Carbazole compound, intermediate, composition and organic electroluminescent device

Abstract

The invention provides a carbazole compound, an intermediate, a composition and an organic electroluminescent device. The carbazole compound has a structure as shown in a formula I. The structure of the carbazole compound is designed, so that the carbazole compound is suitable for being used as a main body material of a light-emitting layer of the organic light-emitting device, and the organic light-emitting device has relatively low driving voltage, 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 specifically relates to a carbazole compound, an intermediate, a composition 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 carbazole compound, an intermediate, a composition and an organic electroluminescent device. In the present invention, the structure of the carbazole compound is designed to make it suitable for use as a main material of the phosphorescent light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has a lower driving voltage, 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 carbazole compound having a structure shown in the following formula I:

[0007]

[0008] Among them, Ar 1 ,Ar 2 One of them is selected from H, and the other is selected from any one of C6-C40 aryl or C6-C30 heteroaryl

[0009] A 1 , A 2 , A 3 Each is independently selected from N or CR, and at least one is selected from N;

[0010] R is selected from any one of H, -CN, C6-C20 aryl or C1-C12 alkyl;

[0011] n is selected from 0 or 1.

[0012] In the present invention, C6-C40 can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.

[0013] C6-C30 can be C6, C8, C10, C12, C16, C20, C24, C28 or C30, etc.

[0014] C6-C20 can be C6, C8, C10, C12, C16 or C20, etc.

[0015] C1-C12 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12.

[0016] It should be noted that, in the present invention, "D" represents a deuterium atom, and the same applies hereinafter.

[0017] 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.

[0018] As a preferred technical solution of the present invention, the carbazole compound has a structure shown in the following formula I-1:

[0019]

[0020] Among them, Ar 1 ,Ar 2 One of them is selected from H, and the other is selected from any one of C6-C40 aryl or C6-C30 heteroaryl

[0021] A 1 , A 2 , A 3 Each is independently selected from N or CR, and at least one is selected from N;

[0022] R is selected from any one of H, -CN, C6-C20 aryl or C1-C12 alkyl;

[0023] n is selected from 0 or 1.

[0024] 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.

[0025] 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.

[0026] Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, anthracenyl, phenanthryl, fluorenyl, triphenylene or fluoranthene.

[0027] Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, octyl and adamantyl.

[0028] As a preferred technical solution of the present invention, the Ar 1 ,Ar 2 One of them is selected from H, and the other is selected from at least one of phenyl, carbazolyl, naphthyl, 9,9-dimethylfluorenyl, dibenzothiophenyl, biphenyl, dibenzofuranyl, triphenylene or fluoranthenyl;

[0029] Preferably, Ar 1 ,Ar 2 One of them is selected from H, and the other is selected from phenyl and biphenyl.

[0030] As the preferred technical solution of the present invention, A 1 , A 2 , A 3 One of them is selected from N, the other two are selected from CR, and the R is selected from H.

[0031] As the preferred technical solution of the present invention, A 1 , A 2 , A 3 Two of them are selected from N, another one is selected from CR, and the R is selected from H.

[0032] As the preferred technical solution of the present invention, A 1 , A 2 , A 3 All are selected from N.

[0033] As a preferred technical solution of the present invention, n is selected from 0.

[0034] As a preferred technical solution of the present invention, n is selected from 1.

[0035] As a preferred technical solution of the present invention, the carbazole compound is selected from any one of the following substituted or unsubstituted compounds:

[0036]

[0037] The substitution means that the hydrogen atoms in the above carbazole compounds can be independently replaced by deuterium atoms.

[0038] Preferably, the carbazole compound is selected from any one of the following compounds:

[0039]

[0040] It should be noted that the present invention does not have any special restrictions on the preparation method of the above-mentioned carbazole compounds, and the commonly used preparation methods in the art are applicable. The preparation method of the compound of formula I provided by the present invention is illustrated as follows:

[0041]

[0042]

[0043] Among them, Ar 1 ,Ar 2 , A 1 , A 2 , A 3 , n has the same definition as above;

[0044] X 1 , X 2 Each is independently selected from any one of fluorine, chlorine, bromine or iodine.

[0045] In a second aspect, the present invention provides an intermediate, wherein the intermediate comprises a compound having a structure shown in the following formula MA:

[0046]

[0047] Among them, X 1 Any one selected from fluorine, chlorine, bromine and iodine;

[0048] Ar 1 ,Ar 2 , n has the same definition as above;

[0049] The intermediate is used to prepare the carbazole compound as described in the first aspect.

[0050] Preferably, the intermediate includes the following compounds:

[0051]

[0052] In a third aspect, the present invention provides a composition comprising a first component and a second component;

[0053] The first component includes the carbazole compound as described in the first aspect;

[0054] 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, the R 303 ,Ar 22Each independently selected from any one or a combination of at least 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 at least two of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothiophenyl, triphenylene, fluorenyl, benzofluorenyl, carbazolyl;

[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 Any one selected from phenyl, diphenyl or terphenyl.

[0071] Preferably, the Ar 22 Any one selected from biphenyl, terphenyl or quaterphenyl.

[0072] Preferably, the R 303is phenyl, the Ar 22 Any one selected from biphenyl, 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 protection scope 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 compound A in the present invention, and any commonly used preparation methods in the art are applicable.

[0098] In a fourth 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 includes the carbazole compound described in the first aspect and / or the composition described in the third 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 carbazole compound described in the first aspect and / or the composition described in the third 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] Y 1 -Y 4 are each independently selected from carbon or nitrogen;

[0110] Y 1 and Y 2 They can be connected by single or double bonds. 3 and Y 4 They can be connected by single or double bonds;

[0111] Cy 1 and Cy 2 Each is 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, triazinyl, dibenzothienyl, N-heterocarbazolyl, wherein Cy 1 and Cy 2 may optionally be 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 92 Each is independently selected from -H, -D, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidine, hydrazine, hydrazone, carboxylic acid, carboxylate, sulfonic acid, sulfonate, phosphoric acid, phosphate, -SF 5, substituted or unsubstituted C1-C60 (for example, C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkyl, substituted or unsubstituted C2-C60 (for example, C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkenyl, substituted or unsubstituted C2-C60 (e.g., C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55, or C60, etc.) alkynyl, substituted or unsubstituted C1-C60 (e.g., C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55, or C60, etc.) alkoxy, substituted or unsubstituted 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, etc.) aryl, substituted or unsubstituted C6-C60 (for example, C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60, etc.) any one of a C24, C30, C32, C36, C40, C42, C54 or C60 (e.g., C24, C30, C32, C36, C40, C42, C54 or C60, etc.) aryloxy group, a substituted or unsubstituted C6-C60 (e.g., C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60, etc.) arylthio group, a substituted or unsubstituted monovalent non-aromatic fused polycyclic group, and a substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group.

[0114] a 1 and a 2 Each is 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] L 1 It 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] 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:

[0130]

[0131] 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;

[0132] Ar 41 ,Ar 42Each 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;

[0133] 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.

[0134] The compound of formula HT-GH4 is selected from any one of the following compounds:

[0135]

[0136]

[0137] 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:

[0138]

[0139] 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;

[0140] 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;

[0141] Ar is selected from any one of triphenylene, fluoranthenylene, dibenzofuranylene or dibenzothiophenylene;

[0142] Ar 1 and Ar 2 Each is 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;

[0143] Ar 1 Between Ar and Ar 2 and Ar 1 ,Ar 2 Each of them can be independently connected by a single bond, O, S, CR 1 R 2 , NR connection or bridging.

[0144] R, R 1 , R 2 Each is independently selected from any one of C1-C20 (for example, C1, C2, C4, C6, C8, C10, C12, C14, C16, C18 or C20, etc.) alkyl, C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl, dibenzofuranyl or dibenzothiophenyl;

[0145] 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.

[0146] Preferably, Ar is a fluoranthenyl group, and m+n>1.

[0147] 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.

[0148] Preferably, the L, Ar 1 ,Ar 2 Each is independently selected from at least one of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, peryl, spirofluorenyl, indenofluorenyl and hydrogenated benzanthryl.

[0149] Preferably, the compound of formula IB is selected from any one of the following compounds 1-112:

[0150]

[0151]

[0152] 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.

[0153] The triarylamine compound or the carbazole compound is used as the hole layer material, and the hole layer material includes the following structure:

[0154]

[0155] 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;

[0156] 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;

[0157] R 701 , R 702 , R 703is 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 702 Can connect via one-touch.

[0158] 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.

[0159] 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.

[0160] In the present invention, there is no special restriction on the electron transport layer material, which exemplarily includes but is not limited to:

[0161]

[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] Alternatively, a thin intermediate layer of a material with a high dielectric constant may be introduced between the metal cathode and the organic semiconductor to form a multilayer structure; the material with a high dielectric constant may also be referred to as an electron injection material, and may be selected from fluorides of alkali metals or alkaline earth metals, and corresponding oxides or carbonates (e.g., LiF, Li 2 O, BaF 2 、MgO、NaF、CsF、Cs 2 CO 3 etc.) or lithium quinolate (LiQ).

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

[0166] Compounds of the present invention

[0167] 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 a lower driving voltage, a higher current efficiency and a longer life. DETAILED DESCRIPTION

[0168] 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.

[0169] Preparation Example 1 Synthesis of Intermediate P1-1

[0170] This preparation example provides an intermediate P1-1 and a synthesis method thereof, and the synthesis method thereof is as follows:

[0171]

[0172] Under nitrogen protection, dry toluene (80 mL), 1-phenyl-3,5-dibromobenzene (3.1 g), 3-phenylcarbazole (2.4 g), Pd(dba) were added to a three-necked flask. 2 (bis(dibenzylideneacetonepalladium, 0.0575g, 0.0001mol), 10% tri-tert-butylphosphine toluene solution (the mass of tri-tert-butylphosphine solution is 0.4g, the amount of tri-tert-butylphosphine is 0.0002mol) and sodium tert-butoxide (1.44g, 0.015mol), heated to 40°C for 4 hours, then heated to 60°C for 2 hours, then heated to reflux for 2 hours, cooled to room temperature, separated by water, and then washed with water until the organic layer is neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, separated by silica gel column chromatography, eluted with a solvent of petroleum ether: ethyl acetate = 20:1 (volume ratio), to obtain intermediate P1-1 (1.9g).

[0173] The intermediate P1-1 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 473.08.

[0174] Preparation Example 2 Synthesis of Intermediate P2-1

[0175] This preparation example provides an intermediate P2-1 and a synthesis method thereof, and the synthesis method thereof is as follows:

[0176]

[0177] Referring to the synthesis method of intermediate P1-1, intermediate P2-1 was prepared using corresponding raw materials.

[0178] The intermediate P2-1 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 549.11.

[0179] Preparation Example 3 Synthesis of Intermediate P3-1

[0180] This preparation example provides an intermediate P3-1 and a synthesis method thereof, and the synthesis method thereof is as follows:

[0181]

[0182] Referring to the synthesis method of intermediate P1-1, intermediate P3-1 was prepared using corresponding raw materials.

[0183] The intermediate P3-1 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 549.11.

[0184] Preparation Example 4 Synthesis of Intermediate P4-1

[0185] This preparation example provides an intermediate P4-1 and a synthesis method thereof, and the synthesis method thereof is as follows:

[0186]

[0187] Referring to the synthesis method of intermediate P1-1, intermediate P4-1 was prepared using corresponding raw materials.

[0188] The intermediate P4-1 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 473.08.

[0189] Preparation Example 5 Synthesis of Intermediate P5-1

[0190] This preparation example provides an intermediate P5-1 and a synthesis method thereof, and the synthesis method thereof is as follows:

[0191]

[0192] Referring to the synthesis method of intermediate P1-1, intermediate P5-1 was prepared using corresponding raw materials.

[0193] The intermediate P5-1 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 480.12.

[0194] Preparation Example 6 Synthesis of Intermediate P6-1

[0195] This preparation example provides an intermediate P6-1 and a synthesis method thereof, and the synthesis method thereof is as follows:

[0196]

[0197] Referring to the synthesis method of intermediate P1-1, intermediate P6-1 was prepared using corresponding raw materials.

[0198] The intermediate P6-1 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 476.10.

[0199] The synthesis method of intermediate P6-0 is as follows:

[0200]

[0201] Under nitrogen protection, 70 mL of toluene, 30 mL of ethanol, and 20 mL of water were added to a three-necked flask in sequence, and then 3.2 g of deuterated 1,3,5-tribromobenzene, 1.2 g of phenylboric acid, 2.12 g of sodium carbonate, and 0.46 g of tetrakistriphenylphosphine palladium were added thereto. The temperature was slowly raised to reflux for reaction for 8 h, and the temperature was lowered to room temperature. Water was added to separate the organic layer, and the organic layer was washed with water, dried with magnesium sulfate, and the desiccant was removed, and the mixture was concentrated to dryness, separated by silica gel column chromatography, and eluted with petroleum ether to obtain 1.2 g of intermediate P6-0.

[0202] The obtained intermediate P6-0 was subjected to mass spectrometry detection, and the peak with the largest mass-to-charge ratio (m / z) was measured to be 314.92, with an abundance of 100%, and another peak was 312.92, with an abundance of about 50%, and 316.91, with an abundance of about 50%.

[0203] Synthesis Example 1

[0204] This synthesis example provides compound P1 and its synthesis method, and its synthesis method is as follows:

[0205]

[0206] Under nitrogen protection, 70 mL of toluene, 30 mL of ethanol, and 20 mL of water were added to a three-necked flask in sequence, and then 4.7 g of intermediate P1-1, 2.9 g of 4,6-diphenyl-1,3,5-triazine-2-boric acid, 2.12 g (0.02 mol) of sodium carbonate, and 0.23 g (0.0002 mol) of tetrakistriphenylphosphine palladium were added thereto, and the temperature was slowly raised to reflux for reaction for 8 h, and the temperature was lowered to room temperature, and water was added to separate, and the organic layer was washed with water, dried with magnesium sulfate, and after removing the desiccant, concentrated to dryness, and separated by silica gel column chromatography, and eluted with petroleum ether: dichloromethane: THF = 10:2:1 (volume ratio) to obtain 3.0 g of compound P1;

[0207] The obtained compound P1 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 626.25.

[0208] Synthesis Example 2-11

[0209] Synthesis Examples 2-11 provide a compound, respectively, the specific structure of the compound is shown in Table 1 below, the compound is synthesized from raw material 1 and raw material 2, and the synthesis method refers to the synthesis of compound P1 in Synthesis Example 1. The obtained compound was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) measured is shown in Table 1 below.

[0210] Table 1

[0211]

[0212]

[0213] Other compounds whose specific synthesis methods are not listed can be synthesized by referring to the above embodiments in combination with common knowledge in the art.

[0214] The specific structures of some compounds used in the following application examples and comparative application examples of the present invention are as follows:

[0215]

[0216]

[0217] Synthesis of compound D3:

[0218]

[0219] Referring to the synthesis of compound P1, compound D3 was prepared.

[0220] The mass spectrometry detection of compound D3 showed that the mass-to-charge ratio (m / z) was 702.28.

[0221] Application Example 1

[0222] This application example provides a green light organic electroluminescent device, using the compound 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:

[0223] ITO / HT-1(80nm) / EB-1(20nm) / host material:PGD-1[5%](35nm) / ETL-1(25nm) / LiF(0.5nm) / Al(150nm).

[0224] The preparation method of the green organic electroluminescent device is as follows:

[0225] 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.

[0226] 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; HT-1 is a hole transport material, and EB-1 is an electron blocking layer.

[0227] The main material of the light-emitting layer of the green organic electroluminescent device provided in this application example is compound P1.

[0228] Application Examples 2-7, Comparative Application Examples 1-3

[0229] Application Examples 2-7 and Comparative Application Examples 1-3 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 3 below for details), and the other preparation steps and conditions are the same as those of Application Example 1.

[0230] Performance Testing

[0231] The voltage, brightness, current efficiency and LT95 of the organic electroluminescent device provided above are tested, wherein the voltage and current efficiency are the brightness of 1000cd / 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 2 below:

[0232] Table 2

[0233] Main material <![CDATA[Luminance / (cd / m 2 )]]> Driving voltage Current efficiency LT95 Application Example 1 P1 1000 1 1 1 Application Example 2 P2 1000 1.03 0.96 1.08 Application Example 3 P3 1000 1.02 0.99 1.09 Application Example 4 P4 1000 1.09 1.06 0.96 Application Example 5 P5 1000 1.02 0.98 1.01 Application Example 6 P6 1000 0.98 1.11 1.02 Application Example 7 P7 1000 1.02 1.03 0.96 Comparative application example 1 D1 1000 1.14 0.94 0.87 Comparative Application Example 2 D2 1000 1.19 0.87 0.94 Comparative Application Example 3 D3 1000 1.12 0.79 0.81

[0234] Compared with Application Example 1, when Application Example 4 is selected from H, the efficiency of the device is improved, but the voltage and life performance are deteriorated.

[0235] Comparing Application Example 4 with Application Example 6, it can be seen that when the structure of the carbazole compound conforms to Formula I-1, the device voltage, efficiency and life performance are all improved.

[0236] From the above content, it can be seen that the present invention designs the structure of the carbazole compound 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 driving voltage, higher current efficiency and longer life.

[0237] Application Examples 8-11 vs. Application Example 4

[0238] Application Examples 8-11 and Comparative Application Example 4 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 two components, and the volume ratio of the two is 1:1 (see Table 3 below for details), and the other preparation steps and conditions are the same as those of Application Example 1.

[0239] Performance Testing

[0240] The brightness, current efficiency and LT95 of the organic electroluminescent device provided above were tested, wherein the current efficiency is the brightness of 1000cd / 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 current efficiency and LT95 are relative values. The specific test results are shown in Table 3 below:

[0241] Table 3

[0242] Main material 1 Main material 2 <![CDATA[Luminance / (cd / m 2 )]]> Current efficiency LT95 Application Example 8 P1 H-13 1000 1 1 Application Example 9 P8 H-13 1000 0.96 1.03 Application Example 10 P9 H-13 1000 1.02 0.89 Application Example 11 P10 H-13 1000 0.92 0.81 Comparative Application Example 4 D1 H-13 1000 0.82 0.70

[0243] 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.

[0244] 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 driving voltage, higher current efficiency and longer life.

[0245] 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 carbazole compound, characterized in that The carbazole compound has a structure shown in the following formula I: wherein one of Ar1 and Ar2 is selected from H, and the other is selected from any one of C6-C40 aryl or C6-C30 heteroaryl 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; n is selected from 0 or 1.

2. The carbazole compound according to claim 1, wherein the carbazole compound has a structure as shown in the following formula I-1: in, One of Ar1 and Ar2 is selected from H, and the other is selected from any one of C6-C40 aryl or C6-C30 heteroaryl 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; n is selected from 0 or 1.

3. The carbazole compound according to any one of claims 1-2, wherein 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.

4. The carbazole compound according to any one of claims 1-2, characterized in that One of Ar1 and Ar2 is selected from H, and the other is selected from at least one of phenyl, carbazolyl, naphthyl, 9,9-dimethylfluorenyl, dibenzothiophenyl, biphenyl, dibenzofuranyl, triphenylene or fluoranthene; Preferably, one of Ar1 and Ar2 is selected from H, and the other is selected from phenyl and biphenyl; Preferably, one of A1, A2 and A3 is selected from N, the other two are selected from CR, and R is selected from H; Preferably, two of A1, A2 and A3 are selected from N, the other one is selected from CR, and R is selected from H; Preferably, A1, A2, and A3 are all selected from N; Preferably, n is selected from 0; Preferably, n is selected from 1.

5. The carbazole compound 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; preferably, the carbazole compound is selected from any one of the following compounds:

6. An intermediate, characterized in that The intermediate includes a compound having a structure shown in the following formula MA: Wherein, X1 is selected from any one of fluorine, chlorine, bromine and iodine; Ar1, Ar2, n have the same meanings as in right 1; Preferably, the intermediate includes the following compounds:

7. A composition, characterized in that The composition comprises a first component and a second component; The first component comprises the carbazole compound according to any one of claims 1 to 5; 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.

8. The composition according to claim 7, characterized in that The R 303 ,Ar 22 Each independently selected from any one or a combination of at least 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 at least two of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothiophenyl, triphenylene, fluorenyl, benzofluorenyl, carbazolyl; 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, S; Preferably, the R 301 , R 302 Each independently selected from methyl or phenyl; Preferably, the R 303 Any one selected from phenyl, diphenyl or terphenyl; Preferably, the Ar 22 Any one selected from biphenyl, terphenyl or quaterphenyl; Preferably, the R 303 is phenyl, the Ar 22 Any one selected from biphenyl, terphenyl or quaterphenyl; Preferably, the R 303 is a diphenyl group, wherein Ar 22 Selected from diphenyl or terphenyl.

9. The composition according to claim 7 or 8, 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 It has the same protection scope as claim 7; preferably, 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 the carbazole compound according to any one of claims 1 to 5 and / or the composition according to any one of claims 7 to 9; Preferably, the organic thin film layer comprises a light-emitting layer, and the main material of the light-emitting layer comprises the carbazole compound according to any one of claims 1 to 5 and / or the composition according to any one of claims 7 to 9; Preferably, the light-emitting layer is a phosphorescent light-emitting layer; Preferably, the organic electroluminescent device is a green organic electroluminescent device.

Images