CN105175313B - A kind of hole injection compound and its organic electroluminescence device - Google Patents

A kind of hole injection compound and its organic electroluminescence device Download PDF

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CN105175313B
CN105175313B CN201510557058.0A CN201510557058A CN105175313B CN 105175313 B CN105175313 B CN 105175313B CN 201510557058 A CN201510557058 A CN 201510557058A CN 105175313 B CN105175313 B CN 105175313B
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compound
hole
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electroluminescence device
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CN105175313A (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 hole such as structural formula I to inject compound, the compound has preferable heat endurance, high-luminous-efficiency, high luminance purity and low driving voltage, it can be used for making organic electroluminescence device, applied to organic solar batteries, Organic Thin Film Transistors or organophotoreceptorswith field.Present invention also offers a kind of organic electroluminescence device, it includes anode, cathode and organic layer, organic layer includes one or more layers in luminescent layer, hole injection layer, hole transmission layer, exciton barrier-layer, electron transfer layer, at least one layer of compound comprising just like structural formula I in organic layer.

Description

A kind of hole injection compound and its organic electroluminescence device
Technical field
The present invention relates to field of organic electroluminescent materials, and in particular to a kind of hole injection compound and its organic electroluminescence Luminescent device, belongs to organic electroluminescence device display technology field.
Background technology
Organic electroluminescence device (OLEDs) is by spin coating or vacuum evaporation deposition one between two metal electrodes 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 produced by cathode is followed to be incorporated in through electron transfer layer through hole transmission layer by the hole that anode produces Luminescent layer forms exciton, then shines.Organic electroluminescence device can be adjusted as desired by the material for changing luminescent layer Section launches the light of various needs.
Organic electroluminescence device has self-luminous, wide viewing angle, low energy consumption, efficiency as a kind of new Display Technique High, thin, rich in 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 environmental-friendly, can apply on flat-panel monitor and a new generation's illumination, can also conduct The backlight of LCD.
Since the invention at the bottom of the 1980s, organic electroluminescence device has industrially been applied, such as As screens such as camera and mobile phones, but current OLED device, since efficiency is low, it is wider that the factors such as service life is short restrict 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.It is voltage-operated in application additionally, due to OLED device When, Joule heat can be produced so that organic material easily crystallizes, and have impact on service life 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 cathode, improves efficiency and the thermostabilization of device.Traditional hole-injecting material, such as copper Phthalocyanine (CuPc), degraded is slow, prepares energy consumption height, is unfavorable for environmental protection, and it can absorb light, influence device Efficiency.Hole mobile material original NPB etc., 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 hole to inject compound, it is the compound with following structural formula I：
Wherein, Ar1And Ar2Separately selected from C6-C60 substitution either unsubstituted aryl, C3-C60 substitution or not Substituted heteroaryl, C6-C60 triaromatic amines base, C6-C30 substitutions or unsubstituted carbazyl, (9,9- dialkyl group) fluorenyl, (9,9- bis- substitutes either unsubstituted aryl) fluorenyl, 9,9- are Spirofluorene-based, C6-C60 substitutes or unsubstituted dibenzothiophenes Base, C6-C60 substitutions or unsubstituted dibenzofuran group；
R1~R4Separately selected from hydrogen, deuterium, halogen, cyano group, nitro, C1-C8 alkyl, C1-C8 alkoxyl, C6-C30 Substitution either unsubstituted aryl, the substitution of C3-C30 or the unsubstituted hetero atom aryl containing one or more, C2-C8 substitutes either unsubstituted allylic alkylation, C2-C8 substitutions or unsubstituted alkynes alkyl.
Wherein preferable mode is：
Ar1Selected from phenyl, by the alkyl-substituted phenyl of C1-C4, naphthyl, by the alkyl-substituted naphthyls of C1-C4, xenyl, By the alkyl-substituted xenyls of C1-C4, (9,9- dialkyl group) fluorenyl, (9,9- bis- substitutes or unsubstituted aryl) fluorenyl；
Ar2Selected from phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, base, fluoranthene base, (9,9- dialkyl group) fluorenyl, (9,9- bis- Substitution either unsubstituted aryl) fluorenyl, 9,9- be Spirofluorene-based, substitution or unsubstituted dibenzothiophene, substitution or not Substituted dibenzofuran group, triaromatic amine base, carbazyl；
Wherein above-mentioned Ar2Can further it be substituted by the alkyl of C1-C4；
R1And R2Separately selected from hydrogen, C1-C8 alkyl, C2-C8 substitutions or unsubstituted alkynes alkyl, C1-C4 alkyl Substituted or unsubstituted phenyl.
Further preferred mode is：
R1And R2Separately selected from methyl, ethyl, propyl group, isopropyl, the tert-butyl group, normal-butyl, n-hexyl, octyl group, penta Base, phenyl；
Ar1Selected from phenyl, naphthyl, xenyl, tolyl；Ar2Selected from the substituted or unsubstituted following aryl of C1-C4 alkyl And heteroaryl：
It is further preferred that the compound that the hole injection compound of the present invention is following structural 1-25：
Can being reacted based on hole injection compound by Buchwald-Hartwig for the present invention is prepared.
The present invention's can be applied in organic electroluminescence device, organic solar batteries based on hole injection compound, Organic Thin Film Transistors or organophotoreceptorswith field.
Present invention also offers a kind of organic electroluminescence device, which includes anode, cathode and organic layer, organic layer Comprising one or more layers in luminescent layer, hole injection layer, hole transmission layer, exciton barrier-layer, electron transfer layer, wherein Contain the organic electroluminescent compounds as described in structural formula I at least one layer in the organic layer：
Wherein Ar1-Ar2、R1-R2It is defined as described above；
Or organic layer is luminescent layer and hole injection layer；
Or organic layer is luminescent layer, hole injection layer, hole transmission layer and electron transfer layer；
Or organic layer is luminescent layer, hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer；
Or organic layer is luminescent layer, hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer and exciton Barrier layer；
Preferably, wherein the layer where compound is injected in the hole as described in structural formula I is hole injection layer；
Preferably, wherein the compound that the hole injection compound as described in structural formula I is structural formula 1-25.
When hole injection compound as described in structural formula I is used for luminescent device and prepares, it can be used alone, can also be with Other compounds are used in mixed way；Hole injection compound as described in structural formula I can be used alone a kind of compound therein, Two or more the compound in structural formula I can also be used at the same time.
The organic electroluminescence device of the present invention, further preferred mode are that the organic electroluminescence device includes sun In pole, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode, wherein hole injection layer Compound containing structural formula I；It is further preferred that the compound that the compound in hole injection layer is structural formula 1-25.
The gross thickness of the organic electroluminescence device organic layer of the present 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 the organic electroluminescence device of the present 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, 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.There is compound described in structural formula I except above-mentioned Outside, other small molecules and macromolecular organic compound can also be included, include but not limited to carbazole compound, triaromatic amine Compound, benzidine compound, compound of fluorene class, phthalocyanine-like compound, six cyano group, six miscellaneous triphen (hexanitrilehexaazatriphenylene), tetra- cyanogen dimethyl-parabenzoquinone (F4- of tetra- fluoro- 7,7' of 2,3,5,6-, 8,8'- TCNQ), polyvinyl carbazole, polythiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer of the organic electroluminescence device of the present invention, has the good characteristics of luminescence, can adjust as needed The scope of visible ray.Following compound can be contained, including but not limited to naphthalene compounds, pyrene compound, fluorenes class chemical combination Thing, luxuriant and rich with fragrance class compound, bend class compound, glimmering anthracene compound, anthracene compound, pentacene class compound, class compound, two Aromatic ethylene class compound, triphenylamine ethylene compounds, aminated compounds, carbazole compound, benzimidazoles compound, furan It is class of muttering compound, metal organic fluorescence complex compound, metal Phosphorescent complex compound (such as Ir, Pt, Os, Cu), polyvinylcarbazole, poly- The organic polymer luminescent materials such as organo-silicon compound, polythiophene, they can be used alone, can also a variety of mixtures make With.
The Organic Electron Transport Material of organic electroluminescence device of the present invention requires good electronic transmission performance, energy It is enough effectively electronics from cathode transport to luminescent layer in, there is 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 cathode In, it is mainly selected from the alkali metal either compound of alkali metal or compound or alkali selected from alkaline-earth metal or 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 either 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, can also be used cooperatively with other electroluminescent organic materials.
Each layer of organic layer in the organic electroluminescence device of the present 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.It can make for metal motor Prepared with vapour deposition method or sputtering method.
Device experimental shows that hole injection compound of the present invention as described in structural formula I, has preferable heat endurance, height Luminous efficiency, high luminance purity and low driving voltage.The organic electroluminescence device made of hole injection compound has Have that electroluminescent efficiency is good and excitation purity is excellent and the advantages of long lifespan.
Brief description of the drawings
Fig. 1 is the mass spectrogram of compound 1；
Fig. 2 is the mass spectrogram of compound 7；
Fig. 3 is the mass spectrogram of compound 21；
Fig. 4 is a kind of organic electroluminescence device structure diagram of the present invention；
Wherein, 110 glass substrate is represented as, 120 are represented as anode, and 130 are represented as hole injection layer, and 140 are represented as sky Cave transport layer, 150 are represented as luminescent layer, and 160 are represented as electron transfer layer, and 170 are represented as electron injecting layer, and 180 are represented as the moon Pole.
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
The bromo- 9,9- dimethyl fluorenes (140g, 0.5mol) of 2-, o-chloraniline (95g, 0.75mol), uncle are added into reaction bulb Butanol potassium (90g, 0.8mol), palladium (3.3g, 15mmol), tri-butyl phosphine tetrafluoroborate (8.7g, 30mmol) and first Benzene (1.5L), be heated to reflux under nitrogen protection 24 it is small when, cool down, wash, it is dry, remove toluene, crude product is crossed column purification and obtained 90g products, yield 57%.
The synthesis of intermediate 1-2
In flask, add intermediate 1-1 (40g, 0.125mol), sodium carbonate (40g, 0.38mol), palladium (0.5g, 2.2mmol), tricyclohexyl phosphine tetrafluoroborate (1.6g, 4.4mmol) and dimethylacetylamide (0.5L), it is small to be heated to reflux 5 When, cooling, subtracts and partial solvent is evaporated off, and cools down, is added to the water, is extracted with ethyl acetate, dry, crosses column purification and obtains 15g productions Product, yield 43%.
The synthesis of intermediate 1-3
Intermediate 1-2 (10g, 35.3mmol) is added into reaction bulb, to bromo-iodobenzene (12g, 42mmol), potassium tert-butoxide (7.9g, 70.6mmol), palladium (0.3g, 1.3mmol), tri-butyl phosphine tetrafluoroborate (0.8g, 2.7mmol) and toluene (150mL), be heated to reflux under nitrogen protection 24 it is small when, cooling, removes toluene, adds dichloromethane, washes, dry, crude product Column is crossed, obtains 10g products, yield 57%.
The synthesis of compound 1
Addition intermediate 1-3 (200mg, 0.45mmol), N in flask, 9- dimethyl -9H- carbazole -3- amine (152mg, 0.45mmol), toluene (10mL), potassium tert-butoxide (60.5mg, 0.54mmol), palladium (5.05mg, 0.023mmol) and Xphos (15.7mg, 0.045mmol), nitrogen protection under be heated to reflux 4 it is small when, reacted, be cooled to room temperature and be spin-dried for solvent, Crude product purifies to obtain white solid (160.8mg, 51.7%) through column chromatography for separation.Mass spectrum such as Fig. 1.
Embodiment 2
The synthesis of compound 7
Intermediate 1-3 (200mg, 0.45mmol), N- (base of naphthalene -2) -9- phenyl -9H- carbazole -3- amine are added in flask (173.8mg, 0.45mmol), toluene (10mL), potassium tert-butoxide (60.5mg, 0.54mmol), palladium (5.05mg, 0.023mmol) and Xphos (15.7mg, 0.045mmol), be heated to reflux under nitrogen protection 4 it is small when.It has been reacted that, be cooled to room Solvent is spin-dried for by temperature, and crude product purifies to obtain white solid (158.7mg, 47.6%) through column chromatography for separation.Mass spectrum such as Fig. 2.
Embodiment 3
The synthesis of compound 21
Intermediate 1-3 (200mg, 0.45mmol), N- (base of benzofuran -3) -9- phenyl -9H- clicks are added in flask Azoles -3- amine (190.9mg, 0.45mmol), toluene (10mL), potassium tert-butoxide (60.5mg, 0.54mmol), palladium (5.05mg, 0.023mmol) and Xphos (15.7mg, 0.045mmol), be heated to reflux under nitrogen protection 4 it is small when.It has been reacted that, be cooled to room Solvent is spin-dried for by temperature, and crude product purifies to obtain white solid (216.2mg, 61.5%) through column chromatography for separation.Mass spectrum such as Fig. 3.
Embodiment 4
The synthesis of compound 24
The synthesis of intermediate 24-1
Added into reaction bulb the bromo- 9- phenyl carbazoles (3.21g, 10mmol) of 3-, 4- triaminotriphenyls amine (2.6g, 10mmol), potassium tert-butoxide (2.2g, 20mmol), palladium (50mg), tri-butyl phosphine tetrafluoroborate (150mg) and toluene (50mL), be heated to reflux under nitrogen protection 24 it is small when, cool down, wash, it is dry, remove toluene, crude product is crossed column purification and obtained 2.9g products, yield 58%.
The synthesis of compound 24
As the synthetic method of compound 1, except replacing N, 9- dimethyl -9H- carbazole -3- amine with intermediate 24-1 Outside, yield 54%.
Embodiment 5
The preparation of organic electroluminescence device
OLED is prepared using the compound 1 of embodiment 1.
First, by electrically conducting transparent ito glass substrate 110 (carrying anode 120 above) (the limited public affairs of South China glass group share Department) pass through successively：Deionized water, ethanol, acetone and deionized water are cleaned, then with oxygen plasma treatment 30 seconds.
Then, the compound 1 for 60nm thickness being deposited on ITO is hole injection layer 130.
Then, NPB is deposited, forms the hole transmission layer 140 of 10nm thickness.
Then, the luminescent layer 150 for crossing 40nm thickness is steamed on hole transmission layer, wherein, MADN is main body luminescent material, and with The BUBD-1 of 3% weight ratio is as doping guest materials.
Then, the Alq of 20nm thickness is deposited on the light-emitting layer3As electron transfer layer 160.
Finally, evaporation 1nm LiF are electron injecting layer 170 and 100nm Al as device cathodes 180.
Prepared device (structure diagram is shown in Fig. 4) is measured with Photo Research PR650 spectrometers 1000cd/m2Driving voltage under brightness is 5.6V.
Embodiment 6
Prepared device is as embodiment 5, in addition to replacing compound 1 with compound 7.
Prepared device (structure diagram is shown in Fig. 4) is measured with Photo Research PR650 spectrometers 1000cd/m2Driving voltage under brightness is 5.5V.
Embodiment 7
Prepared device is as embodiment 5, in addition to replacing compound 1 with compound 21.
Prepared device (structure diagram is shown in Fig. 4) is measured with Photo Research PR650 spectrometers 1000cd/m2Driving voltage under brightness is 5.4V.
Embodiment 8
Prepared device is as embodiment 5, in addition to replacing compound 1 with compound 24.
Prepared device (structure diagram is shown in Fig. 4) is measured with Photo Research PR650 spectrometers 1000cd/m2Driving voltage under brightness is 5.3V.
Comparative example
Prepared device is as embodiment 5, in addition to replacing compound 1 with NPB.
Prepared device (structure diagram is shown in Fig. 4) is measured with Photo Research PR650 spectrometers 1000cd/m2Driving voltage under brightness is 6.8V.
Under the same conditions, the driving of the organic electroluminescence device prepared using the hole injection compound of the present invention Voltage is less than comparative example.As described above, the compound of the present invention has high stability, the organic electroluminescence device tool of preparation There are high efficiency and optical purity.
The structural formula of compound described in device is as follows：
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 can conceive according to the present invention 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 in the protection domain being defined in the patent claims.

Claims (7)

1. compound is injected in a kind of hole, it is characterised in that it is the compound with following structural formula I：
Wherein, R1And R2For methyl；
Ar1For phenyl；Ar2Selected from following aryl and heteroaryl：
。
2. compound is injected in hole as claimed in claim 1, it is characterised in that it is following compounds：
3. a kind of organic electroluminescence device, it includes anode, cathode and organic layer, and organic layer includes luminescent layer, hole is injected It is one or more layers in layer, hole transmission layer, exciton barrier-layer, electron transfer layer, it is characterised in that in organic layer at least One layer includes injection compound in hole as claimed in claim 1.
4. organic electroluminescence device according to claim 3, it is characterised in that the hole injectionization as described in structural formula I Layer where compound is hole injection layer.
5. organic electroluminescence device according to claim 3, it is characterised in that the hole injectionization as described in structural formula I Compound is used alone, or is used in mixed way with other compounds.
6. organic electroluminescence device according to claim 3, it is characterised in that the hole injectionization as described in structural formula I A kind of compound therein is used alone in compound, or uses two or more the compound in structural formula I at the same time.
7. organic electroluminescence device according to claim 3, it includes anode, hole injection layer, hole transmission layer, hair Photosphere, electron transfer layer, electron injecting layer and cathode, it is characterised in that the compound containing structural formula I in hole injection layer.
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