CN105461707B - A kind of phosphorescence host compound and its organic electroluminescence device - Google Patents

A kind of phosphorescence host compound and its organic electroluminescence device Download PDF

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CN105461707B
CN105461707B CN201510961070.8A CN201510961070A CN105461707B CN 105461707 B CN105461707 B CN 105461707B CN 201510961070 A CN201510961070 A CN 201510961070A CN 105461707 B CN105461707 B CN 105461707B
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CN105461707A (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 present invention provides a kind of phosphorescence host compounds containing benzothiazole and benzoxazoles such as structural formula I, the compound has preferable thermal stability, high-luminous-efficiency, high luminance purity, it can be used for making organic electroluminescence device, be applied to organic solar batteries, Organic Thin Film Transistors or organophotoreceptorswith field.The present invention also provides a kind of organic electroluminescence devices, it includes anode, cathode and organic layer, organic layer is comprising one or more layers in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, at least one layer of compound comprising just like structural formula I in organic layer.

Description

A kind of phosphorescence host compound and its organic electroluminescence device
Technical field
The present invention relates to field of organic electroluminescent materials, and in particular to one kind contains benzothiazole and benzoxazoles group Phosphorescence host compound and its organic electroluminescence device, belong to organic electroluminescence device field of display technology.
Background technique
Organic electroluminescence device (OLEDs) is between two metal electrodes by spin coating or vacuum evaporation deposition one The device that layer organic material is prepared, a classical three layer organic electroluminescence device include hole transmission layer, luminescent layer And electron transfer layer.The electronics generated by cathode is followed to be incorporated in through electron transfer layer through hole transmission layer in the hole generated by anode Luminescent layer forms exciton, then shines.Organic electroluminescence device can according to need the material by changing luminescent layer to adjust Section emits the light of various needs.
Organic electroluminescence device has self-luminous, wide viewing angle, low energy consumption, efficiency as a kind of novel display technology High, thin, rich in color, fast response time, Applicable temperature range be wide, low driving voltage, can make flexible and transparent Display panel and the particular advantages such as environmental-friendly can be applied on flat-panel monitor and a new generation's illumination, be can also be used as The backlight of LCD.
Since the invention at the bottom of the 1980s, organic electroluminescence device is industrially applied, such as As screens such as camera and mobile phones, but current OLED device, due to low efficiency, it is wider that the factors such as service life is short restrict it General application, especially 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.It is voltage-operated in application additionally, due to OLED device When, Joule heat can be generated, so that organic material is easy to happen crystallization, affects service life and the efficiency of device, therefore, it is also desirable to Develop the electroluminescent organic material of stability and high efficiency.
Organic electrophosphorescenpolymer phenomenon, breaches theoretical limitation of the organic electroluminescent quantum efficiency lower than 25%, and promotion is arrived 100% (Baldo M.A., Forrest S.R.Et al, Nature, 1998,395,151-154), application also greatly mention The high efficiency of organic electroluminescence device.Generally, electroluminescent phosphorescence needs commonly to be used as phosphorus using host-guest system technology The CBP (4,4'-bis (9-carbazolyl)-biphenyl) of light material of main part has efficient and high triplet energy level, when its work Based on material when, triplet energy state effectively can be transferred to object phosphorescent light-emitting materials from light emitting host material.But by It is easily transmitted and the characteristic of electronics difficulty flowing in the hole of CBP, so that the charge unbalance of luminescent layer, as a result reduces the effect of device Rate.
Summary of the invention
Present invention firstly provides a kind of phosphorescence host compound containing benzothiazole and benzoxazoles, for as follows The compound of structural formula I:
Wherein A and B are separately expressed asZ is selected from O and S；X is selected from CR1R2、N、NR3、O、S、 Se；
R1、R2、R3Separately it is selected from the substitution or unsubstituted of C1-C12 alkyl, C1-C8 alkoxyl, C6-C30 Aryl, the substitution of C3-C30 or unsubstituted heteroaryl.
Preferably, R1And R2Separately selected from C1-C8 alkyl, phenyl, by the alkyl-substituted phenyl of C1-C4, naphthalene, By the alkyl-substituted naphthalene of C1-C4, xenyl, by the alkyl-substituted xenyl of C1-C4.
Preferably, R3Selected from phenyl, xenyl, naphthalene, anthryl, phenanthryl, pyrenyl, base, fluoranthene base, (9,9- dialkyl group) Fluorenyl, (9,9- bis- replace or unsubstituted aryl) fluorenyl, 9,9- are Spirofluorene-based, replace or unsubstituted dibenzothiophenes Base, substitution or unsubstituted dibenzofuran group；Or above-mentioned R3Further replaced the alkyl by C1-C4.
Preferably, R1And R2Separately selected from methyl, ethyl, propyl, isopropyl, tert-butyl, normal-butyl, n-hexyl, Phenyl, naphthalene, xenyl, tolyl；
It is further preferred that the phosphorescence host compound containing benzothiazole and benzoxazoles, is following structural The compound of 1-42:
Phosphorescence host compound containing benzothiazole and benzoxazoles of the invention can be applied in organic electroluminescent Device, organic solar batteries, Organic Thin Film Transistors or organophotoreceptorswith field.
The present invention also provides a kind of organic electroluminescence device, which includes anode, cathode and organic layer, organic layer Include one layer or one in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer Layer or more, wherein at least one layer compound containing benzothiazole and benzoxazoles in the organic layer:
A and B are separately expressed as
Wherein X and Z are defined as described above.
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, barrier layer, luminescent layer, electron transfer layer and electron injection Layer；
Or organic layer is hole transmission layer, luminescent layer, electron injecting layer and hole blocking layer.
Preferably, wherein where the phosphorescence host compound containing benzothiazole and benzoxazoles as described in structural formula I Layer is luminescent layer；
Preferably, wherein the phosphorescence host compound containing benzothiazole and benzoxazoles described in structural formula I is structural formula The compound of 1-42；
When the compound containing benzothiazole and benzoxazoles as described in structural formula I is prepared for luminescent device, Ke Yidan It solely uses, can also be used in mixed way with other compounds；The compound containing benzothiazole and benzoxazoles as described in structural formula I It can be used alone one such compound, it can also be simultaneously using two or more the compound in structural formula I.
Organic electroluminescence device of the invention, further preferred mode are that the organic electroluminescence device includes sun Pole, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode, wherein in luminescent layer containing it is a kind of or it is a kind of with On structural formula I compound；It is further preferred that the chemical combination containing one or more kinds of structural formula 1-42 in luminescent layer Object.
The luminescent layer of organic electroluminescence device contains phosphorescence light emitting guest material and the compound conduct with structural formula I Material of main part, wherein Compounds of structural formula I is as material of main part, and concentration is the 20-99.9% of entire luminous layer weight, preferably 80-99%, more preferably 90-99%.
The overall 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 barrier layer Deng, and obtain blue and green light, yellow light, 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.It may include that other small molecules and macromolecule are organic Compound, including but not limited to carbazole compound, triaromatic amine compound, benzidine compound, compound of fluorene class, phthalocyanine Class compound, the miscellaneous triphen (hexanitrilehexaazatriphenylene) of six cyano six, 2,3,5,6- tetra- fluoro- 7,7', 8, Tetra- cyanogen dimethyl-parabenzoquinone (F4-TCNQ) of 8'-, polyvinyl carbazole, polythiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer of organic electroluminescence device of the invention has the good characteristics of luminescence, can be adjusted according to the needs The range of visible light.Except it is of the invention have Compounds of structural formula I as phosphorescent light body material in addition to, can also arrange in pairs or groups other phosphorescence Material of main part, phosphorescence light emitting guest material may include selected from least one of ruthenium, copper, rhodium, silver, iridium, platinum, gold and osmium metal Metal-organic complex.
The Organic Electron Transport Material of organic electroluminescence device of the present invention requires good electronic transmission performance, energy It reaches in effectively electronics from cathode transport to luminescent layer, there is very big electron mobility.It can choose following compound, but It is not limited to this: oxa- oxazole, thiazole compound, triazole compound, three nitrogen piperazine class compounds, triazine class chemical combination Object, 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 from cathode by the electron injecting layer of organic electroluminescence device of the present invention In, it is mainly selected from the alkali metal perhaps compound of alkali metal or compound or alkali selected from alkaline-earth metal or alkaline-earth metal Metal complex can choose 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 that can also be used with mixture, can also be 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.Metal motor can be made It is prepared with vapour deposition method or sputtering method.
Device experimental shows compound containing benzothiazole and benzoxazoles of the present invention as described in structural formula I, have compared with Good thermal stability, high-luminous-efficiency, high luminance purity.Using the organic electroluminescence based on the compound production containing heterocycle Part has the advantages that electroluminescent efficiency is good and excitation purity is excellent and the service life is long.
Detailed description of the invention
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 schematic diagram of the invention；
Wherein, 110 it is represented as glass substrate, 120 are represented as anode, and 130 are represented as hole injection layer, 140 hole transports Layer, 150 are represented as barrier layer, and 160 are represented as luminescent layer, and 170 are represented as electron transfer layer, and 180 are represented as electron injecting layer, 190 are represented as cathode.
Specific embodiment
In order to describe the present invention in more detail, spy lifts following example, and but not limited to this.
The synthesis of intermediate A
In three-necked flask, be added 3,5- dibromobenzoic acid (5g, 18mmol), o-aminophenol (2.0g, 18mmol) and The polyphosphoric acids (PPA) of 20ml is heated to 185 degree and reacts 6 hours, cooling, and water, filtering is added, and filter cake is obtained with recrystallizing methanol To product 3.8g, yield 61%.
The synthesis of intermediate B
Synthesis step is as the synthetic method of intermediate A, other than replacing o-aminophenol near amino thiophenols, produces Rate 58%.
Embodiment 1
The synthesis of compound 1
In three-necked flask, be added intermediate A (2g, 5.7mmol), 4- dibenzofurans boric acid (2.9g, 13.7mmol), Potassium carbonate (2.4g, 17.1mmol), tetra-triphenylphosphine palladium (40mg), 20ml tetrahydrofuran and 10ml water, under nitrogen protection plus Heat reflux 5 hours, it is cooling, it is extracted with dichloromethane, dry, concentration, crude product obtains product 2.25g through column chromatographic purifying, produces Rate 75%.Nuclear-magnetism such as Fig. 1.
Embodiment 2
The synthesis of compound 5
In single-necked flask, intermediate A (2g, 5.7mmol), carbazole (2.3g, 13.7mmol), sodium tert-butoxide is added It is small to be heated to reflux 2 under nitrogen protection for (1.9g, 17.1mmol), palladium acetate (40mg), x-Phos (100mg) and 20ml toluene When, it is cooling, solvent is removed, crude product obtains product 1.9g, yield 66% through column chromatographic purifying.Nuclear-magnetism such as Fig. 2.
Embodiment 3
The synthesis of compound 6
Intermediate 6-1
In three-necked flask, be added intermediate A (2g, 5.7mmol), 4- dibenzofurans boric acid (1.2g, 5.7mmol), Potassium carbonate (1.57g, 11.4mmol), tetra-triphenylphosphine palladium (40mg), 20ml tetrahydrofuran and 10ml water, under nitrogen protection plus Heat reflux 5 hours, it is cooling, it is extracted with dichloromethane, dry, concentration, crude product obtains product 1.4g, yield through column chromatographic purifying 57%.
The synthesis of compound 6
In three-necked flask, be added intermediate 6-1 (1.4g, 3.2mmol), N- phenyl carbazole -3- boric acid (1g, 3.52mmol), potassium carbonate (0.88g, 6.4mmol), tetra-triphenylphosphine palladium (40mg), 20ml tetrahydrofuran and 10ml water, in nitrogen It is heated to reflux under gas shielded 5 hours, it is cooling, it is extracted with dichloromethane, dry, concentration, crude product is produced through column chromatographic purifying Product 1.6g, yield 81%.
Embodiment 4
The synthesis of compound 8
In three-necked flask, be added intermediate A (1g, 2.9mmol), N- phenyl carbazole -3- boric acid (1.8g, 6.3mmol), Potassium carbonate (1.2g, 8.7mmol), tetra-triphenylphosphine palladium (40mg), 20ml tetrahydrofuran and 10ml water, are heated under nitrogen protection Reflux 5 hours, it is cooling, it is extracted with dichloromethane, dry, concentration, crude product obtains product 1.4g, yield through column chromatographic purifying 71%.
Embodiment 5
The synthesis of compound 21
The synthesis technology of compound 21 is as the synthetic method of compound 1, other than replacing intermediate A with intermediate B, Yield 78%.Nuclear-magnetism such as Fig. 3.
Embodiment 6
The synthesis of compound 24
The synthesis technology of compound 24 is as the synthetic method of compound 5, other than replacing intermediate A with intermediate B, Yield 76%.
Embodiment 7
The synthesis of compound 41
The synthesis technology of compound 41 is as the synthetic method of compound 8, other than replacing intermediate A with intermediate B, Yield is 80%.
Embodiment 8-14
The preparation of organic electroluminescence device
OLED is prepared using the compound of embodiment 1-7.
Firstly, by electrically conducting transparent ito glass substrate 110 (having anode 120 above) (the limited public affairs of South China glass group share Department) successively pass through: deionized water, ethyl alcohol, acetone and deionized water were cleaned, then with oxygen plasma treatment 30 seconds.
Then, the MnO of 50nm thickness is deposited on ITO3(molybdenum oxide) is hole injection layer 130；
Then, the NPB that 25nm thickness is deposited on hole injection layer is hole mobile material 140；
Then, TCTA is deposited, forms the electronic barrier layer 150 of 8nm thickness；
Then, the luminescent layer 160 of 20nm thickness is deposited on electronic barrier layer, wherein shine based on the compounds of this invention Material, and with the Ir of 9.8% weight ratio (ppy)2Acac adulterates guest materials as phosphorescence；
Then, the TPBi of 40nm thickness is deposited on the light-emitting layer as electron transfer layer 170；
Finally, vapor deposition 1nm LiF is electron injecting layer 180 and 80nm Al as device cathodes 190.
Prepared device (structural schematic diagram is shown in Fig. 4) with Photo Research PR650 spectrometer measure 200mA/cm2Brightness under efficiency be such as table 1.
Comparative example
The device of comparative example preparation is as the device preparation method of embodiment 8-14, in addition to replacing the present inventionization with CBP Close object as material of main part outside.
Table 1
As can be seen from the table, under identical current density condition, using the Organic Electricity of the compound of the present invention preparation The efficiency of electroluminescence device is all higher than comparative example, as described above, the compound of the present invention have high stability, preparation it is organic Electroluminescent device has high efficiency and optical purity.
The structural formula of compound described in device is as follows:
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that the ordinary skill of this field is without wound The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician 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 within the scope of protection determined by the claims.

Claims (8)

1. a kind of phosphorescence host compound containing benzothiazole and benzoxazoles, it is characterised in that it is to have the following structure formula The compound of I:
Wherein A and B are separately expressed asZ is selected from O and S；X is selected from N, NR3,O,S,Se；
R3Selected from C1-C12 alkyl, C1-C8 alkoxyl, the substitution of C6-C30 or unsubstituted aryl, C3-C30 substitution or Unsubstituted heteroaryl.
2. the phosphorescence host compound according to claim 1 containing benzothiazole and benzoxazoles, it is characterised in that R3Choosing From phenyl, xenyl, naphthalene, anthryl, phenanthryl, pyrenyl, base, fluoranthene base, (9,9- dialkyl group) fluorenyl, (9,9- bis- replace or The unsubstituted aryl of person) fluorenyl, 9,9- are Spirofluorene-based, replace or unsubstituted dibenzothiophene, substitution or unsubstituted Dibenzofuran group.
3. the phosphorescence host compound according to claim 1 containing benzothiazole and benzoxazoles, it is characterised in that its For the compound of following structural 1-40:
。
4. a kind of organic electroluminescence device comprising anode, cathode and organic layer, organic layer include luminescent layer, hole injection It is layer, hole transmission layer, hole blocking layer, electron injecting layer, one or more layers in electron transfer layer, it is characterised in that such as Layer where phosphorescence host compound described in claim 1 containing benzothiazole and benzoxazoles is luminescent layer.
5. organic electroluminescence device according to claim 4, it is characterised in that contain benzothiazole as described in structural formula I It is used alone with the phosphorescence host compound of benzoxazoles, or is used in mixed way with other compounds.
6. organic electroluminescence device according to claim 4, it is characterised in that contain benzothiazole as described in structural formula I One such compound is used alone with the phosphorescence host compound of benzoxazoles, or simultaneously using two kinds in structural formula I Or two or more compound.
7. organic electroluminescence device according to claim 4, it includes anode, hole transmission layer, luminescent layer, electronics to pass Defeated layer, electron injecting layer and cathode, it is characterised in that the compound containing structural formula I in luminescent layer.
8. organic electroluminescence device according to claim 4, it includes anode, hole transmission layer, luminescent layer, electronics to pass Defeated layer, electron injecting layer and cathode, it is characterised in that the compound contained in luminescent layer is structural formula 1- as claimed in claim 3 40 compound.
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