CN110577508B - Compound with triarylamine as core and application thereof - Google Patents

Compound with triarylamine as core and application thereof Download PDF

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CN110577508B
CN110577508B CN201810580103.8A CN201810580103A CN110577508B CN 110577508 B CN110577508 B CN 110577508B CN 201810580103 A CN201810580103 A CN 201810580103A CN 110577508 B CN110577508 B CN 110577508B
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triarylamine
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李崇
陈海峰
王芳
张兆超
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention discloses a compound taking triarylamine as a core, a preparation method and application thereof, belonging to the field of semiconductor application, wherein the structure of the organic compound provided by the invention is shown as a general formula (1). The compound provided by the invention has higher glass transition temperature and molecular thermal stability, appropriate HOMO and LUMO energy levels and higher Eg, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through device structure optimization.

Description

Compound with triarylamine as core and application thereof
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a compound taking triarylamine as a core, a preparation method thereof and application thereof in an organic electroluminescent device.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and various different functional materials are mutually overlapped together according to purposes to form the OLED light-emitting device. When voltage is applied to electrodes at two ends of the OLED light-emitting device and positive and negative charges in the organic layer functional material film layer are acted through an electric field, the positive and negative charges are further compounded in the light-emitting layer, and OLED electroluminescence is generated.
Currently, the OLED display technology is already applied in the fields of smart phones, tablet computers, and the like, and is further expanded to the large-size application field of televisions, and the like, but compared with the actual product application requirements, the performance of the OLED device, such as light emitting efficiency, service life, and the like, needs to be further improved. Current research into improving the performance of OLED light emitting devices includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the photoelectric functional material of the OLED are required to create the functional material of the OLED with higher performance.
The photoelectric functional materials of the OLED applied to the OLED device can be divided into two categories from the aspect of application, namely charge injection transmission materials and luminescent materials. Further, the charge injection transport material may be classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the light emitting material may be classified into a host light emitting material and a doping material.
In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, as a host material of a light-emitting layer, good bipolar, appropriate HOMO/LUMO energy level, etc. are required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, the OLED device structure applied in industry comprises a hole injection layer, a hole transmission layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transmission layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transmission material, a light emitting material, an electron transmission material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional material has stronger selectivity, and the performance of the same material in the devices with different structures can be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device and the requirements of different functional film layers and photoelectric characteristics of the OLED device, a more suitable OLED functional material or material combination with higher performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display lighting industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop a higher-performance organic functional material as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the applicant of the present invention provides a triarylamine-based compound and applications thereof. The compound takes triarylamine as a core, has higher glass transition temperature, higher molecular thermal stability, proper HOMO and LUMO energy levels and higher Eg, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through device structure optimization.
The technical scheme of the invention is as follows:
a compound taking triarylamine as a core has a structure shown in a general formula (1):
Figure BDA0001688234790000021
in the general formula (1), X represents-O-, -S-, -C (R)6)(R7) -or-N (R)8)-；
L1Is a single bond, substituted or unsubstituted C6-30One of arylene, 5-30 membered heteroarylene substituted or unsubstituted with one or more heteroatoms; the heteroatom is selected from an oxygen atom, a nitrogen atom or a sulfur atom;
R3、R4、R5each independently representIs substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms; the heteroatom is selected from an oxygen atom, a nitrogen atom or a sulfur atom;
R1、R2each independently represents a hydrogen atom, a halogen, a cyano group, C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms; the R is1、R2Are respectively connected with the structure of the general formula (1) through single bonds or benzo structures;
R6～R8are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms;
a represents the number 0, 1, 2, 3 or 4; b represents the number 0, 1, 2 or 3; c represents a number 2, 3 or 4;
the substituent is halogen, cyano, C1-20Alkyl or C6-20And (4) an aryl group.
Further preferably, L is1Is represented by a single bond, C1-10Alkyl-substituted or unsubstituted phenylene radicals, C1-10Alkyl substituted or unsubstituted naphthylene,C1-10Alkyl-substituted or unsubstituted biphenylene, C1-10Alkyl-substituted or unsubstituted terphenylene, C1-10An alkyl substituted or unsubstituted pyridylene group;
the R is3、R4、R5Each independently represents one of phenyl, biphenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothienyl or carbazolyl, and hydrogen atoms in the phenyl, biphenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothienyl or carbazolyl can be optionally substituted by one or more of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl and cyclohexyl;
a and b are respectively and independently 0, 1 or 2; c represents 2;
the R is1、R2、R6～R8Each independently represents one of a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a phenyl group, a biphenyl group, a terphenyl group, a dibenzofuranyl group, a dibenzothiophenyl group or a carbazolyl group, and the hydrogen atom in the phenyl group, the biphenyl group, the terphenyl group, the naphthyl group, the dibenzofuranyl group, the dibenzothiophenyl group or the carbazolyl group may be optionally substituted by one or more of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group or a cyclohexyl group; the R is1、R2Are respectively connected with the structure of the general formula (1) through single bonds or through a benzene structure.
The structure of the compound is preferably represented by any one of general formula (2) to general formula (6):
Figure BDA0001688234790000031
Figure BDA0001688234790000041
preferred specific structures of the compounds are:
Figure BDA0001688234790000042
Figure BDA0001688234790000051
Figure BDA0001688234790000061
Figure BDA0001688234790000071
Figure BDA0001688234790000081
Figure BDA0001688234790000091
Figure BDA0001688234790000092
any one of them.
A preparation method of a compound taking triarylamine as a core relates to the following reaction formula:
Figure BDA0001688234790000093
the preparation method comprises the following steps:
weighing raw material A and raw material B, dissolving with toluene, and adding Pd2(dba)3Triphenylphosphine, potassium tert-butoxide; reacting the mixed solution of the reactants at the reaction temperature of 90-110 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate M; the dosage of the toluene is 30-50mL of toluene used per gram of the raw material A; the molar ratio of the raw material B to the raw material A is 1: 1.0-1.5; the Pd2(dba)3The molar ratio of the potassium tert-butoxide to the raw material A is 0.006-0.02:1, and the molar ratio of the potassium tert-butoxide to the raw material A is 2.0-3.0: 1; the molar ratio of the triphenylphosphine to the raw material A is 2.0-3.0: 1;
weighing intermediate M and raw material C, dissolving with toluene, and adding Pd2(dba)3Triphenylphosphine, potassium tert-butoxide; reacting the mixed solution of the reactants at the reaction temperature of 90-110 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain a target compound; the dosage of the toluene is 30-50mL of toluene used per gram of the intermediate M; the molar ratio of the raw material C to the intermediate M is 1: 1.0-1.5; the Pd2(dba)3The molar ratio of the potassium tert-butoxide to the intermediate M is 0.006-0.02:1The molar ratio of the monomer M is 2.0-3.0: 1; the molar ratio of the triphenylphosphine to the intermediate M is 2.0-3.0: 1.
An organic electroluminescent device containing the compound is characterized in that a plurality of organic thin film layers are arranged between an anode and a cathode of the organic electroluminescent device, and at least one organic thin film layer contains the compound taking triarylamine as a core.
The hole transport layer material of the organic electroluminescent device is the compound taking triarylamine as the core.
An organic electroluminescent device containing the compound is provided with at least 2 hole transport layers between an anode and a cathode of the organic electroluminescent device, and at least one layer of the hole transport layers contains the compound taking triarylamine as a core.
A display element comprising the organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
(1) the compound is a triarylamine compound, has strong hole transmission capability and high hole mobility, can be used as a hole transmission material, and can improve the efficiency of an organic electroluminescent device at high hole transmission rate; under a proper LUMO energy level, the organic electroluminescent device can play a role in blocking electrons, so that the recombination efficiency of excitons in a light-emitting layer is improved, the efficiency roll-off under high current density is reduced, the voltage of the device is reduced, the current efficiency of the device is improved, and the service life of the device is prolonged.
(2) The compound takes triarylamine as a center, 3 connected branched chains are radial, and after the material is formed into a film, all the branched chains can be mutually crossed to form a film layer with high compactness, so that the service life of a device is prolonged.
(3) When the compound is applied to an OLED device, the structure of the device is optimized, so that high film stability can be kept, the photoelectric property of the OLED device can be effectively improved, and the service life of the OLED device can be effectively prolonged.
(4) The compound provided by the invention has higher glass transition temperature and molecular thermal stability, appropriate HOMO and LUMO energy levels and higher Eg, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through device structure optimization.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
in the figure, 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a first hole transport layer, 5 is a second hole transport layer, 6 is a light emitting layer, 7 is an electron transport layer, 8 is an electron injection layer, and 9 is a cathode reflective electrode layer.
Fig. 2 is a graph of the current efficiency of the device of the present invention as a function of temperature.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1:
synthesis of intermediate M
Figure BDA0001688234790000111
Weighing raw material A and raw material B, dissolving with toluene, and adding Pd2(dba)3Triphenylphosphine and potassium tert-butoxide; reacting the mixed solution of the reactants at the reaction temperature of 90-110 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate M; the dosage of the toluene is 30-50mL of toluene used for each gram of the raw material A; the molar ratio of the raw material B to the raw material A is 1: 1.0-1.5; the Pd2(dba)3The molar ratio of the potassium tert-butoxide to the raw material A is 0.006-0.02:1, and the molar ratio of the potassium tert-butoxide to the raw material A is 2.0-3.0: 1; the molar ratio of the triphenylphosphine to the raw material A is 2.0-3.0: 1;
synthesis example of intermediate M-1:
Figure BDA0001688234790000112
a250 ml three-necked flask was charged with 0.01mol of the raw material A-1, 0.012mol of the raw material B-1, 0.03mol of potassium tert-butoxide, and 1X 10 in a nitrogen atmosphere-4molPd2(dba)3，1×10-4Heating and refluxing tri-tert-butylphosphine and 150ml toluene for 12 hr, sampling the sample, and reacting completely; naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain an intermediate M-1; elemental analysis Structure (molecular formula C)36H27N): theoretical value C, 91.30; h, 5.75; n, 2.96; test values are: c, 91.30; h, 5.75; and N, 2.95. ESI-MS (M/z) (M +): theoretical value is 473.21, found 473.64.
Intermediate M-2 and intermediate M-3 were prepared according to the procedure for the preparation of intermediate M-1 in example 1, using the following substitution of the starting materials as shown in table 1 below:
TABLE 1
Figure BDA0001688234790000113
Figure BDA0001688234790000121
Example 2: synthesis of Compound 1:
Figure BDA0001688234790000122
a250 ml three-necked flask was charged with 0.01mol of intermediate M-1, 0.012mol of raw material C-1, 0.03mol of potassium tert-butoxide, 1X 10 mol under an atmosphere of nitrogen gas-4molPd2(dba)3，1×10-4Heating and refluxing tri-tert-butylphosphine and 150ml toluene for 12 hr, sampling the sample, and reacting completely; naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain a compound 1; elemental analysis Structure (molecular formula C)51H39N): theoretical value C, 91.99; h, 5.90; n, 2.10; test values are: c, 91.99; h, 5.90; n, 2.11. ESI-MS (M/z) (M +): theoretical value is 665.31, found 665.86.
Example 3: synthesis of Compound 5:
Figure BDA0001688234790000131
compound 5 was prepared as in example 2, except that intermediate M-1 was replaced with intermediate M-2 and starting material C-1 was replaced with starting material C-2; elemental analysis Structure (molecular formula C)48H33NO): theoretical value C, 90.11; h, 5.20; n, 2.19; test values are: c, 90.12; h, 5.20; and N, 2.19. ESI-MS (M/z) (M +): theoretical value is 639.26, found 639.64.
Example 4: synthesis of compound 17:
Figure BDA0001688234790000132
compound 17 was prepared as in example 2, except that intermediate M-1 was replaced with intermediate M-2 and starting material C-1 was replaced with starting material C-3; elemental analysis Structure (molecular formula C)55H41N): theoretical value C, 92.27; h, 5.77; n, 1.96; test values are: c, 92.28; h, 5.77; and N, 1.95. ESI-MS (M/z) (M +): theoretical value is 715.32, found 715.75.
Example 5: synthesis of compound 30:
Figure BDA0001688234790000133
compound 30 is prepared as in example 2, except that intermediate M-3 is substituted for intermediate M-1 and starting material C-4 is substituted for starting material C-1; elemental analysis Structure (molecular formula C)52H35NO): theoretical value C, 90.54; h, 5.11; n, 2.03; test values are: c, 90.54; h, 5.11; and N, 2.04. ESI-MS (M/z) (M +): theoretical value is 689.27, found 689.64.
Example 6: synthesis of compound 49:
Figure BDA0001688234790000141
compound 49 was prepared as in example 2, except that the starting material C-1 was replaced with the starting material C-5; elemental analysis Structure (molecular formula C)52H35NS): theoretical value C, 88.48; h, 5.00; n, 1.98; s, 4.54; test values are: c, 88.48; h, 5.00; n, 1.99; and S, 4.53. ESI-MS (M/z) (M +): theoretical value is 705.25, found 705.90.
Example 7: synthesis of compound 63:
Figure BDA0001688234790000142
compound 63 is prepared as in example 2, except that intermediate M-1 is replaced with intermediate M-3 and starting material C-1 is replaced with starting material C-6; elemental analysis Structure (molecular formula C)58H40N2): theoretical value C, 91.07; h, 5.27; n, 3.66; test values are: c, 91.06; h, 5.27; n, 3.67. ESI-MS (M/z) (M +): theoretical value is 764.32, found 764.90.
Example 8: synthesis of compound 75:
Figure BDA0001688234790000143
compound 75 can be prepared as in example 2, except that intermediate M-3 is substituted for intermediate M-1 and starting material C-7 is substituted for starting material C-1; elemental analysis Structure (molecular formula C)56H37NO): theoretical value C, 90.90; h, 5.04; n, 1.89; test values are: c, 90.90; h, 5.04; n, 1.88. ESI-MS (M/z) (M +): theoretical value is 739.29, found 739.88.
Example 9: synthesis of compound 100:
Figure BDA0001688234790000151
compound 100 was prepared as in example 2, except that starting material C-8 was used in place of starting material C-1; elemental analysis Structure (molecular formula C)57H43N): theoretical value C, 92.27; h, 5.84; n, 1.89; test values are: c, 92.28; h, 5.84; n, 1.88. ESI-MS (M/z) (M +): theoretical value is 741.34, found 741.79.
Example 10: synthesis of compound 114:
Figure BDA0001688234790000152
compound 114 was prepared as in example 2, except that the starting material C-1 was replaced with the starting material C-9; elemental analysis Structure (molecular formula C)54H37NO): theoretical value C, 90.60; h, 5.21; n, 1.96; test values are: c, 90.60; h, 5.21; and N, 1.97. ESI-MS (M/z) (M +): theoretical value is 715.29, found 715.78.
Example 11: synthesis of compound 128:
Figure BDA0001688234790000153
compound 128 can be prepared as in example 2, except that intermediate M-1 is replaced with intermediate M-2 and starting material C-1 is replaced with starting material C-10; elemental analysis Structure (molecular formula C)60H42N2): theoretical value C, 91.11; h, 5.35; n, 3.54; test values are: c, 91.12; h, 5.35; and N, 3.53. ESI-MS (M/z) (M +): theoretical value is 790.33, found 790.89.
The organic compound of the present invention is used in a light-emitting device, and can be used as a hole transport layer material. The T1 level, thermal property and HOMO level were measured for compounds 1, 5, 17, 30, 49, 63, 75, 100, 114 and 128 of the present invention, respectively, and the results are shown in table 2.
TABLE 2
Compound (I) T1(ev) Tg(℃) Td(℃) HOMO energy level (ev)
Compound 1 2.59 132 408 -5.58
Compound 5 2.58 132 405 -5.59
Compound 17 2.59 140 400 -5.60
Compound 30 2.60 145 401 -5.61
Compound 49 2.58 144 412 -5.57
Compound 63 2.60 145 405 -5.58
Compound 75 2.59 143 398 -5.61
Compound 100 2.61 140 399 -5.62
Compound 114 2.60 141 410 -5.57
Compound 128 2.59 140 407 -5.60
Note: the triplet state energy level T1 is tested by an F4600 fluorescence spectrometer of Hitachi, and the test condition of the material is 2X 10-5 toluene solution; the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy testing system (IPS3) in an atmospheric environment.
As can be seen from the data in table 2 above, the organic compound of the present invention has a suitable HOMO energy level and can be applied to a hole transport layer, and the organic compound of the present invention using triarylamine as a core has a higher triplet energy level and a higher thermal stability, so that the efficiency and the lifetime of the manufactured OLED device containing the organic compound of the present invention are both improved.
The effect of the synthesized compound of the present invention as a hole transport layer material in a device is explained in detail below by device examples 1 to 20 and device comparative example 1. Device examples 2-20 and device comparative example 1 compared with device example 1, the manufacturing processes of the devices were completely the same, and the same substrate material and electrode material were used, and the film thicknesses of the electrode materials were also kept the same, except that the hole transport layer material in the devices was changed. The device stack structure is shown in table 3, and the performance test results of each device are shown in tables 4 and 5.
Device example 1
Device examples used ITO as the anode, Al as the cathode, GH-1, GH-2 and GD-1 co-doped at a weight ratio of 45:45:10 as the light emitting layer material, HAT-CN as the hole injection layer material, HT-1 as the first hole transport layer material, compound 1 prepared in the examples of the present invention as the second hole transport layer material, ET-1 and Liq as the electron transport layer material, and LiF as the electron injection layer material. The specific manufacturing steps are as follows:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes; b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3; c) evaporating a first hole transport layer material HT-1 on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the first hole transport layer material is 60nm, and the first hole transport layer material is a first hole transport layer 4; d) a second hole transport layer material, namely a compound 1 prepared in the embodiment of the invention, is evaporated on the first hole transport layer 4 in a vacuum evaporation mode, wherein the thickness of the compound is 20nm, and the layer is a second hole transport layer 5; e) a luminescent layer 6 is vapor-plated on the second hole transport layer 5, the main materials are GH-1 and GH-2, the doping materials are GD-1, and the mass ratio of GH-1, GH-2 and GD-1 is 45:45:10, and the thickness is 30 nm; f) evaporating hole blocking/electron transport materials ET-1 and Liq on the light emitting layer 6 in a vacuum evaporation mode, wherein the mass ratio of the hole blocking/electron transport materials ET-1 to Liq is 1:1, the thickness of the hole blocking/electron transport materials ET-1 to Liq is 40nm, and the organic material of the layer is used as an electron transport layer 7; g) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the electron transport layer 7, wherein the electron injection layer is an electron injection layer 8; h) on the electron injection layer 8, cathode Al (100nm) was vacuum-evaporated, and this layer was a cathode reflective electrode layer 9.
After the electroluminescent device was fabricated according to the above procedure, IVL data and light decay life of the device were measured, and the results are shown in table 4. The molecular structural formula of the related material is shown as follows:
Figure BDA0001688234790000171
TABLE 3
Figure BDA0001688234790000181
Figure BDA0001688234790000191
The efficiency and lifetime data for each device example and device comparative example 1 are shown in table 4.
TABLE 4
Figure BDA0001688234790000192
As can be seen from the device data results of table 4, the organic light emitting device of the present invention achieves a greater improvement in both efficiency and lifetime over OLED devices of known materials.
In order to compare the efficiency attenuation conditions of different devices under high current density, the efficiency attenuation coefficient is defined
Figure BDA0001688234790000193
It is shown that the ratio between the difference between the maximum efficiency μ 100 of the device and the maximum efficiency μm of the device at a drive current of 100mA/cm2 and the maximum efficiency,
Figure BDA0001688234790000194
the larger the value, the more serious the efficiency roll-off of the device is, and conversely, the problem that the device rapidly decays under high current density is controlled. The efficiency attenuation coefficients were respectively applied to the device examples 1 to 20 and the device comparative example 1
Figure BDA0001688234790000203
The results of the measurement are shown in Table 5:
TABLE 5
Figure BDA0001688234790000201
From the data in table 5, it can be seen that the organic light emitting device of the present invention can effectively reduce the efficiency roll-off by comparing the efficiency roll-off coefficients of the examples and the comparative examples.
Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency test is carried out on the device examples 1, 13 and 19 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 6 and the figure 2.
TABLE 6
Figure BDA0001688234790000202
As can be seen from the data in table 6 and fig. 2, device examples 1, 13, and 19 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased during the temperature increase process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. A compound with triarylamine as a core is characterized in that the structure of the compound is shown as a general formula (3):
Figure FDA0003259953000000011
in the general formula (3), X represents-O-, -S-, -C (R)6)(R7) -or-N (R)8)-；
L1Represents one of a single bond and phenylene;
the R is3、R4、R5Each independently represents a phenyl group;
R1、R2each independently represents one of a hydrogen atom and a phenyl group; the R is1、R2Are respectively connected with the structure of the general formula (3) through single bonds or benzo structures;
R6～R8each independently represents one of methyl and phenyl;
a represents the number 0, 1, 2, 3 or 4; b represents the number 0, 1, 2 or 3.
2. The compound of claim 1, wherein the specific structure of the compound is:
Figure FDA0003259953000000012
Figure FDA0003259953000000021
Figure FDA0003259953000000031
Figure FDA0003259953000000032
any one of them.
3. An organic electroluminescent element comprising the compound according to any one of claims 1 to 2, wherein a plurality of organic thin film layers are provided between an anode and a cathode of the organic electroluminescent element, and at least one of the organic thin film layers contains the triarylamine-based compound.
4. An organic electroluminescent device comprising the compound according to any one of claims 1 to 2, wherein the hole transport layer material of the organic electroluminescent device is the compound having triarylamine as a core.
5. An organic electroluminescent element comprising the compound according to any one of claims 1 to 2, wherein at least 2 hole transport layers are provided between an anode and a cathode of the organic electroluminescent element, and at least one of the hole transport layers contains the triarylamine-based compound.
6. A display element comprising the organic electroluminescent device according to any one of claims 3 to 5.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101535256A (en) * 2006-11-24 2009-09-16 出光兴产株式会社 Aromatic amine derivative and organic electroluminescent element using same
WO2012091471A2 (en) * 2010-12-28 2012-07-05 덕산하이메탈(주) Compound and organic electronic element using same, and electronic device comprising the organic electronic element
WO2016003225A2 (en) * 2014-07-03 2016-01-07 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using same, and electronic device comprising same
WO2016013816A1 (en) * 2014-07-21 2016-01-28 덕산네오룩스 주식회사 Organic electrical element using compound for organic electrical element, and electronic device thereof
CN105529400A (en) * 2014-10-17 2016-04-27 三星显示有限公司 Organic light-emitting device
WO2016175533A2 (en) * 2015-04-27 2016-11-03 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using same, and electronic device comprising same
WO2016186276A1 (en) * 2015-05-20 2016-11-24 삼성에스디아이 주식회사 Organic compound, organic optoelectronic element, and display device

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102134844B1 (en) * 2013-01-30 2020-07-17 삼성디스플레이 주식회사 Amine-based compound and organic light emitting diode comprising the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101535256A (en) * 2006-11-24 2009-09-16 出光兴产株式会社 Aromatic amine derivative and organic electroluminescent element using same
WO2012091471A2 (en) * 2010-12-28 2012-07-05 덕산하이메탈(주) Compound and organic electronic element using same, and electronic device comprising the organic electronic element
WO2016003225A2 (en) * 2014-07-03 2016-01-07 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using same, and electronic device comprising same
WO2016013816A1 (en) * 2014-07-21 2016-01-28 덕산네오룩스 주식회사 Organic electrical element using compound for organic electrical element, and electronic device thereof
CN105529400A (en) * 2014-10-17 2016-04-27 三星显示有限公司 Organic light-emitting device
WO2016175533A2 (en) * 2015-04-27 2016-11-03 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using same, and electronic device comprising same
WO2016186276A1 (en) * 2015-05-20 2016-11-24 삼성에스디아이 주식회사 Organic compound, organic optoelectronic element, and display device

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