WO2019114610A1 - Carbazole tribenzene organic compound, superpolymer, mixture and composition, and use thereof - Google Patents

Abstract

The present invention relates to a carbazole tribenzene organic compound, a superpolymer, a mixture and a composition, and the use thereof, wherein the carbazole tribenzene organic compound has a structure as shown in general formula (I): (I). The carbazole tribenzene organic compound material is simple to synthesize, and when used in a host material of a device, same can improve the luminous efficiency and stability of the device and reduce the production cost of the device.

Description

Oxazole triphenyl organic compounds, polymers, mixtures, compositions and applications thereof

The present application claims priority to Chinese Patent Application No. 200911342814.3, entitled "Organic Compounds and Applications in Organic Electronic Devices", filed on Dec. 14, 2017, the entire contents of In this application.

Technical field

The present invention relates to the field of photovoltaic materials, and in particular to carbazole triphenyl organic compounds, polymers, mixtures, compositions and uses thereof.

Background technique

Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and illumination due to their versatility in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.

Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic matter. An organic electroluminescence device utilizing an organic electroluminescence phenomenon generally has a structure in which a positive electrode and a negative electrode and an organic layer are contained therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic layer has a multilayer structure, and each layer contains a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescence device, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, electrons are injected from the negative electrode into the organic layer, and excitons are formed when the injected holes meet the electrons. The excitons emit light when they transition back to the ground state. Such an organic electroluminescence device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.

Both theory and experiment have proven that luminescent materials are the most important factor in determining the efficiency of OLED devices. At present, a light-emitting layer of an organic electroluminescence device generally uses a mixed system of a host material/dopant as a light-emitting material, which can improve color purity, luminous efficiency, and stability. In general, the choice of host material is critical to the use of the host material/dopant system because the host material greatly affects the efficiency and stability of the OLED device. Preferably, the host material should have a suitable molecular weight for deposition under vacuum, while also requiring a higher glass transition temperature and thermal decomposition temperature to ensure thermal stability, high electrochemical stability to ensure long service life, and easy The amorphous film is formed, and has a good interface with adjacent functional layer materials, and molecular motion is not easily generated.

A large number of host materials are reported in existing patents and literature. For example, the patent document (US2009030202A1, US Pat. No. 2,020,017,730, A1) discloses a structure in which a dibenzofuran and a dibenzothiophene are linked to a 9-position carbazole through a linking group; in addition, dibenzo is also disclosed in the patent document (WO2012048266A1, US Pat. No. 2012086329A1). The structure in which furan and dibenzothiophene are bonded to a plurality of carbazole rings through a nitrogen atom at the 9-position and a carbon atom at the 3-position can reduce the oxidation-reduction potential and improve the electrochemical stability. However, the device efficiency of the above compounds is low, and it is difficult to meet the practical application of the OLED.

Therefore, it is still necessary to further improve the host material to improve the efficiency and life of the OLED, simplify the OLED fabrication process, and reduce the material synthesis cost.

Summary of the invention

Based on this, it is necessary to provide an carbazole triphenyl organic compound, a polymer, a mixture, a composition and an application thereof, and aim to provide a new host material to improve the performance of the device. Another object of the present invention is to provide an application of the organic compounds and compositions of the present invention in organic electronic devices, particularly electroluminescent diodes, and their use in display and illumination techniques.

The technical solution of the present invention is as follows:

An oxazole triphenyl organic compound having the structure represented by the general formula (I):

among them:

When a plurality of the R ₀ , R ₁ , R ₂ , R ₃ , R ₄ or R ₅ are present, a plurality of the R ₀ , R ₁ , R ₂ , R ₃ , R ₄ or R _{5 are the} same or different, The R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from the group consisting of: H, D, a linear alkyl group having 1 to 20 C atoms, and having 1 to 20 C atoms. An alkoxy group, a thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branch or a ring having 3 to 20 C atoms Alkoxy group, a branched or cyclic thioalkoxy group having 3 to 20 C atoms, a silyl group, a substituted keto group having 1 to 20 C atoms, having 2 An alkoxycarbonyl group to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, Isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, having 5 to 40 a substituted or unsubstituted aryl group of a ring atom, a substituted or unsubstituted group having 5 to 40 ring atoms An aryl group having 5 to 40 ring atoms, aryloxy, heteroaryl having 5 to 40 ring atoms, aryloxy groups; said _{R 0, R 1, R 2} , R 3, R 4, R 5 in The groups may be bonded to each other and/or to the ring to which the group is attached to form a monocyclic or polycyclic aliphatic or aromatic ring system;

a is 0, 1, 2 or 3; b is 0, 1, 2, 3 or 4; c is 0, 1, 2, 3 or 4; d is 0, 1, 2, 3 or 4; e is 0, 1, 2, 3 or 4;

Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are each independently selected from CR ₈ or N; and when said Y ¹ , Y ² , Y ³ , Y ⁴ , Y ^When Y ⁶ , Y ⁷ or Y ⁸ is a site bonded to a single bond represented by the formula (I), the Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ or Y ⁸ is a carbon atom;

X is O, S, CR ₆ R ₇ or SiR ₆ R ₇ ;

R ₆ , R ₇ and R _{8 have} the same meanings as R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ .

A carbazole triphenyl high polymer, wherein the repeating unit of the carbazole triphenyl high polymer comprises the structure of the above carbazole triphenyl organic compound.

a carbazole triphenyl mixture comprising a first component which is H1 and a second component of H2; and the H1 is the above carbazole triphenyl organic compound, The H2 is another organic functional material selected from the group consisting of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, a hole blocking material, and a light emitting material. , host material or organic dye.

A carbazole triphenyl composition comprising at least one carbazole triphenyl organic compound as described above, a carbazole triphenyl high polymer as described above or a carbazole triphenyl mixture as described above, And at least one organic solvent.

An organic electronic device comprising a functional layer comprising a carbazole triphenyl organic compound as described above, a carbazole triphenyl high polymer as described above or a carbazole triphenyl mixture as described above.

The above carbazole triphenyl organic compound has simple material synthesis and can be used for the device host material to improve the luminous efficiency and stability of the device and reduce the production cost of the device.

DRAWINGS

1 is a diagram of a semiconductor heterojunction structure showing that when two organic semiconductor materials H1 and H2 are in contact, the relative positions of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) may be Two types, of which the semiconductor heterojunction structure of type I and / or type II are the energy level structure of the mixture according to the invention.

Detailed ways

The present invention provides an organic compound, a mixture, a composition and its use in an organic electronic device. In order to make the objects, technical solutions and effects of the present invention more clear and clear, the present invention will be further described in detail below. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the embodiment of the present invention, the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.

In the embodiment of the present invention, the singlet states and the singlet states have the same meaning and are interchangeable.

In the embodiment of the present invention, the triplet state and the triplet state have the same meaning and are interchangeable.

In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable.

In the present invention, the complex excited state, exciplex, and Exciplex have the same meaning and are interchangeable.

The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤ 3000 g/mol, preferably ≤ 2000 g/mol, preferably ≤ 1500 g/mol.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet energy 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, such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by 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 by quantum simulation calculations (eg by Time-dependent DFT), as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods. See WO2011141110 or as described below in the examples.

It should be noted that the absolute values of HOMO, LUMO, E _T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different HOMO/ LUMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, and E _T are simulations based on Time-dependent DFT, but do not affect the application of other measurement or calculation methods.

In the invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is the third highest occupied orbital level, and so on. (LUMO+1) is defined as the second lowest unoccupied orbital level, (LUMO+2) is the third lowest occupied orbital level, and so on.

In the present invention, C ₁ -C ₆ alkyl means an alkyl group having 1 to 6 carbon atoms. Non-limiting examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1,1-dimethylpropyl 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-ethyl- 2-methylpropyl, 1,1,2-trimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1 , 3-dimethylbutyl, 2-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,3-dimethylbutyl. The alkyl group may be substituted or unsubstituted, and when substituted, the substituent may be substituted at any available point of attachment.

The present invention relates to a carbazole triphenyl organic compound, the structure of the specific formula (I):

among them:

When a plurality of the R ₀ , R ₁ , R ₂ , R ₃ , R ₄ or R ₅ are present, a plurality of the R ₀ , R ₁ , R ₂ , R ₃ , R ₄ or R _{5 are the} same or different, The R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from the group consisting of: H, D, a linear alkyl group having 1 to 20 C atoms, and having 1 to 20 C atoms. An alkoxy group, a thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branch or a ring having 3 to 20 C atoms Alkoxy group, a branched or cyclic thioalkoxy group having 3 to 20 C atoms, a silyl group, a substituted keto group having 1 to 20 C atoms, having 2 An alkoxycarbonyl group to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (-C(=O)NH ₂ ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), formyl group (-C(=O)-H), isocyano group, isocyanate group, sulfur isocyanate groups, isothiocyanate groups, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, a substituted 5 to 40 ring atoms or a a substituted aryl group, a substituted or unsubstituted heteroaryl group having 5 to 40 ring atoms, an aryloxy group having 5 to 40 ring atoms, a heteroaryloxy group having 5 to 40 ring atoms; The groups in R ₀ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ may be bonded to each other and/or to the ring to which the group is bonded to form a monocyclic or polycyclic aliphatic or aromatic ring. system;

a is 0, 1, 2 or 3; b is 0, 1, 2, 3 or 4; c is 0, 1, 2, 3 or 4; d is 0, 1, 2, 3 or 4; e is 0, 1, 2, 3 or 4;

Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are each independently selected from CR ₈ or N; and when said Y ¹ , Y ² , Y ³ , Y ⁴ , Y ^When Y ⁶ , Y ⁷ or Y ⁸ is a site bonded to a single bond represented by the formula (I), the Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ or Y ⁸ is a carbon atom;

X is O, S, CR ₆ R ₇ or SiR ₆ R ₇ ;

R ₆ , R ₇ and R _{8 have} the same meanings as R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ .

In one embodiment, the R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from the group consisting of: H, D, a linear alkyl group having 1 to 10 C atoms, having 1 Alkoxy group to 10 C atoms, thioalkoxy group having 1 to 10 C atoms, branched or cyclic alkyl group having 3 to 10 C atoms, having 3 to 10 C atoms Branched or cyclic alkoxy group, branched or cyclic thioalkoxy group having 3 to 10 C atoms, silyl group, substituted ketone having 1 to 10 C atoms a group, an alkoxycarbonyl group having 2 to 10 C atoms, an aryloxycarbonyl group having 7 to 10 C atoms, a cyano group (-CN), a carbamoyl group (- C(=O)NH ₂ ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), formyl group (-C(=O)-H), isocyanato group , isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, nitro groups, CF ₃ groups, Cl, Br, F, substitutions having 5 to 40 ring atoms or Unsubstituted aryl, substituted or unsubstituted heteroaryl having 5 to 40 ring atoms, aromatic having 5 to 40 ring atoms Group, heteroaryl having 5 to 40 ring atoms, aryl radicals; said _{R 0, R 1, R 2} , R 3, R 4, R 5 in the group may be another and / or with the group The linked rings are bonded to form a monocyclic or polycyclic aliphatic or aromatic ring system.

In one embodiment, the carbazole triphenyl organic compound according to the present invention has a structure represented by the formula (I-1)-formula (I-18):

among them:

R ₀ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ^{8 have} the same meanings as defined above.

In one embodiment, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are each independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 20 ring atoms.

An aromatic ring system or an aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system. The aromatic heterocyclic or aromatic hetero group refers to a hydrocarbon group (containing a hetero atom) containing at least one aromatic heterocyclic ring, and includes a monocyclic group and a polycyclic ring system. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, an aromatic or aromatic heterocyclic ring system includes not only a system of an aromatic group or an aromatic hetero group, but also a plurality of aryl or aryl groups may also be interrupted by short non-aromatic units (<10%). Non-H atoms, preferably less than 5% of 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 aromatic ring systems for the purposes of the present invention.

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

Specifically, examples of the aromatic hetero group are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene, anthracene Oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, Pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.

In another more preferred embodiment, R ₀ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently selected from H, C 1 -C 6 alkyl, or A group containing the following structure:

among them:

X ₁ to X _{8 are} selected from CR ₉ or N;

Y is selected from CR ₁₀ R ₁₁ , SiR ₁₀ R ₁₁ , NR ₁₀ or C(=O), S or O;

R _9, R ₁₀ and R ₁₁ there is a plurality, the plurality of R _9, R ₁₀ and R _{11 are} the same or different, said R _9, R ₁₀ and R ₁₁ are each independently selected from: H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, a thioalkoxy group having 1 to 20 C atoms, and a branch having 3 to 20 C atoms a chain or cyclic alkyl group, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic thioalkoxy group having 3 to 20 C atoms, or a monosilane a group, a substituted keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, cyanogen a radical, a carbamoyl group, a haloformyl group, a formyl group, an isocyanato group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a CF ₃ group, Cl, Br, F, a substituted or unsubstituted aryl group having 5 to 40 ring atoms, a substituted or unsubstituted heteroaryl group having 5 to 40 ring atoms, 5 to 40 ring atom aryloxy groups, having 5 to 4 a heteroaryloxy group of 0 ring atoms; the groups of R ₉ , R ₁₀ and R ₁₁ may be bonded to each other and/or to a ring to which the group is bonded to form a monocyclic or polycyclic aliphatic group Or aromatic ring system. .

In a particularly preferred embodiment, R ₀ to R ₈ comprise at least one group having the structure wherein H on the ring may be optionally substituted:

In one embodiment, the R ₀ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently selected from H, C 1 -C 6 alkyl, or group:

In an embodiment, R _{0 is} selected from H or D.

In an embodiment, R _{1 is} selected from H or phenyl.

In one embodiment, R ₂ , R ₃ , R ₄ are each independently selected from H or C1-C6 alkyl, phenyl.

In one embodiment, R ₂ , R ₃ , R ₄ are each independently selected from H or methyl, phenyl.

In one embodiment, R _{5 is} selected from the group consisting of:

In one embodiment, R ₆ and R ₇ are methyl.

In one embodiment, R ₈ is H, phenyl or biphenyl.

The carbazole triphenyl compound according to the present invention can be used as a functional material in an electronic device. Organic functional materials can be classified into hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injecting materials (EIM), electron blocking materials (EBM), and hole blocking materials (HBM). , Emitter, Host material. In a preferred embodiment, the compound according to the invention may be used as a host material, or an electron transport material, or a hole transport material. In a more preferred embodiment, the compound according to the invention can be used as a phosphorescent host material.

As a phosphorescent host material, there must be an appropriate triplet level, T1. In certain embodiments, the carbazole triphenyl organic compound according to the invention has a T1 ≥ 2.3 eV, preferably ≥ 2.4 eV, more preferably ≥ 2.5 eV, still more preferably ≥ 2.6 eV, and most preferably ≥ 2.7 eV.

It is desirable to have good thermal stability as a phosphorescent host material. In general, the carbazole triphenyl organic compound according to the invention has a glass transition temperature Tg ≥ 100 ° C, and in a preferred embodiment, Tg ≥ 120 ° C, in a more preferred embodiment, Tg ≥ 140 ° C, In a more preferred embodiment, Tg &gt; 160 &lt;0&gt;C, and in a most preferred embodiment, Tg &gt; 180 &lt;0&gt;C.

In certain preferred embodiments, the carbazole triphenyl organic compound according to the invention has ((HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, more More preferably ≥ 0.35 eV, very good ≥ 0.4 eV, preferably ≥ 0.45 eV.

Examples of carbazole triphenyl organic compounds according to the invention are listed below, preferably but not limited to:

The present invention still further relates to a carbazole tritene high polymer, the repeating unit of the carbazole triphenyl high polymer comprising the structure of the carbazole triphenyl organic compound as described above.

In a preferred embodiment, the method for synthesizing the carbazole triphenyl polymer is selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG -BUCHWALD- and ULLMAN.

In a preferred embodiment, the carbazole triphenyl polymer according to the invention has a glass transition temperature (Tg) ≥ 100 ° C, preferably ≥ 120 ° C, more preferably ≥ 140 ° C, more preferably ≥ 160 °C, optimally ≥180 °C.

In a preferred embodiment, the carbazole triphenyl polymer according to the present invention preferably has a molecular weight distribution (PDI) in the range of from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3, more preferably It is more preferably 1 to 2, and most preferably 1 to 1.5.

In a preferred embodiment, the carbazole triphenyl polymer according to the present invention preferably has a weight average molecular weight (Mw) in the range of 10,000 to 1,000,000; more preferably 50,000 to 500,000; more preferably 100,000 to 400,000, more preferably 150,000 to 300,000, and most preferably 200,000 to 250,000.

The present invention also provides a carbazole triphenyl mixture comprising a first component and a second component, the first component being H1, the second component being H2; and the H1 being the above carbazole III a benzene organic compound, the H2 is another organic functional material selected from the group consisting of a hole injection material (HIM), a hole transport material (HTM), a p-dopant, and an electron transport material (ETM). ), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), luminescent material (Emitter), host material (Host) and organic dye. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire disclosure of which is hereby incorporated by reference.

In a particularly preferred embodiment, the mixture comprises at least one carbazole triphenyl organic compound or carbazole triphenyl polymer according to the invention and a phosphorescent host material. Such a carbazole triphenyl mixture may be used as a phosphorescent host material, and may further comprise a phosphorescent emitter, wherein the phosphorescent emitter has a weight percentage of ≤ 25 wt%, preferably ≤ 20 wt%, more preferably ≤ 15 wt%.

The carbazole triphenyl mixture described below is described in detail as a phosphorescent host material.

In certain preferred embodiments, the carbazole triphenyl mixture according to the present invention, at least one of H1 and H2, ((HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more Preferably, it is ≥ 0.3 eV, more preferably ≥ 0.35 eV, very preferably ≥ 0.4 eV, preferably ≥ 0.45 eV.

In a preferred embodiment, as shown in Figure 1, the carbazole triphenyl mixture, wherein H1 and H2 have a type I semiconductor heterojunction structure, i.e., the highest occupied orbital (HOMO) of H1 is lower than The highest occupied orbit (HOMO) of H2, the lowest unoccupied orbit (LUMO) of H1 is higher than the lowest unoccupied orbit (LUMO) of H2.

In a more preferred embodiment, one of H1 and H2 has a TADF characteristic, that is, a singlet level and a triplet level difference (S ₁ -T ₁ ) of H2 or H1 in the carbazole triphenyl mixture. ≤ 0.3 eV, preferably ≤ 0.2 eV, more preferably ≤ 0.15 eV, and most preferably ≤ 0.1 eV.

More preferably, in the carbazole triphenyl mixture, H2 is selected from the group consisting of TADF materials, that is, the singlet energy level and the triplet energy level difference (S ₁ -T ₁ ) ≤ 0.3 eV, preferably ≤ 0.2 eV. More preferably, it is ≤ 0.15 eV, preferably ≤ 0.1 eV.

Some TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064( A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem. Commun., 48, 2012, 11392, Adachi, et. al. Nature Photonics, 6, 2012, 253, Adachi, et. al. Nature, 492, 2012 , 234, Adachi, et. al. J. Am. Chem. Soc, 134, 2012, 14706, Adachi, et. al. Angew. Chem. Int. Ed, 51, 2012, 11311, Adachi, et. .Commun., 48, 2012, 9580, Adachi, et. al. Chem. Commun., 48, 2013, 10385, Adachi, et. al. Adv. Mater., 25, 2013, 3319, Adachi, et. Adv. Mater., 25, 2013, 3707, Adachi, et. al. Chem. Mater., 25, 2013, 3038, Adachi, et. al. Chem. Mater., 25, 2013, 3766, Adachi, et. .J. Mater. Chem. C., 1, 2013, 4599, Adachi, et. al. J. Phys. Chem. A., 117, 2013, 5607, hereby all of the patents or article documents listed above The content is incorporated herein by reference.

Some examples of suitable TADF materials for H2 are listed in the table below:

In another more preferred embodiment, the carbazole triphenyl mixture according to the invention, wherein H2 comprises a compound of the formula (II-1) to formula (II-4):

among them:

L ¹ is an aromatic group having 5 to 30 ring atoms or a heteroaromatic group having 5 to 30 ring atoms;

L ² is a single bond, or is selected from an aromatic group having 5 to 30 ring atoms and a heteroaromatic group having 5 to 30 ring atoms; Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ independently representing an aromatic group having 5 to 30 ring atoms or a heteroaromatic group having 5 to 30 ring atoms;

An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system. A heteroaromatic group refers to a hydrocarbon group (containing a hetero atom) comprising at least one heteroaromatic ring, including a monocyclic group and a polycyclic ring system. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic or heteroaromatic systems, but also wherein multiple aryl or heteroaryl groups may also be interrupted by short non-aromatic units (eg, <10). % of non-H atoms, 5% of 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 aromatic groups for the purposes of this invention.

Specifically, preferred examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzofluorene, triphenylene, anthracene, anthracene, and derivatives thereof.

Specifically, preferred examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene, Carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine , pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.

In a preferred embodiment, a composition according to the present invention, wherein Ar ¹ to Ar ^{6 are} preferably: benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, anthracene, pyridine, pyrimidine, three Oxazine, hydrazine, thioindigo, silicon germanium, carbazole, thiophene, furan, thiazole, triphenylamine, triphenylphosphine oxide, tetraphenyl silicon, snail, spiro silicon germanium and its derivatives;

In a more preferred embodiment, a composition according to the present invention, wherein Ar ¹ to Ar ^{6 are} preferably: benzene, biphenyl, naphthalene, anthracene, phenanthrene, benzophenanthrenequinone, spiro and derivatives thereof Things.

X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ and X ₁₆ are each independently a single bond, or C(R ₁₄ R ₁₅ ), Si(R ₁₄ R ₁₅ ), O, N (R ₁₄ ), P(R ₁₄ ), C=N(R ₁₄ ), C=C(R ₁₄ R ₁₅ ), P(=O)R ₁₄ , S, S=O or SO ₂ ; and X ₉ and X _{10 is} not a single button at the same time, X ₁₁ and X _{12 are} not single bonds at the same time, X ₁₃ and X _{14 are} not single bonds at the same time, and X ₁₅ and X _{16 are} not single bonds at the same time;

R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each independently selected from the group consisting of: H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone group An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic group having 5 to 60 ring atoms or a heteroaromatic group having 5 to 60 ring atoms; ₁₂ , R ₁₃ can be located on any carbon atom on the fused ring;

n is 1, 2, 3, 4, 5 or 6.

In an embodiment, n is 1 or 2. In another embodiment, n is one.

In a more preferred embodiment, the composition according to the invention, wherein H2 comprises a compound of the formula (III-1) - one of the formula (III-4):

among them,

The meanings of L ¹ , X ₉ , X ₁₀ , X ₁₃ , R ₁₂ , R ₁₃ and n are as described above.

L ³ , L ^{4 have} the meaning as L ¹ ;

Ar ¹ and Ar ² each independently represent an aromatic group having 5 to 30 ring atoms or an aromatic hetero group having 5 to 30 ring atoms;

Y ⁹ to Y ²⁴ respectively represent N and C (R ₁₂ ), and adjacent Y ⁹ -Y ²⁴ cannot be N at the same time.

In another preferred embodiment, said H1 and H2 have a type II semiconductor heterojunction structure, and min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ Min(E _T (H1), E _T (H2))+0.2eV, preferably ≤min(E _T (H1), E _T (H2))+0.1eV, more preferably ≤min(ET(H1) , E _T (H2)), particularly preferably ≤min(E _T (H1), E _T (H2))-0.1eV, preferably ≤min(E _T (H1), E _T (H2))-0.15 eV, where LUMO(H1), HOMO(H1) and E _T (H1) are the lowest unoccupied orbits of H1, respectively, the highest occupied orbit, the triplet level, LUMO(H2), HOMO(H2) and E _T (H2) ) is the lowest unoccupied orbit of H2, the highest occupied orbit, and the triplet level.

In a more preferred embodiment, said H2 comprises an electron withdrawing group as shown below:

Where m is 1, 2 or 3;

Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ and Z ⁸ are CR ₁₆ or N, and said Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , At least one of Z ⁷ and Z ⁸ is N;

M ¹ , M ² and/or M ³ are absent or are each independently selected from: N(R ₁₇ ), C(R ₁₇ ) ₂ , Si(R ₁₇ ) ₂ , O, C=N(R ₁₇ ), C=C(R ₁₇ ) ₂ , P(R ₁₇ ), P(=O)R ₁₇ , S, S=O or SO ₂ ;

R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently selected from the group consisting of alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

In a more preferred embodiment, H2 is selected from the group consisting of compounds of the formula (II-5) to formula (II-11):

among them,

Ar ¹¹ , Ar ¹² and Ar ¹³ are each independently an aromatic group having 5 to 60 ring atoms or an aromatic heterocyclic group having 5 to 60 ring atoms;

n is 1, 2 or 3;

Z ¹ , Z ² and Z ³ are each independently CR ₁₆ or N, and at least one of Z ¹ , Z ² and Z ³ is N;

M ¹ , M ² and/or M ³ are absent or are each independently selected from: N(R ₁₇ ), C(R ₁₇ ) ₂ , Si(R ₁₇ ) ₂ , O, C=N(R ₁₇ ), C=C(R ₁₇ ) ₂ , P(R ₁₇ ), P(=O)R ₁₇ , S, S=O or SO ₂ ;

R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently selected from the group consisting of alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

In one embodiment, the H2 has the structure shown in the general formula (IV):

among them:

Z ₁ , Z ₂ , Z _{3 are} independently N or CR ₁₆ , and at least one of Z ₁ , Z ₂ , Z ₃ is N;

Ar ⁷ to Ar ^{9 are the} same or different, and are an aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or non-aromatic group having 5 to 40 ring atoms, or a combination of these systems, in which one or more groups may be further substituted with R _17, or R ₁₇ form a ring system may be further substituted with the group;

Preferably, Ar ⁷ to Ar ^{9 are the} same or different, and are an aromatic or heteroaromatic group having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms. a group, or a non-aromatic group having 5 to 20 ring atoms, or a combination of these systems, wherein one or more groups may be further substituted by R ₁₇ or R ₁₇ may further form with a substituted group Ring system

More preferably, Ar ⁷ to Ar ^{9 are the} same or different, and are a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 15 ring atoms, or an aryloxy group having 5 to 15 ring atoms or a heteroaryloxy group, or a non-aromatic group having 5 to 15 ring atoms, or a combination of these systems, wherein one or more of the groups may be further substituted by R ₁₇ or R ₁₇ may further Substituted groups form a ring system;

R ₁₆ and R ₁₇ have the same meaning as R ₁ ;

m, m1, m2 are independently 1 or 2 or 3; preferably 1.

In a preferred embodiment, a mixture according to the invention is characterized in that, in the case of multiple occurrences, Ar ⁷ -Ar ⁹ in the formula (IV) may be identical or differently selected from the following structural groups. One of them or a combination of them:

Wherein n1 is 1 or 2 or 3 or 4.

In a highly preferred embodiment, the mixture according to the invention, wherein H2 is preferably but not limited to the following structure:

In a more preferred embodiment, the carbazole triphenyl mixture according to the present invention further comprises a luminescent material selected from the group consisting of a singlet illuminant, a triplet illuminant or a TADF illuminant.

In certain embodiments, the carbazole triphenyl mixture further comprises a fluorescent illuminant. The carbazole triphenyl mixture according to the present invention may be used as a fluorescent mixed host material, wherein the fluorescent illuminant has a weight percentage of ≤ 10 wt%, preferably ≤ 9 wt%, more preferably ≤ 8 wt%, particularly preferably ≤ 7 wt. %, preferably ≤ 5 wt%.

In a particularly preferred embodiment, the carbazole triphenyl composition further comprises at least one phosphorescent emitter. The carbazole triphenyl mixture according to the present invention may be used as a phosphorescent host material, wherein the phosphorescent emitter has a weight percentage of ≤ 25 wt%, preferably ≤ 20 wt%, more preferably ≤ 15 wt%.

In another more preferred embodiment, the carbazole triphenyl mixture further comprises a TADF material. The mixture according to the invention herein can be used as the TADF host material, wherein the TADF host material has a weight percentage of ≤ 15% by weight, preferably ≤ 10% by weight, more preferably ≤ 8% by weight.

The fluorescent illuminant, the phosphor illuminant and the phosphorescent host material are described in detail below (but are not limited thereto).

1. Phosphorescent host material:

The phosphorescent host material is also referred to as a triplet host material, and the example of the phosphorescent host material is not particularly limited, and any metal complex or organic compound may be used as a host as long as its triplet level is higher than that of the illuminant, especially triple The illuminant or phosphorescent emitter is higher, and examples of metal complexes that can be used as a triplet host include, but are not limited to, the following general structure:

M3 is a metal; (Y ₃ -Y ₄ ) is a two-dentate ligand, Y ₃ and Y _{4 are} independently selected from C, N, O, P, and S; L is an ancillary ligand; r 2 is an integer The value is from 1 to the maximum coordination number of the metal; in a preferred embodiment, the metal complex that can be used as the triplet host has the following form:

(O-N) is a two-tooth ligand in which the metal is coordinated to the O and N atoms, and r2 is an integer having a value from 1 to the maximum coordination number of the metal;

In one embodiment, M3 is optional for Ir and Pt.

Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzindene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, dibenzoxazole, carbazole, pyridinium, pyrrole dipyridine, Pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine , oxadiazine, anthraquinone, benzimidazole, oxazole, oxazole, dibenzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, Quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furopypyridine, benzothienopyridine, thienopyridine, benzoselenophene Pyridine and selenophene benzopyridine; groups containing a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or The aromatic heterocyclic groups are bonded to each other directly or through at least one of the following groups, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Wherein, each Ar may be further substituted, and the substituent may be hydrogen, hydrazine, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. base.

In a preferred embodiment, the triplet host material can be selected from compounds comprising at least one of the following groups:

R ² -R ⁷ have the same meaning as R ¹ , X _{9 is} selected from CR ¹ R ² or NR ¹ , and Y is selected from CR ¹ R ² or NR ¹ or O or S. R ¹ , n 2 , X ¹ - X ⁸ and Ar ₁ to Ar ₃ have the same meanings as described above.

Examples of suitable triplet host materials are listed in the table below but are not limited to:

2. Fluorescent emitter

Fluorescent emitters are also referred to as singlet emitters, and singlet emitters tend to have longer conjugated pi-electron systems. Heretofore, there have been many examples, such as styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1, indenoindoles and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847, and disclosed in US Pat. No. 7,233,019, KR2006-0006760 A quinone triarylamine derivative.

In a preferred embodiment, the singlet emitter can be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and aromatic amine.

A monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined similarly to amines. An arylamine or an 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 preferably selected from the fused ring system and preferably has at least 14 aromatic ring atoms. Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine. An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9. An aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, preferably at the 9,10 position. The definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is preferably bonded to the 1 or 1,6 position of hydrazine.

Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007 /115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1, the entire contents of which are hereby incorporated by reference. This article is incorporated herein by reference.

An example of a singlet emitter based on a stilbene extreme derivative is US 5121029.

Further preferred singlet emitters can be selected from indenoindole-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindoloindole-amines and benzoindenoindole-diamines , as disclosed in WO 2008/006449, dibenzoindolo-amine and dibenzoindeno-diamine, as disclosed in WO 2007/140847.

Further preferred singlet emitters are selected from the group consisting of ruthenium-based fused ring systems as disclosed in US2015333277A1, US2016099411A1, US2016204355A1.

More preferred singlet emitters may be selected from the derivatives of hydrazine, such as those disclosed in US2013175509A1; triarylamine derivatives of hydrazine, such as triarylamine derivatives of hydrazine containing dibenzofuran units disclosed in CN102232068B; A triarylamine derivative of hydrazine having a specific structure, as disclosed in CN105085334A, CN105037173A. Other materials which can be used as singlet emitters are polycyclic aromatic hydrocarbon compounds, in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , 芘 (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4 (dicyanomethylidene)-6-(4-p-dimethylaminobenzene Vinyl-2-methyl)-4H-pyran (DCM), thiopyran, bis(pyridazinyl)imine boron compound (US 2007/0092753 A1), bis(pyridazinyl)methylene compound, carbostyryl Compounds, oxazinone, benzoxazole, benzothiazole, benzimidazole and pyrrolopyrroledione. Materials for some singlet illuminants can be found in the following patent documents: US 20070252517 A1, US 4769292, US 6020078, US 2007/0252517 A1, US 2007/0252517 A1. The entire contents of the above-listed patent documents are hereby incorporated by reference.

Some examples of suitable singlet emitters are listed in the table below:

3. Phosphorescent emitter

Phosphorescent emitters are also referred to as triplet emitters. In a preferred embodiment, the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Alternatively, these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.

In a preferred embodiment, the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy Re, Cu or Ag, with Os, Ir, Ru, Rh, Re, Pd, Au or Pt being particularly preferred.

Preferentially, the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different pairs Tooth or multidentate ligand. Chelating ligands are beneficial for increasing the stability of metal complexes.

Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene. A quinolinol derivative. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.

In a preferred embodiment, the metal complex that can be used as the triplet emitter has the following form:

Wherein M is a metal selected from a transition metal element or a lanthanide or actinide element, particularly preferably Ir, Pt, Au;

Ar ¹ may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal. Connection; Ar ² may be the same or different each time it appears, is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal; Ar ¹ and Ar ² are bonded by a covalent bond Together, each may carry one or more substituent groups, which may also be joined together by a substituent group; L' may be the same or different at each occurrence, and is a bidentate chelate auxiliary ligand, preferably Is a monoanionic bidentate chelate ligand; q1 can be 0, 1, 2 or 3, preferably 2 or 3; q2 can be 0, 1, 2 or 3, preferably 1 or 0.

Examples of the application of materials for some triplet emitters can be found in the following patent documents and documents: 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, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson et al. Nature 403, (2000) ), 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth. Metals 94 , 1998, 245, US 6824895, US 7029766, US 6835469, US 6830828, US 20010053462 A1, WO 2007095118 A1, US 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1, WO 2013107487A1 , WO 20130 94620A1, WO 2013174471A1, WO 2014031977 A1, WO 2014112450 A1, WO 2014007565 A1, WO 2014038456 A1, WO 2014024131 A1, WO 2014008982 A1, WO 2014023377 A1. The entire contents of the above-listed patent documents and documents are hereby incorporated by reference.

Some examples of suitable triplet emitters are listed in the table below:

It is an object of the present invention to provide a material solution for an evaporated OLED.

In certain embodiments, the carbazole triphenyl organic compound according to the invention has a molecular weight of ≤1100 g/mol, preferably ≤1000 g/mol, very preferably ≤950 g/mol, more preferably ≤900 g/mol, most preferably ≤800 g/ Mol.

Another object of the invention is to provide a material solution for printing OLEDs.

In certain embodiments, the carbazole triphenyl organic compound according to the invention has a molecular weight of ≥ 700 g/mol, preferably ≥ 800 g/mol, very preferably ≥ 900 g/mol, more preferably ≥ 1000 g/mol, most preferably ≥ 1100 g/ Mol.

In other embodiments, the carbazole triphenyl organic compound according to the invention has a solubility in toluene of > 2 mg/ml, preferably > 3 mg/ml, more preferably > 4 mg/ml, most preferably > 5 mg at 25 °C. /ml.

The present invention further relates to a composition or ink comprising the carbazole triphenyl organic compound or the carbazole triphenyl mixture according to any one of the above, and at least one organic solvent.

A carbazole tritium composition according to the invention, said at least one organic solvent being selected from the group consisting of aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic ring a family or an olefinic compound, or a borate or phosphate compound, or a mixture of two or more solvents.

In a preferred embodiment, a carbazole tritium composition according to the present invention, the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic based solvents.

Examples of aromatic or heteroaromatic solvents suitable for the present invention are, but are not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene. , 3-isopropylbiphenyl, p-methyl cumene, dipentylbenzene, triphenylbenzene, pentyltoluene, 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-diisopropylbenzene , cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 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, 1,1-bis(3,4-dimethylphenyl) Ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, etc.;

Examples of aromatic ketone solvents suitable for the present invention are, but are not limited to, 1-tetralone, 2-tetralone, 2-(phenyl epoxy) tetralone, 6-(methoxy Tetrendanone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, etc.;

Examples of aromatic ether-based solvents suitable for the present invention are, but are not limited to, 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H -pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxy Toluene, 4-ethyl ether, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methyl Oxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

In some preferred embodiments, according to the composition of the present invention, the at least one organic solvent may be selected from the group consisting of: an aliphatic ketone, for example, 2-fluorenone, 3-fluorenone, 5-fluorenone, 2 - anthrone, 2,5-hexanedione, 2,6,8-trimethyl-4-indanone, anthrone, phorone, isophorone, di-n-pentyl ketone, etc.; or an aliphatic ether For example, pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, Triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

In still other preferred embodiments, according to the composition of the present invention, the at least one organic solvent may be selected from ester-based solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, benzene. Alkyl formate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolide, alkyl oleate, and the like. Particularly preferred are octyl octanoate, diethyl sebacate, diallyl phthalate, isodecyl isononanoate.

The solvent may be used singly or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the present invention, comprising the organic compound or composition of any one of the above, and at least one organic solvent, may further comprise another organic solvent, An example of an organic solvent, including but not limited to: 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, tetrahydronaphthalene , decalin, hydrazine and/or mixtures thereof.

In a preferred embodiment, the carbazole triphenyl composition according to the invention is a solution.

In another preferred embodiment, the carbazole triphenyl composition according to the invention is a suspension.

The invention also relates to the use of a composition as a printing ink for the preparation of an organic electronic device, particularly preferably by a printing or coating process.

Among them, suitable printing or coating techniques include, but are not limited to, inkjet printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twist roll printing, lithography, flexography Printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are gravure, screen printing and inkjet printing. Gravure printing, ink jet printing will be applied in embodiments of the invention. The solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like. For information on printing techniques and their requirements for solutions, such as solvents and concentrations, viscosity, etc., please refer to Helmut Kipphan's "Printing Media Handbook: Techniques and Production Methods" (Handbook of Print Media: Technologies and Production Methods). ), ISBN 3-540-67326-1.

The preparation method as described above, characterized in that the formed functional layer has a thickness of from 5 nm to 1000 nm.

The invention further relates to the use of an organic compound or mixture according to any of the preceding claims in an organic electronic device.

The invention further relates to an organic electronic device characterized in that the functional layer comprises an organic compound or mixture as described above.

The organic electronic device may be selected from, but not limited to, 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, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.

In certain particularly preferred embodiments, the organic electroluminescent device comprises at least one emissive layer comprising an organic compound or mixture as described above.

In the above light-emitting device, particularly an OLED, a substrate, an anode, at least one light-emitting layer, and a cathode are included.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode can comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of the anode material include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.

The cathode can include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer. In one embodiment, the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or The absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of the cathode material include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF ₂ /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may further include other functional layers such as 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. (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of each of which are hereby incorporated by reference.

The light-emitting device according to the present invention has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.

The invention further relates to the use of an electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.

The present invention will be described with reference to the preferred embodiments thereof, but the present invention is not limited to the embodiments described below. It is to be understood that the scope of the invention is intended to be It is to be understood that the modifications of the various embodiments of the invention are intended to be

Specific embodiment

1. Synthesis of compounds

Example 1: Synthesis of comp-1

Synthesis of Intermediate A:

Take a (1 g, 3.5 mmol), b (1.1 g, 3.5 mmol), Pd(PPh ₃ ) ₄ (0.12 g, 0.11 mmol), K ₂ CO ₄ (0.96, 7 mmol) in a 50 ml round bottom flask. 20 ml of toluene (Toluene), 3.5 ml of water, oil pump to extract the air from the bottle, pass N ₂ , reflux and react overnight, extract by liquid separation, pass through the column (DCM: PE = 1:8), the yield is 65%.

Synthesis of intermediate B:

Taking c (1 g, 4.7 mmol), d (1.33 g, 4.7 mmol), Pd (PPh ₃ ) ₄ (0.16 g, 0.14 mmol), K ₂ CO ₄ (1.3, 9.4 mmol) in a 50 ml round bottom flask. Add 20 ml of toluene (Toluene), add 5 ml of water, pump the air from the bottle, pass N ₂ , stir the reaction at 65 ° C overnight, extract by liquid separation, and pass through the column (pure PE), the yield is 70%.

Synthesis of intermediate C:

Take A (1 g, 2.1 mmol), e (0.64 g, 2.52 mmol), potassium acetate (0.63 g, 6.3 mmol), Pd(dppf)Cl ₂ (0.078 g, 0.1 mmol) in a 100 ml two-necked flask, then Add 30 ml of toluene as a solvent to start stirring, install and seal the device, pass nitrogen, reflux at 105 ° C overnight, extract by liquid separation, pass silica gel (DCM: PE = 1:5), yield 85%.

Synthesis of Compound 1:

C (1 g, 1.9 mmol), B (0.62 g, 1.9 mmol), Pd(PPh ₃ ) ₄ (0.067 g, 0.057 mmol), K ₂ CO ₃ (0.53 g, 3.8 mmol) in a 50 ml round bottom flask Add 20 ml of toluene, add 2 ml of water, extract the air from the bottle with an oil pump, pass N ₂ , stir the reaction overnight, and extract by liquid separation. The yield of the column (DCM:PE=1:8) is 70%.

Example 2: Synthesis of comp-2

Synthesis of intermediate B1:

Taking c1 (1 g, 4.4 mmol), d (1.23 g, 4.4 mmol), Pd(PPh ₃ ) ₄ (0.16 g, 0.13 mmol), K ₂ CO ₄ (1.3, 8.8 mmol) in a 50 ml round bottom flask. Add 20 ml of toluene (Toluene), add 5 ml of water, pump the air from the bottle, pass N ₂ , stir the reaction at 65 ° C overnight, extract by liquid separation, and pass through the column (pure PE), the yield is 68%.

Synthesis of Compound 2:

C (1 g, 1.9 mmol), B1 (0.65 g, 1.9 mmol), Pd(PPh ₃ ) ₄ (0.067 g, 0.057 mmol), K ₂ CO ₃ (0.53 g, 3.8 mmol) in a 50 ml round bottom flask Add 20 ml of toluene (Toluene), add 2 ml of water, extract the air from the bottle with an oil pump, pass N ₂ , stir the reaction overnight, and extract by liquid separation. The yield of the column (DCM:PE=1:8) is 73%.

Example 3: Synthesis of comp-3

Synthesis of intermediate B2:

C2 (1 g, 4.4 mmol), d (1.23 g, 4.4 mmol), Pd(PPh ₃ ) ₄ (0.16 g, 0.13 mmol), K ₂ CO ₄ (1.3, 8.8 mmol) in a 50 ml round bottom flask. Add 20 ml of toluene (Toluene), add 5 ml of water, pump the air from the bottle, pass N ₂ , stir the reaction at 65 ° C overnight, extract by liquid separation, and pass through the column (pure PE), the yield is 67%.

Synthesis of Compound 3:

C (1 g, 1.9 mmol), B2 (0.65 g, 1.9 mmol), Pd (PPh ₃ ) ₄ (0.067 g, 0.057 mmol), K ₂ CO ₃ (0.53 g, 3.8 mmol) in a 50 ml round bottom flask Add 20 ml of toluene (Toluene), add 2 ml of water, pump the air from the bottle, pass N ₂ , stir the reaction overnight, and extract by liquid separation. The yield of the column (DCM:PE=1:8) is 70%.

Example 4: Synthesis of comp-4

Synthesis of intermediate A1:

Take a (1 g, 3.5 mmol), b1 (1.1 g, 3.5 mmol), Pd(PPh ₃ ) ₄ (0.12 g, 0.11 mmol), K ₂ CO ₄ (0.96, 7 mmol) in a 50 ml round bottom flask. 20 ml of toluene (Toluene), 3.5 ml of water, oil pump to extract the air from the bottle, pass N ₂ , reflux and react overnight, extract by liquid separation, pass through the column (DCM: PE = 1:8), the yield is 65%.

Synthesis of intermediate B1:

Same as embodiment 2

Synthesis of intermediate C1:

Taking A1 (1 g, 2.1 mmol), e (0.64 g, 2.52 mmol), potassium acetate (0.63 g, 6.3 mmol), Pd(dppf)Cl ₂ (0.078 g, 0.1 mmol) in a 100 ml two-necked flask, then 30 ml of toluene was added as a solvent to start stirring, and the apparatus was installed and sealed. Nitrogen gas was introduced, and the reaction was refluxed at 105 ° C overnight, and the mixture was separated and extracted with silica gel (DCM:PE = 1:5), yield 83%.

Synthesis of Compound 4:

Take C1 (1 g, 1.9 mmol), B1 (0.65 g, 1.9 mmol), Pd(PPh ₃ ) ₄ (0.067 g, 0.057 mmol), K ₂ CO ₃ (0.53 g, 3.8 mmol) in a 50 ml round bottom flask Add 20 ml of toluene, add 2 ml of water, extract the air from the bottle with an oil pump, pass N ₂ , stir the reaction overnight, and extract by liquid separation. The yield of the column (DCM:PE=1:8) is 72%.

The synthesis of the host materials H2-1 and H2-2 can be referred to WO 2015152650A1, US 20160163995.

2. Compound energy level structure

The energy structure of the organic repeating structural unit can be obtained by quantum calculation, for example, by 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 09W, and the unit is eV. The results are shown in Table 1, where ΔHOMO=HOMO-(HOMO-1):

Table 1

material HOMO HOMO-1 LUMO LUMO+1 S1 T1

[eV] [eV] [eV] [eV] [eV] [eV] Comp-1 -5.68 -5.24 -2.33 -2.11 3.24 2.94 Comp-2 -5.68 -5.30 -2.27 -2.14 3.23 2.97 Comp-3 -5.70 -5.35 -2.24 -2.18 3.23 2.96 Comp-4 -5.69 -5.31 -2.31 -2.25 3.23 2.89 H2-1 -6.01 -5.73 -2.86 -2.66 3.29 2.92 H2-2 -5.67 -5.54 -2.88 -2.60 2.86 2.79

3. Preparation and measurement of OLED devices

The preparation process of the OLED device described above is described in detail by way of specific embodiments. The structure of the OLED device is: ITO/HI/HI-1/HT-2/EML/ET Liq/Liq/Al, and the preparation steps are 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, HI (30 nm), HT-1 (50 nm), HT-2 (10 nm), host material: 10% GD (40 nm), ET: Liq (50: 50; 30 nm), Liq (1 nm), Al (100 nm) ) is formed by thermal evaporation in a high vacuum (1 × 10 ^-6 mbar); the ITO substrate is transferred into a vacuum vapor deposition apparatus, and a high-vacuum (1 × 10 ^-6 mbar) is used to heat the evaporation source. A HI layer having a thickness of 30 nm was formed, and a 30 nm HT-1 and a 10 nm HT-2 layer were sequentially formed by heating on the HI layer. Then the host material (see Table 2) is placed in different evaporation units, and the compound GD is placed in another evaporation unit as a dopant, so that the three materials are vaporized at different rates, so that the weight ratio of the host material: Dopant is 100:10, a 40 nm light-emitting layer was formed on the hole transport layer. Next, ET and LiQ were placed in different evaporation units to be co-deposited at a ratio of 50% by weight, an electron transport layer of 30 nm was formed on the light-emitting layer, and then 1 nm of LiQ was deposited as an electron injection layer on the electron transport layer. Finally, an Al cathode having a thickness of 100 nm was deposited on the electron injecting layer. c. Package: The device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.

The current and voltage (IVL) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and drive voltage. The performance of OLED devices is summarized in Table 2, where lifetime is a relative comparative value.

Table 2

OLED device Body material CE@1000nits T95@1000nits Example 1 Comp-1:H2-1=5:5 61.3 534 Example 2 Comp-1:H2-2=5:5 70.1 728 Example 3 Comp-2:H2-1=5:5 63.4 567 Example 4 Comp-2:H2-2=5:5 69.5 671 Example 5 Comp-3:H2-1=5:5 63.8 493 Example 6 Comp-3:H2-2=5:5 68.2 544 Example 7 Comp-4:H2-1=5:5 62.9 460 Example 8 Comp-4:H2-2=5:5 68.7 519 Comparative example 1 CBP 39.2 100 Comparative example 2 CBP: H2-2=5:5 52.5 233

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 (16)

An carbazole triphenyl organic compound characterized by the structure represented by the specific formula (I):

among them: When a plurality of the R ₀ , R ₁ , R ₂ , R ₃ , R ₄ or R ₅ are present, a plurality of the R ₀ , R ₁ , R ₂ , R ₃ , R ₄ or R _{5 are the} same or different, The R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from the group consisting of: H, D, a linear alkyl group having 1 to 20 C atoms, and having 1 to 20 C atoms. An alkoxy group, a thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branch or a ring having 3 to 20 C atoms Alkoxy group, a branched or cyclic thioalkoxy group having 3 to 20 C atoms, a silyl group, a substituted keto group having 1 to 20 C atoms, having 2 An alkoxycarbonyl group to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, Isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, having 5 to 40 a substituted or unsubstituted aryl group of a ring atom, a substituted or unsubstituted group having 5 to 40 ring atoms An aryl group having 5 to 40 ring atoms, aryloxy, heteroaryl having 5 to 40 ring atoms, aryloxy groups; said _{R 0, R 1, R 2} , R 3, R 4, R 5 in The groups may be bonded to each other and/or to the ring to which the group is attached to form a monocyclic or polycyclic aliphatic or aromatic ring system; a is 0, 1, 2 or 3; b is 0, 1, 2, 3 or 4; c is 0, 1, 2, 3 or 4; d is 0, 1, 2, 3 or 4; e is 0, 1, 2, 3 or 4; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are each independently selected from CR ₈ or N; and when said Y ¹ , Y ² , Y ³ , Y ⁴ , Y ^When Y ⁶ , Y ⁷ or Y ⁸ is a site bonded to a single bond represented by the formula (I), the Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ or Y ⁸ is a carbon atom; X is O, S, CR ₆ R ₇ or SiR ₆ R ₇ ; R ₆ , R ₇ and R _{8 have} the same meanings as R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ . The carbazole triphenyl organic compound according to claim 1, which has a structure represented by the formula (I-1) to the formula (I-18):

The carbazole triphenyl organic compound according to claim 2, wherein said R ₀ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently selected. From H, C1-C6 alkyl, or a group containing the following structure:

among them: X ₁ to X _{8 are} selected from CR ₉ or N; Y is selected from CR ₁₀ R ₁₁ , SiR ₁₀ R ₁₁ , NR ₁₀ , C(=O), S or O; R _9, R ₁₀ or R ₁₁ when there is a plurality, the plurality of R _9, R ₁₀ or R ₁₁ are the same or different, said R _9, R ₁₀ and R ₁₁ are each independently selected from: H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, a thioalkoxy group having 1 to 20 C atoms, and a branch having 3 to 20 C atoms a chain or cyclic alkyl group, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic thioalkoxy group having 3 to 20 C atoms, or a monosilane a group, a substituted keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, cyanogen a radical, a carbamoyl group, a haloformyl group, a formyl group, an isocyanato group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a CF ₃ group, Cl, Br, F, a substituted or unsubstituted aryl group having 5 to 40 ring atoms, a substituted or unsubstituted heteroaryl group having 5 to 40 ring atoms, 5 to 40 ring atom aryloxy groups, having 5 to 4 a heteroaryloxy group of 0 ring atoms; the groups of R ₉ , R ₁₀ and R ₁₁ may be bonded to each other and/or to a ring to which the group is bonded to form a monocyclic or polycyclic aliphatic group Or aromatic ring system. A carbazole triphenyl polymer characterized in that the repeating unit of the carbazole triphenyl polymer comprises the structure of the carbazole triphenyl organic compound according to any one of claims 1 to 3. A carbazole triphenyl mixture comprising a first component and a second component, said first component being H1, said second component being H2; and said H1 is claim 1 The carbazole triphenyl organic compound according to any one of 3, wherein the H2 is another organic functional material selected from the group consisting of a hole injecting material, a hole transporting material, an electron transporting material, and an electron. Injecting material, electron blocking material, hole blocking material, luminescent material, host material or organic dye. The carbazole triphenyl mixture according to claim 5, wherein the H2 is selected from the group consisting of the compounds of the formula (II-1) to the formula (II-4):

among them: L ¹ is an aromatic group having 5 to 30 ring atoms or a heteroaromatic group having 5 to 30 ring atoms; L ² is a single bond, or is selected from an aromatic group having 5 to 30 ring atoms and a heteroaromatic group having 5 to 30 ring atoms; Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ independently representing an aromatic group having 5 to 30 ring atoms or a heteroaromatic group having 5 to 30 ring atoms; X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ and X ₁₆ are each independently a single bond, or C(R ₁₄ R ₁₅ ), Si(R ₁₄ R ₁₅ ), O, N (R ₁₄ ), P(R ₁₄ ), C=N(R ₁₄ ), C=C(R ₁₄ R ₁₅ ), P(=O)R ₁₄ , S, S=O or SO ₂ ; and X ₉ and X _{10 is} not a single button at the same time, X ₁₁ and X _{12 are} not single bonds at the same time, X ₁₃ and X _{14 are} not single bonds at the same time, and X ₁₅ and X _{16 are} not single bonds at the same time; R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each independently selected from the group consisting of: H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone group An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic group having 5 to 60 ring atoms or a heteroaromatic group having 5 to 60 ring atoms; n is 1, 2, 3, 4, 5 or 6. The carbazole tritene mixture according to claim 5 or 6, wherein the singlet state and triplet energy level difference of said H2 is less than or equal to 0.3 eV. The carbazole triphenyl mixture according to claim 5 or 6, wherein said H1 and said H2 have a type I semiconductor heterojunction structure, and said H1 has a highest occupied orbital lower than said H2 Occupying the orbit, the lowest unoccupied orbit of H1 is higher than the lowest unoccupied orbit of H2. The carbazole triphenyl mixture according to claim 5 or 6, wherein the H1 and H2 have a type II semiconductor heterojunction structure; and min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))≤min(ET(H1), ET(H2))+0.1eV; Where LUMO(H1) represents the lowest unoccupied orbit of H1, HOMO(H1) represents the highest occupied orbit of H1, and ET(H1) represents the triplet level of H1; LUMO(H2) represents the lowest unoccupied orbit of H2, HOMO(H2) represents the highest occupied orbit of H2, and ET(H2) represents the triplet level of H2. The carbazole triphenyl mixture according to any one of claims 5 to 9, wherein the H2 comprises at least one electron withdrawing group represented by the following structure:

Where m is 1, 2 or 3; Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ and Z ⁸ are each independently CR ₁₆ or N, and said Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , At least one of Z ⁶ , Z ⁷ and Z ⁸ is N; M ¹ , M ² and/or M ³ are absent or are each independently selected from: N(R ₁₇ ), C(R ₁₇ ) ₂ , Si(R ₁₇ ) ₂ , O, C=N(R ₁₇ ), C=C(R ₁₇ ) ₂ , P(R ₁₇ ), P(=O)R ₁₇ , S, S=O or SO ₂ ; R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently selected from the group consisting of alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. The carbazole triphenyl mixture according to any one of claims 5 to 10, wherein the H2 is selected from the group consisting of a compound represented by any one of the formulae (II-5) to (II-11) :

among them, Ar ¹¹ , Ar ¹² and Ar ¹³ are each independently an aromatic group having 5 to 60 ring atoms or an aromatic hetero group having 5 to 60 ring atoms; n is 1, 2 or 3; Z ¹ , Z ² and Z ³ are each independently CR ₁₆ or N, and at least one of Z ¹ , Z ² and Z ³ is N; M ¹ , M ² and/or M ³ are absent or are each independently selected from: N(R ₁₇ ), C(R ₁₇ ) ₂ , Si(R ₁₇ ) ₂ , O, C=N(R ₁₇ ), C=C(R ₁₇ ) ₂ , P(R ₁₇ ), P(=O)R ₁₇ , S, S=O or SO ₂ ; R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently selected from the group consisting of alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. The carbazole triphenyl mixture according to any one of claims 5 to 11, further comprising at least one luminescent material, the luminescent material being a singlet illuminant, a triplet illuminant or a TADF material . A carbazole triphenyl composition comprising at least one carbazole triphenyl organic compound according to any one of claims 1 to 3, the carbazole triphenyl high polymer according to claim 4 or a right The carbazole triphenyl mixture of any of 5-12, and at least one organic solvent. An organic electronic device comprising a functional layer comprising the carbazole triphenyl organic compound according to any one of claims 1 to 3, and the carbazole triphenyl high according to claim 4. Polymer or a mixture of carbazole triphenyl compounds according to any one of claims 5-12. The organic electronic device according to claim 14, 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. Spintronics, organic sensors and organic plasmon emitting diodes. The organic electronic device according to claim 14, wherein said organic electronic device is an organic electroluminescent device, said organic electroluminescent device comprising at least one light emitting layer, said light emitting layer comprising a right The carbazole triphenyl organic compound according to any one of claims 1 to 3, or the carbazole triphenyl mixture according to any one of claims 5 to 12.

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