CN114249741A - Organic electroluminescent compound and application thereof - Google Patents

Organic electroluminescent compound and application thereof Download PDF

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CN114249741A
CN114249741A CN202111503724.4A CN202111503724A CN114249741A CN 114249741 A CN114249741 A CN 114249741A CN 202111503724 A CN202111503724 A CN 202111503724A CN 114249741 A CN114249741 A CN 114249741A
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organic electroluminescent
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任凯庆
蒋瑞
梁琴
蔡萌萌
朱世俊
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EverDisplay Optronics Shanghai Co Ltd
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Abstract

The first aspect of the invention provides an organic electroluminescent compound, the structure of which is shown in formula (I); wherein X is selected from O or S; a. the1‑A2Each independently selected from substituted or unsubstituted C6‑C60Aryl or substituted or unsubstituted C3‑C60The heteroaryl group of (a); ar (Ar)1And Ar2Each independently selected from substituted or unsubstituted C6‑C60Aryl or substituted or unsubstituted C3‑C60The heteroaryl group of (a). The organic electroluminescent compounds according to the inventionIs a benzo heterocyclic pyrazine derivative, such as a benzofuran/thiophene pyrazine structure, which has good electron withdrawing ability, and forms a structure with electron donating groups and electron withdrawing groups by combining with a triarylamine structure with electron donating ability. In addition, the organic electroluminescent compound contains a stable multi-ring structure, so that the stability of the material is greatly improved, the glass transition temperature of the material is improved due to the larger molecular weight, and the material is prevented from being decomposed after long-time evaporation.

Description

Organic electroluminescent compound and application thereof
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic electroluminescent compound and application thereof.
Background
Organic Electroluminescence (EL) is self-luminous, and by applying an electric field, holes injected from an anode and electrons injected from a cathode are recombined to emit light. Organic Light Emitting Diodes (OLEDs) have excellent display characteristics and qualities such as self-luminescence, wide viewing angle, high efficiency, wide color gamut, flexible display, etc., compared to conventional LCDs, and thus the OLEDs have become a new generation of mainstream flat panel displays.
OLED device structures generally include an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode. Therefore, the OLED functional material with high performance is selected and reasonably matched, and the material system is continuously subjected to iterative upgrade, so that the comprehensive characteristics of high efficiency, long service life and low voltage of the device are exerted. The organic light-emitting material should have the following characteristics: the fluorescent material has high-efficiency fluorescence in a visible light region, high conductivity and good semiconductor characteristics; has good film forming property, and the formed film has better uniformity and the like.
Disclosure of Invention
The invention aims to provide an organic electroluminescent compound and application thereof aiming at the defects in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
the first aspect of the present invention provides an organic electroluminescent compound, wherein the structure of the organic electroluminescent compound is represented by formula (I):
Figure BDA0003402629770000011
wherein X is selected from O or S; a. the1-A2Each independently selected from substituted or unsubstituted C6-C60Aryl or substituted or unsubstituted C3-C60The heteroaryl group of (a); ar (Ar)1And Ar2Each independently selected from substituted or unsubstituted C6-C60Aryl or substituted or unsubstituted C3-C60The heteroaryl group of (a).
Preferably, the organic electroluminescent compound is selected from:
Figure BDA0003402629770000021
Figure BDA0003402629770000031
Figure BDA0003402629770000041
Figure BDA0003402629770000051
Figure BDA0003402629770000061
a second aspect of the present invention provides an organic electroluminescent material comprising: the organic electroluminescent compounds as described above.
A third aspect of the present invention provides an organic electroluminescent layer, the host material comprising: an organic electroluminescent material as described above.
A fourth aspect of the present invention provides an organic electroluminescent device comprising: an organic electroluminescent layer as described above.
Preferably, the method further comprises the following steps: an anode layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer and an anode layer; the organic electroluminescent layer is located between the hole transport layer and the electron transport layer.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
the organic electroluminescent compound is benzo heterocyclic pyrazine derivative, such as benzofuran/thiophene pyrazine structure, which has good electron withdrawing capability, and is combined with triarylamine structure with electron donating capability to form a structure with electron donating group-electron withdrawing group. In addition, the organic electroluminescent compound contains a stable multi-ring structure, so that the stability of the material is greatly improved, the glass transition temperature of the material is improved due to the larger molecular weight, and the material is prevented from being decomposed after long-time evaporation. Meanwhile, the organic electroluminescent compound has simple synthesis method and fewer process steps. The organic electroluminescent compound has good application effect in OLED devices and good industrialization prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1
This example provides a method for preparing compound 3, comprising the steps of:
Figure BDA0003402629770000071
2.0g of 2-bromobenzofuran [2,3-b ] pyrazine, 5.4g of starting material A, 5.0g of potassium carbonate and 0.5g of palladium tetratriphenylphosphine were added in this order to a mixed solution of 300mL of toluene and 150mL of water. Refluxing under argon for 48 hours, cooling to room temperature, extracting, passing through a column, recrystallizing, sublimating, etc. to obtain 2.3g of compound 3. Mass spectrum m/z: a theoretical value of 603.23; found 603.08.
Example 2
This example provides a method of preparing compound 12, comprising the steps of:
Figure BDA0003402629770000081
2.0g of 2-bromobenzofuran [2,3-B ] pyrazine, 5.7g of starting material B, 5.0g of potassium carbonate and 0.5g of palladium tetratriphenylphosphine were added to a mixed solution of 300mL of toluene and 150mL of water, respectively. Refluxing under argon for 48 hours, cooling to room temperature, extracting, passing through a column, recrystallizing, sublimating, etc. to obtain 2.4g of compound 12. Mass spectrum m/z: a theoretical value of 613.22; found 613.09.
Detection examples
This test example provides test data for compound 3 and compound 12 as shown in the following table:
TABLE 1
Compound (I) T1(eV) Tg(℃) Td(℃) HOMO energy level(eV)
Compound 3 2.72 117 397 -5.73
Compound 12 2.87 120 395 -5.64
Wherein the triplet state energy level T1Is tested by an F4600 fluorescence spectrometer of Hitachi, and the testing condition of the material is that the molar concentration is 2 multiplied by 10-5A toluene solution of mol/L; 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 table 1, the compound of the present invention has a high triplet level, a high thermal stability, and a suitable HOMO level, and is suitable for use as a light emitting layer material.
Application examples
The application embodiment provides an organic electroluminescent device, the structure of which sequentially comprises: transparent substrate layer, anode layer, hole injection layer, hole transport layer, organic electroluminescent layer, electron transport layer/hole blocking layer, electron injection layer, cathode layer.
The transparent substrate layer may use a substrate in a conventional organic electroluminescent device, for example: glass or plastic. The anode layer may be transparent and have high conductivityMaterials such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO)2) Zinc oxide (ZnO), and the like. In the fabrication of the organic electroluminescent device according to the embodiment, glass is used as the substrate, and ITO is used as the anode material.
The hole transport region may be a single layer structure formed of a single material, a single layer structure formed of a plurality of different materials, or a multilayer structure formed of a plurality of different materials, for example: the hole transport region may have a single-layer structure formed of different materials, or may have a structure of a hole injection layer/a hole transport layer, or a structure of a hole injection layer/a hole transport layer/a buffer layer, and the hole transport layer may be formed of a triarylamine-based material such as N, N ' -bis (3-tolyl) -N, N ' -diphenyl- [1, 1-biphenyl ] -4,4' -diamine (TPD) or N, N ' -diphenyl-N, N ' -bis (1-naphthyl) - (1,1' -biphenyl) -4,4' -diamine (NPB). NPB is selected as the hole transport material in the fabrication of the organic electroluminescent device according to the present application example.
The organic electroluminescent device structure can be a single light-emitting layer or a multi-light-emitting layer structure. In the present embodiment, a single light emitting layer structure is adopted. In this application embodiment, the light-emitting layer of the organic electroluminescent device includes a host material and a dopant material. The host material is composed of the compound as described above; the doping material is BD, and the mass doping concentration of the doping material is 3% -30%; among them, the mass doping concentration of the doping material in the light-emitting layer is preferably 5% to 15%. The compounds described above can also be used as doping materials for the light-emitting layer.
The electron transport region includes one or more of a hole blocking layer, an electron transport layer, and an electron injection layer, for example: the electron transport region may have a structure of an electron transport layer/an electron injection layer, a structure of a hole blocking layer/an electron transport layer/an electron injection layer, but is not limited thereto; the electron transport layer may be Alq3Or TPBi or the two are matched at the same time.
LiF/Al is selected as a cathode material in the preparation of the organic electroluminescent device of the application embodiment.
The specific structural formula of the material is as follows:
Figure BDA0003402629770000101
the preparation method comprises the following specific steps:
cleaning an ITO anode layer on a transparent glass substrate layer, carrying out ultrasonic cleaning for 15 minutes by sequentially adopting deionized water, acetone and ethanol, and then treating for 2 minutes in a plasma cleaner; evaporating HAT-CN with the film thickness of 10nm, wherein the layer is a hole injection layer; evaporating NPB with the film thickness of 50nm, wherein the layer is used as a hole transport layer; deposition of a light-emitting layer with a film thickness of 40 nm: the compound as described above as a host material and BD as a dopant material, with a dopant concentration of 6%; evaporating TPBi, wherein the film thickness is 35nm, and the layer is used as a hole blocking/electron transporting layer; evaporating LiF to form a film with the thickness of 1nm, wherein the layer is used as an electron injection layer; al was deposited to a film thickness of 80nm, and this layer was used as a cathode layer.
The results of the performance test of each organic electroluminescent device are shown in the following table:
TABLE 2
Figure BDA0003402629770000102
Figure BDA0003402629770000111
Wherein, the device test performance is compared with that of the comparative example, and the current efficiency is 10mA/cm2Measured under the condition; the life test system is an OLED device life tester of MODEL MODEL 58131 of Chroma.
From the above device data, it can be seen that the compounds of the present invention can be applied to the fabrication of OLED light emitting devices. Compared with the known materials, the organic electroluminescent compound can be used as a main material of a light-emitting layer to be applied to the manufacture of OLED light-emitting devices. Compared with the comparative example, the OLED material has the advantages that the efficiency and the service life are greatly improved compared with the known OLED material, and particularly the driving service life of the device is greatly prolonged.
In summary, the organic electroluminescent compounds of the present invention are benzo-heterocycle pyrazine derivatives, such as benzofuran/thiophene pyrazine structures, which have good electron withdrawing ability, and are combined with triarylamine structures having electron donating ability to form structures having electron donating group-electron withdrawing group. In addition, the organic electroluminescent compound contains a stable multi-ring structure, so that the stability of the material is greatly improved, the glass transition temperature of the material is improved due to the larger molecular weight, and the material is prevented from being decomposed after long-time evaporation. Meanwhile, the organic electroluminescent compound has simple synthesis method and fewer process steps. The organic electroluminescent compound has good application effect in OLED devices and good industrialization prospect.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.

Claims (6)

1. An organic electroluminescent compound, wherein the structure of the organic electroluminescent compound is represented by formula (I):
Figure FDA0003402629760000011
wherein X is selected from O or S; a. the1-A2Each independently selected from substituted or unsubstituted C6-C60Aryl or substituted or unsubstituted C3-C60The heteroaryl group of (a); ar (Ar)1And Ar2Each independently selected from substituted or unsubstituted C6-C60Aryl or substituted or unsubstituted C3-C60The heteroaryl group of (a).
2. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound is selected from the group consisting of:
Figure FDA0003402629760000012
Figure FDA0003402629760000021
Figure FDA0003402629760000031
Figure FDA0003402629760000041
Figure FDA0003402629760000051
Figure FDA0003402629760000061
3. an organic electroluminescent material, comprising: the organic electroluminescent compound as claimed in any one of claims 1 to 2.
4. An organic electroluminescent layer, wherein the host material comprises: the organic electroluminescent material as claimed in claim 3.
5. An organic electroluminescent device, comprising: the organic electroluminescent layer as claimed in claim 4.
6. The organic electroluminescent device according to claim 5, further comprising: an anode layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer and an anode layer; the organic electroluminescent layer is located between the hole transport layer and the electron transport layer.
CN202111503724.4A 2021-12-09 2021-12-09 Organic electroluminescent compound and application thereof Pending CN114249741A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105884786A (en) * 2016-05-13 2016-08-24 苏州大学 Benzofuran [2,3-b ] pyrazine derivative and application thereof in organic electroluminescent device
CN110467630A (en) * 2019-07-26 2019-11-19 浙江华显光电科技有限公司 A kind of phosphorescent compound and the organic light emitting diode device using the compound
KR20190140586A (en) * 2018-06-12 2019-12-20 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
CN112514101A (en) * 2018-08-03 2021-03-16 株式会社半导体能源研究所 Light-emitting element, light-emitting device, electronic device, and lighting device
CN113121364A (en) * 2019-12-31 2021-07-16 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, organic electroluminescent device, and electronic device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105884786A (en) * 2016-05-13 2016-08-24 苏州大学 Benzofuran [2,3-b ] pyrazine derivative and application thereof in organic electroluminescent device
KR20190140586A (en) * 2018-06-12 2019-12-20 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
CN112514101A (en) * 2018-08-03 2021-03-16 株式会社半导体能源研究所 Light-emitting element, light-emitting device, electronic device, and lighting device
CN110467630A (en) * 2019-07-26 2019-11-19 浙江华显光电科技有限公司 A kind of phosphorescent compound and the organic light emitting diode device using the compound
CN113121364A (en) * 2019-12-31 2021-07-16 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, organic electroluminescent device, and electronic device

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