CN110323360A - A kind of organic electroluminescence device and its application - Google Patents
A kind of organic electroluminescence device and its application Download PDFInfo
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Abstract
The invention belongs to technical field of semiconductors, more particularly to a kind of organic electroluminescence device and its application, including cathode reflection electrode layer and ito anode layer, there is at least one layer of organic thin film layer between the cathode reflection electrode layer and ito anode layer, contain in the organic thin film layer using triaminobenzene as the compound of core；The triaminobenzene is shown in the compound structure such as general formula (1) of core:, the compounds of this invention is using equal benzene as core, glass transition temperature with higher and molecule thermal stability, and suitable HOMO and lumo energy, higher Eg are optimized by device architecture, can effectively promote the photoelectric properties of OLED device and the service life of OLED device.
Description
Technical field
The invention belongs to technical field of semiconductors more particularly to a kind of organic electroluminescence device and its applications.
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.OLED luminescent device including electrode material film layer and is clipped in different electricity like the structure of sandwich
Organic functional material between the film layer of pole, various different function materials are overlapped mutually depending on the application collectively constitutes OLED hair together
Optical device.OLED luminescent device is as current device, when applying voltage to its two end electrodes, and passes through electric field action organic layer function
Can positive and negative charge in film layer when, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.
Currently, OLED display technology in smart phone, applied by the fields such as tablet computer, further will also be to electricity
Depending on etc. large scales application field extension, still with actual products application require compare, the luminous efficiency and use of OLED device
The performances such as service life also need further to be promoted.Proposing high performance research to OLED luminescent device at present includes: to reduce the drive of device
Dynamic voltage, the luminous efficiency for improving device, the service life for improving device etc..In order to realize that the continuous of performance of OLED device mentions
It rises, not only needs the innovation from OLED device structure and manufacture craft, constantly study and create with greater need for oled light sulfate ferroelectric functional material
Newly, the OLED functional material of higher performance is formulated out.
Oled light sulfate ferroelectric functional material applied to OLED device can be divided into two major classes from purposes, and respectively charge injects
Transmission material and luminescent material.Further, it can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking
Luminescent material, can also be divided into main body luminescent material and doping material by material, hole injection transmission material and hole barrier materials
Material.
In order to make high performance OLED luminescent device, it is desirable that various organic functional materials have good photoelectric properties,
For example, as charge transport materials, it is desirable that have good carrier mobility, high-vitrification conversion temperature etc., as luminous
The material of main part of layer has good bipolarity, HOMO/LUMO energy rank appropriate etc..
The oled light sulfate ferroelectric functional material film layer for constituting OLED device includes at least two layers or more structure, applies in industry
OLED device structure then includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron-transport
A variety of film layers such as layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED device is injected including at least hole
Material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form have rich and various
The characteristics of property.In addition, used photoelectric functional material has stronger choosing for the collocation of the OLED device of different structure
Selecting property, performance of the identical material in different structure device may also be completely totally different.
Therefore, for the industry application requirement of current OLED device and the different function film layer of OLED device, device
Photoelectric characteristic demand, it is necessary to which selection is more suitable for, the higher OLED functional material of performance or combination of materials, is just able to achieve the height of device
Efficiency, the overall characteristic of long-life and low-voltage.For current OLED shows the actual demand of Lighting Industry, OLED at present
The development of material is also far from enough, lags behind the requirement of panel manufacturing enterprise, as the organic of material enterprise development higher performance
Functional material is particularly important.
Summary of the invention
In order to solve the above-mentioned technical problem the present invention provides a kind of organic electroluminescence device and its application.Chemical combination of the present invention
Object is using equal benzene as core, glass transition temperature with higher and molecule thermal stability, suitable HOMO and lumo energy, higher
Eg is optimized by device architecture, can effectively promote the photoelectric properties of OLED device and the service life of OLED device.
The technical scheme to solve the above technical problems is that
A kind of organic electroluminescence device, including cathode reflection electrode layer and ito anode layer, the cathode reflection electrode layer
There is at least one layer of organic thin film layer between ito anode layer, contain in the organic thin film layer using triaminobenzene as core
Compound；The triaminobenzene is shown in the compound structure such as general formula (1) of core:
In general formula (1), Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Independently be expressed as C1~C10Linear or branched alkyl group takes
Generation or unsubstituted phenyl, C1~C10The substituted or unsubstituted xenyl of linear or branched alkyl group, C1~C10Linear chain or branched chain alkane
Substituted or unsubstituted one of the naphthalene of base；
The Ar1、Ar2、Ar3、Ar4、Ar5、Ar6It is also denoted as structure shown in following general formula (2),
In general formula (2), R1、R2、R3、R4、R5、R6、R7、R8In any one be expressed as singly-bound, remaining table independently
It is shown as hydrogen atom, C1~C10One of linear or branched alkyl group；
X is expressed as O, S, C1~C10Methylene, the C of linear or branched alkyl group substitution6~C15Methylene, the C of aryl substitution6
~C15One of the imido grpup that aryl replaces.
Further, work as Ar1、Ar2、Ar3、Ar4、Ar5、Ar6In be shown general formula (2) structure when, Ar1、Ar2、Ar3、
Ar4、Ar5、Ar6In at least there are two being expressed as C1~C10The substituted or unsubstituted xenyl of linear or branched alkyl group, and at least
There is a C1~C10The substituted or unsubstituted xenyl of linear or branched alkyl group is not contraposition connection；Work as Ar1、Ar2、Ar3、Ar4、
Ar5、Ar6In when having one or two for shown general formula (2) structure, and X is C1~C10The methylene that linear or branched alkyl group replaces
When base, Ar1、Ar2、Ar3、Ar4、Ar5、Ar6In at least one be C1~C10The substituted or unsubstituted biphenyl of linear or branched alkyl group
Base, and C1~C10The substituted or unsubstituted xenyl of linear or branched alkyl group is not contraposition connection.
Further, the Ar1、Ar2、Ar3、Ar4、Ar5、Ar6It is respectively and independently selected from following structures:
In any one, wherein R9~R36It is expressed as H, C1~C10Straight chain or branch
Alkyl group.
Further, described using triaminobenzene as the compound of core, meet any of the following general formula (3) into general formula (7)
Kind:
Wherein R37~R48It is expressed as H, C1~C10Linear or branched alkyl group.
Further, the particular compound structural formula of the general formula (1) are as follows:
In any one.
It is further, described using triaminobenzene as the preparation method of the compound of core, comprising the following steps:
It weighs intermediate M and intermediate N is dissolved with toluene, add Pd2(dba)3, triphenylphosphine and potassium tert-butoxide；Lazy
Property atmosphere under, the mixed solution of above-mentioned reactant is reacted 10-24 hours at 90-110 DEG C of reaction temperature, it is cooling, filtering is anti-
Solution is answered, filtrate revolving crosses silicagel column, obtains target compound；The dosage of the toluene is that every gram of intermediate M uses 30-
50mL toluene；The molar ratio of the intermediate N and intermediate M is 1:(1.0-1.5)；The Pd2(dba)3With rubbing for intermediate M
You are than being (0.006-0.02): 1, the molar ratio of the sodium tert-butoxide and intermediate M are (2.0-3.0): 1；The triphenylphosphine
Molar ratio with intermediate M is (2.0-3.0): 1.
Further, the organic thin film layer includes hole transmission layer.
The present invention also provides a kind of display elements, including above-mentioned organic electroluminescence device.
The beneficial effects of the present invention are:
1. the compounds of this invention is equal benzene-like compounds, branch includes tertiary aromatic amine structure, so that it has very strong hole to pass
Movement Capabilities, hole mobility is high, can be used as hole mobile material use, and high hole transport rate can be improved organic electroluminescence hair
The efficiency of optical device；Under suitable lumo energy, and play the role of electronic blocking, promotes exciton answering in luminescent layer
Efficiency is closed, the efficiency roll-off under high current density is reduced, device voltage is reduced, improves current efficiency and the service life of device.
2. the compounds of this invention, centered on equal benzene, 3 branches of connection are radial, and after material filming, each branch can
It intersects to form the high film layer of compactness, to reduce leakage current of the material after OLED device application, therefore improves device
Service life.
3. the compound of the present invention, in application, by device architecture optimization, can keep high film layer to stablize in OLED device
Property, the photoelectric properties of OLED device and the service life of OLED device can be effectively promoted, compound of the present invention shines in OLED
There is good application effect and industrialization prospect in device.
4. compound provided by the invention glass transition temperature with higher and molecule thermal stability, suitable HOMO and
Lumo energy, higher Eg, is optimized by device architecture, can effectively promote the photoelectric properties of OLED device and the longevity of OLED device
Life.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that material cited by the present invention is applied to OLED device；
Fig. 2 is current efficiency variation with temperature curve.
Fig. 3 is that the leakage current that device embodiments 1 of the present invention carry out backward voltage with device made by device comparative example 1 is surveyed
Try curve graph.
In attached drawing, parts list represented by the reference numerals are as follows:
1, transparent substrate layer, 2, ito anode layer, 3, hole injection layer, the 4, first hole transmission layer, the 5, second hole transport
Layer, 6, luminescent layer, 7, electron transfer layer, 8, electron injecting layer, 9, cathode reflection electrode layer.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1:
The synthesis of intermediate N
It weighs raw material I and raw material II is dissolved with toluene, add Pd2(dba)3, triphenylphosphine and potassium tert-butoxide；In inertia
Under atmosphere, the mixed solution of above-mentioned reactant is reacted 10-24 hours at 90-110 DEG C of reaction temperature, cooling, filtering reaction
Solution, filtrate revolving, crosses silicagel column, obtains target compound；The molar ratio of the raw material I and raw material II is 1:(1.0-1.5)；
Pd2(dba)3It is (0.006-0.02) with the molar ratio of raw material I: 1, the molar ratio of sodium tert-butoxide and raw material I are (2.0-3.0): 1；
The molar ratio of triphenylphosphine and raw material I are (2.0-3.0): 1；50-100mL toluene is added in 1g raw material I.
By taking the synthesis of intermediate N 1 as an example:
0.01mol1- aniline, the 2- bromine connection of 0.012mol is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml
Benzene, 0.03mol potassium tert-butoxide, 1 × 10-4molPd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150ml toluene, is heated to reflux
12 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving cross silicagel column, obtain intermediate N 1；Elemental analysis
Structure (molecular formula C18H15N): theoretical value C, 88.13；H,6.16；N,5.71；Test value: C, 88.12；H,6.16；N,5.72.
ESI-MS(m/z)(M+): theoretical value 245.12, measured value 245.88.
According in embodiment 1 prepare intermediate N 1 method come prepare intermediate N 2, intermediate N 3, intermediate N 4,
Intermediate N 5 and intermediate N 6, raw material is corresponding to be replaced as shown in table 1 below:
Table 1
Intermediate A r is prepared according to the method for preparing intermediate N1And Ar2。
The synthesis of intermediate M
Weigh raw material II I and intermediate A r1It is dissolved with toluene, adds Pd2(dba)3, triphenylphosphine and potassium tert-butoxide；?
Under inert atmosphere, the mixed solution of above-mentioned reactant is reacted 10-24 hours at 90-110 DEG C of reaction temperature, cooling, filtering
Reaction solution, filtrate revolving, crosses silicagel column, obtains intermediate A；The molar ratio of the raw material II I and intermediate A r1 is 1:
(1.0-1.5)；Pd2(dba)3Molar ratio with raw material II I is (0.006-0.02): 1, the molar ratio of sodium tert-butoxide and raw material II I
For (2.0-3.0): 1；The molar ratio of triphenylphosphine and raw material II I are (2.0-3.0): 1；50-100mL first is added in 1g raw material II I
Benzene.
It weighs intermediate A and intermediate A r2 is dissolved with toluene, add Pd2(dba)3, triphenylphosphine and potassium tert-butoxide；?
Under inert atmosphere, the mixed solution of above-mentioned reactant is reacted 10-24 hours at 90-110 DEG C of reaction temperature, cooling, filtering
Reaction solution, filtrate revolving, crosses silicagel column, obtains intermediate M；The intermediate A and the molar ratio of intermediate A r2 are 1:
(1.0-1.5)；Pd2(dba)3Molar ratio with intermediate A is (0.006-0.02): 1, the molar ratio of sodium tert-butoxide and intermediate A
For (2.0-3.0): 1；The molar ratio of triphenylphosphine and intermediate A is (2.0-3.0): 1；50-100mL first is added in 1g intermediate A
Benzene.
By taking intermediate M-1 synthesis as an example:
The intermediate of 0.01mol raw material II I, 0.012mol is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml
Ar1-1,0.03mol potassium tert-butoxide, 1 × 10-4molPd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150ml toluene, is heated back
Stream 12 hours samples contact plate, fully reacting；Natural cooling, filtering, filtrate revolving cross silicagel column, obtain intermediate A -1；Element point
Analyse structure (molecular formula C18H13Br2N): theoretical value C, 53.63；H,3.25；Br,39.64；N,3.47；Test value: C, 53.62；H,
3.25；Br,39.65；N,3.47.ESI-MS(m/z)(M+): theoretical value 400.94, measured value 401.80.
The centre of 0.01mol intermediate A -1,0.012mol is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml
Body Ar2-1,0.03mol potassium tert-butoxide, 1 × 10-4molPd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150mL toluene, heating
Reflux 12 hours samples contact plate, fully reacting；Natural cooling, filtering, filtrate revolving cross silicagel column, obtain intermediate M-1；Element
Analyze structure (molecular formula C36H27BrN2): theoretical value C, 76.19；H,4.80；Br,14.08；N,4.94；Test value: C, 76.19；
H,4.80；Br,14.09；N,4.93.ESI-MS(m/z)(M+): theoretical value 566.14, measured value 566.91.
Intermediate M-2, intermediate M-3, intermediate M-4, centre are prepared according to the method for preparing intermediate M-1 among the above
Body M-5, intermediate M-6 and intermediate M-7, raw material is corresponding to be replaced as shown in table 2 below:
Table 2
Embodiment 2: the synthesis of compound 6:
The centre of 0.01mol intermediate M-1,0.012mol is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250mL
Body N-1,0.03mol potassium tert-butoxide, 1 × 10-4molPd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 150ml toluene, is heated back
Stream 12 hours samples contact plate, fully reacting；Natural cooling, filtering, filtrate revolving cross silicagel column, obtain compound 9；Element point
Analyse structure (molecular formula C54H41N3): theoretical value C, 88.61；H,5.65；N,5.74；Test value: C, 88.62；H,5.65；N,
5.73。ESI-MS(m/z)(M+): theoretical value 731.33, measured value 731.66.
Embodiment 3: the synthesis of compound 18:
The preparation method of compound 18 is with embodiment 2, the difference is that intermediate M-1 is replaced with intermediate M-2, it is intermediate
Body N-2 replaces intermediate N 1；Elemental analysis structure (molecular formula C66H49N3): theoretical value C, 89.66；H,5.59；N,4.75；It surveys
Examination value: C, 89.67；H,5.59；N,4.74.ESI-MS(m/z)(M+): theoretical value 883.39, measured value 883.57.
Embodiment 4: the synthesis of compound 27:
The preparation method of compound 27 is with embodiment 2, the difference is that intermediate M-1 is replaced with intermediate M-2, it is intermediate
Body N-3 replaces intermediate N 1；Elemental analysis structure (molecular formula C58H43N3): theoretical value C, 89.08；H,5.54；N,5.37；It surveys
Examination value: C, 89.07；H,5.54；N,5.38.ESI-MS(m/z)(M+): theoretical value 781.35, measured value 781.74.
Embodiment 5: the synthesis of compound 40:
The preparation method of compound 40 is with embodiment 2, the difference is that intermediate M-1 is replaced with intermediate M-3, it is intermediate
Body N-4 replaces intermediate N 1；Elemental analysis structure (molecular formula C63H49N3): theoretical value C, 89.22；H,5.82；N,4.95；It surveys
Examination value: C, 89.23；H,5.82；N,4.95.ESI-MS(m/z)(M+): theoretical value 847.39, measured value 847.85.
Embodiment 6: the synthesis of compound 54:
The preparation method of compound 54 is with embodiment 2, the difference is that intermediate M-1 is replaced with intermediate M-4, it is intermediate
Body N-5 replaces intermediate N 1；Elemental analysis structure (molecular formula C66H53N3): theoretical value C, 89.25；H,6.02；N,4.73；It surveys
Examination value: C, 89.24；H,6.02；N,4.74.ESI-MS(m/z)(M+): theoretical value 887.42, measured value 887.64.
Embodiment 7: the synthesis of compound 72:
The preparation method of compound 72 is with embodiment 2, the difference is that intermediate M-1 is replaced with intermediate M-5, it is intermediate
Body N-5 replaces intermediate N 1；Elemental analysis structure (molecular formula C61H47N3): theoretical value C, 89.13；H,5.76；N,5.11；It surveys
Examination value: C, 89.12；H,5.76；N,5.12.ESI-MS(m/z)(M+): theoretical value 821.38, measured value 821.71.
Embodiment 8: the synthesis of compound 90:
The preparation method of compound 90 is with embodiment 2, the difference is that intermediate M-1 is replaced with intermediate M-6, it is intermediate
Body N-5 replaces intermediate N 1；Elemental analysis structure (molecular formula C70H55N3): theoretical value C, 89.61；H,5.91；N,4.48；It surveys
Examination value: C, 89.62；H,5.91；N,4.47.ESI-MS(m/z)(M+): theoretical value 937.44, measured value 937.69.
Embodiment 9: the synthesis of compound 111:
The preparation method of compound 111 is with embodiment 2, the difference is that intermediate M-1 is replaced with intermediate M-7, in
Mesosome N-6 replaces intermediate N 1；Elemental analysis structure (molecular formula C63H47N3O): theoretical value C, 87.77；H,5.50；N,4.87；
O,1.86；Test value: C, 87.78；H,5.50；N,4.87；O,1.85.ESI-MS(m/z)(M+): theoretical value 861.37, it is real
Measured value is 861.83.
Organic compound of the invention uses in luminescent device, can be used as hole transport layer material use.To this hair
Bright compound 6,18,27,40,54,72,90,111,156,162,171,180,201,233 and 252 carries out T1 energy level, heat respectively
The test of performance, HOMO energy level, testing result are as shown in table 3.
Table 3
Note: triplet T1 is tested by the F4600 Fluorescence Spectrometer of Hitachi, and the test condition of material is 2*10-5's
Toluene solution；Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning calorimeter)
Measurement, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, in Japanese Shimadzu Corporation
TGA-50H thermogravimetric analyzer on be measured, nitrogen flow 20mL/min；Highest occupied molecular orbital HOMO energy level be by
Ionizing energy test macro (IPS3) test, is tested as atmospheric environment.
By upper table data it is found that organic compound of the invention has more appropriate HOMO energy level, hole can be applied to
Transport layer, the present invention make using equal benzene as the organic compound of core triplet with higher and higher thermal stability
Made the OLED device efficiency containing organic compound of the present invention and service life is obtained to get a promotion.
The preparation of device:
In the devices below by way of device embodiments 1-17 and device comparative example 1 compound that the present invention will be described in detail synthesizes
Application effect as hole transmission layer and electronic blocking layer material.Device embodiments 2-17 and device comparative example 1 and device
Embodiment 1 is compared, and the manufacture craft of the device is identical, and uses identical baseplate material and electrode material,
The film thickness of electrode material is also consistent, except that device hole-transporting layer and electronic blocking layer material are changed
Become.Device stack structure is as shown in table 3, and the performance test results of each device are shown in Table 4 and table 5.
Device embodiments 1
Device embodiments use ITO as anode, and Al is as cathode, CBP and Ir (ppy)3Make by weight 90:10 blending
For emitting layer material, HAT-CN is used as hole transmission layer as hole injection layer material, the compound 6 of preparation of the embodiment of the present invention
With electronic blocking layer material, TPBI is as electron transport layer materials, and LiF is as electron injecting layer material.Specific making step
It is as follows:
A) the ito anode layer 2 on transparent substrate layer 1 is cleaned, cleans each 15 with deionized water, acetone, EtOH Sonicate respectively
Minute, then handled 2 minutes in plasma cleaner；B) on ito anode layer 2, sky is deposited by vacuum evaporation mode
Layer material HAT-CN is injected in cave, and with a thickness of 10nm, this layer is as hole injection layer 3；C) on hole injection layer 3, pass through vacuum
The second hole transport layer material NPB is deposited in vapor deposition mode, and with a thickness of 60nm, which is the second hole transmission layer 4；D) in the second sky
In cave transport layer 4, the compound 6 of first hole transport layer material embodiment of the present invention preparation is deposited by vacuum evaporation mode,
With a thickness of 20nm, which is the first hole transmission layer 5；E) luminescent layer 6 is deposited on the first hole transmission layer 5, material of main part is
CBP, dopant material are Ir (ppy)3, CBP and Ir (ppy)3Mass ratio be 9:1 with a thickness of 30nm；F) on luminescent layer 6, lead to
It crosses vacuum evaporation mode and hole barrier/electron transport material TPBI is deposited, with a thickness of 40nm, this layer of organic material is hindered as hole
Gear/electron transfer layer 7 uses；G) on hole barrier/electron transfer layer 7, vacuum evaporation electron injecting layer LiF, with a thickness of
1nm, the layer are electron injecting layer 8；H) on electron injecting layer 8, vacuum evaporation cathode Al (100nm), the layer is that cathode is anti-
Penetrate electrode layer 9.
After the production for completing electroluminescent device according to above-mentioned steps, the IVL data of measurement device and light decay service life, knot
Fruit is shown in Table 4.The molecular structural formula of associated materials is as follows:
Device embodiments 2-17 and comparative example 1
Device embodiments 2-17 and comparative example 1 are identical with the manufacture craft of the device of device embodiments 1, and are adopted
It is also consistent with the film thickness of identical baseplate material and electrode material, electrode material, the difference is that hole transport/electricity
Material used in sub- barrier layer is not identical.Specific data are referring to table 4.
Table 4
The efficiency and lifetime data of each embodiment and comparative example device are shown in Table 5.
Table 5
Organic luminescent device of the invention is either in driving voltage, efficiency it can be seen from the device data result of table 5
Or the service life obtains biggish promotion both with respect to the OLED device of known materials.
In order to compare different components at higher current densities efficiency decay the case where, define efficiency attenuation coefficient φ carry out table
Show, it indicates that driving current is 100mA/cm2When device maximal efficiency μ 100 and the difference of maximal efficiency μm of device and maximum
Ratio between efficiency, φ value is bigger, illustrates that the efficiency roll-off of device is more serious, conversely, illustrating device at higher current densities
The problem of dropping of quickly declining is under control.Carry out the survey of efficiency attenuation coefficient φ respectively to device embodiments 1-17 and comparative example 1
Fixed, testing result is as shown in table 6:
Table 6
From the point of view of the data of table 6, compared by the efficiency attenuation coefficient of embodiment and comparative example it will be seen that this hair
Bright organic luminescent device can be effectively reduced efficiency roll-off.
Work limitation rate is also more stable at low temperature for the OLED device of further material preparation of the present invention, by device reality
It applies example 1,4,8 and device comparative example 1 and carries out efficiency test in -10~80 DEG C of sections, acquired results are as shown in Table 7 and Fig. 2.
Table 7
From the data of table 7 and Fig. 2 it is found that device embodiments 1,4,8 are material of the present invention and the device that known materials are arranged in pairs or groups
Structure is compared with device comparative example 1, and not only Efficiency at Low Temperature is high, but also in temperature elevation process, efficiency is steadily increased.
Further to test beneficial effect caused by the compounds of this invention, by device embodiments 1 of the present invention and device ratio
Compared with the electric leakage current test that device made by example 1 carries out backward voltage, shown in test data Fig. 3, from Fig. 3 it can be seen that using this
The device embodiments 1 of invention compound are compared with device made by device comparative example 1, leakage current very little, and current curve is stablized,
Therefore, after material of the present invention is applied to element manufacturing, there is long service life.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of organic electroluminescence device, which is characterized in that including cathode reflection electrode layer and ito anode layer, the cathode
There is at least one layer of organic thin film layer between reflection electrode layer and ito anode layer, contain in the organic thin film layer with triamido
Benzene is the compound of core；The triaminobenzene is shown in the compound structure such as general formula (1) of core:
In general formula (1), Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Independently be expressed as C1~C10Linear or branched alkyl group replace or
Unsubstituted phenyl, C1~C10The substituted or unsubstituted xenyl of linear or branched alkyl group, C1~C10Linear or branched alkyl group takes
One of generation or unsubstituted naphthalene；
The Ar1、Ar2、Ar3、Ar4、Ar5、Ar6It is also denoted as structure shown in following general formula (2),
In general formula (2), R1、R2、R3、R4、R5、R6、R7、R8In any one be expressed as singly-bound, remaining being expressed as independently
Hydrogen atom, C1~C10One of linear or branched alkyl group；
X is expressed as O, S, C1~C10Methylene, the C of linear or branched alkyl group substitution6~C15Methylene, the C of aryl substitution6~C15
One of the imido grpup that aryl replaces.
2. a kind of organic electroluminescence device according to claim 1, which is characterized in that work as Ar1、Ar2、Ar3、Ar4、Ar5、
Ar6In be shown general formula (2) structure when, Ar1、Ar2、Ar3、Ar4、Ar5、Ar6In at least there are two being expressed as C1~C10Directly
Chain or the substituted or unsubstituted xenyl of branched alkyl, and at least one C1~C10Linear or branched alkyl group replaces or does not take
The xenyl in generation is not contraposition connection；Work as Ar1、Ar2、Ar3、Ar4、Ar5、Ar6In have one or two for shown general formula (2) structure
When, and X is C1~C10When the methylene that linear or branched alkyl group replaces, Ar1、Ar2、Ar3、Ar4、Ar5、Ar6In at least one
For C1~C10The substituted or unsubstituted xenyl of linear or branched alkyl group, and C1~C10Linear or branched alkyl group replaces or does not take
The xenyl in generation is not contraposition connection.
3. a kind of organic electroluminescence device according to claim 1, which is characterized in that the Ar1、Ar2、Ar3、Ar4、Ar5、
Ar6It is respectively and independently selected from following structures:
In any one, wherein R9~R36It is expressed as H, C1~C10Straight chain or branch
Alkyl group.
4. a kind of organic electroluminescence device according to claim 1, which is characterized in that described using triaminobenzene as core
Compound meets the following general formula (3) any one of to general formula (7):
Wherein R37~R48It is expressed as H, C1~C10Linear or branched alkyl group.
5. a kind of organic electroluminescence device according to claim 1, which is characterized in that the specific chemical combination of the general formula (1)
Object structural formula are as follows:
In any one.
6. a kind of organic electroluminescence device according to claim 1, which is characterized in that described using triaminobenzene as core
The preparation method of compound, comprising the following steps:
It weighs intermediate M and intermediate N is dissolved with toluene, add Pd2(dba)3, triphenylphosphine and potassium tert-butoxide；In indifferent gas
Under atmosphere, the mixed solution of above-mentioned reactant is reacted 10-24 hours at 90-110 DEG C of reaction temperature, cooling, filtering reacts molten
Liquid, filtrate revolving, crosses silicagel column, obtains target compound；The dosage of the toluene is that every gram of intermediate M uses 30-50mL first
Benzene；The molar ratio of the intermediate N and intermediate M is 1:(1.0-1.5)；The Pd2(dba)3Molar ratio with intermediate M is
(0.006-0.02): 1, the molar ratio of the sodium tert-butoxide and intermediate M are (2.0-3.0): 1；The triphenylphosphine and centre
The molar ratio of body M is (2.0-3.0): 1.
7. a kind of organic electroluminescence device according to claim 1, which is characterized in that the organic thin film layer includes hole
Transport layer.
8. a kind of display element, which is characterized in that including organic electroluminescence device of any of claims 1-7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335362A (en) * | 2020-09-30 | 2022-04-12 | 江苏三月科技股份有限公司 | Composition for OLED and organic electroluminescent device |
| CN114335364A (en) * | 2020-09-30 | 2022-04-12 | 江苏三月科技股份有限公司 | Composition for organic electroluminescent device and organic electroluminescent device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003229275A (en) * | 2001-11-27 | 2003-08-15 | Semiconductor Energy Lab Co Ltd | Light emitting element |
-
2019
- 2019-03-20 CN CN201910213669.1A patent/CN110323360B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003229275A (en) * | 2001-11-27 | 2003-08-15 | Semiconductor Energy Lab Co Ltd | Light emitting element |
Non-Patent Citations (2)
| Title |
|---|
| ZHIGUOYIN 等: "N1,N1,N3,N3-tetra([1,1′-biphenyl]-4-yl)-N5,N5-diphenylbenzene-1,3,5-triamine: Synthesis, optical properties and application in OLED devices as efficient hole transporting material", 《DYES AND PIGMENTS》 * |
| 王俊杰: "新型三苯胺类空穴传输材料的合成与应用", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335362A (en) * | 2020-09-30 | 2022-04-12 | 江苏三月科技股份有限公司 | Composition for OLED and organic electroluminescent device |
| CN114335364A (en) * | 2020-09-30 | 2022-04-12 | 江苏三月科技股份有限公司 | Composition for organic electroluminescent device and organic electroluminescent device |
| CN114335362B (en) * | 2020-09-30 | 2024-02-13 | 江苏三月科技股份有限公司 | OLED (organic light emitting diode) composition and organic electroluminescent device |
| CN114335364B (en) * | 2020-09-30 | 2024-03-22 | 江苏三月科技股份有限公司 | Composition for organic electroluminescent device and organic electroluminescent device |
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