CN105175314A - Hole transporting compound and organic electroluminescent device thereof - Google Patents

Hole transporting compound and organic electroluminescent device thereof Download PDF

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CN105175314A
CN105175314A CN201510557091.3A CN201510557091A CN105175314A CN 105175314 A CN105175314 A CN 105175314A CN 201510557091 A CN201510557091 A CN 201510557091A CN 105175314 A CN105175314 A CN 105175314A
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compound
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organic electroluminescence
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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 hole transporting compound with the structure represented by formula I. The compound has the advantages of good thermal stability, high luminescence efficiency, high luminescence purity and low driving voltage, can be used for making organic electroluminescence devices, and can be applied in the fields of organic solar cells, organic thin film transistors or organic photoreceptors. The invention also provides an organic electroluminescent device. The organic electroluminescent device comprises an anode, a cathode and an organic layer, the organic layer includes one or more a luminescent layer, a hole injection layer, a hole transporting layer, an exciton barrier layer and an electron transfer layer, and the organic layer contains at least one layer of the compound of the formula I.

Description

A kind of hole transport 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 hole transport compound and organic electroluminescence device thereof, 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, 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.
In organic electroluminescence device, the introducing of hole mobile material and injecting material, can reduce positive charge is transferred to luminescent layer ability from positive pole effectively, improves the efficiency of device and thermally-stabilised.Traditional hole-injecting material, as copperphthalocyanine (CuPc), degraded is slow, and preparation power consumption is high, is unfavorable for environment protection, and its meeting absorb light, affects the efficiency of device.The hole mobile material that NPB etc. are original, thermostability is poor, also largely affects device lifetime.Thus, the electroluminescent organic material developing efficient stable is needed.
Summary of the invention
First the present invention provides a kind of hole transport compound, and it is the compound with following structural formula I:
Wherein, Ar 1and Ar 2separately be selected from C6-C60 to replace or unsubstituted aryl, C3-C60 replacement or unsubstituted heteroaryl, C6-C60 triaromatic amine base, C6-C30 replacement or unsubstituted carbazyl, (9,9-dialkyl group) fluorenyl, (9,9-bis-replaces or unsubstituted aryl) fluorenyl, 9,9-Spirofluorene-based, C6-C60 replaces or unsubstituted dibenzothiophene base, C6-C60 replace or unsubstituted dibenzofuran group;
R 1~ R 4separately be selected from hydrogen, deuterium, halogen, cyano group, nitro, C1-C8 alkyl, C1-C8 alkoxyl group, the replacement of C6-C30 or unsubstituted aryl, C3-C30 replacement or the unsubstituted heteroatoms aryl containing one or more, C2-C8 replaces or unsubstituted allylic alkylation, C2-C8 replace or unsubstituted alkynes alkyl.
Wherein preferred mode is:
Ar 1and Ar 2separately be selected from phenyl, 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, triaromatic amine base, carbazyl;
Wherein, above-mentioned Ar 1and Ar 2can further replace by the alkyl of C1-C4;
R 1~ R 4separately be selected from hydrogen, C1-C8 alkyl, C2-C8 replacement or unsubstituted alkynes alkyl, the substituted or unsubstituted phenyl of C1-C4 alkyl.
Preferred mode is further:
R 1~ R 4independently selected from methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl, normal-butyl, n-hexyl, octyl group, amyl group, phenyl;
Ar 1~ Ar 2separately be selected from the substituted or unsubstituted following aryl of C1-C4 alkyl and heteroaryl:
Further preferably, hole transport compound of the present invention is the compound of following structural 1-22:
Hole transport compound of the present invention can be prepared by Buchwald-Hartwig reaction and ullmann reaction.
Hole transport compound 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, exciton barrier-layer, electron transfer layer, has one deck at least containing, for example the hole transport compound described in structural formula I in wherein said organic layer:
Wherein Ar 1-Ar 2, R 1-R 4definition as previously mentioned.
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, the layer at the hole transport compound place wherein as described in structural formula I is hole transmission layer;
Preferably, the hole transport compound wherein as described in structural formula I is the compound of structural formula 1-22.
When hole transport compound as described in structural formula I is prepared for luminescent device, can be used alone, also can use with other compound; Hole transport compound 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 that this organic electroluminescence device comprises anode, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode further, the compound containing structural formula I in its hole-transporting layer; Further preferably, the compound in hole transmission layer is the compound of structural formula 1-22.
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 at hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and exciton barrier-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.Have except compound described in structural formula I except above-mentioned, other small molecules and macromolecular organic compound can also 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.Except containing except compound of fluorene class of the present invention, can also containing, for example lower compound, include, but are not limited to naphthalene compounds, pyrene compound, compound of fluorene class, luxuriant and rich with fragrance compounds, bend compounds, fluoranthene compounds, anthracene compounds, pentacene compounds, perylene compounds, two aromatic ethylene compounds, triphenylamine ethylene compounds, aminated compounds, carbazole compound, benzimidazoles compound, furfuran compound, metal organic fluorescence complex compound, metal Phosphorescent complex compound is (as Ir, Pt, Os, Cu), polyvinyl carbazole, poly organic silicon compound, the organic polymer luminescent materials such as Polythiophene, they can be used alone, also can use by multiple mixture.The thickness of luminescent layer is preferably 10-50nm.
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 material 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 hole transport compound of the present invention as described in structural formula I, has better thermostability, high-luminous-efficiency, high luminance purity, low driving voltage.The organic electroluminescence device adopting this hole transport compound to make has 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 mass spectrum of compound 1;
Fig. 2 is the mass spectrum of compound 8;
Fig. 3 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 transmission layer, and 140 are represented as luminescent layer, and 150 are represented as electron transfer layer, and 160 are represented as electron injecting layer, and 170 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.
Embodiment 1
The synthesis of compound 1
The synthesis of intermediate 1-1
In there-necked flask; add N-phenyl-9; 9-dimethyl-2-fluorenamine (5.6g; 20mmol), 2; 7-bis-bromo-9; 9-dimethyl fluorene (7g; 20mmol), potassium tert.-butoxide (3.3g; 30mmol), palladium (0.1g), tri-butyl phosphine a tetrafluoro borate (0.3g) and 100mL toluene reflux 12 hours under nitrogen protection, add water, layering; organic over anhydrous dried over sodium sulfate; concentrated, thick product uses column chromatography and obtains 7.6g, and productive rate is 68.5%.
The synthesis of compound 1
In there-necked flask; add intermediate 1-1 (0.5g; 0.9mmol), N; 9-dimethyl-9H-carbazole-3-amine (0.3g, 0.9mmol), to be dissolved in oil of mirbane (10ml), to add salt of wormwood (0.62g subsequently; 4.5mmol), cuprous iodide (6.8mg; 0.036mmol) with phenanthrolene (6.5mg, 0.036mmol), reflux 4 hours under nitrogen protection.Be cooled to room temperature, underpressure distillation is except desolventizing, and thick product uses column chromatography and obtains 240mg, and productive rate is 31%, and mass spectrum is as Fig. 1.
Embodiment 2
The synthesis of compound 8
In there-necked flask; add intermediate 1-1 (0.4g; 0.72mmol), N-(naphthalene-2-base)-9-phenyl-9H-carbazole-3-amine (0.25g; 0.72mmol), be dissolved in oil of mirbane (10ml), add salt of wormwood (0.62g subsequently; 4.5mmol), cuprous iodide (6.8mg; 0.036mmol) with phenanthrolene (6.5mg, 0.036mmol), reflux 4 hours under nitrogen protection.Be cooled to reduced pressure at room temperature distillation except desolventizing, thick product uses column chromatography and obtains 200mg, and productive rate is 32%, and mass spectrum is as Fig. 2.
Embodiment 3
The synthesis of compound 12
By intermediate 1-1 (200mg; 0.36mmol) with cumarone-9-phenyl-9H-carbazole-3-amine (153mg; 0.36mmol) be dissolved in toluene; add potassium tert.-butoxide (48.4mg subsequently; 0.43mmol); add palladium (4.4mg) and tri-butyl phosphine a tetrafluoro borate (20mg) again, reflux 4 hours under nitrogen protection after dissolving simultaneously.Be cooled to room temperature to be spin-dried for by solvent, thick product uses column chromatography and obtains 220mg, productive rate 68%.
Embodiment 4
The synthesis of compound 19
The synthesis of intermediate 19-1
Synthetic method is the same with the synthetic method of intermediate 1-1, and except replace N-phenyl-9,9-dimethyl-2-fluorenamine with N-(biphenyl-4-base)-9,9-dimethyl-9H-fluorenes-2-amine outside, productive rate is 56%.
The synthesis of compound 19
Synthetic method with compound 8 is the same, and except replacing 1-1 with 19-1, productive rate is 42%.
Embodiment 5
The synthesis of compound 22
Synthetic method with compound 12 is the same, and except replacing 1-1 with intermediate 19-1, productive rate is 61%.
Embodiment 6
The preparation of organic electroluminescence device
The compound 1 of embodiment 1 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, evaporation compound 1, forms the hole transmission layer 130 that 60nm is thick.
Then, the compd A lq that evaporation 30nm is thick on hole transmission layer 3as luminescent layer 140.
Then, the Alq that evaporation 20nm is thick on luminescent layer 3as electron transfer layer 150.
Finally, evaporation 1nmLiF is that electron injecting layer 160 and 100nmAl are as device cathodes 170.
Prepared device (structural representation is shown in Fig. 3) records at 150mA/cm with PhotoResearchPR650 spectrograph 2current density under current efficiency be 1.6cd/A.
Embodiment 7
The making method of device except replacing the compound 1 of embodiment 6 with compound 8, other the same with embodiment 6.
Prepared device PhotoResearchPR650 spectrograph records at 150mA/cm 2current density under current efficiency be 1.6cd/A.
Embodiment 8
The making method of device except replacing the compound 1 of embodiment 6 with compound 12, other the same with embodiment 6.
Prepared device PhotoResearchPR650 spectrograph records at 150mA/cm 2current density under current efficiency be 1.8cd/A.
Embodiment 9
The making method of device except replacing the compound 1 of embodiment 6 with compound 19, other the same with embodiment 6.
Prepared device PhotoResearchPR650 spectrograph records at 150mA/cm 2current density under current efficiency be 1.7cd/A.
Embodiment 10
The making method of device except replacing the compound 1 of embodiment 6 with compound 22, other the same with embodiment 6.
Prepared device PhotoResearchPR650 spectrograph records at 150mA/cm 2current density under current efficiency be 1.8cd/A.
Comparative example
The making method of device except replacing the compound 1 of embodiment 6 with compound N PB, other the same with embodiment 6.
Prepared device PhotoResearchPR650 spectrograph records at 150mA/cm 2current density under current efficiency be 1.2cd/A.
At identical conditions, the driving voltage of organic electroluminescence device prepared by hole transport compound of the present invention is applied lower than comparative example.As mentioned above, compound of the present invention has high stability, and organic electroluminescence device prepared by the present invention has low driving voltage, 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. a hole transport compound, is characterized in that it is the compound with following structural formula I:
Wherein, Ar 1and Ar 2separately be selected from C6-C60 to replace or unsubstituted aryl, C3-C60 replacement or unsubstituted heteroaryl, C6-C60 triaromatic amine base, C6-C30 replacement or unsubstituted carbazyl, (9,9-dialkyl group) fluorenyl, (9,9-bis-replaces or unsubstituted aryl) fluorenyl, 9,9-Spirofluorene-based, C6-C60 replaces or unsubstituted dibenzothiophene base, C6-C60 replace or unsubstituted dibenzofuran group;
R 1~ R 4separately be selected from hydrogen, deuterium, halogen, cyano group, nitro, C1-C8 alkyl, C1-C8 alkoxyl group, the replacement of C6-C30 or unsubstituted aryl, C3-C30 replacement or the unsubstituted heteroatoms aryl containing one or more, C2-C8 replaces or unsubstituted allylic alkylation, C2-C8 replace or unsubstituted alkynes alkyl.
2. hole transport compound according to claim 1, is characterized in that wherein,
Ar 1and Ar 2separately be selected from phenyl, 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, triaromatic amine base, carbazyl;
Wherein, above-mentioned Ar 1and Ar 2can further replace by the alkyl of C1-C4;
R 1~ R 4separately be selected from hydrogen, C1-C8 alkyl, C2-C8 replacement or unsubstituted alkynes alkyl, the substituted or unsubstituted phenyl of C1-C4 alkyl.
3. hole transport compound according to claim 1 and 2, is characterized in that, R 1~ R 4independently selected from methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl, normal-butyl, n-hexyl, octyl group, amyl group, phenyl;
Ar 1~ Ar 2separately be selected from the substituted or unsubstituted following aryl of C1-C4 alkyl and heteroaryl:
4. hole transport compound as claimed in claim 1, is characterized in that it is the compound of following structural 1-22:
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, exciton barrier-layer, electron transfer layer, it is characterized in that in organic layer, at least one deck includes hole transport compound as claimed in claim 1.
6. organic electroluminescence device according to claim 5, is characterized in that the layer at the hole transport compound place as described in structural formula I is hole transmission layer.
7. organic electroluminescence device according to claim 5, is characterized in that the organic electroluminescence compound as described in structural formula I is used alone, or and other compound use.
8. organic electroluminescence device according to claim 5, the organic electroluminescence compound 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 hole transmission 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 containing structural formula 1-22 in hole transmission layer.
CN201510557091.3A 2015-09-02 2015-09-02 Hole transporting compound and organic electroluminescent device thereof Pending CN105175314A (en)

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