CN105461707A - Phosphorescent host compound and OELD (Organic Electroluminescent Device) thereof - Google Patents

Phosphorescent host compound and OELD (Organic Electroluminescent Device) thereof Download PDF

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CN105461707A
CN105461707A CN201510961070.8A CN201510961070A CN105461707A CN 105461707 A CN105461707 A CN 105461707A CN 201510961070 A CN201510961070 A CN 201510961070A CN 105461707 A CN105461707 A CN 105461707A
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benzoxazoles
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CN105461707B (en
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黄锦海
苏建华
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Shanghai Taoe Chemical Technology Co Ltd
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Abstract

The invention provides a phosphorescent host compound, which is as shown in a structural formula I, containing benzothiazole and benzoxazole. The phosphorescent host compound provided by the invention has better thermal stability, high luminous efficiency and high luminous purity, can be used for manufacturing OELDs (Organic Electroluminescent Devices) and can be applied to the field of organic solar cells, OTFTs (Organic Thin Film Transistors) or organic photoreceptors. The invention also provides an OELD. The OELD comprises an anode, a cathode and an organic layer, wherein the organic layer comprises one or more than one layers of a luminous layer, a hole injection layer, a hole transporting layer, a hole blocking layer, an electron injection layer and an electron transporting layer; at least one layer in the organic layer contains the compound which is as shown in the formula I.

Description

A kind of phosphorescence host compound and organic electroluminescence device thereof
Technical field
The present invention relates to field of organic electroluminescent materials, be specifically related to a kind of the phosphorescence host compound and the organic electroluminescence device thereof that contain benzothiazole and benzoxazoles group, belong to organic electroluminescence device technique of display field.
Background technology
Organic electroluminescence device (OLEDs) is deposit by spin coating or vacuum evaporation the device that one deck organic materials is prepared between two metal electrodes, and classical three layers of organic electroluminescence device comprise hole transmission layer, luminescent layer and electron transfer layer.The hole produced by anode is followed through hole transmission layer the electronics produced by negative electrode to be combined in luminescent layer through electron transfer layer and is formed exciton, then luminous.Organic electroluminescence device can regulate by the material changing luminescent layer the light launching various needs as required.
Organic electroluminescence device is as a kind of novel technique of display, there is luminous, wide viewing angle, less energy-consumption, efficiency are high, thin, rich color, fast response time, Applicable temperature scope wide, low driving voltage, flexible and the particular advantages such as transparent display panel and environmental friendliness can be made, can be applied in flat-panel monitor and a new generation's illumination, also can as the backlight of LCD.
Since invention at the bottom of the eighties in 20th century, organic electroluminescence device is industrially applied to some extent, such as the screen such as camera and mobile phone, but current OLED due to efficiency low, the factors such as work-ing life is short restrict it and apply widely, particularly large screen display, therefore needs the efficiency improving device.And restrict the performance that one of them important factor is exactly the electroluminescent organic material in organic electroluminescence device.In addition because OLED is when applying voltage-operated, can joule heating be produced, make organic materials easily crystallization occur, have impact on life-span and the efficiency of device, therefore, also need the electroluminescent organic material developing stability and high efficiency.
Organic electrophosphorescenpolymer phenomenon, breaches organic electroluminescent quantum yield lower than the theory restriction of 25%, rises to 100% (BaldoM.A., ForrestS.R.Etal, Nature, 1998,395,151-154), its application also greatly increases the efficiency of organic electroluminescence device.Usually, electroluminescent phosphorescence needs to adopt host-guest system technology, the conventional CBP (4 as phosphorescent light body material, 4'-bis (9-carbazolyl)-biphenyl) there is efficient and high triplet energy level, when it is as material of main part, triplet energy state can effectively from light emitting host material transfer to object phosphorescent light-emitting materials.But the hole due to CBP is easily transmitted and the characteristic of electronics difficulty flowing, and make the charge unbalance of luminescent layer, result reduces the efficiency of device.
Summary of the invention
First the present invention provides a kind of phosphorescence host compound containing benzothiazole and benzoxazoles, and it is the compound with following structural formula I:
Wherein A and B is separately expressed as z is selected from O and S; X is selected from CR 1r 2, N, NR 3, O, S, Se;
R 1, R 2, R 3separately be selected from C1-C12 alkyl, C1-C8 alkoxyl group, the replacement of C6-C30 or unsubstituted aryl, the replacement of C3-C30 or unsubstituted heteroaryl.
Preferably, R 1and R 2separately be selected from C1-C8 alkyl, phenyl, the phenyl replaced by C1-C4 alkyl, naphthyl, the naphthyl replaced by C1-C4 alkyl, xenyl, the xenyl that replaced by C1-C4 alkyl.
Preferably, R 3be selected from phenyl, xenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylene base, fluoranthene base, (9,9-dialkyl group) fluorenyl, (9,9-bis-replaces or unsubstituted aryl) fluorenyl, 9,9-Spirofluorene-based, replace or unsubstituted dibenzothiophene base, replacement or unsubstituted dibenzofuran group; Or above-mentioned R 3further replace by the alkyl of C1-C4.
Preferably, R 1and R 2separately be selected from methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl, normal-butyl, n-hexyl, phenyl, naphthyl, xenyl, tolyl;
Further preferably, the described phosphorescence host compound containing benzothiazole and benzoxazoles, the compound for following structural 1-42:
Phosphorescence host compound containing benzothiazole and benzoxazoles of the present invention can be applied in organic electroluminescence device, organic solar batteries, OTFT or organophotoreceptorswith field.
Present invention also offers a kind of organic electroluminescence device, this device comprises anode, negative electrode and organic layer, it is one or more layers that organic layer comprises in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, has at least one deck to contain the compound of benzothiazole and benzoxazoles in wherein said organic layer:
A and B is separately expressed as
Wherein the definition of X and Z as previously mentioned.
Wherein organic layer is luminescent layer;
Or organic layer is luminescent layer and electron transfer layer;
Or organic layer is luminescent layer, electron transfer layer and electron injecting layer;
Or organic layer is hole transmission layer and luminescent layer;
Or organic layer is hole injection layer, hole transmission layer and luminescent layer;
Or organic layer is hole transmission layer, luminescent layer and electron transfer 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, blocking layer, luminescent layer, electron transfer layer and electron injecting layer;
Or organic layer is hole transmission layer, luminescent layer, electron injecting layer and hole blocking layer.
Preferably, the layer containing the phosphorescence host compound place of benzothiazole and benzoxazoles wherein as described in structural formula I is luminescent layer;
Preferably, the phosphorescence host compound containing benzothiazole and benzoxazoles wherein described in structural formula I is the compound of structural formula 1-42;
When the compound containing benzothiazole and benzoxazoles as described in structural formula I is prepared for luminescent device, can be used alone, also can use with other compound; The compound containing benzothiazole and benzoxazoles as described in structural formula I can be used alone a kind of compound wherein, also can use two or more the compound in structural formula I simultaneously.
Organic electroluminescence device of the present invention, preferred mode is further, this organic electroluminescence device comprises anode, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, the compound wherein containing one or more structural formula I in luminescent layer; Further preferably, the compound containing one or more structural formula 1-42 in luminescent layer.
The luminescent layer of organic electroluminescence device contains phosphorescence light emitting guest material and has the compound of structural formula I as material of main part, wherein Compounds of structural formula I is as material of main part, its concentration is the 20-99.9% of whole luminescent layer weight, and preferred 80-99%, is more preferably 90-99%.
The total thickness of organic electroluminescence device organic layer of the present invention is 1-1000nm, preferred 50-500nm.
Organic electroluminescence device of the present invention is when using the present invention to have the compound of structural formula I, can to arrange in pairs or groups use other materials, as medium on hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and blocking layer, and obtain blue light, green glow, gold-tinted, ruddiness or white light.
The hole transmission layer of organic electroluminescence device of the present invention and hole injection layer, material requested has good hole transport performance, can effectively hole be transferred to luminescent layer from anode.Other small molecules and macromolecular organic compound can be comprised, include but not limited to carbazole compound, triaromatic amine compound, benzidine compound, compound of fluorene class, phthalocyanine-like compound, six cyano group six mix triphen (hexanitrilehexaazatriphenylene), 2,3,5,6-tetra-fluoro-7,7', 8,8'-tetra-cyanogen dimethyl-parabenzoquinone (F4-TCNQ), Polyvinyl carbazole, Polythiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer of organic electroluminescence device of the present invention, has the good characteristics of luminescence, can regulate the scope of visible ray as required.There is Compounds of structural formula I as except phosphorescent light body material except of the present invention, can also arrange in pairs or groups other phosphorescent light body materials, phosphorescence light emitting guest material can comprise the organometallic complex of at least one metal be selected from ruthenium, copper, rhodium, silver, iridium, platinum, gold and osmium.
The Organic Electron Transport Material of organic electroluminescence device of the present invention requires to have good electronic transmission performance, effectively during electronics is from cathode transport to luminescent layer, can have very large electronic mobility.Following compound can be selected, but be not limited thereto: oxa-oxazole, thiazole compound, triazole compound, three nitrogen piperazine compounds, triazine compounds, quinoline compounds, phenazine compounds, siliceous heterocyclic compound, quinolines, phenanthroline compounds, metallo-chelate are (as Alq 3), fluorine substituted benzene compound, benzimidazoles compound.
The electron injecting layer of organic electroluminescence device of the present invention, can effectively electronics be injected into organic layer from negative electrode, mainly be selected from basic metal or alkali-metal compound, or be selected from compound or the alkali metal complex of alkaline-earth metal or alkaline-earth metal, following compound can be selected, but be not limited thereto: the oxide compound of basic metal, alkaline-earth metal, rare earth metal, alkali-metal oxide compound or halogenide, alkaline-earth metal or halogenide, the oxide compound of rare earth metal or the organic complex of halogenide, basic metal or alkaline-earth metal; Be preferably lithium, lithium fluoride, Lithium Oxide 98min, lithium nitride, oxine lithium, caesium, cesium carbonate, oxine caesium, calcium, Calcium Fluoride (Fluorspan), calcium oxide, magnesium, magnesium fluoride, magnesiumcarbonate, magnesium oxide, these compounds can be used alone also can mixture use, also can with other electroluminescent organic materials with the use of.
Every one deck of organic layer in organic electroluminescence device of the present invention, can be prepared by modes such as vacuum vapour deposition, molecular beam vapour deposition method, the dip coating being dissolved in solvent, spin-coating method, stick coating method or spray ink Printings.Vapour deposition method or sputtering method can be used to be prepared for metal motor.
Device experimental shows, the compound that contain benzothiazole and benzoxazoles of the present invention as described in structural formula I, has better thermostability, high-luminous-efficiency, high luminance purity.This is adopted to have based on the organic electroluminescence device that the compound containing heterocycle makes the advantage that electroluminescent efficiency is good and purity of color is excellent and the life-span is long.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic spectrogram of compound 1;
Fig. 2 is the hydrogen nuclear magnetic spectrogram of compound 5;
Fig. 3 is the hydrogen nuclear magnetic spectrogram of compound 21;
Fig. 4 is a kind of organic electroluminescence device structural representation of the present invention;
Wherein, 110 are represented as glass substrate, and 120 are represented as anode, and 130 are represented as hole injection layer, 140 hole transmission layers, and 150 are represented as blocking layer, and 160 are represented as luminescent layer, and 170 are represented as electron transfer layer, and 180 are represented as electron injecting layer, and 190 are represented as negative electrode.
Embodiment
In order to more describe the present invention in detail, especially exemplified by following example, but be not limited thereto.
The synthesis of intermediate A
In there-necked flask, add 3, the polyphosphoric acid (PPA) of 5-dibromobenzoic acid (5g, 18mmol), Ortho-Aminophenol (2.0g, 18mmol) and 20ml, be heated to 185 degree and react 6 hours, cooling, adds water, filters, filter cake recrystallizing methanol obtains product 3.8g, productive rate 61%.
The synthesis of intermediate B
Synthesis step is the same with the synthetic method of intermediate A, except replacing Ortho-Aminophenol with near amino thiophenols, and productive rate 58%.
Embodiment 1
The synthesis of compound 1
In there-necked flask; add intermediate A (2g, 5.7mmol), 4-diphenylene-oxide boric acid (2.9g, 13.7mmol), salt of wormwood (2.4g; 17.1mmol), tetra-triphenylphosphine palladium (40mg), 20ml tetrahydrofuran (THF) and 10ml water; reflux 5 hours under nitrogen protection, cooling, with dichloromethane extraction; dry; concentrated, thick product obtains product 2.25g through column chromatography purification, productive rate 75%.Nuclear-magnetism is as Fig. 1.
Embodiment 2
The synthesis of compound 5
In single port flask; add intermediate A (2g; 5.7mmol), carbazole (2.3g, 13.7mmol), sodium tert-butoxide (1.9g, 17.1mmol), palladium (40mg), x-Phos (100mg) and 20ml toluene; under nitrogen protection; reflux 2 hours, cooling, except desolventizing; thick product obtains product 1.9g through column chromatography purification, productive rate 66%.Nuclear-magnetism is as Fig. 2.
Embodiment 3
The synthesis of compound 6
Intermediate 6-1
In there-necked flask; add intermediate A (2g, 5.7mmol), 4-diphenylene-oxide boric acid (1.2g, 5.7mmol), salt of wormwood (1.57g; 11.4mmol), tetra-triphenylphosphine palladium (40mg), 20ml tetrahydrofuran (THF) and 10ml water; reflux 5 hours under nitrogen protection, cooling, with dichloromethane extraction; dry; concentrated, thick product obtains product 1.4g through column chromatography purification, productive rate 57%.
The synthesis of compound 6
In there-necked flask; add intermediate 6-1 (1.4g, 3.2mmol), N-phenyl carbazole-3-boric acid (1g, 3.52mmol), salt of wormwood (0.88g; 6.4mmol), tetra-triphenylphosphine palladium (40mg), 20ml tetrahydrofuran (THF) and 10ml water; reflux 5 hours under nitrogen protection, cooling, with dichloromethane extraction; dry; concentrated, thick product obtains product 1.6g through column chromatography purification, productive rate 81%.
Embodiment 4
The synthesis of compound 8
In there-necked flask; add intermediate A (1g, 2.9mmol), N-phenyl carbazole-3-boric acid (1.8g, 6.3mmol), salt of wormwood (1.2g; 8.7mmol), tetra-triphenylphosphine palladium (40mg), 20ml tetrahydrofuran (THF) and 10ml water; reflux 5 hours under nitrogen protection, cooling, with dichloromethane extraction; dry; concentrated, thick product obtains product 1.4g through column chromatography purification, productive rate 71%.
Embodiment 5
The synthesis of compound 21
The synthesis technique of compound 21 is the same with the synthetic method of compound 1, except replacing intermediate A by intermediate B, and productive rate 78%.Nuclear-magnetism is as Fig. 3.
Embodiment 6
The synthesis of compound 24
The synthesis technique of compound 24 is the same with the synthetic method of compound 5, except replacing intermediate A by intermediate B, and productive rate 76%.
Embodiment 7
The synthesis of compound 41
The synthesis technique of compound 41 is the same with the synthetic method of compound 8, and except replacing intermediate A by intermediate B, productive rate is 80%.
Embodiment 8-14
The preparation of organic electroluminescence device
The compound of embodiment 1-7 is used to prepare OLED.
First, by electrically conducting transparent ito glass substrate 110 (above with anode 120) (China Nanbo Group Co) warp successively: deionized water, ethanol, acetone and deionized water are cleaned, then use oxygen plasma treatment 30 seconds.
Then, the MnO that evaporation 50nm is thick on ITO 3(molybdenum oxide) is hole injection layer 130;
Then, the NPB that evaporation 25nm is thick on hole injection layer is hole mobile material 140;
Then, evaporation TCTA, forms the electronic barrier layer 150 that 8nm is thick;
Then, the luminescent layer 160 that evaporation 20nm is thick on electronic barrier layer, wherein, the compounds of this invention is main body luminescent material, and with the Ir of 9.8% weight ratio (ppy) 2acac to adulterate guest materials as phosphorescence;
Then, the TPBi that evaporation 40nm is thick on luminescent layer is as electron transfer layer 170;
Finally, evaporation 1nmLiF is that electron injecting layer 180 and 80nmAl are as device cathodes 190.
Prepared device (structural representation is shown in Fig. 4) with PhotoResearchPR650 spectrograph record at 200mA/cm 2brightness under efficiency be as table 1.
Comparative example
Device prepared by comparative example is the same with the device preparation method of embodiment 8-14, except replacing the compounds of this invention as except material of main part with CBP.
Table 1
As can be seen from the table, under identical current density condition, apply the efficiency of organic electroluminescence device prepared by compound of the present invention all higher than comparative example, as mentioned above, compound of the present invention has high stability, and the organic electroluminescence device of preparation has high efficiency and optical purity.
The structural formula of compound described in device is as follows:
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.

Claims (10)

1. contain a phosphorescence host compound for benzothiazole and benzoxazoles, it is characterized in that it is the compound with following structural formula I:
Wherein A and B is separately expressed as z is selected from O and S; X is selected from CR 1r 2, N, NR 3, O, S, Se;
R 1, R 2, R 3separately be selected from C1-C12 alkyl, C1-C8 alkoxyl group, the replacement of C6-C30 or unsubstituted aryl, the replacement of C3-C30 or unsubstituted heteroaryl.
2. the phosphorescence host compound containing benzothiazole and benzoxazoles according to claim 1, is characterized in that R 1and R 2separately be selected from C1-C8 alkyl, phenyl, the phenyl replaced by C1-C4 alkyl, naphthyl, the naphthyl replaced by C1-C4 alkyl, xenyl, the xenyl that replaced by C1-C4 alkyl.
3. the phosphorescence host compound containing benzothiazole and benzoxazoles according to claim 1, is characterized in that R 3be selected from phenyl, xenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylene base, fluoranthene base, (9,9-dialkyl group) fluorenyl, (9,9-bis-replaces or unsubstituted aryl) fluorenyl, 9,9-Spirofluorene-based, replace or unsubstituted dibenzothiophene base, replacement or unsubstituted dibenzofuran group; Or above-mentioned R 3further replace by the alkyl of C1-C4.
4. the phosphorescence host compound containing benzothiazole and benzoxazoles according to claim 1, is characterized in that it is the compound of following structural 1-42:
5. an organic electroluminescence device, it comprises anode, negative electrode and organic layer, it is one or more layers that organic layer comprises in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, to it is characterized in that in organic layer that at least one deck includes the phosphorescence host compound containing benzothiazole and benzoxazoles as claimed in claim 1.
6. organic electroluminescence device according to claim 5, is characterized in that the layer containing the phosphorescence host compound place of benzothiazole and benzoxazoles as described in structural formula I is luminescent layer.
7. organic electroluminescence device according to claim 5, is characterized in that the phosphorescence host compound containing benzothiazole and benzoxazoles as described in structural formula I is used alone, or and other compound use.
8. organic electroluminescence device according to claim 5, the phosphorescence host compound containing benzothiazole and benzoxazoles that it is characterized in that as described in structural formula I is used alone a kind of compound wherein, or uses two or more the compound in structural formula I simultaneously.
9. organic electroluminescence device according to claim 5, it comprises anode, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, it is characterized in that the compound containing structural formula I in luminescent layer.
10. organic electroluminescence device according to claim 5, it comprises anode, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, it is characterized in that the compound contained in luminescent layer is the compound of structural formula 1-42.
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CN106967065A (en) * 2017-03-30 2017-07-21 上海道亦化工科技有限公司 Organic electroluminescent compounds and its luminescent device containing two carbazyl phenyl groups
CN111170956A (en) * 2020-01-10 2020-05-19 黄锦海 Hole transport material composition containing benzoxazole and thiazole group and application thereof
CN111170957A (en) * 2020-01-10 2020-05-19 上海百豪新材料有限公司 Preparation method of hole transport material composition containing benzoxazole and thiazole group

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WO2015115756A1 (en) * 2014-01-28 2015-08-06 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element using same and electronic device thereof

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CN103730582A (en) * 2012-10-12 2014-04-16 三星显示有限公司 Organic light-emitting diode, method of manufacturing the same, and method of forming material layer
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CN106967065A (en) * 2017-03-30 2017-07-21 上海道亦化工科技有限公司 Organic electroluminescent compounds and its luminescent device containing two carbazyl phenyl groups
CN111170956A (en) * 2020-01-10 2020-05-19 黄锦海 Hole transport material composition containing benzoxazole and thiazole group and application thereof
CN111170957A (en) * 2020-01-10 2020-05-19 上海百豪新材料有限公司 Preparation method of hole transport material composition containing benzoxazole and thiazole group
CN111170957B (en) * 2020-01-10 2023-03-21 上海百豪新材料有限公司 Preparation method of hole transport material composition containing benzoxazole and thiazole groups

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