CN105175313A - Hole injection compound and organic electroluminescent device - Google Patents
Hole injection compound and organic electroluminescent device Download PDFInfo
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- CN105175313A CN105175313A CN201510557058.0A CN201510557058A CN105175313A CN 105175313 A CN105175313 A CN 105175313A CN 201510557058 A CN201510557058 A CN 201510557058A CN 105175313 A CN105175313 A CN 105175313A
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- 0 *C1(*)c(cc(c(c2c3cccc2)c2)[n]3-c(cc3)ccc3N(C=*)c3cc(-c4ccccc4*C4C[Al]=C)c4cc3)c2-c2c1cccc2 Chemical compound *C1(*)c(cc(c(c2c3cccc2)c2)[n]3-c(cc3)ccc3N(C=*)c3cc(-c4ccccc4*C4C[Al]=C)c4cc3)c2-c2c1cccc2 0.000 description 1
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Abstract
The invention provides a hole injection 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
Technical field
The present invention relates to field of organic electroluminescent materials, be specifically related to a kind of hole and inject 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 to inject 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
1the phenyl be selected from phenyl, being replaced by C1-C4 alkyl, naphthyl, the naphthyl replaced by C1-C4 alkyl, xenyl, the xenyl, (9 that replaced by C1-C4 alkyl, 9-dialkyl group) fluorenyl, (9,9-bis-replaces or unsubstituted aryl) fluorenyl;
Ar
2be 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
2can further replace by the alkyl of C1-C4;
R
1and R
2separately 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
1and R
2separately be selected from methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl, normal-butyl, n-hexyl, octyl group, amyl group, phenyl;
Ar
1be selected from phenyl, naphthyl, xenyl, tolyl; Ar
2be selected from the substituted or unsubstituted following aryl of C1-C4 alkyl and heteroaryl:
Further preferably, compound is injected in hole of the present invention is the compound of following structural 1-25:
Of the present invention can reaction by Buchwald-Hartwig based on hole injection compound be prepared.
Of the present invention based on hole inject compound 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 organic electroluminescent compounds described in structural formula I in wherein said organic layer:
Wherein Ar
1-Ar
2, R
1-R
2definition as previously mentioned;
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, the layer that compound place is injected in the hole wherein as described in structural formula I is hole injection layer;
Preferably, the compound that compound is structural formula 1-25 is injected in the hole wherein as described in structural formula I.
When hole injection compound as described in structural formula I is prepared for luminescent device, can be used alone, also can use with other compound; Hole injection 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 further, this organic electroluminescence device comprises anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, the compound wherein containing structural formula I in hole injection layer; Further preferably, the compound in hole injection layer is the compound of structural formula 1-25.
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.Can 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 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 present invention injects compound in the hole as described in structural formula I, has better thermostability, high-luminous-efficiency, high luminance purity and low driving voltage.The organic electroluminescence device adopting this hole to inject compound making 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 7;
Fig. 3 is the mass spectrum 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, and 140 are represented as hole transmission layer, and 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 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
Bromo-9, the 9-dimethyl fluorenes (140g, 0.5mol) of 2-, Ortho-Chloro aniline (95g is added in reaction flask; 0.75mol), potassium tert.-butoxide (90g, 0.8mol), palladium (3.3g, 15mmol), tri-butyl phosphine a tetrafluoro borate (8.7g; 30mmol) with toluene (1.5L); reflux 24 hours under nitrogen protection, cooling, washing; dry; removing toluene, thick product is crossed column purification and is obtained 90g product, productive rate 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 a tetrafluoro borate (1.6g, 4.4mmol) and N,N-DIMETHYLACETAMIDE (0.5L), reflux 5 hours, cooling, subtracts and steams remove portion solvent, cooling, be added to the water, be extracted with ethyl acetate, dry, cross column purification and obtain 15g product, productive rate 43%.
The synthesis of intermediate 1-3
Intermediate 1-2 (10g is added in reaction flask; 35.3mmol), to bromo-iodobenzene (12g; 42mmol), potassium tert.-butoxide (7.9g; 70.6mmol), palladium (0.3g; 1.3mmol), tri-butyl phosphine a tetrafluoro borate (0.8g; 2.7mmol) with toluene (150mL); reflux 24 hours under nitrogen protection, cooling, removing toluene; add methylene dichloride; washing, dry, thick product crosses post; obtain 10g product, productive rate 57%.
The synthesis of compound 1
Intermediate 1-3 (200mg is added in flask; 0.45mmol), N; 9-dimethyl-9H-carbazole-3-amine (152mg; 0.45mmol), toluene (10mL), potassium tert.-butoxide (60.5mg; 0.54mmol), palladium (5.05mg; 0.023mmol) with Xphos (15.7mg; 0.045mmol); reflux 4 hours under nitrogen protection; react; be cooled to room temperature to be spin-dried for by solvent, thick product is purified through column chromatography for separation and is obtained white solid (160.8mg, 51.7%).Mass spectrum is as Fig. 1.
Embodiment 2
The synthesis of compound 7
Intermediate 1-3 (200mg is added in flask; 0.45mmol), N-(naphthalene-2 base)-9-phenyl-9H-carbazole-3-amine (173.8mg; 0.45mmol), toluene (10mL), potassium tert.-butoxide (60.5mg; 0.54mmol), palladium (5.05mg; 0.023mmol) with Xphos (15.7mg; 0.045mmol), reflux 4 hours under nitrogen protection.Reacted, be cooled to room temperature and be spin-dried for by solvent, thick product is purified through column chromatography for separation and is obtained white solid (158.7mg, 47.6%).Mass spectrum is as Fig. 2.
Embodiment 3
The synthesis of compound 21
Intermediate 1-3 (200mg is added in flask; 0.45mmol), N-(cumarone-3 base)-9-phenyl-9H-carbazole-3-amine (190.9mg; 0.45mmol), toluene (10mL), potassium tert.-butoxide (60.5mg; 0.54mmol), palladium (5.05mg; 0.023mmol) with Xphos (15.7mg; 0.045mmol), reflux 4 hours under nitrogen protection.Reacted, be cooled to room temperature and be spin-dried for by solvent, thick product is purified through column chromatography for separation and is obtained white solid (216.2mg, 61.5%).Mass spectrum is as Fig. 3.
Embodiment 4
The synthesis of compound 24
The synthesis of intermediate 24-1
The bromo-9-phenyl carbazole of 3-(3.21g is added in reaction flask; 10mmol), 4-triaminotriphenyl amine (2.6g; 10mmol), potassium tert.-butoxide (2.2g, 20mmol), palladium (50mg), tri-butyl phosphine a tetrafluoro borate (150mg) and toluene (50mL), reflux 24 hours under nitrogen protection; cooling; washing, dry, removing toluene; thick product is crossed column purification and is obtained 2.9g product, productive rate 58%.
The synthesis of compound 24
Synthetic method with compound 1 is the same, and except replace N, 9-dimethyl-9H-carbazole-3-amine with intermediate 24-1 outside, productive rate is 54%.
Embodiment 5
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, the compound 1 that evaporation 60nm is thick on ITO is hole injection layer 130.
Then, evaporation NPB, forms the hole transmission layer 140 that 10nm is thick.
Then, hole transmission layer steams and crosses the thick luminescent layer of 40nm 150, wherein, MADN is main body luminescent material, and using the BUBD-1 of 3% weight ratio as doping guest materials.
Then, the Alq that evaporation 20nm is thick on luminescent layer
3as electron transfer layer 160.
Finally, evaporation 1nmLiF is that electron injecting layer 170 and 100nmAl are as device cathodes 180.
Prepared device (structural representation is shown in Fig. 4) records at 1000cd/m with PhotoResearchPR650 spectrograph
2driving voltage under brightness is 5.6V.
Embodiment 6
Prepared device is the same with embodiment 5, except replacing compound 1 with compound 7.
Prepared device (structural representation is shown in Fig. 4) records at 1000cd/m with PhotoResearchPR650 spectrograph
2driving voltage under brightness is 5.5V.
Embodiment 7
Prepared device is the same with embodiment 5, except replacing compound 1 with compound 21.
Prepared device (structural representation is shown in Fig. 4) records at 1000cd/m with PhotoResearchPR650 spectrograph
2driving voltage under brightness is 5.4V.
Embodiment 8
Prepared device is the same with embodiment 5, except replacing compound 1 with compound 24.
Prepared device (structural representation is shown in Fig. 4) records at 1000cd/m with PhotoResearchPR650 spectrograph
2driving voltage under brightness is 5.3V.
Comparative example
Prepared device is the same with embodiment 5, except replacing compound 1 with NPB.
Prepared device (structural representation is shown in Fig. 4) records at 1000cd/m with PhotoResearchPR650 spectrograph
2driving voltage under brightness is 6.8V.
At identical conditions, apply hole of the present invention and inject the driving voltage of organic electroluminescence device prepared by compound lower 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. a compound is injected in hole, it 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. compound is injected in hole according to claim 1, it is characterized in that wherein,
Ar
1the phenyl be selected from phenyl, being replaced by C1-C4 alkyl, naphthyl, the naphthyl replaced by C1-C4 alkyl, xenyl, the xenyl, (9 that replaced by C1-C4 alkyl, 9-dialkyl group) fluorenyl, (9,9-bis-replaces or unsubstituted aryl) fluorenyl;
Ar
2be 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
2can further replace by the alkyl of C1-C4;
R
1and R
2separately be selected from hydrogen, C1-C8 alkyl, C2-C8 replacement or unsubstituted alkynes alkyl, the substituted or unsubstituted phenyl of C1-C4 alkyl.
3. compound is injected in hole according to claim 1 and 2, it is characterized in that wherein
R
1and R
2separately be selected from methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl, normal-butyl, n-hexyl, octyl group, amyl group, phenyl;
Ar
1be selected from phenyl, naphthyl, xenyl, tolyl; Ar
2be selected from the substituted or unsubstituted following aryl of C1-C4 alkyl and heteroaryl:
4. compound is injected in hole as claimed in claim 1, it is characterized in that it is the compound of following structural 1-25:
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, to it is characterized in that in organic layer that at least one deck includes hole as claimed in claim 1 and inject compound.
6. organic electroluminescence device according to claim 5, is characterized in that the layer at the injection compound place, hole as described in structural formula I is hole injection layer.
7. organic electroluminescence device according to claim 5, is characterized in that the hole injection compound as described in structural formula I is used alone, or and other compound use.
8. organic electroluminescence device according to claim 5, is characterized in that hole as described in structural formula I is injected compound and 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 injection layer, 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 injection layer.
10. organic electroluminescence device according to claim 5, it comprises anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, it is characterized in that the compound containing structural formula 1-25 in hole injection layer.
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