The content of the invention
Present invention firstly provides a kind of organic electroluminescent compounds based on phenol piperazine and carbazole, it is with following structure The compound of Formulas I：
Wherein, n is selected from 1-5；A is selected from O, S, NR1、CR2R3, R1-R3Separately it is selected from hydrogen, C1-C12 alkyl, C1-C8 Alkoxy, C2-C8 substitution or unsubstituted allylic alkylation, C2-C8 substitution or unsubstituted alkynes alkyl, the substitution of C6-C30 or The unsubstituted aryl of person.
Preferably, n is 1,2 or 3.
R1It preferably is selected from phenyl, naphthyl, N- aryl (C6-C30), the alkyl-substituted carbazyl of C1-C4, anthryl, phenanthryl, pyrene Ji, perylenes base, fluoranthene base, (9,9- dialkyl group) fluorenyl, (substitutions of 9,9- bis- or unsubstituted aryl) fluorenyl, 9,9- be Spirofluorene-based, Three fragrant (C6-C60) amidos, dibenzothiophenes base, dibenzofuran group, above aryl can by the substitution of the alkyl of C1-C12 or Person is unsubstituted；R2And R3Separately preferably be selected from methyl, ethyl, propyl group, butyl, isopropyl, isobutyl group, isopentyl, hexyl, Cyclohexyl, phenyl, xenyl, tolyl.
It is further preferred that compound of the organic electroluminescent compounds of the invention for following structural 1-30：
Organic electroluminescent compounds based on phenol piperazine and carbazole of the invention can apply organic electroluminescence device, Organic solar batteries, OTFT or organophotoreceptorswith field.
Present invention also offers a kind of organic electroluminescence device, the device includes anode, negative electrode and organic layer, organic layer Comprising at least one of which in luminescent layer, hole injection layer, hole transmission layer, exciton barrier-layer, electron transfer layer, wherein described have At least one layer contains the compound based on phenol piperazine and carbazole as described in structural formula I in machine layer：
Wherein n and A are defined as described above.
Wherein organic layer is hole transmission layer and luminescent layer；
Or organic layer is hole injection layer, hole transmission layer, luminescent layer and electron transfer layer；
Or organic layer is hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer；
Or organic layer is hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and exciton Barrier layer；
Or organic layer is hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and exciton barrier-layer；
Or organic layer is hole transmission layer, luminescent layer, electron injecting layer and exciton barrier-layer.
Preferably, wherein the layer where compound as described in structural formula I is hole transmission layer.
Preferably, the hole transmission layer compound wherein described in structural formula I is the compound of structural formula 1-30.
When the compound based on phenol piperazine and carbazole as described in structural formula I is prepared for luminescent device, can be used alone, Can also be used in mixed way with other compounds；Electroluminescent compounds based on phenol piperazine and carbazole as described in structural formula I can be with A kind of compound therein is used alone, it is also possible to while using the two or more compound in structural formula I.
Organic electroluminescence device of the invention, further preferred mode is that the organic electroluminescence device includes sun Pole, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, contain at least one in its hole-transporting layer The compound of structural formula I；It is further preferred that the compound containing at least one structural formula 1-30 in hole transmission layer.
The gross thickness of organic electroluminescence device organic layer of the invention is 1-1000nm, preferably 50-500nm.
When having the compound of structural formula I using the present invention, can arrange in pairs or groups makes organic electroluminescence device of the invention With other materials, such as in hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and exciton barrier-layer It is medium, and obtain blue and green light, gold-tinted, feux rouges or white light.
The hole transmission layer and hole injection layer of organic electroluminescence device of the present invention, material requested have good hole Transmission performance, can effectively be transferred to hole on luminescent layer from anode.Except above-mentioned with compound described in structural formula I Outward, other small molecules and macromolecular organic compound, including but not limited to carbazole compound, triaromatic amine can also be included Compound, benzidine compound, compound of fluorene class, phthalocyanine-like compound, the miscellaneous triphen (hexanitrilehexaaza of six cyano group six Triphenylene), the cyanogen dimethyl-parabenzoquinones (F4-TCNQ) of 2,3,5,6- tetra- fluoro- 7,7', 8,8'- tetra-, PVK, Polythiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer of organic electroluminescence device of the invention, with the good characteristics of luminescence, can be adjusted as needed The scope of visible ray.Except it is of the invention with Compounds of structural formula I in addition to, can also contain following compound, including but do not limit In naphthalene compounds, pyrene compound, compound of fluorene class, luxuriant and rich with fragrance class compound, class compound in the wrong, phenol piperazine class compound, anthracene class Compound, pentacene class compound, perylene classes compound, two aromatic ethylene class compounds, triphenylamine ethylene compounds, amine chemical combination Thing, carbazole compound, benzimidazoles compound, furfuran compound, metal organic fluorescence complex compound, metal Phosphorescent Complex compound (such as Ir, Pt, Os, Cu), polyvinylcarbazole, poly-organosilicon compound, polythiophene organic polymer luminescent material, it Can be used alone, it is also possible to various mixtures are used.
The Organic Electron Transport Material requirement of organic electroluminescence device of the present invention has good electronic transmission performance, energy It is enough effectively electronics from cathode transport to luminescent layer in, with very big electron mobility.Following compound can be selected, but It is not limited to this：Oxa- oxazole, thiazole compound, triazole compound, three nitrogen piperazine class compounds, triazine class chemical combination Thing, quinoline class compound, phenodiazine anthracene compound, siliceous heterocycle compound, quinolines, ferrosin class compound, Metallo-chelate (such as Alq3), fluorine substituted benzene compound, benzimidazoles compound.
Electronics, effectively can be injected into organic layer by the electron injecting layer of organic electroluminescence device of the present invention from negative electrode In, the compound of alkali metal or alkali metal is mainly selected from, or selected from alkaline-earth metal or the compound or alkali of alkaline-earth metal Metal complex, can select following compound, but not limited to this：Alkali metal, alkaline-earth metal, rare earth metal, alkali metal Oxide or halide, the oxide of alkaline-earth metal or halide, the oxide of rare earth metal or halide, alkali metal Or the organic complex of alkaline-earth metal；Preferably lithium, lithium fluoride, lithia, lithium nitride, 8-hydroxyquinoline lithium, caesium, carbonic acid Caesium, 8-hydroxyquinoline caesium, calcium, calcirm-fluoride, calcium oxide, magnesium, magnesium fluoride, magnesium carbonate, magnesia, these compounds can individually make With can also mixture use, it is also possible to used cooperatively with other electroluminescent organic materials.
Each layer of organic layer in organic electroluminescence device of the invention, can be steamed by vacuum vapour deposition, molecular beam It is prepared by the modes such as plating method, the dip coating for being dissolved in solvent, spin-coating method, stick coating method or inkjet printing.Can make for metal motor It is prepared with vapour deposition method or sputtering method.
Device experimental shows that compound based on phenol piperazine and carbazole of the present invention as described in structural formula I has preferably heat steady It is qualitative, high-luminous-efficiency, luminance purity high, low driving voltage.The organic electroluminescent made using the hole transport compound Device has the advantages that electroluminescent efficiency is good and excitation is excellent and long lifespan.
Brief description of the drawings
Fig. 1 is a kind of organic electroluminescence device structural representation of the invention；
Wherein, 110 glass substrate is represented as, 120 are represented as anode, and 130 are represented as hole transmission layer, and 140 are represented as hair Photosphere, 150 are represented as electron transfer layer, and 160 are represented as electron injecting layer, and 170 are represented as negative electrode.
Specific embodiment
In order to describe the present invention in more detail, especially exemplified by example below, but not limited to this.
Embodiment 1
The synthesis of compound 1
The synthesis of intermediate 1-1
N is separately added into flask9,N10- diphenyl phenanthrene -9,10- diamines (15g), to bromo-iodobenzene (11.77g), Cu (OTf)2(2.52g) and K2CO3(7.68g, 55.6mol), is subsequently added trichloro-benzenes (50g), and 210 are heated under mechanical stirring DEG C or so backflow overnight, reaction completely after stop heating, vacuum distillation remove solvent.Used pillar obtains the faint yellow of 4.02g Solid, yield 18.74%.
The synthesis of compound 1
In flask, add intermediate 1-1 (1g, 2mmol), 7,7- dimethyl -5H- indeno [2,1-b] carbazole (0.56g, 2mmol), potassium carbonate (0.56g, 4mmol), cuprous iodide (0.2g), phenanthroline (0.2g), nitrobenzene (30mL), nitrogen are protected It is heated to reflux under shield 24 hours, is cooled down, add dichloromethane, filtering, concentration, crude product obtains 0.59g, produces through column chromatography purifying Rate 42%.
Embodiment 2
The synthesis of compound 6
The synthesis of intermediate 6-1
In there-necked flask, add 4- boric acid-dibenzofurans (21g, 0.1mol), o-bromonitrobenzene (20g, 0.1mol), potassium carbonate (27.6g, 0.2mol), tetra-triphenylphosphine palladium (1g), tetrahydrofuran (300mL) and water (100mL), in nitrogen It is heated to reflux under gas shielded 12 hours, is cooled down, extracted with dichloromethane, dried, filtering, concentration is stirred with methyl alcohol, filtering is done It is dry to obtain 24g, yield 84%.
The synthesis of intermediate 6-2
In flask, intermediate 6-1 (10g, 35mmol), o-dichlorohenzene (100mL), triethyl phosphite are added (50mL), is heated to reflux 12 hours under nitrogen protection, cooling, and pressurization removes solvent, and crude product obtains 6g through column chromatography purifying, Yield 67%.
The synthesis of compound 6
Synthetic method is raw materials used for intermediate 6-2 and intermediate 1-1 with as compound 1, yield 36%.
Embodiment 3
The synthesis of compound 17
The synthesis of intermediate 17-1
Toward reaction bulb add 7,7- dimethyl -5H- indeno [2,1-b] carbazole (10g, 35.3mmol), to bromo-iodobenzene (12g, 42mmol), potassium tert-butoxide (7.9g, 70.6mmol), palladium (0.3g, 1.3mmol), tri-butyl phosphine tetrafluoro boric acid Salt (0.8g, 2.7mmol) and toluene (150mL), are heated to reflux 24 hours under nitrogen protection, cool down, and remove toluene, add dichloro Methane, washing is dried, and crude product crosses post, obtains 10g products, yield 57%.
The synthesis of intermediate 17-2
In single-necked flask add compound 17-1 (4.37g, 10mmol), connection boric acid frequency receive alcohol ester (3.0g, 12mmol), Potassium acetate (3.0g), the triphenylphosphine palladium of dichloro two (50mg), dioxane (60mL), are heated to 100 DEG C of reaction 12h, while hot mistake Silica gel, filter cake is washed with dichloromethane, revolves solvent evaporated, and crude product column chromatography is purified, and obtains product 2.8g, yield 60%.
The synthesis of compound 17
Intermediate 1-1 (0.51g, 1mmol), intermediate 17-2 (0.48g, 1mmol), four triphenylphosphines are added in flask The wet chemical (10mL) and tetrahydrofuran (20mL) of palladium (50mg), 2M, are heated to reflux 12 hours under nitrogen protection, cold But, extracted with dichloromethane, dried, concentration, crude product obtains 0.43g products, yield 54% by column chromatography.
Embodiment 4
The synthesis of compound 28
The synthesis of intermediate 28-1
As intermediate 17-1, raw materials used be 11- phenyl -11 to synthetic method, 12- indoline simultaneously [2,3-a] click Azoles and to bromo-iodobenzene, yield 45%.
The synthesis of intermediate 28-2
As intermediate 17-2, raw materials used be intermediate 1-1, yield 63% to synthetic method.
The synthesis of compound 28
Synthetic method is raw materials used for intermediate 28-1 and intermediate 28-2 as the synthesis of compound 17, yield 54%.
Embodiment 5-8
The preparation of organic electroluminescence device
OLED is prepared using the compound in the embodiment of the present invention.
First, by electrically conducting transparent ito glass substrate 110 (above with anode 120) (the South China glass group limited public affairs of share Department) pass through successively：Deionized water, ethanol, acetone and deionized water are cleaned, then with oxygen plasma treatment 30 seconds.
Then, this compound (such as following table) is deposited with, the thick hole transmission layers 130 of 60nm are formed.
Then, the thick compound Alq of 30nm are deposited with hole transmission layer3As luminescent layer 140.
Then, the thick Alq of 20nm are deposited with luminescent layer3As electron transfer layer 150.Finally, evaporation 1nm LiF are electricity Sub- implanted layer 160 and 100nm Al are used as device cathodes 170.
Prepared device is measured in maximum current efficiency such as following table with Photo Research PR650 spectrometers.
At identical conditions, the organic electroluminescence device for being prepared using organic electroluminescent compounds of the invention Efficiency is higher than comparative example.As described above, compound of the invention has stability high, organic electroluminescent prepared by the present invention Device has low driving voltage, efficiency high and optical purity.
Structural formula is as follows described in device：
Preferred embodiment of the invention described in detail above.It should be appreciated that the ordinary skill of this area is without wound The property made work just can make many modifications and variations with design of the invention.Therefore, all technical staff in the art Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Scheme, all should be in the protection domain being defined in the patent claims.

Claims (10)

1. a kind of organic electroluminescent compounds based on phenol piperazine and carbazole, it is characterised in that it is with following structural formula I Compound：
Wherein, n is selected from 1-5；A is selected from O, S, NR1、CR2R3, R1-R3Separately it is selected from hydrogen, C1-C12 alkyl, C1-C8 alcoxyls Base, C2-C8 substitutions or unsubstituted allylic alkylation, C2-C8 substitutions or unsubstituted alkynes alkyl, the substitution of C6-C30 or not Substituted aryl.
2. organic electroluminescent compounds based on phenol piperazine and carbazole according to claim 1, it is characterised in that n is 1,2 Or 3.
3. organic electroluminescent compounds based on phenol piperazine and carbazole according to claim 1, it is characterised in that R1Selected from benzene Base, naphthyl, N- aryl (C6-C30), the alkyl-substituted carbazyl of C1-C4, anthryl, phenanthryl, pyrenyl, perylenes base, fluoranthene base, (9, 9- dialkyl group) fluorenyl, (substitutions of 9,9- bis- or unsubstituted aryl) fluorenyl, 9,9- Spirofluorene-based, three fragrant (C6-C60) amidos, Dibenzothiophenes base, dibenzofuran group, or more aryl further by C1-C12 alkyl replace；R2And R3Separately Selected from methyl, ethyl, propyl group, butyl, isopropyl, isobutyl group, isopentyl, hexyl, cyclohexyl, phenyl, xenyl, tolyl.
4. organic electroluminescent compounds based on phenol piperazine and carbazole according to claim 1, it is characterised in that under it is The compound of following formula 1-30：
5. a kind of organic electroluminescence device, it includes anode, negative electrode and organic layer, and organic layer injects comprising luminescent layer, hole At least one of which in layer, hole transmission layer, exciton barrier-layer, electron transfer layer, it is characterised in that at least one of which bag in organic layer Contain the compound based on phenol piperazine and carbazole as claimed in claim 1.
6. organic electroluminescence device according to claim 5, it is characterised in that as described in structural formula I based on phenol piperazine and Layer where the compound of carbazole is hole transmission layer.
7. organic electroluminescence device according to claim 5, it is characterised in that as described in structural formula I based on phenol piperazine and The compound of carbazole is used alone, or is used in mixed way with other compounds.
8. organic electroluminescence device according to claim 5, it is characterised in that as described in structural formula I based on phenol piperazine and The compound of carbazole is used alone a kind of compound therein, or uses the two or more compound in structural formula I simultaneously.
9. organic electroluminescence device according to claim 5, it includes anode, hole transmission layer, luminescent layer, electronics and passes Defeated layer, electron injecting layer and negative electrode, it is characterised in that the compound containing at least one structural formula I in hole transmission layer.
10. organic electroluminescence device according to claim 5, it includes anode, hole transmission layer, luminescent layer, electronics Transport layer, electron injecting layer and negative electrode, it is characterised in that the compound containing at least one structural formula 1-30 in hole transmission layer.
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CN109776542A (en) * 2017-11-10 2019-05-21 北京鼎材科技有限公司 A kind of electroluminescent organic material and its application
CN111557122A (en) * 2018-01-25 2020-08-18 默克专利有限公司 Material for organic electroluminescent device
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CN113683620A (en) * 2021-08-20 2021-11-23 中钢集团南京新材料研究院有限公司 Preparation method of 5H-benzofuro [3,2-c ] carbazole

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