WO2018103746A1

WO2018103746A1 - Carbazole benzene fused ring derivative, polymer, mixture, composition, organic electronic device and preparation method therefor

Info

Publication number: WO2018103746A1
Application number: PCT/CN2017/115310
Authority: WO
Inventors: 胡光; 潘君友
Original assignee: 广州华睿光电材料有限公司
Priority date: 2016-12-08
Filing date: 2017-12-08
Publication date: 2018-06-14
Also published as: CN109790117A

Abstract

Provided is a carbazole benzene fused ring derivative having a general formula as follows: Ar₁ and Ar₂ are independently selected from one of aryl group and heteroaryl group;R₁ and R₂ are independently selected from one of H, D, F, CN, NO₂、CF₃, alkenyl, alkynyl, amine group, acyl, amide group, cyano group, isocyano group, alkoxyl, hydroxyl, carbonyl, sulfuryl, alkyl having 1 to 60 carbon atoms, and cycloalkyl having 3 to 60 carbon atoms, aryl having 6 to 60 carbon atoms, heteroaryl having 3 to 60 carbon atoms, fused aryl having 7 to 60 carbon atoms, and fused heteroaryl having 4 to 60 carbon atoms; Ar₃ and Ar₄ are independently selected from one of aryl having 6 to 60 carbon atoms, heteroaryl having 3 to 60 carbon atoms, fused aryl having 7 to 60 carbon atoms, and fused heteroaryl having 4 to 60 carbon atoms.

Description

Carbazole benzene fused ring derivative, polymer, mixture, composition, organic electronic device and preparation method thereof

Technical field

The invention relates to the field of organic electronic devices, in particular to a carbazole benzene fused ring derivative, a polymer, a mixture, a composition, an organic electronic device and a preparation method thereof.

Background technique

Due to the diversity of molecular structure design, relatively low manufacturing cost, and superior optoelectronic performance, organic semiconductor materials have great potential applications in many optoelectronic devices, such as organic light-emitting diodes (OLEDs) and organic photovoltaic cells (OPVs). There are airport effect tubes (OFETs) and so on. Especially since the double-layer OLED structure was reported by Deng Qingyun et al. (C.W. Tang and S.A. Van Slyke, Appl. Phys. Lett., 1987, 51, 913), organic semiconductor materials have been rapidly developed in the field of flat panel display and illumination.

The organic thin film light-emitting element must satisfy an improvement in luminous efficiency, a reduction in driving voltage, and an improvement in durability. However, there are still many technical issues, among which the high efficiency and long life of components are one of the many problems.

In order to accelerate the process of OLED's large-scale industrialization and improve its photoelectric performance, various new organic photoelectric material systems have been widely designed and developed. Among them, carbazole organic semiconductor materials have a wide range of applications in optoelectronic devices due to their superior optoelectronic properties, redox properties, and stability. In addition, the aromatic group or the aromatic hetero group of the fused ring structure, such as fluoranthene, fluorene, fluorene, phenanthrene, phenanthroline, benzofluoranthene, etc., generally has good carrier transport due to the planar structure of the molecule. Performance and photoelectric response. However, the currently reported carbazoles or organic semiconductor materials having a fused ring structure have certain limitations in carrier transport capability, stability, and lifetime of photovoltaic devices.

CN 104768926 A discloses compounds in which triphenylamine is attached to a fused ring group. Such compounds are used as electron transport layers for blue OLED devices, resulting in a certain improvement in device performance. However, often compared with triphenylamines, carbazole as a class of transporting materials with a greater conjugate, its effect on the performance and lifetime of the device combined with the design of the fused ring structure has not been further studied.

CN 102372694 A discloses a class of compounds in which a carbazole benzene unit is attached to an aromatic group containing a pyridine unit. Such compounds are used as electron transport layers for blue OLED devices, which reduce the voltage of the device and increase the efficiency. However, the large planar conjugated fused ring structure with high electron mobility and photoelectric efficiency, combined with the design of carbazole benzene and aromatic groups containing nitrogen atoms, has not been further developed for device performance and lifetime.

KR 20130059802 discloses a class of compounds in which a carbazole benzene unit is attached to a pyridine, quinoline or isoquinoline. Such compounds employ an aromatic group of a pyridine, quinoline or isoquinoline containing a nitrogen atom, and the number of ring atoms is less than 10. However, the influence of the design of the fused ring structure of the larger conjugate plane and the design of the carbazole benzene unit on the performance and lifetime of the device has not been systematically compared and studied.

In order to further explore the photoelectric properties of such materials, the combination of new structural carbazole fused rings is still to be designed and developed. The novel design combination of carbazole and fused ring gives superior optical properties to such structures.

In addition, in order to reduce production costs and achieve large-area OLED devices, printed OLEDs are becoming one of the most promising technology options. For this, printing OLED materials is the key. However, the small-molecule OLED materials based on evaporation technology developed at present have poor solubility and film forming properties due to their low molecular weight and rigid aromatic molecular structure, especially difficult to form a void-free non-cavitation. Crystal film. Therefore, at present, there is no corresponding material solution for printing OLED, and high-performance small-molecule organic light-emitting diodes are still prepared by vacuum evaporation. Therefore, designing and synthesizing organic small molecule functional compounds with good solubility and film forming properties is particularly important for achieving high performance solution processing of organic light emitting diodes.

Summary of the invention

Based on this, it is necessary to provide a carbazole benzene fused ring derivative which has both high efficiency and long life.

In addition, a polymer, a mixture, a composition, an organic electronic device, and a method of preparing the same are also provided.

A carbazole benzene fused ring derivative having the following formula:

Wherein Ar ₁ and Ar ₂ are each independently selected from the group consisting of an aromatic group and an aromatic hetero group, and at least one of the Ar ₁ and the Ar ₂ is selected from a thick group having 13 to 60 ring atoms. a ring aromatic group and one of 13 to 60 fused ring aromatic groups;

R ₁ and R ₂ are each independently selected from the group consisting of H, D, F, CN, NO ₂ , CF ₃ , alkenyl, alkynyl, amine, acyl, amide, cyano, isocyano, alkoxy, hydroxy, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, an aromatic group having 6 to 60 carbon atoms, and 3 carbon atoms One to 60 heterocyclic aryl groups, one having 7 to 60 fused ring aromatic groups, and one of 4 to 60 fused heterocyclic aryl groups;

Ar ₃ and Ar ₄ are each independently selected from an aromatic group having 6 to 60 carbon atoms, a heterocyclic aromatic group having 3 to 60 carbon atoms, and a condensed aromatic ring having 7 to 60 carbon atoms. a group of one or more fused heterocyclic aryl groups having 4 to 60 carbon atoms;

And, at least one of Ar ₃ and Ar ₄ contains an aromatic hetero ring having an N atom;

n is any integer from 0 to 20; m is any integer from 0 to 20; p is any integer from 0 to 4; q is any integer from 0 to 4, and the p and the q are at most one Is 0.

A polymer comprising repeating structural units of the above formula oxazobenzene fused ring derivatives.

A mixture comprising the above carbazole benzene fused ring derivative and one of the above polymers and an organic functional material selected from the group consisting of a hole injecting material, a hole transporting material, a hole blocking material, and an electron At least one of an injection material, an electron transport material, an electron blocking material, an organic matrix material, a luminescent material, and an organic dye.

A composition comprising a main ingredient and an organic solvent, the main material comprising one of the above-mentioned carbazole benzene fused ring derivatives, the above polymer and the above mixture, the organic solvent comprising a first solvent, The first solvent is at least one of an aromatic solvent, a heteroaromatic solvent, a ketone solvent, an ether solvent, and an ester solvent.

An organic electronic device comprising a functional layer, the material of which comprises one of the above carbazole benzene fused ring derivatives, the above polymer, the above mixture, and one of the above compositions.

A method of producing an organic electronic device comprising the step of forming a functional layer by vapor deposition using one of the above carbazole benzene fused ring derivatives, the above polymer, and the above mixture.

A method of preparing an organic electronic device comprising the step of forming a functional layer by one of printing and coating using the above composition.

Details of one or more embodiments of the invention are set forth in the accompanying drawings and description below. Other features, objects, and advantages of the invention will be apparent from the description and appended claims.

detailed description

In order to facilitate the understanding of the present invention, the present invention will be described more fully hereinafter with reference to the accompanying drawings.

It should be noted that, herein, an aromatic group means a hydrocarbon group containing at least one aromatic ring. Heterocyclic aromatic group means an aromatic hydrocarbon group containing at least one hetero atom. A fused ring aromatic group means that the ring of the aryl group may have two or more rings in which two carbon atoms are shared by two adjacent rings, that is, a fused ring. A fused heterocyclic aryl group refers to a fused ring aromatic hydrocarbon group containing at least one hetero atom.

Herein, the aryl group contains a fused ring aromatic group, and the heterocyclic aryl group contains a fused heterocyclic aryl group. Further, the aromatic group and the heterocyclic aromatic group are not limited to a system including an aromatic ring, and a non-aromatic ring system is also included. For example, pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, etc. The system is also considered to be an aromatic or heterocyclic aromatic group as referred to herein.

And herein, the fused ring aromatic group is not limited to a system including an aromatic group, and the fused heterocyclic aryl group is not limited to a system including a heteroaromatic group, and a plurality of aromatic or heterocyclic aromatic groups may also be short non- The aromatic unit is interrupted (<10% non-H atoms, further less than 5% non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be fused ring aromatic groups.

Specifically, examples of the aromatic group are: benzene, biphenyl, terphenyl, toluene, chlorobenzene, and derivatives thereof.

Specifically, examples of the fused ring aromatic group are: naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, anthracene, benzopyrene, anthracene, anthracene, and derivatives thereof.

Specifically, examples of heterocyclic aromatic groups are: pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene And its derivatives.

Specifically, examples of the fused heterocyclic aromatic group are: benzofuran, benzothiophene, anthracene, oxazole, pyrroloimidazole, pyrrolopyrrol, thienopyrrole, thienothiophene, furopyrrol, furanfuran , thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, o-diazepine, quinoxaline, phenanthridine, pyridine, quinazoline, quinazolinone And its derivatives.

A carbazole benzene fused ring derivative of one embodiment has the following structural formula:

General formula (1)

Wherein, in the formula (1), R ₁ and R ₂ are each independently selected from the group consisting of H, D, F, CN, NO ₂ , CF ₃ , alkenyl, alkynyl, amine, acyl, amide, cyano, Isocyanato group, alkoxy group, hydroxyl group, carbonyl group, sulfone group, alkyl group having 1 to 60 carbon atoms, cycloalkyl group having 3 to 60 carbon atoms, and 6 to 60 carbon atoms Aromatic group, a heterocyclic aryl group having 3 to 60 carbon atoms, a fused ring aromatic group having 7 to 60 carbon atoms, and a fused heterocyclic aryl group having 4 to 60 carbon atoms One of them.

n is any integer from 0 to 20; further, n is any integer from 0 to 10; further, n is any integer from 0 to 5; further, n is any of 0 to 3 An integer.

m is any integer from 0 to 20.

p is any integer from 0 to 4; further, p is any integer from 0 to 3; further, p is any integer from 0 to 2; further, p is any integer from 0 to 1.

q is any integer from 0 to 4, and at most one of p and q is 0. Further, q is any integer from 0 to 3; further, q is any integer from 0 to 2; further, q is any integer from 0 to 1.

In the formula (1), Ar ₃ and Ar ₄ are each independently selected from an aromatic group having 6 to 60 carbon atoms, a heterocyclic aromatic group having 3 to 60 carbon atoms, and 7 carbon atoms. One to 60 fused ring aromatic groups and one of 4 to 60 fused heterocyclic aryl groups. And at least one of Ar ₃ and Ar ₄ contains an aromatic heterocyclic ring having an N atom.

Specifically, in Ar ₃ and Ar ₄ , the aromatic heterocyclic rings having N atoms are each independently selected from

and

one of the;

Among them, in the above aromatic heterocyclic ring having an N atom, hydrogen on the ring may be optionally substituted. And the hydrogen on the ring may be optionally substituted means that the aromatic heterocyclic ring having an N atom may be selected not only from one of the above structures but also one selected from the above structures in which a hydrogen atom is substituted.

In the above aromatic heterocyclic ring having N atom, all X in each of the above structures is selected from one of CR ₃ , N and C, and at least one X in each structure is N, and in two adjacent X At most one is N. In each structure, one to five X are N; further, in each structure, one to three X are N; further, one to two X are N.

Y is selected from one of CR ₄ R ₅ , SiR ₆ R ₇ , NR ₈ , C(=O), S(=O) ₂ , O and S.

R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently selected from the group consisting of H, D, F, CN, NO ₂ , CF ₃ , alkenyl, alkynyl, amine, acyl, amide, cyanide a group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, and 6 carbon atoms ～60 aromatic groups, a heterocyclic aryl group having 3 to 60 carbon atoms, a fused ring aromatic group having 7 to 60 carbon atoms, and a fused heterocyclic ring having 4 to 60 carbon atoms One of the aromatic bases.

Further, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently selected from the group consisting of H, D, F, CN, NO ₂ , CF ₃ , alkenyl, alkynyl, amine, acyl, amide a group, a cyano group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and a carbon number 6 to 30 aromatic groups, 3 to 30 heterocyclic aryl groups, 7 to 30 fused ring aromatic groups, and 4 to 30 carbon atoms One of the fused heterocyclic aryl groups.

Further, in Ar ₃ and Ar ₄ , the aromatic heterocyclic ring having an N atom is each selected from the group consisting of

and

one of the.

Further, both Ar ₃ and Ar ₄ contain an aromatic heterocyclic ring having an N atom.

In the general formula (1), Ar ₁ and Ar ₂ are each independently selected from one of an aromatic group and an aromatic hetero group, and at least one of Ar ₁ and Ar ₂ is selected from the group consisting of 13 to 60 ring atoms. The fused ring aromatic group and one of the fused ring aromatic groups having 13 to 60 ring atoms.

Further, Ar ₁ and Ar ₂ are each independently selected from the group consisting of a fused ring aromatic group having 13 to 50 ring atoms and a fused ring aromatic group having 13 to 50 ring atoms; , Ar ₁ and Ar ₂ are each independently selected from the group consisting of a fused ring aromatic group having 13 to 40 ring atoms and a fused ring aromatic group having 13 to 40 ring atoms; further , Ar ₁ and Ar ₂ are each independently selected from the group consisting of a fused ring aromatic group having 13 to 30 ring atoms and a fused ring aromatic group having 13 to 30 ring atoms; further, Ar ₁ and Ar ₂ are each independently selected from the group consisting of a fused ring aromatic group having 13 to 20 ring atoms and a fused ring aromatic group having 13 to 20 ring atoms.

Specifically, in Ar ₁ and Ar ₂ , the hetero atom in the fused ring arehetero group is at least one selected from the group consisting of Si, N, P, O, S, and Ge; further, in Ar ₁ and Ar ₂ , The hetero atom in the fused ring arehetero group is at least one selected from the group consisting of Si, N, P, O and S; further, in Ar ₁ and Ar ₂ , the hetero atom in the fused ring aryl group is selected from N, One of O and S.

Further, in the formula (1), Ar ₁ and Ar ₂ are each independently selected from the group consisting of a fused ring having 3 to 30 ring atoms, wherein the ring is selected from the group consisting of a three-membered ring and a four-membered ring. One of a five-membered ring and a six-membered ring; further, the ring is one of a five-membered ring and a six-membered ring. Further, the number of ring atoms of Ar ₁ and Ar ₂ is 3 to 20 fused rings; further, the number of ring atoms of Ar ₁ and Ar ₂ is a fused ring having 3 to 10 ring atoms. Further, the number of ring atoms is from 3 to 5 fused rings.

Specifically, Ar ₁ and Ar ₂ are each independently selected from the group consisting of

one of the;

Among them, in the above structural formula of Ar ₁ and Ar ₂ , hydrogen on the ring may be optionally substituted. And H may be optionally substituted on the ring means that Ar ₁ and Ar ₂ may be selected not only from one of the above structures but also one selected from the above structures in which the H atom is substituted.

In the above structural formula of Ar ₁ and Ar ₂ , X is selected from one of CR ₉ and N, and at most one of two adjacent X is N; further, X in each of the above structural formulas is CR ₉ .

R _{9 is} selected from the group consisting of H, D, F, CN, NO ₂ , CF ₃ , alkenyl, alkynyl, amine, acyl, amide, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfone, An alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, an aromatic group having 6 to 60 carbon atoms, and 3 to 60 carbon atoms. A heterocyclic aromatic group, a fused aromatic group having 7 to 60 carbon atoms, and a fused heterocyclic aromatic group having 4 to 60 carbon atoms. Further, R ₉ is a site attached to other groups, or R _{9 is} selected from the group consisting of H, D, F, CN, NO ₂ , CF ₃ , alkenyl, alkynyl, amine, acyl, amide, cyanide a group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and 6 carbon atoms ～30 aromatic groups, a heterocyclic aryl group having 3 to 30 carbon atoms, a fused ring aromatic group having 7 to 30 carbon atoms, and a fused heterocyclic ring having 4 to 30 carbon atoms One of the aromatic bases. Further, R _{9 is} selected from one of H and D.

Y is selected from one of CR ₁₀ R ₁₁ , SiR ₁₂ R ₁₃ , NR ₁₄ , C(=O), S(=O) ₂ , O and S;

R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently selected from the group consisting of H, D, F, CN, NO ₂ , CF ₃ , alkenyl, alkynyl, amine, acyl, amide, cyano, Isocyanato group, alkoxy group, hydroxyl group, carbonyl group, sulfone group, alkyl group having 1 to 60 carbon atoms, cycloalkyl group having 3 to 60 carbon atoms, and 6 to 60 carbon atoms a aryl group, a heterocyclic aryl group having 3 to 60 carbon atoms, a fused ring aromatic group having 7 to 60 carbon atoms, and a fused heterocyclic aryl group having 4 to 60 carbon atoms One of them.

Further, R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently selected from the group consisting of H, D, F, CN, NO ₂ , CF ₃ , alkenyl, alkynyl, amine, acyl, amide, cyanide a group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and 6 carbon atoms ～30 aromatic groups, a heterocyclic aryl group having 3 to 30 carbon atoms, a fused ring aromatic group having 7 to 30 carbon atoms, and a fused heterocyclic ring having 4 to 30 carbon atoms One of the aromatic bases.

Further, Ar ₁ and Ar ₂ are each independently selected from the group consisting of fluorene, fluoranthene, phenanthrene, benzophenanthrene, perylene, tetracene, anthracene, benzopyrene, anthracene, anthracene, oxazole, dibenzofuran and One of the dibenzothiophenes.

Further, in the general formula (1), Ar ₁ and Ar ₂ are each independently selected from the group consisting of

and

one of the.

Alternatively, in other embodiments, in the formula (1), Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently comprise a structural unit

At least one of them, wherein s is any integer from 1 to 4.

Specifically, the carbazole benzene fused ring derivative has a high electron mobility, and the electron mobility of the above carbazole benzene fused ring derivative is ≥10 ^-5 cm ² /Vs; further, the electron mobility is ≥10 ^-4 cm ² / Vs; further, the electron mobility is optimal ≥10 ^-3 cm ² / Vs.

Specifically, the glass transition temperature of the carbazole benzene fused ring derivative is ≥100 ° C; further, the glass transition temperature is ≥110 ° C; further, the glass transition temperature is ≥120 ° C; further, the glass transition temperature is ≥140 ° C.

Specifically, the lowest unoccupied orbital energy level LUMO ≤ -2.7 eV of the carbazole benzene fused ring derivative; further, LUMO ≤ -2.8 eV; further, LUMO ≤ -2.9 eV; further, LUMO ≤ -3.0 eV.

Specifically, the highest occupied orbital energy level HOMO ≤ -5.6 eV of the carbazole benzene fused ring derivative; further, HOMO ≤ -5.7 eV; further, HOMO ≤ -5.8 eV; further, HOMO ≤ -5.9 eV.

Specifically, the triplet level of the carbazole benzene fused ring derivative is T1 ≥ 1.7 eV; further, T1 ≥ 1.9 eV; further, T1 ≥ 2.2 eV; further, T1 ≥ 2.4 eV.

Among the energy level structures of organic materials, the triplet levels E _T , HOMO, and LUMO play a key role. The following is an introduction to the determination of these energy levels.

The HOMO and LUMO levels can be measured by photoelectric effect, for example, XPS (X-ray photoelectron spectroscopy), UPS (UV photoelectron spectroscopy), etc., and can also pass cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter referred to as DFT), have also become effective methods for calculating molecular orbital energy levels.

The triplet energy level E _{T of} organic materials can be measured by low temperature time-resolved luminescence spectroscopy, or can also be obtained by quantum simulation calculations (eg by Time-dependent DFT), as by the commercial software Gaussian 09W (Gaussian Inc.), specific The simulation method can be referred to the method in the patent document WO2011141110, or can also be obtained by the method described later in the embodiment.

It should be noted that the absolute values of HOMO, LUMO and E _T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods may lead to different results, for example, the starting point and the peak point on the CV curve. Different HOMO/LUMO values are given. Therefore, a reasonable and meaningful comparison should use the same measurement method and the same evaluation method. The values of HOMO, LUMO, and E _T in the present embodiment are obtained based on the simulation of Time-dependent DFT. It should be noted that the acquisition of HOMO, LUMO, and E _T is not limited to the method, and they may also pass other measurements. The method or calculation method is obtained, but the energy level values determined by different methods should be mutually calibrated.

Further, a part of the hydrogen atom of the structural formula of the carbazole benzene fused ring derivative is substituted by hydrazine; further, the structural formula of the carbazole benzene fused ring derivative has a hydrogen atom number of 10% substituted by hydrazine; further The number of hydrogen atoms substituted by deuterium is 20%; further, the number of hydrogen atoms substituted by deuterium is 30%; further, the number of hydrogen atoms substituted by deuterium is 40%.

Specifically, the carbazole benzene fused ring derivative is selected from one of the following compounds, but is not limited to the following compounds:

The above carbazole benzene fused ring derivative has at least the following advantages: the nitrogen atom on the carbazole of the above carbazole benzene fused ring derivative is linked to a large plane conjugated fused ring aromatic structure, which is advantageous for achieving better current carrying current. Sub-transmission and photoelectric response, better energy level matching, improve the photoelectric performance and stability of such compounds and optoelectronic devices, thereby providing a material solution for a light-emitting device with high manufacturing efficiency and long life.

The polymer of one embodiment comprises a repeating structural unit of a carbazole benzene fused ring derivative of the formula (1). Here, the polymer is a non-conjugated polymer in which a structural unit of a carbazole benzene fused ring derivative represented by the formula (1) is on a side chain. Alternatively, the polymer may also be a conjugated polymer.

Herein, the polymer, that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer. In this embodiment, the polymer also includes a dendrimer, wherein the dendrimer can be the literature [Dendrimers and Dendrons, Wiley-VCH Ver lag GmbH & Co. KGaA, 2002, Dendrites disclosed in Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle., or synthetically synthesized by the synthetic methods described above.

A conjugated polymer is a polymer whose backbone backbone is mainly composed of sp ² hybrid orbitals of C atoms, such as polyacetylene polyacetylene and poly(phenylene vinylene), and C atoms in its main chain. It can also be substituted by other non-C atoms, and is still considered to be a conjugated polymer when the sp ² hybrid on the backbone is interrupted by some natural defects. And herein, the conjugated polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.

Further, the carbazole benzene fused ring derivative is a small molecule material. Wherein, there is no repeating structure in the "small molecule" referred to herein, and it is not a polymer, an oligomer, a dendrimer, and a blend; and the molecular mass is ≤3000 g/mmol; further, a small molecule The molecular mass is ≤ 2000 g / mmol; further, the molecular mass of the small molecule is ≤ 1500 g / mmol.

The mixture of one embodiment, which is a solventless type, can be used for vapor deposition to prepare OLED devices. The mixture of the present embodiment includes the above carbazole benzene fused ring derivative and one of the above polymers and an organic functional material.

Here, the polymer herein is a polymer comprising the above-mentioned repeating structural unit of the carbazole benzene fused ring derivative represented by the formula (1).

Specifically, in the embodiment, the relative molar mass of the carbazole benzene fused ring derivative is 1000 g/mol; further, the relative molar mass of the carbazole benzene fused ring derivative is 900 g/mol; further The relative molar mass of the carbazole benzene fused ring derivative is 850 g/mol; further, the relative molar mass of the carbazole benzene fused ring derivative is 800 g/mol; further, the carbazole benzene fused ring The relative molar mass of the derivatives was 700 g/mol.

The organic functional material is selected from the group consisting of a hole (also called a hole) injection material (HIM), a hole transport material (HTM), a hole blocking material (HBM), an electron injection material (EIM), an electron transport material (ETM), and an electron. At least one of a barrier material (EBM), an organic host material (Host), a luminescent material, and an organic dye. The luminescent material is selected from at least one of a singlet illuminant (fluorescent illuminant), a triplet illuminant (phosphorescent illuminant), and an organic thermal excitation delayed fluorescent material (TADF material). The organic matrix material referred to herein is already clearly capable of functioning as an organic matrix material.

Specifically, the organic functional material may be a small molecule material or a high polymer material. The organic functional material may be an organic functional material as disclosed in WO2010135519A1, US20090134784A1 and WO2011110277A1.

In the present embodiment, in the above mixture, the carbazole benzene fused ring derivative or the above polymer is 50% by weight to 99.9% by weight; further, the carbazole benzene fused ring derivative or the above polymer The weight percentage of the carbazole benzene fused ring derivative or the above polymer is 60% to 95%; further, the carbazole benzene fused ring derivative Or the above polymer has a weight percentage of 70% to 90%.

In one embodiment, the mixture comprises a carbazole benzene fused ring derivative and one of the above polymers, and further comprises a fluorescent luminescent material (singlet light illuminant).

In another embodiment, the mixture comprises a carbazole benzene fused ring derivative and one of the above polymers, and further comprises a thermally activated delayed fluorescent luminescent material (TADF).

In another embodiment, the mixture includes a carbazole benzene fused ring derivative and one of the above polymers, and further includes a fluorescent luminescent material and a TADF material.

The following is a detailed description of (but not limited to) fluorescent luminescent materials (single-state illuminants), phosphorescent luminescent materials (heavy illuminants) and TADF materials:

(1) Singlet emitter (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. To date, there have been many examples, such as styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1, and indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.

Specifically, the singlet emitter is one selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrenephosphine, styrene ether, and aromatic amine.

Wherein, the monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine; wherein the amine is preferably an aromatic amine. The dibasic styrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine; wherein the amine is preferably an aromatic amine. The ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine; wherein the amine is preferably an aromatic amine. The tetrabasic styrene amine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one; wherein the amine is preferably an aromatic amine. Among them, in this paragraph, styrene is stilbene, which may be further substituted.

The definitions of styrene phosphine and styrene ether are similar to those of the above amines and will not be described herein.

An arylamine (aromatic amine) refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is a fused ring system, and preferably the total number of carbon atoms is greater than or equal to 14.

Specifically, the aromatic amine is selected from one of aromatic amide, aromatic guanidine diamine, aromatic guanamine, aromatic guanidine diamine, aromatic thiamine, and aromatic quinone diamine. The aromatic decylamine refers to a compound in which one of the diarylamine groups is directly bonded to the oxime; further, the diarylamine group is at the position of 9 of oxime. The aromatic oxime diamine refers to a compound in which two diaryl arylamine groups are directly bonded to the oxime; further, the two diaryl arylamine groups are attached to the oxime 9,10, respectively. Among them, the definitions of aromatic decylamine, aromatic guanidine diamine, aromatic thiamine and aromatic quinone diamine are similar to aromatic decylamine. Wherein, the diarylamine groups of the aromatic decylamine and the aromatic quinone diamine are preferably both attached to the 1 position of the oxime, or the diarylamine groups of the aromatic decylamine and the aromatic oxime diamine are respectively linked to芘 1 and 6 positions.

Among them, the singlet emitters based on styrylamine and arylamine may be WO2006/000388, WO2006/058737, WO2006/000389, WO2007/065549, WO2007/115610, US7250532B2, DE102005058557A1, CN1583691A, JP 08053397A, US6251531 B1, US2006 Singlet illuminators as disclosed in EP 1 957 606 A1 and US 2008/0113101 A1.

Singlet emitters based on styrylamine and its derivatives are singlet emitters as disclosed in U.S. Patent 5,212,029.

Further, the singlet emitter is one selected from the group consisting of an indeno-amine and an indeno-diamine, such as the benzoindole-amine or benzoindole-diamine disclosed in WO2006/122630 , a dibenzoindolo-amine or a dibenzoindeno-diamine as disclosed in WO 2008/006449, and an indeno-amine or an indeno-diamine disclosed in WO2007/140847.

The singlet illuminant may also be a polycyclic aromatic hydrocarbon compound, such as the following compounds and derivatives thereof: such as 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene, anthracene (eg 2,5,8,11-tetra-t-butylindole), indenoindole, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1,1 '-Biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as the aryl fluorene disclosed in US20060222886), arylene vinyl (such as US5121029 and US5130603) Disclosed subaromatic vinyl), cyclopentadiene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran (eg 4 (dicyanomethylidene) - 6-(4-p-Dimethylaminostyryl-2-methyl)-4H-pyran (DCM)), thiopyran, bis(pyridazinyl)imide boron compound (as disclosed in US 2007/0092753 A1) Imine boron compound), bis(pyridazinyl)methylene compound, carbostyryl compound, oxazinone, benzoxazole, benzothiazole, benzimidazole and pyrrolopyrroledione. The singlet emitters can also be singlet emitters as disclosed in US20070252517 A1, US4769292, US6020078, US2007/0252517 A1 and US2007/0252517 A1.

In the present embodiment, the singlet illuminant is the following compound, but is not limited to the following compounds:

(2) Thermally activated delayed fluorescent luminescent material (TADF):

Traditional organic fluorescent materials can only use 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. The thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔE _st ), and triplet excitons can be converted into singlet exciton luminescence by inter-system crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation, and the quantum efficiency in the device can reach 100%.

The TADF material needs to have a small singlet-triplet energy level difference, typically ΔE _st <0.3 eV, further ΔE _st <0.2 eV; further, ΔE _st <0.1 eV; further, ΔE _st <0.05 eV. And TADF materials have better fluorescence quantum efficiency. The TADF material may be CN103483332 (A), TW201309696 (A), TW201309778 (A), TW201343874 (A), TW201350558 (A), US20120217869 (A1), WO2013133359 (A1), WO2013154064 (A1), and literature (Adachi, et. Al. Adv. Mater., 21, 2009, 4802), literature (Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302), literature (Adachi, et. al. Appl. Phys. Lett. , 101, 2012, 093306), literature (Adachi, et. al. Chem. Commun., 48, 2012, 11392), literature (Adachi, et. al. Nat. Photon., 6, 2012, 253), literature ( Adachi, et. al. Nature, 492, 2012, 234), literature (Adachi, et. al. J. Am. Chem. Soc, 134, 2012, 14706), literature (Adachi, et. al. Angew. Chem. Int. Ed, 51, 2012, 11311), literature (Adachi, et. al. Chem. Commun., 48, 2012, 9580), literature (Adachi, et. al. Chem. Commun., 48, 2013, 10385) , literature (Adachi, et.al. Adv. Mater., 25, 2013, 3319), literature (Adachi, et. al. Adv. Mater., 25, 2013, 3707), literature (Adachi, et.al.Chem .Mater., 25, 2013, 3038), literature (Adachi, et. al. Chem. Mater., 25, 2013, 3766), literature (Adachi, et. al. J. Mater. Chem. C., 1, 2013, 4599), TADF material disclosed in the literature (Adachi, et. al. J. Phys. Chem. A., 117, 2013, 5607).

In the present embodiment, the TADF luminescent material is the following compound, but is not limited to the following compounds:

(3) Triplet illuminator (Triplet Emitter)

Triplet emitters are also known as phosphorescent emitters. Specifically, the triplet emitter is a metal complex having the formula M(L)n. Wherein M is a metal atom; L may be the same or different at each occurrence; L is an organic ligand which is bonded to the metal atom M by one or more positional bonds or coordination; n is a value greater than one. Integer; further, n is 1, 2, 3, 4, 5 or 6. Further, the metal complex is attached to the polymer through one or more positions; further, the metal complex is linked to the polymer via an organic ligand.

Further, the metal atom M is selected from one of a transition metal element, a lanthanoid element, and a lanthanoid element; further, the metal atom M is selected from the group consisting of Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, One of Gd, Tb, Dy, Re, Cu, and Ag; further, the metal atom M is selected from one of Os, Ir, Ru, Rh, Re, Pd, and Pt.

Further, L is a chelating ligand, ie, a ligand, coordinated to the metal through at least two binding sites; further, L has two bidentate ligands, three bidentate ligands, and two multidentate Ligand or three multidentate ligands. Wherein, the bidentate ligands may be the same or the same; the multidentate ligands may be the same or different. Chelating ligands are beneficial for increasing the stability of metal complexes.

Specifically, the organic ligand is selected from the group consisting of a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, and a 2 phenyl group. One of the quinoline derivatives. Further, the organic ligand may be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand may preferably be derived from acetone acetate or picric acid.

Further, the structural formula of the metal complex of the triplet emitter is as follows:

General formula (6)

In the general formula (6), M is as defined above; each of Ar ₁ may be the same or different, Ar ₁ is a cyclic group, and each Ar ₁ contains at least one donor atom, that is, a lone pair An atom of an electron, such as nitrogen or phosphorus, is coordinated to the metal through its cyclic group; each occurrence of Ar ₂ may be the same or different, a cyclic group, and each Ar ₂ contains at least one C atom , through which a cyclic group is attached to a metal; Ar ₁ and Ar ₂ are linked together by a covalent bond, each of which may carry one or more substituent groups, which may also be linked together by a substituent group; When present, may be the same or different, is an ancillary ligand, preferably a bidentate chelate ligand, further a monoanionic bidentate chelate ligand; m is selected from one of 1, 2 and 3, further, m 2 or 3, further, m is 3; n is selected from one of 0, 1, and 2, further, n is 0 or 1, and further, n is 0.

In particular, the triplet emitters can be patented WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485 , US Pat. The triplet emitters disclosed in 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A and WO 2009118087A1 may also be in the literature (Baldo, Thompson et al. Nature 403, (2000), 750-753). ), literature (Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624), literature (J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124), literature (Kido et Al. Chem. Lett. 657, 1990), literature (Johnson et al., JACS 105, 1983, 1795), literature (Wrig The triplet emitters disclosed in hton, JACS 96, 1974, 998) and in the literature (Ma et al., Synth. Metals 94, 1998, 245).

In the present embodiment, the triplet emitter is the following compound, but is not limited to the following compounds:

The composition of one embodiment is a solvent-based composition, can be used as a coating or ink, and can be applied to an organic electronic device as a material of a functional layer. The organic electronic device is selected from the group consisting of an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, and an organic spintronic device. , organic sensors and organic plasmon emission diodes (Organic One of the Plasmon Emitting Diodes. The composition may be a solution or a suspension.

Wherein, the composition comprises a main ingredient and an organic solvent, and the main ingredient comprises one of the above carbazole benzene fused ring derivatives, the above polymer and the above mixture. Here, the polymer herein is a polymer comprising the above-mentioned repeating structural unit of the carbazole benzene fused ring derivative represented by the formula (1). The mixture herein is the mixture described above and will not be described again here.

In the present embodiment, the molar mass of the carbazole benzene fused ring derivative and the polymer are both ≥700 g/mol, and further, the molar mass of the carbazole benzene fused ring derivative and the polymer are both ≥800 g/mol; The molar mass of the oxazobenzene fused ring derivative and the polymer are both ≥900 g/mol; further, the molar mass of the carbazole benzene fused ring derivative and the polymer are both ≥1000 g/mol; further, the carbazole benzene is thick The molar mass of the cyclic derivative and the polymer are both ≥1100 g/mol.

In the present embodiment, the solubility of the carbazole benzene fused ring derivative and the polymer in toluene is ≥10 mg/ml at 25 ° C; further, the carbazole benzene fused ring derivative and the polymer in toluene Solubility ≥ 15 mg / ml; further, the solubility of the carbazole benzene fused ring derivative and the polymer in toluene ≥ 20 mg / ml.

Specifically, the composition of the present embodiment has a surface tension of about 19 dyne/cm to 50 dyne/cm at an operating temperature or at 25 ° C; further 22 dyne/cm to 35 dyne/cm; and further 25 dyne/cm to 33 dyne/cm. .

Specifically, the composition of the present embodiment has a viscosity at an operating temperature or 25 ° C of about 1 cps to 100 cps; further from 1 cps to 50 cps; further from 1.5 cps to 20 cps; further from 4.0 cps to 20 cps. At this time, the composition can be used for inkjet printing.

Since the composition of the present embodiment is used as a printing material, the viscosity and surface tension of the composition are important parameters. Only compositions with suitable parameters can be adapted to a particular substrate and to a particular printing method. Among them, the viscosity of the composition can be adjusted by different methods, such as by selecting a suitable solvent and the concentration of the main ingredient. The viscosity of the composition is adjusted so as to facilitate printing in accordance with a usual printing method.

Specifically, in the composition of the present embodiment, the weight percentage of the main material is 0.3% to 30%; further 0.5% to 20%; further 0.5% to 1%; further 0.5% to 10%; further It is 1% to 5%.

Specifically, the organic solvent includes a first solvent. The first solvent is at least one selected from the group consisting of an aromatic solvent, a heteroaromatic solvent, a ketone solvent, an ether solvent, and an ester solvent.

Further, the aromatic solvent is selected from at least one of a chain aliphatic substituted aromatic compound and a cyclic aliphatic substituted aromatic compound.

Specifically, the aromatic solvent and the heteroaromatic solvent are selected from the group consisting of p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, and 3-isopropylbiphenyl. , p-Methyl cumene, dipentylbenzene, triphenylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2 , 3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-pair Isopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichloro Benzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine , 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1 At least one of 1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, and dibenzyl ether.

Specifically, the ketone solvent is selected from the group consisting of 1-tetralone, 2-tetralone, 2-(phenyl epoxy)tetralone, 6-(methoxy)tetralone, acetophenone , a derivative of propiophenone, benzophenone, 1-tetralone, a derivative of 2-tetralone, a derivative of 2-(phenyl epoxy)tetralone, 6-(methoxy At least one of a derivative of a tetralone, a derivative of acetophenone, a derivative of propiophenone, and a derivative of benzophenone. Among them, a derivative of 1-tetralone, a derivative of 2-tetralone, a derivative of 2-(phenyl epoxy)tetralone, and a 6-(methoxy)tetralone The derivative, the derivative of acetophenone, the derivative of propiophenone, and the derivative of benzophenone may be 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4 -methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-indolone, anthrone, 2-nonanone, 3- Anthrone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, phorone, di-n-pentyl ketone, and the like.

Specifically, the ether solvent is selected from the group consisting of 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4- Ethyl phenethyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidylphenyl Ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxy Methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, pentyl ether c-hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, At least one of diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether .

Specifically, the ester solvent is selected from the group consisting of alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenyl acetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkane At least one of a lactone and an alkyl oleate.

Further, the first solvent is at least one selected from the group consisting of an aliphatic ketone and an aliphatic ether. Specifically, the aliphatic ketone is selected from the group consisting of 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2,5-hexanedione, 2,6,8-trimethyl-4-indanone At least one of phorone and di-n-pentyl ketone. The aliphatic ether is selected from the group consisting of pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, and triethylene glycol diethylene glycol. At least one of ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

Further, the organic solvent further includes a second solvent, wherein the second solvent is selected from the group consisting of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole , morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide At least one of tetrahydronaphthalene, decalin and hydrazine.

The mixture of the present embodiment is capable of producing an organic electronic device by printing or coating.

Among them, the printing method may be inkjet printing or Nozzle Printing. The coating method can be typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roll printing, lithography, flexographic printing, rotary printing, spraying, brushing, pad printing, Slit type extrusion coating, etc. Further, the coating method is gravure printing; the printing method is jet printing or inkjet printing.

Further, the mixture further includes at least one of a surfactant, a lubricant, a wetting agent, a dispersing agent, a hydrophobic agent, and a binder. It is used to adjust the viscosity of the mixture, film forming properties, adhesion, and the like. According to Helmut Kipphan, "Handbook of Print Media: Techno logies and Production Methods", ISBN 3-540-67326-1, for printing techniques and solvents, concentrations, Adjust the viscosity and so on.

An organic electronic device of an embodiment is an organic light emitting diode comprising a substrate, an anode, a functional layer, and a cathode.

Wherein, the functional layer comprises a light-emitting layer, and the material of the light-emitting layer comprises one of the above carbazole benzene fused ring derivatives, the above polymer, the above mixture and the above composition. Here, the polymer herein is a polymer comprising the above-mentioned repeating structural unit of the carbazole benzene fused ring derivative represented by the formula (1). At this time, the organic functional material in the mixture includes the luminescent material, that is, the luminescent material is the self-fluorescent illuminant, phosphorescent illuminant or TADF material described above. Further, the luminescent material is a fluorescent illuminant or a TADF material.

Further, the functional layer may further include a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer. At least one of (HBL). The material of these functional layers includes one of the above-mentioned carbazole benzene fused ring derivatives, polymers and mixtures. When the material of the functional layer includes a mixture, the organic functional materials in the mixture have the corresponding ones as described above. The functional material, for example, the organic functional material in the material of the hole transport layer is the hole transport material described above, and the organic functional layer in the material of the electron transport layer is the electron transport material described above, the electron injection layer The material is the electron injecting material described above. Alternatively, the material of the above functional layer may be a material commonly used in the art.

In particular, the substrate may be opaque or transparent. Transparent substrates can be used to make transparent light-emitting components. For example, the transparent substrate may be a substrate disclosed in the literature (Bulovic et al. Nature 1996, 380, p29) and the literature (Gu et al., Appl. Phys. Lett. 1996, 68, p2606). The substrate may be a rigid substrate or an elastic substrate.

Specifically, the substrate is a plastic, metal, semiconductor wafer or glass. Further, the substrate has a smooth surface. No surface defects are ideal for substrates.

Further, the substrate is flexible. The substrate is a polymer film or plastic; the substrate has a glass transition temperature Tg of 150 ° C or more; further, more than 200 ° C; further, more than 250 ° C; further, more than 300 ° C. Specifically, the substrate is selected from one of poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The material of the anode includes one of a conductive metal, a metal oxide, and a conductive polymer. The anode can easily inject holes into the light-emitting layer, the hole injection layer, or the hole transport layer.

Specifically, the work function of the anode and the organic functional material (luminescent material) in the light-emitting layer, the p-type semiconductor material of the hole injection layer, the p-type semiconductor material of the hole transport layer, or the p-type semiconductor material of the electron blocking layer The absolute value of the difference in the HOMO level (or valence band) level is less than 0.5 eV; further, less than 0.3 eV; and further, less than 0.2 eV.

Specifically, the anode material is selected from one of Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, and aluminum-doped zinc oxide (AZO). The anode material can be obtained by physical vapor deposition. The physical vapor deposition method is specifically RF magnetron sputtering, vacuum thermal evaporation or electron beam (e-beam) evaporation.

It should be noted that the anode material is not limited to the above materials, and the anode material may also be patterned ITO.

The material of the cathode is selected from one of a conductive metal and a metal oxide. The material of the cathode is such that electrons can be easily injected into the electron injecting layer, the electron transporting layer or the light emitting layer.

Further, the work function of the cathode and the LUMO level of the organic functional material (luminescent material) of the light-emitting layer, the n-type semiconductor material of the electron injecting layer, the n-type semiconductor material of the electron transporting layer or the n-type semiconductor material of the hole blocking layer The absolute value of the difference in the (or conduction band) energy level is less than 0.5 eV; further, less than 0.3 eV, and further, less than 0.2 eV. In principle, all materials which can be used as cathodes of OLEDs are possible as cathode materials for the organic electronic devices of the present embodiment.

Further, the cathode material is selected from the group consisting of Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF ₂ /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, and ITO. . The cathode material can be obtained by physical vapor deposition. The physical vapor deposition method is specifically RF magnetron sputtering, vacuum thermal evaporation or electron beam (e-beam) evaporation.

The organic electronic device of the present embodiment has an emission wavelength of 300 nm to 1000 nm, further, an emission wavelength of 350 to 900 nm, and further, an emission wavelength of 400 to 800 nm.

The above organic electronic device can be applied to various electronic devices. For example, display devices, lighting devices, light sources or sensors, and the like.

A method of producing an organic electronic device according to an embodiment includes the step of forming a functional layer by vapor deposition using the above carbazole benzene fused ring derivative, the above polymer, and the above mixture. The mixture of the present embodiment is a solventless type mixture as described above.

A method of producing an organic electronic device according to another embodiment, comprising the step of forming a functional layer by printing or coating using the above composition. At this time, the composition is a solvent-based composition as described above. Among them, the printing method may be inkjet printing or Nozzle Printing. The coating method can be typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roll printing, lithography, flexographic printing, rotary printing, spraying, brushing, pad printing, Slit type extrusion coating, etc.

The following is part of the example:

Example 1

The carbazole benzene fused ring derivative 9-(3,5-bis(3-fluoranthene)-3,6-bis(4-(3-pyridyl)phenyl)-9H-carbazole of this example The synthesis process is as follows:

9-(3,5-Dibromophenyl)-3,6-bis(4-(3-pyridyl)phenyl)-9H-indazole (35 g, 0.05 mol), fluoranthene-3-boronic acid (24.6 g) , 0.1 mol), Pd(PPh ₃ ) ₄ (2.9 g. 0.0025 mol), potassium carbonate (11.4 g, 0.1 mol), water 100 mL and 1.4-dioxane 500 mL, heated to 100 ° C under nitrogen atmosphere And the reaction is kept for 12 hours, and then cooled, extracted, dried, concentrated and purified to obtain 9-(3,5-bis(3-fluoranthene)-3,6-bis(4-(3-pyridine)benzene. Base)-9H-carbazole, yield 75%.

The synthetic route is as follows:

Example 2

The synthesis process of the carbazole benzene fused ring derivative 9-(3,5-bis(3-fluoranthene))-3-(4-(3-pyridyl)phenyl)-9H-carbazole of this example is as follows :

9-(3,5-Dibromophenyl)-3-(4-(3-pyridyl)phenyl)-9H-indazole (27.7 g, 0.05 mol), fluoranthene-3-boronic acid (24.6 g, 0.1) Mol), Pd(PPh ₃ ) ₄ (2.9g, 0.0025mol), potassium carbonate (11.4g, 0.1mol), water 100mL and 1.4-dioxane 500mL under nitrogen protection, heated to 100 ° C, and The reaction was incubated for 12 hours, cooled, extracted, dried, concentrated and purified to give 9-(3,5-bis(3-fluoranthene)-3-(4-(3-pyridyl)phenyl)-9H- Carbazole, yield 76%.

The synthetic route is as follows:

Example 3

The synthesis process of the carbazole benzene fused ring derivative 9-(3,5-bis(2-indolyl)-3-(4-(3-pyridyl)phenyl)-9H-carbazole of this example is as follows:

9-(3,5-Dibromophenyl)-3-(4-(3-pyridyl)phenyl)-9H-indazole (27.6 g, 0.05 mol), hydrazine-2-boronic acid (22.2 g, 0.1 mol) ), Pd(PPh ₃ ) ₄ (2.9g, 0.0025mol), potassium carbonate (11.4g, 0.1mol), water 100mL and 1.4-dioxane 500mL, nitrogen protection, heated to 100 under nitrogen protection conditions °C, and the reaction was incubated for 12 hours, then cooled, extracted, dried, concentrated and purified to give 9-(3,5-bis(2-indol))-3-(4-(3-pyridyl)phenyl)- 9H-carbazole, yield 80%.

The synthetic route is as follows:

Example 4

Synthesis of 9-(3,5-bis(2-indenyl)-3,6-bis(4-(3-pyridyl)phenyl)-9H-carbazole as a carbazole benzene fused ring derivative of this example The process is as follows:

9-(3,5-Dibromophenyl)-3,6-bis(4-(3-pyridyl)phenyl)-9H-indazole (35.3 g, 0.05 mol), hydrazine-2-boronic acid (22.2 g) , 0.1 mol), Pd(PPh ₃ ) ₄ (2.9 g, 0.0025 mol), potassium carbonate (11.4 g, 0.1 mol), water 100 mL and 1.4-dioxane 500 mL, heated to 100 ° C under nitrogen protection And the reaction is kept for 12 hours, and then cooled, extracted, dried, concentrated and purified to obtain 9-(3,5-bis(2-indene)-3,6-bis(4-(3-pyridine)phenyl )-9H-carbazole, yield 71%.

The synthetic route is as follows:

Example 5

The synthesis process of the carbazole benzene fused ring derivative 9-(3,5-bis(3-fluoranthene)-3-(3-pyridine)-9H-carbazole of this example is as follows:

9-(3,5-Dibromophenyl)-3-(3-pyridine)-9H-indazole (23.8 g, 0.05 mol), fluoranthene-3-boronic acid (24.6 g, 0.1 mol), Pd (PPh) ₃ ) ₄ (2.9g.0.0025mol), potassium carbonate (11.4g. 0.1mol), water 100mL and 1.4-dioxane 500mL under nitrogen protection, heated to 100 ° C, and kept warm for 12 hours, and then After cooling, extraction, drying, concentration and purification, 9-(3,5-bis(3-fluoranthene)-3-(3-pyridine)-9H-carbazole was obtained in a yield of 72%.

The synthetic route is as follows:

Example 6

The synthesis process of the carbazole benzene fused ring derivative 9-(3,5-bis(3-fluoranthene)-3,6-bis(3-pyridine)-9H-carbazole of this example is as follows:

9-(3,5-Dibromophenyl)-3,6-bis(3-pyridine)-9H-indazole (27.7 g, 0.05 mol), fluoranthene-3-boronic acid (24.6 g, 0.1 mol), Pd(PPh ₃ ) ₄ (2.9g.0.0025mol), potassium carbonate (11.4g, 0.1mol), water 100mL and 1.4-dioxane 500mL were heated to 100 ° C under nitrogen protection, and the reaction was kept 12 After cooling, extraction, drying, concentration and purification, 9-(3,5-bis(3-fluoranthene)-3,6-bis(3-pyridine)-9H-carbazole was obtained in a yield of 81. %.

The synthetic route is as follows:

Comparative example 1

The synthesis of the compound 2-(4-(9,10-bis(2-naphthalene)indole-2-)phenyl)-1-phenyl-1-H-benzimidazole of Comparative Example 1 was as follows:

Take 9,10-bis(2-naphthalene)indole-2-boronic acid (47.4 g, 0.1 mol) and 2-(4-bromophenyl)-1-phenyl-1-H-benzimidazole (34.9 g, 0.1 Mol) was placed in a 1 L double-necked round bottom flask, 500 ml of toluene was added as a solvent, and the apparatus was installed. Then, potassium carbonate (20.7 g, 0.15 mol) was completely dissolved in 100 ml of water, and then a round bottom flask was added, and finally Pd was taken. (PPh ₃ ) ₄ (3.4 g, 0.003 mol) was placed in a flask, and the air in the bottle was evacuated with an oil pump, and nitrogen gas was introduced thereto, and the mixture was heated under reflux for 12 hours, and cooled. The reaction solution was transferred to a rotary flask, and most of the solvent was evaporated to dryness, extracted with dichloromethane, washed three times with water, then dried over anhydrous magnesium sulfate, filtered, dried and purified to afford 2-(4-(9, 10-bis(2-naphthalene)indole-2-)phenyl)-1-phenyl-1-H-benzimidazole, yield 74%.

The synthetic route is as follows:

Test:

Energy levels of the compounds prepared in Examples 1 to 6 and Comparative Example 1 were tested:

The energy level of the organic material can be obtained by quantum calculation, for example, by using TD-DFT (time-dependent density functional theory) by Gaussian 03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. First, the semi-empirical method "Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method. Calculated "TD-SCF/DFT/Default Spin/B3PW91" and the base group "6-31G(d)" (Charge 0/Spin Singlet). The HOMO and LUMO levels are calculated according to the following calibration formula, and S1 and T1 are used directly.

HOMO(eV)=((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)=((LUMO(G)×27.212)-2.0041)/1.385

Among them, HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree. The results of the compounds of Examples 1 to 6 and Comparative Example 1 are shown in Table 1:

Table 1

	HOMO[eV]HOMO[eV]	LUMO[eV]LUMO[eV]	T1[eV]T1[eV]	S1[eV]S1[eV]
实施例1Example 1	-5.73-5.73	-3.00-3.00	2.282.28	2.522.52
实施例2Example 2	-5.74-5.74	-2.97-2.97	2.282.28	2.522.52
实施例3Example 3	-5.71-5.71	-2.87-2.87	1.741.74	2.992.99
实施例4Example 4	-5.70-5.70	-2.89-2.89	1.741.74	2.992.99
实施例5Example 5	-5.81-5.81	-2.97-2.97	2.282.28	2.522.52
实施例6Example 6	-5.84-5.84	-3.00-3.00	2.282.28	2.512.51
对比例1Comparative example 1	-5.56-5.56	-2.83-2.83	1.661.66	2.832.83

Examples 7 to 12 and Comparative Example 2

The structures of the organic light emitting diodes (OLED devices) of Examples 7 to 12 and Comparative Example 2 were all ITO/HIL (50 nm) / HTL (35 nm) / Host: 5% Dopant (25 nm) / ETL (28 nm) / LiQ (1 nm) ) / Al (150 nm) / cathode. "/" indicates the layer.

The compound prepared in Example 1 is the material of the electron transport layer (ETL) of Example 7, and the compound prepared in Example 2 is the material of the electron transport layer (ETL) of Example 8, prepared in Example 3. The compound was the material of the electron transport layer (ETL) of Example 9, the compound prepared in Example 4 was the material of the electron transport layer (ETL) of Example 10, and the compound prepared in Example 5 was the electron transport of Example 11. The material of the layer (ETL), the compound prepared in Example 6 was the material of the electron transport layer (ETL) of Example 12, and the compound prepared in Comparative Example 1 was the material of the electron transport layer (ETL) of Comparative Example 2.

The materials of the hole injection layer (HIL), the material of the hole transport layer (HTL), and the material of the host of Examples 7 to 12 and Comparative Example 2 were the same as those of the anthracene derivative and the Dopant.

The material of the hole injection layer (HIL) is a triarylamine derivative; the material of the hole transport layer (HTL) is a triarylamine derivative; the material of Host is an anthracene derivative, and the material of Dopant is a triarylamine derivative.

The specific preparation process of the organic light emitting diodes of Examples 7 to 12 and Comparative Example 1 is as follows:

a, ITO (indium tin oxide) conductive glass substrate cleaning: using a variety of solvents (such as one or several of chloroform, acetone or isopropanol) cleaning, and then UV ozone treatment;

b, HIL (50 nm), HTL (35 nm), EML (25 nm), ETL (28 nm): thermally evaporated in a high vacuum (1 x 10 ^-6 mbar, mbar).

c, cathode: LiQ / Al (1nm / 150nm) in a high vacuum (1 × 10 ^-6 mbar) in the thermal evaporation;

d. Package: The device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.

test:

The current-voltage (J-V) characteristics of the organic light-emitting diodes of Examples 7 to 12 and Comparative Example 2 were tested using a characterization apparatus, Also record important parameters such as luminous efficiency, lifetime and color coordinates (see Table 2). The color coordinates X ≤ 0.14, Y ≤ 0.0.09 of the devices of Examples 7 to 12 using the compounds prepared in Examples 1 to 6 as the materials of the electron transport layer, respectively, were examined, and Comparative Example 1 was used. The device X of Comparative Example 2, which was a material of the electron transport layer, was 0.18 and Y was 0.15. Obviously, the color coordinates of the devices of Examples 7 to 12 were more superior than those of Comparative Example 2.

Further, the luminous efficiency of Examples 7 to 12 using the compounds prepared in Examples 1 to 6 as the material of the electron transporting layer was at least 4.8 cd/A, and the device of Comparative Example 2 was only 3.6 cd/A, that is, the examples were employed. The devices of Examples 7 to 12 in which the obtained compound was used as a material of the electron transport layer had more excellent luminous efficiency.

In Table 2, T ₉₅ , 1000 nits represents the initial luminance at 1000, and the luminance is attenuated to 95% of the time), and the lifetimes of the organic light-emitting diodes of Examples 7 to 12 recorded in Table 2 are relative to the organic ratio of Comparative Example 2 The multiple of the light emitting diode, for example, the lifetime of the organic light emitting diode of Comparative Example 2 is 1, and the lifetime of Example 7 in Table 2 is 3.7, which is 3.7 times the lifetime of the organic light emitting diode of Embodiment 7, Example 8 The same is true for ~12, which is not described here. As can be seen from Table 2, the lifetime of the devices of Examples 7 to 12 is more than twice the life of Comparative Example 2, and has a long life. This is because the nitrogen atom on the above carbazole benzene fused ring derivative is linked to a large plane conjugated fused ring aromatic structure, achieving better carrier transport and photoelectric response, and better energy level matching, thereby Achieve higher efficiency, longer life and more blue coordinates.

Table 2

The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be considered as the scope of this manual.

The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims

A carbazole benzene fused ring derivative having the following formula:

Wherein Ar 1 and Ar 2 are each independently selected from the group consisting of an aromatic group and an aromatic hetero group, and at least one of the Ar 1 and the Ar 2 is selected from a thick group having 13 to 60 ring atoms. a ring aromatic group and one of 13 to 60 fused ring aromatic groups;

R 1 and R 2 are each independently selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyano, isocyano, alkoxy, hydroxy, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, an aromatic group having 6 to 60 carbon atoms, and 3 carbon atoms One to 60 heterocyclic aryl groups, one having 7 to 60 fused ring aromatic groups, and one of 4 to 60 fused heterocyclic aryl groups;

Ar 3 and Ar 4 are each independently selected from an aromatic group having 6 to 60 carbon atoms, a heterocyclic aromatic group having 3 to 60 carbon atoms, and a condensed aromatic ring having 7 to 60 carbon atoms. a group of one or more fused heterocyclic aryl groups having 4 to 60 carbon atoms;

And, at least one of Ar 3 and Ar 4 contains an aromatic hetero ring having an N atom;

n is any integer from 0 to 20; m is any integer from 0 to 20; p is any integer from 0 to 4; q is any integer from 0 to 4, and the p and the q are at most one Is 0.
The carbazole benzene fused ring derivative according to claim 1, wherein the aromatic heterocyclic ring having an N atom in the Ar 3 and Ar 4 is independently selected from the group consisting of

one of the;

Wherein X is selected from one of CR 3 , N and C, at least one of X in each structure is N, and at most one of two adjacent X is N;

Y is selected from one of CR 4 R 5 , SiR 6 R 7 , NR 8 , C(=O), S(=O) 2 , O and S;

R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyanide a group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, and 6 carbon atoms ～60 aromatic groups, a heterocyclic aryl group having 3 to 60 carbon atoms, a fused ring aromatic group having 7 to 60 carbon atoms, and a fused heterocyclic ring having 4 to 60 carbon atoms One of the aromatic groups, and the hydrogen on the ring may be optionally substituted.
The carbazole benzene fused ring derivative according to any one of claims 1 to 2, wherein the aromatic heterocyclic ring having an N atom in Ar 3 and Ar 4 is independently selected from the group consisting of

and
one of the.
The carbazole benzene fused ring derivative according to any one of claims 1 to 3, wherein the Ar 1 and the Ar 2 are each independently selected from the group consisting of

and
one of the;

Wherein X is selected from one of CR 9 , N and C, and at most one of the two adjacent X is N;

Y is selected from one of CR 10 R 11 , SiR 12 R 13 , NR 14 , C(=O), S(=O) 2 , O and S;

R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyanide a group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, and 6 carbon atoms ～60 aromatic groups, a heterocyclic aryl group having 3 to 60 carbon atoms, a fused ring aromatic group having 7 to 60 carbon atoms, and a fused heterocyclic ring having 4 to 60 carbon atoms One of the aromatic groups, and the hydrogen on the ring may be optionally substituted.
The carbazole benzene fused ring derivative according to any one of claims 1 to 4, wherein the Ar 1 and the Ar 2 are each independently selected from the group consisting of

and
one of the.
A polymer comprising a repeating structural unit of the carbazole benzene fused ring derivative according to any one of claims 1 to 5.
A mixture comprising one of the carbazole benzene fused ring derivatives according to any one of claims 1 to 5 and the polymer according to claim 6, and an organic functional material selected from the group consisting of At least one of an injection material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, an organic matrix material, a light emitting material, and an organic dye.
A composition comprising a main ingredient and an organic solvent, the main material comprising the carbazole benzene fused ring derivative according to any one of claims 1 to 5, the polymer according to claim 6, and the method according to claim 7. In one of the mixtures, the organic solvent includes a first solvent, and the first solvent is at least one of an aromatic solvent, a heteroaromatic solvent, a ketone solvent, an ether solvent, and an ester solvent.
The composition according to claim 8, wherein in the composition, the main ingredient is present in an amount of from 0.3% to 30% by weight.
An organic electronic device comprising a functional layer, the material of the functional layer comprising the carbazole benzene fused ring derivative according to any one of claims 1 to 5, the polymer according to claim 6, and the method of claim 7. Said mixture and one of the compositions of any one of claims 8 to 9.
The organic electronic device according to claim 10, wherein the organic electronic device is selected from the group consisting of an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, and an organic self. One of a spin-on device, an organic sensor, and an organic plasmon emitting diode.
The organic electronic device according to any one of claims 10 to 11, wherein the functional layer comprises one of an electron transport layer and an electron injection layer, and the material of the electron transport layer and the electron injection layer The carbazole benzene fused ring derivative according to any one of claims 1 to 5, the polymer according to claim 6, the mixture according to claim 7, and the composition according to any one of claims 8 to 9. Kind.
The organic electronic device according to any one of claims 10 to 12, wherein the functional layer comprises a light-emitting layer, and the material of the light-emitting layer comprises the carbazole benzene according to any one of claims 1 to 5. A fused ring derivative, a polymer according to claim 6, a mixture according to claim 7, and a composition according to any one of claims 8 to 9.
A method for producing an organic electronic device, comprising using the carbazole benzene fused ring derivative according to any one of claims 1 to 5, the polymer according to claim 6, and the mixture according to claim 7. A step of vapor forming a functional layer.
A method of producing an organic electronic device comprising the step of forming a functional layer by one of printing and coating using the composition according to any one of claims 8 to 9.