Compound containing azabenzene structure and organic electroluminescent device thereof

Abstract

The invention discloses a compound containing an azabenzene structure and an organic electroluminescent device thereof, and belongs to the technical field of semiconductor materials. The structure of the compound containing the azabenzene structure is shown as a general formula (1-1), the compound has good stability and good hole blocking capacity, and when the compound is used as a material of an organic electroluminescent device, the efficiency of the device is remarkably improved, and the service life of the device is remarkably prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of semiconductor materials, and particularly to a compound containing a nitrogen heterobenzene structure and an organic electroluminescent device thereof. Background Art

[0002] The technology of organic electroluminescent devices (OLED: Organic Light Emission Diodes) can be used to manufacture new display products and can also be used to make new lighting products, and is expected to replace existing liquid crystal displays and fluorescent lamp lighting, with a very broad application prospect. An organic electroluminescent device has a sandwich-like structure, including electrode material layers and an organic optoelectronic functional material layer sandwiched between different electrode material layers. The organic optoelectronic functional material layer includes at least one light-emitting layer, and various different organic optoelectronic functional materials are stacked together according to their uses to jointly form an organic electroluminescent device. As a current device, when a voltage is applied to the two electrodes of the organic electroluminescent device and positive and negative charges are acted on by an electric field in the organic optoelectronic functional material layer, the positive and negative charges are further recombined in the light-emitting layer, that is, organic electroluminescence is generated.

[0003] Currently, the display technology of organic electroluminescent devices has been applied in the fields of smart phones, tablet computers, televisions, etc. However, compared with the actual product application requirements, the performance such as the luminous efficiency and service life of organic electroluminescent devices still needs to be further improved. In order to continuously improve the performance of organic electroluminescent devices, it is necessary to continuously research and innovate organic optoelectronic functional materials to create higher-performance organic optoelectronic functional materials.

[0004] The organic optoelectronic functional materials applied to organic electroluminescent devices can be classified into two categories according to their uses, namely charge injection and transport materials and light-emitting materials. Further, the charge injection and transport materials can be further divided into electron injection and transport materials, electron blocking materials, hole injection and transport materials, and hole blocking materials. For an organic electroluminescent device, holes are injected from the anode, electrons are injected from the cathode, and they are transported in the organic functional layer, and finally meet in the light-emitting layer to form excitons, and the excitons recombine to emit light. The hole blocking layer is located between the light-emitting layer and the electron transport layer, and can block the diffusion or movement of holes to the electron transport layer, and can also reduce the energy loss of excitons, playing an interface modification and electron injection / transport auxiliary regulation role. Since the current existing hole blocking layer materials have poor electron regulation ability and hole and exciton blocking ability, it is difficult to obtain an efficient electron-hole balance inside the light-emitting layer, and it is difficult to obtain high-efficiency and long-life devices. Therefore, it is necessary to further improve the electron injection ability and transport ability of the hole blocking layer materials, as well as the hole and exciton blocking ability, and improve the stability of the materials to achieve an efficient balance of excitons and improve the efficiency and service life of the devices. Summary of the Invention

[0005] In view of the above problems existing in the prior art, the present invention provides a compound containing a nitrogen heterobenzene structure and an organic electroluminescent device thereof. The compound of the present invention contains a nitrogen heterobenzene and a 9,9'-spirobisheteroanthracenefluorene structure, and the nitrogen heterobenzene and the 9,9'-spirobisheteroanthracenefluorene structure are connected by a bridging group, so that the compound has excellent hole blocking ability and good material stability. When used as a hole blocking material in an organic electroluminescent device, it can effectively improve the luminous efficiency and working life of the device.

[0006] The specific technical solution provided by the present invention is as follows: A compound containing a nitrogen heterobenzene structure, and the structure of the compound is shown in the general formula (1-1):

[0007]

[0008] In the general formula (1-1), Z 1 , Z 2 , Z 3 each independently represents CH or N; at least one of Z 1 , Z 2 , Z 3 represents N; Z 1 , Z 2 , Z 3 may be the same or different;

[0009] Ar 1 , Ar 2 each independently represents a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group; Ar 1 , Ar 2 may be the same or different;

[0010] L 1 , L 2 each independently represents a single bond, a substituted or unsubstituted C 3 -C 20 subcycloalkyl group, a substituted or unsubstituted C 6 -C 30 subarylene group, a substituted or unsubstituted 5-30 membered heteroarylene group; L 1 , L 2 may be the same or different; L 1 , L 2 are not both single bonds at the same time;

[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 of general formula (1-2) and L 2 ;

[0014] In general formula (1-2), X 1 , X 2 each independently represents an oxygen atom or a sulfur atom; X 1 , X 2 may be the same or different;

[0015] The substituents substituting the substitutable groups are deuterium atoms, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, cyano, C 6 -C 30 aryl, 5-30-membered heteroaryl.

[0016] Furthermore, the Ar 1 , Ar 2 each independently represents substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 3 -C 20 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted N-phenylcarbazolyl; Ar 1 , Ar 2 may be the same or different;

[0017] The L 1 , L 2 each independently represents a single bond, substituted or unsubstituted C 3 -C 20 subcycloalkyl, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted pyridinylene; L 1 , L 2 may be the same or different; L 1 , L2 Not a single bond at the same time;

[0018] The substituents replacing the above-mentioned substituable groups are deuterium atoms, C 1 -C 20 alkyl groups, C 3 -C 20 cycloalkyl groups, cyano groups, phenyl groups, naphthyl groups, biphenyl groups, terphenyl groups, pyridyl groups, pyrimidinyl groups, phenanthryl groups, dibenzofuranyl groups, dibenzothiophenyl groups, carbazolyl groups.

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

[0020]

[0021] In general formulas (2-1) to (2-4), the meanings of Z 1 、Z 2 、Z 3 、Ar 1 、Ar 2 、L 1 、L 2 、X 1 、X 2 are the same as the definitions above.

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

[0023]

[0024] In general formulas (3-1) to (3-5), the meanings of Ar 1 、Ar 2 、L 1 、L 2 、X 1 、X 2 are the same as the definitions above.

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

[0026]

[0027]

[0028]

[0029] In general formulas (4-1) to (4-37), the meanings of Z 1 、Z 2 、Z 3 、Ar 1 、Ar2 and R 1 have the same meanings as defined above. Further, the structure of the compound is represented by any one of General Formulas (5-1) to (5-37):

[0030]

[0031]

[0032]

[0033]

[0034] In General Formulas (5-1) to (5-37), Z 1 , Z 2 , Z 3 , Ar 1 , Ar 2 , X 1 , X 2 have the same meanings as defined above. Further, each of the Ar 1 , Ar 2 independently represents:

[0035]

[0036]

[0037] The L 1 , L 2 each independently represents a single bond or the following structure:

[0038]

[0039] any one of;

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

[0041] any one of; X 1 , X 2 each independently represents an oxygen atom or a sulfur atom; X 1 , X 2 can be the same or different.

[0042] Further, the X 1 , X 2 represents an oxygen atom.

[0043] Further, the X 1 , X 2 represents a sulfur atom.

[0044] Further, the Ar 1 and Ar 2 are represented as phenyl groups.

[0045] Further, any hydrogen atom in the compound with a nitrogen heterocyclic benzene structure can be replaced by a deuterium atom.

[0046] Further, 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, which sequentially includes a substrate, a first electrode and a second electrode. There are multiple organic thin film layers between the first electrode and the second electrode, and the organic thin film layer contains the compound with a nitrogen heterobenzene structure according to the present invention.

[0082] Further, 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, and the electron transport region thin film layer contains the compound with a nitrogen heterobenzene structure according to the present invention.

[0083] Further, the electron transport region thin film layer includes a hole blocking layer, and the hole blocking layer contains the compound with a nitrogen heterobenzene structure according to the present invention.

[0084] Further, the electron transport region thin film layer includes a hole blocking layer, an electron transport layer and an electron injection layer, and the hole blocking layer contains the compound with a nitrogen heterobenzene structure according to the present invention.

[0085] Further, 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, and the hole blocking layer contains the compound with a nitrogen heterobenzene structure according to the present invention.

[0086] The beneficial technical effect of the present invention is as follows:

[0087] The compounds of the present invention contain a pyridine and a 9,9'-spirobifluorene structure, and the pyridine and 9,9'-spirobifluorene structure are connected by a bridging group. Therefore, the compounds protected by the present invention have more excellent hole blocking and exciton blocking capabilities, can efficiently block the diffusion or movement of holes to the electron transport layer, better confine the holes in the light-emitting region, ensure the excitons formed by more hole-electron pairs in the light-emitting layer, increase the exciton concentration, and further improve the light-emitting efficiency and device lifetime.

[0088] The structural characteristics of the compounds of the present invention endow the compounds with more excellent electron regulation capabilities, supplement the electron transport layer, have appropriate electron injection and transport properties, can better adapt to the electron-hole balance in the light-emitting layer, and improve the light-emitting efficiency and device lifetime of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0089] Figure 1 It is a schematic structural diagram of the materials listed in the present invention applied to an OLED device. 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 It is a 1H NMR spectrum of Compound 83 in Synthesis Example 7 of the present invention.

[0091] Figure 3 It is a 1H NMR spectrum of Compound 81 in Synthesis Example 6 of the present invention.

[0092] Figure 4 It is a 1H NMR spectrum of Compound 107 in Synthesis Example 9 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0093] The technical solutions of the present invention will be described in detail below in combination with the implementation examples.

[0094] In the present invention, unless otherwise specified, HOMO means the highest occupied molecular orbital, and LUMO means the lowest unoccupied molecular orbital. In addition, in the present invention, the HOMO and LUMO energy levels are expressed in absolute values, and the comparison between energy levels is also a comparison of the absolute values. Those skilled in the art know that the larger the absolute value of the energy level, the lower the energy of the energy level.

[0095] In the accompanying drawings, for the sake of clarity, the dimensions of layers and regions may be exaggerated. It will also be understood that when a layer or element is referred to as being "on" another layer or substrate, the layer or element may be directly on the other layer or substrate, or there may also be an intermediate layer. In addition, 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 also be one or more intermediate layers.

[0096] In the present invention, when describing electrodes, organic electroluminescent devices, and other structures, terms indicating orientation such as "upper" and "lower" are only used to represent the orientation in a specific state, and do not mean that the relevant structures can only exist in the described orientation; on the contrary, if the structure can be transformed in position, such as being inverted, the orientation of the structure will be changed accordingly. Specifically, in the present invention, the "lower" side of the electrode refers to the side of the electrode close to the substrate during the preparation process, and the opposite side away from the substrate is the "upper" side.

[0097] The substituted or unsubstituted C 6 -C 30 aryl group in the present invention refers to an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms, preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted condensed tetraphenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted group, a substituted or unsubstituted di-p-terphenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, and combinations thereof or fused rings of the foregoing group combinations, but not limited thereto.

[0098] The C 6 -C 30 aryl group in the present invention refers to an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms, preferably a phenyl group, a naphthyl group, an anthryl group, a fluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirofluorenyl group, a phenanthryl group, a condensed tetraphenyl group, a pyrenyl group, a biphenyl group, a p-terphenyl group, a m-terphenyl group, group, a di-p-terphenyl group, a perylenyl group, an indenyl group, and combinations thereof or fused rings of the foregoing group combinations, but not limited thereto.

[0099] The substituted or unsubstituted C 6 -C 30The arylene group refers to an arylene group having 6 to 30 carbon atoms, preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and is preferably a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted dimethylfluorenylene group, a substituted or unsubstituted diphenylfluorenylene group, a substituted or unsubstituted spirofluorenylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted condensed tetraphenyl group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted group, a substituted or unsubstituted meta-linked terphenyl group, a substituted or unsubstituted perylene group, a substituted or unsubstituted indenyl group, and their combinations or fused rings of the foregoing group combinations, but not limited thereto.

[0100] The substituted or unsubstituted 5-30 membered heteroaryl group described in the present invention refers to a heteroaryl group having 5 to 30 ring-forming atoms, preferably a heteroaryl group having 5 to 20 ring-forming atoms, more preferably a heteroaryl group having 5 to 10 ring-forming atoms, and is preferably a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuryl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted dibenzofuryl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted N-phenylcarbazolyl group, and their combinations or fused rings of the foregoing group combinations, but not limited thereto.

[0101] The 5- to 30-membered heteroaryl group described in the present invention refers to a heteroaryl group having 5 to 30 ring atoms, preferably a heteroaryl group having 5 to 20 ring atoms, more preferably a heteroaryl group having 5 to 10 ring atoms, preferably furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuryl, benzothienyl, benzimidazolyl, indolyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, benzoxazinyl, benzothiazinyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, fluorenyl, dibenzofuryl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, and combinations thereof or fused rings of combinations of the foregoing groups, but not limited thereto.

[0102] The substituted or unsubstituted 5- to 30-membered heteroarylene group described in the present invention refers to a heteroarylene group having 5 to 30 ring atoms, preferably a heteroarylene group having 5 to 20 ring atoms, more preferably a heteroarylene group having 5 to 10 ring atoms, preferably substituted or unsubstituted heteroarylene, substituted or unsubstituted thienylene, substituted or unsubstituted pyrrolylene, substituted or unsubstituted pyrazolylene, substituted or unsubstituted imidazolylene, substituted or unsubstituted triazolylene, substituted or unsubstituted oxazolylene, substituted or unsubstituted thiazolylene, substituted or unsubstituted oxadiazolylene, substituted or unsubstituted thiadiazolylene, substituted or unsubstituted pyridinylene, substituted or unsubstituted pyrimidinylene, substituted or unsubstituted pyrazinylene, substituted or unsubstituted triazinylene, substituted or unsubstituted benzofurylene, substituted or unsubstituted benzothienylene, substituted or unsubstituted benzimidazolylene, substituted or unsubstituted indolylene, substituted or unsubstituted quinolinylene, substituted or unsubstituted isoquinolinylene, substituted or unsubstituted quinazolinylene, substituted or unsubstituted quinoxalinylene, substituted or unsubstituted naphthyridinylene, substituted or unsubstituted benzoxazinylene, substituted or unsubstituted benzothiazinylene, substituted or unsubstituted acridinylene, substituted or unsubstituted phenazinylene, substituted or unsubstituted phenothiazinylene, substituted or unsubstituted phenoxazinylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted dibenzofurylene, substituted or unsubstituted dibenzothienylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted N-phenylcarbazolylene, and combinations thereof or fused rings of combinations of the foregoing groups, but not limited thereto.

[0103] The C 1 -C 20 alkyl group (including linear alkyl and branched alkyl) refers 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 not limited thereto.

[0104] The C described in the present invention 3 -C 20 The cycloalkyl group refers to a saturated hydrocarbon group including 3 to 10 carbon atoms as ring-forming atoms. In this article, C 4 -C 9 cycloalkyl group is preferably used, more preferably C 5 -C 8 cycloalkyl group, particularly preferably C 5 -C 7 cycloalkyl group. Non-limiting examples thereof may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl, and cycloheptyl.

[0105] The C 3 -C 20 The cycloalkylene group refers to a saturated hydrocarbon group including 3 to 10 carbon atoms as ring-forming atoms. In this article, C 4 -C 9 cycloalkylene group is preferably used, more preferably C 5 -C 8 cycloalkylene group, particularly preferably C 5 -C 7 cycloalkylene group. Non-limiting examples thereof may include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, 4-methylcyclohexylene, 4,4-dimethylcyclohexylene, adamantylene, and cycloheptylene.

[0106] Organic electroluminescent device

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

[0108] The organic electroluminescent device of the present invention sequentially includes a substrate, a first electrode, an organic thin film layer, and a second electrode. Among them, 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. In addition, a light extraction layer may be provided on the second electrode.

[0109] The layers that the organic electroluminescent device of the present invention may include and the positional relationship of each layer are as follows: 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 exist, 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 of the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices can be used. Examples are transparent substrates such as glass or transparent plastic substrates; opaque substrates such as silicon substrates; flexible PI film substrates. Different substrates have different mechanical strengths, thermal stabilities, transparencies, surface smoothnesses, and water resistances. Depending on the nature of the substrate, its usage direction is different. In the present invention, a transparent glass substrate is preferably used, and the thickness of the substrate is not particularly limited.

[0111] The first electrode is formed on the substrate, and the first electrode and the second electrode can be opposite to each other. The first electrode can be an anode or a cathode. In the present invention, the first electrode is used as an 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 the anode material include, but are not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 )), 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 can have a single-layer structure or a multi-layer structure including two or more layers. In addition, the thickness of the anode depends on the material used and is usually 50 - 500 nm, preferably 70 - 300 nm, and more preferably 100 - 200 nm.

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

[0113] The hole injection layer may include a host material and a P-type doping 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 doping material is a compound having charge conductivity selected from those disclosed in the prior art, and may be selected from the compounds disclosed in the following patent documents: WO2011073149A, EP1968131A1, EP2276085A1, EP2213662A1, EP1722602A1, EP2045848A1, DE102007031220A1, US20100181555A1, US20100102709A1, WO2009003455A1, WO2010094378A1, WO2011120709A1, US20100096600A1, DE102012209523A1, CN101728485A, and WO2012095143A1, but not limited thereto.

[0114] For example, the compounds shown below:

[0115]

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

[0117] The thickness of the hole injection layer of the present invention may 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 having a high hole mobility, which can transfer holes from the anode or the hole injection layer to the light-emitting layer.

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

[0120]

[0121]

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

[0123] The electron blocking layer requires the triplet (T1) energy level of the material to be higher than that of the host material in the light-emitting layer, which can play a role in blocking the energy loss of the light-emitting layer material; the HOMO energy level of the electron blocking layer material is between the HOMO energy levels of the hole transport layer material and the host material of the light-emitting layer, which is conducive to the injection of holes from the positive electrode into the light-emitting layer. At the same time, it is required that the electron blocking layer material has a high hole mobility, which is conducive to hole transport and reduces the device application power; the LUMO energy level of the electron blocking layer material is higher than the LUMO energy level of the host material of the light-emitting layer, playing a role in electron blocking, that is, it is required that the electron blocking layer material has a wide bandgap (Eg). The electron blocking layer materials meeting the above conditions can be triarylamine derivatives, fluorene derivatives, spirofluorene derivatives, dibenzofuran derivatives, carbazole derivatives, etc.

[0124] In one embodiment of the present invention, as the electron blocking layer material of the present invention, it can be arbitrarily selected from the compounds disclosed in the following prior arts:

[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 can emit 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 can include a host material and a doping material. The host material can be divided into a red light host material, a green light host material, a blue light host material, etc. The doping material can be divided into a red light doping material, a green light doping material, a blue light doping material, etc. Taking the blue light device as an example in the present invention, as the host material and the guest material of the light-emitting layer of the organic electroluminescent device of the present invention, among them, the host material can be one or a combination of two of anthracene derivatives, quinoxaline derivatives, triazine derivatives, xanthenone derivatives, benzophenone derivatives, carbazole derivatives, pyridine derivatives or pyrimidine derivatives. The guest material can be pyrene derivatives, boron derivatives, chrysene derivatives, spirofluorene derivatives, iridium complexes or platinum complexes.

[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] The 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 that of the light emitting layer host material, which can block the energy loss of the light emitting layer material; the HOMO energy level of the material is lower than that of the light emitting layer host material, which plays a role in blocking holes. At the same time, it is required that the hole blocking layer material has a suitable electron mobility to facilitate electron transport and reduce the device application power; the hole blocking layer material meeting the above conditions is the compound containing a nitrogen heterocyclic structure described above in the present 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] The electron transport layer can be disposed above the hole blocking layer. The electron transport layer material is a material that can easily receive electrons from the cathode and transfer the received electrons to the light emitting layer. Preferably, a material with a high electron mobility is used. As the electron transport layer of the organic electroluminescent device of the present invention, the following compounds disclosed in the prior art can be used as the electron transport layer materials for organic electroluminescent devices:

[0132]

[0133] In a preferred embodiment of the present invention, the electron transport layer further includes other compounds commonly used in the electron transport layer, for example, 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, the electron injection layer can be disposed between the electron transport layer and the cathode. The electron injection layer material is usually preferably a material with a low work function, so that electrons can be easily injected into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material of 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, Cs 2 CO 3 、CsF, Csq, NaF, MgF 2 、CaF 2 、Al 2 O 3 、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 a cathode or an anode. In the present invention, the second electrode is used as the cathode. The material for forming the cathode can be a material with a low work function, such as a metal, an alloy, a conductive compound, or a mixture thereof. Non-limiting examples of the cathode material can include lithium (Li), ytterbium (Yb), magnesium (Mg), aluminum (Al), calcium (Ca), and aluminum-lithium (Al-Li), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The thickness of the cathode depends on the material used and is generally 5-100 nm, preferably 7-50 nm, and more preferably 10-25 nm.

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

[0139]

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

[0141] The organic electroluminescent device may further include a packaging structure. The packaging structure can be a protective structure for preventing external substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The packaging structure can be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.

[0142] Method for manufacturing an organic electroluminescent device

[0143] The present invention also relates to a method for manufacturing the above-mentioned organic electroluminescent device, which includes successively laminating a first electrode, an organic thin film layer, and a second electrode on a substrate. Among them, the organic thin film layer is formed by successively 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 successively 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 successively laminating a hole blocking layer, an electron transport layer, and an electron injection layer on the light-emitting layer from bottom to top. Additionally, optionally, a light extraction layer can 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 thereto. Among them, vacuum evaporation means heating the material and depositing it on the substrate in a vacuum environment.

[0145] In the present invention, the vacuum evaporation method is preferably used to form each layer, and it can be carried out at a temperature of about 100 - 500 °C, at a rate of about 10 -8 -10 -2 Torr of vacuum degree and at a rate of about . The vacuum degree is preferably 10 -6 -10 -2 Torr, more preferably 10 -5 -10 -3 Torr. The rate is about , more preferably about

[0146] In addition, it should be noted that the materials used in the present invention for forming each layer can be formed into a film alone and used as a single layer, or can be formed into a film after being mixed with other materials and used as a single layer, and can also be a stacked structure between layers formed into a film alone, a stacked structure between layers formed into a film after being mixed, or a stacked structure between a layer formed into a film alone and a layer formed into a film after being mixed.

[0147] Display device

[0148] The present invention also relates to a display device including the above-mentioned organic electroluminescent device, especially a flat panel display device. In a preferred embodiment, the display device may include one or more of the above-mentioned organic electroluminescent devices, and in the case of including multiple devices, the devices are stacked horizontally 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, 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 the first electrode of the organic electroluminescent device. The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor, or an oxide semiconductor, but is not limited thereto.

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

[0150] Examples

[0151] I. Compound preparation examples

[0152] The present invention will be specifically described below with reference to the accompanying drawings and examples.

[0153] The raw materials involved in the synthesis examples of the present invention can be purchased from the market or prepared 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, successively add raw material A-1 (2.14 g, 5 mmol), raw material A-11 (0.86 g, 5.5 mmol), K 2 CO 3 (2.07 g, 15 mmol), tetrahydrofuran (100 mL), water (50 mL). Pass nitrogen for 30 min to displace air, add Pd(PPh 3 ) 4 (0.12 g, 0.1 mmol), and heat under reflux for 8 h under nitrogen protection. Take the reaction solution for TLC detection and find that raw material A-1 has completely reacted. After the reaction is completed, naturally cool the reaction system to room temperature, rotary evaporate to remove the solvent. The residue is dissolved in 100 ml of dichloromethane, washed with 150 ml of water, poured into a separatory funnel, shaken, and left to stand for liquid separation. After liquid separation, the aqueous phase is extracted with dichloromethane (25 ml × 4). The combined organic phases are dried over anhydrous magnesium sulfate, filtered, and the filtrate is rotary evaporated to remove dichloromethane to obtain the crude product. The crude product is purified by silica gel chromatography column 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, in a round-bottom flask, successively add Intermediate P-1 (2.29 g, 5 mmol), raw material A-12 (1.94 g, 5.5 mmol), K 2 CO 3 (2.07 g, 15 mmol), tetrahydrofuran (100 mL), water (50 mL). Pass nitrogen for 30 min to displace air, add Pd(PPh 3 ) 4 (0.12 g, 0.1 mmol), and heat under reflux for 10 h under nitrogen protection. Take the reaction solution for TLC detection and find that Intermediate P-1 has completely reacted. After the reaction is completed, naturally cool the reaction system to room temperature, rotary evaporate to remove the solvent. The residue is dissolved in 100 ml of dichloromethane, washed with 150 ml of water, poured into a separatory funnel, shaken, and left to stand for liquid separation. After liquid separation, the aqueous phase is extracted with dichloromethane (30 ml × 4). The combined organic phases are dried over anhydrous magnesium sulfate, filtered, and the filtrate is rotary evaporated to remove dichloromethane to obtain the crude product. The crude product is purified by silica gel chromatography column to obtain Compound 39.

[0158] Example 2: Synthesis of Compound 40:

[0159]

[0160] Preparation of Intermediate P-2: Referring to the preparation of Intermediate P-1, the difference lies in replacing raw material A-11 with raw material A-4 and replacing raw material A-1 with raw material A-6. LC-MS: Test value: 464.22 ([M+H] + ), theoretical value: 463.07.

[0161] Preparation of Intermediate Q-2: Under nitrogen protection, in a round-bottom flask, successively add Intermediate P-2 (2.32 g, 5 mmol), raw material A-19 (1.40 g, 5.5 mmol), KOAC (1.47 g, 15 mmol), dioxane (100 mL), pass nitrogen for 30 min to displace air, add Pd(PPh 3 ). 4 (0.12 g, 0.1 mmol), and heat under reflux for 24 h under nitrogen protection. Take the reaction solution for TLC detection and find that Intermediate P-2 has completely reacted. After the reaction is completed, naturally cool the reaction system to room temperature, pour it into a separatory funnel, shake it, and let it stand for layering. After liquid separation, the aqueous phase is extracted with dichloromethane (30 ml * 4). The organic phases are combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated by rotary evaporation to remove dichloromethane to obtain Intermediate Q-2. LC-MS: Test value: 512.09 ([M+H] + ), theoretical value: 511.24.

[0162] Preparation of Compound 40: In a round-bottom flask, successively add Intermediate Q-2 (2.81 g, 5.5 mmol), raw material A-1 (2.14 g, 5 mmol), K 2 CO 3 (2.07 g, 15 mmol), tetrahydrofuran (100 mL), water (50 mL), pass nitrogen for 30 min to displace air, add palladium acetate (0.011 g, 0.05 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.072 g, 0.15 mmol), and heat under reflux for 18 h under nitrogen protection. Take the reaction solution for TLC detection and find that raw material A-1 has completely reacted. After the reaction is completed, naturally cool the reaction system to room temperature, concentrate the solvent by rotary evaporation, dissolve the residue in 120 ml of dichloromethane, wash it with 50 ml of water, pour it into a separatory funnel, shake it, and let it stand for layering. After liquid separation, the aqueous phase is extracted with dichloromethane (50 ml * 3). The organic phases are combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated by rotary evaporation to remove dichloromethane to obtain the crude product. The crude product is 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, with the difference that raw material A-4 is used to replace raw material A-11, and raw material A-7 is used to replace 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, with the difference that Intermediate P-3 is used to replace Intermediate P-2. LC-MS: Test value: 512.27 ([M+H] + ), theoretical value: 511.24.

[0167] Preparation of Compound 41: Refer to the preparation of Compound 40, with the difference that Intermediate Q-3 is used to replace Intermediate Q-2.

[0168] Example 4: Synthesis of Compound 77:

[0169]

[0170] Preparation of Intermediate P-4: Refer to the preparation of Intermediate P-1, with the difference that raw material A-20 is used to replace raw material A-11. LC-MS: Test value: 459.26 ([M+H] + ), theoretical value: 458.11.

[0171] Preparation of Compound 77: Refer to the preparation of Compound 39, with the difference that raw material A-21 is used to replace raw material A-12, and Intermediate P-4 is used to replace Intermediate P-1.

[0172] Example 5: Synthesis of Compound 79:

[0173]

[0174] Preparation of Intermediate P-5: Refer to the preparation of Intermediate Q-2, with the difference that raw material A-1 is used to replace 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, with the difference that Intermediate P-5 is used to replace Intermediate Q-2, and raw material A-7 is used to replace raw material A-1. LC-MS: Test value: 579.26 ([M+H] + ), theoretical value: 578.09.

[0176] Preparation of Compound 79: Refer to the preparation of Intermediate P-1, with the difference that raw material A-4 is used to replace raw material A-11, and Intermediate Q-5 is used to replace raw material A-1.

[0177] Example 6: Synthesis of Compound 81:

[0178]

[0179] Preparation of Intermediate P-6: Refer to the preparation of Intermediate P-1, with the difference that raw material A-4 is used to replace raw material A-11, and raw material A-9 is used to replace raw material A-1. LC-MS: Measured value: 464.20 ([M+H] + ), Theoretical value: 463.07.

[0180] Preparation of Intermediate Q-6: Refer to the preparation of Intermediate Q-2, with the difference that Intermediate P-6 is used to replace Intermediate P-2. LC-MS: Measured value: 512.17 ([M+H] + ), Theoretical value: 511.24.

[0181] Preparation of Compound 81: Refer to the preparation of Compound 40, with the difference that Intermediate Q-6 is used to replace Intermediate Q-2.

[0182] Example 7: Synthesis of Compound 83:

[0183]

[0184] Preparation of Compound 83: Refer to the preparation of Intermediate P-1, with the difference that raw material A-22 is used to replace raw material A-11, and Intermediate P-4 is used to replace 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, with the difference that raw material A-20 is used to replace raw material A-11, and raw material A-2 is used to replace raw material A-1. LC-MS: Measured value: 459.04 ([M+H] + ), Theoretical value: 458.11.

[0188] Preparation of Compound 95: Refer to the preparation of Compound 39, with the difference that raw material A-22 is used to replace raw material A-12, and Intermediate P-8 is used to replace Intermediate P-1.

[0189] Example 9: Synthesis of Compound 107:

[0190]

[0191] Preparation of Intermediate P-9: Refer to the preparation of Intermediate P-1, except that raw material A-20 is used to replace raw material A-11, and raw material A-3 is used to replace 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-22 is used to replace raw material A-12, and Intermediate P-9 is used to replace Intermediate P-1.

[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-14 is used to replace raw material A-11, and Intermediate P-1 is used to replace raw material A-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 to replace 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-14 is used to replace raw material A-12, and Intermediate P-11 is used to replace 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 to replace raw 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, with the difference that raw material A-12 is used to replace raw material A-11, and raw material A-7 is used to replace raw material A-1. LC-MS: Test value: 540.25 ([M+H] + ) and theoretical value: 539.10.

[0209] Preparation of Compound 181: Refer to the preparation of Compound 40, with the difference that Intermediate P-5 is used to replace Intermediate Q-2, and Intermediate P-14 is used to replace raw material A-1.

[0210] Example 15: Synthesis of Compound 200:

[0211]

[0212] Preparation of Intermediate P-15: Refer to the preparation of Compound 40, with the difference that Intermediate P-5 is used to replace Intermediate Q-2, and raw material A-13 is used to replace raw material A-1. LC-MS: Test value: 579.28 ([M+H] + ) and theoretical value: 578.09.

[0213] Preparation of Compound 200: Refer to the preparation of Compound 39, with the difference that Intermediate P-15 is used to replace Intermediate P-1.

[0214] Example 16: Synthesis of Compound 202:

[0215]

[0216] Preparation of Intermediate P-20: Refer to the preparation of Intermediate P-1, with the difference that raw material A-12 is used to replace raw material A-11, and raw material A-13 is used to replace raw material A-1. LC-MS: Test value: 540.04 ([M+H] + ) and theoretical value: 539.10.

[0217] Preparation of Compound 202: Refer to the preparation of Compound 40, with the difference that Intermediate P-5 is used to replace Intermediate Q-2, and Intermediate P-20 is used to replace raw material A-1.

[0218] Example 17: Synthesis of Compound 225:

[0219]

[0220] Preparation of Intermediate P-16: Refer to the preparation of Compound 40, with the difference that Intermediate P-5 is used to replace Intermediate Q-2, and starting material A-9 is used to replace starting material A-1. LC-MS: Measured value: 579.14 ([M+H] + ), theoretical value: 578.09.

[0221] Preparation of Compound 225: Refer to the preparation of Compound 39, with the difference that Intermediate P-16 is used to replace Intermediate P-1, and starting material A-14 is used to replace starting material A-12.

[0222] Example 18: Synthesis of Compound 240:

[0223]

[0224] Preparation of Intermediate P-17: Refer to the preparation of Intermediate Q-2, with the difference that starting material A-24 is used to replace Intermediate P-2. LC-MS: Measured value: 512.12 ([M+H] + ),theoretical value: 511.24.

[0225] Preparation of Compound 240: Refer to the preparation of Compound 40, with the difference that Intermediate P-11 is used to replace starting 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, with the difference that starting material A-12 is used to replace starting material A-11, and starting material A-15 is used to replace starting material A-1. LC-MS: Measured value: 514.13 ([M+H] + ),theoretical value: 513.08.

[0229] Preparation of Compound 290: Refer to the preparation of Compound 40, with the difference 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, with the difference that starting material A-4 is used to replace starting material A-11, and starting material A-17 is used to replace starting material A-1. LC-MS: Measured 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 P-5 is used to replace Intermediate Q-2, and Intermediate P-19 is used to replace Raw Material A-1. LC-MS: Test value: 690.38 ([M+H] + ) and theoretical value: 689.19.

[0234] Preparation of Compound 339: Refer to the preparation of Compound 39, except that Intermediate Q-19 is used to replace Intermediate P-1, and Raw Material A-16 is used to replace Raw Material A-12.

[0235] Example 21: Synthesis of Compound 351:

[0236]

[0237] Preparation of Compound 351: Refer to the preparation of Compound 39, except that Intermediate Q-19 is used to replace Intermediate P-1, and Raw Material A-18 is used to replace Raw Material A-12.

[0238] Example 22: Synthesis of Compound 385:

[0239]

[0240] Preparation of Intermediate P-22: Dissolve Raw Material A-25 (0.94 g, 3.0 mmol) in dry THF (10 mL) and cool 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 to the solution within 5 minutes. The resulting mixture was stirred at the same temperature for 2 hours, and then a solution of Raw Material A-26 (0.7 g, 2.4 mmol) in dry THF (50 mL) was added dropwise within 10 minutes, and the mixture was warmed to 20 °C and kept overnight. Add brine (150 mL), and extract the mixture 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: Test value: 476.86 ([M+H] + ) and theoretical value: 475.99.

[0241] Preparation of Intermediate Q-22: Dissolve Intermediate P-22 (1.43 g, 3.0 mmol) in acetic acid (50 mL), heat the solution to reflux, then add 37% aqueous HCl solution (5 mL), and stir the mixture under reflux for 2 h. Add water (50 mL), and extract the mixture with dichloromethane (3 × 50 mL). The combined organic extracts were washed with saturated NaHCO 3Washed with solution (2×20 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by flash 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 starting material A-14 was used instead of starting material A-11, and intermediate Q-22 was used instead of starting material A-1.

[0243] Example 23: Synthesis of compound 402:

[0244]

[0245] Preparation of intermediate P-23: Refer to the preparation of intermediate P-22, except that starting material A-27 was used instead of starting material A-26. LC-MS: Measured 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-23 was used instead of intermediate P-22. LC-MS: Measured 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 starting material A-20 was used instead of starting material A-11, and intermediate Q-23 was used instead of starting material A-1. LC-MS: Measured value: 475.29 ([M+H] + ), theoretical value: 474.08.

[0248] Preparation of compound 402: Refer to the preparation of intermediate P-1, except that starting material A-22 was used instead of starting material A-11, and intermediate R-23 was used instead of starting material A-1.

[0249] The structural characterizations of the compounds obtained in each example are shown in Table 1:

[0250] Table 1

[0251]

[0252]

[0253]

[0254] II. Device Preparation Examples

[0255] The application effects of the compounds synthesized according to the present invention as hole blocking layer materials in devices are described in detail below through Device Examples 1-37 and Device Comparative Examples 1-6. Compared with Device Comparative Examples 1-6, the manufacturing processes of the devices in Device Examples 1-37 are exactly the same, and the same substrate materials and electrode materials are used. The film thicknesses of the electrode materials are also consistent. The only difference is that the hole blocking layer materials in the devices are changed. The device layer structures are shown in Table 2, and the performance test results of each device are shown in Table 3.

[0256] The molecular structural formulas of the related materials are as follows:

[0257]

[0258] The structures of the comparative compounds HB-1, HB-2, HB-3, HB-4, HB-5, and HB-6 are shown above. All of the above materials are commercially available or obtained by conventional preparation means in the art.

[0259] Device comparison example 1

[0260] The specific preparation process is as follows:

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

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

[0263] Table 2

[0264]

[0265]

[0266]

[0267]

[0268] The devices prepared in II were tested for their current efficiency, CIEy, and LT95 lifetime. The current efficiency and CIEy were tested using an IVL (current-voltage-luminance) test system (Suzhou FushiDa Scientific Instruments Co., Ltd.), and the current density during the test was 10 mA / cm 2 . LT95 refers to the time when the device luminance decays to 95% of the initial luminance, and the current density during the test was 30 mA / cm 2 ; the lifetime test system was the EAS-62C type OLED device lifetime tester from System Technology Research Co., Ltd. of Japan; the test results are shown in Table 3 below.

[0269] Table 3

[0270]

[0271]

[0272] It can be seen from the device test data results in Table 3 above that, 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 devices prepared using the compound of the present invention as the hole blocking layer material have improved current efficiency and extended device lifetime. For example, its lifetime is basically more than 1.25 times that of the comparative devices 1-6.

[0273] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A compound containing a nitrogen heterobenzene structure, characterized in that: The structure of the compound is shown in general formula (1-1): In the general formula (1-1), Z1, Z2, and Z3 are each independently represented by CH or N; at least one of Z1, Z2, and Z3 is represented by N; Z1, Z2, and Z3 may be the same or different; Ar1 and Ar2 are each independently 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 membered heteroaryl; Ar1 ​​and Ar2 may be the same or different; L1 and L2 are each independently a single bond, a substituted or unsubstituted C3-C 20 cycloalkylene, substituted or unsubstituted C6-C 30 arylene, substituted or unsubstituted 5-30 membered heteroarylene; L1 and L2 may be the same or different; L1 and L2 are not single bonds at the same time; R1 represents the structure shown in general formula (1-2); The asterisk * in the general formula (1-2) indicates the connection position between the general formula (1-2) and L2; In the general formula (1-2), X1 and X2 are each independently an oxygen atom or a sulfur atom; X1 and X2 may be the same or different; The substituents for the above substitutable groups are deuterium atoms, C1-C 20 Alkyl, C3-C 20 Cycloalkyl, cyano, C6-C 30 The invention also includes aryl and 5-30 membered heteroaryl.

2. The compound containing nitrogen heterobenzene structure according to claim 1, characterized in that The Ar1 and Ar2 are each independently represented by a substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted N-phenylcarbazolyl; Ar1 ​​and Ar2 may be the same or different; The L1 and L2 are each independently a single bond, a substituted or unsubstituted C3-C 20 substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothienylene, substituted or unsubstituted pyridylene; L1 and L2 may be the same or different; L1 and L2 are not single bonds at the same time; The substituents for the above substitutable groups are deuterium atoms, C1-C 20 Alkyl, C3-C 20 Cycloalkyl, cyano, phenyl, naphthyl, biphenyl, terphenyl, pyridyl, pyrimidinyl, phenanthryl, dibenzofuranyl, dibenzothienyl, carbazolyl.

3. The compound containing nitrogen heterobenzene structure according to claim 1, characterized in that The structure of the compound is shown in any one of the general formulas (2-1) to (2-4): In general formula (2-1) to general formula (2-4), the meanings of Z1, Z2, Z3, Ar1, Ar2, L1, L2, X1, and X2 are the same as those defined in claim 1.

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

5. The compound containing nitrogen heterobenzene structure according to claim 1, characterized in that The structure of the compound is shown in any one of the general formulas (4-1) to (4-37): In general formula (4-1) to general formula (4-37), the meanings of Z1, Z2, Z3, Ar1, Ar2, and R1 are the same as those defined in claim 1.

6. The compound containing nitrogen heterobenzene structure according to any one of claims 1 to 5, characterized in that: The Ar1 and Ar2 are independently represented by: Any of; The L1 and L2 are independently represented by a single bond or the following structure: Any of; The general formula (1-2) is represented by the following structure: Any of; X1 and X2 each independently represent an oxygen atom or a sulfur atom; X1 and X2 may be the same or different.

7. The compound containing nitrogen heterobenzene structure according to any one of claims 1 to 6, characterized in that: Any hydrogen atom in the compound containing a nitrogen heterobenzene structure may be substituted by a deuterium atom.

8. The compound containing nitrogen heterobenzene structure according to claim 1, characterized in that The specific structure of the compound is any one of the following structures:

9. An organic electroluminescent device, comprising a substrate, a first electrode and a second electrode in sequence, wherein a plurality of organic thin film layers are provided between the first electrode and the second electrode, wherein: The organic thin film layer contains the compound containing a nitrogen-containing heterobenzene structure according to any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, characterized in that: The organic thin film layer comprises a hole transport region thin film layer, a light emitting region thin film layer and an electron transport region thin film layer, and the electron transport region thin film layer contains the nitrogen-containing heterobenzene structure compound according to any one of claims 1 to 8.

11. The organic electroluminescent device according to claim 10, characterized in that: The electron transport region thin film layer comprises a hole blocking layer, and the hole blocking layer contains the nitrogen-containing heterobenzene structure compound according to any one of claims 1 to 8.

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