The invention relates to an azabenzene and spiro-(adamantane-2, 9apos; compound with-fluorene structure and organic electroluminescent device thereof

Abstract

The invention discloses a compound containing azabenzene and spiro-(adamantane-2, 9 '-fluorene) structures and an organic electroluminescent device thereof, and belongs to the technical field of semiconductor materials. The structure of the compound disclosed by the invention is shown as a general formula (1): # imgabs0 #, and the compound containing the azabenzene and spiro-(adamantane-22, 9 '-fluorene) structure is applied to an organic thin film layer of an organic electroluminescent device, and is particularly applied to a hole blocking layer in an electron transmission region thin film layer of the organic thin film layer. The compound has good stability and good hole blocking capability, 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 in particular to a compound containing a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) 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. It is expected to replace existing liquid crystal displays and fluorescent lamp lighting, and has a very broad application prospect. An organic electroluminescent device has a sandwich-like structure, including electrode material layers and an organic optoelectronic functional material sandwiched between different electrode material layers. Various different organic 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 smartphones, 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. The excitons recombine to emit light, and the hole blocking layer is located between the light-emitting layer and the electron transport layer, which 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. At the same time, the current existing hole blocking layer materials also have a narrow heat resistance window and poor electron tolerance. Therefore, it is necessary to further improve the electron injection ability and transport ability, hole and exciton blocking ability of the hole blocking layer materials, improve the stability of the materials, 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 and a spiro-(adamantane-2,9'-fluorene) structure, and an organic electroluminescent device thereof. In the compound of the present invention, the connection sites of the spiro-(adamantane-2,9'-fluorene) are fixed and bridged in an asymmetric manner, so that the compound has excellent hole blocking ability and good material stability. When applied to an organic electroluminescent device, it can effectively reduce the operating voltage of the device, improve the luminous efficiency and operating life of the device.

[0006] A compound containing a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) structure, and the structures of the nitrogen heterobenzene and the spiro-(adamantane-2,9'-fluorene) compound are shown in the general formula (1):

[0007]

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

[0009] Ar1 and Ar2 each independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group; Ar1 and Ar2 can be the same or different;

[0010] R1 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, an alkyl group with 1 to 20 carbon atoms or a cycloalkyl group with 3 to 20 carbon atoms;

[0011] L1 and L2 each independently represent a single bond, a C3-C20 sub-cycloalkyl group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group; L1 and L2 can be the same or different;

[0012] In the general formula (1), the asterisk * represents the connection positions of the phenyl group with R1, L1, and L2 respectively;

[0013] R2 represents a structure shown in the general formula (2) or the general formula (3);

[0014]

[0015] In the general formula (2), the asterisk * indicates the connection position of the general formula (2) and L2;

[0016] In the general formula (3), ring A represents any one of a substituted or unsubstituted naphthyl group or a substituted or unsubstituted phenanthryl group;

[0017] In the general formula (3), the asterisk * indicates the connection position of the general formula (3) and L2;

[0018] Any unsubstituted carbon on any benzene ring, naphthalene ring or phenanthrene ring in the general formula (3) can be used as the connection site with L2;

[0019] R3, R4, R5, and R6 represent any one of a hydrogen atom, deuterium, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridyl group, a pyrimidinyl group, and a phenanthryl group;

[0020] The substituents substituting the above-mentioned substituable groups are selected from deuterium, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a cyano group, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridyl group, and a phenanthryl group.

[0021] Furthermore, the compound containing a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) structure is any one of the general formulas (4) and (5):

[0022]

[0023] In the general formulas (4) to (5), the meanings of Ar1, Ar2, R1, R2, L1, L2, Z1, Z2, and Z3 are the same as those defined in the general formula (1);

[0024] The asterisk * indicates the connection positions of the phenyl group with R1, L1, and L2 respectively.

[0025] Furthermore, the compound containing a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) structure is any one of the general formulas (6), (7), (8), (9), (10), (11), (12), (13), and (14):

[0026]

[0027] In the general formulas (6) to (14), the meanings of Ar1, Ar2, R1, R2, L1, L2, Z1, Z2, and Z3 are the same as those defined in the general formula (1).

[0028] Further, the compound containing azabenzene and spiro-(adamantane-2,9'-fluorene) structures is any one of general formula (15) to general formula (51):

[0029]

[0030]

[0031] In general formula (15) to general formula (51), the meanings of Ar1, Ar2, R1, R2, Z1, Z2, and Z3 are the same as the definitions in general formula (1).

[0032] Further, the compound containing azabenzene and spiro-(adamantane-2,9'-fluorene) structures is any one of general formula (52) to general formula (74):

[0033]

[0034]

[0035] In general formula (52) to general formula (74), the meanings of Ar1, Ar2, R1, R2, Z1, Z2, and Z3 are the same as the definitions in general formula (1).

[0036] Further, general formula (3) is represented as any one of general formula 3a, general formula 3b, general formula 3c, general formula 3d, and general formula 3e:

[0037]

[0038] Any unsubstituted carbon on any benzene ring or naphthalene ring in general formula 3a, general formula 3b, general formula 3c, general formula 3d, and general formula 3e can serve as the connection site with general formula (1);

[0039] In general formula 3a, the connection site with general formula (1) is any one of the sites 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; the connection site of R7 is any one of the sites 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;

[0040] In general formula 3b, the connection site with general formula (1) is any one of the sites 1', 2', 3', 4', 5', 6', 7', 8', 9', or 10'; the connection site of R7 is any one of the sites 1', 2', 3', 4', 5', 6', 7', 8', 9', or 10';

[0041] In general formula 3c, the connection site with general formula (1) is any one of the sites 1", 2", 3", 4", 5", 6", 7", 8", 9", or 10"; the connection site of R7 is any one of the sites 1", 2", 3", 4", 5", 6", 7", 8", 9", or 10";

[0042] In General Formula 3d, the connection site with General Formula (1) is any one of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; the connection site of R7 is any one of 15, 16, 17, 18, 19, 20, 21 or 22.

[0043] In General Formula 3e, the connection site with General Formula (1) is any one of 11’, 12’, 13’, 14’, 15’, 16’, 17’, 18’, 19’, 20’, 21’ or 22’; the connection site of R3 is any one of 11’, 12’, 13’ or 14’.

[0044] In General Formulas 3a to 3e, the meaning of R7 is the same as the definition in General Formula (1).

[0045] Furthermore, R2 is represented by the following structures:

[0046] Any one of them.

[0047] Furthermore, L1 and L2 each independently represent a single bond,

[0048]

[0049] Any one of them;

[0050] Ar1, Ar2, and R1 each independently represent

[0051] Any one of them; R1 can also be represented as

[0052] R3 is represented as a hydrogen atom, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-hexyl,

[0053] Any one of them.

[0054] Furthermore, in General Formula (1), Z1, Z2, and Z3 are all represented as N.

[0055] Furthermore, any hydrogen atom in a compound containing a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) structure can be replaced by a deuterium atom.

[0056] Further, the specific structure of the compound containing a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) structure is any one of the following structures:

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] The present invention also discloses an organic electroluminescent device, which 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 and a spiro-(adamantane-2,9'-fluorene) structure according to the present invention.

[0080] Preferably, 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 and a spiro-(adamantane-2,9'-fluorene) structure according to the present invention.

[0081] Preferably, the electron transport region thin film layer includes a hole blocking layer, and the hole blocking layer contains the compound with a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) structure according to the present invention.

[0082] Furthermore, 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 and a spiro-(adamantane-2,9'-fluorene) structure according to the present invention.

[0083] The beneficial technical effects of the present invention are as follows:

[0084] In the compound with a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) structure according to the present invention, the nitrogen heterobenzene structure and the spiro-(adamantane-2,9'-fluorene) are connected by an asymmetric special bridging method, and the connection site of the spiro-(adamantane-2,9'-fluorene) is fixed. Therefore, the compound protected by the present invention has more excellent hole blocking and exciton blocking capabilities, can efficiently block the diffusion or movement of holes to the electron transport layer, enables the holes to be better restricted in the light-emitting region, ensures more excitons formed by holes and electrons in the light-emitting layer, increases the exciton concentration, and further improves the light-emitting efficiency and the device lifetime.

[0085] In the compound with a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) structure protected by the present invention, the nitrogen heterobenzene structure and the spiro-(adamantane-2,9'-fluorene) are connected by an asymmetric special bridging method, and the connection site of the spiro-(adamantane-2,9'-fluorene) is fixed. Therefore, the compound protected by the present invention has more excellent electron regulation capabilities, supplements the electron transport layer, has appropriate electron injection and transport properties, can better adapt to the electron-hole balance situation inside the light-emitting layer, and improves the device light-emitting efficiency and the device lifetime.

[0086] The compounds protected by the present invention have a low evaporation temperature and chemical stability, enabling the formation of an evaporated film with good film phase stability and a wide heat resistance window, thereby ensuring the stability in device fabrication and product use. BRIEF DESCRIPTION OF THE DRAWINGS

[0087] Figure 1 It is a schematic structural diagram of the materials listed in the present invention applied to an OLED device.

[0088] 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; 11 is a light extraction layer.

[0089] Figure 2 It is a 1H NMR spectrum of Compound 100 of the present invention in deuterated chloroform. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0090] The technical solutions of the present invention will be described in detail below in combination with the embodiments.

[0091] In the present invention, unless otherwise specified, HOMO means the highest occupied molecular orbital, and LUMO means the lowest unoccupied molecular orbital.

[0092] In the drawings, for clarity, the sizes 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 also 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.

[0093] In the present invention, when describing electrodes, organic electroluminescent devices, and other structures, the terms indicating directions such as "upper" and "lower" are only for the directions in a specific state, and do not mean that the related structures can only exist in the described directions; on the contrary, if the structure can be transformed in position, for example, inverted, the direction 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.

[0094] The C1-C20 alkyl groups (including straight-chain alkyl groups and branched-chain alkyl groups) described in the present invention are preferably C1-C10 alkyl groups, more preferably C1-C4 alkyl groups, and preferably 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 thereto.

[0095] The C3-C20 cycloalkyl group described in the present invention preferably uses a C5-C10 cycloalkyl group, and its non-limiting examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl, and cycloheptyl.

[0096] Organic electroluminescent device

[0097] The organic electroluminescent device of the present invention can 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.

[0098] 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 can be provided on the second electrode.

[0099] The layers that the organic electroluminescent device of the present invention can include and the positional relationship of each layer are as follows: it can 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.

[0100] 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.

[0101] A first electrode is formed on a substrate, and the first electrode and the second electrode can face each other. The first electrode can be an anode or a cathode. In the present invention, the first electrode serves 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 (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 can have a single-layer structure or a multi-layer structure including two or more layers. Additionally, the thickness of the anode depends on the material used and is typically 50 - 500 nm, preferably 70 - 300 nm, and more preferably 100 - 200 nm.

[0102] A hole injection layer, a hole transport layer, and an electron blocking layer can be disposed between the first electrode and the light-emitting layer.

[0103] The hole injection layer can contain a host material and a P-type doping material. The host material can 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 with charge conductivity selected from those disclosed in the prior art and can 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 is not limited thereto.

[0104] For example, the following compounds are shown:

[0105]

[0106] According to the present invention, P-1 is preferably used as the P-type doping material.

[0107] 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.

[0108] The material of the hole transport layer is preferably a material with a high hole mobility, which can transfer holes from the anode or the hole injection layer to the light-emitting layer.

[0109] Preferably, as the hole transport layer material of the present invention, it can be arbitrarily selected from the compounds disclosed in the following prior arts:

[0110]

[0111] 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.

[0112] The electron blocking layer requires that the triplet (T1) energy level of the material is higher than the T1 energy level of the host material in the light emitting layer, and 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 light emitting layer host material, 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 light emitting layer host material, playing a role in blocking electrons, that is, it is required that the electron blocking layer material has a wide bandgap (Eg). Electron blocking layer materials meeting the above conditions can be triarylamine derivatives, fluorene derivatives, spirofluorene derivatives, dibenzofuran derivatives, carbazole derivatives, etc.

[0113] 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:

[0114]

[0115] 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.

[0116] 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. In this invention, taking the blue light device as an example, 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.

[0117] 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.

[0118] 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 play a role in blocking 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, playing 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 azabenzene and spiro-(adamantane-2,9'-fluorene) structures described above in the present invention.

[0119] 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.

[0120] 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. A material with a high electron mobility is preferred. As the electron transport layer material 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 material for organic electroluminescent devices:

[0121]

[0122] 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.

[0123] 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.

[0124] 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 a material preferably having 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, Cs2CO3, CsF, Csq, NaF, MgF2, CaF2, Al2O3, Yb.

[0125] 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.

[0126] 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.

[0127] Optionally, in order to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., 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.

[0128]

[0129] The thickness of the light extraction layer is generally 5-300 nm, preferably 20-100 nm, and more preferably 40-80 nm.

[0130] 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.

[0131] Method for manufacturing an organic electroluminescent device

[0132] 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 from bottom to top on the first electrode. 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 from bottom to top on the first electrode. 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 from bottom to top on the light-emitting layer. 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.

[0133] 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.

[0134] In the present invention, the vacuum evaporation method is preferably used to form each of the layers, where the vacuum evaporation can be carried out at a temperature of about 100 - 500 °C and at a rate of about 10 -8 -10 -2 Torr and at a rate of about . The degree of vacuum is preferably 10 -6 -10 -2 Torr, more preferably 10 -5 -10 -3 Torr. The rate is about and more preferably about

[0135] In addition, it should be noted that the materials for forming each layer in the present invention 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, or 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.

[0136] Display device

[0137] The present invention also relates to a display device including the above-mentioned organic electroluminescent device, particularly 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 a plurality of devices, the devices are stacked horizontally or vertically. The display device may further 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.

[0138] The following examples are intended to better explain the present invention, but the scope of the present invention is not limited thereto.

[0139] Examples

[0140] I. Compound Preparation Examples

[0141] The present invention will be specifically described below with reference to the accompanying drawings and examples.

[0142] The raw materials involved in the synthesis examples of the present invention can all be purchased from the market or prepared by conventional preparation methods in the art;

[0143] Preparation of Intermediate C1 and Intermediate E1:

[0144]

[0145] Under nitrogen protection, in a round-bottom flask, successively add raw material A1 (7.93 g, 25 mmol), raw material B1 (8.41 g, 30 mmol), K2CO3 (10.37 g, 75 mmol), dioxane (210 mL), water (35 mL). Pass nitrogen for 30 min to displace air, then add bis(triphenylphosphine)palladium(II) dichloride PdCl2(PPh3)2 (0.53 g, 0.75 mmol). Heat under reflux for 17 h under nitrogen protection. Take a TLC test of the reaction solution and find that raw material A1 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 150 ml of dichloromethane, washed with 100 ml of water, poured into a separatory funnel, shaken, and allowed to stand for liquid separation. After liquid separation, the aqueous phase is extracted with dichloromethane (60 ml * 3). The combined organic phases are dried over anhydrous magnesium sulfate, filtered, and the filtrate is rotary evaporated to remove dichloromethane to obtain a crude product. The crude product is purified by silica gel column chromatography to obtain intermediate C1. LC-MS: Measured value: 342.87 ([M + H] + ); Exact mass: 341.98.

[0146] Under nitrogen protection, in a round-bottom flask, successively add intermediate C1 (6.19 g, 18 mmol), raw material D1 (9.07 g, 22 mmol), K2CO3 (7.46 g, 54 mmol), tetrahydrofuran (150 mL), water (50 mL). Pass nitrogen for 40 min to displace air, then add Pd(PPh3)4 (0.42 g, 0.36 mmol). Heat under reflux for 20 h under nitrogen protection. Take a TLC test of the reaction solution and find that intermediate C1 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 100 ml of water, poured into a separatory funnel, shaken, and allowed to stand for liquid separation. After liquid separation, the aqueous phase is extracted with dichloromethane (50 ml * 3). The combined organic phases are dried over anhydrous magnesium sulfate, filtered, and the filtrate is rotary evaporated to remove dichloromethane to obtain a crude product. The crude product is purified by silica gel column chromatography to obtain intermediate E1. LC-MS: Measured value: 549.19 ([M + H] + ); Exact mass: 548.23.

[0147] Intermediates C2 to C6 are prepared by the synthesis method of intermediate C1, with the difference that different raw materials A and raw materials B are used. The raw materials A and raw materials B used are shown in Table 1; Intermediates E2 to E5, E9 are prepared by the synthesis method of intermediate E1, with the difference that intermediate C2 to C6 are used to replace intermediate C1 respectively and react with raw material D1. The intermediate C2 to C6 and the synthesized intermediates E2 to E5, E9 are shown in Table 1.

[0148] Intermediates E11 to E16 were prepared by the synthesis method of intermediate E1, with the difference that raw materials C11 to C16 were used to replace intermediate C1 respectively and reacted with raw material D1. The raw materials C11 to C16 used and the synthesized intermediates E11 to E16 are shown in Table 2;

[0149] Table 1

[0150]

[0151]

[0152] Table 2

[0153]

[0154] Example 1: Synthesis of Compound 1

[0155]

[0156] Under nitrogen protection, in a 250 ml round-bottom flask, intermediate E11 (7.10 g, 15 mmol), raw material F1 (6.47 g, 18 mmol), K2CO3 (6.22 g, 45 mmol), tetrahydrofuran (100 mL), and water (50 mL) were added successively. Nitrogen was passed for 30 min to displace air, and palladium acetate (0.10 g, 0.45 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.64 g, 1.35 mmol) were added. The mixture was heated under reflux for 17 h under nitrogen protection. The reaction solution was detected by TLC and found that intermediate E11 had completely reacted. After the reaction was completed, 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 100 ml of water, poured into a separatory funnel, shaken, and allowed to stand for layer separation. After liquid separation, the aqueous phase was extracted with dichloromethane (75 ml * 3). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by rotary evaporation to remove dichloromethane to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain Compound 1. Elemental analysis: C 49 H 39 N3; Theoretical values: C, 87.86; H, 5.87; N, 6.27; Test values: C, 87.83; H, 5.89; N, 6.28. LC-MS: Measured value: 670.38 ([M + H] + ) and exact mass: 669.31.

[0157] Example 2: Synthesis of Compound 23

[0158]

[0159] Compound 23 was prepared according to the synthesis method of compound 1 in Example 1, with the difference that intermediate E12 was selected to replace intermediate E11. Elemental analysis: C 49 H 39 N3; Theoretical values: C, 87.86; H, 5.87; N, 6.27; Measured values: C, 87.85; H, 5.85; N, 6.31. LC-MS: Measured value: 670.27 ([M+H] + ) and exact mass: 669.31.

[0160] Example 3: Synthesis of compound 27

[0161]

[0162] Compound 27 was prepared according to the synthesis method of compound 1 in Example 1, with the difference that intermediate E1 was selected to replace intermediate E11. Elemental analysis: C 55 H 43 N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Measured values: C, 88.51; H, 5.82; N, 5.67. LC-MS: Measured value: 746.14 ([M+H] + ) and exact mass: 745.35.

[0163] Example 4: Synthesis of compound 32

[0164]

[0165] Compound 32 was prepared according to the synthesis method of compound 1 in Example 1, with the difference that intermediate E2 was selected to replace intermediate E11. Elemental analysis: C 53 H 41 N3; Theoretical values: C, 88.42; H, 5.74; N, 5.84; Measured values: C, 88.46; H, 5.79; N, 5.79. LC-MS: Measured value: 720.07 ([M+H] + ) and exact mass: 719.33.

[0166] Example 5: Synthesis of compound 45

[0167]

[0168] Compound 45 was prepared according to the synthesis method of compound 1 in Example 1, with the difference that intermediate E13 was selected to replace intermediate E11. Elemental analysis: C 49 H 39N3; Theoretical values: C, 87.86; H, 5.87; N, 6.27; Test values: C, 87.89; H, 5.85; N, 6.35. LC-MS: Measured value: 670.03 ([M+H] + ), exact mass: 669.31.

[0169] Example 6: Synthesis of Compound 52

[0170]

[0171] Under nitrogen protection, in a round-bottom flask, successively add raw material G1 (4.77 g, 15 mmol), bis(pinacolato)diboron (4.57 g, 18 mmol), potassium acetate (4.91 g, 50 mmol), dioxane (120 ml). Pass nitrogen for 30 min to displace air, add Pd(PPh3)4 (0.520 g, 0.45 mmol), and heat under reflux for 14 h under nitrogen protection. Take a TLC test of the reaction solution and find that the raw material G1 has completely reacted. After the reaction is completed, naturally cool the reaction system to room temperature, rotary evaporate to remove the solvent, dissolve the residue in 100 ml of dichloromethane, wash with 100 ml of water, pour it into a separatory funnel, shake and then let it stand for layer separation. After liquid separation, extract the aqueous phase with dichloromethane (50 ml * 3). Combine the organic phases, add anhydrous magnesium sulfate for drying, filter, and rotary evaporate the filtrate to remove dichloromethane to obtain intermediate F2. LC-MS: Measured value: 410.13 ([M+H] + ); exact mass: 409.20.

[0172] Compound 52 was prepared according to the synthesis method of Compound 1 in Example 1, with the difference that intermediate E13 was selected to replace intermediate E11, and intermediate F2 was selected to replace raw material F1. Elemental analysis: C 53 H 41 N3; Theoretical values: C, 88.42; H, 5.74; N, 5.84; Test values: C, 88.50; H, 5.70; N, 5.81. LC-MS: Measured value: 720.22 ([M+H] + ), exact mass: 719.33.

[0173] Example 7: Synthesis of Compound 56

[0174]

[0175] Compound 56 was prepared according to the synthesis method of Compound 1 in Example 1, with the difference that intermediate E14 was selected to replace intermediate E11. Elemental analysis: C 49 H 39N3; Theoretical values: C, 87.86; H, 5.87; N, 6.27; Test values: C, 87.84; H, 5.90; N, 6.39. LC-MS: Measured value: 670.16 ([M+H] + ), exact mass: 669.31.

[0176] Example 8: Synthesis of Compound 100

[0177]

[0178]

[0179] Intermediate D2 was prepared according to the synthesis method of Intermediate F2, except that starting material H1 was used instead of starting material G1, and starting material J1 was used instead of bis(pinacolato)diboron. LC-MS of Intermediate D2: Measured value: 489.18 ([M+H] + ), exact mass: 488.29. Intermediate E6 was prepared according to the synthesis method of Intermediate E11, except that Intermediate D2 was used instead of starting material D1. LC-MS of Intermediate E6: Measured value: 549.36 ([M+H] + ), exact mass: 548.23.

[0180] Compound 100 was prepared according to the synthesis method of Compound 1 in Example 1, except that Intermediate E6 was used instead of Intermediate E11. Elemental analysis: C 55 H 43 N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Test values: C, 88.55; H, 5.85; N, 5.62. LC-MS: Measured value: 746.23 ([M+H] + ), exact mass: 745.35.

[0181] Example 9: Synthesis of Compound 102

[0182]

[0183] Intermediate E7 was prepared according to the synthesis method of Intermediate E6, except that starting material C11 was used instead of starting material C10. LC-MS of Intermediate E7: Measured value: 549.42 ([M+H] + ), exact mass: 548.23.

[0184] Compound 102 was prepared according to the synthesis method of Compound 1 in Example 1, except that Intermediate E7 was used instead of Intermediate E11. Elemental analysis: C 55 H 43N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Test values: C, 88.50; H, 5.80; N, 5.75. LC-MS: Measured value: 746.44 ([M+H] + ) and exact mass: 745.35.

[0185] Example 10: Synthesis of Compound 124

[0186]

[0187] Compound 124 was prepared according to the synthesis method of Compound 1 in Example 1, with the difference that intermediate E15 was selected to replace intermediate E11 and raw material F3 was selected to replace raw material F1. Elemental analysis: C 55 H 43 N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Test values: C, 88.58; H, 5.83; N, 5.72. LC-MS: Measured value: 746.01 ([M+H] + ) and exact mass: 745.35.

[0188] Example 11: Synthesis of Compound 131

[0189]

[0190] Compound 131 was prepared according to the synthesis method of Compound 1 in Example 1, with the difference that intermediate E5 was selected to replace intermediate E11 and raw material F5 was selected to replace raw material F1. Elemental analysis: C 55 H 43 N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Test values: C, 88.48; H, 5.84; N, 5.77. LC-MS: Measured value: 746.35 ([M+H] + ) and exact mass: 745.35.

[0191] Example 12: Synthesis of Compound 136

[0192]

[0193] Compound 136 was prepared according to the synthesis method of Compound 1 in Example 1, with the difference that intermediate E12 was selected to replace intermediate E11 and raw material F3 was selected to replace raw material F1. Elemental analysis: C 55 H 43 N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Test values: C, 88.62; H, 5.80; N, 5.65. LC-MS: Measured value: 746.29 ([M+H] +), Exact mass: 745.35.

[0194] Example 13: Synthesis of Compound 138

[0195]

[0196] Compound 138 was prepared according to the synthesis method of Compound 1 in Example 1, except that intermediate E14 was used instead of intermediate E11, and raw material F4 was used instead of raw material F1. Elemental analysis: C 55 H 43 N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Measured values: C, 88.70; H, 5.74; N, 5.58. LC-MS: Measured value: 746.08 ([M+H] + ), Exact mass: 745.35.

[0197] Example 14: Synthesis of Compound 148

[0198]

[0199] Compound 148 was prepared according to the synthesis method of Compound 1 in Example 1, except that intermediate E3 was used instead of intermediate E11, and raw material F3 was used instead of raw material F1. Elemental analysis: C 55 H 43 N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Measured values: C, 88.60; H, 5.76; N, 5.64. LC-MS: Measured value: 746.39 ([M+H] + ), Exact mass: 745.35.

[0200] Example 15: Synthesis of Compound 152

[0201]

[0202] Compound 152 was prepared according to the synthesis method of Compound 1 in Example 1, except that intermediate E13 was used instead of intermediate E11, and raw material F5 was used instead of raw material F1. Elemental analysis: C 55 H 43 N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Measured values: C, 88.65; H, 5.85; N, 5.52. LC-MS: Measured value: 746.16 ([M+H] + ), Exact mass: 745.35.

[0203] Example 16: Synthesis of Compound 154

[0204]

[0205] Compound 154 was prepared according to the synthesis method of Compound 1 in Example 1, except that intermediate E13 was selected to replace intermediate E11, and raw material F3 was selected to replace raw material F1. Elemental analysis: C 55 H 43 N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Measured values: C, 88.73; H, 5.66; N, 5.65. LC-MS: Measured value: 746.42 ([M+H] + ), Exact mass: 745.35.

[0206] Example 17: Synthesis of Compound 198

[0207]

[0208] Compound 198 was prepared according to the synthesis method of Compound 1 in Example 1, except that intermediate E4 was selected to replace intermediate E11. Elemental analysis: C 53 H 49 N3; Theoretical values: C, 87.44; H, 6.78; N, 5.77; Measured values: C, 87.41; H, 6.82; N, 5.80. LC-MS: Measured value: 728.13 ([M+H] + ), Exact mass: 727.39.

[0209] Example 18: Synthesis of Compound 452

[0210]

[0211] Compound 452 was prepared according to the synthesis method of Compound 1 in Example 1, except that intermediate E6 was selected to replace intermediate E11, and raw material F6 was selected to replace raw material F1. Elemental analysis: C 56 H 44 N2; Theoretical values: C, 90.29; H, 5.95; N, 3.76; Measured values: C, 90.25; H, 5.91; N, 3.74. LC-MS: Measured value: 745.24 ([M+H] + ), Exact mass: 744.35.

[0212] Example 19: Synthesis of Compound 563

[0213]

[0214] Compound 563 was prepared according to the synthesis method of Compound 1 in Example 1, except that intermediate E6 was selected to replace intermediate E11, and raw material F5 was selected to replace raw material F1. Elemental analysis: C 61 H 47N3; Theoretical values: C, 89.13; H, 5.76; N, 5.11; Test values: C, 89.16; H, 5.79; N, 5.06. LC-MS: Measured value: 822.45 ([M+H] + ), exact mass: 821.38.

[0215] Example 20: Synthesis of Compound 571

[0216]

[0217] Intermediate F7 was prepared according to the synthesis method of Intermediate F2, with the difference that raw material G2 was selected to replace raw material G1. LC-MS of Intermediate F7: Measured value: 512.09 ([M+H] + ); exact mass: 511.24.

[0218] Compound 571 was prepared according to the synthesis method of Compound 1 in Example 1, with the difference that Intermediate E16 was selected to replace Intermediate E11 and Intermediate F7 was selected to replace raw material F1. Elemental analysis of Compound 571: C 59 H 45 N3; Theoretical values: C, 89.02; H, 5.70; N, 5.28; Test values: C, 89.05; H, 5.74; N, 5.22. LC-MS: Measured value: 796.13 ([M+H] + ), exact mass: 795.36.

[0219] Example 21: Synthesis of Compound 145

[0220]

[0221] Compound 145 was prepared according to the synthesis method of Compound 1 in Example 1, with the difference that Intermediate E9 was selected to replace Intermediate E11 and raw material F3 was selected to replace raw material F1. Elemental analysis: C 55 H 43 N3; Theoretical values: C, 88.56; H, 5.81; N, 5.63; Test values: C, 88.75; H, 5.67; N, 5.69. LC-MS: Measured value: 746.11 ([M+H] + ), exact mass: 745.35.

[0222] Example 22: Synthesis of Compound 288

[0223]

[0224] Under nitrogen protection, in a dried round-bottom flask, magnesium strip (1.17 g, 48 mmol) and tetrahydrofuran (25 mL) were successively added. Nitrogen was passed for 30 min to displace air. Iodine (0.51 g, 2 mmol) was added. After stirring for 10 min, a mixed solution of intermediate C2 (12.7 g, 40 mmol) dissolved in tetrahydrofuran (60 mL) was slowly added. The mixture was heated to 66 °C and reacted for 4 h, and then cooled to room temperature to obtain a Grignard reagent solution. Under nitrogen protection, in a dried round-bottom flask, raw material K1 (5.41 g, 36 mmol) and tetrahydrofuran (50 mL) were successively added. The mixture was stirred and nitrogen was passed for 30 min to displace air. The prepared Grignard reagent solution was slowly added dropwise at room temperature, and the mixture was heated to reflux and reacted for 6 h. The mixture was cooled to room temperature, dilute hydrochloric acid aqueous solution (3 mol / L, 200 mL) was added, and the mixture was stirred for 20 min. The solvent was removed by rotary evaporation. The residue was dissolved in 100 mL of diethyl ether, washed with 100 mL of water, poured into a separatory funnel, shaken, and allowed to stand for layer separation. After liquid separation, the aqueous phase was extracted with diethyl ether (50 mL × 3). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by rotary evaporation to remove diethyl ether, and purified by recrystallization from hexane twice to obtain intermediate M1. LC-MS: Measured value: 389.42 ([M+H] + ), exact mass: 388.16.

[0225] Under nitrogen protection, in a round-bottom flask, intermediate M1 (7.78 g, 20 mmol) and acetic acid (90 mL) were successively added. Nitrogen was passed for 30 min to displace air. 3 mL of hydrochloric acid (35%) was added, and the mixture was heated to 110 °C and reacted for 4 h. The reactant was cooled to room temperature, 100 mL of ice water was added, and filtration was carried out. The filter cake was dissolved in 100 mL of dichloromethane in a 500 mL flask, washed with 100 mL of water, poured into a separatory funnel, shaken, and allowed to stand for layer separation. After liquid separation, the aqueous phase was extracted with dichloromethane (50 mL × 3). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by rotary evaporation to remove dichloromethane to obtain a crude product, and the crude product was purified by silica gel column chromatography to obtain intermediate E8. LC-MS: Measured value: 371.24 ([M+H] + ), exact mass: 370.15.

[0226] Compound 288 was prepared according to the synthesis method of compound 1 in Example 1, with the difference that intermediate E8 was selected to replace intermediate E11 and intermediate F7 was selected to replace raw material F1. Elemental analysis of compound 288: C 53 H 41 N3; theoretical values: C, 88.42; H, 5.74; N, 5.84; measured values: C, 88.35; H, 5.84; N, 5.82. LC-MS: Measured value: 720.19 ([M+H] + ), exact mass: 719.33.

[0227] Example 23: Synthesis of Compound 580

[0228]

[0229]

[0230] Intermediate M2 was prepared according to the synthesis method of Intermediate M1, with the difference that Intermediate C1 was selected to replace Intermediate C2. LC-MS of Intermediate M2: Measured value: 415.09 ([M+H] + ); Exact mass: 414.18.

[0231] Intermediate E10 was prepared according to the synthesis method of Intermediate E8, with the difference that Intermediate M2 was selected to replace Intermediate M1. LC-MS of Intermediate E10: Measured value: 397.35 ([M+H] + ); Exact mass: 396.16.

[0232] Intermediate F8 was prepared according to the synthesis method of Intermediate F2, with the difference that starting material G2 was selected to replace starting material G1 and starting material J1 was selected to replace bis(pinacolato)diboron. LC-MS of Intermediate F8: Measured value: 588.41 ([M+H] + ); Exact mass: 587.27.

[0233] Compound 580 was prepared according to the synthesis method of Compound 1 in Example 1, with the difference that Intermediate E10 was selected to replace Intermediate E11 and Intermediate F8 was selected to replace starting material F1. Elemental analysis of Compound 580: C 61 H 47 N3; Theoretical values: C, 89.13; H, 5.76; N, 5.11; Test values: C, 89.16; H, 5.71; N, 5.15. LC-MS: Measured value: 822.17 ([M+H] + ); Exact mass: 821.38.

[0234] II. Device Fabrication Examples

[0235] 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 1-34 and Device Comparative Examples 1-15. Compared with Device Comparative Examples 1-15, the manufacturing processes of the devices in Device Examples 1-34 are exactly the same, and the same substrate materials and electrode materials are used, and the film thicknesses of the electrode materials are also kept consistent. The difference is that the hole blocking layer materials in the devices are changed. The device layer structures are shown in Table 3, and the performance test results of each device are shown in Table 4.

[0236] The molecular structural formulas of the related materials are shown below:

[0237]

[0238]

[0239] For the comparative compounds HB-1, HB-2, HB-3, HB-4, HB-5, HB-6, HB-7, HB-8, HB-9, HB-10, HB-11, HB-12, HB-13, HB-14, and HB-15, their structures are shown above. All of the above materials were obtained commercially.

[0240] Device Comparison Example 1

[0241] The specific preparation process is as follows:

[0242] 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 6 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.

[0243] Device Examples 1-34 and Device Comparative Examples 2-15 were prepared in a method similar to that of Device Comparative Example 1, except that the hole blocking layer materials in Table 3 below were used.

[0244] Table 3

[0245]

[0246]

[0247]

[0248]

[0249] III. Device Test Examples

[0250] 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 4 below.

[0251] Table 4

[0252]

[0253]

[0254]

[0255] It can be seen from the device test data results in Table 4 above that compared with the comparative devices using HB-1, HB-2, HB-3, HB-4, HB-5, HB-6, HB-7, HB-8, HB-9, HB-10, HB-11, HB-12, HB-13, HB-14, HB-15 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 efficiency is basically more than 1.08 times that of the devices of Comparative Examples 1 to 15, and its lifetime is more than 1.20 times that of the devices of Comparative Examples 1 to 15.

[0256] The structural formulas of the comparative compounds HB-1 to HB-15 used in the device comparative examples are close to the compound structure of the present invention, with only slight differences, only the difference in the connection site of spiro-(adamantane-2,9'-fluorene) and the difference in the intermediate bridging mode; and the difference in the bridging mode between spiro-(adamantane-2,9'-fluorene) and azobenzene after benzofused, however, the compound of the present invention as the hole-blocking layer material has achieved better technical effects than the comparative compounds.

[0257] 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 and a spiro-(adamantane-2,9'-fluorene) structure, characterized in that, The structures of the azabenzene and spiro-(adamantane-2,9'-fluorene) compounds are shown in general formula (1): In general formula (1), Z1, Z2, and Z3 each independently represent CH or N; at least one of Z1, Z2, and Z3 is N; Z1, Z2, and Z3 can be the same or different; Ar1 and Ar2 each independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group; Ar1 and Ar2 can be the same or different; R1 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a C1-C20 alkyl group, or a C3-C20 cycloalkyl group; L1 and L2 each independently represent a single bond, a C3-C20 sub-cycloalkyl group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group; L1 and L2 can be the same or different; In general formula (1), the asterisk * represents the connection positions of the phenyl group with R1, L1, and L2 respectively; R2 represents a structure shown in general formula (2) or general formula (3); In general formula (3), ring A represents any one of a substituted or unsubstituted naphthyl group and a substituted or unsubstituted phenanthryl group; In general formula (3), the asterisk * represents the connection position of general formula (3) with L2; Any unsubstituted carbon on any benzene ring, naphthalene ring, or phenanthrene ring in general formula (3) can serve as the connection site with L2; R3, R4, R5, and R6 represent any one of a hydrogen atom, deuterium, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridyl group, a pyrimidinyl group, and a phenanthryl group; The substituents substituting the above-mentioned groups that can be substituted are selected from deuterium, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a cyano group, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridyl group, and a phenanthryl group.

2. The compound with a nitrogen heterobenzene and spiro-(adamantane-2,9'-fluorene) structure according to claim 1, characterized in that, The compounds with the azabenzene and spiro-(adamantane-2,9'-fluorene) structures are any one shown in general formula (4) and general formula (5): In general formulas (4) to (5), the meanings of Ar1, Ar2, R1, R2, L1, L2, Z1, Z2, and Z3 are the same as those defined in claim 1; The asterisk * represents the connection positions of the phenyl group with R1, L1, and L2 respectively.

3. A compound having a structure of nitrogen-containing heteroarene and spiro-(adamantane-2,9'-fluorene) as claimed in claim 1, characterized in that, The compounds with the azabenzene and spiro-(adamantane-2,9'-fluorene) structures are any one of general formula (6), general formula (7), general formula (8), general formula (9), general formula (10), general formula (11), general formula (12), general formula (13), and general formula (14): In General Formulas (6) to (14), the meanings of Ar1, Ar2, R1, R2, L1, L2, Z1, Z2, and Z3 are the same as those defined in Claim 1.

4. A compound having a structure of nitrogen-containing heteroarene and spiro-(adamantane-2,9'-fluorene), characterized in that, The compound containing a nitrogen heterocyclic benzene and a spiro-(adamantane-2,9'-fluorene) structure is any one of General Formulas (15) to (51): In General Formulas (15) to (51), the meanings of Ar1, Ar2, R1, R2, Z1, Z2, and Z3 are the same as those defined in Claim 1.

5. A compound having a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) structure according to claim 1, characterized in that, The General Formula (3) is represented as any one of General Formula 3a, General Formula 3b, General Formula 3c, General Formula 3d, and General Formula 3e: Any unsubstituted carbon on any benzene ring or naphthalene ring in General Formula 3a, General Formula 3b, General Formula 3c, General Formula 3d, and General Formula 3e can be used as the connection site with General Formula (1); In General Formula 3a, the connection site with General Formula (1) is any one of the sites 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; the connection site of R7 is any one of the sites 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; In General Formula 3b, the connection site with General Formula (1) is any one of the sites 1', 2', 3', 4', 5', 6', 7', 8', 9', or 10'; the connection site of R7 is any one of the sites 1', 2', 3', 4', 5', 6', 7', 8', 9', or 10'; In General Formula 3c, the connection site with General Formula (1) is any one of the sites 1'', 2'', 3'', 4'', 5'', 6'', 7'', 8'', 9'', or 10''; the connection site of R7 is any one of the sites 1'', 2'', 3'', 4'', 5'', 6'', 7'', 8'', 9'', or 10''; In General Formula 3d, the connection site with General Formula (1) is any one of the sites 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; the connection site of R7 is any one of the sites 15, 16, 17, 18, 19, 20, 21, or 22; In General Formula 3e, the connection site with General Formula (1) is any one of the sites 11', 12', 13', 14', 15', 16', 17', 18', 19', 20', 21', or 22'; the connection site of R3 is any one of the sites 11', 12', 13', or 14'; In General Formulas 3a to 3e, the meaning of R3 is the same as that defined in Claim 1; R7 represents any one of a hydrogen atom, deuterium, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridyl group, a pyrimidinyl group, and a phenanthryl group.

6. A compound having a nitrogen heterobenzene and a spiro-(adamantane-2,9'-fluorene) structure according to any one of claims 1-5, characterized in that, The L1 and L2 each independently represent a single key, any one of; Ar1, Ar2, and R1 each independently represent any one of; R1 may also represent R3, R4, R5, R6, and R7 are each independently a hydrogen atom, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-hexyl, or any one of the following.

7. A compound having a structure of azabenzene and spiro-(adamantane-2,9'-fluorene) according to claim 1, characterized in that, In the General Formula (1), Z1, Z2, and Z3 are all represented as N.

8. A compound having a structure of azabenzene and spiro-(adamantane-2,9'-fluorene) according to any one of claims 1-7, characterized in that, Any hydrogen atom in the compound containing a nitrogen heterocyclic benzene and a spiro-(adamantane-2,9'-fluorene) structure according to any one of Claims 1-7 can be replaced by a deuterium atom.

9. A compound having a structure of nitrogen-containing heteroarene and spiro-(adamantane-2,9'-fluorene), characterized in that, The specific structure of the compound containing a nitrogen heterocyclic benzene and a spiro-(adamantane-2,9'-fluorene) structure is any one of the following structures:

10. An organic electroluminescent device, comprising a substrate, a first electrode and a second electrode, wherein there are multiple organic thin film layers between the first electrode and the second electrode, and is characterized in that, The organic thin film layer contains the compound containing a nitrogen heterocyclic benzene and a spiro-(adamantane-2,9'-fluorene) structure according to any one of Claims 1 to 9; Preferably, 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 having a nitrogen-containing heteroarene and a spiro-(adamantane-2,9'-fluorene) structure according to any one of claims 1 to 9; Preferably, the electron transport region thin film layer includes a hole blocking layer, and the hole blocking layer contains the compound having a nitrogen-containing heteroarene and a spiro-(adamantane-2,9'-fluorene) structure according to any one of claims 1 to 9.

11. An organic electroluminescent device according to claim 10, characterized in that, 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 having a nitrogen-containing heteroarene and a spiro-(adamantane-2,9'-fluorene) structure according to any one of claims 1 to 9.

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