CN105669466B - A kind of compound and its organic electroluminescence device based on fluoranthene - Google Patents

A kind of compound and its organic electroluminescence device based on fluoranthene Download PDF

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CN105669466B
CN105669466B CN201610149510.4A CN201610149510A CN105669466B CN 105669466 B CN105669466 B CN 105669466B CN 201610149510 A CN201610149510 A CN 201610149510A CN 105669466 B CN105669466 B CN 105669466B
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fluoranthene
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CN105669466A (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 present invention provides a kind of organic electroluminescent compounds based on fluoranthene, the compound has preferable thermal stability, high-luminous-efficiency, high luminance purity, low driving voltage, it can be used for making organic electroluminescence device, be applied to organic solar batteries, perovskite battery, Organic Thin Film Transistors or organophotoreceptorswith field.The present invention also provides a kind of organic electroluminescence devices, it includes anode, cathode and organic layer, organic layer includes at least one layer in luminescent layer, hole injection layer, hole transmission layer, exciton barrier-layer, electron transfer layer, and at least one layer includes the compound just like structural formula I in organic layer.

Description

A kind of compound and its organic electroluminescence device based on fluoranthene
Technical field
The present invention relates to field of organic electroluminescent materials, and in particular to a kind of organic electroluminescent chemical combination based on fluoranthene Object and its organic electroluminescence device belong to organic electroluminescence device display technology field.
Background technology
Organic electroluminescence device (OLEDs) is between two metal electrodes by spin coating or vacuum evaporation deposition one 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.The electronics generated by cathode is followed to be incorporated in through electron transfer layer through hole transmission layer in the hole generated by anode Luminescent layer forms exciton, then shines.Organic electroluminescence device can be adjusted as desired by the material for changing luminescent layer Section emits the light of various needs.
Organic electroluminescence device has self-luminous, wide viewing angle, low energy consumption, efficiency as a kind of novel display technology High, thin, rich in color, fast response time, Applicable temperature range be wide, low driving voltage, can make flexible with it is transparent Display panel and the particular advantages such as environmental-friendly can be applied on flat-panel monitor and a new generation's illumination, be can also be used as The backlight of LCD.
Since the invention at the bottom of the 1980s, organic electroluminescence device is industrially applied, such as As screens such as camera and mobile phones, but current OLED device, since efficiency is low, it is wider that the factors such as service life is short restrict it General application, especially 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 device When, it will produce Joule heat so that organic material is easy to happen crystallization, affects service life and the efficiency of device, therefore, it is also desirable to Develop the electroluminescent organic material of stability and high efficiency.
In organic electroluminescence device, the introducing of hole mobile material and injection material can be effectively reduced positive electricity Lotus is transferred to the ability of luminescent layer from anode, improves efficiency and the thermostabilization of device.Traditional hole-injecting material, such as copper Phthalocyanine (CuPc), degradation is slow, prepares energy consumption height, is unfavorable for environmental protection, and it can absorb light, influence device Efficiency.Hole mobile material original NPB etc., thermal stability is poor, also largely influences device lifetime.Thus, it needs Develop the electroluminescent organic material of efficient stable.
Invention content
Present invention firstly provides a kind of organic electroluminescent compounds based on fluoranthene, are to have the following structure Formulas I Compound：
Wherein, Ar1And Ar2Separately it is selected from the substitution of C6-C30 or unsubstituted aryl；
R1And R2Separately it is selected from hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C1-C8 alkoxyl, C2-C8 substitutions Either unsubstituted allylic alkylation, C2-C8 substitutions or unsubstituted alkynes alkyl；
L is selected from singly-bound, phenyl, naphthalene；
X is selected from O, S, Se, CR4R5Or NR6；
R4、R5And R6Separately it is selected from hydrogen, C1-C12 alkyl, C1-C8 alkoxyl, C2-C8 substitutions or unsubstituted Allylic alkylation, C2-C8 replace either unsubstituted alkynes alkyl, the substitution of C6-C30 or unsubstituted aryl.
Preferably, Ar1And Ar2Separately it is selected from phenyl, naphthalene, naphthalene, N- aryl (C6-C30) carbazyl, C1-C4 Alkyl-substituted carbazyl, anthryl, phenanthryl, pyrenyl, base, fluoranthene base, (9,9- dialkyl group) fluorenyl, (9,9- bis- replace or The unsubstituted aryl of person) fluorenyl, 9,9- be Spirofluorene-based, three fragrant (C6-C60) amidos, dibenzothiophene, dibenzofuran group, The above aryl can by the alkyl of C1-C12 replace or it is unsubstituted.
Preferably, R1And R2Separately it is selected from hydrogen and methyl；
Preferably, X is selected from O, S, Se, CR4R5；R4And R5Separately it is selected from hydrogen, C1-C8 alkyl, phenyl, tolyl.
It is further preferred that the organic electroluminescent compounds based on fluoranthene of the present invention are the change of following structural 1-48 Close object：
A kind of organic electroluminescent compounds based on fluoranthene of the present invention can be reacted by Buchwald-Hartwig It is prepared with ullmann reaction.
A kind of organic electroluminescent compounds based on fluoranthene of the present invention can be applied in organic electroluminescence device, have Machine solar cell, perovskite battery, Organic Thin Film Transistors or organophotoreceptorswith field.
The present invention also provides a kind of organic electroluminescence device, which includes anode, cathode and organic layer, organic layer Including at least one layer in luminescent layer, hole injection layer, hole transmission layer, exciton barrier-layer, electron transfer layer, wherein described have Contain the organic electroluminescent compounds as described in structural formula I at least one layer in machine layer：
Wherein Ar1、Ar2, L, X and R1-R2It is defined as described above.
Wherein organic layer is hole transmission layer and luminescent layer；
Or organic layer is hole injection layer, hole transmission layer, luminescent layer and electron transfer layer；
Or organic layer is hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer；
Or organic layer is hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and exciton Barrier layer；
Or organic layer is hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and exciton barrier-layer；
Or organic layer is hole transmission layer, luminescent layer, electron injecting layer and exciton barrier-layer.
Preferably, layer where the organic electroluminescent compounds based on fluoranthene as described in structural formula I is hole transmission layer.
Preferably, the organic electroluminescent compounds based on fluoranthene as described in structural formula I are the chemical combination of structural formula 1-48 Object.
When the organic electroluminescent compounds based on fluoranthene as described in structural formula I are prepared for luminescent device, Ke Yidan It solely uses, can also be used in mixed way with other compounds；The organic electroluminescent compounds based on fluoranthene as described in structural formula I One such compound is can be 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 are that the organic electroluminescence device includes sun Pole, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode contain structural formula I in hole-transporting layer Compound；It is further preferred that the compound containing structural formula 1-48 in hole transmission layer.
The overall thickness of the organic electroluminescence device organic layer of the present invention is 1-1000nm, preferably 50-500nm.
The film thickness of the organic electroluminescence device luminescent layer of the present invention is preferably 10-50nm.
When having the compound of structural formula I 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 exciton barrier-layer It is medium, and obtain blue and green light, yellow light, 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 in addition to above-mentioned Outside, it may include other small molecules and macromolecular organic compound, including but not limited to carbazole compound, triaromatic amine chemical combination Object, benzidine compound, compound of fluorene class, phthalocyanine-like compound, six cyano, six miscellaneous triphen (hexanitrilehexaazatr Iphenylene tetra- cyanogen dimethyl-parabenzoquinone (F4-TCNQ) of), tetra- fluoro- 7,7' of 2,3,5,6-, 8,8'-, gathers at polyvinyl carbazole Thiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer of the organic electroluminescence device of the present invention has the good characteristics of luminescence, can be adjusted according to the needs The range of visible light.In addition to the compound of fluorene class that can contain the present invention, following compound can also be contained, including but unlimited In naphthalene compounds, pyrene compound, compound of fluorene class, luxuriant and rich with fragrance class compound, bend class compound, glimmering anthracene compound, anthracene class Close object, pentacene class compound, class compound, two aromatic ethylene class compounds, triphenylamine ethylene compounds, amine chemical combination Object, carbazole compound, benzimidazoles compound, furfuran compound, metal organic fluorescence complex compound, metal Phosphorescent Complex compound (such as Ir, Pt, Os, Cu, Au), polyvinylcarbazole, poly-organosilicon compound, polythiophene organic macromolecular LED material Material, they can be used alone, can also a variety of mixtures uses.
The Organic Electron Transport Material of organic electroluminescence device of the present invention requires good electronic transmission performance, energy In reaching effectively electronics from cathode transport to luminescent layer, there is prodigious 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 Object, 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 cathode In, it is mainly selected from the alkali metal either compound of alkali metal or the compound selected from alkaline-earth metal or alkaline-earth metal or alkali Metal complex can select following compound, and 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 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.Metal motor can be made It is prepared with vapour deposition method or sputtering method.
Device experimental shows organic electroluminescent compounds based on fluoranthene of the present invention as described in structural formula I, have compared with Good thermal stability, high-luminous-efficiency, high luminance purity, low driving voltage.Had using what the organic electroluminescent compounds made Organic electroluminescence devices have the advantages that electroluminescent efficiency is good and excitation purity is excellent and long lifespan.
Description of the drawings
Fig. 1 is a kind of organic electroluminescence device structural schematic diagram of the present invention；
Wherein, 110 it is represented as glass substrate, 120 are represented as anode, and 130 are represented as hole transmission layer, and 140 are represented as sending out Photosphere, 150 are represented as electron transfer layer, and 160 are represented as electron injecting layer, and 170 are represented as cathode.
Specific implementation mode
In order to describe the present invention in more detail, spy lifts following example, and but not limited to this.
Embodiment 1
The synthesis of compound 1
The synthesis of intermediate 1-1
In flask, be added 3- fluoranthene amine (22g, 0.1mol), iodobenzene (21g, 0.1mol), potassium hydroxide (8g, 0.2mol), cuprous iodide (2g), phenanthroline (2g) and ortho-xylene 300ml, nitrogen are heated to reflux 10 hours, cooling, mistake Filter, concentration, crude product purify to obtain 24g, yield 83% through column chromatography.
The synthesis of intermediate 1-2
In flask, intermediate 1-1 (20g, 68mmol), 4,4 '-diiodides (27.7g, 68mmol), potassium carbonate is added (19g, 136mmol), cuprous iodide (2g), phenanthroline (2g) and o-dichlorohenzene 300ml, nitrogen are heated to reflux 10 hours, heat Filtering, concentration, crude product purify to obtain 37g, yield 65% through column chromatography.
The synthesis of compound 1
In flask, be added intermediate 1-2 (3g, 5.3mmol), N- (4- dibenzofuran groups)-aniline (1.6g, 6.3mmol), sodium tert-butoxide (1.5g, 16mmol), palladium (100mg), X-phos (200mg) and toluene (30ml), in nitrogen It is heated to reflux under protection 10 hours, it is cooling, solvent is removed, crude product purifies to obtain product 2.9g, yield 78% through column chromatography.
Embodiment 2
The synthesis of compound 2
The synthesis of intermediate 2-1
Synthetic method replaces iodobenzene, yield 75% as intermediate 1-1, with to iodine biphenyl.
The synthesis of intermediate 2-2
Synthetic method replaces intermediate 1-1, yield 60% as intermediate 1-2, with intermediate 2-1.
The synthesis of compound 2
Synthetic method is replaced with intermediate 2-2 outside 1-2 as the synthesis of compound 1, yield 69%.
Embodiment 3
The synthesis of compound 3
The synthesis of intermediate 3-1
For synthetic method as with synthesis compound 1, two raw materials are respectively 3- fluoranthene amine and 1- bromonaphthalenes, yield 83%.
The synthesis of intermediate 3-2
Synthetic method replaces 1-1, yield 71% as with intermediate 1-2, with intermediate 3-1.
The synthesis of compound 3
Synthetic method replaces intermediate 1-1, yield 79% as the synthetic method of compound 1, with intermediate 3-2.
Embodiment 4
The synthesis of compound 11
Synthetic method is as the synthetic method of compound 1, in addition to replacing N- with N- (4- dibenzothiophenes)-aniline Outside (4- dibenzofuran groups)-aniline, yield 81%.
Embodiment 5
The synthesis of compound 12
Synthetic method is as the synthetic method of compound 1, with intermediate 2-2 and N- (4- dibenzothiophenes)-aniline For raw material, yield 70%.
Embodiment 6
The synthesis of compound 22
In synthetic method as compound 1, in addition to raw material N- [1,1 '-biphenyl -4- bases] -9,9- dimethyl -9H- fluorenes - 2- amine replaces outside N- (4- dibenzofuran groups)-aniline, yield 69%.
Embodiment 7
The synthesis of compound 24
Synthetic method is as the synthetic method of compound 3, in addition to being replaced with N- (9,9- dimethyl -2- fluorenyls)-aniline Outside N- (4- dibenzofuran groups)-aniline, yield 85%.
Embodiment 8
The synthesis of compound 28
Synthetic method is as the synthetic method of compound 1, in addition to N- (3- dibenzofuran groups) -4- isopropyl anilines Outside instead of N- (4- dibenzofuran groups)-aniline, yield 86%.
Embodiment 9
The synthesis of compound 37
Synthetic method is as the synthetic method of compound 1, in addition to replacing N- with N- (2- dibenzofuran groups)-naphthalidine Outside (4- dibenzofuran groups)-aniline, yield 59%.
Embodiment 10
The synthesis of compound 39
Synthetic method is as the synthetic method of compound 1, in addition to replacing N- with N- (2- dibenzothiophenes)-aniline Outside (4- dibenzofuran groups)-aniline, yield 81%.
Embodiment 11
The synthesis of compound 45
The synthesis of intermediate 45-1
In flask, 3- fluoranthene boronic acids (2.5g, 10mmol) are added, to bromo-iodobenzene (2.8g, 10mmol), potassium carbonate (2.7g, 20mmol), tetra-triphenylphosphine palladium (100mg), tetrahydrofuran (30ml) and water (10ml), are heated back under nitrogen protection Stream 10 hours, it is cooling to remove solvent, it is extracted with dichloromethane, dry, concentration, crude by column chromatography purifies to obtain 3.2g, produces Rate 90%.
The synthesis of intermediate 45-2
In flask, be added intermediate 45-1 (3g, 8.4mmol), aniline (1g, 11mmol), sodium tert-butoxide (1.9g, 20mmol), palladium (100mg), X-phos (200mg) and toluene (30ml), are heated to reflux 10 hours under nitrogen protection, cold But, solvent is removed, crude product purifies to obtain product 2.1g, yield 68% through column chromatography.
The synthesis of intermediate 45-3
Synthetic method replaces intermediate as the synthetic method of intermediate 1-2, with N- (4- dibenzofuran groups)-phenyl Outside 1-1, yield 74%.
The synthesis of compound 45
Synthetic method replaces intermediate 1-1 as the synthetic method of compound, with intermediate 45-3, with intermediate 45-2 Instead of N- (4- dibenzofuran groups)-aniline, yield 55%.
Embodiment 12
The synthesis of compound 9
For synthetic method as the synthetic method of compound 45, raw material is N- (3- fluoranthene base) -9,9- dimethyl -2- fluorenamines With intermediate 45-3, yield 82%.
Embodiment 13
The synthesis of compound 10
For synthetic method as the synthesis of compound 1, raw material is intermediate 1-2 and N- (4- dibenzofuran groups) -9,9- Dimethyl -2- fluorenamines, yield 76%.
Embodiment 14
The synthesis of compound 26
For synthetic method as the synthesis of compound 1, raw material is intermediate 1-2 and N- phenyl -9,9- diphenyl -2- fluorenes Amine, yield 67%.
Embodiment 15-28
The preparation of organic electroluminescence device
OLED is prepared using the compound of embodiment 1-11 and 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) it passes through successively：Deionized water, ethyl alcohol, acetone and deionized water were cleaned, then with oxygen plasma treatment 30 seconds.
Then, the compounds of this invention is deposited and compares compound (such as following table), forms the hole transmission layer 130 of 60nm thickness.
Then, the Alq of 30nm thickness is deposited on the hole transport layer3As luminescent layer 140.
Then, the Alq of 20nm thickness is deposited on the light-emitting layer3As electron transfer layer 150.
Finally, vapor deposition 1nm LiF are electron injecting layer 160 and 100nm Al as device cathodes 170.
Prepared device (structural schematic diagram is shown in Fig. 1) with Photo Research PR650 spectrometers measure 150mA/cm2Current density under efficiency it is as shown in the table.
Table 1
Embodiment Compound Current efficiency (cd/A) Color
15 1 1.7 Green
16 2 1.8 Green
17 3 1.7 Green
18 11 1.6 Green
19 12 1.7 Green
20 22 1.7 Green
21 24 1.6 Green
22 28 1.9 Green
23 37 1.7 Green
24 39 1.8 Green
25 45 1.9 Green
26 9 1.9 Green
27 10 1.7 Green
28 26 1.8 Green
Comparative example 1 NPB 1.2 Green
Under the same conditions, the organic electroluminescence device prepared using the organic electroluminescent compounds of the present invention Driving voltage is less than comparative example, as described above, the compound of the present invention has high stability, organic electroluminescence prepared by the present invention Luminescent device has low driving voltage, high efficiency and optical purity.
The structural formula of compound described in device is as follows：
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without It needs creative work according to the present invention can conceive and makes many modifications and variations.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 solution, all should be in the protection domain being defined in the patent claims.

Claims (5)

1. a kind of organic electroluminescent compounds based on fluoranthene, it is characterised in that it is following structural 1-30,32-46,48 Compound：
2. a kind of organic electroluminescence device comprising anode, cathode and organic layer, organic layer include luminescent layer, hole injection At least one layer in layer, hole transmission layer, exciton barrier-layer, electron transfer layer, it is characterised in that in the organic layer at least One layer contains the organic electroluminescent compounds based on fluoranthene as described in claim 1.
3. organic electroluminescence device according to claim 2, it is characterised in that as described in structural formula 1-30,32-46,48 Organic electroluminescent compounds based on fluoranthene where layer be hole transmission layer.
4. organic electroluminescence device according to claim 2, it is characterised in that as described in structural formula 1-30,32-46,48 Organic electroluminescent compounds based on fluoranthene be used alone, or be used in mixed way with other compounds.
5. organic electroluminescence device according to claim 2, it is characterised in that as described in structural formula 1-30,32-46,48 Organic electroluminescent compounds based on fluoranthene one such compound is used alone, or use simultaneously structural formula 1-30, Two or more compounds in 32-46,48.
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