A phthalazin compound, an organic electroluminescence device and application thereof

Abstract

This invention provides a diazanaphthalene compound, an organic electroluminescent device, and their applications. The diazanaphthalene compound has the structure shown in Formula I or Formula II. This invention designs the structure of the diazanaphthalene compound to make it suitable as the main material for the light-emitting layer of an organic electroluminescent device, thereby enabling the organic electroluminescent device to have high current efficiency and long lifetime.

Description

Technical Field

[0001] This invention belongs to the field of organic electroluminescent materials technology, specifically relating to a diazanaphthalene compound, an organic electroluminescent device, and its applications. Background Technology

[0002] Compared to other flat panel displays (e.g., liquid crystal displays (LCDs), plasma display panels (PDPs), field emission displays (FEDs), etc.), organic light-emitting devices (OLEDs) have a simpler structure, various processing advantages, higher brightness, excellent viewing angle characteristics, faster response speed, and lower driving voltage. Therefore, they have been fully developed for use as light sources for flat panel displays (e.g., wall-mounted TVs), or as backlight units for displays, lighting fixtures, advertising boards, etc.

[0003] The structure of an organic light-emitting diode (OLED) consists of an anode, a cathode, and an organic layer between them. To improve the efficiency and stability of OLEDs, the organic layer is a multilayer structure comprising different materials. To meet the increasingly demanding requirements for OLED devices, there is an urgent need to develop a wider variety of materials to improve the performance of OLED devices in terms of current efficiency, lifetime, and other aspects. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a diazanaphthalene compound, an organic electroluminescent device, and its applications. In this invention, the structure of the diazanaphthalene compound is designed to be suitable as the main material for the light-emitting layer of an organic electroluminescent device, thereby enabling the organic electroluminescent device to exhibit high current efficiency and long lifespan.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a diazanaphthalene compound having the structure shown in Formula I or the structure shown in Formula II:

[0007]

[0008] In this context, X is independently selected from either C or Si.

[0009] Dashed lines indicate single keys or non-existent keys.

[0010] Ar1 is independently selected from any one of C6-C40 arylene or C6-C30 heteroarylene.

[0011] Ar2 is independently selected from any one of single bond, C6-C40 arylene, and C6-C30 heteroarylene. When Ar2 is a single bond, the two N-containing fused rings are directly connected by a single bond.

[0012] Ar3 is independently selected from any one of C6-C40 aryl and C6-C30 heteroaryl.

[0013] Ar4 and Ar5 are each independently selected from any one of hydrogen atom, C6-C40 aryl, or C6-C30 heteroaryl.

[0014] In the structure shown in Formula I or Formula II, each hydrogen atom is independently substituted or not substituted by at least one of a deuterium atom (-D), a halogen, -CN, a C6-C20 aryl, a C1-C12 straight-chain or branched alkyl, or a C1-C12 alkoxy.

[0015] In this invention, the structure of diazanaphthalene compounds is designed to make them suitable as the main material for the light-emitting layer of organic electroluminescent devices. The organic electroluminescent devices prepared in this way have high current efficiency and long lifespan.

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

[0017] In this invention, C6-C40 can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.

[0018] The C6-C30 can be C6, C8, C10, C12, C16, C20, C24, C28, or C30, etc.

[0019] The C1-C12 can be C1, C2, C4, C6, C8, C10, or C12, etc.

[0020] The C6-C20 can be C6, C8, C10, C12, C16, or C20, etc.

[0021] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0022] As a preferred embodiment of the present invention, the C6-C40 aryl group is selected from any one or a combination of at least two of the following: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, naphthyl, pyrene, perylene, spirofluorenyl, triphenylene, fluoranyl, hydrogenated benzo[a]anthrayl, ind[a]fluorenyl, benzo[a]ind[a]fluorenyl, dibenzo[a]ind[a]fluorenyl, naphthyl, or benzo[a]naphthyl.

[0023] Preferably, the C6-C40 arylene is selected from any one or a combination of at least two of the following: phenylene, biphenylene, terphenylene, naphthylene, anthracene, phenanthrene, fluorene, benzo[a]fluorene, dibenzo[a]fluorene, naphthylene, pyrene, perylene, spirofluorene, phenylenetriphenylene, fluorenylene, hydrogenated benzo[a]anthraylene, indo[a]fluorene, benzo[a]indo[a]fluorene, dibenzo[a]indo[a]fluorene, naphthylene, or benzo[a]naphthylene.

[0024] As a preferred embodiment of the present invention, the C6-C30 heteroaryl group is selected from any one or a combination of at least two of carbazolyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, dinaphthothiophenyl or carbazolyl.

[0025] Preferably, the C6-C30 heteroaryl group is selected from any one or a combination of at least two of the following: carbazolyl, dibenzofuranyl, dibenzothiophene, naphthobenzofuranyl, naphthobenzothiophene, dinaphthofuranyl, dinaphthothiophene, or carbazolyl.

[0026] As a preferred embodiment of the present invention, the C6-C20 aryl group is selected from any one or a combination of at least two of phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorene, triphenylene, or fluoranthracene.

[0027] Preferably, the C1-C12 straight-chain or branched alkyl group is selected from any one or a combination of at least two of methyl, ethyl, propyl, butyl, pentyl or adamantyl.

[0028] Preferably, the C1-C12 alkoxy group is selected from any one or a combination of at least two of methoxy, ethoxy, propoxy, butoxy, or pentoxy.

[0029] As a preferred embodiment of the present invention, each of the Ar1 molecules is independently selected from phenylene oxide.

[0030] Preferably, each of the Ar2 molecules is independently selected from any one or a combination of at least two of the following: single bond, carbazolyl, phenylene, naphthylene, diphenylene, dibenzofuranyl, dibenzothiophene, and 9,9-dimethylfluorene.

[0031] Preferably, each of the Ar3 groups is independently selected from any one or a combination of at least two of the following: carbazolyl, phenyl, dibenzofuranyl, dibenzothiophene, 9,9-dimethylfluorenyl, and naphthyl.

[0032] Preferably, Ar4 and Ar5 are each independently selected from any one or a combination of at least two of the following: hydrogen atom, carbazole group, phenyl group, dibenzofuran group, dibenzothiophene group, 9,9-dimethylfluorenyl group, and naphthyl group.

[0033] Preferably, the hydrogen atoms in the structure shown in Formula I or Formula II are each independently substituted or not substituted by at least one of deuterium, -F, -CN, phenyl, naphthyl, biphenyl, methyl, ethyl, propyl, tert-butyl, methoxy, ethoxy, propoxy or butoxy.

[0034] As a preferred embodiment of the present invention, the diazanaphthalene compound is selected from any one of the following substituted or unsubstituted compounds:

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] The substitution refers to the replacement of at least one hydrogen atom in the above compound with a deuterium atom.

[0044] Preferably, the diazanaphthalene compound further includes the above-mentioned compound containing... Replace with The compound; where * represents the linking site of the group.

[0045] For the above compounds Replace with Examples of compounds are given, such as those in compound P1. Replace with Compound PC1 was subsequently obtained, and the compounds in compound P3 were removed. Replace with Compound PC3 was subsequently obtained. The structures of P1, PC1, P3, and PC3 are shown in the figure below. Other compounds can be understood in a similar way.

[0046]

[0047] Preferably, the diazanaphthalene compound is selected from any one of the following compounds:

[0048]

[0049]

[0050] The diazanaphthalene compounds can be prepared by the following method:

[0051] The diazonaphthalene compounds have the structure shown in Formula I. The preparation method is as follows:

[0052]

[0053] The diazonaphthalene compounds have the structure shown in Formula II. The preparation method is as follows:

[0054]

[0055] X1 and X2 are each independently selected from any one of fluorine, chlorine, bromine, and iodine; X, Ar1, Ar2, Ar3, Ar4, and Ar5 have the same limitations as the diazanaphthalene compounds described in the first aspect.

[0056] The specific preparation process of the above compounds can be referred to conventional preparation methods in this field.

[0057] In a second aspect, the present invention provides an intermediate of a diazanaphthalene compound as described in the first aspect, the intermediate having the structure shown in Formula IA or the structure shown in Formula II-A:

[0058]

[0059] In this context, X1 and X2 each independently represent any one of fluorine, chlorine, bromine, or iodine; the dashed line indicates a single bond or the absence of a bond.

[0060] X, Ar1, and Ar5 have the same limitations as the diazanaphthalene compounds described in the first aspect.

[0061] The intermediate is used to prepare diazanaphthalene compounds as described in the first aspect.

[0062] Preferably, the intermediate comprises the following compounds:

[0063]

[0064] It should be noted that the present invention does not impose any special restrictions on the preparation method of the intermediate, which can be prepared according to commonly used preparation methods in the art.

[0065] Thirdly, 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; the material of the organic thin film layer comprises a diazanaphthalene compound as described in the first aspect.

[0066] As a preferred embodiment of the present invention, the organic thin film layer includes a light-emitting layer, and the main material of the light-emitting layer includes diazanaphthalene compounds as described in the first aspect.

[0067] Preferably, the light-emitting layer includes a phosphorescent light-emitting layer, and the main material of the phosphorescent light-emitting layer includes a diazanaphthalene compound as described in the first aspect.

[0068] As a preferred embodiment of the present invention, the organic thin film layer further includes a hole layer.

[0069] Preferably, the hole layer comprises an electron blocking layer, the material of which comprises a compound having a structure as shown in Formula A:

[0070]

[0071] Among them, R 601 It is selected from any one of tert-butyl-substituted phenyl, methylcyclopentyl-substituted phenyl, methylcyclohexyl-substituted phenyl, methylcyclopentyl, methylcyclohexyl or tert-butyl.

[0072] Ring A and ring B are each independently selected from benzene rings or naphthalene rings.

[0073] Ar 601 Selected from phenylene or naphthylene.

[0074] m, n, and p are each independently selected from 0 or 1.

[0075] In the compound with the structure shown in Formula A, each hydrogen atom may be independently replaced by a deuterium atom or not.

[0076] It should be noted that when n is 1, Ar 601 Selected from phenylene or naphthylene.

[0077] Preferably, the material of the electron blocking layer is selected from any one of the following substituted or unsubstituted compounds:

[0078]

[0079]

[0080] The substitution refers to the replacement of at least one hydrogen atom in the above compound with a deuterium atom.

[0081] Preferably, the organic electroluminescent device is a blue organic electroluminescent device.

[0082] The material of the light-emitting layer in this invention includes a host material and a dopant material, wherein the dopant material is also called a dye or a phosphorescent material. The host material of the light-emitting layer can be a single compound or a mixture of two or more compounds.

[0083] The light-emitting layer includes a phosphorescent light-emitting layer, which may be a blue phosphorescent light-emitting layer, a green phosphorescent light-emitting layer, a red phosphorescent light-emitting layer, or a yellow phosphorescent light-emitting layer.

[0084] The volume percentage of the main material in the phosphorescent luminescent layer is 60% to 99.9% (e.g., 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or 99.9%), preferably 70% to 99.5%, and more preferably 85% to 95%.

[0085] In this invention, the doping material of the light-emitting layer can be a phosphorescent material, also known as a triplet luminescent material, which refers to the light emitted by a substance from a triplet excited state. This invention does not impose any specific limitations on the selection of the phosphorescent material; commonly used doping materials for light-emitting layers in the art are applicable, including but not limited to: compounds having a structure as shown in formula PD.

[0086]

[0087] M is selected from any one of Ir, Pt, Pd, Os, Ti, Zr, Hf, Eu, Tb, Tm, Cu, or Au.

[0088] Y1, Y2, Y3, and Y4 are each independently selected from carbon or nitrogen.

[0089] The dashed lines represent single or double bonds, meaning that Y1 and Y2 can be connected by a single or double bond, and Y3 and Y4 can be connected by a single or double bond.

[0090] Cy1 and Cy2 are each independently selected from any one of phenyl, naphthyl, fluorenyl, spirofluorenyl, indyl, pyrroleyl, thiopheneyl, furanyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, benzoquinolinyl, quinoxalinyl, quinazolinyl, carbazoleyl, benzimidazolyl, benzofuranyl, benzothiopheneyl, isobenzothiopheneyl, benzimidazolyl, benzozolyl, triazolyl, tetrazolyl, diazolyl, triazinyl, dibenzofuranyl, dibenzothiopheneyl, N-hexacarbazolyl, N-hexadibenzofuranyl, wherein Cy1 and Cy2 may optionally be linked to each other via a single bond or an organic linking group.

[0091] Any two or more ligands of M can be connected by single or double bonds, or by O or S bridging, or by any chemical group or chemical structure to form a structure that conforms to chemical principles.

[0092] R 91 and R 92 Each group is independently selected from -H, -D, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidine, hydrazine, hydrazone, carboxylic acid group, carboxylate group, sulfonic acid group, sulfonate group, phosphate group, phosphate group, -SF5, substituted or unsubstituted C1-C60 (e.g., C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55, or C60, etc.) straight-chain or branched alkyl groups, substituted or unsubstituted C2 groups. -C60 (e.g., 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, etc.) Alkoxy groups (C25, C30, C35, C40, C45, C50, C55, or C60, etc.), substituted or unsubstituted C2-C10 heterocyclic alkyl groups (e.g., C2, C3, C4, C5, C6, C7, C8, C9, or C10), substituted or unsubstituted C6-C60 aryl groups (e.g., C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54, or C60, etc.), substituted or unsubstituted C6-C60 alkyl groups. (For example, it can be any of the following: C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60, etc.) aryloxy group, substituted or unsubstituted C6-C60 (for example, it can be any of the following: C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60, etc.) arylthio group, substituted or unsubstituted monovalent non-aromatic fused polycyclic group, substituted or unsubstituted monovalent non-aromatic fused heterocyclic group.

[0093] a1 and a2 are each independent integers selected from 1 to 5, for example, they can be 1, 2, 3, 4 or 5.

[0094] b is an integer selected from 0 to 4, for example, it can be 0, 1, 2, 3 or 4.

[0095] a is selected from 1, 2, or 3.

[0096] L1 can be any one of a monovalent organic ligand, a divalent organic ligand, or a trivalent organic ligand.

[0097] Preferably, the PD compound is selected from any one of the following compounds:

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] In this invention, the organic thin film layer further includes a hole layer, which comprises a hole injection layer, a hole transport layer, and an electron blocking layer.

[0105] The hole injection layer material includes a P-type dopant. The P-type dopant is a material 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 from the hole injection layer to the anode. In this invention, the absolute value of the LUMO of the P-type dopant and the absolute value of the HOMO of the hole layer material are 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.

[0106] The P-type dopant is present in the hole injection layer at a volume percentage of 1% to 10% (e.g., 1%, 2%, 4%, 6%, 8%, or 10%). In this invention, no particular limitation is made on the type of P-type dopant; exemplarily, compounds D-1 to D-13 disclosed in CN113728453A or compounds HI-1 to HI-9 as described below can be used.

[0107]

[0108] In this invention, the material of the hole layer (including the hole injection layer, the hole transport layer, and the electron blocking layer) has the structure shown in the following formula HT-GH4:

[0109]

[0110] Among them, L 41Selected from single-bonded, C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl, and C6-C20 (e.g., C6, C8, C10, C12, C16 or C20, etc.) heteroaryl.

[0111] Ar 41 Ar 42 Each is independently selected from C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl groups and C6-C20 (e.g., C6, C8, C10, C12, C16 or C20, etc.) heteroaryl groups.

[0112] X is selected from CR 41 R 42 Or NR 43 , where R 41 R 42 R 43 Each is independently selected from substituted or unsubstituted phenyl groups (the substituents are selected from C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) straight-chain or branched alkyl groups, C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) alkoxy groups, dibenzofuranyl groups, naphthyl groups, triphenylene groups, fluoranyl groups, 9,9-dimethylfluorenyl groups, biphenyl groups, substituted or unsubstituted dibenzofuranyl groups (the substituents are phenyl groups), substituted or unsubstituted dibenzothiophenyl groups (the substituents are phenyl groups), dibenzofuran-substituted thiophenyl groups, and any one of C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) straight-chain or branched alkyl groups, R 41 R 42 A ring can be formed by connecting the links with a single key.

[0113] Preferably, the compound of formula HT-GH4 is selected from any one of the following compounds:

[0114]

[0115]

[0116]

[0117] Hole blocking layers (HBLs) can confine holes and / or excitons within the emissive layer to improve device current efficiency and lifetime. Compared to emissive layer materials closest to the HBL interface, HBL materials exhibit lower HOMO (larger absolute values) and / or higher triplet energies.

[0118] An electron transport layer (ETL) may comprise a material capable of transporting electrons. The ETL may be intrinsic (undoped) or doped, and doping can be used to enhance conductivity. In this invention, there are no particular limitations on the ETL material; any metal complex or organic compound can be used, as long as it can transport electrons. Generally, ETL materials contain at least one of the following structural segments: pyridine, pyrimidine, triazine, benzimidazole, benzoxazole, benzothiazole, azinaphthalene, aziphene, azicarbazole, azidibenzofuran, and azidibenzothiophene.

[0119] In this invention, no special restrictions are placed on the material of the electron transport layer, and exemplary examples include, but are not limited to, the following compounds:

[0120]

[0121] In this invention, the cathode material is a metal with low work function (e.g., alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.)), a metal alloy composed of multiple metals (an alloy composed of alkali metals or alkaline earth metals 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 function can also be used, such as Ag or Al. In this case, combinations of the metals are typically used, such as Ca / Ag, Mg / Ag, or Ba / Ag.

[0122] Alternatively, a thin interlayer of material with a high dielectric constant can be introduced 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 can be an alkali metal or alkaline earth metal fluoride, as well as the corresponding oxide or carbonate (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.) or lithium quinoline (LiQ).

[0123] Fourthly, the present invention provides a display device comprising the organic electroluminescent device as described in the third aspect.

[0124] Compared with the prior art, the present invention has the following beneficial effects:

[0125] In this invention, the structure of the diazanaphthalene compound is designed to make it suitable as the main material for the light-emitting layer of an organic electroluminescent device, thereby enabling the organic electroluminescent device to have high current efficiency and long lifespan. Detailed Implementation

[0126] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0127] Example 1

[0128] A diazanaphthalene compound P1, the synthesis method of which is as follows:

[0129]

[0130] Under nitrogen protection, 100 mL of toluene, 40 mL of ethanol, and 20 mL of water were added sequentially to a 500 mL three-necked flask. Then, 0.01 mol of P1-1, 0.01 mol of boric acid 1, 0.02 mol of potassium carbonate, and 0.0002 mol of tetraphenylphosphine palladium were added. The mixture was slowly heated to reflux and reacted for 6 hours. After cooling to room temperature, water was added to separate the organic layer. The organic layer was washed with water and dried with magnesium sulfate. After removing the desiccant, the mixture was concentrated to dryness and separated by silica gel column chromatography. The elution was performed with petroleum ether:ethyl acetate = 20:1 (volume ratio) to obtain the diazanaphthalene compound P1.

[0131] Mass spectrometry analysis of the diazanaphthalene compound P1 revealed a mass-to-charge ratio (m / z) of 705.26.

[0132] Examples 2 to 7

[0133] Examples 2 through 7 each provide a diazanaphthalene compound. The synthesis method of the diazanaphthalene compound is the same as that provided in Example 1. The corresponding diazanaphthalene compound is obtained by reacting a carbazole borate compound with a chlorinated derivative. The specific structural formulas of the corresponding carbazole borate compound, the chlorinated derivative, and the prepared diazanaphthalene compound are shown in Table 1 below. The prepared diazanaphthalene compound was detected by mass spectrometry, and the mass-to-charge ratio (m / z) data are shown in Table 1 below.

[0134] Table 1

[0135]

[0136]

[0137]

[0138] Example 8

[0139] A diazanaphthalene compound P6, the synthesis method of said diazanaphthalene compound P6 is as follows:

[0140]

[0141] Under nitrogen protection, 100 mL of toluene, 40 mL of ethanol, and 20 mL of water were added sequentially to a 500 mL three-necked flask. Then, 0.01 mol of P1-1, 0.01 mol of boric acid 2, 0.02 mol of potassium carbonate, and 0.0002 mol of tetraphenylphosphine palladium were added. The mixture was slowly heated to reflux and reacted for 6 hours. After cooling to room temperature, water was added to dissolve the organic layer. The organic layer was washed with water and dried with magnesium sulfate. After removing the desiccant, the mixture was concentrated to dryness and separated by silica gel column chromatography. Elution was performed with petroleum ether:ethyl acetate = 20:1 (volume ratio) to obtain the diazanaphthalene compound P6.

[0142] The obtained diazanaphthalene compound P6 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was found to be 781.29.

[0143] Examples 9 to 11

[0144] Examples 9 to 11 each provide a diazanaphthalene compound. The synthesis method of the diazanaphthalene compound is the same as that provided in Example 8. The corresponding diazanaphthalene compound is obtained by reacting a carbazole borate compound with a chlorinated derivative. The specific structural formulas of the corresponding carbazole borate compound, the chlorinated derivative, and the prepared diazanaphthalene compound are shown in Table 2 below. The prepared diazanaphthalene compound was detected by mass spectrometry, and the mass-to-charge ratio (m / z) data are shown in Table 2 below.

[0145] Table 2

[0146]

[0147]

[0148] Other diazanaphthalene compounds for which specific synthesis methods are not listed can be synthesized by referring to the above examples and combining them with common knowledge in the field.

[0149] The specific structures of some of the compounds used in the following application examples and comparative application examples are as follows:

[0150]

[0151]

[0152]

[0153] Application Example 1

[0154] This application example provides an organic electroluminescent device, using the compound provided by the present invention as the host material of the light-emitting layer. The structure of the organic electroluminescent device is as follows:

[0155] ITO / HT-1: HI-2[5%](80nm) / HT-1(30nm) / EB-1(20nm) / Main material: PBD-1[5%](35nm) / ETL-1(25nm) / LiF(0.5nm) / Al(150nm).

[0156] The method for fabricating the organic electroluminescent device is as follows:

[0157] The material was placed inside a vacuum chamber, and the vacuum was evacuated to 1×10⁻⁶. -5 ~1×10 -6 Pa is sequentially vacuum-deposited onto a cleaned ITO substrate to fabricate OLED devices.

[0158] Wherein PBD-1[5%] refers to the doping ratio of the dye, that is, the volume ratio of the host material to the dye PBD-1 is 95:5; HT-1:HI-2[5%] refers to the ratio of the P-type dopant, that is, the volume ratio of the hole layer material HT-1 to the P-type dopant HI-2 is 95:5. HT-1 is the material of the hole transport layer; HT-1:HI-2[5%] is used as the material of the hole injection layer, and EB-1 is the material of the electron blocking layer.

[0159] The main material of the light-emitting layer of the organic electroluminescent device provided in this application example is a diazanaphthalene compound P1.

[0160] Application Example 2-11

[0161] Application Examples 2-11 provide an organic electroluminescent device, which differs from Application Example 1 only in that the main material of the light-emitting layer, the diazanaphthalene compound P1, is replaced with other compounds (see Table 3 below). The other preparation steps and conditions are the same as in Application Example 1.

[0162] Comparative Application Examples 1-3

[0163] Comparative Application Examples 1-3 provide an organic electroluminescent device, which differs from Application Example 1 only in that the main material of the light-emitting layer, the diazanaphthalene compound P1, is replaced with other compounds (see Table 3 below). The other preparation steps and conditions are the same as in Application Example 1.

[0164] Performance testing

[0165] The brightness, driving voltage, current efficiency, and LT95 of the organic electroluminescent devices provided above were tested using an OLED-1000 multi-channel accelerated aging lifetime and photoluminescence performance analysis system manufactured by Hangzhou Yuanfang. The current efficiency was measured at a brightness of 1000 cd / m². 2 The corresponding value, LT95, refers to maintaining an initial device current density of 10 mA / cm². 2The time required for the device efficiency to drop to 95% of the efficiency corresponding to the initial current density remains unchanged. The current efficiency and LT95 for Application Examples 1-11 and Comparative Application Examples 2-3 are relative values ​​compared to Comparative Application Example 1. Specific test results are shown in Table 4 below:

[0166] Table 3

[0167] Application Example 1 P1 1000 1.49 1.69 Application Example 2 P2 1000 1.58 1.74 Application Example 3 P5 1000 1.64 1.63 Application Example 4 P6 1000 2.13 1.76 Application Example 5 P7 1000 2.07 1.93 Application Example 6 P10 1000 1.38 2.03 Application Example 7 P18 1000 1.92 1.71 Application Example 8 P22 1000 1.22 1.38 Application Example 9 P23 1000 1.37 1.41 Application Example 10 PC1 1000 1.48 2.58 Application Example 11 P2-D 1000 1.61 2.01 Comparative Application Example 1 H1 1000 1 1 Comparative Application Example 2 H5 1000 1.27 1.25 Comparative Application Example 3 H6 1000 1.23 1.31

[0168] As shown in Table 3, the organic electroluminescent device prepared by designing the structure of diazanaphthalene compounds and using these compounds as the main material of the light-emitting layer has high current efficiency and long lifespan.

[0169] Application Example 12

[0170] This application example provides an organic electroluminescent device, using the diazanaphthalene compound provided by this invention as the host material of the light-emitting layer. The structure of the organic electroluminescent device is as follows:

[0171] ITO / HT-1: HI-2[5%](80nm) / HT-1(30nm) / EB-1(20nm) / Main material: PBD-2[5%](35nm) / ETL-1(25nm) / LiF(0.5nm) / Al(150nm).

[0172] The method for fabricating the organic electroluminescent device is as follows:

[0173] The material was placed inside a vacuum chamber, and the vacuum was evacuated to 1×10⁻⁶. -5 ~1×10 -6 Pa is sequentially vacuum-deposited onto a cleaned ITO substrate to fabricate OLED devices.

[0174] Where PBD-2 [5%] refers to the doping ratio of the dye, that is, the volume ratio of the host material to the dye PBD-2 is 95:5; HT-1:HI-2 [5%] refers to the ratio of the P-type dopant, that is, the volume ratio of the hole layer material HT-1 to the P-type dopant HI-2 is 95:5. HT-1 is the material of the hole transport layer; HT-1:HI-2 [5%] is used as the material of the hole injection layer, and EB-1 is the material of the electron blocking layer.

[0175] The main material of the light-emitting layer of the organic electroluminescent device provided in this application example is a diazanaphthalene compound, P3.

[0176] Application Example 13-17

[0177] Application Examples 13-17 provide an organic electroluminescent device, which differs from Application Example 12 only in that the main material of the light-emitting layer, the diazanaphthalene compound P3, is replaced with other compounds (see Table 4 below). The other preparation steps and conditions are the same as in Application Example 12.

[0178] Compare and contrast with example 4-8

[0179] Comparative Application Examples 4-8 provide an organic electroluminescent device, which differs from Application Example 12 only in that the main material of the light-emitting layer, the diazanaphthalene compound P3, is replaced with other compounds (see Table 4 below). The other preparation steps and conditions are the same as in Application Example 12.

[0180] The performance of the organic electroluminescent devices provided in the above application examples and comparative application examples was tested using the methods described above. The specific test results are shown in Table 4 below.

[0181] Table 4

[0182] Application Example 12 P3 1000 1.64 1.61 Application Example 13 P4 1000 1.65 1.44 Application Example 14 P8 1000 1.58 2.88 Application Example 15 P9 1000 1.76 2.52 Application Example 16 P20 1000 1.45 2.66 Application Example 17 PC3 1000 1.55 1.92 Comparative Application Example 4 H2 1000 1 1 Comparative Application Example 5 H3 1000 1.11 1.36 Comparative Application Example 6 H4 1000 0.98 1.11 Comparative Application Example 7 H7 1000 1.19 1.21 Comparative Application Example 8 H8 1000 1.21 1.17

[0183] As shown in Table 4, the organic electroluminescent device prepared by designing the structure of diazanaphthalene compounds and using these compounds as the main material of the light-emitting layer has high current efficiency and long lifespan.

[0184] By comparing the relevant data of Application Examples 1-11 with Comparative Application Examples 1-3, and by comparing the relevant data of Application Examples 12-17 with Comparative Application Examples 4-8, it can be seen that the present invention, through design... With nitrogen-containing naphthalene rings ( The curve and * indicate specific sites of connection. The resulting compound is suitable as the host material of the light-emitting layer. The organic electroluminescent device prepared in this way has high current efficiency and long lifetime.

[0185] Application Examples 18-19

[0186] Application Examples 18-19 provide an organic electroluminescent device, which differs from Application Examples 12-13 only in that the electron blocking layer EB-1 is replaced with EB-2, while the other preparation steps and conditions are the same as in Application Examples 12-13.

[0187] The performance of the organic electroluminescent device provided in the above application example was tested using the same method as described above, and the test data are shown in Table 5 below.

[0188] Table 5

[0189] Application Example 18 P3 1000 1.81 1.99 Application Example 19 P4 1000 1.93 1.73

[0190] As shown in Tables 4 and 5, using compound EB-2 as the electron blocking layer material can further improve the current efficiency and lifetime of organic electroluminescent devices.

[0191] In summary, this invention designs the structure of diazanaphthalene compounds to make them suitable as the main material for the light-emitting layer of organic electroluminescent devices, thereby enabling the organic electroluminescent devices to have high current efficiency and long lifespan.

[0192] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A diazanaphthalene compound, characterized in that, The diazanaphthalene compounds have the structure shown in Formula I or the structure shown in Formula II: In this case, X is independently selected from C or Si; Dashed lines indicate single bonds or absence of bonds; Ar1 is independently selected from phenylene; Ar2 is independently selected from single bonds or phenylene; Ar3 is independently selected from phenyl, , Any one of them; Ar4 atoms are each independently selected from hydrogen atoms, , , Any one of them; The linking site of the representative group; Ar5 is selected from hydrogen atoms; In the structure shown in Formula I or Formula II, each hydrogen atom is independently substituted or not substituted by at least one of deuterium atom and methyl group.

2. The diazanaphthalene compound according to claim 1, characterized in that, The diazanaphthalene compounds are selected from any one of the following substituted or unsubstituted compounds: The substitution refers to the replacement of at least one hydrogen atom in the above compound with a deuterium atom.

3. The diazanaphthalene compound according to claim 2, characterized in that, The diazanaphthalene compound further includes the compound described in claim 2. Replace with Compounds; In this context, * represents the linking site of a functional group.

4. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode; The material of the organic thin film layer includes diazanaphthalene compounds as described in any one of claims 1-3.

5. The organic electroluminescent device according to claim 4, characterized in that, The organic thin film layer includes a light-emitting layer, and the main material of the light-emitting layer includes a diazanaphthalene compound as described in any one of claims 1-3.

6. The organic electroluminescent device according to claim 5, characterized in that, The light-emitting layer includes a phosphorescent light-emitting layer, and the main material of the phosphorescent light-emitting layer includes a diazanaphthalene compound as described in any one of claims 1-3.

7. The organic electroluminescent device according to claim 5, characterized in that, The organic thin film layer also includes a cavity layer.

8. The organic electroluminescent device according to claim 7, characterized in that, The hole layer includes an electron blocking layer; the material of the electron blocking layer includes a compound having a structure as shown in Formula A: Formula A; Among them, R 601 It is selected from any one of tert-butyl-substituted phenyl, methylcyclopentyl-substituted phenyl, methylcyclohexyl-substituted phenyl, methylcyclopentyl, methylcyclohexyl or tert-butyl; Ring A and ring B are each independently selected from benzene rings or naphthalene rings; Ar 601 Selected from phenylene or naphthylene; m, n, and p are each independently selected from 0 or 1; In the compound with the structure shown in Formula A, each hydrogen atom may be independently replaced by a deuterium atom or not.

9. The organic electroluminescent device according to claim 8, characterized in that, The material of the electron blocking layer is selected from any one of the following substituted or unsubstituted compounds: ； The substitution refers to the replacement of at least one hydrogen atom in the above compound with a deuterium atom.

10. The organic electroluminescent device according to claim 4, characterized in that, The organic electroluminescent device is a blue organic electroluminescent device.

11. A display device, characterized in that, The display device includes an organic electroluminescent device as described in any one of claims 4-10.

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