Composition containing carbazole compound and organic electroluminescent device

Abstract

The invention provides a composition containing a carbazole compound and an organic electroluminescent device. The composition containing the carbazole compound comprises a first component and a second component, the first component is a carbazole compound, and the carbazole compound has a structure as shown in a formula I or a formula II; the second component comprises a compound A; the compound A is obtained by condensing any two adjacent carbon atoms on the ring A in the group I-A and the group I-B. The composition containing the carbazole compound is designed, and the structure of the carbazole compound is further designed, so that the carbazole compound is suitable for being used as a main body material of a phosphorescent light-emitting layer of the organic electroluminescent device, and the organic electroluminescent device has relatively high current efficiency and relatively long service life.

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescent materials, and in particular relates to a composition containing carbazole compounds and an organic electroluminescent device. Background Art

[0002] The structure of an organic electroluminescent device is specifically: an anode, a cathode, and an organic layer between the two. In order to improve the efficiency and stability of an organic electroluminescent element, the organic material layer includes multiple layers with different materials, such as a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer, a light-emitting layer, an electron transport layer (ETL), and an electron injection layer (EIL). Currently, organic electroluminescence has become a mainstream display technology, and accordingly, various new OLED materials have also been developed.

[0003] In order to meet people's higher requirements for OLED devices, the field is in urgent need of developing more types of materials to improve the performance of OLED devices in terms of current efficiency, life span, etc. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide a composition containing a carbazole compound and an organic electroluminescent device. In the present invention, by designing the composition and further designing the structure of the carbazole compound, the composition is suitable for being used as a main material of a phosphorescent light-emitting layer of an organic electroluminescent device, so that the organic electroluminescent device has a higher current efficiency and a longer life.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a composition containing a carbazole compound, wherein the composition containing a carbazole compound comprises a first component and a second component;

[0007] The first component is a carbazole compound, and the carbazole compound has a structure shown in the following formula I or formula II:

[0008]

[0009] Wherein, in the compound of formula I, R1, R2, and R3 are each independently selected from a hydrogen atom or a deuterium atom, and at least one of R1, R2, and R3 is selected from a deuterium atom (-D);

[0010] In the compound of formula I, Ar is selected from any one of a single bond, a C6-C40 arylene group or a C6-C30 heteroarylene group;

[0011] In the compound of formula I, Ar1 and Ar2 are each independently selected from any one of H, C6-C40 aryl or C6-C30 heteroaryl;

[0012] In the compound of formula I, A1, A2, A3 are each independently selected from N or CR, and at least one is selected from N; R is selected from any one of H, -CN, C6-C20 aryl or C1-C12 alkyl;

[0013] In the compound of formula I, a and b are each independently selected from 0 or 1, and at least one of a and b is selected from 1;

[0014] In the compound of formula II, R4, R5, R6, R7, and R8 are each independently selected from a hydrogen atom or a deuterium atom, and at least one of R4, R5, R6, R7, and R8 is selected from a deuterium atom (-D);

[0015] In the compound of formula II, Ar is selected from any one of a single bond, a C6-C40 arylene group or a C6-C30 heteroarylene group;

[0016] In the compound of formula II, Ar1 and Ar2 are each independently selected from any one of H, C6-C40 aryl or C6-C30 heteroaryl;

[0017] In the compound of formula II, A1, A2, A3 are each independently selected from N or CR, and at least one is selected from N; R is selected from any one of H, -CN, C6-C20 aryl or C1-C12 alkyl;

[0018] In the compound of formula II, a and b are each independently selected from 0 or 1, and at least one of a and b is selected from 1;

[0019] The hydrogen atoms in the compound of formula I and the compound of formula II can each independently be substituted by at least one of a deuterium atom (-D), -F, -CN, a C6-C20 aryl group, a triphenylmethyl group, a triphenylsilyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

[0020] In the compound of formula I / compound of formula II provided by the present invention, one side is a nitrogen-containing heterocycle and the other side is a carbazole structure, the HOMO of the molecule is mainly distributed on the carbazole structure side, and the LUMO of the molecule is mainly distributed on the nitrogen heterocycle side. When used as a main material of the light-emitting layer, the compound of formula I / compound of formula II is in an excited state, and electron transfer or energy transfer occurs within the molecule at this time, which will affect the luminous efficiency of the device. Therefore, how to block the energy transfer or electron transfer between the carbazole structure side and the nitrogen heterocycle side is a problem that needs to be considered.

[0021] The applicant has found that by replacing the H atoms on the benzene ring / naphthalene ring between the carbazole structure and the nitrogen heterocycle with D atoms, the energy transfer or electron transfer between the carbazole structure and the nitrogen heterocycle can be effectively blocked, and accordingly, the luminous efficiency of the device is improved. At the same time, the life of the device is improved.

[0022] In the present invention, the structure of the carbazole compound is designed to make it suitable as the main material of the phosphorescent light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency and longer life.

[0023] In the present invention, C6-C40 can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.

[0024] C6-C30 can be C6, C8, C10, C12, C16, C20, C24, C28 or C30, etc.

[0025] C6-C20 can be C6, C8, C10, C12, C16 or C20, etc.

[0026] C1-C12 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12.

[0027] It should be noted that, in the present invention, "-D" represents a deuterium atom, and the same shall apply hereinafter.

[0028] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0029] As a preferred technical solution of the present invention, the C6-C40 arylene group is selected from phenylene, biphenylene, terphenylene, naphthylene, anthracene, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthofluorenyl, pyrenyl, perylene, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenyl, benzoindenyl, dibenzoindenyl, naphthofluorenyl, tetraphenylmethane Or any one of or a combination of at least two of benzonaphthofluorenyl.

[0030] As a preferred technical solution of the present invention, the C6-C30 heteroaryl group is selected from any one of a carbazolyl group, a dibenzothiophenyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, a dinaphthofuranyl group, a dinaphthothiophenyl group or a carbazolyl group.

[0031] As a preferred technical solution of the present invention, the C6-C40 aromatic group is selected from any one or a combination of at least two of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrene, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl, tetraphenylmethane or benzonaphthofluorenyl.

[0032] As a preferred technical solution of the present invention, the C6-C30 heteroaryl group is selected from any one of carbazolyl, dibenzothiophenyl, dibenzofuranyl, naphthiobenzofuranyl, naphthiobenzothiophenyl, dinaphthofuranyl, and dinaphthothiophenyl, or a combination of at least two thereof.

[0033] Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, anthracenyl, phenanthryl, fluorenyl, triphenylene or fluoranthene.

[0034] Preferably, the C1-C12 alkyl group is selected from any one of a methyl group, an ethyl group, a propyl group, a n-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, an octyl group and an adamantyl group.

[0035] Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and octyloxy.

[0036] As a preferred technical solution of the present invention, in the compound of formula I and the compound of formula II, the Ar is independently selected from any one of a single bond, a phenylene group, a carbazolyl group, a biphenylene group, a fluorenyl group, a naphthyl group, a triphenylene group, a fluoranthenyl group, an indenofluorenyl group, a dibenzothienyl group, a naphthoxybenzofuranyl group or a naphthoxybenzothienyl group or a carbazolyl group.

[0037] Preferably, in the compound of formula I and formula II, the Ar is independently selected from at least one of a single bond, a phenylene group, a carbazolyl group, a naphthyl group, a 9,9-dimethylfluorenyl group, a dibenzothienyl group, a dibenzofuranyl group or a biphenylene group, and is further preferably any one of a single bond, a phenylene group, a biphenylene group or a carbazolyl group.

[0038] As a preferred technical solution of the present invention, in the compound of formula I and the compound of formula II, Ar1 and Ar2 are each independently selected from any one of H, phenyl, carbazolyl, biphenyl, 9,9-dimethylfluorenyl, naphthyl, triphenylene, fluoranthene, indenofluorenyl, dibenzofuranyl, dibenzothienyl, naphthiobenzofuranyl or naphthiobenzothienyl, or a combination of at least two thereof.

[0039] Preferably, in the compound of formula I and the compound of formula II, Ar1 and Ar2 are each independently selected from at least one of H, phenyl, carbazolyl, naphthyl, 9,9-dimethylfluorenyl, dibenzothiophenyl, biphenyl, dibenzofuranyl, triphenylene or fluoranthene, and more preferably at least one of phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl and carbazolyl.

[0040] As a preferred technical solution of the present invention, any one of A1, A2, and A3 is selected from N, the other two are CR, and R is selected from H or -CN.

[0041] Preferably, any two of A1, A2, and A3 are selected from N, the other one is CR, and R is selected from H or -CN.

[0042] Preferably, A1, A2, A3 are all selected from N.

[0043] Preferably, in Formula I, R1, R2, and R3 are all selected from deuterium atoms.

[0044] Preferably, in Formula II, R4, R5, R6, R7, and R8 are all selected from deuterium atoms.

[0045] As a preferred technical solution of the present invention, the hydrogen atoms in the compound of formula I and the compound of formula II can be independently substituted by at least one of -D, -F, -CN, phenyl, naphthyl, biphenyl, triphenylmethyl, triphenylsilyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy or butoxy.

[0046] Preferably, the hydrogen atoms in the compound of formula I and the compound of formula II can be independently substituted by at least one of -D, -F, -CN, phenyl, naphthyl, methyl, ethyl, tert-butylmethoxy, ethoxy and propoxy.

[0047] As a preferred technical solution of the present invention, the carbazole compound is selected from any one of the following substituted or unsubstituted compounds:

[0048]

[0049]

[0050]

[0051]

[0052] The substitution means that the hydrogen atoms in the above carbazole compounds can be independently replaced by deuterium atoms. Preferably, the carbazole compound is selected from any one of the following compounds:

[0053]

[0054] As a preferred technical solution of the present invention, the second component includes compound A;

[0055] The compound A is obtained by fusing a group having a structure as shown in Formula IA with any two adjacent carbon atoms on the ring A in the group having a structure as shown in Formula IB:

[0056]

[0057] Among them, * indicates the fusion site;

[0058] X is selected from O, S, R 301 , R 302 are each independently selected from C1-C6 alkyl, C6-C30 aryl or C6-C20 heteroaryl, and R 301 , R 302 Can be connected to form a ring through a single bond, R 303 is selected from C6-C30 aryl or C6-C20 heteroaryl, and the dotted line indicates the attachment site;

[0059] Ar 22 is selected from C6-C30 aryl or C6-C20 heteroaryl;

[0060] The hydrogen atoms in compound A may be independently substituted by at least one of -F, -CN, C6-C20 aryl, C1-C6 alkyl, and C1-C6 alkoxy.

[0061] In compound A, the C6-C30 may be C6, C10, C12, C18, C24 or C30, etc.

[0062] The C6-C20 may be C6, C10, C12, C18 or C20, etc.

[0063] The C1-C6 can be C1, C2, C3, C4, C5 or C6.

[0064] As a preferred technical solution of the present invention, in compound A, the R 303 ,Ar 22Each independently selected from any one or a combination of two of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, peryl, spirofluorenyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuran, naphthobenzothiophene, dinaphthofuran, dinaphthothiophene, hydrogenated benzene anthracenyl, indenofluorenyl, indolecarbazolyl, indenocarbazolyl, terphenyl, quaterphenyl, imidazolyl, benzimidazolyl, pyridyl, pyrimidinyl, piperazinyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, benzoquinoxalinyl, benzoquinazolinyl, N heterophenanthrenyl, diazophananthrenyl, carbazolyl, benzocarbazolyl, naphthocarbazolyl, dibenzocarbazolyl, triazinyl;

[0065] The substituted substituents are each independently selected from at least one of C1-C12 (for example, C1, C2, C5, C6, C8, C10 or C12, etc.) alkyl, C1-C12 (for example, C1, C2, C5, C6, C8, C10 or C12, etc.) alkoxy, and C6-C12 (for example, C6, C7, C8, C9, C10, C11 or C12) aryl.

[0066] As a preferred technical solution of the present invention, the R 303 ,Ar 22 Each independently selected from any one or a combination of two of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothiophenyl, triphenylene, fluorenyl, carbazolyl, benzofluorenyl;

[0067] The substituted substituent is selected from at least one of methyl, ethyl, tert-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl or naphthyl.

[0068] Preferably, X is selected from O and S.

[0069] Preferably, the R 301 , R 302 Each is independently selected from methyl or phenyl.

[0070] Preferably, the R 303 Selected from phenyl, diphenyl or terphenyl.

[0071] Preferably, the Ar 22 Selected from diphenyl, terphenyl or quaterphenyl.

[0072] Preferably, the R 303 is phenyl, the Ar22 Selected from diphenyl, terphenyl or quaterphenyl.

[0073] Preferably, the R 303 is a diphenyl group, wherein Ar 22 Selected from diphenyl or terphenyl.

[0074] As a preferred technical solution of the present invention, the compound A has a structure as shown in formulas I-1 to I-30: and the compounds shown in formulas I-1 to I-30 can each independently be substituted by at least one of -F, -CN, C6-C20 (for example, C6, C10, C12, C18 or C20, etc.) aryl, C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkyl, and C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkoxy;

[0075]

[0076] Among them, R 303 ,Ar 22 Has the same definition as above.

[0077] As a preferred technical solution of the present invention, the compound A is selected from any one of the following compounds:

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] Preferably, the compound A is selected from any one of the following compounds:

[0094]

[0095]

[0096]

[0097] It should be noted that there is no special limitation on the preparation method of the above-mentioned compounds in the present invention, and the commonly used preparation methods in the art are applicable.

[0098] In a second aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode and an organic thin film layer disposed between the anode and the cathode;

[0099] The organic thin film layer material comprises the composition as described in the first aspect.

[0100] As a preferred technical solution of the present invention, the organic thin film layer includes a light-emitting layer, and the main material of the light-emitting layer includes the composition as described in the first aspect.

[0101] Preferably, the light-emitting layer is a phosphorescent light-emitting layer.

[0102] As a preferred technical solution of the present invention, the organic electroluminescent device is a green organic electroluminescent device.

[0103] The luminescent layer in the present invention includes a luminescent layer main material and a doping material, wherein the doping material is also called a dye or a phosphorescent luminescent material. The luminescent layer main material can be a single compound or a mixture of two or more compounds.

[0104] The light-emitting layer includes a phosphorescent light-emitting layer, and the phosphorescent light-emitting layer includes a green phosphorescent light-emitting layer, a red phosphorescent light-emitting layer, a yellow phosphorescent light-emitting layer, and a blue phosphorescent light-emitting layer.

[0105] The volume percentage of the main material in the phosphorescent layer is 60% to 99.9% (for example, it can be 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or 99.9%, etc.), preferably 70% to 99.5%, and more preferably 85% to 95%.

[0106] In the present invention, the doping material of the light-emitting layer may be a phosphorescent material, which is also called a triplet light-emitting material, and refers to the light emitted by a substance from a triplet excited state. The specific selection of the phosphorescent material in the present invention is not particularly limited, and the doping materials of the light-emitting layer commonly used in the art are applicable, including but not limited to: a compound having a structure shown in the following formula PD:

[0107]

[0108] Wherein, M is selected from any one of Ir, Pt, Pd, Os, Ti, Zr, Hf, Eu, Tb, Tm, Cu or Au;

[0109] Y1-Y4 are each independently selected from carbon or nitrogen;

[0110] Y1 and Y2 can be connected by a single bond or a double bond, and Y3 and Y4 can be connected by a single bond or a double bond;

[0111] Cy1 and Cy2 are each independently selected from phenyl, naphthyl, fluorenyl, spirofluorenyl, indenyl, pyrrolyl, thienyl, furanyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, isoquinolyl, benzoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, benzimidazolyl, benzofuranyl, benzothienyl, isobenzothienyl, benzimidazolyl, benzoxazolyl, triazolyl, tetrazolyl, oxadiazolyl, triazine, dibenzothienyl, N-heterocarbazolyl, wherein Cy1 and Cy2 may be optionally linked to each other via a single bond or an organic linking group;

[0112] Any two ligands of M, or more than two ligands, may be connected by a single bond or a double bond, or may be bridged by O or S, or may be connected by any chemical group or chemical structure to form a structural form that conforms to chemical principles;

[0113] R 91 and R 92each independently selected from -H, -D, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid, carboxylate, sulfonic acid, sulfonate, phosphoric acid, phosphate, -SF5, substituted or unsubstituted C1-C60 (e.g., C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkyl, substituted or unsubstituted C2-C6 C2-C60 (for example, C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkynyl, substituted or unsubstituted C1-C60 (for example, C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) C2-C10 (for example, C2, C3, C4, C5, C6, C7, C8, C9 or C10) heterocycloalkyl, substituted or unsubstituted C6-C60 (for example, C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) aryl, substituted or unsubstituted C6-C60 (for example, C2, C3, C4, C5, C6, C7, C8, C9 or C10) For example, it can be any one of C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) aryloxy, substituted or unsubstituted C6-C60 (for example, it can be C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) arylthio, substituted or unsubstituted monovalent non-aromatic fused polycyclic group, and substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group.

[0114] a1 and a2 are each independently an integer selected from 1-5, for example, 1, 2, 3, 4 or 5;

[0115] b is an integer selected from 0-4, for example, 0, 1, 2, 3 or 4;

[0116] a is selected from 1, 2 or 3;

[0117] L1 is a monovalent organic ligand, a divalent organic ligand or a trivalent organic ligand.

[0118] Preferably, the compound of formula PD is selected from any one of the following compounds:

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125] In the present invention, the organic thin film layer includes a hole layer, and the hole layer includes a hole injection layer, a hole transport layer and an electron blocking layer.

[0126] The hole injection layer material includes a P-type dopant. The P-type dopant refers to a dopant that coexists with the hole injection layer material in the OLED device and can oxidize the hole injection layer material, thereby acting as an electron acceptor and promoting the movement of holes in the hole injection layer to the anode. In the present invention, the difference between the absolute value of the LUMO of the P-type dopant and the absolute value of the HOMO of the hole layer material is greater than -0.2V, preferably greater than -0.1eV, more preferably greater than 0eV, more preferably greater than 0.1eV, and more preferably greater than 0.2eV.

[0127] The P-type dopant is present in the hole injection layer in a volume percentage of 1% to 10% (e.g., 1%, 2%, 4%, 6%, 8% or 10%). In the present invention, there is no particular limitation on the type of the P-type dopant, and illustratively, the compounds D-1 to D-13 disclosed in CN113728453A or the compounds HI-1 to HI-9 described below can be selected:

[0128]

[0129]

[0130] In the present invention, the hole layer material (including the hole injection layer, the hole transport layer and the electron blocking layer) has a structure shown in the following formula HT-GH4:

[0131]

[0132] Among them, L 41 is selected from a single bond, a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl, or a C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl;

[0133] Ar 41 ,Ar42 Each is independently selected from C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl, C6-C20 (for example, C6, C8, C10, C12, C16 or C20, etc.) heteroaryl;

[0134] X is selected from CR 41 R 42 or NR 43 , where R 41 , R 42 , R 43 are each independently selected from substituted or unsubstituted phenyl (the substituted substituent is selected from C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkyl, C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkoxy, naphthyl, triphenylene, fluoranthene, 9,9-dimethylfluorenyl, biphenyl, substituted or unsubstituted group (the substituted substituent is phenyl), substituted or unsubstituted dibenzothienyl (the substituted substituent is phenyl), substituted thienyl, C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkyl, any one of R 41 , R 42 They can be linked to form rings via single bonds.

[0135] The compound of formula HT-GH4 is selected from any one of the following compounds:

[0136]

[0137]

[0138]

[0139] In the present invention, the hole layer material (including the hole injection layer, the hole transport layer and the electron blocking layer) also includes a compound having a structure shown in the following formula IA or a compound having a structure shown in the following formula IB:

[0140]

[0141] Wherein, L is selected from any one of C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) arylene, dibenzofuranyl or dibenzothiophenyl;

[0142] m is selected from an integer between 0 and 4 (for example, it can be 0, 1, 2, 3 or 4), and n is selected from 0 or 1;

[0143] Ar is selected from any one of triphenylene, fluoranthenylene, dibenzofuranylene or dibenzothiophenylene;

[0144] Ar1 and Ar2 are each independently selected from any one of a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl group, dibenzofuran or dibenzothiophenyl group;

[0145] Ar1 and Ar, Ar2 and Ar, and Ar1 and Ar2 can each independently be connected or bridged by a single bond, O, S, CR1R2, or NR.

[0146] R, R1, and R2 are each independently selected from any one of a C1-C20 (e.g., C1, C2, C4, C6, C8, C10, C12, C14, C16, C18, or C20, etc.) alkyl group, a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl group, a dibenzofuranyl group, or a dibenzothiophenyl group;

[0147] H in the compound of formula IB and the compound of formula IA can each independently be replaced by at least one of -F, -CN, -D (deuterium atom), C1-C6 alkyl, C1-C6 alkoxy, phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

[0148] Preferably, Ar is a fluoranthenyl group, and m+n>1.

[0149] Preferably, H in the compound of formula IB and the compound of formula IA can be replaced by at least one of -F, -CN, -D, C1-C3 alkyl (for example, methyl, ethyl or propyl), C1-C3 alkoxy (for example, methoxy, ethoxy or propoxy), phenyl, biphenyl, triphenylene, and fluoranthene.

[0150] Preferably, L, Ar1, Ar2 are each independently selected from at least one of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrene, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

[0151] Preferably, the compound of formula IB is selected from any one of the following compounds 1-112:

[0152]

[0153] In the OLED device provided by the present invention, the hole layer material may include conventional hole materials in the art in addition to the compound described in formula HT-GH4, the compound of formula IB, and the compound of formula IA, without special restrictions. Exemplary includes but is not limited to: triarylamine compounds or carbazole compounds. Triarylamine compounds or carbazole compounds containing more than 3 N atoms are preferred, because the HOMO of triarylamine compounds or carbazole compounds containing more than 3 N atoms is higher (smaller absolute value), and is more suitable for use as hole injection layer materials. Triarylamine compounds or carbazole compounds containing 2 or 1 N atoms can be used as hole transport layer materials. Some compounds or carbazole compounds containing 1 N atom, if they have a higher LUMO, can also be used as electron blocking layer materials.

[0154] The triarylamine compound or the carbazole compound is used as the hole layer material, and the hole layer material includes the following structure:

[0155]

[0156] Among them, Ar 601 ~Ar 609 Each independently selected from a substituted or unsubstituted C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl, a substituted or unsubstituted dibenzothienyl, a substituted or unsubstituted naphthobenzofuranyl, a substituted or unsubstituted naphthobenzothienyl, a substituted or unsubstituted dinaphthofuranyl, a substituted or unsubstituted dinaphthothienyl;

[0157] And Ar 601 ~Ar 609 Ar atoms adjacent to or connected to the same N atom 601 ~Ar 609 , can be connected by single key or through O, S, CR 701 R 702 NR 703 bridging;

[0158] R 701 , R 702 , R 703 is selected from C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aromatic groups, C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl groups, C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) alkyl groups, and R 701 , R 702Can connect via one-touch.

[0159] The hole blocking layer (HBL) can confine holes and / or excitons within the EL to improve the current efficiency and lifetime of the device. Compared with the EL material closest to the HBL interface, the HBL material has a lower HOMO (larger absolute value) and / or higher triplet energy.

[0160] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped, and doping may be used to enhance conductivity. In the present invention, there is no particular restriction on the ETL material, and any metal complex or organic compound may be used as long as it can transport electrons. The general electron transport layer material contains the following structural fragments: at least one of a pyridine structure, a pyrimidine structure, a triazine structure, a benzimidazole structure, a benzoxazole structure, a benzothiazole structure, an N-naphthalene structure, an N-coffee structure, an N-carbazole structure, and an N-dibenzothiophene structure.

[0161] In the present invention, there is no special restriction on the electron transport layer material, which exemplarily includes but is not limited to:

[0162]

[0163] In the present invention, the material of the cathode is a metal with a low work function (e.g., alkaline earth metal, alkali metal, main group metal or lanthanide element (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.)), a metal alloy composed of multiple metals (alloy composed of alkali metal or alkaline earth metal and silver, such as an alloy composed of magnesium and silver) or a multilayer structure. If the cathode material is a multilayer structure, in addition to the metals mentioned above, other metals with relatively high work functions, such as Ag or Al, can also be used. In this case, a combination of the metals is usually used, such as Ca / Ag, Mg / Ag or Ba / Ag.

[0164] It is also possible to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor to form a multilayer structure; the material with a high dielectric constant can also be called an electron injection material, and fluorides of alkali metals or alkaline earth metals, and corresponding oxides or carbonates (such as LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.) or lithium quinoline (LiQ) can be selected.

[0165] Compared with the prior art, the present invention has the following beneficial effects:

[0166] In the present invention, the specific composition of the composition containing the carbazole compound is designed, and the structure of the carbazole compound and the structure of compound A are further designed to make it suitable as the main material of the phosphorescent light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency and longer life. DETAILED DESCRIPTION

[0167] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0168] The specific structures of some compounds used in the following application examples and comparative application examples of the present invention are as follows:

[0169]

[0170] Application Example 1

[0171] This application example provides a green light organic electroluminescent device, using the composition provided by the present invention as a main material of the light-emitting layer, and the structure of the green light organic electroluminescent device is:

[0172] ITO / HT-1: HI-2[5%](80nm) / HT-1(30nm) / EB-2(20nm) / host material: PGD-1[5%](35nm) / ETL-1(25nm) / LiF(0.5nm) / Al(150nm).

[0173] The preparation method of the green organic electroluminescent device is as follows:

[0174] The material was placed in a vacuum chamber and evacuated to 1×10 -5 ~1×10 -6 Pa was vacuum evaporated onto the cleaned ITO substrate in sequence to prepare an OLED device.

[0175] PGD-1[5%] refers to the doping ratio of the dye, that is, the volume ratio of the main material to the dye PGD-1 is 95:5. The main material is two components, and the volume ratio of the two is 1:1. HT-1:HI-2[5%] refers to the ratio of the P-type dopant, that is, the volume ratio of the hole material HT-1 and the P-type dopant HI-2 is 95:5. HT-1 is a hole transport material; HT-1:HI-2[5%] is used as a hole injection layer, and EB-2 is an electron blocking layer.

[0176] The main materials of the light-emitting layer of the green organic electroluminescent device provided in this application example are compound P1 and H-601.

[0177] Application Example 2-12, Comparative Application Example 1

[0178] Application Examples 2-12 and Comparative Application Example 1 respectively provide a green light organic electroluminescent device, which differs from Application Example 1 only in that the main material of the light-emitting layer is replaced with other compounds (see Table 1 below for details), and the other preparation steps and conditions are the same as those of Application Example 1.

[0179] Performance Testing

[0180] The brightness, current efficiency and LT95 of the organic electroluminescent device provided above were tested, wherein the voltage and current efficiency were the values ​​of brightness of 1000 cd / m 2 The corresponding value, LT95, refers to maintaining the initial current density of the device at 10mA / cm 2 The time required for the device efficiency to drop to 95% of the efficiency corresponding to the initial current density is constant. The driving voltage, current efficiency and LT95 are relative values. The specific test results are shown in Table 1 below:

[0181] Table 1

[0182] Main material 1 Main material 2 <![CDATA[Luminance / (cd / m 2 )]]> Driving voltage Current efficiency LT95 Application Example 1 P1 H-601 1000 1 1 1 Application Example 2 P4 H-601 1000 0.98 0.99 1.05 Application Example 3 P5 H-601 1000 0.88 1.01 0.94 Application Example 4 P10 H-601 1000 1.03 1.04 1.22 Application Example 5 P1 H-4 1000 0.97 / 1.10 Application Example 6 P4 H-4 1000 0.93 / 1.15 Application Example 7 P5 H-4 1000 1.01 / 1.09 Application Example 8 P10 H-4 1000 1.02 / 1.38 Application Example 9 P1 HC21 1000 / 1.09 1.08 Application Example 10 P4 HC21 1000 / 1.21 1.09 Application Example 11 P5 HC21 1000 / 1.20 1.02 Application Example 12 P10 HC21 1000 / 1.56 1.31 Comparative application example 1 D1 H-601 1000 1.09 0.91 0.88

[0183] The “ / ” indicates that this data does not exist.

[0184] From the above content, it can be known that the present invention designs the structure of the carbazole compound to make it suitable as one of the main materials of the phosphorescent light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency and longer life.

[0185] In summary, the structure of the carbazole compound is designed in the present invention to make it suitable as the main material of the phosphorescent light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has a lower current efficiency and a longer life.

[0186] The applicant declares that the present invention illustrates the detailed process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A composition containing a carbazole compound, characterized in that: The composition containing carbazole compounds comprises a first component and a second component; The first component is a carbazole compound, and the carbazole compound has a structure shown in the following formula I or formula II: Wherein, in the compound of formula I, R1, R2, and R3 are each independently selected from a hydrogen atom or a deuterium atom, and at least one of R1, R2, and R3 is selected from a deuterium atom; In the compound of formula I, Ar is selected from any one of a single bond, a C6-C40 arylene group or a C6-C30 heteroarylene group; In the compound of formula I, Ar1 and Ar2 are each independently selected from any one of H, C6-C40 aryl or C6-C30 heteroaryl; In the compound of formula I, A1, A2, A3 are each independently selected from N or CR, and at least one is selected from N; R is selected from any one of H, -CN, C6-C20 aryl or C1-C12 alkyl; In the compound of formula I, a and b are each independently selected from 0 or 1, and at least one of a and b is selected from 1; In the compound of formula II, R4, R5, R6, R7, and R8 are each independently selected from a hydrogen atom or a deuterium atom, and at least one of R4, R5, R6, R7, and R8 is selected from a deuterium atom; In the compound of formula II, Ar is selected from any one of a single bond, a C6-C40 arylene group or a C6-C30 heteroarylene group; In the compound of formula II, Ar1 and Ar2 are each independently selected from any one of H, C6-C40 aryl or C6-C30 heteroaryl; In the compound of formula II, A1, A2, A3 are each independently selected from N or CR, and at least one is selected from N; R is selected from any one of H, -CN, C6-C20 aryl or C1-C12 alkyl; In the compound of formula II, a and b are each independently selected from 0 or 1, and at least one of a and b is selected from 1; The hydrogen atoms in the compound of formula I and the compound of formula II may be independently substituted by at least one of a deuterium atom, -F, -CN, a C6-C20 aryl group, a triphenylmethyl group, a triphenylsilyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

2. The composition containing carbazole compounds according to claim 1, characterized in that: The C6-C40 arylene group is selected from any one or a combination of at least two of phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrylene, fluorenylene, benzofluorenylene, dibenzofluorenylene, naphthofluorenylene, pyrenylene, perylene, spirofluorenylene, triphenylene, fluoranthenylene, hydrogenated benzanthrylene, indenofluorenylene, benzoindenofluorenylene, dibenzoindenofluorenylene, naphthofluorenylene, tetraphenylmethane or benzonaphthofluorenylene; Preferably, the C6-C30 heteroarylene group is selected from any one of a carbazolylene group, a dibenzothiophenylene group, a naphthobenzofuranyl group, a naphthobenzothiophenylene group, a dinaphthofuranyl group, a dinaphthothiophenylene group or a carbazolylene group; Preferably, the C6-C40 aryl group is selected from any one or a combination of at least two of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl, tetraphenylmethane or benzonaphthofluorenyl; Preferably, the C6-C30 heteroaryl group is selected from any one or a combination of at least two of carbazolyl, dibenzothiophenyl, dibenzofuranyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl and dinaphthothiophenyl; Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, anthracenyl, phenanthryl, fluorenyl, triphenylene or fluoranthenyl; Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, octyl and adamantyl; Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and octyloxy.

3. The composition containing carbazole compounds according to claim 1 or 2, characterized in that: In the compound of formula I and formula II, the Ar is independently selected from any one of a single bond, a phenylene group, a carbazolyl group, a biphenylene group, a fluorenyl group, a naphthyl group, a triphenylene group, a fluoranthenyl group, an indenofluorenyl group, a dibenzothienyl group, a naphthobenzofuranyl group, a naphthobenzothienyl group, or a carbazolyl group; Preferably, in the compound of formula I and formula II, the Ar is independently selected from at least one of a single bond, a phenylene group, a carbazolyl group, a naphthyl group, a 9,9-dimethylfluorenyl group, a dibenzothienyl group, a dibenzofuranyl group or a biphenylene group, and is further preferably any one of a single bond, a phenylene group, a biphenylene group or a carbazolyl group; Preferably, in the compound of formula I and formula II, Ar1 and Ar2 are each independently selected from any one or a combination of at least two of H, phenyl, carbazolyl, biphenyl, 9,9-dimethylfluorenyl, naphthyl, triphenylene, fluoranthenyl, indenofluorenyl, dibenzofuranyl, dibenzothienyl, naphthobenzofuranyl or naphthobenzothienyl; Preferably, in the compound of formula I and formula II, Ar1 and Ar2 are each independently selected from at least one of H, phenyl, carbazolyl, naphthyl, 9,9-dimethylfluorenyl, dibenzothiophenyl, biphenyl, dibenzofuranyl, triphenylene or fluoranthenyl, and more preferably at least one of phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl and carbazolyl; Preferably, any one of A1, A2, and A3 is selected from N, the other two are CR, and R is selected from H or -CN; Preferably, any two of A1, A2, and A3 are selected from N, the other is CR, and R is selected from H or -CN; Preferably, A1, A2, A3 are all selected from N.

4. The composition containing carbazole compounds according to any one of claims 1 to 3, characterized in that: In formula I, R1, R2, and R3 are all selected from deuterium atoms; Preferably, in Formula II, R4, R5, R6, R7, and R8 are all selected from deuterium atoms; Preferably, the hydrogen atoms in the compound of formula I and the compound of formula II can be independently substituted by at least one of -D, -F, -CN, phenyl, naphthyl, biphenyl, triphenylmethyl, triphenylsilyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy or butoxy; Preferably, the hydrogen atoms in the compound of formula I and the compound of formula II can be independently substituted by at least one of -D, -F, -CN, phenyl, naphthyl, methyl, ethyl, tert-butylmethoxy, ethoxy and propoxy.

5. The composition containing carbazole compounds according to any one of claims 1 to 4, characterized in that: The carbazole compound is selected from any one of the following substituted or unsubstituted compounds: The substitution means that the hydrogen atoms in the above carbazole compounds can be independently replaced by deuterium atoms.

6. The composition containing carbazole compounds according to any one of claims 1 to 5, characterized in that: The second component includes compound A; The compound A is obtained by fusing a group having a structure as shown in Formula IA with any two adjacent carbon atoms on the ring A in the group having a structure as shown in Formula IB: Among them, * indicates the fusion site; X is selected from O, S, R 301 , R 302 are each independently selected from C1-C6 alkyl, C6-C30 aryl or C6-C20 heteroaryl, and R 301 , R 302 Can be connected to form a ring through a single bond, R 303 is selected from C6-C30 aryl or C6-C20 heteroaryl, and the dotted line indicates the attachment site; Ar 22 is selected from C6-C30 aryl or C6-C20 heteroaryl; The hydrogen atoms in compound A may be independently substituted by at least one of -F, -CN, C6-C20 aryl, C1-C6 alkyl, and C1-C6 alkoxy.

7. The composition containing carbazole compounds according to claim 6, characterized in that: In compound A, R 303 ,Ar 22 Each independently selected from any one or a combination of two of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, peryl, spirofluorenyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuran, naphthobenzothiophene, dinaphthofuran, dinaphthothiophene, hydrogenated benzene anthracenyl, indenofluorenyl, indolecarbazolyl, indenocarbazolyl, terphenyl, quaterphenyl, imidazolyl, benzimidazolyl, pyridyl, pyrimidinyl, piperazinyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, benzoquinoxalinyl, benzoquinazolinyl, N heterophenanthrenyl, diazophananthrenyl, carbazolyl, benzocarbazolyl, naphthocarbazolyl, dibenzocarbazolyl, triazinyl; The substituted substituents are each independently selected from at least one of a C1-C12 alkyl group, a C1-C12 alkoxy group, and a C6-C12 aryl group; Preferably, the R 303 ,Ar 22 Each independently selected from any one or a combination of two of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothiophenyl, triphenylene, fluorenyl, carbazolyl, benzofluorenyl; The substituted substituent is selected from at least one of methyl, ethyl, tert-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl or naphthyl; Preferably, X is selected from O and S; Preferably, the R 301 , R 302 Each independently selected from methyl or phenyl; Preferably, the R 303 Selected from phenyl, diphenyl or terphenyl; Preferably, the Ar 22 Selected from diphenyl, terphenyl or quaterphenyl; Preferably, the R 303 is phenyl, the Ar 22 Selected from diphenyl, terphenyl or quaterphenyl; Preferably, the R 303 is a diphenyl group, wherein Ar 22 Selected from diphenyl or terphenyl.

8. The composition containing carbazole compounds according to claim 6 or 7, characterized in that: The compound A has a structure as shown in formulas I-1 to I-30: and the compounds shown in formulas I-1 to I-30 can each independently be substituted by at least one of -F, -CN, C6-C20 aryl, C1-C6 alkyl, and C1-C6 alkoxy; Among them, R 303 ,Ar 22 Has the same definition as claim 6.

9. The composition containing carbazole compounds according to any one of claims 6 to 8, characterized in that: The compound A is selected from any one of the following compounds: Preferably, the compound A is selected from any one of the following compounds:

10. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and an organic thin film layer arranged between the anode and the cathode; The organic thin film layer material comprises a composition containing a carbazole compound as claimed in any one of claims 1 to 9; Preferably, the organic thin film layer comprises a light-emitting layer, and the main material of the light-emitting layer comprises the composition containing carbazole compounds according to any one of claims 1 to 9; Preferably, the light-emitting layer is a phosphorescent light-emitting layer; Preferably, the organic electroluminescent device is a green organic electroluminescent device.

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