Compound containing azabenzene and naphthofuran acene structures and organic electroluminescent device thereof

Abstract

The invention discloses a compound containing azabenzene and naphthofuran acene structures and an organic electroluminescent device thereof, and belongs to the technical field of semiconductor materials. The structure of the compound containing the azabenzene and naphthofuran acene structure is as shown in a general formula (1). The compound containing the azabenzene and naphthofuran acene structure has good electron regulation and control capability and hole and exciton blocking capability, and also has good stability; when the compound containing the azabenzene and naphthofuran acene structure is used as a hole blocking layer material of the organic light-emitting device, the light-emitting efficiency of the organic light-emitting device can be remarkably improved, and the working life of the organic light-emitting device can be remarkably prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of semiconductor materials, in particular to a compound containing a nitrogen-containing heterobenzene and naphthofuranbenzene structure and an organic electroluminescent device thereof. BACKGROUND

[0002] Organic electroluminescent device (OLED: Organic Light Emission Diodes) technology can be used to manufacture new display products and new lighting products, and is expected to replace existing liquid crystal display and fluorescent lamp lighting, and has a very wide application prospect. The organic electroluminescent device has a sandwich-like structure, including electrode material film layers and organic optoelectronic functional material layers sandwiched between different electrode material film layers, and the organic optoelectronic functional material layer at least contains a light-emitting layer. Various different organic optoelectronic functional materials are stacked together according to the purpose to jointly form an organic electroluminescent device. As a current device, when a voltage is applied to the electrodes at both ends of the organic electroluminescent device, and the positive and negative charges in the organic optoelectronic functional material layer are subjected to an electric field, the positive and negative charges are further recombined in the light-emitting layer, i.e. organic electroluminescence is generated.

[0003] At present, organic electroluminescent device display technology has been applied in the fields of smart phones, tablet computers, televisions and the like. However, compared with the actual product application requirements, the performance of the organic electroluminescent device, such as luminous efficiency and service life, still needs to be further improved. In order to continuously improve the performance of the organic electroluminescent device, the organic optoelectronic functional material needs to be continuously researched and innovated, and a higher performance organic optoelectronic functional material needs to be created.

[0004] The organic optoelectronic functional material applied to the organic electroluminescent device can be divided into two categories according to the purpose, which are charge injection and transport material and light-emitting material. Further, the charge injection and transport material can be divided into electron injection and transport material, electron blocking material, hole injection and transport material, and hole blocking material. For the organic electroluminescent device, holes are injected from the anode, electrons are injected from the cathode, and are transported in the organic functional layer, finally meet to form excitons in the light-emitting layer, and the excitons recombine to emit light. 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 also can reduce the energy loss of excitons, play the role of interface modification and electron injection / transport auxiliary regulation. Since the existing hole blocking layer material has poor electron regulation ability and poor hole and exciton blocking ability, it is difficult to obtain efficient electron and hole balance in the light-emitting layer, and it is difficult to obtain high efficiency and long service life of the device, so it is necessary to further improve the electron injection and transport ability of the hole blocking layer material, and the hole and exciton blocking ability, and to improve the stability of the material, to achieve efficient balance of excitons, and to improve the efficiency and service life of the device. SUMMARY

[0005] In order to solve the above problems in the prior art, the present application provides a compound containing a nitrogen-containing heterobenzene and a naphthofuranbenzene structure and an organic electroluminescent device, the compound has excellent hole blocking ability and good material stability, and can effectively improve the luminous efficiency and service life of the device when applied to the organic electroluminescent device.

[0006] A compound containing a nitrogen-containing heterobenzene and a naphthofuranbenzene structure, the compound has a structure as shown in general formula (1):

[0007]

[0008] In general formula (1), Z1, Z2, and Z3 each independently represent N;

[0009] Ar1 and Ar2 each independently represent substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 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 pyrimidyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, or substituted or unsubstituted carbazolyl; Ar1 and Ar2 can be the same or different;

[0010] L represents a structure as shown in general formula (2), general formula (3), general formula (4), general formula (5), general formula (6), general formula (7), general formula (8), general formula (9), general formula (10), or general formula (11);

[0011]

[0012] Ar3 represents a structure as shown in general formula (12), general formula (13), general formula (14), general formula (15), or general formula (16);

[0013]

[0014]

[0015] In general formula (2) to general formula (16), the asterisk * represents a connection position;

[0016] In General Formula (4) to General Formula (6), L1, L2, L3, L4, L5, L6 each independently represents a single bond, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted pyridinylene group; L1, L2, L3, L4, L5, L6 can be the same or different; at least one of L1, L2 does not represent a single bond; at least one of L3, L4 does not represent a single bond; at least one of L5, L6 does not represent a single bond;

[0017] In General Formula (6) to General Formula (11), R1, R2, R3, R4, R5, R6 each independently 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 pyrimidyl group;

[0018] When L represents General Formula (5), L3 is a single bond and L4 is an unsubstituted phenylene group, L3 can be connected to Ar3 only via the asterisk *;

[0019] When L represents General Formula (5), L4 is a single bond and L3 is an unsubstituted phenylene group, L4 can be connected to Ar3 only via the asterisk *;

[0020] When L represents General Formula (8), R3 is an unsubstituted phenyl group, Ar3 does not represent General Formula (13), General Formula (15), General Formula (16);

[0021] When L represents General Formula (9), R4 is an unsubstituted phenyl group, Ar3 does not represent General Formula (13), General Formula (15);

[0022] In General Formula (12) to General Formula (16), X1 each occurrence, the same or different, each independently represents an oxygen atom or a sulfur atom;

[0023] Ring A represents a naphthyl group;

[0024] The substituents that can substitute the above substituents are a hydrogen atom, a deuterium atom, 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, a pyrimidyl group, a phenanthryl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group.

[0025] Further, any hydrogen atom in the compound represented by General Formula (1) can be substituted with a deuterium atom.

[0026] Further, the hydrogen atoms in the compound represented by General Formula (1) are partially or entirely substituted with deuterium atoms.

[0027] Further, L in the general formula (1) comprises at least one ortho-phenylene or meta-phenylene.

[0028] Further, L5, L6 in the general formula (6) comprises at least one ortho-phenylene or meta-phenylene.

[0029] Further, the nitrogen-containing heterobenzo and naphthofurano-benzene structure compound is any one of the general formula (2-1), the general formula (2-2), the general formula (2-3), the general formula (2-4), the general formula (2-5), the general formula (2-6), the general formula (2-7), the general formula (2-8), the general formula (2-9), the general formula (2-10), the general formula (2-11), the general formula (2-12), the general formula (2-13), the general formula (2-14), the general formula (2-15), the general formula (2-16), the general formula (2-17), or the general formula (2-18):

[0030]

[0031] In the general formula (2-1) to the general formula (2-18), the meanings of Ar1, Ar2, Ar3, R1, R2, R3, R4, R5, R6, L1, L2, L3, L4, L5, L6, Z1, Z2, and Z3 are the same as defined in claim 1.

[0032] The asterisk * indicates the connection position of the phenylene group with R1, L5, and L6, respectively.

[0033] Further, any hydrogen atom in the compound represented by the general formula (2-1) to the general formula (2-18) can be substituted with a deuterium atom.

[0034] Further, the general formula (2-9) comprises at least one ortho-phenylene or meta-phenylene.

[0035] Further, L5, L6 in the general formula (2-9) comprises at least one ortho-phenylene or meta-phenylene.

[0036] Further, when L in the general formula (1) is represented by the general formula (7), Ar3 is any one of the general formula (12), the general formula (13), the general formula (14), or the general formula (15).

[0037] Furthermore, the compound containing nitrogen-containing heterobenzene and naphthofuranacene structures is any one of the general formula (2-19), general formula (2-20), general formula (2-21), general formula (2-22), general formula (2-23), general formula (2-24), general formula (2-25), general formula (2-26), general formula (2-27), general formula (2-28), general formula (2-29), general formula (2-30), general formula (2-31), general formula (2-32), general formula (2-33), general formula (2-34), general formula (2-35) to general formula (2-67);

[0038]

[0039]

[0040]

[0041] In general formulae (2-19) to (2-67), the meanings of Ar1, Ar2, Ar3, R1, Z1, Z2, and Z3 are the same as those defined above.

[0042] Furthermore, any hydrogen atom in the compounds represented by the general formula (2-19) to the general formula (2-67) may be replaced by a deuterium atom.

[0043] Furthermore, the compound containing nitrogen-containing heterobenzene and naphthofuranacene structures is any one of the general formulas (3-1), (3-2), (3-3), (3-4), (3-5), (3-6), (3-7), (3-8), and (3-9):

[0044]

[0045] In general formulae (3-1) to (3-9), the meanings of Ar1, Ar2, Ar3, R1, L5, L6, Z1, Z2, and Z3 are the same as those defined above.

[0046] Furthermore, any hydrogen atom in the compounds represented by general formula (3-1) to general formula (3-9) may be replaced by a deuterium atom.

[0047] Furthermore, the general formulas (3-1) to (3-9) contain at least one ortho-phenylene group or meta-phenylene group.

[0048] Furthermore, at least one of L5 and L6 in the general formula (3-1) to the general formula (3-9) represents an ortho-phenylene group or a meta-phenylene group.

[0049] Furthermore, the compound containing nitrogen-containing heterobenzene and naphthofuranacene structures is any one of the general formulas (4-1) to (4-14):

[0050]

[0051] In general formulae (4-1) to (4-14), the meanings of Ar1, Ar2, R1, Ar3, Z1, Z2, and Z3 are the same as those defined above.

[0052] Furthermore, any hydrogen atom in the compounds represented by general formula (4-1) to general formula (4-14) may be replaced by a deuterium atom.

[0053] Furthermore, Ar3 represents any one of the following general formulas:

[0054]

[0055] In the general formulae 5a to 5q, X1 has the same meaning as defined above.

[0056] Furthermore, the L1, L2, L3, L4, L5, and L6 are each independently represented by a single bond,

[0057] Any of;

[0058] Furthermore, the Expressed as:

[0059] Any of;

[0060] Ar1 and Ar2 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-hexyl,

[0061] Any of the following;

[0062] R1, R2, R3, R4, R5, and R6 are each independently represented by

[0063] Any of the following;

[0064] The substituents for the above substitutable groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-hexyl,

[0065] Any one of them.

[0066] Furthermore, the specific structure of the compound containing nitrogen-containing heterobenzene and naphthofuranacene structures is any one of the following structures:

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

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[0082]

[0083]

[0084]

[0085]

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[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119] The application also discloses an organic electroluminescent device comprising a substrate, a first electrode and a second electrode, wherein a plurality of organic thin film layers are arranged between the first electrode and the second electrode, and the organic thin film layers comprise the nitrogen-containing heterobenzene and naphthofuranbenzene compound.

[0120] Preferably, the organic thin film layers comprise 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 comprises the nitrogen-containing heterobenzene and naphthofuranbenzene compound.

[0121] Preferably, the electron transport region thin film layer comprises a hole blocking layer, and the hole blocking layer comprises the nitrogen-containing heterobenzene and naphthofuranbenzene compound.

[0122] Preferably, the hole transport region thin film layer comprises a hole injection layer, a hole transport layer and an electron blocking layer, and the electron transport region thin film layer comprises a hole blocking layer, an electron transport layer and an electron injection layer, and the hole blocking layer comprises the nitrogen-containing heterobenzene and naphthofuranbenzene compound.

[0123] Technical effects

[0124] The application has the beneficial technical effects of:

[0125] The compound protected by the application has more excellent hole blocking and exciton blocking capabilities, can efficiently block the diffusion or movement of holes to the electron transport layer, makes the holes better limited in the light-emitting region, ensures more excitons formed by holes and electrons in the light-emitting layer, improves the exciton concentration, and further improves the light-emitting efficiency and device lifetime.

[0126] The structural characteristics of the compound of the application make the compound of the application have more excellent electron regulation capability, supplement the electron transport layer, have suitable electron injection and transport performance, better adapt to the electron-hole balance in the light-emitting layer, and improve the light-emitting efficiency of the device and the device lifetime.

[0127] The compound protected by the application has lower evaporation temperature and chemical stability, makes the evaporation film formation have good film phase stability and a wider heat resistance window, and further ensures the stability in device manufacturing and product use. BRIEF DESCRIPTION OF DRAWINGS

[0128] Figure 1 The application illustrates the structure of the material applied to the OLED device.

[0129] In the figure, 1, transparent substrate layer; 2, anode layer; 3, hole injection layer; 4, hole transport layer; 5, electron blocking layer; 6, light emitting layer; 7, hole blocking layer; 8, electron transport layer; 9, electron injection layer; 10, cathode layer; 11, light extraction layer.

[0130] Figure 2 NMR spectrum of compound 343 of the present application in deuterated chloroform.

[0131] Figure 3 NMR spectrum of compound 648 of the present application in deuterated chloroform. DETAILED DESCRIPTION

[0132] The technical solutions of the present application will be described in detail below in combination with embodiments.

[0133] In the present application, unless otherwise specified, HOMO means the highest occupied orbital of a molecule, and LUMO means the lowest unoccupied orbital of a molecule.

[0134] In the drawings, the dimensions of layers and regions can be exaggerated for the sake of clarity. It will also be understood that when a layer or element is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or intervening layers can also be present. Furthermore, it will be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers can also be present.

[0135] In the present application, when describing electrodes and organic electroluminescent devices, as well as other structures, the words "upper", "lower", and the like indicating orientation are used only to indicate the orientation in a certain specific state, and do not mean that the relevant structure can only exist in the described orientation; on the contrary, if the structure can be transformed in position, for example, inverted, the orientation of the structure is changed accordingly. Specifically, in the present application, the "lower" side of an electrode refers to the side of the electrode that is close to the substrate during the preparation process, and the opposite side, away from the substrate, is the "upper" side.

[0136] The C1-C20 alkyl group (including linear alkyl and branched alkyl) described in the present application refers to methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, hexyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl, and the like, but is not limited thereto.

[0137] The C3-C20 cycloalkyl group described in the present application refers to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentyl, cyclooctyl, adamantyl, and the like, but is not limited thereto.

[0138] Organic electroluminescent device

[0139] The organic electroluminescent device of the present application can be a bottom emission organic electroluminescent device, a top emission organic electroluminescent device or a stacked organic electroluminescent device, and is not particularly limited thereto.

[0140] The organic electroluminescent device of the present application comprises, in order, a substrate, a first electrode, an organic thin film layer and a second electrode. 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, the hole transport region thin film layer comprising a hole injection layer, a hole transport layer and an electron blocking layer, the electron transport region thin film layer comprising a hole blocking layer, an electron transport layer and an electron injection layer, and further, a light extraction layer can be provided on the second electrode.

[0141] The organic electroluminescent device of the present application can comprise the following layers and the positional relationship of each layer: 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, wherein 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.

[0142] As the substrate of the organic electroluminescent device of the present application, any substrate commonly used for organic electroluminescent devices can be used. Examples are transparent substrates such as glass or transparent plastic substrates; non-transparent substrates such as silicon substrates; flexible PI film substrates. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, water resistance. Depending on the properties of the substrate, its use direction is different. In the present application, it is preferred to use a transparent glass substrate, and the thickness of the substrate is not particularly limited.

[0143] A first electrode is formed on a substrate, and the first electrode and a second electrode can be opposite to each other. The first electrode can be an anode or a cathode, and in the present application, the first electrode serves as an anode, and the anode material is preferably a material having a high work function so that holes are easily injected into an 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. In addition, the thickness of the anode depends on the material used, and is generally 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm.

[0144] 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.

[0145] The hole injection layer can include a host material and a P-type dopant material, the host material can be selected from conventional hole transport materials in the prior art, and is preferably the same organic material as the hole transport layer, and the P-type dopant material is a compound having charge conductivity 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.

[0146] For example, the following compounds:

[0147]

[0148] According to the present application, P-1 is preferably used as the P-type dopant material.

[0149] The thickness of the hole injection layer of the present application can be 1-100 nm, preferably 2-50 nm, and more preferably 5-20 nm.

[0150] The material of the hole transport layer is preferably a material having a high hole mobility, which enables the transfer of holes from the anode or the hole injection layer to the light-emitting layer.

[0151] Preferably, as the hole transport layer material of the present application, the following compounds disclosed in the prior art can be optionally selected:

[0152]

[0153] The thickness of the hole transport layer of the present application can be 5-200 nm, preferably 10-180 nm, and more preferably 20-150 nm.

[0154] 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, 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 level of the hole transport layer material and the HOMO energy level of the light-emitting layer host material, which is conducive to the injection of holes from the positive electrode into the light-emitting layer, while the electron blocking layer material requires high hole mobility, which is conducive to hole transport and reduces the power consumption of the device; the LUMO energy level of the electron blocking layer material is higher than the LUMO energy level of the light-emitting layer host material, which plays a role in electron blocking, that is, the electron blocking layer material requires a wide band gap (Eg). The electron blocking layer material that meets the above conditions can be a triarylamine derivative, a fluorene derivative, a spirofluorene derivative, a diphenylfuran derivative, a carbazole derivative, etc.

[0155] In an embodiment of the present application, as the electron blocking layer material of the present application, the following compounds disclosed in the prior art can be optionally selected:

[0156]

[0157] According to the present application, the thickness of the electron blocking layer can be 1-200 nm, preferably 5-150 nm, and more preferably 5-50 nm.

[0158] According to the present application, the light-emitting layer is located between the electron blocking layer and the hole blocking layer, and the material of the light-emitting layer is a material that can emit visible light by receiving holes from the hole transport region and electrons from the electron transport region, respectively, and combining the received holes and electrons. The light-emitting layer can include a host material and a dopant material. The host material can be divided into a red light host material, a green light host material, a blue light host material, etc., and the dopant material can be divided into a red light dopant material, a green light dopant material, a blue light dopant material, etc. The present application takes a blue light device as an example, and the host material and the guest material of the light-emitting layer of the organic electroluminescent device of the present application, wherein the host material can be one or a combination of two of anthracene derivatives, quinoxaline derivatives, triazine derivatives, xanthone derivatives, benzophenone derivatives, carbazole derivatives, pyridine derivatives, or pyrimidine derivatives. The guest material can be a pyrene derivative, a boron derivative, a fluorene derivative, a spirofluorene derivative, an iridium complex, or a platinum complex.

[0159] The thickness of the light-emitting layer of the present application can be 5-60 nm, preferably 10-50 nm, and more preferably 20-45 nm.

[0160] A hole-blocking layer can be disposed on the light-emitting layer. The triplet (T1) energy level of the hole-blocking layer material is higher than the T1 energy level of the host material of the light-emitting layer, which can block the energy loss of the light-emitting layer material; the HOMO energy level of the material is lower than the HOMO energy level of the host material of the light-emitting layer, which plays a role in blocking holes, and at the same time requires the hole-blocking layer material to have a suitable electron mobility, which is conducive to electron transport and reduces the power consumption of the device; the hole-blocking layer material meeting the above conditions is the compound of the nitrogen-containing heterobenzene and naphthofuranbenzene structure described above.

[0161] The thickness of the hole-blocking layer of the present application can be 2-200 nm, preferably 5-150 nm, and more preferably 5-50 nm, but the thickness is not limited to this range.

[0162] An electron transport layer can be disposed on the hole-blocking layer. The electron transport layer material is a material that easily receives electrons from the cathode and transfers the received electrons to the light-emitting layer. A material having a high electron mobility is preferred. As the electron transport layer material of the organic electroluminescent device of the present application, the following compounds disclosed in the prior art can be used for the electron transport layer material of the organic electroluminescent device:

[0163]

[0164] In a preferred embodiment of the present application, the electron transport layer further includes other compounds commonly used in the electron transport layer, for example, Alq3, LiQ, and preferably LiQ.

[0165] The thickness of the electron transport layer of the present application can be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm.

[0166] According to the present application, an electron injection layer can be disposed between the electron transport layer and the cathode. The electron injection layer material is generally a material having a low work function, which allows easy injection of electrons 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 application, the following materials disclosed in the prior art can be used for the electron injection layer material of the organic electroluminescent device: LiF, Cs2CO3, CsF, Csq, NaF, MgF2, CaF2, Al2O3, Yb.

[0167] The thickness of the electron injection layer of the present application 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.

[0168] According to the present application, the second electrode can be either a cathode or an anode, as previously described. In the present application, the second electrode is used as a cathode. The material used to form the cathode can be a material having 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 typically 5-100 nm, preferably 7-50 nm, and more preferably 10-25 nm.

[0169] 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 the second electrode (i.e., the cathode) of the device. The following compounds disclosed in the art in the prior art can be used as the light extraction layer material.

[0170]

[0171]

[0172] The thickness of the light extraction layer is typically 5-300 nm, preferably 20-100 nm, and more preferably 40-80 nm.

[0173] The organic electroluminescent device can further include an encapsulation structure. The encapsulation structure can be a protective structure that prevents external substances, such as moisture and oxygen, from entering the organic layer of the organic electroluminescent device. The encapsulation structure 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.

[0174] Method of manufacturing an organic electroluminescent device

[0175] The present application also relates to a method of manufacturing the above-described organic electroluminescent device, which includes sequentially laminating a first electrode, an organic thin film layer, and a second electrode on a substrate. The organic thin film layer is formed by sequentially laminating a hole transport region thin film layer, i.e., a hole injection layer, a hole transport layer, and an electron blocking layer, on the first electrode from bottom to top, a light emitting region thin film layer, and an electron transport region thin film layer, i.e., a hole blocking layer, an electron transport layer, and an electron injection layer, on the light emitting layer from bottom to top. In addition, optionally, a light extraction layer can also be laminated on the second electrode to improve the light extraction efficiency of the organic electroluminescent device.

[0176] As for the lamination, a method such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing or LITI, but not limited thereto, can be used. Among them, the vacuum evaporation means that the material is heated and plated on the substrate in a vacuum environment.

[0177] In the present application, it is preferable to use a vacuum evaporation method to form the respective layers, in which vacuum evaporation can be performed at a temperature of about 100 to 500°C at a rate of about 10 -8 -10 -2 Torr and a rate of about The vacuum degree is preferably 10 -6 -10 -2 Torr, and more preferably 10 -5 -10 -3 Torr. The rate is about and more preferably about

[0178] In addition, it should be noted that the materials used to form the respective layers according to the present application can be used as a single layer by being individually deposited, or can be used as a single layer by being deposited after being mixed with other materials, or can be used as a stacked structure between layers deposited individually, a stacked structure between layers deposited after being mixed, or a stacked structure between layers deposited individually and layers deposited after being mixed.

[0179] Display device

[0180] The present application also relates to a display device, particularly a flat panel display device, comprising the above-described organic electroluminescent device. In a preferred embodiment, the display device can comprise one or more of the above-described organic electroluminescent devices, and in the case of comprising a plurality of devices, the devices are combined in a lateral or longitudinal stack. The display device can further comprise at least one thin film transistor. The thin film transistor can comprise a gate electrode, a source electrode and a drain electrode, a gate insulating layer, and an active layer, wherein one of the source electrode and the drain electrode can be electrically connected to the first electrode of the organic electroluminescent device. The active layer can comprise crystalline silicon, amorphous silicon, an organic semiconductor, or an oxide semiconductor, but it is not limited thereto.

[0181] The following examples are intended to better illustrate the present application, but not to limit the scope thereof.

[0182] Example

[0183] I. Compound preparation example

[0184] The present application will be specifically described below with reference to the accompanying drawings and examples.

[0185] The raw materials involved in the synthesis examples of the present application can be purchased from the market or prepared by conventional preparation methods in the art;

[0186] Preparation of intermediate M1, intermediate F1:

[0187]

[0188] Under the protection of nitrogen, raw material A2 (8.45 g, 20 mmol), raw material B1 (2.68 g, 22 mmol), K2CO3 (8.29 g, 60 mmol), tetrahydrofuran (150 mL), water (50 mL) were added in sequence in a round-bottom flask, the air was replaced by nitrogen for 30 min, Pd(PPh3)4 (0.462 g, 0.4 mmol) was added, and the reaction was heated to reflux under the protection of nitrogen for 13 h. TLC detection of the reaction liquid showed that raw material A2 was completely reacted. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, the residue was dissolved in dichloromethane 150 ml, washed with water 100 ml, poured into a separatory funnel, shaken and separated, the aqueous phase was extracted with dichloromethane (60 ml*3), the organic phase was combined and dried over anhydrous magnesium sulfate, filtered, and the filtrate was rotary evaporated to remove dichloromethane to obtain a crude product, which was purified by silica gel column chromatography to obtain intermediate M1. LC-MS: measured value: 420.22 ([M+H] + ); accurate mass: 419.12.

[0189]

[0190] Under the protection of nitrogen, raw material E1 (4.46 g, 15 mmol), raw material D1 (5.94 g, 18 mmol), potassium acetate (4.91 g, 50 mmol), dioxane (120 ml) were added in sequence in a round-bottom flask, the air was replaced by nitrogen for 30 min, Pd(PPh3)4 (0.347 g, 0.3 mmol) was added, and the reaction was heated to reflux under the protection of nitrogen for 14 h. TLC detection of the reaction liquid showed that raw material E1 was completely reacted. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, the residue was dissolved in dichloromethane 100 ml, washed with water 120 ml, poured into a separatory funnel, shaken and separated, the aqueous phase was extracted with dichloromethane (60 ml*3), the organic phase was combined and dried over anhydrous magnesium sulfate, filtered, and the filtrate was rotary evaporated to remove dichloromethane to obtain intermediate F1. LC-MS: measured value: 421.33 ([M+H] + ), accurate mass: 420.19.

[0191] The intermediates M2 to M15 were prepared by the synthetic method of the intermediate M1, except that different raw materials A and B were used, and the raw materials A and B used are shown in Table 1; the intermediates F2 to F4, F6 to F8, F10, F13 to F15 were prepared by the synthetic method of the intermediate F1, except that different raw materials D and E were used, and the raw materials D and E used are shown in Table 2.

[0192] Table 1

[0193]

[0194]

[0195] Table 2

[0196]

[0197]

[0198]

[0199] Example 1: Synthesis of compound 1

[0200]

[0201] Under nitrogen protection, raw material A1 (4.20 g, 10 mmol), intermediate F1 (5.04 g, 12 mmol), K2CO3 (4.15 g, 30 mmol), tetrahydrofuran (90 mL), water (45 mL) were sequentially added into a 250 mL round-bottom flask, nitrogen was replaced for 30 min to replace air, palladium acetate (0.067 g, 0.30 mmol) was added, 2-dicyclohexylphosphino-2',4',6'-triisopropyl biphenyl (0.429 g, 0.90 mmol) was added, and the reaction was heated to reflux under nitrogen protection for 17 h. TLC detection of the reaction liquid showed that raw material A1 was completely reacted. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, the residue was dissolved in 100 mL of dichloromethane, 100 mL of water was added for washing, and the mixture was poured into a separatory funnel, shaken and allowed to stand to separate the layers. The aqueous phase was extracted with dichloromethane (50 mL*3), the organic phases were combined and dried over anhydrous magnesium sulfate, filtered, and the filtrate was rotary evaporated to remove dichloromethane to obtain a crude product, which was purified by silica gel column chromatography to obtain compound 1. Elemental analysis: C 49 H 31 N3O; Theoretical value: C, 86.83; H, 4.61; N, 6.20; Test value: C, 86.81; H, 4.65; N, 6.25. LC-MS: measured value: 678.03 ([M+H]+), accurate mass: 677.25.

[0202] Example 2: Synthesis of compound 2

[0203]

[0204] Compound 2 was prepared according to the procedure for the synthesis of compound 1 in Example 1, except that intermediate F2 was used in place of intermediate Fl. Elemental analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.80; H, 4.60; N, 6.29. LC-MS: found: 678.32 ([M+H] + ), exact mass: 677.25.

[0205] Example 3: Synthesis of compound 3

[0206]

[0207] Compound 3 was prepared according to the procedure for the synthesis of compound 1 in Example 1, except that intermediate F3 was used in place of intermediate Fl. Elemental analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.77; H, 4.68; N, 6.18. LC-MS: found: 678.41 ([M+H] + ), exact mass: 677.25.

[0208] Example 4: Synthesis of compound 21

[0209]

[0210] Compound 21 was prepared according to the procedure for the synthesis of compound 1 in Example 1, except that intermediate F6 was used in place of intermediate Fl. Elemental analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.89; H, 4.55; N, 6.22. LC-MS: found: 678.06 ([M+H] + ), exact mass: 677.25.

[0211] Example 5: Synthesis of compound 31

[0212]

[0213] Compound 31 was prepared according to the procedure for the synthesis of compound 1 in Example 1, except that intermediate Ml was used in place of starting material Al. Elemental analysis: C 49 H31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.97; H, 4.49; N, 6.23. LC-MS: Obs. 678.08 ([M+H] + ), exact mass: 677.25.

[0214] Example 6: Synthesis of compound 34

[0215]

[0216] Compound 34 was prepared according to the procedure for the synthesis of compound 1 in Example 1, except that intermediate M13 was used to replace starting material A1; intermediate F4 was used to replace intermediate Fl. Elemental Analysis: C 55 H 35 N3O; Calc: C, 87.62; H, 4.68; N, 5.57; Found: C, 87.65; H, 4.61; N, 5.58. LC-MS: Obs. 754.43 ([M+H] + ), exact mass: 753.28.

[0217] Example 7: Synthesis of compound 41

[0218]

[0219] Compound 41 was prepared according to the procedure for the synthesis of compound 1 in Example 1, except that intermediate M1 was used to replace starting material A1; intermediate F7 was used to replace intermediate Fl. Elemental Analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.97; H, 4.49; N, 6.23. LC-MS: Obs. 678.08 ([M+H] + ), exact mass: 677.25.

[0220] Example 8: Synthesis of compound 52

[0221]

[0222] Compound 52 was prepared according to the procedure for the synthesis of compound 1 in Example 1, except that intermediate F8 was used to replace intermediate Fl. Elemental Analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.97; H, 4.49; N, 6.23. LC-MS: Obs. 678.08 ([M+H] + ), exact mass: 677.25.

[0223] Example 9: Synthesis of compound 98

[0224]

[0225] Compound 98 was prepared according to the procedure for synthesis of compound 1 in Example 1, except that starting material A4 was used to replace starting material Al; starting material F9 was used to replace intermediate Fl. Elemental Analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.88; H, 4.69; N, 6.10. LC-MS: Found: 678.37 ([M+H] + ), Exact Mass: 677.25.

[0226] Example 10: Synthesis of compound 142

[0227]

[0228] Compound 142 was prepared according to the procedure for synthesis of compound 1 in Example 1, except that intermediate M2 was used to replace starting material Al; starting material F9 was used to replace intermediate Fl. Elemental Analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.70; H, 4.64; N, 6.30. LC-MS: Found: 678.11 ([M+H] + ), Exact Mass: 677.25.

[0229] Example 11: Synthesis of compound 179

[0230]

[0231] Compound 179 was prepared according to the procedure for synthesis of compound 1 in Example 1, except that intermediate M3 was used to replace starting material Al; starting material F9 was used to replace intermediate Fl. Elemental Analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.92; H, 4.63; N, 6.08. LC-MS: Found: 678.29 ([M+H] + ), Exact Mass: 677.25

[0232] Example 12: Synthesis of compound 270

[0233]

[0234] Compound 270 was prepared according to the procedure for synthesis of Compound 1 in Example 1, except intermediate M4 was used to replace starting material A1; and starting material F9 was used to replace intermediate F1. Elemental Analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.74; H, 4.73; N, 6.05. LC-MS: Obs. 678.09 ([M+H] + ), Exact Mass: 677.25.

[0235] Example 13: Synthesis of Compound 275

[0236]

[0237] Compound 275 was prepared according to the procedure for synthesis of Compound 1 in Example 1, except intermediate M5 was used to replace starting material A1; and starting material F9 was used to replace intermediate F1. Elemental Analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.74; H, 4.73; N, 6.05. LC-MS: Obs. 678.09 ([M+H] + ), Exact Mass: 677.25.

[0238] Example 14: Synthesis of Compound 312

[0239]

[0240] Compound 312 was prepared according to the procedure for synthesis of Compound 1 in Example 1, except intermediate M6 was used to replace starting material A1; and starting material F5 was used to replace intermediate F1. Elemental Analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.79; H, 4.59; N, 6.28. LC-MS: Obs. 678.20 ([M+H] + ), Exact Mass: 677.25.

[0241] Example 15: Synthesis of Compound 313

[0242]

[0243] Compound 313 was prepared according to the procedure for synthesis of Compound 1 in Example 1, except intermediate M6 was used to replace starting material A1; and starting material F9 was used to replace intermediate F1. Elemental Analysis: C 49 H 31N3O; Theory: C, 86.83; H, 4.61; N, 6.20; Test: C, 86.68; H, 4.80; N, 6.14. LC-MS: Found: 678.38 ([M+H] + ), exact mass: 677.25.

[0244] Example 16: Synthesis of compound 337

[0245]

[0246] Compound 337 was prepared according to the procedure for synthesis of compound 1 in Example 1, except that intermediate M11 was used to replace starting material A1. Elemental Analysis: C 55 H 35 N3O; Theory: C, 87.62; H, 4.68; N, 5.57; Test: C, 87.65; H, 4.65; N, 5.55. LC-MS: Found: 754.05 ([M+H] + ), exact mass: 753.28.

[0247] Example 17: Synthesis of compound 343

[0248]

[0249] Compound 343 was prepared according to the procedure for synthesis of compound 1 in Example 1, except that intermediate M3 was used to replace starting material A1. Elemental Analysis: C 55 H 35 N3O; Theory: C, 87.62; H, 4.68; N, 5.57; Test: C, 87.55; H, 4.72; N, 5.59. LC-MS: Found: 754.05 ([M+H] + ), exact mass: 753.28.

[0250] Example 18: Synthesis of compound 364

[0251]

[0252] Compound 364 was prepared according to the procedure for synthesis of compound 1 in Example 1, except that starting material A8 was used to replace starting material A1; intermediate F8 was used to replace intermediate Fl. Elemental Analysis: C 49 H 31 N3O; Theory: C, 86.83; H, 4.61; N, 6.20; Test: C, 86.84; H, 4.62; N, 6.24. LC-MS: Found: 678.19 ([M+H] + ), exact mass: 677.25.

[0253] Example 19: Synthesis of compound 384

[0254]

[0255] Compound 384 was prepared according to the procedure described in Example 1 for the synthesis of compound 1, except that starting material A9 was used to replace starting material Al; and intermediate F10 was used to replace intermediate Fl. Elemental Analysis: C 49 H 31 N3O; Calc: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.86; H, 4.66; N, 6.12. LC-MS: Found: 678.31 ([M+H] + ), Exact Mass: 677.25.

[0256] Example 20: Synthesis of compound 433

[0257]

[0258] Compound 433 was prepared according to the procedure described in Example 1 for the synthesis of compound 1, except that intermediate M7 was used to replace starting material Al; and starting material F9 was used to replace intermediate Fl. Elemental Analysis: C 47 H 29 N3O; Calc: C, 86.61; H, 4.49; N, 6.45; Found: C, 86.48; H, 4.57; N, 6.47. LC-MS: Found: 652.35 ([M+H] + ), Exact Mass: 651.23.

[0259] Example 21: Synthesis of compound 442

[0260]

[0261] Compound 442 was prepared according to the procedure described in Example 1 for the synthesis of compound 1, except that intermediate M8 was used to replace starting material Al; and starting material Fl l was used to replace intermediate Fl. Elemental Analysis: C 47 H 29 N3O; Calc: C, 86.61; H, 4.49; N, 6.45; Found: C, 86.67; H, 4.46; N, 6.40. LC-MS: Found: 652.14 ([M+H] + ), Exact Mass: 651.23.

[0262] Example 22: Synthesis of compound 482

[0263]

[0264] Compound 482 was prepared according to the procedure described in Example 1 for the synthesis of compound 1, except intermediate M9 was used instead of starting material A1; and starting material F9 was used instead of intermediate F1. Elemental Analysis: C 43 H 27 N3O; Calc: C, 85.83; H, 4.52; N, 6.98; Found: C, 85.81; H, 4.55; N, 6.92. LC-MS: Found: 602.07 ([M+H] + ), Exact Mass: 601.22.

[0265] Example 23: Synthesis of compound 495

[0266]

[0267] Compound 495 was prepared according to the procedure described in Example 1 for the synthesis of compound 1, except intermediate M1 was used instead of starting material A1; and starting material F9 was used instead of intermediate F1. Elemental Analysis: C 43 H 27 N3O; Calc: C, 85.83; H, 4.52; N, 6.98; Found: C, 85.86; H, 4.50; N, 6.96. LC-MS: Found: 602.40 ([M+H] + ), Exact Mass: 601.22.

[0268] Example 24: Synthesis of compound 532

[0269]

[0270] Compound 532 was prepared according to the procedure described in Example 1 for the synthesis of compound 1, except starting material F9 was used instead of intermediate F1. Elemental Analysis: C 43 H 27 N3O; Calc: C, 85.83; H, 4.52; N, 6.98; Found: C, 85.79; H, 4.57; N, 6.91. LC-MS: Found: 602.18 ([M+H] + ), Exact Mass: 601.22.

[0271] Example 25: Synthesis of compound 558

[0272]

[0273] Compound 558 was prepared according to the procedure described in Example 1 for the synthesis of compound 1, except intermediate M10 was used instead of starting material A1; and starting material F11 was used instead of intermediate F1. Elemental Analysis: C 47 H 29N3O; Theory: C, 86.61; H, 4.49; N, 6.45; Found: C, 86.72; H, 4.41; N, 6.38. LC-MS: Obs. 652.46 ([M+H] + ), exact mass: 651.23.

[0274] Example 26: Synthesis of compound 600

[0275]

[0276] Compound 600 was prepared according to the procedure for the synthesis of compound 1 in Example 1, except that intermediate F12 was used in place of intermediate Fl. Elemental Analysis: C 49 H 31 N3S; Theory: C, 84.82; H, 4.50; N, 6.06; S, 4.62; Found: C, 84.81; H, 4.55; N, 6.03; S, 4.61. LC-MS: Obs. 694.11 ([M+H] + ), exact mass: 693.22.

[0277] Example 27: Synthesis of compound 5

[0278]

[0279] Compound 5 was prepared according to the procedure for the synthesis of compound 1 in Example 1, except that intermediate F13 was used in place of intermediate Fl. Elemental Analysis: C 49 H 31 N3O; Theory: C, 86.83; H, 4.61; N, 6.20; Found: C, 86.72; H, 4.70; N, 6.36. LC-MS: Obs. 678.11 ([M+H] + ), exact mass: 677.25.

[0280] Example 28: Synthesis of compound 140

[0281]

[0282] Compound 140 was prepared according to the procedure for the synthesis of compound 1 in Example 1, except that intermediate M12 was used in place of starting material Al; starting material F14 was used in place of intermediate Fl. Elemental Analysis: C 59 H 37 N3O; Theory: C, 88.14; H, 4.64; N, 5.23; Found: C, 88.12; H, 4.69; N, 5.21. LC-MS: Obs. 804.41 ([M+H] + ), exact mass: 803.29.

[0283] Example 29: Synthesis of compound 648

[0284]

[0285] Compound 648 was prepared according to the procedure described in Example 1 for the synthesis of compound 1, except that intermediate F14 was used in place of intermediate Fl. Elemental Analysis: C 55 H 35 N3O; Calc: C, 87.62; H, 4.68; N, 5.57; Found: C, 87.57; H, 4.60; N, 5.68. LC-MS: Found: 754.29 ([M+H] + ), Exact Mass: 753.28.

[0286] Example 30: Synthesis of compound 914

[0287]

[0288] Compound 914 was prepared according to the procedure described in Example 1 for the synthesis of compound 1, except that intermediate F15 was used in place of intermediate Fl. Elemental Analysis: C 61 H 39 N3O; Calc: C, 88.27; H, 4.74; N, 5.06; Found: C, 88.21; H, 4.78; N, 5.09. LC-MS: Found: 830.07 ([M+H] + ), Exact Mass: 829.31.

[0289] Example 31: Synthesis of compound 1372

[0290]

[0291] Compound 1372 was prepared according to the procedure described in Example 1 for the synthesis of compound 1, except that intermediate M14 was used in place of starting material Al; intermediate F14 was used in place of intermediate Fl. Elemental Analysis: C 54 H 34 N4O; Calc: C, 85.92; H, 4.54; N, 7.42; Found: C, 85.96; H, 4.56; N, 7.40. LC-MS: Found: 755.15 ([M+H] + ), Exact Mass: 754.27.

[0292] Example 32: Synthesis of compound 1400

[0293]

[0294] Compound 1400 was prepared according to the synthetic procedure of Compound 1 in Example 1 except that intermediate M15 was used instead of starting material A1. Elemental Analysis: C 61 H 39 N3O; Calc: C, 88.27; H, 4.74; N, 5.06; Found: C, 88.24 H, 4.70; N, 5.10. LC-MS: Found: 830.15 ([M+H] + ), Exact Mass: 829.31.

[0295] II. Device Preparation Examples

[0296] The application effects of the compounds synthesized according to the present application as hole blocking layer materials in devices are illustrated in detail below through Device Examples 1-70 and Device Comparative Examples 1-20. Device Examples 1-70 and Device Comparative Examples 1-20 have the same device preparation process, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also kept consistent, the only difference is that the hole blocking layer material in the devices is changed. The device layer structure is shown in Table 3, and the performance test results of each device are shown in Table 4.

[0297] The molecular structural formulas of the related materials are as follows:

[0298]

[0299]

[0300] The structures of 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, HB-15, HB-16, HB-17, HB-18, HB-19, HB-20 are shown above. The above materials are all commercially available.

[0301] Device Comparative Example 1

[0302] The specific preparation process is as follows:

[0303] As Figure 1As shown, the transparent substrate layer 1 is transparent glass, Ag (100 nm) is evaporated as the anode layer 2. On the anode layer 2, HT-1 and P-1 are evaporated as the hole injection layer 3 with a film thickness of 10 nm by using a vacuum evaporation device, the mass ratio of HT-1 and 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 above-mentioned electron blocking material is evaporated, the light-emitting layer 6 of the organic electroluminescent device is made, BH-1 is used as the host material, and BD-1 is used as the dopant material, the doping ratio of the dopant material is 3% by weight, and the film thickness of the light-emitting layer 6 is 20 nm. After the above-mentioned 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-mentioned hole blocking layer 7, ET-1 and LiQ are continuously evaporated, the mass ratio of ET-1 and LiQ is 1:1. The film thickness of the material evaporated in vacuum is 30 nm, which is the electron transport layer 8. On the electron transport layer 8, a LiF layer with a film thickness of 1 nm is made by using a vacuum evaporation device, which is the electron injection layer 9. On the electron injection layer 9, an Mg:Ag electrode layer with a film thickness of 16 nm is made by using a vacuum evaporation device, the mass ratio of Mg and Ag is 1:9, which is the cathode layer 10. On the cathode layer 10, CP-1 with a thickness of 65 nm is evaporated in vacuum as the light extraction layer 11.

[0304] Device Examples 1-70 and Device Comparative Examples 2-20 were prepared in a similar manner to Device Comparative Example 1, except that the hole blocking layer materials in Table 3 below were used.

[0305] Table 3

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313] III. Device Test Examples

[0314] The devices prepared in Example II were tested for current efficiency, CIEy and LT95 lifetime. The current efficiency and CIEy were tested using IVL (current-voltage-luminance) test system (Suzhou Fudashan Scientific Instrument Co., Ltd.), and the current density during the test was 10 mA / cm 2 . LT95 refers to the time for the luminance of the device to decay to 95% of the initial luminance, and the current density during the test was 30 mA / cm 2 ; the lifetime test system was EAS-62C type OLED device lifetime tester of Japan System Technique Co., Ltd.; and the test results are shown in Table 4 below.

[0315] Table 4

[0316]

[0317]

[0318]

[0319] As can be seen from the device test data results in Table 4 above, 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, HB-16, HB-17, HB-18, HB-19, HB-20 as the hole blocking layer material, the devices prepared using the compound of the present application as the hole blocking layer material have improved current efficiency and prolonged device lifetime, for example, the efficiency thereof is substantially 1.08 times or more than that of device comparative example 1 to device comparative example 16, and the lifetime thereof is 1.20 times or more than that of device comparative example 1 to device comparative example 16.

[0320] The comparative compounds HB-1 to HB-20 used in the device comparative examples have structural formula close to that of the compound of the present application, however, the compound of the present application as the hole blocking layer material has achieved better technical effect than the comparative compounds.

[0321] The above description is merely preferred embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A compound containing a nitrogenous heterobenzene and a naphthofurophtalene structure, characterized in that, The compound structure of the nitrogen-containing heterobenzene and naphthofurano-benzene class is shown in general formula (1): In general formula (1), Z1, Z2, Z3 each independently represents N; Ar1, Ar2 each independently represents substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 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 pyrimidyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl; Ar1, Ar2 can be the same or different; L represents the structure shown in general formula (2), general formula (3), general formula (4), general formula (5), general formula (6), general formula (7), general formula (8), general formula (9), general formula (10) or general formula (11); Ar3 represents the structure shown in general formula (12), general formula (13), general formula (14), general formula (15), general formula (16); In general formula (2) to general formula (16), the asterisk * represents the connection position; In general formula (4) to general formula (6), L1, L2, L3, L4, L5, L6 each independently represents a single bond, substituted or unsubstituted C3-C20 cycloalkylene, substituted or unsubstituted phenylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted pyridylene; L1, L2, L3, L4, L5, L6 can be the same or different; at least one of L1, L2 does not represent a single bond; at least one of L3, L4 does not represent a single bond; at least one of L5, L6 does not represent a single bond; In general formula (6) to general formula (11), R1, R2, R3, R4, R5, R6 each independently represents 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 pyrimidyl; When L represents general formula (5), L3 is a single bond, and L4 is unsubstituted phenylene, L3 can only be connected to Ar3 through the asterisk *; When L represents general formula (5), L4 is a single bond, and L3 is unsubstituted phenylene, L4 can only be connected to Ar3 through the asterisk *; When L represents general formula (8), R3 is unsubstituted phenyl, Ar3 does not represent general formula (13), general formula (15), general formula (16); When L represents general formula (9), R4 is unsubstituted phenyl, Ar3 does not represent general formula (13), general formula (15); In general formula (12) to general formula (16), X1 each occurrence, the same or different, each independently represents an oxygen atom or a sulfur atom; Ring A represents naphthyl; The substituents of the substituents that can be substituted in the above are hydrogen atom, deuterium atom, C1-C20 alkyl, C3-C20 cycloalkyl, cyano, phenyl, naphthyl, biphenyl, terphenyl, pyridyl, pyrimidyl, phenanthryl, dibenzofuranyl, dibenzothiophenyl, carbazolyl.

2. The compound according to claim 1, wherein the compound contains nitrogen-containing heterobenzene and naphthofuranacene structures, The nitrogen-containing heterobenzene and naphthofurano-benzene structure-containing compound is any one of general formula (2-1), general formula (2-2), general formula (2-3), general formula (2-4), general formula (2-5), general formula (2-6), general formula (2-7), general formula (2-8), general formula (2-9), general formula (2-10), general formula (2-11), general formula (2-12), general formula (2-13), general formula (2-14), general formula (2-15), general formula (2-16), general formula (2-17), general formula (2-18): In general formula (2-1) to general formula (2-18), the meanings of Ar1, Ar2, Ar3, R1, R2, R3, R4, R5, R6, L1, L2, L3, L4, L5, L6, Z1, Z2, Z3 are the same as defined in claim 1; The asterisk * indicates the connecting position of the phenylene group with R1, L5 and L6, respectively; Preferably, the nitrogen-containing heterobenzene and naphthofurano-benzene structure-containing compound is any one of general formula (2-19), general formula (2-20), general formula (2-21), general formula (2-22), general formula (2-23), general formula (2-24), general formula (2-25), general formula (2-26), general formula (2-27), general formula (2-28), general formula (2-29), general formula (2-30), general formula (2-31), general formula (2-32), general formula (2-33), general formula (2-34), general formula (2-35) to general formula (2-67). In general formula (2-19) to general formula (2-67), the meanings of Ar1, Ar2, Ar3, R1, Z1, Z2, Z3 are the same as defined in claim 1.

3. The compound according to claim 1, wherein the compound is a compound having a nitrogen-containing heterobenzene and naphthofuropbenzene structure, characterized in that, The nitrogen-containing heterobenzene and naphthofurano-benzene structure-containing compound is any one of general formula (3-1), general formula (3-2), general formula (3-3), general formula (3-4), general formula (3-5), general formula (3-6), general formula (3-7), general formula (3-8), general formula (3-9): In general formula (3-1) to general formula (3-9), the meanings of Ar1, Ar2, Ar3, R1, L5, L6, Z1, Z2, Z3 are the same as defined in claim 1.

4. The compound according to claim 1, wherein The nitrogen-containing heterobenzene and naphthofurano-benzene structure-containing compound is any one of general formula (4-1) to general formula (4-14): In general formula (4-1) to general formula (4-14), the meanings of Ar1, Ar2, Ar3, R1, Z1, Z2, Z3 are the same as defined in claim 1.

5. The compound according to claim 1, wherein The Ar3 represents any one of the following general formulae: In general formula 5a to general formula 5q, the meaning of X1 is the same as defined in claim 1.

6. A compound according to any one of claims 1 to 5, characterized in that each of L1, L2, L3, L4, L5, L6independently represents any one of each of L1, L2, L3, L4, L5, L6independently represents any one of Preferably, the is represented by: any of: Ar1, Ar2each independently represents a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, an n-hexyl group, any one of the following: R1, R2, R3, R4, R5, R6 each independently is any one of the intermediates; The substituents for the above substitutable groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-hexyl, Any of the foregoing.

7. The compound according to claim 1, wherein the compound is a compound having a nitrogen-containing heterobenzene and naphthofurophenyl structure, characterized in that, Any hydrogen atom in the compound represented by general formula (1) can be substituted by deuterium atom.

8. The compound according to claim 1, wherein The specific structure of the nitrogen-containing heterobenzene and naphthofurano-benzene structure-containing compound is any one of the following structures:

9. An organic electroluminescent device comprising a substrate, a first electrode and a second electrode, between which there is a multilayer organic thin film layer, characterized in that, The organic thin film layer contains the nitrogen-containing heterobenzene and naphthofuroparabenzene structure compound according to any one of claims 1 to 8. Preferably, 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 and naphthofuroparabenzene structure compound according to any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, wherein The electron transport region thin film layer comprises a hole blocking layer, and the hole blocking layer contains the nitrogen-containing heterobenzene and naphthofuroparabenzene structure compound according to any one of claims 1 to 8. Preferably, the hole transport region thin film layer comprises a hole injection layer, a hole transport layer and an electron blocking layer, the electron transport region thin film layer comprises a hole blocking layer, an electron transport layer and an electron injection layer, and the hole blocking layer contains the nitrogen-containing heterobenzene and naphthofuroparabenzene structure compound according to any one of claims 1 to 8.

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