CN106977514A - A kind of organic electroluminescent compounds and its luminescent device containing carbazole derivates - Google Patents

A kind of organic electroluminescent compounds and its luminescent device containing carbazole derivates Download PDF

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CN106977514A
CN106977514A CN201710204789.6A CN201710204789A CN106977514A CN 106977514 A CN106977514 A CN 106977514A CN 201710204789 A CN201710204789 A CN 201710204789A CN 106977514 A CN106977514 A CN 106977514A
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organic
compound
containing carbazole
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黄锦海
苏建华
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Shanghai Taoe Chemical Technology Co Ltd
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    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract

The invention provides a kind of organic electroluminescent compounds containing carbazole derivates, the compound has preferable heat endurance, high-luminous-efficiency, high luminance purity, it 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, it includes anode, negative electrode and organic layer, organic layer includes at least one layer of compound containing carbazole derivates comprising just like structural formula I at least one layer in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, organic layer.

Description

A kind of organic electroluminescent compounds and its luminescent device containing carbazole derivates
Technical field
The present invention relates to field of organic electroluminescent materials, and in particular to a kind of organic electroluminescence hair containing carbazole derivates Optical compounds and its organic electroluminescence device, belong to organic electroluminescence device display technology field.
Background technology
Organic electroluminescence device (OLEDs) is by spin coating or vacuum evaporation deposition one between two metal electrodes The device that layer organic material is prepared from, a classical three layer organic electroluminescence device includes 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 formation exciton, then lights.Organic electroluminescence device can be adjusted as desired by the material of luminescent layer is changed The light of the various needs of section transmitting.
Organic electroluminescence device is 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 be applied on flat-panel monitor and a new generation's illumination, can also conduct LCD backlight.
Since invention at the bottom of 1980s, organic electroluminescence device has industrially been applied, such as 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.Applying voltage-operated additionally, due to OLED When, Joule heat can be produced so that organic material is easily crystallized, 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 high efficiency of organic electroluminescence device.Usually, electroluminescent phosphorescence needs to use host-guest system technology, conventional to be used 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 electronics hardly possible flowing in CBP hole 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 carbazole derivates, it is with following structure The compound of Formulas I：
Wherein, Ar is selected from hydrogen, deuterium, halogen, cyano group, straight chain or with side chain C1-C12 alkyl, straight chain or with branch Chain C1-C8 alkoxyl, substitution or unsubstituted C6-C30 aryl, substitution or unsubstituted C3-C30 heteroaryls, three fragrance Amido, carbazyl, triaryl phosphinyl；
L is selected from singly-bound, substitution or unsubstituted C6-C30 aryl, substitution or unsubstituted C3-C30 heteroaryls；
X and Y one of them be selected from O, S, Se, CR1R2、NR3, another is sky；Wherein R1-R3Separately it is selected from Hydrogen, deuterium, halogen, cyano group, straight chain or C1-C12 alkyl with side chain, straight chain or C1-C8 alkoxyl with side chain, take Generation or unsubstituted C6-C30 aryl.
Preferably, Ar be selected from hydrogen, deuterium, methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, isopropyl, isobutyl group, The tert-butyl group, cyclohexyl, phenyl, xenyl, terphenyl, diphenyl benzene, naphthyl, phenanthryl, fluorenyl, anthryl, dibenzofuran group, Dibenzothiophenes base, benzo phenanthryl, Qu Ji, fluoranthene base, pyrenyl, perylene base, carbazyl, triaromatic amine base, above aryl can enter C1-C12 alkyl of one step by straight chain or with side chain replaces.
Preferably, L is selected from phenyl, naphthyl, xenyl.
Preferably, R1And R2Separately it is selected from methyl, ethyl, propyl group, phenyl, xenyl；R3Selected from phenyl, biphenyl Base, naphthyl.
It is further preferred that the organic electroluminescent compounds containing carbazole derivates of the present invention are following structural 1- 112 compound：
The present invention the organic electroluminescent compounds containing carbazole derivates can apply organic electroluminescence 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 Include at least one in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer Layer, wherein the compound containing carbazole derivates that at least one layer contains as described in structural formula I in the organic layer：
Wherein X, Y, L and Ar are 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 be luminescent layer, hole transmission layer, hole injection At least one layer in layer.
Preferably, the hole transmission layer compound wherein described in structural formula I is structural formula 1-112 compound.
When the compound containing carbazole derivates as described in structural formula I is used for luminescent device preparation, it can be used alone, It can also be used in mixed way with other compounds；Electroluminescent compounds containing carbazole derivates as described in structural formula I can be with A kind of compound therein is used alone, the two or more compounds in structural formula I can also be used simultaneously.
The organic electroluminescence device of the present 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 At least one structural formula I compound；It is further preferred that containing at least one structural formula 1-112 compound in luminescent layer.
The gross thickness of the organic electroluminescence device organic layer of the present invention is 1-1000nm, preferably 50-500nm.
The organic electroluminescence device of the present invention is when having structural formula I compound using the present invention, and can arrange in pairs or groups makes 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.There is compound described in structural formula I except above-mentioned 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, the miscellaneous triphen (hexanitrilehexaaza of six cyano group six Triphenylene), the cyanogen dimethyl-parabenzoquinones (F4-TCNQ) of 2,3,5,6- tetra- fluoro- 7,7', 8,8'- tetra-, PVK, Polythiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer of the organic electroluminescence device of the present invention, with the good characteristics of luminescence, can be adjusted as needed The scope of visible ray.In addition to the present invention is with Compounds of structural formula I, following compound can also be contained, including but not limit In 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 Compound, pentacene class compound, perylene classes compound, two aromatic ethylene class compounds, triphenylamine ethylene compounds, amine chemical combination Thing, 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, it is mainly selected from the compound of alkali metal or alkali metal, or compound or alkali selected from alkaline-earth metal or alkaline-earth metal Metal complex, can select following compound, but not limited to this：Alkali metal, alkaline-earth metal, rare earth metal, alkali metal Oxide 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, can also be used cooperatively with other electroluminescent organic materials.
Each layer of organic layer in the organic electroluminescence device of the present invention, can be steamed by vacuum vapour deposition, molecular beam It is prepared by the modes such as plating method, the dip coating for being dissolved in solvent, spin-coating method, stick coating method or inkjet printing.It can make for metal motor Prepared with vapour deposition method or sputtering method.
Device experimental shows that compound containing carbazole derivates of the present invention as described in structural formula I has preferably heat steady Qualitative, high-luminous-efficiency, high luminance purity.Using the organic of organic electroluminescent compounds making for containing carbazole derivates Electroluminescent device 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, 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
The synthesis of intermediate A 2
The synthesis of intermediate A 1
In three-necked flask, add 2- boric acid-dibenzofurans (21g, 0.1mol), o-bromonitrobenzene (20g, 0.1mol), potassium carbonate (27.6g, 0.2mol), tetra-triphenylphosphine palladium (1g), tetrahydrofuran (300mL) and water (100mL), in nitrogen It is heated to reflux under gas shielded 12 hours, cools down, extracted with dichloromethane, dried, filtered, concentration is stirred with methanol, is filtered, and is done It is dry to obtain 21g, yield 72%.
The synthesis of intermediate A 2
In flask, intermediate A 1 (20g, 69mmol), o-dichlorohenzene (200mL), triethyl phosphite are added (100mL), is heated to reflux 12 hours under nitrogen protection, cooling, and pressurization removes solvent, and crude product is obtained through column chromatography purifying 6.2g, yield 35%.
The synthesis of intermediate B 2
The synthesis of intermediate B 1
Synthetic method is with intermediate A 1, in addition to replacing 2- boric acid dibenzofurans with 2- boric acid dibenzothiophenes, Yield 83%.
The synthesis of intermediate B 2
Synthetic method is with A2, in addition to replacing intermediate A 1 with intermediate B 1, yield 28%.
Intermediate C2 synthesis
Intermediate C1 synthesis
Synthetic method is with intermediate A 1, in addition to replacing 2- boric acid dibenzofurans with 4- boric acid dibenzofurans, Yield 84%.
Intermediate C2 synthesis
Synthetic method is with intermediate A 2, in addition to replacing intermediate A 1 with intermediate C1, yield 67%.
Intermediate D2 synthesis
Intermediate D1 synthesis
Synthetic method is with A1, in addition to replacing 2- boric acid dibenzofurans with 4- boric acid dibenzothiophenes, yield 76%.
Intermediate D2 synthesis
Synthetic method is with A2, in addition to replacing intermediate A 1 with D1, yield 74%.
The synthesis of intermediate E 3
The synthesis of intermediate E 1
In flask, bromo- 2, the 4- dinitro benzenes (10g, 31mmol) of 1,5- bis-, phenyl boric acid (11g, 92mmol), carbon are added Sour potassium (16g, 124mmol), tetra-triphenylphosphine palladium (0.5g), tetrahydrofuran (150mL) and water (50mL), add under nitrogen protection Heat backflow 12 hours, cooling is extracted with dichloromethane, is dried, and is filtered, and concentration uses ethanol agitation and filtration, obtains product 7.3g, Yield 74%.
The synthesis of intermediate E 2
In flask, intermediate E 1 (8g, 25mmol), triethyl phosphite (20mL), o-dichlorohenzene (50mL) are added, It is heated to reflux 24 hours, cools down, removal of solvent under reduced pressure under nitrogen protection, add methanol stirring, filtering obtains 2.4g, yield 38%.
The synthesis of intermediate E 3
In flask, add intermediate E 2 (3g, 12mmol), iodobenzene (2.4g, 12mmol), potassium carbonate (3.3g, 24mmol), cuprous iodide (0.3g), phenanthroline (0.3g) and dimethyl sulfoxide (DMSO) (30mL), 10 are heated to reflux under nitrogen protection Hour, reaction is finished, removal of solvent under reduced pressure, and crude product obtains 2.2g, yield 56% through column chromatography purifying.
Intermediate 1a synthesis
7,7- dimethyl -5H- indenos [2,1-b] carbazole (10g, 35.3mmol) is added into reaction flask, to bromo-iodobenzene (12g, 42mmol), potassium tert-butoxide (7.9g, 70.6mmol), palladium (0.3g, 1.3mmol), tri-butyl phosphine tetrafluoro boric acid Salt (0.8g, 2.7mmol) and toluene (150mL), are heated to reflux 24 hours under nitrogen protection, cool down, remove toluene, add dichloro Methane, is washed, and is dried, and crude product crosses post, obtains 10g products, yield 57%.
Following compound is prepared with similar method：
Intermediate 2a synthesis
Intermediate 1a (4.37g, 10mmol), connection boric acid frequency are added in single-necked flask and receives alcohol ester (3.0g, 12mmol), vinegar Sour potassium (3.0g), 1,1'- double Diphenyl phosphino ferrocene palladium chloride (50mg), dioxane (60mL), are heated to 100 DEG C of reactions 12 hours, silica gel is crossed while hot, filter cake is washed with dichloromethane, solvent evaporated is revolved, and crude product is purified with column chromatography, obtains product 2.8g, yield 60%.
Following compound is prepared with similar method：
Intermediate 3a synthesis
Benzonitrile (5g, 49mmol), the bromo- PAs of 5- (8.3g, 49mmol), cuprous bromide are added in single port bottle (1g), phenanthroline (1g), zinc iodide (3g), o-dichlorohenzene (50mL), 130 degree of blowing air react 24 hours, are cooled to room temperature Diluted afterwards with ethyl acetate, be filtered to remove inorganic salts, column chromatography for separation is used after filtrate concentration.White solid 5.7g is obtained, is produced Rate 47%.
Following compound is prepared with similar method:
Embodiment 1
The synthesis of compound 2
In flask, add intermediate 2a (1.8g, 3.7mmol), intermediate 3b (1.2g, 3.7mmol), potassium carbonate (1g, 7.5mmol), tetra-triphenylphosphine palladium (0.3g), tetrahydrofuran (20mL) and water (10mL), are heated to reflux 12 small under nitrogen protection When, cooling is extracted with dichloromethane, is dried, concentration, and crude product obtains 1.3g, yield 58% through column chromatography purifying.
Embodiment 2-12
Following compound is prepared with similar method：
Embodiment 2-16
Following compound is prepared with similar method：
Embodiment 13-24
The preparation of organic electroluminescence device
OLED is prepared using the compound in the embodiment of the present invention.
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, the thick electronic barrier layers 150 of 5nm are formed.
Then, the thick luminescent layers 160 of 20nm are deposited on electronic barrier layer, wherein, the compounds of this invention is luminous for main body Material, and with 3% weight than Ir (ppy)3It is used as phosphorescence doping guest materials.
Then, the thick BmPYPB of 40nm are deposited on luminescent layer and are used as electron transfer layer 170.
Finally, evaporation 1nm LiF are that electron injecting layer 180 and 80nm Al are used as device cathodes 190.
Prepared device (structural representation is shown in Fig. 1) measured with Photo Research PR650 spectrometers 5000cd/m2Brightness under current efficiency be such as table 1.
Comparative example
Device prepared by comparative example is with embodiment 13-24 device preparation method, except replacing the present inventionization with CBP Compound as material of main part outside.
Table 1
Embodiment Compound Current efficiency (cd/A) Glow color
13 2 51 Green glow
14 7 54 Green glow
15 14 56 Green glow
16 21 55 Green glow
17 38 57 Green glow
18 66 54 Green glow
19 78 56 Green glow
20 82 57 Green glow
21 91 53 Green glow
22 100 58 Green glow
23 102 57 Green glow
24 106 56 Green glow
Comparative example CBP 45 Green glow
Structural formula is as follows described in device：
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, the compound of the present invention has height Stability, the organic electroluminescence device of preparation has high efficiency and optical purity.
Preferred embodiment of the invention described in detail above.It should be appreciated that the ordinary skill of this area is without wound The property made work just can make many modifications and variations according to the design of the present invention.Therefore, all technical staff in the art Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Scheme, all should be in the protection domain being defined in the patent claims.

Claims (10)

1. a kind of organic electroluminescent compounds containing carbazole derivates, it is characterised in that it is with following structural formula I's Compound：
Wherein, Ar is selected from hydrogen, deuterium, halogen, cyano group, straight chain or with side chain C1-C12 alkyl, straight chain or with side chain C1- C8 alkoxies, substitution or unsubstituted C6-C30 aryl, substitution or unsubstituted C3-C30 heteroaryls, triaromatic amine base, Carbazyl, triaryl phosphinyl；
L is selected from singly-bound, substitution or unsubstituted C6-C30 aryl, substitution or unsubstituted C3-C30 heteroaryls；
X and Y one of them be selected from O, S, Se, CR1R2、NR3, another is sky；Wherein R1-R3Separately selected from hydrogen, deuterium, Halogen, cyano group, straight chain or C1-C12 alkyl with side chain, straight chain or C1-C8 alkoxyl with side chain, substitution or Unsubstituted C6-C30 aryl.
2. the organic electroluminescent compounds according to claim 1 containing carbazole derivates, it is characterised in that Ar is selected from Hydrogen, deuterium, methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, isopropyl, isobutyl group, the tert-butyl group, cyclohexyl, phenyl, connection Phenyl, terphenyl, diphenyl benzene, naphthyl, phenanthryl, fluorenyl, anthryl, dibenzofuran group, dibenzothiophenes base, benzophenanthrene Base, Qu Ji, fluoranthene base, pyrenyl, perylene base, carbazyl, triaromatic amine base, or more aryl further by straight chain or with side chain C1-C12 alkyl substitution.
3. the organic electroluminescent compounds according to claim 1 containing carbazole derivates, it is characterised in that L is selected from benzene Base, naphthyl, xenyl.
4. the organic electroluminescent compounds according to claim 1 containing carbazole derivates, it is characterised in that R1And R2Point Not independently selected from methyl, ethyl, propyl group, phenyl, xenyl；R3Selected from phenyl, xenyl, naphthyl.
5. the organic electroluminescent compounds according to claim 1 containing carbazole derivates, it is characterised in that under it is Following formula 1-112 compound：
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 layer in layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, it is characterised in that in organic layer At least one layer includes the compound as claimed in claim 1 containing carbazole derivates.
7. organic electroluminescence device according to claim 6, it is characterised in that spreading out containing carbazole as described in structural formula I Layer where biological compound is at least one layer in luminescent layer, hole transmission layer, hole injection layer.
8. organic electroluminescence device according to claim 6, it is characterised in that spreading out containing carbazole as described in structural formula I Biological compound is used alone, or is used in mixed way with other compounds.
9. organic electroluminescence device according to claim 6, it is characterised in that spreading out containing carbazole as described in structural formula I A kind of compound therein is used alone in biological compound, or uses the two or more compounds in structural formula I simultaneously.
10. organic electroluminescence device according to claim 6, its comprising anode, hole injection layer, hole transmission layer, Luminescent layer, electron transfer layer, electron injecting layer and negative electrode, it is characterised in that contain at least one structural formula I change in luminescent layer Compound.
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Application publication date: 20170725