CN107068909B - A kind of organic electroluminescence device of ketone compounds of diaryl anthracene containing 10,10- and its application - Google Patents
A kind of organic electroluminescence device of ketone compounds of diaryl anthracene containing 10,10- and its application Download PDFInfo
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
The invention discloses one kind to contain 10, the organic electroluminescence device of 10- diaryl anthracene ketone compounds and its application, the device includes hole transmission layer, luminescent layer, electron transfer layer, the device emitting layer material is to contain 10,10- diaryl anthrone is the compound of core group, shown in the structural formula of the compound such as general formula (1).The present invention is with 10,10- diaryl anthrone is the material of core group because having lesser triplet state and singlet energy difference, therefore it is easily achieved energy transmission between Subjective and Objective material, the energy to scatter and disappear in the form of heat originally is set to be easily obtained utilization, to be easier to obtain the high efficiency of device, further, when dopant material is selected as fluorescent material, it is easier to obtain the luminous radiation of dopant material, to be easier to obtain the long-life of material.
Description
Technical field
The present invention relates to technical field of semiconductors, are with 10,10- diaryl anthrone more particularly, to a kind of emitting layer material
Organic electroluminescence device and its application for the compound of core.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can both be used to make
New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting,
Application prospect is very extensive.
Structure of the OLED luminescent device like sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it
Between organic functional material, various different function materials are overlapped mutually depending on the application collectively constitutes OLED luminescent device together.
As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through electric field action organic layer functional material
Positive and negative charge in film layer, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.
Application of the Organic Light Emitting Diode (OLED) in terms of large-area flat-plate is shown and is illuminated causes industry and
The extensive concern of art circle.However, traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, device
The internal quantum efficiency of part is lower (up to 25%).External quantum efficiency is generally lower than 5%, and there are also very big with the efficiency of phosphorescent devices
Gap.Although phosphor material can efficiently use electricity since the strong SO coupling in heavy atom center enhances intersystem crossing
The singlet exciton formed and Triplet exciton are excited, makes the internal quantum efficiency of device up to 100%.But phosphor material exists
Expensive, stability of material is poor, and device efficiency tumbles the problems such as serious and limits it in the application of OLEDs.Hot activation is prolonged
Slow fluorescence (TADF) material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.It should
Class material generally has poor (the △ E of small singlet-tripletST), triplet excitons can be changed by anti-intersystem crossing
It shines at singlet exciton.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation, device it is interior
Quantum efficiency can achieve 100%.Meanwhile material structure is controllable, and property is stablized, and it is cheap to be not necessarily to precious metal, in OLED
Field has a extensive future.
Although theoretically 100% exciton utilization rate may be implemented in TADF material, following problem there are in fact:
(1) T1 the and S1 state for designing molecule has strong CT feature, very small S1-T1 state energy gap, although can pass through
TADF process realizes high T1→S1State exciton conversion ratio, but low S1 state radiation transistion rate is also resulted in, therefore, it is difficult to have both
(or realizing simultaneously) Gao Jizi utilization rate and high fluorescent radiation efficiency；
(2) even if doping device has been used to mitigate T exciton concentration quenching effect, the device of most of TADF materials is in height
Efficiency roll-off is serious under current density.
For current OLED shows the actual demand of Lighting Industry, the development of OLED material is also far from enough at present, falls
Afterwards in the requirement of panel manufacturing enterprise, the organic functional material as material enterprise development higher performance is particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the present invention provides a kind of ketone compounds containing 10,10- diaryl anthracene
Organic electroluminescence device.The present invention is based on TADF mechanism using 10,10- diaryl anthrone be the compound of core as hair
Photosphere material is applied on Organic Light Emitting Diode, has good photoelectric properties, can satisfy OLED device enterprise, especially
The demand of OLED display panel and OLED Illumination Enterprise.
Technical scheme is as follows:
A kind of organic electroluminescence device of the ketone compounds Han 10,10- diaryl anthracene, which includes hole transport
Layer, luminescent layer, electron transfer layer, the device emitting layer material contain the chemical combination with 10,10- diaryl anthrone for core group
Object, shown in the structural formula of the compound such as general formula (1):
In general formula (1), Ar1、Ar2Expression hydrogen ,-Ar-R or-R independently；And Ar1、Ar2It is not simultaneously hydrogen；
Wherein, Ar indicates phenyl, xenyl, terphenyl, naphthalene, anthryl or phenanthryl；
R is indicated using general formula (2), general formula (3), general formula (4) or general formula (5):
Wherein, X1For oxygen atom, sulphur atom, C1-10The alkylene of alkylidene, aryl substitution that linear or branched alkyl group replaces
One of the amido that base, alkyl or aryl replace；
R1、R2Structure shown in selection hydrogen or general formula (6) independently, general formula (7):
A isX2、X3Respectively oxygen atom, sulphur atom, C1-10The alkylene that linear or branched alkyl group replaces
One of the amido that base, the alkylidene of aryl substitution, alkyl or aryl replace；
General formula (6), general formula (7) and CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL4-CL5Key, CL‘1-CL’2Key, CL‘2-CL’3
Key, CL‘3-CL’4Key or CL‘4-CL’5Key connection；
R3Indicate phenyl, xenyl, naphthalene, anthryl or phenanthryl.
When a is indicated in the compoundAnd and CL4-CL5Key or CL‘4-CL’5When key connection, X1And X2Position weight
It is folded, only take X1Or X2；X3It is expressed as oxygen atom, sulphur atom, C1-10Alkylidene, the aryl of linear or branched alkyl group substitution replace
Alkylidene, one of the amido that replaces of alkyl or aryl.
R in the compound are as follows:
In appoint
It is a kind of.
The concrete structure formula of the 10,10- diaryl anthracene ketone compounds are as follows:
Material of main part of the material as luminescent layer shown in the general formula (1)；The dopant material of the luminescent layer is under use
One of column general formula (8), (9), (10), material shown in (11):
In general formula (8), B1-B10 is selected as hydrogen, C1-30Linear or branched alkyl group replace alkyl or alkoxy, replace or
Unsubstituted C6-30Aryl, it is substituted or unsubstituted 3 yuan to 30 unit's heteroaryls；B1-B10 is not hydrogen simultaneously；
In general formula (9), Y1-Y6 one kind independent for being expressed as oxygen, carbon, nitrogen-atoms； It is expressed as containing there are two the groups of atom to pass through the connected cyclization of any chemical bond；
Y1~Y4 one kind independent for being expressed as oxygen, carbon, nitrogen-atoms in general formula (10), general formula (11)；It is expressed as being connected to containing the group there are two atom by any chemical bond
Ring.
The material of the hole transmission layer is the compound containing triarylamine group, and the structural formula general formula of the compound is such as
Shown in general formula (12):
D1-D3 respectively independently indicates substituted or unsubstituted C in general formula (12)6-30Aryl, it is substituted or unsubstituted 3 yuan extremely
30 unit's heteroaryls；D1-D3 can be same or different.
The material of the electron transfer layer is general formula (13), (14), (15), (16), one in material shown in (17)
Kind:
General formula (13), general formula (14), general formula (15), general formula (16), E1-E10 is selected as hydrogen, C in general formula (17)1-30Straight chain
Or alkyl or alkoxy, substituted or unsubstituted C that branched alkyl replaces6-30Aryl, substituted or unsubstituted 3 yuan to 30 yuan it is miscellaneous
Aryl；E1-E10 is not hydrogen simultaneously.
The luminescent device further includes hole injection layer；The hole injection layer material be having structure general formula (18),
(19), one of material shown in (20):
In general formula (18), F1-F3 respectively independently indicates substituted or unsubstituted C6-30It is aryl, 3 yuan substituted or unsubstituted
To 30 unit's heteroaryls；F1-F3 can be same or different；
In general formula (19), general formula (20), G1-G6 expression hydrogen atom independent, itrile group, halogen, amide groups, alcoxyl
Base, ester group, nitro, C1-30Carbon atom, the substituted or unsubstituted C of linear or branched alkyl group substitution6-30Aryl, 3 yuan to 30 yuan it is miscellaneous
Aryl；G1-G6 is not hydrogen simultaneously.
The luminescent device further includes electron injecting layer；The electron injecting layer material is one in lithium, lithium salts or cesium salt
Kind；The lithium salts is 8-hydroxyquinoline lithium, lithium fluoride, lithium carbonate, Lithium Azide；The cesium salt is cesium fluoride, cesium carbonate, nitrine
Change caesium.
Compound shown in the general formula (1) can also be used as the dopant material of luminescent layer.
The mass ratio of the material of main part of the dopant material and luminescent layer of the luminescent layer is 0.005~0.2:1.
A kind of application of the organic electroluminescence device, the organic electroluminescence device are used to prepare top-illuminating OLED
Luminescent device.
A kind of application of the organic electroluminescence device, the organic electroluminescence device are applied to AM-OLED and show
Device.
The present invention is beneficial to be had the technical effect that
The ketone compounds of diaryl anthracene containing 10,10- for forming OLED luminescent device of the present invention have the structure of TADF
Feature, very small S1-T1 state energy gap easy to accomplish is poor, in excitation, the anti-system of triplet state easy to accomplish to singlet
Between alter more, make originally cannot shine, dispersed heat is converted into the energy that can produce luminous energy in the form of heat, and be expected to obtain pole
High efficiency.
It is analyzed based on principles above, OLED luminescent device of the present invention, both can choose fluorescent material as doping material
Material, also can choose phosphor material as dopant material, can also be by TADF material of the present invention directly as dopant material
It uses.
It is described with 10,10- diaryl anthrone be core compound as OLED luminescent device material of main part collocation iridium,
Platinum class phosphor material or anthracene class fluorescent material in use, device current efficiency, power efficiency and external quantum efficiency obtain very
It is big to improve；Meanwhile device lifetime is promoted clearly.Further, on OLED device layer structure matching, hole is introduced
After electron injecting layer, keep transparent anode, metallic cathode and organic material contact interface more stable, hole, electron injection effect
It is promoted；Hole transmission layer again can lamination be two or more layers, the hole transmission layer of adjacent luminescent layer side can be named as electricity again
Sub- barrier layer (EBL) provides electronic blocking effect, promotes exciton combined efficiency in luminescent layer, adjacent hole injection layer side
Hole transmission layer then play the role of hole transport and reduce exciton transfer barrier；Electron transfer layer again can lamination be two layers or
The electron transfer layer of multilayer, adjacent luminescent layer side can be named as hole blocking layer (HBL) again, provide hole barrier effect,
Promote exciton combined efficiency in luminescent layer, the electron transfer layer of adjacent electron injecting layer side then plays electron-transport and reduction
The effect of exciton transfer barrier.It should be mentioned, however, that each of these layers are not necessarily present.
The combined effect of OLED device compound of the present invention: so that the driving voltage of device reduces, current efficiency, function
Rate efficiency, external quantum efficiency are further enhanced, and it is obvious that device lifetime promotes effect.Have in OLED luminescent device good
Application effect, have good industrialization prospect.
Make us against expectation, it has been found that, the compound combination being more particularly described hereinafter realizes this purpose,
And lead to the improvement of organic electroluminescence device, especially voltage, efficiency and the improvement in service life.This especially suitable for red or
The electroluminescent device of green phosphorescent, especially when using device architecture and combination of materials of the invention, situation is such.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of stacked OLED device of the embodiment of the present invention；
In Fig. 1: 1 be transparent substrates, 2 be ito anode layer, 3 be hole injection layer (HIL), 4 be hole transmission layer (HTL),
5 be electronic barrier layer (EBL), 6 be luminescent layer (EML), 7 be hole blocking layer (HBL), 8 be electron transfer layer (ETL), 9 be electricity
Sub- implanted layer (EIL), 10 are cathode reflection electrode layer.
Fig. 2 is the structural formula of critical materials used in device embodiments of the present invention.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
The preparation of 1 compound 1 of embodiment
In the 1L there-necked flask equipped with constant pressure funnel, it is added magnesium metal (5.1g, 0.21mol), it will be to bromo-iodobenzene
(56.6g, 0.20mol) is dissolved in 300g tetrahydrofuran, is placed in constant pressure funnel, and nitrogen protection, heating three are used
Temperature reaches 65 DEG C in mouth bottle to bottle, and the tetrahydrofuran solution to bromo-iodobenzene is added by constant pressure funnel, is firstly added
50mL slowly instills remainder after reacting initiation, and 1h is added dropwise, and reacts 2h under reflux temperature, is cooled to room temperature transfer
It is stand-by into constant pressure funnel；
Anthraquinone (41.6g, 0.20mol) is dissolved among 200g tetrahydrofuran and is added in 2L there-necked flask, is then slowly dripped
In addition stating stand-by solution, 3h is reacted under reflux temperature, after reaction, is cooled to 25 DEG C, the above reaction solution is slowly poured into
In the dilute hydrochloric acid that 200g mass concentration is 10%, 15min is stirred, organic phase is collected in liquid separation, and decompression is sloughed solvent, obtained sticky
Liquid is directly used in reaction in next step without purification；
250g benzene is added into above-mentioned gained thick liquid, it is molten to be added with stirring 1.42g (0.01mol) boron trifluoride ether
Liquid, 60~65 DEG C of reaction 4h, quenching reaction, removed under reduced pressure solvent, column chromatograph to obtain compound 1, HPLC purity 99.5%, yield
45%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C26H17BrO, theoretical value 424.0463, test value
424.0466。
Elemental analysis (C26H17BrO): theoretical value C:73.42, H:4.03, O:3.76, test value: C:73.44, H:
4.01 O:3.79.
The preparation of 2 compound 2 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, 8.51g (0.02mol) compound 1,7.62g is added
(0.03mol) duplex pinacol borate, 3.92g (0.04mol) potassium acetate, 0.30g pd2(dba)3, 0.20g tri-tert
Phosphorus, 100ml toluene are heated to reflux 20 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph
To compound 2, HPLC purity 99.7%, yield 87.57%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C32H29BO3, theoretical value 472.2210, test value
472.2215。
Elemental analysis (C32H29BO3): theoretical value C:81.36, H:6.19, O:10.16, test value: C:81.40, H:
6.15 O:10.18.
The preparation of 3 compound 3 of embodiment
In the 1L there-necked flask equipped with constant pressure funnel, it is added magnesium metal (5.1g, 0.21mol), by equal tribromo-benzene
(63.0g, 0.2mol) is dissolved in 300g tetrahydrofuran, is placed in constant pressure funnel, using nitrogen protection, heats three mouthfuls
Bottle reaches 65 DEG C to temperature in bottle, and the tetrahydrofuran solution of equal tribromo-benzene is added by constant pressure funnel, is firstly added 50mL,
After reacting initiation, remainder is slowly instilled, 1h is added dropwise, and reacts 2h under reflux temperature, is cooled to room temperature and is transferred to perseverance
It presses stand-by in funnel.Anthraquinone (41.6g, 0.2mol) is dissolved among 200g tetrahydrofuran and is added in 2L there-necked flask, is then delayed
Slowly above-mentioned stand-by solution is added dropwise, reacts 3h under reflux temperature, after reaction, is cooled to 25 DEG C, the above reaction solution is slowly inclined
Enter in the dilute hydrochloric acid that 200g mass concentration is 10%, stir 15min, organic phase is collected in liquid separation, and decompression is sloughed solvent, glued
Thick liquid is directly used in reaction in next step without purification.
250g benzene is added into above-mentioned gained thick liquid, it is molten to be added with stirring 1.42g (0.01mol) boron trifluoride ether
Liquid, 60~65 DEG C of reaction 4h, quenching reaction, removed under reduced pressure solvent, column chromatograph to obtain target product compound 3, HPLC purity
99.7%, yield 42%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C26H16Br2O, theoretical value 501.9568, test value
501.9562。
Elemental analysis (C26H16Br2O): theoretical value C:61.93, H:3.20, O:3.17, test value: C:61.96, H:
3.24 O:3.15.
The preparation of 4 compound C01 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M01,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 20
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.6%, yield 76.00%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C38H25NO2, theoretical value 527.1885, test value
527.1894。
Elemental analysis (C38H25NO2): theoretical value C:86.50, H:4.78, N:2.65, O:6.06, test value: C:
86.45, H:4.79, N:2.68, O:6.08.
The preparation of 5 compound C04 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M02,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.5%, yield 62.35%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C50H32N2O2, theoretical value 676.2515, test value
676.2519。
Elemental analysis (C50H32N2O2), theoretical value C:88.73, H:4.77, N:4.14, O:2.36, test value: C:
88.76, H:4.81, N:4.10, O:2.33.
The preparation of 6 compound C09 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M03,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.8%, yield 70.06%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C47H33NO, theoretical value 627.2562, test value
676.2519。
Elemental analysis (C47H33NO), theoretical value C:89.92, H:5.30, N:2.23, O:2.55, test value: C:89.90,
H:5.31, N:2.20, O:2.59.
The preparation of 7 compound C14 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M04,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.4%, yield 61.37%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C44H27NO2, theoretical value 601.2042, test value
601.2039。
Elemental analysis (C44H27NO2), theoretical value C:87.83, H:4.52, N:2.33, O:5.32, test value: C:
87.88, H:4.52, N:2.30, O:5.30.
The preparation of 8 compound C19 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M05,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.7%, yield 67.55%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C42H27NO, theoretical value 561.2093, test value
561.2088。
Elemental analysis (C42H27NO), theoretical value C:89.81, H:4.85, N:2.49, O:2.85, test value: C:89.83,
H:4.88, N:2.47, O:2.82.
The preparation of 9 compound C20 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 2,0.03mol compound M06,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.4%, yield 66.32%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C48H41NO, theoretical value 637.2406, test value
637.2411。
Elemental analysis (C48H41NO), theoretical value C:90.40, H:4.90, N:2.20, O:2.51, test value: C:90.36,
H:4.88, N:2.23, O:2.53.
The preparation of 10 compound C26 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 2,0.03mol compound M07,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.2%, yield 60.21%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C56H36N2O, theoretical value 752.2828, test value
752.2824。
Elemental analysis (C56H36N2O), theoretical value C:89.33, H:4.82, N:3.72, O:2.13, test value: C:
89.35, H:4.80, N:3.74, O:2.11.
The preparation of 11 compound C31 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 2,0.03mol compound M08,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.9%, yield 64.58%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C53H37NO, theoretical value 703.2875, test value
703.2871。
Elemental analysis (C53H37NO), theoretical value C:90.44, H:5.30, N:1.99, O:2.27, test value: C:90.42,
H:5.32, N:1.97, O:2.29.
The preparation of 12 compound C45 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 2,0.03mol compound M09,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.1%, yield 61.17%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C50H31NO3, theoretical value 693.2304, test value
693.2309。
Elemental analysis (C50H31NO3), theoretical value C:86.56, H:4.50, N:2.02, O:6.92, test value: C:
86.58, H:4.51, N:2.00, O:6.91.
The preparation of 13 compound C48 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M10,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.9%, yield 67.58%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C50H39NO, theoretical value 669.3032, test value
669.3037。
Elemental analysis (C50H39NO), theoretical value C:89.65, H:5.87, N:2.09, O:2.39, test value: C:89.68,
H:5.84, N:2.06, O:2.42.
The preparation of 14 compound C51 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M11,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.7%, yield 65.74%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C50H39NO, theoretical value 669.3032, test value
669.3036。
Elemental analysis (C50H39NO), theoretical value C:89.65, H:5.87, N:2.09, O:2.39, test value: C:89.67,
H:5.85, N:2.08, O:2.40.
The preparation of 15 compound C53 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M12,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.9%, yield 66.68%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C47H33NO2, theoretical value 643.2511, test value
643.2516。
Elemental analysis (C47H33NO2), theoretical value C:87.69, H:5.17, N:2.18, O:4.97, test value: C:
87.66, H:5.21, N:2.17, O:4.97.
The preparation of 16 compound C56 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M13,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.8%, yield 65.88%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C47H33NO2, theoretical value 643.2511, test value
643.2515。
Elemental analysis (C47H33NO2), theoretical value C:87.69, H:5.17, N:2.18, O:4.97, test value: C:
87.68, H:5.18, N:2.20, O:4.95.
The preparation of 17 compound C57 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M14,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.9%, yield 64.81%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C47H33NO2, theoretical value 643.2511, test value
643.2518。
Elemental analysis (C47H33NO2), theoretical value C:87.69, H:5.17, N:2.18, O:4.97, test value: C:
87.66, H:5.18, N:2.19, O:4.97.
The preparation of 18 compound C64 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M15,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.5%, yield 59.68%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C47H33NO2, theoretical value 643.2511, test value
643.2514。
Elemental analysis (C47H33NO2), theoretical value C:87.65, H:5.17, N:2.18, O:4.97, test value: C:
87.68, H:5.15, N:2.15, O:5.02.
The preparation of 19 compound C71 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M16,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.9%, yield 68.86%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C44H30N2O, theoretical value 602.2358, test value
602.2355。
Elemental analysis (C44H30N2O), theoretical value C:87.68, H:5.02, N:4.65, O:2.65, test value: C:
87.69, H:5.05, N:4.63, O:2.63.
The preparation of 20 compound C76 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M17,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.7%, yield 67.55%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C50H32N2O2, theoretical value 692.2464, test value
692.2462。
Elemental analysis (C50H32N2O2), theoretical value C:86.68, H:4.66, N:4.04, O:4.62, test value: C:
86.67, H:4.67, N:4.05, O:4.61.
The preparation of 21 compound C83 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M18,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.3%, yield 63.28%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C53H38N2O, theoretical value 718.2984, test value
718.2981。
Elemental analysis (C53H38N2O), theoretical value C:88.55, H:5.33, N:3.90, O:2.23, test value: C:
88.58, H:5.31, N:3.88, O:2.23.
The preparation of 22 compound C87 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M19,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.4%, yield 61.64%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C47H34N2O, theoretical value 642.2671, test value
642.2673.Elemental analysis (C47H34N2O), theoretical value C:87.82, H:5.33, N:4.36, O:2.49, test value: C:
87.80, H:5.35, N:4.37, O:2.48.
The preparation of 23 compound C88 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M20,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.7%, yield 63.72%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C44H28N2O2, theoretical value 616.2151, test value
616.2155.Elemental analysis (C44H28N2O2), theoretical value C:85.69, H:4.58, N:4.54, O:5.19, test value: C:
85.67, H:4.59, N:4.55, O:5.19.
The preparation of 24 compound C89 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 1,0.03mol compound M21,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.8%, yield 66.82%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C51H35NO, theoretical value 677.2719, test value
677.2722。
Elemental analysis (C51H35NO), theoretical value C:90.37, H:5.20, N:2.07, O:2.36, test value: C:90.33,
H:5.21, N:2.09, O:2.37.
The preparation of 25 compound C97 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 3,0.03mol compound M01,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.9%, yield 63.58%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C50H32N2O3, theoretical value 708.2413, test value
708.2411。
Elemental analysis (C50H32N2O3), theoretical value C:84.73, H:4.55, N:3.95, O:6.77, test value: C:
84.75, H:4.58, N:3.96, O:6.71.
The preparation of 26 compound C98 of embodiment
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol compound 3,0.03mol compound M22,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene are heated to reflux 24
Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain target product, HPLC purity
99.7%, yield 60.54%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C56H44N2O, theoretical value 760.3454, test value
760.3458。
Elemental analysis (C56H44N2O), theoretical value C:88.39, H:5.83, N:3.68, O:2.10, test value: C:
88.37, H:5.85, N:3.66, O:2.12.
The compounds of this invention can be used as emitting layer material, to the compounds of this invention C47, compound C98, current material
CBP carries out the test of hot property, luminescent spectrum, fluorescence quantum efficiency and cyclic voltammetric stability, testing result such as 1 institute of table
Show.
Table 1
| Compound | Tg(℃) | Td(℃) | λPL(nm) | Φf | Cyclic voltammetric stability |
| Compound C47 | 133 | 385 | 485 | 65.2 | It is excellent |
| Compound C98 | 128 | 378 | 490 | 62.8 | It is excellent |
| Material C BP | 113 | 353 | 369 | 26.1 | Difference |
Note: glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning calorimetry
Instrument) measurement, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, public in Japanese Shimadzu
It is measured on the TGA-50H thermogravimetric analyzer of department, nitrogen flow 20mL/min；λPLIt is sample solution fluorescence emission wavelengths,
General health SR-3 spectroradiometer is opened up using Japan to measure；Φ f is that solid powder fluorescence quantum efficiency (utilizes U.S.'s marine optics
Maya2000Pro fiber spectrometer, Lan Fei company, the U.S. C-701 integrating sphere and marine optics LLS-LED light source composition
Solid fluorescence quantum efficiency test system, reference literature Adv.Mater.1997 are tested, 9,230-232 method is measured).
Cyclic voltammetric stability is identified by the redox characteristic of cyclic voltammetry test material；Test-strips
Part: test sample is dissolved in the methylene chloride and acetonitrile mixed solvent that volume ratio is 2:1, and concentration 1mg/mL, electrolyte is 0.1M
The organic solution of tetrabutyl ammonium tetrafluoroborate or hexafluorophosphate.Reference electrode is Ag/Ag+ electrode, is titanium to electrode
Plate, working electrode are ITO electrode, and cycle-index is 20 times.
By upper table data it is found that the compounds of this invention has suitable luminescent spectrum, higher Φ f is suitable as shining
Layer material；Meanwhile the compounds of this invention has preferable oxidation-reduction stability, higher thermal stability, so that using this hair
The OLED device efficiency of bright compound and service life get a promotion.
In the devices below by way of device embodiments 1~16 and device comparative example 1 the present invention will be described in detail compound combination
Application effect.The production of device embodiments 2~16, the device compared with device embodiments 1 of device comparative example 1 of the present invention
Technique is identical, and uses identical baseplate material and electrode material, the difference is that device survey stepped construction,
Collocation material and thicknesses of layers are different.Device stack structure is as shown in table 2.The performance test results of each embodiment device are such as
Shown in table 3.
Device embodiments 1
Device stack structure is as shown in device architecture schematic diagram 1: including hole transmission layer 4, luminescent layer 6, electron transfer layer
8。
Ito anode layer 2 (thickness: 150nm)/hole transmission layer 4 (thickness: 120nm, material: HT6)/luminescent layer 6 (thickness:
40nm, material: compound C01 and GD1 is constituted by weight 90:10 blending) (the thickness: 35nm, material: ET2 of/electron transfer layer 8
And EI1, mass ratio 1:1)/Al (thickness: 100nm).
Specific preparation process is as follows:
Ito anode layer 2 (film thickness 150nm) is washed, is successively carried out after progress neutralizing treatment, pure water, drying ultraviolet
Line-ozone washing is to remove the organic residue on the transparent surface ITO.
On the ito anode layer 2 after the washing, using vacuum deposition apparatus, hole transmission layer 4, hole transport is deposited
Layer material uses HT6, and film thickness 120nm, this layer is as the hole transmission layer 4 in device architecture；
On hole transmission layer 4, by vacuum evaporation mode, luminescent layer 6 is deposited, emitting layer material uses compound C01
As material of main part, for GD1 as dopant material, doping mass ratio is 90:10, and luminescent layer film thickness is 40nm, this layer is as device
Luminescent layer 6 in part structure；
On luminescent layer 6, by vacuum evaporation mode, be deposited electron transfer layer 8, electron transport layer materials using ET2 and
EI1 mixing and doping, doping mass ratio are 1:1, and film thickness 35nm, this layer is as the electron transfer layer 8 in device architecture；
On electron transfer layer 8, by vacuum evaporation mode, evaporation cathode aluminium layer, film thickness 100nm, this layer is cathode
Reflection electrode layer 10 uses.
After completing the production of OLED luminescent device as described above, anode and cathode is connected with well known driving circuit
Come, the luminous efficiency of measurement device, the I-E characteristic of luminescent spectrum and device.
Device embodiments 2
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, luminescent layer 6
With electron transfer layer 8.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HI1)/hole transmission layer 4 is (thick
Degree: 110nm, material: HT2) (thickness: 40nm, material: compound C04 and GD2 is by weight 88:12 blending structure for/luminescent layer 6
At)/electron transfer layer 8 (thickness: 35nm, material: ET02 and EI1, mass ratio 1:1)/Al (thickness: 100nm).
Device embodiments 3
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, luminescent layer
6, electron transfer layer 8 and electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HI2)/hole transmission layer 4 is (thick
Degree: 110nm, material: HT4) (thickness: 40nm, material: compound C09 and GD2 is by weight 88:12 blending structure for/luminescent layer 6
At)/electron transfer layer 8 (thickness: 35nm, material: ET3 and EI1, mass ratio 1:1)/electron injecting layer 9 (thickness: 1nm, material:
LiN3)/Al (thickness: 100nm).
Device embodiments 4
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, electronics resistance
Barrier 5, luminescent layer 6 and electron transfer layer 8.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HI1)/hole transmission layer 4 is (thick
Degree: 90nm, material: HT3)/electronic barrier layer 5 (thickness: 20nm, material: EB2) (thickness: 40nm, material: chemical combination of/luminescent layer 6
Object C19 and GD3 is constituted by weight 89:11 blending)/electron transfer layer 8 (thickness: 35nm, material: ET3 and EI1, mass ratio 1:
1)/Al (thickness: 100nm).
Device embodiments 5
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, luminescent layer
6, electron transfer layer 8 and electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 50nm, material: HI3 and HT3, in mass ratio 5:
95 blendings are constituted)/hole transmission layer 4 (thickness: 70nm, material: HT3) (thickness: 40nm, material: compound C31 of/luminescent layer 6
Constituted with GD3 by weight 89:11 blending)/electron transfer layer 8 (thickness: 35nm, material: ET3)/electron injecting layer 9 (thickness:
1nm, material: Li)/Al (thickness: 100nm).
Device embodiments 6
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, luminescent layer
6, electron transfer layer 8 and electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 50nm, material: HI4 and HT3, in mass ratio 5:
95 blendings are constituted)/hole transmission layer 4 (thickness: 70nm, material: HT6) (thickness: 40nm, material: compound C53 of/luminescent layer 6
Constituted with GD4 by weight 92:8 blending)/electron transfer layer 8 (thickness: 35nm, material: ET4 and EI1, mass ratio 1:1)/electricity
Sub- implanted layer 9 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 7
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, electronics resistance
Barrier 5, luminescent layer 6, hole blocking layer 7 and electron transfer layer 8.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HI1)/hole transmission layer 4 is (thick
Degree: 90nm, material: HT6)/electronic barrier layer 5 (thickness: 20nm, material: EB1) (thickness: 40nm, material: chemical combination of/luminescent layer 6
Object C57 and GD4 is constituted by weight 92:8 blending)/hole blocking layer 7 (thickness: 20nm, material: HB1)/electron transfer layer 8
(thickness: 15nm, material: ET2 and EI1, mass ratio 1:1)/Al (thickness: 100nm).
Device embodiments 8
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, electronics resistance
Barrier 5, luminescent layer 6, electron transfer layer 8 and electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 50nm, material: HI5 and HT3, in mass ratio 5:
95 blendings are constituted)/hole transmission layer 4 (thickness: 50nm, material: HT5)/electronic barrier layer 5 (thickness: 20nm, material: EB3)/
Luminescent layer 6 (thickness: 40nm, material: compound C64 and GD5 is constituted by weight 92:8 blending)/electron transfer layer 8 (thickness:
35nm, material: ET2 and EI1, mass ratio 1:1)/electron injecting layer 9 (thickness: 1nm, material: Cs2CO3)/Al (thickness:
100nm)。
Device embodiments 9
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, electronics resistance
Barrier 5, luminescent layer 6, electron transfer layer 8 and electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 50nm, material: HI6 and HT4, in mass ratio 5:
95 blendings are constituted)/hole transmission layer 4 (thickness: 50nm, material: HT6)/electronic barrier layer 5 (thickness: 20nm, material: EB2)/
Luminescent layer 6 (thickness: 40nm, material: compound C71 and GD6 is constituted by weight 95:5 blending)/electron transfer layer 8 (thickness:
35nm, material: ET2 and EI1, mass ratio 1:1)/electron injecting layer 9 (thickness: 1nm, material: EI1)/Al (thickness: 100nm).
Device embodiments 10
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, electronics resistance
Barrier 5, luminescent layer 6, hole blocking layer 7, electron transfer layer 8 and electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HI1)/hole transmission layer 4 is (thick
Degree: 90nm, material: HT3)/electronic barrier layer 5 (thickness: 20nm, material: EB1) (thickness: 40nm, material: chemical combination of/luminescent layer 6
Object C77 and GD5 is constituted by weight 92:8 blending)/hole blocking layer 7 (thickness: 25nm, material: HB1)/electron transfer layer 8
(thickness: 10nm, material: ET5)/electron injecting layer 9 (thickness: 1nm, material: EI1)/Al (thickness: 100nm).
Device embodiments 11
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, electronics resistance
Barrier 5, luminescent layer 6, hole blocking layer 7, electron transfer layer 8 and electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 50nm, material: HI5 and HT6, in mass ratio 5:
95 blendings are constituted)/hole transmission layer 4 (thickness: 50nm, material: HT6)/electronic barrier layer 5 (thickness: 20nm, material: EB2)/
Luminescent layer 6 (thickness: 40nm, material: compound C83 and GD4 is constituted by weight 92:8 blending)/hole blocking layer 7 (thickness:
15nm, material: HB1)/electron transfer layer 8 (thickness: 20nm, material: ET2 and EI1, mass ratio 1:1)/electron injecting layer 9 (thickness
Degree: 1nm, material: Li2CO3)/Al (thickness: 100nm).
Device embodiments 12
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, luminescent layer
6, hole blocking layer 7, electron transfer layer 8 and electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 50nm, material: HI5 and HT3, in mass ratio 5:
95 blendings are constituted)/hole transmission layer 4 (thickness: 70nm, material: HT6) (thickness: 40nm, material: compound C88 of/luminescent layer 6
Constituted with GD6 by weight 95:5 blending)/hole blocking layer 7 (thickness: 15nm, material: HB1)/electron transfer layer 8 (thickness:
20nm, material: ET6)/electron injecting layer 9 (thickness: 1nm, material: CsF)/Al (thickness: 100nm).
Device embodiments 13
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, electronics resistance
Barrier 5, luminescent layer 6, electron transfer layer 8 and electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 50nm, material: HI5 and HT3, in mass ratio 5:
95 blendings are constituted)/hole transmission layer 4 (thickness: 50nm, material: HT6)/electronic barrier layer 5 (thickness: 20nm, material: EB2)/
Luminescent layer 6 (thickness: 40nm, material: compound C89 and GD2 is constituted by weight 88:12 blending)/electron transfer layer 8 (thickness:
35nm, material: ET2 and EI1, mass ratio 1:1)/electron injecting layer 9 (thickness: 1nm, material: CsN3)/Al (thickness: 100nm).
Device embodiments 14
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, electronics resistance
Barrier 5, luminescent layer 6, hole blocking layer 7 and electron transfer layer 8.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 50nm, material: HI5 and HT3, in mass ratio 5:
95 blendings are constituted)/hole transmission layer 4 (thickness: 50nm, material: HT6)/electronic barrier layer 5 (thickness: 20nm, material: EB2)/
Luminescent layer 6 (thickness: 40nm, material: compound C97, GH2 and GD2 are constituted by weight 60:30:10 blending)/hole blocking layer
7 (thickness 15nm, material: EB2)/electron transfer layers 8 (thickness: 20nm, material: ET2 and EI1, mass ratio 1:1)/Al (thickness:
100nm)。
Device embodiments 15
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, electronics resistance
Barrier 5, luminescent layer 6, hole blocking layer 7, electron transfer layer 8 and electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 50nm, material: HI5 and HT6, in mass ratio 5:
95 blendings are constituted)/hole transmission layer 4 (thickness: 50nm, material: HT6)/electronic barrier layer 5 (thickness: 20nm, material: EB2)/
Luminescent layer 6 (thickness: 40nm, material: GH3 and compound C75 is constituted by weight 88:12 blending)/hole blocking layer 7 (thickness:
25nm, material: HB1)/electron transfer layer 8 (thickness: 10nm, material: ET5)/electron injecting layer 9 (thickness: 1nm, material:
EI1)/Al (thickness: 100nm).
Device embodiments 16
Device stack structure is as shown in device architecture schematic diagram 1: including hole injection layer 3, hole transmission layer 4, electronics resistance
Barrier 5, luminescent layer 6 and electron transfer layer 8.
Ito anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HI1)/hole transmission layer 4 is (thick
Degree: 90nm, material: HT6)/electronic barrier layer 5 (thickness: 20nm, material: EB1) (thickness: 40nm, material: GH4 of/luminescent layer 6
Constituted with compound C99 by weight 92:8 blending)) (thickness: 35nm, material: ET3 and EI1, mass ratio of/electron transfer layer 8
1:1)/Al (thickness: 100nm).
Device comparative example 1
Device stack structure is as shown in device architecture schematic diagram 1: including hole transmission layer 4, luminescent layer 6, electron transfer layer 8
With electron injecting layer 9.
Ito anode layer 2 (thickness: 150nm)/hole transmission layer 4 (thickness: 120nm, material: HTI)/luminescent layer 6 (thickness:
40nm, material: GH1 and GD1 is constituted by weight 90:10 blending)/electron transfer layer 8 (thickness: 35nm, material: ET1)/electronics
Implanted layer 9 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
The OLED is characterized by standard method, from current/voltage/luminous density characteristic line that Lambert emission characteristic is presented
It calculates, and the measurement service life.It determines in 1000cd/m2Electroluminescent spectrum under brightness calculates CIEx and y color coordinates, device
Test data is as shown in table 3.
Table 2
Table 3
Note: for device detection performance using comparative example 1 as reference, 1 device performance indexes of comparative example is set as 1.0.Compare
The current efficiency of example 1 is 32.6cd/A (@1000cd/m2)；Driving voltage is 5.6v (@1000cd/m2)；LT95 under 5000 brightness
Life time decay is 3.5Hr.
Table 3 summarizes the OLED device in 1000cd/m2Voltage needed for brightness, the current efficiency reached and electroluminescent hair
The chromaticity coordinates of light spectrum, and in 5000cd/m2LT95 Decay under brightness.1 comparative device comparative example 1 of device embodiments,
Replace luminescent layer material of main part of the invention, and by combination of materials of the invention at laminated device after, device voltage reduces, electric current
Improved efficiency 60%, 6 times of life-span upgrading；The material adapted and device stack that device embodiments 2~13 are designed by the present invention combine,
So that device data is further promoted；Such as device embodiments 14, of the invention with 10,10- diaryl anthrone is core group
When material is as hybrid agent material, extraordinary performance data is further obtained；Such as device embodiments 15,16, this hair
It is bright with 10,10- diaryl anthrone be core group material as luminescent layer dopant material in use, equally obtain it is very good
Performance data.
To sum up, the foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (14)
1. a kind of organic electroluminescence device of the ketone compounds Han 10,10- diaryl anthracene, the device include hole transmission layer,
Luminescent layer, electron transfer layer, it is characterised in that it is core group that the device emitting layer material, which is with 10,10- diaryl anthrone,
Compound, shown in the structural formula of the compound such as general formula (1):
In general formula (1), Ar1、Ar2Expression hydrogen ,-Ar-R or-R independently；And Ar1、Ar2It is not simultaneously hydrogen；
Wherein, Ar indicates phenyl, xenyl, terphenyl, naphthalene, anthryl or phenanthryl；
R is indicated using general formula (2), general formula (3), general formula (4) or general formula (5):
Wherein, X1For oxygen atom, sulphur atom, C1-10Alkylidene, the benzene of alkylidene, phenyl substitution that linear or branched alkyl group replaces
One of the amido that base replaces；
R1、R2Structure shown in selection hydrogen or general formula (6) independently, general formula (7):
A isX2It is expressed as oxygen atom, sulphur atom, C1-10Alkylidene, the phenyl of linear or branched alkyl group substitution
Or one of amido of naphthyl substituted；X3It is expressed as oxygen atom, sulphur atom, C1-10The alkylidene of linear or branched alkyl group substitution,
One of the amido that phenyl replaces；
General formula (6), general formula (7) and CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL4-CL5Key, CL‘1-CL’2Key, CL‘2-CL’3Key,
CL‘3-CL’4Key or CL‘4-CL’5Key connection；
R3Indicate phenyl, xenyl, naphthalene, anthryl or phenanthryl.
2. organic electroluminescence device according to claim 1, it is characterised in that the compound is indicated as a
And and CL4-CL5Key or CL‘4-CL’5When key connection, X1And X2Position overlapping, only take X1Or X2；X3It is former to be expressed as oxygen atom, sulphur
Son, C1-10One of the amido that alkylidene, the phenyl of linear or branched alkyl group substitution replace.
3. organic electroluminescence device according to claim 1, it is characterised in that R in the compound are as follows:
Any one of.
4. a kind of organic electroluminescence device described in claim 1, it is characterised in that the R can be with are as follows:
5. organic electroluminescence device according to claim 1, it is characterised in that 10, the 10- diaryl anthracene ketone
Close the concrete structure formula of object are as follows:
6. organic electroluminescence device according to claim 1, it is characterised in that material shown in the general formula (1) is as hair
The material of main part of photosphere；The dopant material of the luminescent layer is using in material shown in general formula (8), (9), (10), (11)
One kind:
In general formula (8), B1-B10 is selected as hydrogen, C1-30The alkyl or alkoxy, substituted or unsubstituted that linear or branched alkyl group replaces
C6-30Aryl, it is substituted or unsubstituted 3 yuan to 30 unit's heteroaryls；B1-B10 is not hydrogen simultaneously；
In general formula (9), Y1-Y6 one kind independent for being expressed as oxygen, carbon, nitrogen-atoms； It is expressed as containing there are two the groups of atom to pass through the connected cyclization of any chemical bond；
Y1~Y4 one kind independent for being expressed as oxygen, carbon, nitrogen-atoms in general formula (10), general formula (11)；It is expressed as being connected to containing the group there are two atom by any chemical bond
Ring.
7. organic electroluminescence device according to claim 1, it is characterised in that the material of the hole transmission layer be containing
There is the compound of triarylamine group, shown in the structural formula general formula such as general formula (12) of the compound:
D1-D3 respectively independently indicates substituted or unsubstituted C in general formula (12)6-30It is aryl, 3 yuan to 30 yuan substituted or unsubstituted
Heteroaryl；D1-D3 can be same or different.
8. organic electroluminescence device according to claim 1, it is characterised in that under the material of the electron transfer layer is
One of column general formula (13), (14), (15), (16), material shown in (17):
General formula (13), general formula (14), general formula (15), general formula (16), E1-E10 is selected as hydrogen, C in general formula (17)1-30Straight chain or branch
The alkyl or alkoxy, substituted or unsubstituted C that alkyl group replaces6-30Aryl, substituted or unsubstituted 3 yuan to 30 yuan heteroaryls
Base；E1-E10 is not hydrogen simultaneously.
9. organic electroluminescence device according to claim 1, it is characterised in that the luminescent device further includes hole note
Enter layer；The hole injection layer material is having structure general formula (18), (19), one of material shown in (20):
In general formula (18), F1-F3 respectively independently indicates substituted or unsubstituted C6-30It is aryl, 3 yuan to 30 yuan substituted or unsubstituted
Heteroaryl；F1-F3 can be same or different；
In general formula (19), general formula (20), G1-G6 expression hydrogen atom independent, itrile group, halogen, amide groups, alkoxy, ester
Base, nitro, C1-30Carbon atom, the substituted or unsubstituted C of linear or branched alkyl group substitution6-30Aryl, 3 yuan to 30 unit's heteroaryls；
G1-G6 is not hydrogen simultaneously.
10. organic electroluminescence device according to claim 1, it is characterised in that the luminescent device further includes electronics note
Enter layer；The electron injecting layer material is one of lithium, lithium salts or cesium salt；The lithium salts be 8-hydroxyquinoline lithium, lithium fluoride,
Lithium carbonate, Lithium Azide；The cesium salt is cesium fluoride, cesium carbonate, cesium azide.
11. organic electroluminescence device according to claim 1, it is characterised in that compound shown in the general formula (1) is done
It is used for the dopant material of luminescent layer.
12. according to organic electroluminescence device described in claim 1, it is characterised in that the dopant material of the luminescent layer and shine
The mass ratio of the material of main part of layer is 0.005~0.2:1.
13. a kind of application of any one of claim 1~12 organic electroluminescence device, it is characterised in that the Organic Electricity
Electroluminescence device is used to prepare top-illuminating OLED luminescent device.
14. a kind of application of any one of claim 1~12 organic electroluminescence device, it is characterised in that the Organic Electricity
Electroluminescence device is applied to AM-OLED display.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6093864A (en) * | 1989-03-20 | 2000-07-25 | Idemitsu Kosan Co., Ltd. | Aromatic dimethylidyne compounds |
| CN1576999A (en) * | 2003-07-10 | 2005-02-09 | 株式会社丰田自动织机 | Display |
| CN102232068A (en) * | 2009-04-24 | 2011-11-02 | 出光兴产株式会社 | Aromatic amine derivative and organic electroluminescent element using same |
| CN102471353A (en) * | 2009-12-21 | 2012-05-23 | 出光兴产株式会社 | Pyrene derivative and organic electroluminescent element using same |
| CN103026789A (en) * | 2011-06-03 | 2013-04-03 | 松下电器产业株式会社 | Method for manufacturing organic electroluminescent display panel, and device for manufacturing organic electroluminescent display panel |
| JP2013203930A (en) * | 2012-03-29 | 2013-10-07 | Three Bond Co Ltd | Curable composition |
| KR20140055921A (en) * | 2012-10-29 | 2014-05-09 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
| CN104183721A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic light emitting diode and preparation method thereof |
-
2016
- 2016-04-25 CN CN201610259331.6A patent/CN107068909B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6093864A (en) * | 1989-03-20 | 2000-07-25 | Idemitsu Kosan Co., Ltd. | Aromatic dimethylidyne compounds |
| CN1576999A (en) * | 2003-07-10 | 2005-02-09 | 株式会社丰田自动织机 | Display |
| CN102232068A (en) * | 2009-04-24 | 2011-11-02 | 出光兴产株式会社 | Aromatic amine derivative and organic electroluminescent element using same |
| CN102471353A (en) * | 2009-12-21 | 2012-05-23 | 出光兴产株式会社 | Pyrene derivative and organic electroluminescent element using same |
| CN103026789A (en) * | 2011-06-03 | 2013-04-03 | 松下电器产业株式会社 | Method for manufacturing organic electroluminescent display panel, and device for manufacturing organic electroluminescent display panel |
| JP2013203930A (en) * | 2012-03-29 | 2013-10-07 | Three Bond Co Ltd | Curable composition |
| KR20140055921A (en) * | 2012-10-29 | 2014-05-09 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
| CN104183721A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic light emitting diode and preparation method thereof |
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