阅读说明：本技术 一种有机电致发光化合物及有机电致发光器件 (Organic electroluminescent compound and organic electroluminescent device ) 是由 钱超 许军 于 2020-06-29 设计创作，主要内容包括：本发明公开了一种有机电致发光化合物及有机电致发光器件,其结构式如下式1所示：<Image he="505" wi="664" file="DDA0002558856860000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,m、n、p相同或不同,各自独立的为0或1,且m+n+p＝1；苯环A与苯环B通过单键连接或不通过单键连接；Ar1、Ar2、Ar3、Ar4、Ar5、Ar6为式2所示：<Image he="277" wi="408" file="DDA0002558856860000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>R为取代或未取代的C6-C60的芳基、或者取代或未取代的C6-C60的杂芳基；q为0或1；L为亚苯基或亚萘基,将本发明有机电致发光化合物作为发光层材料使用应用于有机电致发光器件中,所制备的有机电致发光器件使用寿命得到很大程度提升,所以具有很广阔的应用前景。(The invention discloses an organic electroluminescent compound and an organic electroluminescent device, and the structural formula of the organic electroluminescent compound is shown as the following formula 1: wherein m, n, p are the same or different and are each independently 0 or 1, and m + n + p is 1; the benzene ring A and the benzene ring B are connected through a single bond or not; ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 are shown as formula 2: r is substituted or unsubstituted aryl of C6-C60, or substituted or unsubstituted heteroaryl of C6-C60; q is 0 or 1; l is phenylene or naphthylene, the organic electroluminescent compound is used as a luminescent layer material and applied to an organic electroluminescent device, and the service life of the prepared organic electroluminescent device is greatly prolonged, so that the organic electroluminescent device has a wide application prospect.)

1. An organic electroluminescent compound, characterized in that its structural formula is shown in formula 1 below:

wherein m, n, p are the same or different and are each independently 0 or 1, and m + n + p is 1;

the benzene ring A and the benzene ring B are connected through a single bond or not;

ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 are shown as formula 2:

r is substituted or unsubstituted aryl of C6-C60, or substituted or unsubstituted heteroaryl of C6-C60;

q is 0 or 1;

l is phenylene or naphthylene.

2. The organic electroluminescent compound according to claim 1, wherein n and p are 0 when the benzene ring A and the benzene ring B are not connected by a single bond.

3. The organic electroluminescent compound according to claim 1, wherein L is a phenylene group.

4. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound is any one of the structural formulae represented by the following formula (3) to formula (10):

5. the organic electroluminescent compound according to claim 1, wherein R is a substituted or unsubstituted aryl group of C6 to C30, or a substituted or unsubstituted heteroaryl group of C6 to C30.

6. The organic electroluminescent compound according to claim 1, wherein R is a phenyl group, a biphenyl group, a terphenyl group, an anthracenyl group, a naphthyl group, a phenanthryl group, an oxyfluorenyl group, a thiofluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a fluorenyl group, a 9, 9-dimethylfluorenyl group, a 9, 9-diphenylfluorenyl group, a 9-methyl-9-phenylfluorenyl group, a 9,9' -spirobifluorenyl group;

the phenyl, the biphenyl, the terphenyl, the anthryl, the naphthyl, the phenanthryl, the oxyfluorenyl, the thiofluorenyl, the carbazolyl, the N-phenylcarbazolyl, the fluorenyl, the 9, 9-dimethylfluorenyl, the 9, 9-diphenylfluorenyl, the 9-methyl-9-phenylfluorenyl and the 9,9' -spirobifluorenyl are substituted or unsubstituted by at least one hydrogen of deuterium, a halogen atom, a cyano group, a methoxy group, a linear or branched alkyl group of C1-C4, a deuterated linear or branched alkyl group of C1-C4, a cycloalkyl group of C1-C10, a deuterated cycloalkyl group of C1-C10, a phenyl group, a deuterated phenyl group, a biphenyl group and a deuterated biphenyl group;

and/or

Wherein at least one carbon is substituted or unsubstituted with nitrogen.

7. The organic electroluminescent compound of claim 1, wherein R is one of the substituents of the following formulae:

8. the organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound is one of the following compounds:

9. an organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, the organic layer comprising a light-emitting layer, the organic layer containing the organic electroluminescent compound according to any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, wherein the first electrode is an anode, the second electrode is a cathode, and the organic layer comprises at least one selected from the group consisting of:

i) a hole transport region including at least one selected from a hole injection layer, a hole transport layer, a buffer layer, and an electron blocking layer between the first electrode and the light emitting layer; and

ii) an electron transport region comprising at least one layer selected from the group consisting of an electron transport layer, a hole blocking layer, and an electron injection layer between the light emitting layer and the second electrode;

wherein the hole transport layer comprises the organic electroluminescent compound according to any one of claims 1 to 8;

and/or the buffer layer comprises the organic electroluminescent compound of any one of claims 1 to 8;

and/or the electron blocking layer comprises the organic electroluminescent compound according to any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to an organic electroluminescent compound and an organic electroluminescent device.

Background

Organic Light-emitting Devices (OLEDs) are spontaneous Light-emitting Devices that utilize the following principle: when an electric field is applied, the fluorescent substance emits light by recombination of holes injected from the positive electrode and electrons injected from the negative electrode. The self-luminous device has the characteristics of low voltage, high brightness, wide viewing angle, quick response, good temperature adaptability and the like, is ultrathin, can be manufactured on a flexible panel and the like, and is widely applied to the fields of mobile phones, tablet computers, televisions, illumination and the like.

The organic electroluminescent device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers or recommended by a user, and the different functional materials are mutually overlapped together according to the purpose to form the organic electroluminescent device. When the organic electroluminescent device is used as a current device, voltage is applied to two end electrodes of the organic electroluminescent device, positive and negative charges are generated in the organic layer functional material film layer under the action of an electric field, the positive and negative charges are further compounded in the light emitting layer to generate light, and the process is electroluminescence.

The research on the improvement of the performance of the organic electroluminescent device 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 organic electroluminescent device, not only the innovation of the structure and the manufacturing process of the organic electroluminescent device is required, but also the continuous research and innovation of the organic electro-photoelectric functional material are required, and the organic electroluminescent functional material with higher performance is created.

In terms of the actual demand of the current organic electroluminescent industry, the development of the current organic electroluminescent materials is far from enough and lags behind the requirements of panel manufacturing enterprises.

Disclosure of Invention

The purpose of the invention is as follows: in view of the above technical problems, the present invention provides an organic electroluminescent compound and an organic electroluminescent device.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:

an organic electroluminescent compound having a structural formula as shown in formula 1 below:

wherein m, n, p are the same or different and are each independently 0 or 1, and m + n + p is 1;

the benzene ring A and the benzene ring B are connected through a single bond or not;

ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 are shown as formula 2:

r is substituted or unsubstituted aryl of C6-C60, or substituted or unsubstituted heteroaryl of C6-C60;

q is 0 or 1;

l is phenylene or naphthylene.

Further, when the benzene ring A and the benzene ring B are not connected by a single bond, n and p are both 0.

Further, L is phenylene.

Further, it is any of structural formulae represented by the following formulae (3) to (10):

further, R is substituted or unsubstituted aryl of C6-C30, or substituted or unsubstituted heteroaryl of C6-C30.

Further, R is phenyl, biphenyl, terphenyl, anthracenyl, naphthyl, phenanthryl, oxyfluorenyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl;

the phenyl, the biphenyl, the terphenyl, the anthryl, the naphthyl, the phenanthryl, the oxyfluorenyl, the dibenzofluorenyl, the carbazolyl, the N-phenylcarbazolyl, the fluorenyl, the 9, 9-dimethylfluorenyl, the 9, 9-diphenylfluorenyl, the 9-methyl-9-phenylfluorenyl and the 9,9' -spirobifluorenyl are substituted or unsubstituted by deuterium, a halogen atom, a cyano group, a methoxy group, a C1-C4 linear or branched alkyl group, a C1-C4 deuterated linear or branched alkyl group, a C1-C10 cycloalkyl group, a C1-C10 deuterated cycloalkyl group, a phenyl group, a deuterated phenyl group, the biphenyl group and the deuterated biphenyl group

And/or

Wherein at least one carbon is substituted or unsubstituted with nitrogen.

Further, R is one of the following structural formula substituents:

further, the organic electroluminescent compound is one of the following compounds:

an organic electroluminescent device comprising a first electrode, a second electrode and an organic layer formed between the first electrode and the second electrode, the organic layer comprising a light-emitting layer, the organic layer containing the above organic electroluminescent compound.

Further, the first electrode is an anode, the second electrode is a cathode, and the organic layer comprises at least one selected from the group consisting of:

i) a hole transport region including at least one selected from a hole injection layer, a hole transport layer, a buffer layer, and an electron blocking layer between the first electrode and the light emitting layer; and

ii) an electron transport region comprising at least one layer selected from the group consisting of an electron transport layer, a hole blocking layer, and an electron injection layer between the light emitting layer and the second electrode;

wherein the hole transport layer comprises the above organic electroluminescent compound;

and/or, the buffer layer comprises the organic electroluminescent compound;

and/or the electron blocking layer comprises the organic electroluminescent compound.

One embodiment of the organic electroluminescent device provided by the invention is as follows:

the organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode.

Wherein the hole transport layer and/or the electron blocking layer is/are the organic electroluminescent compound.

Another embodiment of the organic electroluminescent device provided by the present invention is:

the organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, a buffer layer, an electron blocking layer, a luminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode.

Wherein the hole transport layer and/or the buffer layer and/or the electron blocking layer are/is the organic electroluminescent compound.

The room temperature of the invention is 25 +/-5 ℃.

The invention has the beneficial effects that:

the organic electroluminescent compound designed by the invention is shown as a formula I, a 1,1 dimethyl indane structure indicated by an arrow a is introduced into a group of spirobifluorene or diphenylfluorene, the introduction of the structure greatly improves the hole mobility of the material, simultaneously reduces the HOMO energy level of the material, further improves the luminous efficiency and the service life of an organic electroluminescent device prepared by using the material, and greatly reduces the driving voltage of the device due to the reduction of the HOMO energy level and the improvement of the mobility.

Drawings

Fig. 1 is a schematic structural diagram of an organic electroluminescent device provided by the present invention;

the reference numbers in the figures represent respectively:

1-anode, 2-hole injection layer, 3-hole transport layer, 4-electron blocking layer, 5-luminescent layer, 6-hole blocking layer, 7-electron transport layer, 8-electron injection layer and 9-cathode.

FIG. 2 is a schematic structural diagram of another organic electroluminescent device provided by the present invention;

the reference numbers in the figures represent respectively:

10-anode, 11-hole injection layer, 12-hole transport layer, 13-buffer layer, 14-electron barrier layer, 15-luminescent layer, 16-hole barrier layer, 17-electron transport layer, 18-electron injection layer and 19-cathode.

FIG. 3 is a nuclear magnetic hydrogen spectrum of organic electroluminescent compound 1 prepared in example 1 of the present invention;

fig. 4 is a DSC chart of the organic electroluminescent compound 1 prepared in example 1 of the present invention, and it can be seen from fig. 4 that the Tm value of the organic electroluminescent compound 1 is 286.54 ℃.

FIG. 5 is an HPLC chromatogram of organic electroluminescent compound 1 prepared in example 1 of the present invention;

fig. 6 is a TGA spectrum of the organic electroluminescent compound 1 prepared in example 1 of the present invention, and it can be seen from fig. 6 that Td of the organic electroluminescent compound 1 is 458.62 ℃.

Fig. 7 is a HOMO map of organic electroluminescent compound 1 prepared in example 1 of the present invention, and it can be seen from fig. 7 that the HOMO value of organic electroluminescent compound 1 is 5.50 eV.

FIG. 8 is a graph showing the life of organic electroluminescent devices in application example 1 and comparative example 1 of the present invention;

as can be seen from fig. 8, T97% lifetimes of the organic electroluminescent devices prepared in application example 1 and comparative example 1 of the present invention were 155h and 89h, respectively.

FIG. 9 is a graph showing the life of organic electroluminescent devices in application example 1 and comparative example 1 of the present invention;

as can be seen from fig. 9, T97% lifetimes of the organic electroluminescent devices prepared in application example 26 and comparative example 3 of the present invention were 496h and 382h, respectively.

FIG. 10 is a graph showing the life of organic electroluminescent devices in application example 1 and comparative example 1 of the present invention;

as can be seen from fig. 10, T97% lifetimes of the organic electroluminescent devices prepared in application example 33 of the present invention and comparative example 5 were 313h and 251h, respectively.

Detailed Description

Embodiments of the various aspects are further illustrated and described below. It should be understood that the description herein is not intended to limit the claims to the particular aspects described. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the disclosure as defined by the appended claims.

As used herein, a "Ca to Cb" hydrocarbyl group is defined as a hydrocarbyl group having a carbon number of "a" (inclusive) to "b" (inclusive). As used herein, "a and/or b" means "a" or "b" or "a and b".

As used herein, in "substituted" or "unsubstituted," the term "substituted" means that at least one hydrogen in the group is re-coordinated to deuterium, a hydrocarbon group, a hydrocarbon derivative group, a halogen, or a cyano (-CN). The term "unsubstituted" means that at least one hydrogen in the group does not re-coordinate with deuterium, a hydrocarbon group, a hydrocarbon derivative group, a halogen, or a cyano (-CN) group. Examples of the hydrocarbon group or hydrocarbon derivative group may include C1 to C30 alkyl groups, C2 to C30 alkenyl groups, C2 to C30 alkynyl groups, C6 to C30 aryl groups, C5 to C30 heteroaryl groups, C1 to C30 alkylamino groups, C6 to C30 arylamino groups, C6 to C30 heteroarylamino groups, C6 to C30 arylheteroarylamino groups, and the like, but are not limited thereto.