CN106831798A - Compound and its organic electroluminescence device containing five-membered ring structure - Google Patents

Compound and its organic electroluminescence device containing five-membered ring structure Download PDF

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CN106831798A
CN106831798A CN201710055511.7A CN201710055511A CN106831798A CN 106831798 A CN106831798 A CN 106831798A CN 201710055511 A CN201710055511 A CN 201710055511A CN 106831798 A CN106831798 A CN 106831798A
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compound
membered ring
electroluminescence device
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CN106831798B (en
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黄锦海
苏建华
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Shanghai Taoe Chemical Technology Co Ltd
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Abstract

The invention provides a kind of organic electroluminescent compounds containing five-membered ring structure, the compound has preferable heat endurance, high-luminous-efficiency, luminance purity high, can be used for making organic electroluminescence device, be applied to organic solar batteries, OTFT or organophotoreceptorswith field.Present invention also offers a kind of organic electroluminescence device, it includes anode, negative electrode and organic layer, organic layer includes at least one of which in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, and at least one of which includes the compound just like structural formula I in organic layer.

Description

Compound and its organic electroluminescence device containing five-membered ring structure
Technical field
The present invention relates to field of organic electroluminescent materials, and in particular to a kind of organic electroluminescence hair containing five-membered ring structure Optical compounds and its organic electroluminescence device, belong to organic electroluminescence device display technology field.
Background technology
Organic electroluminescence device (OLEDs) is to deposit one by spin coating or vacuum evaporation between two metal electrodes The device that layer organic material is prepared from, the three of classics layers of organic electroluminescence device include hole transmission layer, luminescent layer And electron transfer layer.The hole produced by anode through hole transmission layer with the electronics that is produced by negative electrode through combined with electron transfer layer Luminescent layer forms exciton, then lights.Organic electroluminescence device can be adjusted as desired by the material for changing luminescent layer The light of the various needs of section transmitting.
Organic electroluminescence device as a kind of new Display Technique, with self-luminous, wide viewing angle, low energy consumption, efficiency High, thin, rich 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 environment-friendly, can apply on flat-panel monitor and a new generation's illumination, it is also possible to as The backlight of LCD.
Since invention at the bottom of the eighties in 20th century, organic electroluminescence device has industrially been applied, such as Used as screens such as camera and mobile phones, but current OLED is low due to efficiency, and it is wider that the factor such as service life is short restricts 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.Run in applied voltage additionally, due to OLED When, Joule heat can be produced so that organic material is susceptible to crystallization, have impact on life-span 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 less than 25%, and lifting is arrived 100% (Baldo M.A., Forrest S.R.Et al, Nature, 1998,395,151-154), its application is also greatly carried The efficiency of organic electroluminescence device high.Usually, electroluminescent phosphorescence is needed using host-guest system technology, conventional as phosphorus The CBP (4,4'-bis (9-carbazolyl)-biphenyl) of light material of main part has efficient and high triplet energy level, when its work During for material of main part, triplet energy state effectively can be transferred to object phosphorescent light-emitting materials from light emitting host material.But by Easily transmitted and the characteristic of the difficult flowing of electronics in the hole of CBP so that the charge unbalance of luminescent layer, as a result reduce the effect of device Rate.
The content of the invention
Present invention firstly provides a kind of organic electroluminescent compounds containing five-membered ring structure, it is with following structure The compound of Formulas I：
Wherein, R1-R10Separately selected from hydrogen, deuterium, halogen, cyano group, nitro, C1-C8 alkyl, C1-C8 alkoxyl, The substitution of C6-C30 or unsubstituted aryl, the substitution of C3-C30 or the unsubstituted hetero atom containing one or more Aryl, C2-C8 substitutions or unsubstituted allylic alkylation, C2-C8 substitutions or unsubstituted alkynes alkyl；Ar is selected from taking for C6-C30 Generation or unsubstituted aryl, the substitution of C3-C30 or unsubstituted heteroaryl；X is independently selected from O, S.
Preferably, R1And R2Separately it is selected from hydrogen, methyl, ethyl, propyl group, isopropyl, the tert-butyl group, normal-butyl, benzene Base, naphthyl；R3-R10Separately it is selected from hydrogen and methyl.
Preferably, Ar be selected from phenyl, naphthyl, three and phenyl, N- aryl (C6-C30) or C1-C4 alkyl-substituted click Oxazolyl, anthryl, phenanthryl, pyrenyl, perylenes base, fluoranthene base, (9,9- dialkyl group) fluorenyl, (substitutions of 9,9- bis- or unsubstituted aryl) Fluorenyl, 9,9- are Spirofluorene-based, three fragrant (C6-C60) amidos, substitution or unsubstituted dibenzothiophenes base, replace or do not take The dibenzofuran group in generation, pyridine radicals, pyrimidine radicals, pyridazinyl, triazine radical, imidazole radicals, oxazolyls, thiazolyl, thiadiazolyl group, quinoline Quinoline base, isoquinolyl, quinazolyl, quinoxalinyl, azepine dibenzofuran group, azepine dibenzothiophenes base, imidazole radicals, the above Group further can be replaced by C1-C8 alkyl or C6-C10 aryl.
It is further preferred that the organic electroluminescent compounds containing five-membered ring structure of the invention are following structural 1- 54 compound：
A kind of organic electroluminescent compounds containing five-membered ring structure of the invention can be applied in organic electroluminescent Device, organic solar batteries, OTFT or organophotoreceptorswith field.
Present invention also offers a kind of organic electroluminescence device, the device includes anode, negative electrode and organic layer, organic layer In comprising luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer at least one Layer, wherein at least one layer organic electroluminescent compounds contained as described in structural formula I in the organic layer：
Wherein R1-R10, X and Ar it is 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 transfer layer, electron injecting layer and hole blocking layer；
Or organic layer is hole transmission layer, luminescent layer, electron injecting layer and hole blocking layer.
Preferably, wherein the layer where compound as described in structural formula I is luminescent layer, hole transmission layer, hole injection layer.
Preferably, the compound wherein described in structural formula I is the compound of structural formula 1-54.
When the organic electroluminescent compounds containing five-membered ring structure as described in structural formula I are prepared for luminescent device, Can be used alone, it is also possible to and other compounds are used in mixed way；The Organic Electricity containing five-membered ring structure as described in structural formula I Electro luminescent compounds can be used alone a kind of compound therein, it is also possible to while using two or more in structural formula I Compound.
Organic electroluminescence device of the invention, further preferred mode is that the organic electroluminescence device includes sun Contain in pole, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, wherein luminescent layer The compound of more than one structural formula I；It is further preferred that in luminescent layer the structural formula 1-54 containing more than one chemical combination Thing.
The luminescent layer of organic electroluminescence device contains phosphorescence light emitting guest material and the compound conduct with structural formula I , used as material of main part, its concentration is the 20-99.9% of entirely luminous layer weight, preferably for material of main part, wherein Compounds of structural formula I 80-99%, more preferably 90-99%.
The gross 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, gold-tinted, 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.Except the compound with I of the present invention can be used Outward, other small molecules and macromolecular organic compound, including but not limited to carbazole compound, triaromatic amine can also be included Compound, benzidine compound, compound of fluorene class, phthalocyanine-like compound, the miscellaneous triphen of six cyano group six (hexanitrilehexaazatriphenylene), the cyanogen dimethyl-parabenzoquinone (F4- of 2,3,5,6- tetra- fluoro- 7,7', 8,8'- tetra- TCNQ), PVK, polythiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer of organic electroluminescence device of the invention, with the good characteristics of luminescence, can be adjusted as needed The scope of visible ray.Except it is of the invention with Compounds of structural formula I in addition to, can also contain following compound, but not limited to this, Naphthalene compounds, pyrene compound, compound of fluorene class, luxuriant and rich with fragrance class compound, class compound in the wrong, glimmering anthracene compound, anthracene class chemical combination Thing, pentacene class compound, perylene classes compound, two aromatic ethylene class compounds, triphenylamine ethylene compounds, aminated compounds, Benzimidazoles compound, furfuran compound, organic metal chelate complex.
The Organic Electron Transport Material requirement of organic electroluminescence device of the present invention has good electronic transmission performance, energy It is enough effectively electronics from cathode transport to luminescent layer in, with 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 negative electrode In, the compound of alkali metal or alkali metal is mainly selected from, or selected from alkaline-earth metal or the compound or alkali of 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 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 can also mixture use, it is also possible to 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.Can make for metal motor It is prepared with vapour deposition method or sputtering method.
Device experimental shows, organic electroluminescent compounds containing five-membered ring structure of the present invention as described in structural formula I, With preferable heat endurance, high-luminous-efficiency, luminance purity high.Contain the organic electroluminescent chemical combination of five-membered ring structure using this The organic electroluminescence device that thing makes has the advantages that electroluminescent efficiency is good and excitation is excellent and long lifespan.
Brief description of the drawings
Fig. 1 is a kind of organic electroluminescence device structural representation of the invention；
Wherein, 110 glass substrate is represented as, 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 negative electrode.
Specific 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 7
The synthesis of intermediate 7-1
In flask, o-bromobenzoic acid methyl esters (10g, 47mmol), 2- furan boronic acids (5.3g, 47mmol), carbonic acid are added Potassium (12.8g, 94mmol), tetra-triphenylphosphine palladium (0.5g), tetrahydrofuran (100ml) and water (30ml), the lower heating of nitrogen protection Backflow 12 hours, cooling is extracted with dichloromethane, is dried, concentration, and crude product obtains 6.5g, yield 68% through column chromatography purifying.
The synthesis of intermediate 7-2
In flask, intermediate 7-1 (6g, 30mmol) is added, the methyl-magnesium-chloride tetrahydrofuran of 3M is added dropwise under ice bath (30ml, 90mmol), is warmed to room temperature reaction 12 hours, is slowly added to watery hydrochloric acid, is extracted with ethyl acetate, and dries, and concentration is added 50ml phosphoric acid, is stirred 12 hours, adds water, then is extracted with dichloromethane, dries, concentration, and crude product is obtained through column chromatography purifying 3.1g products, yield 57%.
The synthesis of intermediate 7-3
In flask, middle 7-2 (5g, 27mmol) and N, N- diformamide (50ml) are added, be slowly added under ice bath N-bromo-succinimide (4.8g, 27mmol).Reacted 5 hours under lucifuge, add water, then extracted with dichloromethane, it is organic Layer is washed with water three times, dries concentration, and crude product obtains 6.1g, yield 86% through column chromatography purifying.
The synthesis of intermediate 7-4
In flask, intermediate 7-3 (3g, 11.5mmol), 2- nitrobenzene boronic acids (1.9g, 11.5mmol), carbonic acid are added Potassium (3.2g, 23mmol), tetra-triphenylphosphine palladium (0.2g), tetrahydrofuran (30ml) and water (10ml), nitrogen protection is lower to heat back Stream 12 hours, cooling is extracted with dichloromethane, dries concentration, and crude product obtains 2.6g, yield 73% through column chromatography purifying.
The synthesis of intermediate 7-5
In flask, intermediate 7-4 (5.4g, 17.7mmol), triphenylphosphine (9.3g, 35.4mmol) and adjacent dichloro are added Benzene (60ml), is heated to reflux 5 hours under nitrogen protection, removes solvent, and crude product obtains 3.4g, yield through column chromatography purifying 70%.
The synthesis of compound 7
In there-necked flask, add intermediate 7-5 (0.9g, 3.3mmol), 3,5- diphenyl -1- bromobenzenes (1g, 3.3mmol), sodium tert-butoxide (0.64g, 6.6mmol), palladium (0.1g), X-phos (0.2g), ortho-xylene (20ml), It is heated to reflux 10 hours under nitrogen protection, is cooled down, remove solvent, crude product obtains 1.1g, yield 68% through column chromatography purifying.Matter Spectrum 501.63.
Embodiment 2
The synthesis of compound 10
In flask, intermediate 7-5 (1g, 3.7mmol), DMF (20ml) are added, be slowly added to hydrogen Change sodium (115mg, 4.8mmol), react 10 minutes, add chloro- 4, the 6- diphenyl of 2--triazine (0.99g, 3.7mmol), room temperature is anti- Answer 5 hours, add water, filtering, filter cake tetrahydrofuran and ethyl alcohol recrystallization, be filtrated to get 1.59g, yield 85%.Mass spectrum 504.68。
Embodiment 3
The synthesis of compound 25
Synthetic method as compound 7, except replacing 3,5- hexichol with 2- (3- bromophenyls) -4,6- diphenyl-triazine Outside bromide benzene, yield 57%.Mass spectrum 580.71.
Embodiment 4
The synthesis of compound 37
The synthesis of intermediate 37-1
Synthetic method as intermediate 7-1, in addition to replacing 2- furan boronic acids with 2- thienyl boric acids, yield 72%.
The synthesis of intermediate 37-2
Synthetic method as intermediate 7-2, in addition to replacing intermediate 7-1 with intermediate 37-1, yield 62%.
The synthesis of intermediate 37-3
Synthetic method as intermediate 7-3, in addition to replacing intermediate 7-2 with intermediate 37-2, yield 91%.
The synthesis of intermediate 37-4
Synthetic method as intermediate 7-4, in addition to replacing intermediate 7-3 with intermediate 37-3, yield 83%.
The synthesis of intermediate 37-5
Synthetic method as intermediate 7-5, in addition to replacing intermediate 7-4 with intermediate 37-4, yield 65%.
The synthesis of compound 37
Synthetic method as the synthetic method of compound 10, yield 88%.Mass spectrum 520.69.
Embodiment 5
The synthesis of compound 52
Synthetic method as the synthetic method of compound 25, in addition to replacing intermediate 7-5 with intermediate 37-5, yield 66%.Mass spectrum 596.59.
Embodiment 6-10
The preparation of organic electroluminescence device
OLED is prepared using the compound of embodiment.
First, by electrically conducting transparent ito glass substrate 110 (above with anode 120) (the South China glass group limited public affairs of share Department) pass through successively：Deionized water, ethanol, acetone and deionized water are cleaned, then with oxygen plasma treatment 30 seconds.
Then, the thick MnO of 3nm are deposited with ITO3(molybdenum oxide) is hole injection layer 130.
Then, it is hole mobile material 140 that the thick TAPC of 50nm are deposited with hole injection layer.
Then, TCTA is deposited with, the thick electronic barrier layers 150 of 5nm are formed.
Then, the thick luminescent layers 160 of 20nm are deposited with electronic barrier layer, wherein, the compounds of this invention is luminous for main body Material, and with 3% weight than Ir (ppy)3As phosphorescence doping guest materials.
Then, the thick BmPYPB of 40nm are deposited with luminescent layer as electron transfer layer 170.
Finally, evaporation 1nm LiF are electron injecting layer 180 and 80nm Al as device cathodes 190.
Prepared device (structural representation is shown in Fig. 1) Photo Research PR650 spectrometers measure 5000cd/m2Brightness under current efficiency be such as table 1.
Comparative example
Comparative example prepare device as embodiment 5-8 part preparation methods, except replaced with CBP the compounds of this invention make Outside for material of main part.
Table 1
Embodiment Compound Current efficiency (cd/A) Glow color
6 7 47 Green glow
7 10 54 Green glow
8 25 57 Green glow
9 37 53 Green glow
10 52 56 Green glow
Comparative example CBP 45 Green glow
As can be seen from the table, new organic materials of the invention are used for organic electroluminescence device, can reduce work Voltage, improves device efficiency, is the phosphorescent light body material with premium properties.As described above, compound of the invention has height Stability, the organic electroluminescence device of preparation has efficiency and optical purity high.
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 one of ordinary skill in the art without Need creative work just can make many modifications and variations with design of the invention.Therefore, all technologies in the art Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Technical scheme, all should be in the protection domain being defined in the patent claims.

Claims (10)

1. a kind of organic electroluminescent compounds containing five-membered ring structure, it is characterised in that it is with following structural formula I Compound：
Wherein, R1-R10Separately it is selected from hydrogen, deuterium, halogen, cyano group, nitro, C1-C8 alkyl, C1-C8 alkoxyl, C6-C30 Substitution or unsubstituted aryl, the substitution of C3-C30 or the unsubstituted hetero atom aryl containing one or more, C2-C8 replaces or unsubstituted allylic alkylation, C2-C8 substitutions or unsubstituted alkynes alkyl；Ar be selected from C6-C30 substitution or The unsubstituted aryl of person, the substitution of C3-C30 or unsubstituted heteroaryl；X is independently selected from O, S.
2. organic electroluminescent compounds containing five-membered ring structure according to claim 1, it is characterised in that R1And R2Point Not independently selected from hydrogen, methyl, ethyl, propyl group, isopropyl, the tert-butyl group, normal-butyl, phenyl, naphthyl.
3. organic electroluminescent compounds containing five-membered ring structure according to claim 1, it is characterised in that R3-R10Point Not independently selected from hydrogen and methyl.
4. organic electroluminescent compounds containing five-membered ring structure according to claim 1, it is characterised in that Ar is selected from Phenyl, naphthyl, three and phenyl, the alkyl-substituted carbazyl of N- aryl (C6-C30) or C1-C4, anthryl, phenanthryl, pyrenyl, Perylene base, fluoranthene base, (9,9- dialkyl group) fluorenyl, (substitutions of 9,9- bis- or unsubstituted aryl) fluorenyl, 9,9- are Spirofluorene-based, three virtues Fragrant (C6-C60) amido, substitution or unsubstituted dibenzothiophenes base, substitution or unsubstituted dibenzofuran group, pyridine Base, pyrimidine radicals, pyridazinyl, triazine radical, imidazole radicals, oxazolyls, thiazolyl, thiadiazolyl group, quinolyl, isoquinolyl, quinazoline Base, quinoxalinyl, azepine dibenzofuran group, azepine dibenzothiophenes base, imidazole radicals, or more group further by C1-C8 Alkyl or C6-C10 aryl replace.
5. organic electroluminescent compounds containing five-membered ring structure according to claim 1, it is characterised in that under it is The compound of following formula 1-54：
6. a kind of organic electroluminescence device, it includes anode, negative electrode and organic layer, and organic layer injects comprising luminescent layer, hole At least one of which in layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, it is characterised in that described organic At least one layer contains the organic electroluminescent compounds containing five-membered ring structure as claimed in claim 1 in layer.
7. organic electroluminescence device according to claim 6, it is characterised in that contain five-membered ring as described in structural formula I Layer where the organic electroluminescent compounds of structure is at least one of which in luminescent layer, hole transmission layer, hole injection layer.
8. organic electroluminescence device according to claim 6, it is characterised in that contain five-membered ring as described in structural formula I The organic electroluminescent compounds of structure are the compound of structural formula 1-54.
9. organic electroluminescence device according to claim 6, it is characterised in that contain five-membered ring as described in structural formula I The organic electroluminescent compounds of structure are used alone, or are used in mixed way with other compounds.
10. organic electroluminescence device according to claim 6, it is characterised in that contain five yuan as described in structural formula I The organic electroluminescent compounds of ring structure are used alone a kind of compound therein, or use two kinds in structural formula I simultaneously Compound above.
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CN106083809A (en) * 2015-04-28 2016-11-09 三星显示有限公司 Compound, the organic luminescent device including this compound and display device

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KR20190067290A (en) * 2017-12-06 2019-06-17 삼성디스플레이 주식회사 Condensed-cyclic compound and organic light emitting device comprising the same
KR102462420B1 (en) 2017-12-06 2022-11-03 삼성디스플레이 주식회사 Condensed-cyclic compound and organic light emitting device comprising the same
WO2020071664A1 (en) * 2018-10-05 2020-04-09 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using same, and electronic device thereof
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CN109535175A (en) * 2018-11-28 2019-03-29 上海道亦化工科技有限公司 A kind of double triaromatic amine compounds, application and the luminescent device of the spiro structure containing five-membered ring
US11524967B2 (en) * 2019-08-06 2022-12-13 Luminescence Technology Corp. Heteroacene and organic electroluminescence device using the same

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