Organic compound with fluorene as core and application thereof in organic electroluminescent device
阅读说明：本技术 一种以芴为核心的有机化合物及其在有机电致发光器件上的应用 (Organic compound with fluorene as core and application thereof in organic electroluminescent device ) 是由 赵四杰 张兆超 唐丹丹 谢丹丹 于 2019-03-28 设计创作，主要内容包括：本发明公开了一种以芴为核心的有机化合物及其在有机电致发光器件上的应用,该有机化合物的结构如通式(I)所示。本发明有机化合物具有较高的玻璃化温度和分子热稳定性,合适的HOMO和LUMO能级,作为电子阻挡层材料或发光层材料应用于有机发光二极管,可有效降低高电流密度下的效率滚降,降低器件电压,提高器件的电流效率和寿命。<Image he="573" wi="692" file="DDA0002010477510000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses an organic compound taking fluorene as a core and application thereof in an organic electroluminescent device. The organic compound has higher glass transition temperature and molecular thermal stability, and proper HOMO and LUMO energy levels, is used as an electron blocking layer material or a light-emitting layer material to be applied to an organic light-emitting diode, can effectively reduce the efficiency roll-off under high current density, reduce the voltage of a device, improve the current efficiency of the device and prolong the service life of the device.)
1. An organic compound with fluorene as a core is characterized in that the structure of the compound is shown as a general formula (I):
wherein the content of the first and second substances,
m and n are respectively and independently 0, 1, 2, 3 or 4, and m + n is more than or equal to 1;
Ar1、Ar2each independently represents substituted or unsubstituted C6-30One of arylene, substituted or unsubstituted 5-30 membered heteroarylene containing one or more heteroatoms;
R1、R2each independently represents hydrogen or a structure represented by the general formula (II), and R1、R2Not hydrogen at the same time;
in the general formula (II), R5、R6Each independently represents a hydrogen atom, a structure represented by the general formula (III), the general formula (IV) or the general formula (V), and R5、R6Not hydrogen at the same time;
in the general formula (IV) and the general formula (V), X1、X2、X3Each independently represents an oxygen atom, a sulfur atom, a selenium atom, -C (R)11)(R12)-、-N(R13) -or-Si (R)14)(R15)-；X2May also represent a single bond;
R11～R15each independently is represented by C1-10Alkyl, substituted or unsubstituted C6-30One of aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms; r11And R12、R14And R15May be bonded to each other to form a ring;
general formula (III), general formula (IV) or general formula (V) by CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL'1-CL'2Key, CL'2-CL'3Bond or CL'3-CL'4Is connected with a parallel ring of the general formula (II);
R3、R4independently represent hydrogen, halogen, cyano, C1-30Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms, structures of formula (III), formula (IV), and R3、R4Not hydrogen at the same time;
when R is3、R4Represented by the structure shown in the general formula (III) or the general formula (IV), wherein the general formula (III) or the general formula (IV) is connected with two adjacent positions marked by the symbol in the general formula (I) in a ring-merging mode through the two adjacent positions marked by the symbol;
the substituent of the substitutable group is selected from cyano, halogen and C1-10Alkyl radical, C6-30One or more of aryl and 5-30 membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
2. The organic compound of claim 1, wherein Ar is Ar1、Ar2Each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene groupAny one of a phenyl group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrenylene group, a substituted or unsubstituted pyridinylene group, a substituted or unsubstituted naphthyridinylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted dibenzothiophenylene group;
the R is11～R15Each independently represents any one of methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, biphenyl, naphthyl, pyridyl, naphthyridinyl or dibenzofuranyl;
the substituent of the substitutable group is one or more selected from methyl, ethyl, propyl, isopropyl, tertiary butyl, amyl, phenyl, biphenyl, naphthyl, pyridyl, naphthyridinyl or dibenzofuranyl.
3. The organic compound of claim 1, wherein the structure of formula (II) is:
4. The compound of claim 1, wherein the compound has the specific formula:
any one of the above.
5. An organic electroluminescent device comprising at least one functional layer containing the fluorene-based organic compound according to any one of claims 1 to 4.
6. An organic electroluminescent device comprising an electron blocking layer, wherein the electron blocking layer contains the fluorene-based organic compound according to any one of claims 1 to 4.
7. An organic electroluminescent device comprising a light-emitting layer, wherein the light-emitting layer contains the fluorene-based organic compound according to any one of claims 1 to 4.
8. A lighting or display element, characterized in that the element comprises an organic electroluminescent device according to any one of claims 5 to 7.
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic compound taking fluorene as a core and application thereof in an organic electroluminescent device.
Background
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 present applicant provides an organic compound with fluorene as a core and an application thereof in an organic electroluminescent device. The compound takes fluorene as a core, is used as an electron barrier layer material or a luminescent layer material to be applied to an organic light-emitting diode, can effectively reduce the efficiency roll-off under high current density, reduce the voltage of a device, improve the current efficiency of the device and prolong the service life of the device.
The technical scheme for solving the technical problems is as follows:
an organic compound with fluorene as a core is characterized in that the structure of the compound is shown as a general formula (I):
wherein the content of the first and second substances,
m and n are respectively and independently 0, 1, 2, 3 or 4, and m + n is more than or equal to 1;
Ar1、Ar2each independently represents substituted or unsubstituted C6-30One of arylene, substituted or unsubstituted 5-30 membered heteroarylene containing one or more heteroatoms;
R1、R2each independently represents hydrogen or a structure represented by the general formula (II), and R1、R2Not hydrogen at the same time;
in the general formula (II), R5、R6Each independently represents a hydrogen atom, a structure represented by the general formula (III), the general formula (IV) or the general formula (V), and R5、R6Not hydrogen at the same time;
in the general formula (IV) and the general formula (V), X1、X2、X3Each independently represents an oxygen atom, a sulfur atom, a selenium atom, -C (R)11)(R12)-、-N(R13) -or-Si (R)14)(R15)-；X2May also represent a single bond;
R11～R15each independently is represented by C1-10Alkyl, substituted or unsubstituted C6-30One of aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms; r11And R12、R14And R15May be bonded to each other to form a ring;
general formula (III), general formula (IV) or general formula (V) by CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL'1-CL'2Key, CL'2-CL'3Bond or CL'3-CL'4Is connected with a parallel ring of the general formula (II);
R3、R4independently represent hydrogen, halogen, cyano, C1-30Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms, structures of formula (III), formula (IV), and R3、R4Not hydrogen at the same time;
when R is3、R4Represented by the structure shown in the general formula (III) or the general formula (IV), wherein the general formula (III) or the general formula (IV) is connected with two adjacent positions marked by the symbol in the general formula (I) in a ring-merging mode through the two adjacent positions marked by the symbol;
the substituent of the substitutable group is selected from cyano, halogen and C1-10Alkyl radical, C6-30One or more of aryl and 5-30 membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
Further, Ar is1、Ar2Each independently represents any one of a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted naphtylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted dibenzothiophenylene group;
the R is11～R15Each independently represents any one of methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, biphenyl, naphthyl, pyridyl, naphthyridinyl or dibenzofuranyl;
the substituent of the substitutable group is one or more selected from methyl, ethyl, propyl, isopropyl, tertiary butyl, amyl, phenyl, biphenyl, naphthyl, pyridyl, naphthyridinyl or dibenzofuranyl.
Further, the structure of the general formula (II) is:
one kind of (1). Further, the specific structural formula of the compound is:
any one of the above.
An organic electroluminescent device comprising at least one functional layer containing said fluorene-based organic compound.
An organic electroluminescent device comprising an electron blocking layer containing the fluorene-based organic compound.
An organic electroluminescent device comprises a light-emitting layer containing the organic compound having fluorene as a core.
A lighting or display element comprising said organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
the organic compound is an organic luminescent functional layer material, has the characteristics of difficult intermolecular crystallization and aggregation and good film forming property, and the rigid group in the organic compound molecule can improve the thermal stability of the material.
The organic compound structure of the invention ensures that the distribution of electrons and holes in the luminous layer is more balanced, and under the proper HOMO energy level, the hole injection/transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, and improves the recombination efficiency of excitons in the luminescent layer; when the fluorene derivative is used as a light-emitting functional layer material of an OLED light-emitting device, aryl or heteroaryl substituted fluorene is adopted to match with a branched chain in the range of the invention, so that the exciton utilization rate and the high fluorescence radiation efficiency can be effectively 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.
The organic compound has good application effect in OLED luminescent devices and good industrialization prospect.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
wherein, 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a luminescent layer, 7 is an electron transport layer, 8 is an electron injection layer, 9 is a cathode reflection electrode layer, and 10 is a light extraction layer.
FIG. 2 shows the current efficiencies of the OLED devices of the embodiment of the present invention and the OLED device of the comparative example 1 at the temperature range of-10 to 80 ℃.
Detailed Description
- 上一篇：一种医用注射器针头装配设备
- 下一篇：一种光稳定剂中间体及其制备方法