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CN107344946A - A kind of spiral shell carbazoles organic electroluminescent compounds and its organic electroluminescence device - Google Patents

A kind of spiral shell carbazoles organic electroluminescent compounds and its organic electroluminescence device Download PDF

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Publication number
CN107344946A
CN107344946A CN201710496289.4A CN201710496289A CN107344946A CN 107344946 A CN107344946 A CN 107344946A CN 201710496289 A CN201710496289 A CN 201710496289A CN 107344946 A CN107344946 A CN 107344946A
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layer
organic
compound
carbazoles
electroluminescence device
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黄锦海
苏建华
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Shanghai Taoe Chemical Technology Co Ltd
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Shanghai Taoe Chemical Technology Co Ltd
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Abstract

The invention provides a kind of spiral shell carbazoles organic electroluminescent compounds, and it has following structure：The compound has preferable heat endurance, high-luminous-efficiency, high luminance purity, can be used for making organic electroluminescence device, applied to 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 includes at least one layer in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, luminescent layer includes compound just like structural formula I, and the organic electroluminescence device has that electroluminescent efficiency is good and excitation is excellent and the advantages of long lifespan.

Description

A kind of spiral shell carbazoles organic electroluminescent compounds and its organic electroluminescence device
Technical field
The present invention relates to field of organic electroluminescent materials, and in particular to a kind of spiral shell carbazoles electroluminescent organic material and Its organic electroluminescence device, belong to organic electroluminescence device display technology field.
Technical background
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.Hole follows the electronics as caused by negative electrode to be incorporated in through electron transfer layer through hole transmission layer as caused by anode Luminescent layer forms exciton, then lights.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 environment-friendly, it can apply on flat-panel monitor and a new generation's illumination, can also conduct LCD backlight.
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, because 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 When, Joule heat can be produced so that organic material easily crystallizes, and 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%, its application also greatly increases the efficiency of organic electroluminescence device.Usually, electroluminescent phosphorescence needs to use host and guest Body doping techniques, the conventional CBP (4,4'-bis (9-carbazolyl)-biphenyl) as phosphorescent light body material have height Effect and high triplet energy level, when it is as material of main part, triplet energy state effectively can be transferred to from light emitting host material Object phosphorescent light-emitting materials.But because CBP hole is easily transmitted and the characteristic of the difficult flowing of electronics so that the electric charge of luminescent layer is not Balance, as a result reduce the efficiency of device.
The content of the invention
Present invention firstly provides a kind of spiral shell carbazoles electroluminescent organic material, and it is the chemical combination with following structural formula I Thing：
Wherein, X is derived from-N=,-NR9,-O- ,-S-；Y is derived from-N=,-NR9,-O- ,-S-, and be-N=when X and Y differences；
R1-R9Separately selected from hydrogen, C1-C12 alkyl, substitution or unsubstituted C6-C30 aryl, substitution or The unsubstituted C3-C30 of person heteroaryl, substitution either unsubstituted 5 or 6 circle heterocycles alkyl, substitution or unsubstituted C12- Triaromatic amine base, the carbazyl of C30 two aromatic aminos, substitution or unsubstituted C18-C30.
A is expressed as singly-bound or sky.
Preferably, X1For-N=when, Y is selected from-O- ,-S-；During Y-N=, X is selected from-O- ,-S-；
Preferably, R1-R3、R5-R8Separately substitute or unsubstituted selected from C1-C12 alkyl, by C1-C12 alkyl C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl by C1-C12 alkyl.
Preferably, R4Selected from hydrogen, benzene, naphthalene, three and phenyl, C6-C30 N- aryl, C1-C4 alkyl-substituted carbazole Base, indyl, carbazole indyl, fluorenes carbazyl, anthryl, phenanthryl, pyrenyl, base, fluoranthene base, (9,9- dialkyl group) fluorenyl, (9, 9- bis- substitutes or unsubstituted aryl) fluorenyl, 9,9- be Spirofluorene-based, C18-C60 triaromatic amine base, is substituted by C1-C12 alkyl Or unsubstituted C12-C30 dibenzofuran group, pyridine radicals, pyrimidine radicals, pyridazinyl, triazine radical, imidazole radicals, oxazolyls, Thiazolyl, thiadiazolyl group, quinolyl, isoquinolyl, quinazolyl, quinoxalinyl, azepine dibenzofuran group, imidazole radicals, or Above aryl or heteroaryl are further substituted by C1-C12 alkyl.
It is further preferred that the spiral shell carbazoles organic electroluminescent compounds of the present invention are following structural 1-48 chemical combination Thing：
Present invention also offers a kind of organic electroluminescence device, the device includes anode, negative electrode and organic layer, organic layer Include at least one in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer Layer, wherein at least one layer electroluminescent organic material contained as described in structural formula I in the organic layer：
Wherein R1-R8, X, Y and A 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 spiral shell carbazole compound as described in structural formula I is luminescent layer.
Preferably, the spiral shell carbazole compound wherein described in structural formula I is structural formula 1-48 compound.
The organic electroluminescent compounds containing spiral shell carbazole compound as described in structural formula I are prepared for luminescent device When, it can be used alone, can also be used in mixed way with other compounds；Spiral shell carbazoles organic electroluminescence hair as described in structural formula I Optical compounds can be used alone a kind of compound therein, can also use the two or more chemical combination in structural formula I simultaneously Thing.
The organic electroluminescence device of the present invention, further preferred mode are 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 More than one structural formula I compound；It is further preferred that the chemical combination containing more than one structural formula 1-48 in luminescent layer Thing.
The gross thickness of the organic electroluminescence device organic layer of the present invention is 1-1000nm, preferably 50-500nm.
When having structural formula I compound 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 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, effectively hole can be transferred on luminescent layer from anode.Except the compound with I of the present invention can be used Outside, 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, six cyano group, six miscellaneous triphen (hexanitrilehexaazatriphenylene) the cyanogen dimethyl-parabenzoquinone (F4- of, tetra- fluoro- 7,7' of 2,3,5,6-, 8,8'- tetra- TCNQ), PVK, 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.Except the present invention there is 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, glimmering anthracene compound, anthracene class chemical combination Thing, pentacene class compound, class compound, two aromatic ethylene class compounds, triphenylamine ethylene compounds, aminated compounds, Benzimidazoles compound, furfuran compound, organic metal chelate complex.
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.
The electron injecting layer of organic electroluminescence device of the present invention, electronics effectively can be injected into organic layer from negative electrode In, it is mainly selected from the compound of alkali metal or alkali metal, or compound or alkali selected from alkaline-earth metal either 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, it 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 spiral shell carbazoles organic electroluminescent compounds of the present invention as described in structural formula I, have preferable Heat endurance, high-luminous-efficiency, high luminance purity.Made using the organic electroluminescent compounds for containing carbazole derivates Organic electroluminescence device has that electroluminescent efficiency is good and excitation is excellent and the advantages of long lifespan.
Brief description of the drawings
Fig. 1 is a kind of organic electroluminescence device structural representation 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 barrier layer, and 160 are represented as luminescent layer, and 170 are represented as electron transfer layer, and 180 are represented as electronics note Enter layer, 190 are represented as negative electrode.
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
Intermediate 1-1 synthesis
In 250mL single-necked flasks, addition 2- amino -6- bromophenols (25g, 0.13mol), benzoic acid (16.25g, 0.13mol) and 50mL polyphosphoric acids, react 6 hours at 160 DEG C.After reaction terminates, question response mixture is cooled to room temperature, water Wash, be filtrated to get crude product, crude product purifies through column chromatography, obtains white solid 25.75g, yield 70.7%.
Intermediate 1-2 synthesis
By intermediate 1-1 (25.75g, 0.09mol), triisopropyl borate ester (21.20g, 0.11mol) and dried Tetrahydrofuran (150mL) mixing add three-necked flask in, at -78 DEG C argon gas protection in, stir 15 minutes, then pass through again Disposable syringe injects the hexane solution (37.6mL, 0.09mol) of 2.5M n-BuLis into mixture, and continues to stir 2 hours.Then, react 3 hours at room temperature.After reaction terminates, watery hydrochloric acid is added into mixed reaction solution, regulation pH value is to weak Acidity, then repeatedly extracted with dichloromethane, merging obtains organic phase, and rotary evaporation removes organic solvent.Crude product oil Ether recrystallizes, and obtains white solid 16.85g, yield 75.3%.
Intermediate 1-3 synthesis
Intermediate 1-2 (8.5g, 36mmol) and 2- methyl-bromobenzoates (7.6g, 36mmol) are dissolved in 100mL tetrahydrochysene furans Again with potassium carbonate (10g, 72mmol) in muttering, 50mL water, which is mixed, to be added in single-necked flask.Under argon gas protection, then to mixing Tetrakis triphenylphosphine palladium (0.28g, 0.24mmol) is added in thing, is heated to reflux 4 hours.After reaction terminates, question response mixture Room temperature is cooled to, revolving removes tetrahydrofuran, then washed, and dichloromethane extracts three times (each 10mL).Merge organic phase, nothing Aqueous sodium persulfate is dried, and crude product is purified with row column chromatography, obtains 10.6g, yield 90%.
Intermediate 1-4 synthesis
Intermediate 1-3 (18.0g, 55mmol) and 100mL polyphosphoric acids are added in single-necked flask, react 6 at 160 DEG C Hour.After reaction terminates, question response mixture is cooled to room temperature, washing, is filtrated to get crude product, alcohol is washed, and obtains green solid 13g, yield 81%.
The synthesis of compound 1
Intermediate 9- (2- bromophenyls)-carbazole (3g, 9.3mmol) and dried tetrahydrofuran (40mL) are mixed Add in three-necked flask, at -78 DEG C in argon gas protection, stir 15 minutes, then again by disposable syringe to mixture The hexane solution (3.7mL, 9.3mmol) of middle injection 2.5M n-BuLis, and continue stirring 1 hour.Addition is dissolved in 100mL tetra- The intermediate 1-4 (2.8g, 9.3mmol) of hydrogen furans, low-temp reaction were moved to and reacted 3 hours at room temperature after 1 hour.Reaction terminates Afterwards, repeatedly extracted with dichloromethane, merging obtains organic phase, and rotary evaporation removes organic solvent.Crude product is with carrying out column chromatography After purification, 50mL glacial acetic acid and 1mL concentrated hydrochloric acids are added, is heated to reflux 1 hour.After reaction terminates, rotary evaporation removes organic molten Agent, crude by column chromatography purify to obtain product 2.2g, yield 46%.
Embodiment 2
The synthesis of compound 8
Intermediate 8-1 synthesis
The bromo- 2- iodo-benzoic acids methyl esters (6.3g, 18.5mmol) of intermediate 1-2 (4.0g, 16.8mmol) and 5- are dissolved in Again with potassium carbonate (4.56g, 33.6mmol) in 50mL tetrahydrofurans, 25mL water, which is mixed, to be added in single-necked flask.Argon gas Under protection, then tetrakis triphenylphosphine palladium (0.28g, 0.24mmol) is added into mixture, be heated to reflux 4 hours.Reaction terminates Afterwards, question response mixture is cooled to room temperature, and revolving removes tetrahydrofuran, then washed, and dichloromethane extracts three times (every time 10mL).Merge organic phase, anhydrous sodium sulfate drying, crude product is purified with row column chromatography, obtains 5.67g, yield 82.7%.
Intermediate 8-2 synthesis
Intermediate 8-1 (20.0g, 49mmol) and 100mL polyphosphoric acids are added in single-necked flask, react 6 at 160 DEG C Hour.After reaction terminates, question response mixture is cooled to room temperature, washing, is filtrated to get crude product, alcohol is washed, and obtains green solid 15g, yield 84.3%.
Intermediate 8-3 synthesis
Synthetic method is as the synthesis of compound 1, yield 38%.
The synthesis of compound 8
Synthetic method is as intermediate 8-1, and raw materials used is intermediate 8-3 and 4- dibenzofuran boric acid, and yield is 83%.
Embodiment 3
The synthesis of compound 11
Synthetic method is as intermediate 8-1, and raw materials used is intermediate 8-3 and 9- phenyl carbazole 3- boric acid, and yield is 72%.
Embodiment 4
The synthesis of compound 13
Synthetic method is as compound 1, and raw materials used is intermediate 1-4 and 2- bromine triphenylamine, yield 41%.
Embodiment 5
The synthesis of compound 25
Intermediate 25-1 synthesis
Synthetic method is as intermediate 1-1, and raw material is 2- amino -6- bromo thiophenols, yield 69%.
Intermediate 25-2 synthesis
Synthetic method is as intermediate 1-2, in addition to replacing intermediate 1-1 with intermediate 25-1, yield 71%.
Intermediate 25-3 synthesis
Synthetic method is as with intermediate 1-3, in addition to replacing intermediate 1-2 with intermediate 25-2, yield 87%.
Intermediate 25-4 synthesis
Synthetic method is as with intermediate 1-4, in addition to replacing intermediate 1-3 with intermediate 25-3, yield 82%.
The synthesis of compound 25
Synthetic method is as the synthesis of compound 1, and in addition to replacing intermediate 1-4 with intermediate 25-4, yield is 51%.
Embodiment 6
The synthesis of compound 30
Intermediate 30-1 synthesis
For synthetic method as intermediate 25-3, raw materials used is the bromo- 2- iodo-benzoic acids methyl esters of intermediate 25-2 and 5-, production Rate is 55%.
Intermediate 30-2 synthesis
Synthetic method is as intermediate 25-4, in addition to replacing intermediate 25-3 with intermediate 30-2, yield 82%.
Intermediate 30-3 synthesis
For synthetic method as the synthesis of compound 1, raw materials used is intermediate 30-2 and 9- (2- bromophenyls)-carbazole, Yield is 46%.
The synthesis of compound 30
Synthetic method is as compound 8, and raw materials used is intermediate 30-3 and 9- phenanthrene boric acid, yield 77%.
Embodiment 7
The synthesis of compound 37
Synthetic method is as compound 1, and raw materials used is intermediate 25-4 and 2- bromine triphenylamine, yield 38%.
Embodiment 8-14
The preparation of organic electroluminescence device
Use the compound of embodiment and the preparation OLED of comparative example
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 thick MnO of 3nm are deposited on ITO3(molybdenum oxide) is hole injection layer 130,
Then, it is hole mobile material 140 that the thick TAPC of 50nm are deposited on hole injection layer,
Then, TCTA is deposited, forms the thick electronic barrier layers 150 of 5nm.
Then, the thick luminescent layers 160 of 20nm are deposited on electronic barrier layer, wherein, the compounds of this invention lights for main body Material, and with 3% weight than Ir (ppy)3Guest materials is adulterated as phosphorescence.
Then, the thick BmPYPB of 40nm are deposited on 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) with Photo Research PR650 spectrometers measure 5000cd/m2Brightness under current efficiency be such as table 1.
Comparative example 1
Device prepared by comparative example is as embodiment 8-14 device preparation methods, except replacing chemical combination of the present invention with CBP Thing as material of main part outside.
Table 1
Embodiment Compound Current efficiency (cd/A) Glow color
8 1 56 Green glow
9 8 54 Green glow
10 11 55 Green glow
11 13 53 Green glow
12 25 55 Green glow
13 30 54 Green glow
14 37 56 Green glow
Comparative example 1 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, device efficiency is improved, is the phosphorescent light body material with premium properties.As described above, the compound of the present invention has height Stability, the organic electroluminescence device of preparation has 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 one of ordinary skill in the art without Creative work can is needed to make many modifications and variations according to the design of the present 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 spiral shell carbazoles organic electroluminescent compounds, it is characterised in that be the compound with following structural formula I：
Wherein, X is derived from-N=,-NR9,-O- ,-S-；Y is derived from-N=,-NR9,-O- ,-S-, and be-N=when X and Y differences；
R1-R9Separately selected from hydrogen, C1-C12 alkyl, substitution either unsubstituted C6-C30 aryl, substitution or not Substituted C3-C30 heteroaryl, substitution either unsubstituted 5 or 6 circle heterocycles alkyl, substitution or unsubstituted C12-C30 Triaromatic amine base, the carbazyl of two aromatic aminos, substitution or unsubstituted C18-C30；
A is expressed as singly-bound or sky.
2. spiral shell carbazoles organic electroluminescent compounds according to claim 1, it is characterised in that when X is-N=, Y choosings From-O- ,-S-；When Y is-N=, X is selected from-O- ,-S-.
3. spiral shell carbazoles organic electroluminescent compounds according to claim 1, it is characterised in that R1-R3、R5-R8Respectively Substitute or unsubstituted C6-C30 aryl, taken by C1-C12 alkyl independently selected from C1-C12 alkyl, by C1-C12 alkyl Generation or unsubstituted C3-C30 heteroaryl.
4. spiral shell carbazoles organic electroluminescent compounds according to claim 1, it is characterised in that R4Selected from hydrogen, benzene, naphthalene, Three and phenyl, C6-C30 N- aryl, C1-C4 alkyl-substituted carbazyl, indyl, carbazole indyl, fluorenes carbazyl, anthracene Base, phenanthryl, pyrenyl, base, fluoranthene base, (9,9- dialkyl group) fluorenyl, (9,9- bis- substitutes or unsubstituted aryl) fluorenyl, 9, 9- is Spirofluorene-based, C18-C60 triaromatic amine base, is substituted or unsubstituted C12-C30 dibenzofurans by C1-C12 alkyl Base, pyridine radicals, pyrimidine radicals, pyridazinyl, triazine radical, imidazole radicals, oxazolyls, thiazolyl, thiadiazolyl group, quinolyl, isoquinolyl, Quinazolyl, quinoxalinyl, azepine dibenzofuran group, imidazole radicals, or more aryl or heteroaryl further by C1-C12's Alkyl substitutes.
5. spiral shell carbazoles organic electroluminescent compounds according to claim 1, it is characterised in that be following structural 1- 48 compound：
6. a kind of organic electroluminescence device, the device includes anode, negative electrode and organic layer, and organic layer includes luminescent layer, hole At least one layer in implanted layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, it is characterised in that its Described in organic layer at least one layer contain spiral shell carbazoles electroluminescent organic material as claimed in claim 1.
7. organic electroluminescence device according to claim 6, it is characterised in that the spiral shell carbazoles as described in structural formula I Layer where organic electroluminescent compounds is luminescent layer.
8. organic electroluminescence device according to claim 6, it is characterised in that the spiral shell carbazoles as described in structural formula I Organic electroluminescent compounds are structural formula 1-48 compound.
9. organic electroluminescence device according to claim 6, it is characterised in that the spiral shell carbazoles as described in structural formula I A kind of compound therein is used alone in organic electroluminescent compounds, or uses the two or more changes in structural formula I simultaneously Compound.
10. organic electroluminescence device according to claim 6, it is characterised in that the organic electroluminescence device has The gross thickness of machine layer is 1-1000nm.
CN201710496289.4A 2017-06-26 2017-06-26 A kind of spiral shell carbazoles organic electroluminescent compounds and its organic electroluminescence device Pending CN107344946A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111961063A (en) * 2020-07-31 2020-11-20 北京燕化集联光电技术有限公司 Oxygen-containing multi-heterocyclic compound and application thereof
CN112142666A (en) * 2019-06-27 2020-12-29 关东化学株式会社 Spiroacridine-based compound, hole transport material containing the compound, and organic electronic device containing the compound in a hole transport layer
CN113214254A (en) * 2021-04-09 2021-08-06 华南理工大学 Hole-transport-type main body material, preparation method thereof and application thereof in preparation of organic electroluminescent device
CN115696943A (en) * 2021-07-30 2023-02-03 宁波卢米蓝新材料有限公司 An organic electroluminescent device and its photoelectric product

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104903328A (en) * 2012-12-21 2015-09-09 默克专利有限公司 Materials for Organic Electroluminescent Devices
CN106029830A (en) * 2014-02-21 2016-10-12 默克专利有限公司 Materials for organic electroluminescent devices
CN106749289A (en) * 2016-11-24 2017-05-31 上海道亦化工科技有限公司 A kind of organic electroluminescent compounds and its luminescent device with spiro structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104903328A (en) * 2012-12-21 2015-09-09 默克专利有限公司 Materials for Organic Electroluminescent Devices
CN106029830A (en) * 2014-02-21 2016-10-12 默克专利有限公司 Materials for organic electroluminescent devices
CN106749289A (en) * 2016-11-24 2017-05-31 上海道亦化工科技有限公司 A kind of organic electroluminescent compounds and its luminescent device with spiro structure

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112142666A (en) * 2019-06-27 2020-12-29 关东化学株式会社 Spiroacridine-based compound, hole transport material containing the compound, and organic electronic device containing the compound in a hole transport layer
CN111961063A (en) * 2020-07-31 2020-11-20 北京燕化集联光电技术有限公司 Oxygen-containing multi-heterocyclic compound and application thereof
CN111961063B (en) * 2020-07-31 2022-11-11 北京燕化集联光电技术有限公司 Oxygen-containing multi-heterocyclic compound and application thereof
CN113214254A (en) * 2021-04-09 2021-08-06 华南理工大学 Hole-transport-type main body material, preparation method thereof and application thereof in preparation of organic electroluminescent device
CN115696943A (en) * 2021-07-30 2023-02-03 宁波卢米蓝新材料有限公司 An organic electroluminescent device and its photoelectric product

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