CN106749289B - A kind of organic electroluminescent compounds and its luminescent device with spiro structure - Google Patents
A kind of organic electroluminescent compounds and its luminescent device with spiro structure Download PDFInfo
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Abstract
The present invention provides a kind of organic electroluminescent compounds with spiro structure, the compound has preferable thermal stability, high-luminous-efficiency, high luminance purity, it can be used for making organic electroluminescence device, be applied to organic electroluminescence device, organic solar batteries, 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, hole blocking layer, electron injecting layer, electron transfer layer, at least one layer of compound comprising just like structural formula I in organic layer.
Description
Technical field
The present invention relates to field of organic electroluminescent materials, and in particular to a kind of organic electroluminescent with spiro structure
Object and its organic electroluminescence device are closed, organic electroluminescence device field of display technology is belonged to.
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.
Organic electrophosphorescenpolymer phenomenon, breaches theoretical limitation of the organic electroluminescent quantum efficiency lower than 25%, and promotion is arrived
100% (Baldo M.A., Forrest S.R.Et al, Nature, 1998,395,151-154), application also greatly mention
The high efficiency of organic electroluminescence device.Generally, electroluminescent phosphorescence needs commonly to be used as phosphorus using host-guest system technology
The CBP (4,4'-bis (9-carbazolyl)-biphenyl) of light material of main part has efficient and high triplet energy level, when its work
Based on material when, triplet energy state effectively can be transferred to object phosphorescent light-emitting materials from light emitting host material.But by
It is easily transmitted and the characteristic of electronics difficulty flowing in the hole of CBP, so that the charge unbalance of luminescent layer, as a result reduces the effect of device
Rate.
Summary of the invention
Present invention firstly provides a kind of organic electroluminescent compounds with spiro structure, to have the following structure Formulas I
Compound:
A is selected from O, S and NR, and wherein R is selected from substitution or the unsubstituted aryl, the substitution of C3-C30 or not of C6-C30
Substituted heteroaryl；
Z1-Z8It is separately selected from CH and N, wherein the number of N is 1-2；
L is selected from the substitution or unsubstituted heteroaryl of singly-bound, the substitution of C6-C30 or unsubstituted aryl, C3-C30
Base.
Preferably, R is phenyl ring.
Preferably, L is singly-bound or phenyl ring.
It is further preferred that the organic electroluminescent compounds with spiro structure are the compound of following structural 1-44:
A kind of organic electroluminescent compounds with spiro structure of the invention can apply organic electroluminescence device,
Organic solar batteries, 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
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 organic electroluminescent chemical combination with spiro structure contained as described in structural formula I in the organic layer
Object:
Wherein A, L and Z1-Z8It 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 organic electroluminescent compounds with spiro structure as described in structural formula I is hair
Photosphere, hole transmission layer, at least one layer in hole injection layer.
Preferably, wherein the organic electroluminescent compounds described in structural formula I with spiro structure are structural formula 1-44's
Compound.
It, can be with when organic electroluminescent compounds with spiro structure as described in structural formula I are prepared for luminescent device
It is used alone, can also be used in mixed way with other compounds；The organic electroluminescent with spiro structure as described in structural formula I
Closing object 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 injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode wherein contain in luminescent layer
The compound of at least one structural formula I；It is further preferred that containing the compound of at least one structural formula 1-44 in luminescent layer.
The luminescent layer of organic electroluminescence device contains phosphorescence light emitting guest material and the compound conduct with structural formula I
Material of main part, wherein Compounds of structural formula I is as material of main part, and concentration is the 20-99.9% of entire luminous layer weight, preferably
80-99%, more preferably 90-99%.
The overall thickness of organic electroluminescence device organic layer of the invention is 1-1000nm, preferably 50-500nm.
When having the compound of structural formula I using the present invention, can arrange in pairs or groups makes organic electroluminescence device of the invention
With other materials, such as in hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and barrier layer
Deng, and obtain blue and green light, 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.It may include that other small molecules and macromolecule are organic
Compound, including but not limited to carbazole compound, triaromatic amine compound, benzidine compound, compound of fluorene class, phthalocyanine
Class compound, the miscellaneous triphen (hexanitrilehexaazatriphenylene) of six cyano six, 2,3,5,6- tetra- fluoro- 7,7', 8,
Tetra- cyanogen dimethyl-parabenzoquinone (F4-TCNQ) of 8'-, 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.Except it is of the invention there is Compounds of structural formula I in addition to, 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, 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 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 organic electroluminescent compounds with spiro structure of the present invention as described in structural formula I, has
Preferable thermal stability, high-luminous-efficiency, high luminance purity.The device made of the organic electroluminescent electron transport compound
Have the advantages that electroluminescent 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 injection layer, 140 hole transports
Layer, 150 are represented as barrier layer, and 160 are represented as luminescent layer, and 170 are represented as electron transfer layer, and 180 are represented as electron injecting layer,
190 are represented as 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 1
The synthesis of intermediate 1-1
Bromo- 9,9 '-spiral shell, two fluorenes (20g, 51mmol) of 4-, 2- chloroaniline (10g, 76mmol), the tert-butyl alcohol are added in flask
Sodium (10g, 102mmol), palladium acetate (0.5g), X-phos (1g) and ortho-xylene (200ml), are heated to reflux 8 hours, heat filtering
Inorganic matter is removed, cooling, concentration, crude product obtains product 13g, yield 58% through column chromatographic purifying.
The synthesis of intermediate body 1-2
In flask, intermediate 1-1 (12g, 27mmol), potassium carbonate (7.5g, 54mmol), three hexamethylene of tetrafluoro boric acid is added
Base phosphine (1g), palladium acetate (0.5g) and dimethyl acetamide (150ml), are heated to reflux 8 hours under nitrogen protection, are removed under reduced pressure
Most of solvent, it is cooling, water and methylene chloride, extraction is added, organic layer is concentrated through dry, and crude product is obtained through column chromatographic purifying
Product 5.8g, yield 53%.
The synthesis of intermediate 1-3
In flask, intermediate 1-2 (5g, 12.3mmol), bromo-iodobenzene (5.2g, 18mmol), potassium hydroxide is added
(1.3g, 125mmol), cuprous iodide (0.5g), Phen (0.5g) and ortho-xylene (80ml) add under nitrogen protection
Heat reflux 10 hours, it is cooling, solvent is removed, crude by column chromatography purifies to obtain product 5.6g, yield 83%.
The synthesis of intermediate 1-4
In three-necked flask, be added intermediate 1-3 (5g, 8.9mmol), connection boric acid pinacol ester (3.4g, 13.3mmol),
Potassium acetate (1.7g, 17.8mmol), two triphenylphosphine palladium of dichloro (0.5g), dioxane (60ml), are heated under nitrogen protection
Reflux 12 hours, heat filtering remove inorganic matter, and concentration is added ethyl alcohol and tetrahydrofuran recrystallization, obtains product 4.1g, yield
77%.
The synthesis of compound 1
In flask, be added intermediate 1-4 (1.5g, 2.5mmol), the chloro- benzofuran of 3- [3,2-c] pyridine (0.69g,
3mmol), potassium carbonate (0.69g, 5mmol), tetra-triphenylphosphine palladium (0.3g), tetrahydrofuran (20ml) and water (10ml), in nitrogen
Under protection, it is heated to reflux, it is cooling, solvent is removed, is extracted with dichloromethane, is concentrated, crude product obtains 1.3g through column chromatographic purifying,
Yield 81%.MS:e/z=648.44.
Embodiment 2
The synthesis of compound 7
The synthesis of intermediate 7-1
Synthetic method is as intermediate 1-3, in addition to other than bromo-iodobenzene between being replaced to bromo-iodobenzene, yield 75%.
The synthesis of intermediate 7-2
Synthetic method is as intermediate 1-4, other than replacing intermediate 1-4 with intermediate 7-1, yield 82%.
The synthesis of compound 7
Synthetic method is as compound 1, other than replacing intermediate 1-4 with intermediate 7-2, yield 71%.MS:e/z
=648.35.
Embodiment 3
The synthesis of compound 23
Synthetic method is as with compound 1, in addition to replacing the chloro- benzo furan of 3- with 3- chloro- benzothiophene [3,2-c] pyridine
It mutters outside [3,2-c] pyridine, yield 79%.MS:e/z=664.36.
Embodiment 4
The synthesis of compound 29
Synthetic method is as compound 7, in addition to replacing the chloro- benzofuran of 3- with 3- chloro- benzothiophene [3,2-c] pyridine
Outside [3,2-c] pyridine, yield 76%.MS:e/z=664.19.
Embodiment 5-8
The preparation of organic electroluminescence device:
OLED is prepared using the compound of embodiment:
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 MnO of 3nm thickness is deposited on ITO3(molybdenum oxide) is hole injection layer 130.
Then, the TAPC that 50nm thickness is deposited on hole injection layer is hole mobile material 140.
Then, TCTA is deposited, forms the electronic barrier layer 150 of 5nm thickness.
Then, the luminescent layer 160 of 20nm thickness is deposited on electronic barrier layer, wherein shine based on the compounds of this invention
Material, and with the Ir of 3% weight ratio (ppy)3Guest materials is adulterated as phosphorescence.
Then, the BmPYPB of 40nm thickness is deposited on the light-emitting layer as electron transfer layer 170.
Finally, vapor deposition 1nm LiF is electron injecting layer 180 and 80nm Al as device cathodes 190.
Prepared device (structural schematic diagram is shown in Fig. 1) with Photo Research PR650 spectrometer measure
5000cd/m2Brightness under external quantum efficiency be such as table 1.
Comparative example 1
The device of comparative example preparation is as embodiment 5-8 part preparation method, in addition to replacing the compounds of this invention to make with CBP
Based on outside material.
Table 1
| Embodiment | Compound | Current efficiency (cd/A) | Luminescent color |
| 5 | 1 | 56 | Green light |
| 6 | 7 | 57 | Green light |
| 7 | 23 | 59 | Green light |
| 8 | 29 | 55 | Green light |
| Comparative example 1 | CBP | 45 | Green light |
Structural formula 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 excellent performance.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 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 (9)
1. a kind of organic electroluminescent compounds with spiro structure, it is characterised in that it is the chemical combination for having the following structure Formulas I
Object:
A is selected from O, S；
Z1-Z8It is separately selected from CH and N, wherein the number of N is 1-2；
Substitution or unsubstituted aryl of the L selected from C3-C30.
2. the organic electroluminescent compounds according to claim 1 with spiro structure, it is characterised in that L is phenyl ring.
3. the organic electroluminescent compounds according to claim 1 with spiro structure, it is characterised in that it is following knot
The compound of structure formula 1-44:
4. a kind of organic electroluminescence device comprising anode, cathode and organic layer, organic layer include luminescent layer, hole injection
Layer, hole transmission layer, hole blocking layer, electron injecting layer, at least one layer in electron transfer layer, it is characterised in that in organic layer
At least one layer includes the organic electroluminescent compounds as described in claim 1 with spiro structure.
5. organic electroluminescence device according to claim 4, it is characterised in that there is spiro structure as described in structural formula I
Organic electroluminescent compounds where layer be luminescent layer, hole transmission layer, at least one layer in hole injection layer.
6. organic electroluminescence device according to claim 4, it is characterised in that there is spiro structure as described in structural formula I
Organic electroluminescent compounds be used alone, or be used in mixed way with other compounds.
7. organic electroluminescence device according to claim 4, it is characterised in that there is spiro structure as described in structural formula I
Organic electroluminescent compounds one such compound is used alone, or simultaneously using two or more in structural formula I
Compound.
8. organic electroluminescence device according to claim 4, it includes anode, hole injection layer, hole transmission layer, hairs
Photosphere, electron transfer layer, electron injecting layer and cathode, it is characterised in that contain the chemical combination of at least one structural formula I in luminescent layer
Object.
9. organic electroluminescence device according to claim 4, it includes anode, hole injection layer, hole transmission layer, hairs
Photosphere, electron transfer layer, electron injecting layer and cathode, it is characterised in that the compound contained in luminescent layer is such as claim 3
The compound of the structural formula 1-44.
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| CN107163066A (en) * | 2017-06-26 | 2017-09-15 | 上海道亦化工科技有限公司 | A kind of spiral shell azole organic electroluminescent compounds and its organic electroluminescence device |
| CN107344946A (en) * | 2017-06-26 | 2017-11-14 | 上海道亦化工科技有限公司 | A kind of spiral shell carbazoles organic electroluminescent compounds and its organic electroluminescence device |
| CN107311955A (en) * | 2017-06-26 | 2017-11-03 | 上海道亦化工科技有限公司 | A kind of spiro fluorene class organic electroluminescent compounds and its organic electroluminescence device |
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| CN104903328A (en) * | 2012-12-21 | 2015-09-09 | 默克专利有限公司 | Materials for organic electroluminescent devices |
| WO2015192939A1 (en) * | 2014-06-18 | 2015-12-23 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| WO2015192941A1 (en) * | 2014-06-18 | 2015-12-23 | Merck Patent Gmbh | Compositions for electronic devices |
| WO2016023608A1 (en) * | 2014-08-13 | 2016-02-18 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| KR20160038813A (en) * | 2014-09-30 | 2016-04-07 | 주식회사 엘지화학 | Hetero-cyclic compound and organic light emitting device comprising the same |
| CN106029830A (en) * | 2014-02-21 | 2016-10-12 | 默克专利有限公司 | Materials for organic electroluminescent devices |
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| 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 |
| WO2015192939A1 (en) * | 2014-06-18 | 2015-12-23 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| WO2015192941A1 (en) * | 2014-06-18 | 2015-12-23 | Merck Patent Gmbh | Compositions for electronic devices |
| WO2016023608A1 (en) * | 2014-08-13 | 2016-02-18 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| KR20160038813A (en) * | 2014-09-30 | 2016-04-07 | 주식회사 엘지화학 | Hetero-cyclic compound and organic light emitting device comprising the same |
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