A compound containing a nitrogen-containing heteroarene structure and an organic electroluminescent device thereof

Abstract

The application discloses a compound containing a nitrogen-containing heterobenzene structure and an organic electroluminescent device thereof, and belongs to the technical field of semiconductor materials. The compound containing the nitrogen-containing heterobenzene structure has the structure as shown in a general formula (1-1), has good stability, and has good hole blocking capability. When the compound is used as a material of an organic electroluminescent device, the device efficiency and the device life are both significantly improved.

Description

Technical Field

[0001] This invention relates to the field of semiconductor materials technology, and in particular to a compound containing a nitrogen-containing heterobenzene structure and its organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) technology can be used to manufacture novel display products and lighting products, and is expected to replace existing liquid crystal displays and fluorescent lighting, with a very wide range of applications. OLEDs have a sandwich-like structure, including electrode material layers and organic optoelectronic functional material layers sandwiched between different electrode material layers. Each organic optoelectronic functional material layer contains at least one light-emitting layer. Various different organic optoelectronic functional materials are stacked together according to their intended use to form the OLED. As a current-driven device, when a voltage is applied to its two electrodes, and an electric field is applied to the positive and negative charges in the organic optoelectronic functional material layer, the positive and negative charges recombine in the light-emitting layer, thus generating organic electroluminescence.

[0003] Currently, organic light-emitting diode (OLED) display technology has been applied in smartphones, tablets, televisions, and other fields. However, compared with the requirements of actual product applications, the luminous efficiency and lifespan of OLEDs still need further improvement. To continuously improve the performance of OLEDs, ongoing research and innovation in organic optoelectronic functional materials are needed to create higher-performance organic optoelectronic functional materials.

[0004] Organic optoelectronic functional materials used in organic electroluminescent devices can be broadly classified into two categories based on their applications: charge injection transport materials and luminescent materials. Further, charge injection transport materials can be categorized into electron injection transport materials, electron blocking materials, hole injection transport materials, and hole blocking materials. In organic electroluminescent devices, holes are injected from the anode, and electrons are injected from the cathode, transporting within the organic functional layer. They eventually meet in the luminescent layer to form excitons, which recombine to emit light. The hole blocking layer, located between the luminescent and electron transport layers, prevents holes from diffusing or moving into the electron transport layer and reduces exciton energy loss, thus acting as an interface modifier and assisting in electron injection / transport regulation. Currently, existing hole blocking layer materials have poor electron control and hole / exciton blocking capabilities, making it difficult to achieve efficient electron-hole balance within the luminescent layer and thus hindering the development of high-efficiency, long-lifetime devices. Therefore, it is necessary to further improve the electron injection and transport capabilities, as well as the hole / exciton blocking capabilities, of hole blocking layer materials, enhance material stability, achieve efficient exciton balance, and ultimately improve device efficiency and lifetime. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, this invention provides a compound containing a azirbenzene structure and its organic electroluminescent device. The compound contains azirbenzene and 9,9'-spirodiacetyl fluorene structures, which are linked by bridging groups, giving the compound excellent hole-blocking ability and good material stability. When used as a hole-blocking material in organic electroluminescent devices, it can effectively improve the luminous efficiency and lifespan of the devices.

[0006] The present invention provides the following specific technical solution: a compound containing a nitrogen-containing benzene structure, the structure of which is shown in general formula (1-1):

[0007]

[0008] In general formula (1-1), Z1, Z2, and Z3 are each independently represented as CH or N; at least one of Z1, Z2, and Z3 is represented as N; Z1, Z2, and Z3 can be the same or different.

[0009] Ar1 and Ar2 are each independently represented as substituted or unsubstituted C1-C. 20 Alkyl, substituted or unsubstituted C3-C 20 cycloalkyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted 5-30 member heteroaryl; Ar1 ​​and Ar2 may be the same or different;

[0010] L1 and L2 are independently represented as single-bonded, substituted, or unsubstituted C3-C bonds. 20 Cycloalkylene, substituted or unsubstituted C6-C 30 The arylene group, substituted or unsubstituted 5-30 member heteroarylene group; L1 and L2 can be the same or different; L1 and L2 are not both single bonds;

[0011] R1 is represented by the structure shown in general formula (1-2);

[0012]

[0013] In general formula (1-2), the asterisk * indicates the connection position between general formula (1-2) and L2;

[0014] In general formula (1-2), X1 and X2 are each independently represented as oxygen atoms or sulfur atoms; X1 and X2 can be the same or different;

[0015] The substituents that replace the above-mentioned substituted groups are deuterium atoms, C1-C... 20 Alkyl, C3-C 20 cycloalkyl, cyano, C6-C 30Aryl groups, and heteroaryl groups priced between 5 and 30 yuan.

[0016] Furthermore, Ar1 and Ar2 are each independently represented as substituted or unsubstituted C1-C. 20 Alkyl, substituted or unsubstituted C3-C 20 The cycloalkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted diphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted phenanthyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted carbazoyl group, substituted or unsubstituted N-phenylcarbazoyl group; Ar1 ​​and Ar2 may be the same or different;

[0017] L1 and L2 are each independently represented as single-bonded, substituted, or unsubstituted C3-C bonds. 20 The compounds are cycloalkylene, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrene, substituted or unsubstituted diphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiopheneyl, substituted or unsubstituted pyridylene; L1 and L2 may be the same or different; L1 and L2 are not both single bonds;

[0018] The substituents that replace the above-mentioned substituted groups are deuterium atoms, C1-C... 20 Alkyl, C3-C 20 Cycloalkyl, cyano, phenyl, naphthyl, diphenyl, terphenyl, pyridyl, pyrimidinyl, phenanthryl, dibenzofuranyl, dibenzothiopheneyl, carbazoleyl.

[0019] Furthermore, the structure of the compound is shown in any one of general formulas (2-1) to (2-4):

[0020]

[0021] In general formulas (2-1) to (2-4), the meanings of Z1, Z2, Z3, Ar1, Ar2, L1, L2, X1, and X2 are the same as those defined above.

[0022] Furthermore, the structure of the compound is shown in any one of general formulas (3-1) to (3-5):

[0023]

[0024] In general formulas (3-1) to (3-5), the meanings of Ar1, Ar2, L1, L2, X1, and X2 are the same as those defined above.

[0025] Furthermore, the structure of the compound is shown in any one of general formulas (4-1) to (4-37):

[0026]

[0027]

[0028]

[0029] In formulas (4-1) to (4-37), Z1, Z2, Z3, Ar1, Ar2, and R1 have the same meanings as defined above. Furthermore, the structure of the compound is shown in any one of formulas (5-1) to (5-37):

[0030]

[0031]

[0032]

[0033]

[0034] In general formulas (5-1) to (5-37), the meanings of Z1, Z2, Z3, Ar1, Ar2, X1, and X2 are the same as those defined above. Furthermore, Ar1 and Ar2 are each independently represented as follows:

[0035]

[0036]

[0037] L1 and L2 are each independently represented as a single bond or the following structure:

[0038]

[0039] any one of them;

[0040] The general formula (1-2) is represented by the following structure:

[0041] Any one of them; X1 and X2 are independently represented as oxygen atoms or sulfur atoms; X1 and X2 can be the same or different.

[0042] Furthermore, X1 and X2 represent oxygen atoms.

[0043] Furthermore, X1 and X2 represent sulfur atoms.

[0044] Furthermore, Ar1 and Ar2 are phenyl groups.

[0045] Furthermore, any hydrogen atom in the compound containing the nitrogen-containing heterobenzene structure can be replaced by a deuterium atom.

[0046] Furthermore, the specific structure of the compound is any one of the following structures:

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081] The present invention also provides an organic electroluminescent device, comprising a substrate, a first electrode, and a second electrode in sequence, wherein a multilayer organic thin film layer is provided between the first electrode and the second electrode, and the organic thin film layer contains a compound with a nitrogen-containing heterobenzene structure as described in the present invention.

[0082] Furthermore, the organic thin film layer includes a hole transport region thin film layer, a light emission region thin film layer, and an electron transport region thin film layer, wherein the electron transport region thin film layer contains a compound with a nitrogen-containing heterobenzene structure as described in this invention.

[0083] Furthermore, the electron transport region thin film layer includes a hole blocking layer containing a compound with the nitrogen-containing heterobenzene structure described in this invention.

[0084] Furthermore, the electron transport region thin film layer comprises a hole blocking layer, an electron transport layer, and an electron injection layer, wherein the hole blocking layer contains a compound with a nitrogen-containing heterobenzene structure as described in this invention.

[0085] Furthermore, the hole transport region thin film layer includes a hole injection layer, a hole transport layer, and an electron blocking layer, and the electron transport region thin film layer includes a hole blocking layer, an electron transport layer, and an electron injection layer, wherein the hole blocking layer contains a compound with a nitrogen-containing heterobenzene structure as described in this invention.

[0086] The beneficial technical effects of this invention are as follows:

[0087] The compounds of this invention contain azirbenzene and 9,9'-spirodianthracene fluorene structures, which are linked by bridging groups. This gives the compounds protected by this invention superior hole blocking and exciton blocking capabilities, effectively preventing holes from diffusing or moving into the electron transport layer. This better confines holes to the luminescent region, ensuring that more excitons are formed from holes and electrons in the luminescent layer, increasing the exciton concentration, and thus improving luminescent efficiency and device lifetime.

[0088] The structural features of the compounds in this invention enable them to have superior electronic control capabilities, supplement the electron transport layer, and possess suitable electron injection and transport performance. They can better adapt to the electron-hole balance within the luminescent layer, thereby improving the device's luminous efficiency and lifespan. Attached Figure Description

[0089] Figure 1 This is a schematic diagram of the structure of an OLED device using the materials listed in this invention. In the figure, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, 10 is a cathode layer, and 11 is a light extraction layer.

[0090] Figure 2 This is the 1H NMR spectrum of compound 83 in Example 7 of the present invention.

[0091] Figure 3 This is the 1H NMR spectrum of compound 81 in Example 6 of the present invention.

[0092] Figure 4 The above is the 1H NMR spectrum of compound 107 in Example 9 of the present invention. Detailed Implementation

[0093] The technical solution of the present invention will be described in detail below with reference to the implementation scheme.

[0094] In this invention, unless otherwise stated, HOMO refers to the highest occupied orbital of a molecule, and LUMO refers to the lowest empty orbital of a molecule. Furthermore, in this invention, HOMO and LUMO energy levels are represented by absolute values, and comparisons between energy levels are made by comparing their absolute values. Those skilled in the art know that the larger the absolute value of an energy level, the lower its energy.

[0095] In the accompanying drawings, the dimensions of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "above" another layer or substrate, the layer or element may be located directly above that other layer or substrate, or there may be intermediate layers. Furthermore, it will be understood that when a layer is referred to as being "between" two layers, the layer may be the only layer between the two layers, or there may be one or more intermediate layers.

[0096] In this invention, the terms "upper" and "lower," used to indicate orientation when describing electrodes, organic electroluminescent devices, and other structures, only indicate orientation in a specific state and do not imply that the related structures can only exist in the stated orientation. Conversely, if a structure can be repositioned, such as by inverting it, the orientation of the structure changes accordingly. Specifically, in this invention, the "lower" side of an electrode refers to the side of the electrode closer to the substrate during fabrication, while the opposite side farther from the substrate is the "upper" side.

[0097] The substituted or unsubstituted C6-C described in this invention 30 The aryl group refers to an aryl group with 6 to 30 carbon atoms, preferably an aryl group with 6 to 20 carbon atoms, and more preferably an aryl group with 6 to 10 carbon atoms. It is preferably a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pyrene, substituted or unsubstituted biphenyl, substituted or unsubstituted para-triphenyl, substituted or unsubstituted meta-triphenyl, substituted or unsubstituted... The group may contain, but is not limited to, substituted or unsubstituted triphenyl, substituted or unsubstituted peryl, substituted or unsubstituted indole, and combinations thereof or combinations of the foregoing groups forming a fused ring.

[0098] The C6-C described in this invention 30 The aryl group refers to an aryl group with 6 to 30 carbon atoms, preferably an aryl group with 6 to 20 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms. Other preferred aryl groups include phenyl, naphthyl, anthraceneyl, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, phenanthrene, tetraphenyl, pyrene, biphenyl, para-triphenyl, and meta-triphenyl. Fused rings of alkyl, triphenyl, peryl, indole, and combinations thereof or combinations thereof, but not limited to these.

[0099] The substituted or unsubstituted C6-C described in this invention 30The arylene group refers to an arylene group having 6 to 30 carbon atoms, preferably an arylene group having 6 to 20 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. It is preferably a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted anthracene, a substituted or unsubstituted fluorene, a substituted or unsubstituted dimethylfluorene, a substituted or unsubstituted diphenylfluorene, a substituted or unsubstituted spirofluorene, a substituted or unsubstituted phenanthyl, a substituted or unsubstituted tetraphenylene, a substituted or unsubstituted pyrene, a substituted or unsubstituted diphenylene, a substituted or unsubstituted para-triphenylene, a substituted or unsubstituted meta-triphenylene, or a substituted or unsubstituted phenylene. The group may contain, but is not limited to, substituted or unsubstituted triphenylene, substituted or unsubstituted perylene, substituted or unsubstituted indenyl, and combinations thereof or combinations of the foregoing groups forming a fused ring.

[0100] The substituted or unsubstituted 5-30 member heteroaryl group described in this invention refers to a heteroaryl group with 5 to 30 cyclic atoms, preferably a heteroaryl group with 5 to 20 cyclic atoms, more preferably a heteroaryl group with 5 to 10 cyclic atoms, and preferably substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrrole, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or Unsubstituted benzothiophene group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted naphthinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzothiazinyl group, substituted or unsubstituted acridineyl group, substituted or unsubstituted benziazinyl group, substituted or unsubstituted benziazinyl group, substituted or unsubstituted benziazinyl group, substituted or unsubstituted fumonyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophene group, substituted or unsubstituted carbazoyl group, substituted or unsubstituted N-phenylcarbazoyl group, and combinations thereof or fused rings of the foregoing groups, but not limited thereto.

[0101] In this invention, the 5-30 cyclic heteroaryl group refers to a heteroaryl group with 5 to 30 cyclic atoms, preferably a heteroaryl group with 5 to 20 cyclic atoms, more preferably a heteroaryl group with 5 to 10 cyclic atoms, preferably furanyl, thiopheneyl, pyrroleyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, oxadiazolyl, thiazolyl, pyridinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiopheneyl, benzoimidazolyl, indolyl, quinolinyl, isoquinolinyl, quinazolinyl, quinolinyl, naphridinyl, benzooxazinyl, benzothiazinyl, acridineyl, benazinoyl, benazinothiazinyl, benazinoyl, fumonyl, dibenzofuranyl, dibenzothiopheneyl, carbazoleyl, N-phenylcarbazoleyl, and combinations thereof or fused rings of the aforementioned groups, but not limited thereto.

[0102] In this invention, the substituted or unsubstituted 5-30 member heteroaryl group refers to a heteroaryl group with 5 to 30 cyclic atoms, preferably a heteroaryl group with 5 to 20 cyclic atoms, more preferably a heteroaryl group with 5 to 10 cyclic atoms, and preferably substituted or unsubstituted furanyl, substituted or unsubstituted thiopheneyl, substituted or unsubstituted pyrroleyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or Unsubstituted benzothiophene group, substituted or unsubstituted benzoimidazolyl group, substituted or unsubstituted indole group, substituted or unsubstituted quinolino group, substituted or unsubstituted isoquinolino group, substituted or unsubstituted quinazolino group, substituted or unsubstituted quinolino group, substituted or unsubstituted naphthinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzothiazinyl group, substituted or unsubstituted acridineyl group, substituted or unsubstituted phenazinyl group, substituted or unsubstituted phenathiazinyl group, substituted or unsubstituted phenoxazinyl group, substituted or unsubstituted fenenyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophene group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted N-phenylcarbazolyl group, and combinations thereof or combinations of the foregoing groups forming a fused ring, but not limited thereto.

[0103] The C1-C of this invention 20 Alkyl groups (including straight-chain alkyl and branched-chain alkyl) refer to methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl, etc., but are not limited to these.

[0104] The C3-C of this invention20 Cycloalkyl refers to a saturated hydrocarbon group comprising 3 to 10 carbon atoms as cyclic atoms. In this document, C4-C9 cycloalkyl groups are preferred, C5-C8 cycloalkyl groups are more preferred, and C5-C7 cycloalkyl groups are particularly preferred. Non-limiting examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl, and cycloheptyl.

[0105] The C3-C of this invention 20 Cycloalkylene refers to a saturated hydrocarbon group comprising 3 to 10 carbon atoms as cyclic atoms. In this document, C4-C9 cycloalkylene is preferred, C5-C8 cycloalkylene is more preferred, and C5-C7 cycloalkylene is particularly preferred. Non-limiting examples may include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, 4-methylcyclohexylene, 4,4-dimethylcyclohexylene, adamantylene, and cycloheptylene.

[0106] Organic electroluminescent devices

[0107] The organic electroluminescent device of the present invention can be a bottom-emitting organic electroluminescent device, a top-emitting organic electroluminescent device, or a multilayer organic electroluminescent device, and there is no specific limitation thereto.

[0108] The organic electroluminescent device of the present invention comprises, in sequence, a substrate, a first electrode, an organic thin film layer, and a second electrode. The organic thin film layer includes a hole transport region thin film layer, a light-emitting region thin film layer, and an electron transport region thin film layer. The hole transport region thin film layer includes a hole injection layer, a hole transport layer, and an electron blocking layer. The electron transport region thin film layer includes a hole blocking layer, an electron transport layer, and an electron injection layer. Additionally, a light extraction layer may be disposed on the second electrode.

[0109] The organic electroluminescent device of the present invention may include the following layers and their positional relationships: it may include a substrate, a first electrode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a second electrode, and a light extraction layer. If the above layers are present, the first electrode is on the substrate, the hole injection layer is on the first electrode, the hole transport layer is on the hole injection layer, the electron blocking layer is on the hole transport layer, the light-emitting layer is on the electron blocking layer, the hole blocking layer is on the light-emitting layer, the electron transport layer is on the hole blocking layer, the electron injection layer is on the electron transport layer, the second electrode is on the electron injection layer, and the light extraction layer is on the second electrode.

[0110] As the substrate for the organic electroluminescent device of this invention, any substrate commonly used in organic electroluminescent devices can be used. Examples include transparent substrates, such as glass or transparent plastic substrates; opaque substrates, such as silicon substrates; and flexible PI film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Their application varies depending on their properties. In this invention, a transparent glass substrate is preferred, and the thickness of the substrate is not particularly limited.

[0111] A first electrode is formed on a substrate, and the first electrode and a second electrode may be opposite each other. The first electrode can be an anode or a cathode. In this invention, the first electrode serves as the anode, and the anode material is preferably a material with a high work function so that holes can be easily injected into the organic functional material layer. Non-limiting examples of anode materials include, but are not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The first electrode may have a single-layer structure or a multilayer structure comprising two or more layers. In addition, the thickness of the anode depends on the material used, typically 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm.

[0112] The hole injection layer, hole transport layer, and electron blocking layer can be disposed between the first electrode and the light-emitting layer.

[0113] The hole injection layer may comprise a host material and a p-type doped material. The host material may be selected from conventional hole transport materials in the prior art, preferably the same organic material as the hole transport layer. The p-type doped material is selected from charge-conducting compounds disclosed in the prior art, and may be selected from compounds disclosed in the following patent documents: WO2011073149A, EP1968131A1, EP2276085A1, EP2213662A1, EP1722602A1, EP2 045848A1, DE102007031220A1, US20100181555A1, US20100102709A1, WO2009003455A1, WO2010094378A1, WO2011120709A1, US20100096600A1, DE102012209523A1, CN101728485A and WO2012095143A1, but not limited to these.

[0114] For example, the compounds shown below:

[0115]

[0116] According to the present invention, P-1 is preferably used as the P-type doped material.

[0117] The thickness of the hole injection layer of the present invention can be 1-100 nm, preferably 2-50 nm, and more preferably 5-20 nm.

[0118] The material of the hole transport layer is preferably a material with high hole mobility, which enables holes to be transferred from the anode or hole injection layer to the light-emitting layer.

[0119] Preferably, the hole transport layer material of the present invention may be selected from the compounds disclosed in the prior art:

[0120]

[0121]

[0122] The thickness of the hole transport layer of the present invention can be 5-200 nm, preferably 10-180 nm, and more preferably 20-150 nm.

[0123] The electron blocking layer requires that its triplet (T1) energy level be higher than that of the host material in the emissive layer, thus blocking energy loss from the emissive layer material. The HOMO energy level of the electron blocking layer material should be between that of the hole transport layer material and the host material of the emissive layer, facilitating hole injection from the positive electrode into the emissive layer. Simultaneously, the electron blocking layer material should possess high hole mobility to promote hole transport and reduce the power consumption of the device. The LUMO energy level of the electron blocking layer material should be higher than that of the host material of the emissive layer, serving as an electron blocker; that is, the electron blocking layer material should have a wide bandgap (Eg). Electron blocking layer materials meeting these conditions can be triarylamine derivatives, fluorene derivatives, spirofluorene derivatives, dibenzofuran derivatives, carbazole derivatives, etc.

[0124] In one embodiment of the present invention, the electron blocking layer material may be selected from the compounds disclosed in the prior art:

[0125]

[0126] According to the present invention, the thickness of the electron blocking layer can be 1-200 nm, preferably 5-150 nm, and more preferably 5-50 nm.

[0127] According to the present invention, the light-emitting layer is located between the electron blocking layer and the hole blocking layer. The material of the light-emitting layer is a material that emits visible light by respectively receiving holes from the hole transport region and electrons from the electron transport region, and combining the received holes and electrons. The light-emitting layer may include a host material and a dopant material. The host material may be classified as a red light host material, a green light host material, a blue light host material, etc., and the dopant material may be classified as a red light dopant material, a green light dopant material, a blue light dopant material, etc. The present invention takes a blue light device as an example, using it as the host material and guest material of the light-emitting layer of the organic electroluminescent device of the present invention. The host material may be one or a combination of two of the following: anthracene derivatives, quinoxaline derivatives, triazine derivatives, xanthone derivatives, diphenyl ketone derivatives, carbazole derivatives, pyridine derivatives, or pyrimidine derivatives. The guest material may be a pyrene derivative, a boron derivative, a quinolone derivative, a spirofluorene derivative, an iridium complex, or a platinum complex.

[0128] The thickness of the light-emitting layer of the present invention can be 5-60 nm, preferably 10-50 nm, and more preferably 20-45 nm.

[0129] A hole-blocking layer can be disposed above the light-emitting layer. The triplet (T1) energy level of the hole-blocking layer material is higher than the T1 energy level of the main material of the light-emitting layer, which can block the energy loss of the light-emitting layer material; the HOMO energy level of the material is lower than the HOMO energy level of the main material of the light-emitting layer, which can block holes. At the same time, the hole-blocking layer material is required to have a suitable electron mobility to facilitate electron transport and reduce the power consumption of the device. The hole-blocking layer material that meets the above conditions is the nitrogen-containing heterobenzene compound described above in this invention.

[0130] The thickness of the hole blocking layer of the present invention can be 2-200 nm, preferably 5-150 nm and more preferably 5-50 nm, but the thickness is not limited to this range.

[0131] An electron transport layer can be disposed above a hole blocking layer. The electron transport layer material is one that readily receives electrons from the cathode and transfers them to the light-emitting layer. Preferably, a material with high electron mobility is used. As the electron transport layer of the organic electroluminescent device of the present invention, compounds disclosed in the prior art can be used as the electron transport layer material for the organic electroluminescent device:

[0132]

[0133] In a preferred embodiment of the invention, the electron transport layer further includes other compounds conventionally used in electron transport layers, such as Alq3, Liq, preferably Liq.

[0134] The thickness of the electron transport layer of the present invention can be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm.

[0135] According to the present invention, an electron injection layer may be disposed between the electron transport layer and the cathode. The electron injection layer material is generally preferably a material with a low work function, which facilitates electron injection into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material for the organic electroluminescent device of the present invention, the following electron injection layer materials for organic electroluminescent devices disclosed in the prior art can be used: LiF, Cs₂CO₃, CsF, Csq, NaF, MgF₂, CaF₂, Al₂O₃, and Yb.

[0136] The thickness of the electron injection layer of the present invention can be 0.1-5 nm, preferably 0.5-3 nm and more preferably 0.8-1.5 nm, but the thickness is not limited to this range.

[0137] According to the present invention, as described above, the second electrode can be either a cathode or an anode. In this invention, the second electrode is used as the cathode. The material used to form the cathode can be a material with low work function, such as a metal, alloy, conductive compound, or a mixture thereof. Non-limiting examples of cathode materials may include lithium (Li), ytterbium (Yb), magnesium (Mg), aluminum (Al), calcium (Ca), as well as aluminum-lithium (Al-Li), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The thickness of the cathode depends on the material used, typically 5-100 nm, preferably 7-50 nm, and more preferably 10-25 nm.

[0138] Optionally, to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., a CPL layer) may be added above the second electrode (i.e., the cathode) of the device. The following compounds disclosed in the art in the prior art can be used as light extraction layer materials.

[0139]

[0140] The thickness of the light extraction layer is typically 5-300 nm, preferably 20-100 nm, and more preferably 40-80 nm.

[0141] Organic electroluminescent devices may also include an encapsulation structure. The encapsulation structure may be a protective structure that prevents external substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass or metal can; or a thin film covering the entire surface of the organic layer.

[0142] Methods for fabricating organic electroluminescent devices

[0143] The present invention also relates to a method for fabricating the above-mentioned organic electroluminescent device, comprising sequentially laminating a first electrode, an organic thin film layer, and a second electrode on a substrate. The organic thin film layer is formed by sequentially laminating a hole transport region thin film layer, a light-emitting region thin film layer, and an electron transport region thin film layer on the first electrode from bottom to top. The hole transport region thin film layer is formed by sequentially laminating a hole injection layer, a hole transport layer, and an electron blocking layer on the first electrode from bottom to top. The electron transport region thin film layer is formed by sequentially laminating a hole blocking layer, an electron transport layer, and an electron injection layer on the light-emitting layer from bottom to top. Optionally, a light extraction layer may also be laminated on the second electrode to improve the light extraction efficiency of the organic electroluminescent device.

[0144] Regarding lamination, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, or LITI can be used, but are not limited to these. Among them, vacuum evaporation refers to heating the material and depositing it onto the substrate in a vacuum environment.

[0145] In this invention, vacuum evaporation is preferably used to form the various layers, wherein the vapor deposition process can be carried out at a temperature of about 100-500°C for about 10... -8 -10 -2 The vacuum degree and about Vacuum evaporation is performed at a rate of [missing information]. The vacuum level is preferably 10 [missing information]. -6 -10 -2 Torr, more preferably 10 -5 -10 -3 Torr. The rate is approximately More preferably, about

[0146] In addition, it should be noted that the materials used to form each layer described in this invention can be used as a single layer by forming a film on their own, or they can be used as a single layer by mixing with other materials to form a film. They can also be a stacked structure between layers that are formed on their own, a stacked structure between layers that are formed by mixing, or a stacked structure between layers that are formed on their own and layers that are formed by mixing.

[0147] Display device

[0148] The present invention also relates to a display device including the aforementioned organic electroluminescent devices, particularly a flat panel display device. In a preferred embodiment, the display device may include one or more of the aforementioned organic electroluminescent devices, and in the case of multiple devices, the devices are stacked laterally or vertically. The display device may also include at least one thin-film transistor. The thin-film transistor may include a gate electrode, a source electrode and a drain electrode, a gate insulating layer and an active layer, wherein one of the source electrode and the drain electrode may be electrically connected to a first electrode of the organic electroluminescent device. The active layer may include crystalline silicon, amorphous silicon, organic semiconductor or oxide semiconductor, but is not limited thereto.

[0149] The following examples are intended to better explain the present invention, but the scope of the invention is not limited thereto.

[0150] Example

[0151] I. Compound Preparation Examples

[0152] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0153] All raw materials involved in the synthesis embodiments of the present invention can be purchased from the market or obtained by conventional preparation methods in the art;

[0154] Example 1: Synthesis of compound 39:

[0155]

[0156] Preparation of intermediate P-1: Under nitrogen protection, in a round-bottom flask, raw material A-1 (2.14 g, 5 mmol), raw material A-11 (0.86 g, 5.5 mmol), K2CO3 (2.07 g, 15 mmol), tetrahydrofuran (100 mL), and water (50 mL) were added sequentially. Nitrogen gas was purged for 30 min to replace the air. Pd(PPh3)4 (0.12 g, 0.1 mmol) was added, and the mixture was heated under nitrogen protection and refluxed for 8 h. TLC analysis of the reaction solution showed that starting material A-1 reacted completely. After the reaction was complete, the reaction system was naturally cooled to room temperature, and the solvent was removed by rotary evaporation. The residue was dissolved in 100 ml of dichloromethane, washed with 150 ml of water, poured into a separatory funnel, shaken, and allowed to stand for separation. The aqueous phase was extracted with dichloromethane (25 ml * 4). The organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and the filtrate was rotary evaporated to remove dichloromethane to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain intermediate P-1. LC-MS: Measured value: 459.35 ([M+H) + Theoretical value: 458.11.

[0157] Preparation of compound 39: Under nitrogen protection, intermediate P-1 (2.29 g, 5 mmol), raw material A-12 (1.94 g, 5.5 mmol), K2CO3 (2.07 g, 15 mmol), tetrahydrofuran (100 mL), and water (50 mL) were added sequentially to a round-bottom flask. Nitrogen gas was purged for 30 min to replace the air. Pd(PPh3)4 (0.12 g, 0.1 mmol) was added, and the mixture was heated under nitrogen protection and refluxed for 10 h. TLC analysis of the reaction solution showed that intermediate P-1 reacted completely. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, the residue was dissolved in 100 ml of dichloromethane, washed with 150 ml of water, poured into a separatory funnel, shaken, and allowed to stand for separation. The aqueous phase was extracted with dichloromethane (30 ml * 4), the organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and the filtrate was removed by rotary evaporation to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain compound 39.

[0158] Example 2: Synthesis of compound 40:

[0159]

[0160] Preparation of intermediate P-2: Refer to the preparation of intermediate P-1, except that raw material A-4 replaces raw material A-11, and raw material A-6 replaces raw material A-1. LC-MS: Test value: 464.22 ([M+H]) + Theoretical value: 463.07.

[0161] Preparation of intermediate Q-2: Under nitrogen protection, intermediate P-2 (2.32 g, 5 mmol), starting material A-19 (1.40 g, 5.5 mmol), KOAC (1.47 g, 15 mmol), and dioxane (100 mL) were added sequentially to a round-bottom flask. Nitrogen gas was purged for 30 min to replace the air. Pd(PPh3)4 (0.12 g, 0.1 mmol) was then added, and the mixture was heated under reflux for 24 h under nitrogen protection. TLC analysis of the reaction solution showed that intermediate P-2 reacted completely. After the reaction was complete, the reaction system was naturally cooled to room temperature, poured into a separatory funnel, shaken, and allowed to stand for separation. The aqueous phase was extracted with dichloromethane (30 mL * 4). The organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and the filtrate was rotary evaporated to remove dichloromethane, yielding intermediate Q-2. LC-MS: Measured value: 512.09 ([M+H)) + Theoretical value: 511.24.

[0162] Preparation of compound 40: In a round-bottom flask, intermediate Q-2 (2.81 g, 5.5 mmol), raw material A-1 (2.14 g, 5 mmol), K2CO3 (2.07 g, 15 mmol), tetrahydrofuran (100 mL), and water (50 mL) were added sequentially. Nitrogen gas was purged for 30 min to replace the air. Palladium acetate (0.011 g, 0.05 mmol) and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.072 g, 0.15 mmol) were added. The mixture was heated under nitrogen protection and refluxed for 18 h. TLC analysis of the reaction solution showed that the reaction of raw material A-1 was complete. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, the residue was dissolved in 120 ml of dichloromethane, washed with 50 ml of water, poured into a separatory funnel, shaken, and allowed to stand for separation. The aqueous phase was extracted with dichloromethane (50 ml * 3), the organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and the filtrate was removed by rotary evaporation to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain compound 40.

[0163] Example 3: Synthesis of compound 41:

[0164]

[0165] Preparation of intermediate P-3: Refer to the preparation of intermediate P-1, except that raw material A-4 replaces raw material A-11, and raw material A-7 replaces raw material A-1. LC-MS: Test value: 464.15 ([M+H]) + Theoretical value: 463.07.

[0166] Preparation of intermediate Q-3: Refer to the preparation of intermediate Q-2, except that intermediate P-2 is replaced with intermediate P-3. LC-MS: Test value: 512.27 ([M+H]) + Theoretical value: 511.24.

[0167] Preparation of compound 41: Refer to the preparation of compound 40, except that intermediate Q-2 is replaced by intermediate Q-3.

[0168] Example 4: Synthesis of compound 77:

[0169]

[0170] Preparation of intermediate P-4: Refer to the preparation of intermediate P-1, except that raw material A-20 is used instead of raw material A-11. LC-MS: Measured value: 459.26 (M+H) + Theoretical value: 458.11.

[0171] Preparation of compound 77: Refer to the preparation of compound 39, except that raw material A-12 is replaced by raw material A-21 and intermediate P-1 is replaced by intermediate P-4.

[0172] Example 5: Synthesis of compound 79:

[0173]

[0174] Preparation of intermediate P-5: Refer to the preparation of intermediate Q-2, except that raw material A-1 is used instead of intermediate P-2. LC-MS: Test value: 475.34 ([M+H]) + Theoretical value: 474.20.

[0175] Preparation of intermediate Q-5: Refer to the preparation of compound 40, except that intermediate Q-2 was replaced by intermediate P-5, and starting material A-1 was replaced by starting material A-7. LC-MS: Measured value: 579.26 ([M+H]) + Theoretical value: 578.09.

[0176] Preparation of compound 79: Refer to the preparation of intermediate P-1, except that raw material A-4 is used instead of raw material A-11, and intermediate Q-5 is used instead of raw material A-1.

[0177] Example 6: Synthesis of compound 81:

[0178]

[0179] Preparation of intermediate P-6: Similar to the preparation of intermediate P-1, except that raw material A-4 replaces raw material A-11, and raw material A-9 replaces raw material A-1. LC-MS: Test value: 464.20 (M+H) + Theoretical value: 463.07.

[0180] Preparation of intermediate Q-6: Refer to the preparation of intermediate Q-2, except that intermediate P-6 is used instead of intermediate P-2. LC-MS: Test value: 512.17 ([M+H]) + Theoretical value: 511.24.

[0181] Preparation of compound 81: Refer to the preparation of compound 40, except that intermediate Q-2 is replaced by intermediate Q-6.

[0182] Example 7: Synthesis of Compound 83:

[0183]

[0184] Preparation of compound 83: Refer to the preparation of intermediate P-1, except that raw material A-22 is used instead of raw material A-11, and intermediate P-4 is used instead of raw material A-1.

[0185] Example 8: Synthesis of Compound 95:

[0186]

[0187] Preparation of intermediate P-8: Refer to the preparation of intermediate P-1, except that raw material A-20 replaces raw material A-11, and raw material A-2 replaces raw material A-1. LC-MS: Test value: 459.04 (M+H) + Theoretical value: 458.11.

[0188] Preparation of compound 95: Refer to the preparation of compound 39, except that raw material A-12 is replaced by raw material A-22 and intermediate P-1 is replaced by intermediate P-8.

[0189] Example 9: Synthesis of compound 107:

[0190]

[0191] Preparation of intermediate P-9: Similar to the preparation of intermediate P-1, except that raw material A-20 replaces raw material A-11, and raw material A-3 replaces raw material A-1. LC-MS: Test value: 459.36 (M+H) + Theoretical value: 458.11.

[0192] Preparation of compound 107: Refer to the preparation of compound 39, except that raw material A-12 is replaced by raw material A-22 and intermediate P-1 is replaced by intermediate P-9.

[0193] Example 10: Synthesis of compound 133:

[0194]

[0195] Preparation of compound 133: Refer to the preparation of intermediate P-1, except that raw material A-11 is replaced by raw material A-14, and raw material A-1 is replaced by intermediate P-1.

[0196] Example 11: Synthesis of compound 135:

[0197]

[0198] Preparation of intermediate P-11: Refer to the preparation of intermediate P-1, except that raw material A-23 is used instead of raw material A-11. LC-MS: Test value: 459.06 (M+H) +Theoretical value: 458.11.

[0199] Preparation of compound 135: Refer to the preparation of compound 39, except that raw material A-12 is replaced by raw material A-14 and intermediate P-1 is replaced by intermediate P-1.

[0200] Example 12: Synthesis of compound 171:

[0201]

[0202] Preparation of compound 171: Refer to the preparation of compound 40, except that intermediate P-1 is used to replace raw material A-1 and intermediate Q-6 is used to replace intermediate Q-2.

[0203] Example 13: Synthesis of Compound 176:

[0204]

[0205] Preparation of compound 176: Refer to the preparation of compound 40, except that intermediate P-1 is used instead of starting material A-1.

[0206] Example 14: Synthesis of compound 181:

[0207]

[0208] Preparation of intermediate P-14: Refer to the preparation of intermediate P-1, except that raw material A-12 replaces raw material A-11, and raw material A-7 replaces raw material A-1. LC-MS: Test value: 540.25 ([M+H]) + Theoretical value: 539.10.

[0209] Preparation of compound 181: Refer to the preparation of compound 40, except that intermediate P-5 is used to replace intermediate Q-2 and intermediate P-14 is used to replace starting material A-1.

[0210] Example 15: Synthesis of Compound 200:

[0211]

[0212] Preparation of intermediate P-15: Refer to the preparation of compound 40, except that intermediate Q-2 was replaced by intermediate P-5, and starting material A-1 was replaced by starting material A-13. LC-MS: Measured value: 579.28 ([M+H]) + Theoretical value: 578.09.

[0213] Preparation of compound 200: Refer to the preparation of compound 39, except that intermediate P-1 is replaced by intermediate P-15.

[0214] Example 16: Synthesis of compound 202:

[0215]

[0216] Preparation of intermediate P-20: Refer to the preparation of intermediate P-1, except that raw material A-11 is replaced by raw material A-12, and raw material A-1 is replaced by raw material A-13. LC-MS: Test value: 540.04 ([M+H]) + Theoretical value: 539.10.

[0217] Preparation of compound 202: Refer to the preparation of compound 40, except that intermediate P-5 is used to replace intermediate Q-2 and intermediate P-20 is used to replace starting material A-1.

[0218] Example 17: Synthesis of compound 225:

[0219]

[0220] Preparation of intermediate P-16: Refer to the preparation of compound 40, except that intermediate Q-2 was replaced by intermediate P-5, and starting material A-1 was replaced by starting material A-9. LC-MS: Measured value: 579.14 ([M+H]) + Theoretical value: 578.09.

[0221] Preparation of compound 225: Refer to the preparation of compound 39, except that intermediate P-1 is replaced by intermediate P-16 and starting material A-12 is replaced by starting material A-14.

[0222] Example 18: Synthesis of compound 240:

[0223]

[0224] Preparation of intermediate P-17: Refer to the preparation of intermediate Q-2, except that intermediate P-2 is replaced with starting material A-24. LC-MS: Test value: 512.12 ([M+H]) + Theoretical value: 511.24.

[0225] Preparation of compound 240: Refer to the preparation of compound 40, except that intermediate P-11 is used to replace raw material A-1 and intermediate P-17 is used to replace intermediate Q-2.

[0226] Example 19: Synthesis of Compound 290:

[0227]

[0228] Preparation of intermediate P-18: Refer to the preparation of intermediate P-1, except that raw material A-12 replaces raw material A-11, and raw material A-15 replaces raw material A-1. LC-MS: Test value: 514.13 ([M+H]) + Theoretical value: 513.08.

[0229] Preparation of compound 290: Refer to the preparation of compound 40, except that intermediate P-5 is used to replace intermediate Q-2 and intermediate P-18 is used to replace starting material A-1.

[0230] Example 20: Synthesis of compound 339:

[0231]

[0232] Preparation of intermediate P-19: Refer to the preparation of intermediate P-1, except that raw material A-4 replaces raw material A-11, and raw material A-17 replaces raw material A-1. LC-MS: Test value: 422.06 (M+H) + Theoretical value: 421.00.

[0233] Preparation of intermediate Q-19: Refer to the preparation of compound 40, except that intermediate Q-2 was replaced by intermediate P-5, and starting material A-1 was replaced by intermediate P-19. LC-MS: Measured value: 690.38 ([M+H]) + Theoretical value: 689.19.

[0234] Preparation of compound 339: Refer to the preparation of compound 39, except that intermediate P-1 is replaced by intermediate Q-19 and raw material A-12 is replaced by raw material A-16.

[0235] Example 21: Synthesis of compound 351:

[0236]

[0237] Preparation of compound 351: Refer to the preparation of compound 39, except that intermediate P-1 is replaced by intermediate Q-19 and starting material A-12 is replaced by starting material A-18.

[0238] Example 22: Synthesis of compound 385:

[0239]

[0240] Preparation of intermediate P-22: Starting material A-25 (0.94 g, 3.0 mmol) was dissolved in dry THF (10 mL) and cooled to -80 °C. Then, at -80 °C, a 1.6 mol / L n-BuLi hexane solution (1.88 mL, 3.0 mmol) was added dropwise over 5 minutes. The resulting mixture was stirred at the same temperature for 2 hours, and then dry THF (50 mL) containing dissolved starting material A-26 (0.7 g, 2.4 mmol) was added dropwise over 10 minutes. The mixture was heated to 20 °C and maintained overnight. Brine (150 mL) was added, and the mixture was extracted with dichloromethane (3 × 150 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain intermediate P-22. LC-MS: Measured value: 476.86 ([M+H)) + Theoretical value: 475.99.

[0241] Preparation of intermediate Q-22: Intermediate P-22 (1.43 g, 3.0 mmol) was dissolved in acetic acid (50 mL), the solution was heated to reflux, and then 37% HCl aqueous solution (5 mL) was added. The mixture was refluxed and stirred for 2 h. Water (50 mL) was added, and the mixture was extracted with dichloromethane (3 × 50 mL). The combined organic extracts were washed with saturated NaHCO3 solution (2 × 20 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by rapid chromatography on silica gel to give intermediate Q-22. LC-MS: Measured value: 458.91 ([M+H) + Theoretical value: 457.98.

[0242] Preparation of compound 385: Refer to the preparation of intermediate P-1, except that raw material A-11 is replaced by raw material A-14 and raw material A-1 is replaced by intermediate Q-22.

[0243] Example 23: Synthesis of compound 402:

[0244]

[0245] Preparation of intermediate P-23: Refer to the preparation of intermediate P-22, except that raw material A-26 is replaced with raw material A-27. LC-MS: Test value: 461.13 ([M+H]) + Theoretical value: 460.01.

[0246] Preparation of intermediate Q-23: Refer to the preparation of intermediate Q-22, except that intermediate P-22 is replaced by intermediate P-23. LC-MS: Test value: 443.07 (M+H) + Theoretical value: 442.00.

[0247] Preparation of intermediate R-23: Refer to the preparation of intermediate P-1, except that raw material A-11 is replaced by raw material A-20, and raw material A-1 is replaced by intermediate Q-23. LC-MS: Test value: 475.29 ([M+H]) + Theoretical value: 474.08.

[0248] Preparation of compound 402: Refer to the preparation of intermediate P-1, except that raw material A-11 is replaced by raw material A-22 and raw material A-1 is replaced by intermediate R-23.

[0249] The structural characterization of the compounds obtained in each embodiment is shown in Table 1:

[0250] Table 1

[0251]

[0252]

[0253]

[0254] II. Device Fabrication Examples

[0255] The following describes in detail the application effects of the compounds synthesized according to the present invention as hole blocking layer materials in devices through device Examples 1-37 and device Comparative Examples 1-6. Device Examples 1-37 are manufactured using the same process as Comparative Examples 1-6, employing the same substrate and electrode materials with consistent electrode film thickness. The only difference is the change in the hole blocking layer material. The device layer structures are shown in Table 2, and the performance test results for each device are shown in Table 3.

[0256] The molecular structural formulas of the relevant materials are shown below:

[0257]

[0258] The structures of compounds HB-1, HB-2, HB-3, HB-4, HB-5, and HB-6 are shown above. All of these materials were commercially available or obtained using conventional methods in the art.

[0259] Device Comparison Example 1

[0260] The specific preparation process is as follows:

[0261] like Figure 1As shown, the transparent substrate layer 1 is transparent glass. Ag (100nm) is deposited as the anode layer 2. On the anode layer 2, HT-1 and P-1 with a thickness of 10nm are deposited using a vacuum evaporation apparatus as the hole injection layer 3, with a mass ratio of HT-1 to P-1 of 97:3. Next, HT-1 with a thickness of 130nm is deposited as the hole transport layer 4. Subsequently, EB-1 with a thickness of 5nm is deposited as the electron blocking layer 5. After the electron blocking materials are deposited, the light-emitting layer 6 of the organic electroluminescent device is fabricated, using BH-1 as the host material and BD-1 as the dopant material, with a doping ratio of 3% by weight, and a light-emitting layer thickness of 20nm. After the light-emitting layer 6, HB-1 is deposited with a thickness of 5nm as the hole blocking layer 7. On the hole blocking layer 7, ET-1 and Liq are deposited with a mass ratio of ET-1 to Liq of 1:1. The vacuum-deposited film of this material is 30 nm thick, and this layer is the electron transport layer 8. On the electron transport layer 8, a 1 nm thick LiF layer is fabricated using a vacuum evaporation apparatus; this layer is the electron injection layer 9. On the electron injection layer 9, a 16 nm thick Mg:Ag electrode layer is fabricated using a vacuum evaporation apparatus, with a Mg to Ag mass ratio of 1:9; this layer is used as the cathode layer 10. On the cathode layer 10, a 65 nm thick CP-1 layer is vacuum-deposited as the light extraction layer 11.

[0262] Device Examples 1-37 and Device Comparative Examples 2-6 were prepared in the same manner as Device Comparative Example 1, except that the hole blocking layer materials in Table 2 below were used.

[0263] Table 2

[0264]

[0265]

[0266]

[0267]

[0268] The devices fabricated in Part II were tested to measure their current efficiency, CIEy, and LT95 lifetime. Current efficiency and CIEy were measured using an IVL (current-voltage-luminance) testing system (Suzhou Fushida Scientific Instruments Co., Ltd.), with a current density of 10 mA / cm². 2 LT95 refers to the time it takes for the device's brightness to decay to 95% of its initial brightness, and the current density during the test is 30 mA / cm². 2 The lifetime testing system was the EAS-62C OLED device lifetime tester from System Technology Inc., Japan; the test results are shown in Table 3 below.

[0269] Table 3

[0270]

[0271]

[0272] As can be seen from the device test data in Table 3 above, compared with the comparative devices using HB-1, HB-2, HB-3, HB-4, HB-5 and HB-6 as hole blocking layer materials, the device prepared using the compound of the present invention as the hole blocking layer material has improved current efficiency and extended device life. For example, its life is basically more than 1.25 times that of the comparative devices 1-6.

[0273] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A compound containing a nitrogen-containing heterobenzene structure, characterized in that, The structure of the compound is shown in general formula (1-1): General formula (1-1) In general formula (1-1), Z1 is represented by N; Z2 and Z3 are each independently represented as CH or N; At least one of Z2 and Z3 is represented as N; Z1, Z2, and Z3 can be the same or different; Ar1 and Ar2 can be independently represented as substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, or substituted or unsubstituted triphenyl; Ar1 ​​and Ar2 can be the same or different; L1 and L2 can be independently represented as substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, or substituted or unsubstituted diphenylene; L1 and L2 can be the same or different; At least one of L1 and L2 is represented as a substituted phenylene; R1 is represented by the structure shown in general formula (1-2); General formula (1-2) In general formula (1-2), the asterisk * indicates the connection position between general formula (1-2) and L2; In general formula (1-2), X1 and X2 are each independently represented as oxygen atoms or sulfur atoms; X1 and X2 can be the same or different; The substituents that replace the above-mentioned substituted groups are deuterium, cyano, phenyl, naphthyl, and diphenyl.

2. The compound containing a nitrogen-containing heterobenzene structure according to claim 1, characterized in that, Ar1 and Ar2 are each independently represented as substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted diphenyl; Ar1 ​​and Ar2 may be the same or different; L1 and L2 are each independently represented as substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, or substituted or unsubstituted diphenylene; L1 and L2 may be the same or different; At least one of L1 and L2 is represented as a substituted phenylene; The substituents that replace the above-mentioned substituted groups are deuterium, cyano, phenyl, naphthyl, and diphenyl.

3. The compound containing a nitrogen-containing heterobenzene structure according to claim 1, characterized in that, The structure of the compound is shown in any one of general formulas (2-1) to (2-3): General formula (2-1) General formula (2-2) General formula (2-3) In general formulas (2-1) to (2-3), Z1, Z2, Z3, Ar1, Ar2, L1, L2, X1, and X2 have the same meanings as defined in claim 1.

4. The compound containing a nitrogen-containing heterobenzene structure according to claim 1, characterized in that, The structure of the compound is shown in any one of general formulas (3-3) to (3-5): General formula (3-3) General formula (3-4) General formula (3-5) In general formulas (3-3) to (3-5), Ar1, Ar2, L1, L2, X1, and X2 have the same meanings as defined in claim 1.

5. A compound containing a nitrogen-containing benzene structure, characterized in that, The structure of the compound is shown in any one of general formulas (4-1) to (4-11) and (4-17) to (4-18): General formula (4-1) General formula (4-2) General formula (4-3) General formula (4-4) General formula (4-5) General formula (4-6) General formula (4-7) General formula (4-8) General formula (4-9) General formula (4-10) General formula (4-11) General formula (4-17) General formula (4-18) In general formulas (4-1) to (4-11) and (4-17) to (4-18), Z1 represents N; Z2 and Z3 are each independently represented as CH or N; At least one of Z2 and Z3 is represented as N; Z1, Z2, and Z3 can be the same or different; Ar1 and Ar2 can be independently represented as substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, or substituted or unsubstituted triphenyl; Ar1 ​​and Ar2 can be the same or different; R1 is represented by the structure shown in general formula (1-2); General formula (1-2) In general formula (1-2), X1 and X2 are each independently represented as oxygen atoms or sulfur atoms; X1 and X2 can be the same or different; The substituents that replace the above-mentioned substituted groups are deuterium, cyano, phenyl, naphthyl, and diphenyl.

6. The compound containing a nitrogen-containing heterobenzene structure according to claim 1, characterized in that, Ar1 and Ar2 are each represented independently as follows: , , , , , , , , , , any one of them; L1 and L2 are each independently represented by the following structures: , , , , , , , , , , , , , , , , , , , , , , , , or any one of them; At least one of L1 and L2 is represented as: , , , , , , , or ; The general formula (1-2) is represented by the following structure: , , any one of them; X1 and X2 can be represented independently as oxygen atoms or sulfur atoms; X1 and X2 can be the same or different.

7. A compound containing a nitrogen-containing heterobenzene structure, characterized in that, The structure of the compound is shown in any one of general formulas (4-12), (4-13), and (4-15): General formula (4-12) General formula (4-13) General formula (4-15) In general formulas (4-12), (4-13), and (4-15), Z1 represents N; Z2 and Z3 are each independently represented as CH or N; At least one of Z2 and Z3 is represented as N; Z1, Z2, and Z3 can be the same or different; Ar1 and Ar2 can be independently represented as substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, or substituted or unsubstituted triphenyl; Ar1 ​​and Ar2 can be the same or different; R1 can be represented as the structure shown below: , any one of them; X1 and X2 can be independently represented as oxygen atoms or sulfur atoms; X1 and X2 can be the same or different. The substituents that replace the above-mentioned substituted groups are deuterium, cyano, phenyl, naphthyl, and diphenyl.

8. A compound containing a nitrogen-containing heterobenzene structure, characterized in that, The structure of the compound is shown in general formula (4-16): General formula (4-16) In general formula (4-16), Z1 is represented by N; Z2 and Z3 are each independently represented as CH or N; At least one of Z2 and Z3 is represented as N; Z1, Z2, and Z3 can be the same or different; Ar1 and Ar2 can be independently represented as substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, or substituted or unsubstituted triphenyl; Ar1 ​​and Ar2 can be the same or different; R1 can be represented as the structure shown below: , any one of them; X1 and X2 can be independently represented as oxygen atoms or sulfur atoms; X1 and X2 can be the same or different. The substituents that replace the above-mentioned substituted groups are deuterium, cyano, phenyl, naphthyl, and diphenyl.

9. A compound containing a nitrogen-containing heterobenzene structure, characterized in that, The specific structure of the compound is any one of the following structures: (1) (4) (7) (10) (11) (12) (13) (15) (19) (20) (21) (22) (23) (25) (26) (32) (33) (34) (35) (37) (38) (39) (41) (42) (43) (44) (45) (46) (47) (48) (49) (50) (51) (52) (53) (54) (55) (56) (57) (58) (59) (60) (61) (62) (63) (64) (65) (66) (73) (74) (75) (76) (77) (80) (81) (82) (85) (86) (87) (88) (89) (90) (91) (92) (94) (95) (96) (97) (98) (99) (100) (101) (102) (103) (104) (105) (106) (108) (109) (110) (111) (112) (113) (114) (122) (123) (124) (125) (127) (128) (129) (130) (131) (132) (133) (134) (135) (136) (137) (138) (139) (140) (141) (142) (143) (144) (145) (146) (147) (149) (150) (151) (152) (153) (154) (155) (156) (157) (158) (159) (160) (161) (162) (163) (164) (165) (166) (167) (168) (169) (171) (172) (173) (174) (176) (177) (178) (179) (181) (182) (183) (184) (186) (187) (188) (189) (191) (192) (193) (194) (196) (197) (198) (199) (200) (201) (202) (204) (205) (206) (207) (208) (209) (210) (212) (213) (214) (215) (216) (220) (221) (222) (223) (225) (226) (227) (228) (230) (231) (232) (233) (235) (236) (237) (238) (240) (241) (242) (243) (245) (246) (247) (248) (250) (251) (252) (253) (255) (256) (257) (258) (260) (261) (262) (263) (265) (266) (267) (268) (270) (271) (272) (273) (275) (276) (277) (278) (280) (281) (282) (283) (285) (286) (287) (288) (290) (291) (292) (293) (295) (296) (297) (298) (300) (301) (302) (303) (305) (306) (307) (308) (310) (311) (312) (313) (315) (316) (317) (318) (320) (321) (322) (325) (326) (327) (328) (330) (331) (332) (333) (335) (336) (337) (338) (339) (340) (341) (342) (343) (344) (346) (347) (348) (349) (351) (352) (353) (354) (356) (357) (358) (359) (360) (361) (362) (363) (364) (365) (366) (367) (368) (369) (370) (371) (372) (373) (374) (375) (376) (377) (379) (380) (381) (384) (385) (386) (387) (388) (390) (392) (393) (394) (395) (396) (397) (398) (399) (400) (401) (403) (404) (405) (406) (407) (408) (411) (412) (413) (414) (416) (417) (418) (419) (420) (421) (422) (423) (424) (425) (426) (427) (428) (429) (430) (431) (432) (433) (434) (435) (436) (437) (438) (439) (440) (441) (442) (443) (444) (445) (446) (447) (448) (449) (450) (451) (452) (453) (454) (455) (456) (457) (458) (459) (460)。 10. An organic electroluminescent device, comprising a substrate, a first electrode, and a second electrode, wherein a multilayer organic thin film layer is disposed between the first electrode and the second electrode, characterized in that, The organic thin film layer contains a compound with a nitrogen-containing heterobenzene structure as described in any one of claims 1 to 9.

11. The organic electroluminescent device according to claim 10, characterized in that, The organic thin film layer includes a hole transport region thin film layer, a light emission region thin film layer, and an electron transport region thin film layer, wherein the electron transport region thin film layer contains a compound with a nitrogen-containing heterobenzene structure as described in any one of claims 1 to 9.

12. The organic electroluminescent device according to claim 11, characterized in that, The electron transport region thin film layer includes a hole blocking layer, which contains a compound with a nitrogen-containing heterobenzene structure as described in any one of claims 1 to 9.

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