CN106432181B - A kind of compound and its organic electroluminescence device containing five rings spiro structure - Google Patents

A kind of compound and its organic electroluminescence device containing five rings spiro structure Download PDF

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CN106432181B
CN106432181B CN201610858581.1A CN201610858581A CN106432181B CN 106432181 B CN106432181 B CN 106432181B CN 201610858581 A CN201610858581 A CN 201610858581A CN 106432181 B CN106432181 B CN 106432181B
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CN106432181A (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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    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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Abstract

The present invention provides a kind of organic electroluminescent compounds containing five rings spiro structure, 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, at least one layer of compound comprising just like structural formula I in organic layer.

Description

A kind of compound and its organic electroluminescence device containing five rings spiro 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 rings spiro structure Optical compounds and its organic electroluminescence device belong to organic electroluminescence device field of display technology.
Background technique
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 according to need the material by changing luminescent layer to adjust 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 and 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, due to low efficiency, 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, Joule heat can be generated, 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 the efficiency and thermostabilization of device.Traditional hole-injecting material, such as copper Phthalocyanine (CuPc), degradation is slow, and preparation energy consumption is high, is unfavorable for environmental protection, and it can absorb light, influence device Efficiency.NPB etc. original hole mobile material, thermal stability is poor, also largely influences device lifetime.Thus, it needs Develop the electroluminescent organic material of efficient stable.
Summary of the invention
Present invention firstly provides a kind of organic electroluminescent compounds containing five rings spiro structure, to have the following structure The compound of Formulas I:
Wherein, R1~R8Separately it is selected from hydrogen, D-atom, halogen, cyano, nitro, C1-C8 alkyl, C1-C8 alcoxyl Base, the substitution of C6-C30 or unsubstituted aryl, C3-C30 substitution or unsubstituted contain one or more miscellaneous original The aryl of son, C2-C8 replaces or unsubstituted allylic alkylation, C2-C8 substitution or unsubstituted alkynes alkyl；
Ar1And Ar2Separately it is selected from C6-C60 substitution or unsubstituted aryl, C3-C60 substitution or unsubstituted Heteroaryl, three fragrant (C6-C60) amidos, substitution or unsubstituted carbazyl (C6-C30), (9,9- dialkyl group) fluorenyl, (9,9- bis- replaces or unsubstituted aryl) fluorenyl, 9,9- is Spirofluorene-based, C6-C60 replaces or unsubstituted dibenzothiophenes Base, C6-C60 replaces or unsubstituted dibenzofuran group；
Further, Ar1And Ar2Singly-bound, substitution or unsubstituted methylene, oxygen atom or sulphur can also be passed through each other Atom is formed by connecting ring；
X is selected from S and O.
Preferably, R1-R8For hydrogen；
Ar1And Ar2Alkyl-substituted click separately selected from phenyl, naphthalene, N- aryl (C6-C30) or C1-C4 Oxazolyl, anthryl, phenanthryl, pyrenyl, base, fluoranthene base, (9,9- dialkyl group) fluorenyl, (9,9- bis- replaces or unsubstituted aryl) Fluorenyl, 9,9- are Spirofluorene-based, three fragrant (C6-C60) amidos, dibenzothiophene, dibenzofuran group, and the above aryl can be into one Step is replaced or unsubstituted by the alkyl of C1-C12.
It is further preferred that Ar1And Ar2Separately selected from the substituted or unsubstituted following aryl of C1-C4 alkyl and miscellaneous Aryl:
It is further preferred that the compound of the invention containing five rings spiro structure is the compound of following structural 1-20:
A kind of organic electroluminescent compounds containing five rings spiro structure of the invention can pass through Buchwald- Hartwig reaction and ullmann reaction are prepared.
Organic electroluminescent compounds containing five rings spiro structure of the invention can apply organic electroluminescence device, Organic solar batteries, 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 Comprising at least one layer in luminescent layer, hole injection layer, hole transmission layer, exciton barrier-layer, electron transfer layer, wherein described have Contain the compound containing five rings spiro structure as described in structural formula I at least one layer in machine layer:
Wherein Ar1、Ar2, X and R1-R8It 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, wherein the layer where compound as described in structural formula I is hole transmission layer.
Preferably, the compound that wherein compound described in structural formula I is structural formula 1-20.
When the compound containing five rings spiro structure as described in structural formula I is prepared for luminescent device, it can be used alone, It can also be used in mixed way with other compounds；The compound containing five rings spiro structure as described in structural formula I can be used alone One such compound, can also be simultaneously using the two or more compounds in structural formula I.
Organic electroluminescence device of the 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 at least one in hole-transporting layer The compound of structural formula I；It is further preferred that containing the compound of at least one structural formula 1-20 in hole transmission layer.
The overall thickness of organic electroluminescence device organic layer of the invention is 1-1000nm, preferably 50-500nm；Luminescent layer Film thickness be preferably 10-50nm.
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 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 It outside, can also include other small molecules and macromolecular organic compound, including but not limited to carbazole compound, triaromatic amine Close object, benzidine compound, compound of fluorene class, phthalocyanine-like compound, the miscellaneous triphen of six cyano six (hexanitrilehexaazatriphenylene), tetra- cyanogen dimethyl-parabenzoquinone (F4- of 2,3,5,6- tetra- fluoro- 7,7', 8,8'- TCNQ), polyvinyl carbazole, polythiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer of organic electroluminescence device of the invention has the good characteristics of luminescence, can be adjusted according to the needs The range of visible light.Following compound, including but not limited to naphthalene compounds, pyrene compound, fluorenes class chemical combination can be contained Object, bends class compound, glimmering anthracene compound, anthracene compound, pentacene class compound, class compound, two at luxuriant and rich with fragrance class compound Aromatic ethylene class compound, triphenylamine ethylene compounds, aminated compounds, carbazole compound, benzimidazoles compound, furan Class of muttering compound, metal Phosphorescent complex compound (such as Ir, Pt, Os, Cu), polyvinylcarbazole, gathers metal organic fluorescence complex compound The organic polymer luminescent materials such as organo-silicon compound, polythiophene, they can be used alone, and can also be made with a variety of mixtures With.
The Organic Electron Transport Material of organic electroluminescence device of the present invention requires good electronic transmission performance, energy It reaches in effectively electronics from cathode transport to luminescent layer, there is very big electron mobility.It can choose following compound, 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 from cathode by the electron injecting layer of organic electroluminescence device of the present invention In, it is mainly selected from the alkali metal perhaps compound of alkali metal or compound or alkali selected from alkaline-earth metal or alkaline-earth metal Metal complex can choose 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 that can also be used with mixture, can also be 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.Metal motor can be made It is prepared with vapour deposition method or sputtering method.
Device experimental shows that compound containing five rings spiro structure of the present invention as described in structural formula I has preferably heat steady Qualitative, high-luminous-efficiency, high luminance purity, low driving voltage.Had using the device of hole transport compound production electroluminescent The advantage that luminous efficiency is good and excitation purity is excellent and the service life is long.
Detailed description of the invention
Fig. 1 is a kind of organic electroluminescence device structural schematic diagram of the 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 embodiment
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 9
The synthesis of intermediate 9-1
In three-necked flask, thienyl boric acid (10g, 78mmol), adjacent bromo-iodobenzene (24g, 86mmol), potassium carbonate is added (27g, 0.2mol), tetrahydrofuran (200ml) and water (100ml), tetra-triphenylphosphine palladium (0.5g) are heated to reflux under nitrogen protection It is 10 hours, cooling, it is extracted with dichloromethane, is concentrated, crude product obtains 14g, yield 75% through column chromatographic purifying.
The synthesis of intermediate 9-2
In three-necked flask, intermediate 9-1 (8g, 34mmol), dry tetrahydrofuran (80ml) is added, it is cold under nitrogen protection But subzero 70 degree are arrived, the n-BuLi (14ml) of 2.5M is slowly added to, drips off reaction 1 hour, 60ml is then added dissolved with Fluorenone The tetrahydrofuran solution of (6.1g, 34mmol).It adds, is slowly increased to room temperature, react 2 hours, methylene chloride extraction is added, it is dense Contracting is added acetic acid (80ml) and concentrated hydrochloric acid (3ml), is heated to reflux 5 hours, cooling, removes solvent, and crude product methylene chloride is molten Agent, washing, the dry concentration of organic layer, crude product obtain 7.4g, yield 68% through column chromatographic purifying.
The synthesis of intermediate 9-3
In three-necked flask, intermediate 9-2 (7g, 22mmol), n,N-Dimethylformamide (50ml) is added, is slowly added to Bromo-succinimide (4.3g, 24mmol) reacts at room temperature 12 hours.Water is added, is extracted with dichloromethane, dry, concentration, slightly Product obtains 7.5g through column chromatographic purifying.Yield 85%.
The synthesis of compound 9
In flask, be added intermediate 9-3 (2g, 5mmol), 2- (4- xenyl) -9,9- dimethyl fluorene (1.8g, 5mmol), sodium tert-butoxide (1g, 10mmol), palladium acetate (50mg) and X-phos (100mg), ortho-xylene (30ml), nitrogen are protected It is heated to reflux under shield 24 hours, it is cooling, solvent is removed, crude product obtains 1.8g, yield 53% with column chromatographic purifying.Mass spectrum 681.88。
Embodiment 2
The synthesis of compound 14
Synthetic method is as compound 9, in addition to N, 9- diphenyl -9H- carbazole -3- amine replaces 2- (4- xenyl) - Outside 9,9- dimethyl fluorenes, yield 42%, mass spectrum 654.82.
Embodiment 3
The preparation of organic electroluminescence device
OLED is prepared using the compound 9 in the embodiment of the present invention 1.
Firstly, by electrically conducting transparent ito glass substrate 110 (having anode 120 above) (the limited public affairs of South China glass group share Department) successively pass through: deionized water, ethyl alcohol, acetone and deionized water were cleaned, then with oxygen plasma treatment 30 seconds.
Then, the compounds of this invention 9 is deposited, forms the hole transmission layer 130 of 60nm thickness.
Then, the compound 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 is 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 spectrometer measure 150mA/cm2Current density under device efficiency be 1.7cd/A, emit green light.
Embodiment 4
Prepared device as embodiment 3, in addition to use compound 14 replace compound 9 as hole transmission layer other than.
Prepared device (structure such as Fig. 1) is measured with Photo Research PR650 spectrometer in 150mA/cm2's Device efficiency under current density is 1.9cd/A, emits green light.
Comparative example
The device of comparative example preparation is as embodiment 3, in addition to using NPB to replace the compounds of this invention 9 as hole transport Layer.
Prepared device (structure such as Fig. 1) is measured with Photo Research PR650 spectrometer in 150mA/cm2's Device efficiency under current density is 1.2cd/A, emits green light.
At identical conditions, the organic electroluminescence device prepared using organic electroluminescent compounds of the invention Efficiency is higher than comparative example.As described above, the compound of the present invention has high stability, organic electroluminescent prepared by the present invention Device has low driving voltage, high efficiency and optical purity.
Structural formula described in device is as follows:
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that the ordinary skill of this field is without wound The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician 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 within the scope of protection determined by the claims.

Claims (8)

1. a kind of organic electroluminescent hole transport compound containing five rings spiro structure, it is characterised in that it is with following knot The compound of structure Formulas I:
Wherein, R1~R8Separately it is selected from hydrogen, D-atom, C1-C8 alkyl；
Ar1And Ar2Separately it is selected from the substituted or unsubstituted following aryl of C1-C4 alkyl and heteroaryl:
Further, Ar1And Ar2Can be formed by connecting ring by singly-bound each other；
X is S.
2. the organic electroluminescent compounds according to claim 1 containing five rings spiro structure, it is characterised in that under it is The compound of following formula 1-5,7-10,14,15,19,20:
3. a kind of organic electroluminescence device comprising anode, cathode and organic layer, organic layer include luminescent layer, hole injection Layer, hole transmission layer, exciton barrier-layer, at least one layer in electron transfer layer, it is characterised in that at least one layer of packet in organic layer Contain the compound as claimed in claim 1 or 2 containing five rings spiro structure.
4. organic electroluminescence device according to claim 3, it is characterised in that contain five rings spiral shell as described in structural formula I Layer where the compound of structure is hole transmission layer.
5. organic electroluminescence device according to claim 3, it is characterised in that contain five rings spiral shell as described in structural formula I The compound of structure is used alone, or is used in mixed way with other compounds.
6. organic electroluminescence device according to claim 3, it is characterised in that contain five rings spiral shell as described in structural formula I One such compound is used alone in the compound of structure, or simultaneously using the two or more compounds in structural formula I.
7. organic electroluminescence device according to claim 3, it includes anode, hole transmission layer, luminescent layer, electronics to pass Defeated layer, electron injecting layer and cathode, it is characterised in that contain the compound of at least one structural formula I in hole transmission layer.
8. organic electroluminescence device according to claim 3, it includes anode, hole transmission layer, luminescent layer, electronics to pass Defeated layer, electron injecting layer and cathode, it is characterised in that the compound contained in hole transmission layer is the knot as shown in claim 2 The compound of structure formula 1-5,7-10,14,15,19,20.
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