WO2019206292A9 - Organic electroluminescent device and display comprising same - Google Patents

Abstract

Disclosed is an organic electroluminescent device, successively comprising, from bottom to top, a substrate, a first electrode, an organic functional material layer and a second electrode, wherein the organic functional material layer comprises a hole transport zone arranged over the first electrode, a luminous layer arranged over the hole transport zone and comprising host and guest materials, and an electron transport zone arranged over the luminous layer, wherein the hole transport zone successively comprises, from top to bottom, a hole injection layer, a hole transport layer and an electron blocking layer; the hole transport layer comprises first and second organic materials; and the HOMO energy level of the first organic material is within the range of -5.2 eV to -5.6 eV, and the HOMO energy level of the second organic material is within the range of -5.4 eV to -5.9 eV, where |HOMO_{first organic material}|< |HOMO_{second organic material}|.

Description

Organic electroluminescence device and display including the same

The present invention relates to the field of semiconductor technology, and more particularly, to an organic electroluminescent device and a display including the same.

Organic electroluminescence device technology can be used to manufacture both new display products and new lighting products. It is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has a wide application prospect. An organic electroluminescent device is a current device. When a voltage is applied to the electrodes at both ends and an electric field is applied to the positive and negative charges in the functional material film layer of the organic layer, the positive and negative charges are further recombined in the organic light emitting layer, resulting in Electroluminescence.

Organic electroluminescent devices generally have a multi-layer structure, and various auxiliary function layers other than the light-emitting layer also play a vital role in device performance. Reasonable device structures can effectively improve device performance. Electron injection layers, electron transport layers, hole blocking layers, light emitting layers, electron blocking layers, hole transport layers, and hole injection layers are widely used to improve device performance.

Current research on improving the performance of organic electroluminescent devices includes: reducing the driving voltage of the device, improving the light emitting efficiency of the device, and increasing the service life of the device. In order to achieve the continuous improvement of the performance of organic electroluminescent devices, not only innovations in the structure and manufacturing process of organic electroluminescent devices are required, but also continuous research and innovation of organic electroluminescent functional materials are needed to produce higher performance organic electroluminescent devices. Luminous functional materials.

Carriers (holes and electrons) in an organic electroluminescent device are injected into the device by two electrodes of the device under the driving of an electric field, respectively, and the composite light is emitted when the light emitting layer meets. Hole transport materials used in existing organic electroluminescent devices are known, such as

The HOMO energy level and the HOMO energy level of the electron blocking layer material are greatly different, and it is easy to form an accumulated charge at the material interface, which affects the life of the OLED device.

In addition, in organic electroluminescent devices, not all the energy levels of the materials can be well matched, and the potential barrier between them severely hinders the effective injection of holes. A reasonable energy level structure is conducive to the formation of stepped potential barriers in the layers of the device, which can reduce the potential barrier for hole injection and lower the driving voltage of the device, thereby improving the light emitting efficiency and lifetime of the device.

Therefore, there is an ongoing need to develop organic electroluminescent devices having excellent luminous efficiency and lifetime.

The present invention aims to provide an organic electroluminescence device having improved luminous efficiency, heat resistance and service life, and a display including the same.

An object of the present invention is achieved by providing an organic electroluminescence device, which is provided with a substrate, a first electrode, an organic functional material layer, and a second electrode in this order from bottom to top. The organic functional material layer includes:

A hole-transporting region located on the first electrode;

A light-emitting layer, which is located on the hole-transporting region and includes a host material and a guest material;

An electron-transporting region located above the light-emitting layer,

The hole transporting region includes a hole injection layer, a hole transporting layer, and an electron blocking layer in this order from bottom to top.

The hole transport layer includes first and second organic materials, wherein the HOMO energy level of the first organic material is -5.2eV to -5.6eV, preferably -5.3eV to -5.5eV, and more preferably -5.35eV to -5.5eV, and the HOMO energy level of the second organic material is -5.4eV to -5.9eV, preferably -5.4eV to -5.7eV, more preferably -5.48eV to -5.68eV, and the HOMO _{first organic material} | <| HOMO _{Second Organic Material} |.

In an organic electroluminescent device including a hole-transporting layer containing the first and second organic materials of the present invention, the HOMO of the first and second organic materials is defined, and this energy level matching causes the anode to block electrons The potential barrier between layers is reduced, which facilitates the injection of holes from the anode into the electron blocking layer, improves the efficiency of hole injection, reduces the driving voltage of the device, reduces the accumulated charge at the interface contact, and improves the device's Stability and service life; In addition, the higher glass transition temperature of the hole transport layer of the present invention improves the heat resistance of the device. And the organic film layer composed of two different materials can effectively improve the molecular arrangement and the interaction force between the molecules, making the film layer more stable, reducing the leakage current of the device and increasing the service life of the device.

Another object of the present invention is achieved by providing a display including the above-mentioned organic electroluminescent device.

FIG. 1 schematically illustrates a cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

FIG. 2 schematically illustrates an energy transfer mechanism diagram of an organic electroluminescent device according to an embodiment of the present invention.

3-7 schematically illustrate a combined structure of a light-emitting layer in an organic electroluminescent device including a hole-transporting layer of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings, but it is not intended to limit the present invention.

Any numerical range listed herein is meant to include all sub-ranges with the same numerical precision included in the listed range. For example, "1.0 to 10.0" means all subranges (and including 1.0 and 10.0) included between the listed minimum value 1.0 and the listed maximum value 10.0, that is, having a minimum value equal to or greater than 1.0 and equal to Or all subranges of the maximum value less than 10.0. Any maximum numerical limitation listed herein is intended to include all smaller numerical limitations incorporated herein, and any minimum numerical limitation listed herein is intended to include all larger numerical limitations incorporated herein. Accordingly, the applicant reserves the right to modify this specification, including the claims, to explicitly describe any sub-scope that falls within the scope explicitly described herein.

It should be understood that the abbreviation "HT" used herein means the organic material constituting the hole transport layer, for example, HT-I means the first organic material, and HT-II means the second organic material.

In the drawings, the size of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or intervening layers may also be present. In addition, it will also 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 may also be present. The same reference numerals indicate the same elements throughout.

Hereinafter, an organic electroluminescent device according to an embodiment will be described.

FIG. 1 schematically illustrates a cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention. Referring to FIG. 1, an organic electroluminescent device according to an embodiment of the present invention is provided with a substrate 1, a first electrode 2, a hole transport region A, a light emitting layer 6, an electron transport region B, and a second electrode 10 in this order from bottom to top. The hole transporting region A includes a hole injection layer 3, the hole transporting layer 4, and an electron blocking layer 5 in order from bottom to top, and the electron transporting region B includes a hole blocking layer 7, electron transporting layer 8, and electrons in order from bottom to top. Injected layer 9.

As the substrate of the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices can be selected. 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 strength, thermal stability, transparency, surface smoothness, and water resistance. Depending on the nature, the direction of use is different. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.

A first electrode is formed on the substrate, and the first electrode and the second electrode may face each other. The first electrode may be an anode. The first electrode may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the first electrode is a transmissive electrode, the first electrode may be formed using a transparent metal oxide, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), or indium tin zinc oxide ( ITZO) and so on. When the first electrode is a semi-transmissive electrode or a reflective electrode, the first electrode may include Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, or a metal mixture. The thickness of the first electrode layer depends on the material used, and is usually 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm.

The organic functional material layer provided between the first electrode and the second electrode includes a hole transport region, a light emitting layer, and an electron transport region in this order from bottom to top.

The hole transporting region may be disposed between the first electrode and the light emitting layer. The hole transport region may include, but is not limited to, a hole injection layer, a hole transport layer, and an electron blocking layer. For example, referring to FIG. 1, the hole transporting region may include a hole injection layer, a hole transporting layer, and an electron blocking layer disposed on the first electrode in this order from bottom to top.

Generally, organic materials having p-type properties, which are easily oxidized and electrochemically stable when they are oxidized, are mainly used as hole injection materials or hole transport materials. At the same time, organic materials with n-type properties, which are easily reduced and electrochemically stable when reduced, are used as electron injection materials or electron transport materials. As the light-emitting layer material, a material having both p-type and n-type properties is preferred, which is stable when it is oxidized and reduced, and also preferably has high luminescence for converting excitons into light when excitons are formed. Efficient materials.

The material of the hole injection layer is generally a material that preferably has a high work function, so that holes are easily injected into the organic material layer. In the present invention, the material of the hole injection layer contains at least one of the materials represented by the general formulae (17), (18) or (19):

Among them, in the general formula (17), F ₁ -F ₃ each independently represent a substituted or unsubstituted C _6-30 aryl group, a substituted or unsubstituted 3 to 30 membered heteroaryl group, and F ₁ -F ₃ Can be the same or different;

In the general formula (18) and the general formula (19), G _{1 to} G ₆ each independently represent hydrogen, nitrile, halogen, amido, alkoxy, ester, nitro, CR ₁₁ , substituted or unsubstituted C _6-30 aryl, 3- to 30-membered heteroaryl, wherein R ₁₁ is a linear or branched C _1-20 alkyl, provided that G ₁ -G _{6 are} not hydrogen at the same time;

Wherein in the case of a heteroaryl group, the heteroatom is selected from at least one of N, O, and S atoms.

In a preferred embodiment of the present invention, the material of the hole injection layer used is selected from one of the following (a) to (j):

The thickness of the hole injection layer of the present invention may be 5 to 100 nm, preferably 5 to 50 nm, and more preferably 5 to 20 nm.

The hole transporting layer of the present invention may be provided on the hole injection layer. The hole transport layer material includes a first organic material and a second organic material, wherein a ratio of the first organic material to the second organic material is 1:99 to 99: 1, preferably 10:90 to 90:10, more It is preferably 30:70 to 70:30, based on mass. In addition, the HOMO energy level of the first organic material is -5.2eV to -5.6eV, preferably -5.3eV to -5.5eV, more preferably -5.35eV to -5.5eV, and the HOMO energy of the second organic material is The order is -5.4 eV to -5.9 eV, preferably -5.4 eV to -5.7 eV, more preferably -5.48 eV to -5.68 eV, and | HOMO _{first organic material} | <| HOMO _{second organic material} |.

FIG. 2 schematically illustrates an energy transfer mechanism of an organic electroluminescent device according to an embodiment of the present invention, where a represents a hole injection layer, b represents a hole transport layer, c represents an electron blocking layer, and d represents a light emitting layer. , E represents the host of the light-emitting layer, and f represents the electron transport layer.

In one embodiment, the absolute value of the difference between the HOMO energy levels of the second organic material and the electron blocking material is ≦ 0.4ev. The smaller energy barrier between the hole-transporting material and the electron-blocking layer material allows holes to be easily injected into the electron-blocking layer via the hole-transporting layer, and then transported into the light-emitting layer.

In a preferred embodiment of the present invention, the first and second organic materials of the present invention are each independently selected from one of the general formula (1), the general formula (2), and the general formula (3):

Among them, in the general formula (1)

X and X ₁ are each independently selected from a single bond, a carbon atom, N- (R ₅ ), a sulfur atom, an oxygen atom, a vinylidene group, a linear or branched C _1-20 alkyl-substituted alkylene group, One of a linear or branched C _1-20 alkyl-substituted silylene group and a C _6-20 aryl-substituted alkylene group;

If R ₅ is present, it may be the same or differently selected from a hydrogen atom, a tritium atom, a deuterium atom, a tritium atom, a fluorine atom, a phosphoric acid or a salt thereof, a linear or branched C _1-20 alkyl-substituted alkyl group , Linear or branched C _1-20 alkyl-substituted silylene, aryl having 5 to 30 carbon atoms, 5 to 30 carbon atoms, and at least one heteroatom selected from N, O, and S Heteroaryl, wherein in the case of the latter two, the group may be optionally substituted by a linear or branched C _1-20 alkyl, C _6-20 aryl, C _5-20 heteroaryl ;

Z represents a nitrogen atom or CR ₆ , wherein R ₆ may be the same or differently selected from a hydrogen atom, a tritium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a linear or branched C _{1- 20} alkyl substituted alkyl, straight or branched C _1-20 alkyl substituted silylene, aryl having 5 to 30 carbon atoms, 5 to 30 carbon atoms, and at least one selected from N A heteroaryl group of O, S and O, wherein in the case of the latter two, the group may be optionally a linear or branched C _1-20 alkyl group, C _6-20 aryl group, C _5-20 heteroaryl substitutions in which two or more R ₆ groups may be connected to each other and may form a ring structure;

Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent a single bond, a linear or branched C _1-20 alkylene group, an arylene group having 5 to 30 carbon atoms, a linear or branched chain C _1-20 alkyl-substituted silylene, heteroarylene having 5 to 30 carbon atoms and at least one heteroatom selected from N, O, and S, wherein in the case of the latter two, the group The group may be optionally substituted with a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, and a C _5-20 heteroaryl group, wherein the Ar1 and Ar2 groups may also be connected to form a ring;

m, n, p, q, s, and t are equal to 0 or 1; and m + n + p + q≥1 and m + n + s + t≥1;

R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a structure represented by the general formula (4), the general formula (5) or the general formula (6), provided that R ₁ , R ₂ , R ₃ And R _{4 are} not hydrogen atoms at the same time;

Among them, in the general formula (4) and the general formula (5):

X ₂ and X ₃ each independently represent a single bond, an oxygen atom, a sulfur atom, a vinylidene group, a linear or branched C _1-20 alkyl-substituted alkylene group, a linear or branched C _1-20 Alkyl substituted silyl, C _6-20 aryl substituted alkylene, C _1-20 alkyl substituted imine, C _6-20 aryl substituted imine, C _5-20 heteroaryl One of the substituted imines;

Y ₁ may identically or differently represent an N atom or CR, wherein R may identically or differently represent a hydrogen atom, a tritium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a linear or branched C _1-20 alkyl substituted alkyl, linear or branched C _1-20 alkyl substituted silyl, aryl having 5 to 30 carbon atoms, 5 to 30 carbon atoms, and at least one selected A heteroaryl group from a heteroatom of N, O, and S, wherein in the case of the latter two, the group may be optionally a linear or branched C _1-20 alkyl, C _6-20 aryl , C _5-20 heteroaryl substitution; wherein two or more R groups can be connected to each other and can form a ring structure;

R ₆ and R ₇ each independently represent a hydrogen atom, a tritium atom, a deuterium atom, a tritium atom, a fluorine atom, a phosphoric acid or a salt thereof, a linear or branched C _1-20 alkyl-substituted alkyl group, a straight chain or a branched group C _1-20 alkyl substituted silyl groups of the chain, aryl groups having 5 to 30 carbon atoms, heteroaryl groups having 5 to 30 carbon atoms and at least one heteroatom selected from N, O and S, A structure represented by formula (7) or formula (6); wherein in the case of an aryl group and a heteroaryl group, the group may be optionally a linear or branched C _1-20 alkyl group, C _{6- 20} aryl, C _5-20 heteroaryl substitution;

Among them, in the general formula (7):

Y ₂ may identically or differently represent an N atom or CR ₁₀ , wherein R ₁₀ may identically or differently represent a hydrogen atom, a tritium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a straight chain or Branched C _1-20 alkyl substituted alkyl, straight or branched C _1-20 alkyl substituted silyl, aryl having 5 to 30 carbon atoms, having 5 to 30 carbon atoms, and at least A heteroaryl heteroaryl group selected from N, O, and S, wherein in the case of the latter two, the group may be optionally a linear or branched C _1-20 alkyl group, C _6-20 Aryl, C _5-20 heteroaryl substitution;

X ₄ and X ₅ each independently represent a single bond, an oxygen atom, a sulfur atom, a vinylidene group, a linear or branched C _1-20 alkyl-substituted alkylene group, a linear or branched C _1-20 Alkyl substituted silyl, C _6-20 aryl substituted alkylene, C _1-20 alkyl substituted imine, C _6-20 aryl substituted imine, C _5-20 heteroaryl One of the substituted imines;

The general formula (7) is connected to the general formula (4) or the general formula (5) by a ring method, and * is indicated as a connection site. When connected, only two adjacent sites can be taken. When formula (4) or formula (5) is cyclically linked, the connection site Y _{1 is} represented as a carbon atom;

In the general formula (6):

R ₈ and R ₉ each independently represent an aryl group having 5 to 30 carbon atoms, a heteroaryl group having 5 to 30 carbon atoms, and at least one hetero atom selected from N, O, and S, and the group may be Optionally substituted by a linear or branched C _1-20 alkyl group, C _6-20 aryl group, C _5-20 heteroaryl group; R ₈ and R ₉ may also be linked to form a ring;

In the general formula (2):

L ₁ , L ₂ , and L ₃ each independently represent a single bond, an arylene group having 5 to 30 carbon atoms, a sub-heterocycle having 5 to 30 carbon atoms, and at least one hetero atom selected from N, O, and S Aryl, where in the case of the latter two, the group may be optionally substituted with a linear or branched C _1-20 alkyl group, C _6-20 aryl group, C _5-20 heteroaryl group; L _1. L ₂ and L ₃ can be connected to each other and form a ring structure;

Ar ₅ , Ar ₆ , and Ar ₇ each independently represent an arylene group having 5 to 30 carbon atoms, a heteroarylene group having 5 to 30 carbon atoms, and at least one hetero atom selected from N, O, and S, Imine having 5 to 30 carbon atoms, said group may be optionally substituted by straight or branched C _1-20 alkyl, C _6-20 aryl, C _5-20 heteroaryl; Ar ₅ , Ar ₆ , Ar ₇ can be connected to each other and can form a ring structure;

Ar ₅ , Ar ₆ , and Ar _{7 may} each be independently represented as one of the general formula (4), the general formula (5), and the general formula (6), wherein the groups X ₂ and X ₃ on the general formula , Y ₁ , R ₆ , R ₇ and * have the meanings as described above;

In the general formula (3):

D ₁ , D ₂ , and D ₃ each independently represent a single bond, an arylene group having 5 to 30 carbon atoms, a sub-heterocycle having 5 to 30 carbon atoms, and at least one hetero atom selected from N, O, and S Aryl, where in the case of the latter two, the group may be optionally substituted with a linear or branched C _1-20 alkyl group, C _6-20 aryl group, C _5-20 heteroaryl group; L _1. L ₂ and L ₃ can be connected to each other and form a ring structure;

Ar ₈ , Ar ₉ , and Ar ₁₀ each independently represent an arylene group having 5 to 30 carbon atoms, a heteroarylene group having 5 to 30 carbon atoms, and at least one hetero atom selected from N, O, and S, Imine having 5 to 30 carbon atoms, said group may be optionally substituted by straight or branched C _1-20 alkyl, C _6-20 aryl, C _5-20 heteroaryl; Ar ₈ , Ar ₉ , Ar ₁₀ can be connected to each other and can form a ring structure;

At least one of Ar ₈ , Ar ₉ , and Ar ₁₀ is one of the general formula (4), the general formula (5), and the general formula (6); wherein the groups on the general formula are X ₂ , X ₃ , and Y ₁ , R ₆ , R ₇ and * each have the meanings described above.

In a preferred embodiment of the present invention, the general formula (2) is represented as one of the general formula (9) to the general formula (12):

among them

Ar ₅ to Ar ₇ represent an arylene group having 5 to 30 carbon atoms, a heteroarylene group having 5 to 30 carbon atoms and at least one hetero atom selected from N, O, and S, and 5 to 30 carbon atoms An imino group, the group may be optionally substituted with a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, and a C _5-20 heteroaryl group;

And L ₁ -L ₃ , R ₆ -R ₉ , Y ₁ and X ₂ -X ₃ all have the meanings described above.

In a preferred embodiment of the present invention, the general formula (3) is represented as one of the general formula (13) to the general formula (16):

among them

Ar ₈ and Ar ₁₀ represent an arylene group having 5 to 30 carbon atoms, a heteroarylene group having 5 to 30 carbon atoms and at least one hetero atom selected from N, O, and S, and 5 to 30 carbon atoms An imino group, the group may be optionally substituted with a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; and

And D ₁ -D ₃ , R ₆ -R ₉ , Y ₁ and X ₂ -X ₃ all have the meanings described above.

In a preferred embodiment of the present invention, the first organic material is selected from one of the following compounds:

In a preferred embodiment of the present invention, the second organic material is selected from one of the following compounds:

The hole transport layer material of the present invention has a hole mobility of 1 × 10 ^-5 to 1 × 10 ^-2 cm ² / (V · s), preferably 1 × 10 ^-4 to 1 × 10 ^-2 cm ² / (V · s) and more preferably 1 × 10 ^-4 to 1 × 10 ^-3 cm ² / (V · s).

The glass transition temperature of the hole transport layer material of the present invention is ≧ 120 ° C., preferably ≧ 130 ° C. and more preferably ≧ 140 ° C.

The thickness of the hole transport layer material of the present invention may be 1-200 nm, and preferably 10-100 nm.

The electron blocking layer may be disposed on the hole transport layer; the material of the electron blocking layer is preferably a material having a high T1 and a low LUMO, which can block electron loss and energy loss. For example, the electron blocking layer used in the present invention may be

The thickness of the electron blocking layer of the present invention may be 5 to 200 nm, preferably 10 to 150 nm, and more preferably 20 to 100 nm.

The light emitting layer may be disposed on the hole transport region. The material of the light emitting layer is a material capable of emitting visible light by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the received holes and electrons. Specific examples thereof include metal complexes of hydroxyquinoline derivatives, various metal complexes, anthracene derivatives, bisstyrene benzene derivatives, fluorene derivatives, oxazole derivatives, and poly-p-styrene derivatives, etc. , But not limited to this. In addition, the light emitting layer may include a host material and a guest material. As the host material and the guest material of the light-emitting layer of the organic electroluminescence device of the present invention, a light-emitting layer material for an organic electroluminescence device known in the prior art can be used. Benzimidazole derivatives, polydialkylfluorene derivatives, or 4,4′-bis (9-carbazolyl) biphenyl (CBP); the guest material may be, for example, quinacridone, coumarin, red fluorescent Alkenes, pyrenes and their derivatives, benzopyran derivatives, rhodamine derivatives or aminostyrene derivatives. In a preferred embodiment of the present invention, the light-emitting layer host material used is selected from a combination of one or more of the following EMH-1 to EMH-22:

In addition, in order to improve the fluorescent or phosphorescent characteristics, the light emitting material may further include a phosphorescent or fluorescent material. Specific examples of the phosphorescent material include phosphorescent materials of metal complexes such as iridium, platinum, and the like. For example, green phosphorescent materials such as Ir (ppy) ₃ [fac-tri (2-phenylpyridine) iridium], blue phosphorescent materials such as FIrpic and FIr6, and red phosphorescent materials such as Btp2Ir (acac) can be used. For the fluorescent material, those commonly used in the art may be used. In a preferred embodiment of the present invention, the light-emitting layer guest material used is selected from one of the following EMD-1 to EMD-23:

In the light-emitting layer of the present invention, the ratio of the host material to the guest material used is 99: 1-70: 30, preferably 99: 1-85: 15 and more preferably 97: 3-87: 13, based on mass meter.

In addition, in order to obtain a high-efficiency organic electroluminescent device, in addition to the fluorescent or phosphorescent host and guest materials used above, the light-emitting layer may use another guest material, or a variety of guest materials. The guest material may be simple Fluorescent materials, delayed fluorescence (TADF) materials, or phosphorescent materials, or a combination of different fluorescent materials, TADF materials, and phosphorescence. The light-emitting layer can be a single light-emitting layer material, or it can be a composite light-emitting layer superimposed horizontally or vertically. material. The light-emitting layers constituting the above-mentioned organic electroluminescent device are exemplified by the following various structures:

(1) a single organic light emitting layer material;

(2) any combination of the blue organic light-emitting layer material and the green, yellow, or red light-emitting layer material, regardless of the order, as shown in FIG. 3;

(3) Any combination of blue organic light-emitting layer material and green, yellow, or red light-emitting layer material, regardless of the order, as shown in FIG. 4;

(4) The blue organic light emitting layer material, the green organic light emitting layer material, and the red organic light emitting layer material are arranged laterally, as shown in FIG. 5;

(5) a combination of a blue organic light-emitting layer material and a green, yellow, or red light-emitting layer material, and charge transfer through the connection layer to form a two-layer device structure, as shown in FIG. 6;

(6) Any combination of the blue organic light-emitting layer material and the green, yellow, or red light-emitting layer material, and charge transfer through the connection layer to form a three-layer device structure, as shown in FIG. 7.

Preferably, the organic light emitting functional layer includes a light emitting layer including one or a combination of at least two of blue, green, red, and yellow organic light emitting layer materials.

As described above, in FIGS. 3 to 5, G represents light, 6 represents a light emitting layer, and EM1, EM2, and EM3 represent different materials of the light emitting layer.

In FIGS. 6 and 7, 6 represents a light-emitting layer, 300 represents an organic light-emitting functional layer, and 610, 620, and 630 represent connection layers.

In order to adjust the effective combination of carrier charges in the light-emitting layer, the film thickness of the light-emitting layer 6 constituting the OLED light-emitting body described above can be arbitrarily adjusted as required, or light-emitting layers that cannot be colored can be alternately superimposed and combined as required, and light can be emitted adjacently. In the organic layer of the layer, a charge blocking layer for different functional purposes is added. Preferably, the thickness of the light emitting layer of the present invention may be 5-60 nm, preferably 10-50 nm, and more preferably 20-45 nm.

In the present invention, the electron transporting region includes a hole blocking layer, an electron transporting layer, and an electron injection layer disposed on the light emitting layer in order from bottom to top, but is not limited thereto.

The hole blocking layer is a layer that blocks holes injected from the anode from passing through the light emitting layer and entering the cathode, thereby extending the life of the device and improving the efficiency of the device. The hole blocking layer of the present invention may be provided above the light emitting layer. As the material of the hole blocking layer of the organic electroluminescent device of the present invention, a compound having a hole blocking effect known in the prior art can be used, for example, phenanthroline derivatives such as bath copper spirit (called BCP), aluminum (III) metal complexes of hydroxyquinoline derivatives such as bis (2-methyl-8-quinoline) -4-phenylphenate (BAlq), various rare earth complexes, oxazole derivatives, Triazole derivatives, triazine derivatives, 9,9 ′-(5- (6-([1,1′-biphenyl] -4-yl) -2-phenylpyrimidin-4-yl) -1, Pyrimidine derivatives such as 3-phenylene) bis (9H-carbazole) (CAS number: 1345338-69-3) and the like. The thickness of the hole blocking layer of the present invention may be 2-200 nm, preferably 5-150 nm, and more preferably 10-100 nm.

The electron transport layer may be disposed on the light emitting layer or, if present, 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. Materials having high electron mobility are preferred. As the electron-transporting layer of the present invention, the organic electroluminescent device can be used in the prior art known electron transport layer material for organic electroluminescent devices, for example, Alq _3, BAlq as quinolinol derivative represented by the Metal complexes, various metal complexes, triazole derivatives, 2,4-bis (9,9-dimethyl-9H-fluoren-2-yl) -6- (naphthalene-2-yl) Triazine derivatives such as -1,3,5-triazine (CAS number: 1459162-51-6), 2- (4- (9,10-bis (naphthalene-2-yl) anthracen-2-yl) benzene ) -1-phenyl-1H-benzo [d] imidazole (CAS number: 561064-11-7, commonly known as LG201) and other imidazole derivatives, triazine derivatives, oxadiazole derivatives, and thiadiazole derivatives , Carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silicon-based compound derivatives, and the like. The thickness of the electron transport layer of the present invention may be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm.

The electron injection layer may be disposed on the electron transport layer. The material of the electron injection layer is generally a material which preferably has a low work function, so that electrons are easily injected into the organic functional material layer. As the material of the electron injecting layer of the organic electroluminescent device of the present invention, an electron injecting layer material for an organic electroluminescent device known in the prior art can be used, for example, lithium; a lithium salt, such as lithium 8-hydroxyquinoline, Lithium fluoride, lithium carbonate, or lithium azide; or cesium salt, cesium fluoride, cesium carbonate, or cesium azide. The thickness of the electron injection layer of the present invention may be 0.1-5 nm, preferably 0.5-3 nm, and more preferably 0.8-1.5 nm.

The second electrode may be disposed above the electron transport region. The second electrode may be a cathode. The second electrode EL2 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the second electrode is a transmissive electrode, the second electrode may include, for example, Li, Yb, Ca, LiF / Ca, LiF / Al, Al, Mg, BaF, Ba, Ag, or a compound or mixture thereof; when the second electrode is a half electrode For a transmissive electrode or a reflective electrode, the second electrode may include Ag, Mg, Yb, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or Its compounds or mixtures.

Depending on the materials used, the organic electroluminescent device of the present invention may be a top emission type, a bottom emission type, or a double-sided emission type.

In the case where the organic electroluminescent device is a top emission type, the first electrode may be a reflective electrode, and the second electrode may be a transmissive electrode or a semi-transmissive electrode. In the case where the organic electroluminescent device is a bottom emission type, the first electrode may be a transmissive electrode or a semi-transmissive electrode, and the second electrode may be a reflective electrode.

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

In the process of preparing an organic electroluminescent device, for example, the organic electroluminescent device of the present invention can be prepared by sequentially laminating a first electrode, an organic functional material layer, and a second electrode on a substrate. In this regard, a physical vapor deposition method such as a sputtering method or an electron beam vapor method, or a vacuum evaporation method may be used, but is not limited thereto. And, the above-mentioned compound can be used to form an organic functional material layer by, for example, a vacuum deposition method, a vacuum evaporation method, or a solution coating method. In this regard, the solution coating method means, but is not limited to, a spin coating method, a dip coating method, a jet printing method, a screen printing method, a spray method, and a roll coating method. Vacuum evaporation means heating and plating a material onto a substrate in a vacuum environment. In the present invention, the respective layers are preferably formed using a vacuum evaporation method.

In addition, it should be noted that the materials for forming each layer according to the present invention may be formed into a single layer and used as a single layer, or may be mixed with other materials and formed into a film and used as a single layer. A layered structure between the layers of the film, a layered structure between the layers formed into the film after mixing, or a layered structure of the layer formed into the film alone and the layer formed into the film after mixing.

In another aspect of the present invention, it relates to a display including one or more organic electroluminescence devices of the present invention, and in the case of including a plurality of devices, the devices are combined horizontally or vertically in combination.

In a preferred embodiment, the display may include a device each having an organic light emitting material layer of three colors of blue, green, and red, and the device has a hole transport layer having the same film thickness and material. In another preferred embodiment, the display consists of a device that can include organic light emitting material layers each having three colors of blue, green, and red, and the devices have hole transport layers of the same material but different film thicknesses.

In another preferred embodiment, the display may include a device each having an organic light emitting material layer of three colors of blue, green, and red, and the device has hole transport with the same film thickness but at least two combinations of materials Floor. In yet another preferred embodiment, the display may include devices each having an organic light-emitting material layer of three colors of blue, green, and red, and the devices have blanks with different film thicknesses and at least two combinations of materials. Cavity transmission layer.

It should be noted that exemplary embodiments have been disclosed herein, and although specific terms are used therein, these terms are used and interpreted only as general and descriptive meanings, and not for limiting purposes. Unless stated otherwise, features, characteristics, and / or elements described in connection with a particular embodiment may be used alone or in combination with features, characteristics, and / or elements described in connection with other embodiments.

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

Examples

The detection methods used in this article are as follows:

Glass transition temperature Tg: measured by differential scanning calorimetry (DSC, DSC204F1 Differential Scanning Calorimeter, Germany), heating rate 10 ° C / min;

HOMO level: There are many methods or instrumental methods for testing the HOMO level of organic optoelectronic materials, including CV (cyclic voltammetry), UPS (ultraviolet photoelectron spectroscopy), and AC series equipment manufactured by Riken Instrument Co., Ltd. ( Atmospheric photoelectron spectroscopy), IPS series equipment (vacuum photoelectron spectroscopy) produced by Xindi Tianyi Co., Ltd., in addition to the above methods, can also determine the level of HOMO energy level by Gaussian calculation and combined with semi-empirical judgment, and accurately measure The HOMO energy level is very important for studying the structural matching of OLED devices. Among all the above HOMO energy level determination methods, the CV method is affected by solvents, and the data accuracy and reproducibility are relatively poor. Others include the UPS method, AC method, and IPS method. Fundamentally, they are measurements of ultraviolet photoelectron spectroscopy Principle, in which UPS measurement not only requires ultra-high vacuum, the equipment value is expensive, but because of the person who measures, and the instrument settings, the data analysis results vary greatly. In principle, the AC method requires the sample to be placed in an aerobic dry air environment. The oxygen element has a certain effect on the sample. The data reproducibility and consistency are relatively poor. The IPS method measures the HOMO energy level. In a vacuum environment, UV monochromatic light is directly applied to the surface of the sample, and the HOMO energy level is determined by measuring the photoelectron current, which is a direct measurement. Based on the above analysis and practice, the inventors believe that the IPS measurement method has the highest reproducibility, consistency, and accuracy when measuring the HOMO energy level of OLED materials. The HOMO energy levels of all materials involved in the present invention are IPS measurement methods. The specific measurement method is as follows:

Using vacuum evaporation equipment, under the pressure of 1.0E-5Pa, the evaporation rate is controlled to

The material is vapor-deposited on the ITO substrate with a film thickness of 60-80 nm, and then the HOMO energy level of the sample film is measured by using an IPS3 measurement device, and the measurement environment is a vacuum environment below 10-2Pa;

Eg energy level: Based on the ultraviolet spectrophotometry (UV absorption) baseline of the single film of the material and the rising side of the first absorption peak, a tangent line is drawn, and the value of the tangent line and the baseline crossing point are used to calculate.

LUMO energy level: calculated based on the difference between the aforementioned HOMO energy level and Eg energy level.

Work function of electrode material: Tested in atmospheric environment using surface work function tester developed by Shanghai University.

Hole mobility: The material was made into a single charge device and measured by the SCLC method.

Preparation of hole transport layer material

I. The first organic material used in the preparation:

Preparation of compound HT1-1

Under a nitrogen atmosphere, add 500 mol of raw material I-1, 0.03 mol of raw material II-1, 0.03 mol of sodium tert-butoxide, 5 × 10 ^-5 mol Pd ₂ (dba) ₃ and 5 × 10 ^-5 into a 500 ml three-necked flask. mol of tri-tert-butyl phosphorus, then 150 ml of toluene was added to dissolve it, heated to 100 ° C, refluxed for 24 hours, and the reaction was observed by TLC until the reaction was completed. It was left to cool to room temperature, filtered, and the filtrate was rotary distilled to no fractions. The obtained substance was purified through a silica gel column (petroleum ether as eluent) to obtain the target product, with a purity of 99.6% and a yield of 70.4%.

Elemental analysis structure (Molecular formula C ₆₀ H ₄₂ N ₄ ): Theoretical value: C, 87.99; H, 5.17; N, 6.84; Test value: C, 87.97; H, 5.18; N, 6.85.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 818.34, and the measured value is 818.62.

Preparation of compound HTI-9

It is prepared according to the synthesis method of compound HTI-1, the difference is that the raw material II-2 is used instead of the raw material II-1. The purity of the obtained target product is 99.9% and the yield is 71.7%.

Elemental analysis structure (molecular formula C ₅₄ H ₄₄ N ₂ ): Theoretical value: C, 89.96; H, 6.15; N, 3.89; Test value: C, 89.97; H, 6.13; N, 3.90.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 720.35, and the measured value is 720.65.

Preparation of compound HTI-28

Under a nitrogen atmosphere, 0.01 mol of raw material I-2 and 0.03 mol of raw material II-3 were added to a 500 ml three-necked flask, dissolved in a mixed solvent (90 ml of toluene, 45 ml of ethanol), and then 0.04 mol of Na ₂ CO ₃ aqueous solution (2M) was added. The mixture was stirred for 1 hour, and then 1 × 10 ^-4 mol Pd (PPh ₃ ) _{4 was added} , and heated under reflux for 15 hours. The reaction was observed by TLC until the reaction was complete. It was left to cool, filtered, and the filtrate was rotary distilled to no fractions. The obtained substance was purified through a silica gel column (petroleum ether as eluent) to obtain the target product, with a purity of 99.6% and a yield of 72.2%.

Elemental analysis structure (molecular formula C ₄₂ H ₂₅ NO ₃ ): Theoretical value: C, 85.26; H, 4.26; N, 2.37; Test value: C, 85.24; H, 4.24; N, 2.39.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 591.18, and the measured value is 591.35.

Preparation of compound HTI-41

Prepared according to the synthetic method of compound HTI-1, the difference is that raw material III-4 is used instead of raw material II-1, the purity of the obtained target product is 99.5%, and the yield is 68.8%.

Elemental analysis structure (Molecular formula C ₇₂ H ₅₄ N ₄ ): Theoretical value: C, 88.67; H, 5.58; N, 5.74; Test value: C, 88.64; H, 5.60; N, 5.73.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 974.43, and the measured value is 974.61.

Preparation of compound HTI-52

It is prepared according to the synthetic method of compound HTI-1, the difference is that raw material III-5 is used instead of raw material II-1. The purity of the obtained target product is 99.8%, and the yield is 72.9%.

Elemental analysis structure (Molecular formula C ₅₆ H ₄₀ N ₂ ): Theoretical value: C, 90.78; H, 5.44; N, 3.78; Test value: C, 90.76; H, 5.45; N, 3.79.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 740.32, and the measured value is 740.62.

Preparation of compound HTI-57

Under a nitrogen atmosphere, add 0.015 mol of raw material I-3, 0.01 mol of raw material II-6, 0.03 mol of sodium tert-butoxide, 5 × 10 ^-5 mol Pd ₂ (dba) ₃ and 5 × 10 ^-5 into a 500 ml three-necked flask. mol of tri-tert-butyl phosphorus, then 150 ml of toluene was added to dissolve it, heated to 100 ° C, refluxed for 24 hours, and the reaction was observed by TLC until the reaction was completed. It was left to cool to room temperature, filtered, and the filtrate was rotary distilled to no fractions. The obtained substance was purified through a silica gel column (petroleum ether as eluent) to obtain the target product, with a purity of 99.7% and a yield of 77.5%.

Elemental analysis structure (Molecular formula C ₆₀ H ₄₄ N ₂ ): Theoretical value: C, 90.87; H, 5.59; N, 3.53; Test value: C, 90.86; H, 5.58; N, 3.56.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 792.35, and the measured value is 792.67.

Preparation of compound HTI-63

Prepared according to the synthetic method of compound HTI-57, the difference is that raw material I-4 is used instead of raw material I-3, and raw material II-7 is used instead of raw material II-6. The purity of the obtained target product is 99.9% and the yield is 73.9%.

Elemental analysis structure (molecular formula C ₅₂ H ₃₇ N): Theoretical value: C, 92.41; H, 5.52; N, 2.07; Test value: C, 92.42; H, 5.50; N, 2.08.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 675.29, and the measured value is 675.58.

Preparation of compound HTI-72

Prepared according to the synthetic method of compound HTI-57, the difference is that raw material I-5 is used instead of raw material I-3, and raw material II-7 is used instead of raw material II-6. The purity of the obtained target product is 99.6%, and the yield is 72.6%.

Elemental analysis structure (molecular formula C ₅₄ H ₃₉ N): Theoretical value: C, 92.40; H, 5.60; N, 2.00; Test value: C, 92.38; H, 5.61; N, 2.01.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 701.31, and the measured value is 701.55.

Preparation of compound HTI-86

Prepared according to the synthetic method of compound HTI-57, the difference is that the raw material I-6 is used instead of the raw material I-3, and the raw material II-8 is used instead of the raw material II-6. The purity of the obtained target product is 99.9% and the yield is 75.4%.

Elemental analysis structure (molecular formula C ₅₂ H ₃₉ N): Theoretical value: C, 92.13; H, 5.80; N, 2.07; Test value: C, 92.11; H, 5.82; N, 2.07.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 677.31, and the measured value is 677.51.

Preparation of compound HTI-101

Prepared according to the synthetic method of compound HTI-57, the difference is that raw material I-7 is used instead of raw material I-3, and raw material II-9 is used instead of raw material II-6. The purity of the obtained target product is 99.7%, and the yield is 74.3%.

Elemental analysis structure (Molecular formula C ₅₅ H ₄₁ NO): Theoretical value: C, 90.25; H, 5.65; N, 1.91; Test value: C, 90.24; H, 5.64; N, 1.90.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 731.32, and the measured value is 731.66.

Preparation of compound HTI-114

Prepared according to the synthetic method of compound HTI-57, the difference is that raw material I-8 is used instead of raw material I-3, and raw material II-7 is used instead of raw material II-6. The purity of the obtained target product is 99.6%, and the yield is 77.6%.

Elemental analysis structure (molecular formula C ₅₅ H ₄₃ N): Theoretical value: C, 92.01; H, 6.04; N, 1.95; Test value: C, 92.02; H, 6.02; N, 1.96.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 717.34, and the measured value is 717.54.

Preparation of compound HTI-124

Prepared according to the synthetic method of compound HTI-57, the difference is that raw material I-9 is used instead of raw material I-3, and raw material II-9 is used instead of raw material II-6. The purity of the obtained target product is 99.7%, and the yield is 78.8%.

Elemental analysis structure (molecular formula C ₅₄ H ₄₁ NO): Theoretical value: C, 90.09; H, 5.74; N, 1.95; Test value: C, 90.07; H, 5.76; N, 1.97.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 719.32, and the measured value is 719.53.

Preparation of compound HTI-134

Prepared according to the synthetic method of compound HTI-57, the difference is that the raw material I-10 is used instead of the raw material I-3, and the raw material II-9 is used instead of the raw material II-6. The purity of the obtained target product is 99.6%, and the yield is 75.1%.

Elemental analysis structure (Molecular formula C ₆₃ H ₅₇ N): Theoretical value: C, 91.37; H, 6.94; N, 1.69; Test value: C, 91.35; H, 6.96; N, 1.68.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 827.45, and the measured value is 827.77.

Preparation of compound HTI-144

Prepared according to the synthetic method of compound HTI-57, the difference is that raw material I-11 is used instead of raw material I-3, and raw material II-7 is used instead of raw material II-6. The purity of the obtained target product is 99.8%, and the yield is 74.9%.

Elemental analysis structure (Molecular formula C ₅₈ H ₄₇ N): Theoretical value: C, 91.90; H, 6.25; N, 1.85; Test value: C, 91.92; H, 6.24; N, 1.84.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 757.37, and the measured value is 757.57.

Preparation of compound HTI-162

Prepared according to the synthetic method of compound HTI-57, the difference is that raw material I-12 is used instead of raw material I-3, and raw material II-9 is used instead of raw material II-6. The purity of the obtained target product is 99.7%, and the yield is 75.7%.

Elemental analysis structure (Molecular formula C ₄₉ H ₄₁ N): Theoretical value: C, 91.41; H, 6.42; N, 2.18; Test value: C, 91.43; H, 6.41; N, 2.16.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 643.32, and the measured value is 643.60.

Preparation of compound HTI-176

Prepared according to the synthetic method of compound HTI-57, the difference is that raw material I-13 is used instead of raw material I-3 and raw material II-9 is used instead of raw material II-6. The purity of the obtained target product is 99.6%, and the yield is 73.6%.

Elemental analysis structure (Molecular formula C ₆₀ H ₄₉ N ₃ ): Theoretical value: C, 88.74; H, 6.08; N, 5.17; Test value: C, 88.71; H, 6.09; N, 5.20.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 811.39, and the measured value is 811.65.

II. The second organic material used in the preparation:

Preparation of compound HTII-7

Under a nitrogen atmosphere, add 0.015 mol of raw material IV-1, 0.01 mol of raw material V-1, 0.03 mol of sodium tert-butoxide, 5 × 10 ^-5 mol Pd ₂ (dba) ₃ and 5 × 10 ^-5 into a 500 ml three-necked flask. mol tri-tert-butyl phosphorus. Then 150 ml of toluene was added to dissolve it, heated to 100 ° C, and refluxed for 24 hours. The reaction was observed by TLC until the reaction was complete. It was left to cool to room temperature, filtered, and the filtrate was rotary distilled to no fractions. The obtained substance was purified through a silica gel column (petroleum ether as eluent) to obtain the target product, with a purity of 99.5% and a yield of 77.3%.

Elemental analysis structure (Molecular formula C ₅₃ H ₄₁ N ₃ ): Theoretical value: C, 88.42; H, 5.74; N, 5.84; Test value: C, 88.43; H, 5.75; N, 5.82.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 719.33, and the measured value is 719.64.

Preparation of compound HTII-21

Prepared according to the synthetic method of compound HTII-7, except that raw material III-2 is used instead of raw material III-1, and raw material IV-2 is used instead of raw material IV-1. The purity of the obtained target product is 99.9% and the yield is 75.5%.

Elemental analysis structure (molecular formula C ₅₄ H ₃₉ N): Theoretical value: C, 92.40; H, 5.60; N, 2.00; Test value: C, 92.41; H, 5.61; N, 1.98.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 701.31, and the measured value is 701.52.

Preparation of compound HTII-37

Under a nitrogen atmosphere, add 0.03 mol of raw material III-3, 0.01 mol of raw material IV-4, 0.04 mol of sodium tert-butoxide, 5 × 10 ^-5 mol Pd ₂ (dba) ₃ and 5 × 10 ^-5 into a 500 ml three-necked flask. mol of tri-tert-butyl phosphorus, then 150 ml of toluene was added to dissolve it, heated to 100 ° C, refluxed for 24 hours, and the reaction was observed by TLC until the reaction was completed. It was left to cool to room temperature, filtered, and the filtrate was rotary distilled to no fractions. The obtained substance was purified through a silica gel column (petroleum ether as eluent) to obtain the target product, with a purity of 99.7% and a yield of 74.6%.

Elemental analysis structure (molecular formula C ₅₄ H ₃₅ NO ₂ ): Theoretical value: C, 88.86; H, 4.83; N, 1.92; Test value: C, 88.85; H, 4.84; N, 1.91.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 729.27, and the measured value is 729.45.

Preparation of compound HTII-41

Prepared according to the synthetic method of compound HTII-7, except that raw material III-4 is used instead of raw material III-1, and raw material IV-4 is used instead of raw material IV-1. The purity of the obtained target product is 99.8%, and the yield is 76.1%.

Elemental analysis structure (molecular formula C ₅₁ H ₃₇ NO): Theoretical value: C, 90.10; H, 5.49; N, 2.06; Test value: C, 90.11; H, 5.47; N, 2.07.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 679.29, and the measured value is 679.63.

Preparation of compound HTII-52

Prepared according to the synthetic method of compound HTII-7, except that raw material III-5 is used instead of raw material III-1, and raw material IV-5 is used instead of raw material IV-1. The purity of the obtained target product is 99.7% and the yield is 75.6%.

Elemental analysis structure (molecular formula C ₅₄ H ₃₆ N ₂ O): Theoretical value: C, 88.98; H, 4.98; N, 3.84; Test value: C, 88.96; H, 4.99; N, 3.85.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 728.28, and the measured value is 728.56.

Preparation of compound HTII-78

Prepared according to the synthetic method of compound HTII-7, except that raw material III-6 is used instead of raw material III-1, and raw material IV-6 is used instead of raw material IV-1. The purity of the obtained target product is 99.9% and the yield is 75.1%.

Elemental analysis structure (molecular formula C ₅₂ H ₃₇ N): Theoretical value: C, 92.41; H, 5.52; N, 2.07; Test value: C, 92.42; H, 5.53; N, 2.05.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 675.29, and the measured value is 675.65.

Preparation of compound HTII-102

Prepared according to the synthetic method of compound HTII-7, except that raw material III-7 is used instead of raw material III-1, and raw material IV-4 is used instead of raw material IV-1. The purity of the obtained target product is 99.7% and the yield is 77.4%.

Elemental analysis structure (Molecular formula C ₄₉ H ₃₅ N): Theoretical value: C, 92.41; H, 5.52; N, 2.07; Test value: C, 92.42; H, 5.53; N, 2.05.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 637.28, and the measured value is 637.55.

Preparation of compound HTII-132

It is prepared according to the synthetic method of compound HTII-7, except that the raw material III-8 is used instead of the raw material III-1. The purity of the obtained target product is 99.7% and the yield is 75.6%.

Elemental analysis structure (molecular formula C ₅₅ H ₄₁ NO): Theoretical value: C, 90.25; H, 5.65; N, 1.91; Test value: C, 90.23; H, 5.66; N, 1.90.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 731.32, and the measured value is 731.64.

Preparation of compound HTII-148

Prepared according to the synthetic method of compound HTII-7, except that the raw material III-9 is used instead of raw material III-1, and the raw material IV-6 is used instead of raw material IV-1 to obtain a target product with a purity of 99.6% and a yield of 73.8%.

Elemental analysis structure (molecular formula C ₅₂ H ₃₉ NO): Theoretical value: C, 90.01; H, 5.67; N, 2.02; Test value: C, 90.03; H, 5.64; N, 2.03.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 693.61, and the measured value is 693.30.

Preparation of compound HTII-164

Prepared according to the synthetic method of compound HTII-7, except that raw material III-10 is used instead of raw material III-1, and raw material IV-7 is used instead of raw material IV-1. The purity of the obtained target product is 99.5%, and the yield is 73.8%.

Elemental analysis structure (molecular formula C ₅₅ H ₄₃ N): Theoretical value: C, 92.01; H, 6.04; N, 1.95; Test value: C, 92.02; H, 6.02; N, 1.96.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 717.34, and the measured value is 717.57.

Preparation of compound HTII-192

Prepared according to the synthetic method of compound HTII-7, except that raw material III-11 is used instead of raw material III-1, and raw material IV-8 is used instead of raw material IV-1. The purity of the obtained target product is 99.6%, and the yield is 76.1%.

Elemental analysis structure (Molecular formula C ₅₄ H ₃₉ N): Theoretical value: C, 92.40; H, 5.60; N, 2.00; Test value: C, 92.41; H, 5.58; N, 2.01.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 701.31, and the measured value is 701.54.

Preparation of compound HTII-232

It is prepared according to the synthetic method of compound HTII-7, except that the raw material III-12 is used instead of the raw material III-1. The purity of the obtained target product is 99.7% and the yield is 73.3%.

Elemental analysis structure (molecular formula C ₆₃ H ₅₇ N): Theoretical value: C, 91.37; H, 6.94; N, 1.69; Test value: C, 91.36; H, 6.93; N, 1.70.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 827.45, and the measured value is 827.71.

Preparation of compound HTII-243

Prepared according to the synthetic method of compound HTII-7, except that raw material III-13 is used instead of raw material III-1, and raw material IV-7 is used instead of raw material IV-1. The purity of the obtained target product is 99.5% and the yield is 73.6%.

Elemental analysis structure (Molecular formula C ₆₂ H ₅₅ N): Theoretical value: C, 91.47; H, 6.81; N, 1.72; Test value: C, 91.45; H, 6.82; N, 1.73.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 813.43, and the measured value is 813.66.

Preparation of compound HTII-266

Prepared according to the synthetic method of compound HTII-7, except that raw material III-14 is used instead of raw material III-1, and raw material IV-9 is used instead of raw material IV-1. The purity of the obtained target product is 99.6%, and the yield is 75.9%.

Elemental analysis structure (molecular formula C ₄₅ H ₃₂ N ₂ O): Theoretical value: C, 87.63; H, 5.23; N, 4.54; Test value: C, 87.61; H, 5.24; N, 4.55.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 616.25, and the measured value is 616.51.

Preparation of compound HTII-277

It is prepared according to the synthetic method of compound HTII-7, except that the raw material III-15 is used instead of the raw material III-1, and the raw material IV-10 is used instead of the raw material IV-1.

Elemental analysis structure (molecular formula C ₄₆ H ₃₁ NO): Theoretical value: C, 90.02; H, 5.09; N, 2.28; Test value: C, 90.01; H, 5.07; N, 2.29 ;.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 613.24, and the measured value is 613.44.

Preparation of compound HTII-314

Prepared according to the synthetic method of compound HTII-7, except that raw material III-16 is used instead of raw material III-1, and raw material IV-11 is used instead of raw material IV-1. The purity of the obtained target product is 99.8%, and the yield is 76.3%.

Elemental analysis structure (molecular formula C ₄₆ H ₃₁ NO ₂ ): Theoretical value: C, 87.73; H, 4.96; N, 2.22; Test value: C, 87.71; H, 4.97; N, 2.23.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 629.24, and the measured value is 629.52.

Preparation of compound HTII-335

Prepared according to the synthetic method of compound HTII-7, the difference is that raw material III-10 is used instead of raw material III-1, and raw material IV-12 is used instead of raw material IV-1.

Elemental analysis structure (molecular formula C ₄₉ H ₃₇ NO): Theoretical value: C, 89.74; H, 5.69; N, 2.14; Test value: C, 89.74; H, 5.69; N, 2.14.

ESI-MS (m / z) (M ⁺ ): The theoretical value is 655.29, and the measured value is 655.57.

Table 1 shows the prepared first and second organic materials, the electron blocking layer material (EB1) adjacent thereto, the host material (EMH-1, EMH-7, and EMH-13) of the luminescent material, and the guest material (EMD- 1. EMD-8 and EMD-13) test results of each energy level.

Table 1

Material name	Tg (℃)	HOMO energy level (ev)	LUMO energy level (ev)	Hole mobility (cm 2 / (V · s)
EB1	145	-5.86	-2.51	1.2 E-4
EMH-1	127	-6.0	-3.0	4.8E-11
EMH-7	-	-5.82	-2.55	-
EMH-13	-	-5.8	-2.64	-
EMD-1	150	-5.5	-2.7	-
EMD-8	-	-5.43	-3.07	-
EMD-13	-	-5.36	-2.65	-
HTI-1	149.4	-5.27	-2.26	7.1 E-4
HTI-9	148.4	-5.45	-2.42	5.5 E-4
HTI-28	128.8	-5.35	-2.53	6.2 E-4
HTI-41	147.7	-5.44	-2.43	4.7 E-4
HTI-52	123.6	-5.50	-2.35	2.5 E-4
HTI-57	131.1	-5.47	-2.47	7.1 E-4
HTI-63	136.2	-5.49	-2.41	8.8 E-4
HTI-72	133.6	-5.47	-2.38	8.9 E-4
HTI-86	135.5	-5.49	-2.45	6.8 E-4
HTI-101	149.8	-5.45	-2.39	6.7 E-4
HTI-114	141.9	-5.42	-2.41	6.5 E-4
HTI-124	145.5	-5.47	-2.37	5.4 E-4
HTI-134	142.7	-5.43	-2.43	7.4 E-4
HTI-144	135.2	-5.45	-2.41	8.2 E-4
HTI-162	136.5	-5.48	-2.49	8.1 E-4
HTI-176	138.3	-5.46	-2.37	5.8 E-4
HTII-7	139.4	-5.48	-2.42	3.6 E-4
HTII-21	132	-5.58	-2.59	6.8 E-4
HTII-37	156.6	-5.7	-2.39	6.1 E-4
HTII-41	122.7	-5.6	-2.46	6.6 E-4
HTII-52	158.2	-5.7	-2.4	5.3 E-4
HTII-78	141.3	-5.66	-2.36	6.4 E-4
HTII-102	145.2	-5.68	-2.34	5.7 E-4
HTII-132	148.9	-5.54	-2.35	6.1 E-4
HTII-148	131.4	-5.58	-2.41	3.5 E-4
HTII-164	145.5	-5.66	-2.39	5.4 E-4
HTII-192	135.8	-5.5	-2.35	9.3 E-4
HTII-232	151.1	-5.59	-2.37	6.6 E-4
HTII-243	148.3	-5.63	-2.34	7.6 E-4
HTII-266	133.7	-5.66	-2.4	5.2 E-4
HTII-277	148.9	-5.54	-2.36	4.7 E-4
HTII-314	146.1	-5.63	-2.38	4.3 E-4
HTII-335	147.5	-5.61	-2.35	4.1 E-4

As can be seen from the results in Table 1, the HOMO energy level of the first organic material of the present invention is between -5.2eV and -5.6eV, and the HOMO energy level of the second organic material is between -5.4eV and -5.9eV, | HOMOfirst _{organic material} | <| HOMOsecond _{organic material} |; and the absolute value of the difference between the HOMO energy levels of the second organic material and the electron blocking layer material is ≦ 0.4ev.

Example 1

Using CIC evaporation equipment (manufactured by Changzhou Industry), the first organic material HTI-1 and the second organic material HTII-7 were placed in two evaporation sources, and controlled under a pressure of 1.0E ^-5 Pa. The evaporation rate of the first organic material 1 is

Control the evaporation rate of the second organic material 1 to

Co-mixing to obtain the hole transport layer material 1 of the present invention.

Example 2

The preparation process of Example 1 was repeated, except that the evaporation rate of the first organic material HTI-1 was

The evaporation rate of the second organic material HTII-7 is

A hole transport layer material 2 was obtained.

Example 3

The preparation process of Example 1 was repeated, except that the evaporation rate of the first organic material HTI-1 was

The evaporation rate of the second organic material HTII-7 is

A hole transport layer material 3 was obtained.

Example 4

The preparation process of Example 1 was repeated, except that the evaporation rate of the first organic material HTI-1 was

The evaporation rate of the second organic material HTII-7 is

A hole transport layer material 4 is obtained.

Example 5

The preparation process of Example 1 was repeated, except that the evaporation rate of the first organic material HTI-1 was

The evaporation rate of the second organic material HTII-7 is

A hole transport layer material 5 is obtained.

Example 6

The preparation process of Example 1 was repeated, except that the first organic material HTI-9 and the second organic material HTII-37 were used to obtain the hole transport layer material 6.

Example 7

The preparation process of Example 1 was repeated, except that the first organic material HTI-28 and the second organic material HTII-21 were used to obtain the hole transport layer material 7.

Example 8

The preparation process of Example 1 was repeated, except that the first organic material HTI-41 and the second organic material HTII-41 were used to obtain the hole transport layer material 8.

Example 9

The preparation process of Example 3 was repeated, except that the first organic material HTI-41 and the second organic material HTII-41 were used to obtain the hole transport layer material 9.

Example 10

The preparation process of Example 1 was repeated, except that the first organic material HTI-52 and the second organic material HTII-52 were used to obtain the hole transport layer material 10.

Example 11

The preparation process of Example 1 was repeated, except that the first organic material HTI-57 and the second organic material HTII-78 were used to obtain the hole transport layer material 11.

Example 12

The manufacturing process of Example 1 was repeated, except that the first organic material HTI-63 and the second organic material HTII-102 were used to obtain the hole transport layer material 12.

Example 13

The preparation process of Example 1 was repeated, except that the first organic material HTI-72 and the second organic material HTII-132 were used to obtain the hole transport layer material 13.

Example 14

The manufacturing process of Example 1 was repeated, except that the first organic material HTI-72 and the second organic material HTII-148 were used to obtain the hole transport layer material 14.

Example 15

The preparation process of Example 2 was repeated, except that the first organic material HTI-72 and the second organic material HTII-164 were used to obtain the hole transport layer material 15.

Example 16

The manufacturing process of Example 1 was repeated, except that the first organic material HTI-86 and the second organic material HTII-164 were used to obtain the hole transport layer material 16.

Example 17

The preparation process of Example 1 was repeated, except that the first organic material HTI-101 and the second organic material HTII-192 were used to obtain the hole transport layer material 17.

Example 18

The preparation process of Example 1 was repeated, except that the first organic material HTI-114 and the second organic material HTII-192 were used to obtain the hole transport layer material 18.

Example 19

The preparation process of Example 1 was repeated, except that the first organic material HTI-124 and the second organic material HTII-232 were used to obtain the hole transport layer material 19.

Example 20

The manufacturing process of Example 1 was repeated, except that the first organic material HTI-134 and the second organic material HTII-243 were used to obtain the hole transport layer material 20.

Example 21

The preparation process of Example 2 was repeated, except that the first organic material HTI-134 and the second organic material HTII-243 were used to obtain the hole transport layer material 21.

Example 22

The preparation process of Example 2 was repeated, except that the first organic material HTI-134 and the second organic material HTII-243 were used to obtain the hole transport layer material 22.

Example 23

The manufacturing process of Example 1 was repeated, except that the first organic material HTI-134 and the second organic material HTII-266 were used to obtain the hole transport layer material 23.

Example 24

The preparation process of Example 1 was repeated, except that the first organic material HTI-144 and the second organic material HTII-277 were used to obtain the hole transport layer material 24.

Example 25

The preparation process of Example 1 was repeated, except that the first organic material HTI-162 and the second organic material HTII-314 were used to obtain the hole transport layer material 25.

Example 26

The preparation process of Example 5 was repeated, except that the first organic material HTI-162 and the second organic material HTII-314 were used to obtain the hole transport layer material 26.

Example 27

The preparation process of Example 1 was repeated, except that the first organic material HTI-176 and the second organic material HTII-335 were used to obtain the hole transport layer material 27.

Preparation of organic electroluminescent device

It should be noted that the vacuum evaporation is performed under the following conditions: using a CIC evaporation equipment (manufactured by Changzhou Industry), and controlling the evaporation rate at a pressure of 1.0E ^-5 Pa

Device Preparation Example 1

Follow this process:

a) Use transparent glass as the substrate, apply ITO with a thickness of 150 nm as the anode layer, and then ultrasonically clean each with deionized water, acetone, and ethanol for 15 minutes, and then treat in a plasma cleaner for 2 minutes;

b) On the washed first electrode layer, HAT-CN is evaporated by a vacuum evaporation method to a thickness of 10 nm, and this layer is used as a hole injection layer;

c) On the hole injection layer, the hole transport layer material 1 obtained in Example 1 for preparing the hole transport layer material by vacuum evaporation is used as a hole transport layer; the thickness is 90 nm;

d) On the hole transport layer, EB1 is evaporated by vacuum evaporation to a thickness of 20 nm, and this layer is an electron blocking layer;

e) On the electron blocking layer, the light-emitting layer material is evaporated by vacuum evaporation. The host material is EMH-7 and EMH-9, and the guest material is EMD-8. The mass ratio of EMH-7, EMH-9 and EMD-8 45:45:10, thickness is 40nm;

f) LG201 and Liq are vapor-deposited on the light-emitting layer by vacuum evaporation. The mass ratio of LG201 and Liq is 50:50 and the thickness is 40nm. This layer is used as an electron transport layer.

g) On the electron transport layer, LiF is deposited by vacuum evaporation to a thickness of 1 nm, and this layer is an electron injection layer;

h) Above the electron injection layer, Al is vacuum evaporated to a thickness of 100 nm, and this layer is a second electrode layer.

Device Preparation Example 2-10

The process is carried out according to the device preparation example 1, except that in step c) the hole transport layer materials 2-10 obtained in the example 2-10 of preparing the hole transport layer material are used.

Device Preparation Example 11

According to the process of device preparation example 1, the difference is that the thickness of the hole transport layer in step c) is 160 nm; in step e), the host material is EMH-13, the guest material is EMD-8, and EMH-13 The mass ratio with EMD-8 is 90:10, and the thickness is 40nm.

Device Preparation Examples 12-13

The process is carried out according to the device preparation example 11 except that the hole transport layer material 2-3 obtained in the embodiment 2-3 for preparing the hole transport layer material is used in step c).

Device Preparation Examples 14-20

It is carried out according to the procedure of Device Preparation Example 11 except that in step c) the hole transport layer materials 12-18 obtained in Examples 12-18 of preparing the hole transport layer materials are used.

Device Preparation Example 21

It is carried out according to the process of Device Preparation Example 1 except that the film thickness of the hole transport layer in step c) is 50 nm; the host material in step e) is EMH-1, and the guest material is EMD-1, and EMH-1 and EMD-1 has a mass ratio of 95: 5 and a thickness of 25 nm.

Device Preparation Examples 22-30

It is carried out according to the process of Device Preparation Example 21, except that the hole transport layer materials 19-27 obtained in Examples 19-27 of preparing the hole transport layer materials are respectively used in step c).

Comparative Examples 1-10

It is performed according to the process of Device Preparation Example 1 except that only the first organic material or the second organic material listed in Table 2 below is used as the material of the hole transport layer.

Table 2:

Comparative Examples 11-25

It was performed according to the process of Device Preparation Example 11 except that only the first organic material or the second organic material listed in Table 3 below was used as the material of the hole transport layer.

table 3:

Comparative Examples 26-38

It was performed according to the process of Device Preparation Example 21, except that only the first organic material or the second organic material listed in Table 4 below was used as the material of the hole transport layer.

Table 4:

Table 5-7 shows the results of measuring the performance of the produced organic electroluminescence device at a current density of 10 mA / cm ² .

Table 5: Performance results of organic electroluminescent devices prepared by Inventive Examples 1-10 and Comparative Examples 1-10

Note: * represents comparative example

LT95 refers to the time it takes for the device brightness to decay to 95% at a current density of 10 mA / cm ² ;

The life test system is an OLED device life tester which is jointly researched by the owner of the present invention and Shanghai University.

The notes also apply to Tables 6 and 7 below.

Table 6: Performance results of organic electroluminescent devices prepared by Inventive Examples 11-20 and Comparative Examples 11-25

Table 7: Performance results of organic electroluminescent devices prepared by Inventive Examples 21-30 and Comparative Examples 26-38

From the results in Table 5, it can be seen that the driving voltages of the devices prepared by the device preparation examples 1 to 10 of the present invention are significantly lower than those of the comparative examples 1 to 10 using the organic material alone as the material of the hole transport layer. , And the luminous brightness, luminous efficiency (that is, current efficiency) and life are significantly improved. As can be seen from the results in Table 6, compared with Comparative Examples 11 to 25, the driving voltages of the devices prepared in Device Preparation Examples 11 to 20 of the present invention were also significantly reduced, and the light emission brightness and light emission efficiency (ie, current Both efficiency and lifespan are significantly improved. From the results in Table 7, it can be seen that compared with Comparative Examples 26 to 38, the driving voltages of the devices prepared in Device Preparation Examples 21 to 30 of the present invention are also significantly reduced, and the light emission brightness and light emission efficiency (ie, current Both efficiency and lifespan are significantly improved.

Finally, it is explained that the above embodiments are only used to illustrate the technical solution of the present invention, but not limiting. Those skilled in the art without departing from the spirit and scope of the technical solution of the present invention, make modifications or equivalent substitutions to the technical solution of the present invention, which should be covered by the scope of the claims of the present invention.

Claims (12)

1. An organic electroluminescent device is provided with a substrate, a first electrode, an organic functional material layer, and a second electrode in this order from bottom to top. The organic functional material layer includes:

   A hole-transporting region located on the first electrode;

   A light-emitting layer, which is located on the hole-transporting region and includes a host material and a guest material;

   An electron-transporting region located above the light-emitting layer,

   The hole transporting region includes a hole injection layer, a hole transporting layer, and an electron blocking layer in this order from bottom to top.

   The hole transport layer includes first and second organic materials, wherein the HOMO energy level of the first organic material is -5.2eV to -5.6eV, preferably -5.3eV to -5.5eV, and more preferably -5.35eV to -5.5eV, and the HOMO energy level of the second organic material is -5.4eV to -5.9eV, preferably -5.4eV to -5.7eV, more preferably -5.48eV to -5.68eV, and the HOMO _{first organic material} | <| HOMO _{Second Organic Material} |.
2. The organic electroluminescent device according to claim 1, wherein an absolute value of a difference between HOMO energy levels of the second organic material and the electron blocking layer material is ≤ 0.4v.
3. The organic electroluminescent device according to claim 1 or 2, wherein the ratio of the first and second organic materials is 1:99 to 99: 1, preferably 10:90 to 90:10, and more preferably 30. : 70 to 70:30, based on mass.
4. The organic electroluminescent device according to any one of claims 1 to 3, wherein the first and second organic materials are each independently selected from the general formula (1), the general formula (2), or the general formula (3) Either:

   

   Among them, in the general formula (1)

   X and X ₁ are each independently selected from a single bond, a carbon atom, N- (R ₅ ), a sulfur atom, an oxygen atom, a vinylidene group, a linear or branched C _1-20 alkyl-substituted alkylene group, One of a linear or branched C _1-20 alkyl-substituted silylene group and a C _6-20 aryl-substituted alkylene group;

   If R ₅ is present, it may be the same or differently selected from a hydrogen atom, a tritium atom, a deuterium atom, a tritium atom, a fluorine atom, a phosphoric acid or a salt thereof, a linear or branched C _1-20 alkyl-substituted alkyl group , Linear or branched C _1-20 alkyl-substituted silyl groups, aryl groups having 5 to 30 carbon atoms, having 5 to 30 carbon atoms and at least one heteroatom selected from N, O and S Heteroaryl, wherein in the case of the latter two, the group may be optionally substituted with a linear or branched C _1-20 alkyl group, C _6-20 aryl group, C _5-20 heteroaryl group;

   Z represents a nitrogen atom or CR ₆ , wherein R ₆ may be the same or differently selected from a hydrogen atom, a tritium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a linear or branched C _{1- 20} alkyl substituted alkyl, straight or branched C _1-20 alkyl substituted silyl, aryl having 5 to 30 carbon atoms, 5 to 30 carbon atoms, and at least one selected from N, Heteroaryl of heteroatoms of O and S, wherein in the case of the latter two, the group may optionally be a linear or branched C _1-20 alkyl, C _6-20 aryl, C _{5 -20} heteroaryl substitutions in which two or more R ₆ groups may be connected to each other and may form a ring structure;

   Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent a single bond, a linear or branched C _1-20 alkylene group, a linear or branched C _1-20 alkyl-substituted silyl group, Arylene having 5 to 30 carbon atoms, heteroarylene having 5 to 30 carbon atoms and at least one heteroatom selected from N, O, and S, wherein in the case of the latter two, the group The group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, and a C _5-20 heteroaryl group, wherein the Ar ₁ and Ar ₂ groups may also be directly connected to form a ring or through C, O, S, N are connected into a ring;

   m, n, p, q, s, and t are equal to 0 or 1; and m + n + p + q≥1 and m + n + s + t≥1;

   R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a structure represented by the general formula (4), the general formula (5) or the general formula (6), provided that R ₁ , R ₂ , R ₃ And R _{4 are} not hydrogen atoms at the same time;

   

   Among them, in the general formula (4) and the general formula (5):

   X ₂ and X ₃ each independently represent a single bond, an oxygen atom, a sulfur atom, a vinylidene group, a linear or branched C _1-20 alkyl-substituted alkylene group, a linear or branched C _1-20 Alkyl substituted silyl, C _6-20 aryl substituted alkylene, C _1-20 alkyl substituted imine, C _6-20 aryl substituted imine, C _5-20 heteroaryl One of the substituted imines;

   Y ₁ may identically or differently represent an N atom or CR ₇ , wherein R ₇ may identically or differently represent a hydrogen atom, a tritium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a straight chain or a branch Chain C _1-20 alkyl substituted alkyl, linear or branched C _1-20 alkyl substituted silyl, aryl having 5 to 30 carbon atoms, 5 to 30 carbon atoms, and at least one selected A heteroaryl group from a heteroatom of N, O, and S, wherein in the case of the latter two, the group may be optionally a linear or branched C _1-20 alkyl, C _6-20 aryl , C _5-20 heteroaryl substitution; wherein two or more R ₇ groups can be connected to each other and can form a ring structure;

   R ₈ and R ₉ each independently represent a hydrogen atom, a tritium atom, a deuterium atom, a tritium atom, a fluorine atom, a phosphoric acid or a salt thereof, a linear or branched C _1-20 alkyl-substituted alkyl group, a straight chain or a branched group C _1-20 alkyl substituted silyl groups of the chain, aryl groups having 5 to 30 carbon atoms, heteroaryl groups having 5 to 30 carbon atoms and at least one heteroatom selected from N, O and S, A structure represented by formula (7) or formula (6); wherein in the case of an aryl group and a heteroaryl group, the group may be optionally a linear or branched C _1-20 alkyl group, C _{6- 20} aryl, C _5-20 heteroaryl substitution;

   

   Among them, in the general formula (7):

   Y ₂ may identically or differently represent an N atom or CR ₁₄ , wherein R ₁₄ may identically or differently represent a hydrogen atom, a tritium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a straight chain or Branched C _1-20 alkyl substituted alkyl, straight or branched C _1-20 alkyl substituted silyl, aryl having 5 to 30 carbon atoms, having 5 to 30 carbon atoms, and at least A heteroaryl heteroaryl group selected from N, O, and S, wherein in the case of the latter two, the group may be optionally a linear or branched C _1-20 alkyl group, C _6-20 Aryl, C _5-20 heteroaryl substitution; wherein two or more R ₁₂ groups may be connected to each other and may form a ring structure;

   X ₄ and X ₅ each independently represent a single bond, an oxygen atom, a sulfur atom, a vinylidene group, a linear or branched C _1-20 alkyl-substituted alkylene group, a linear or branched C _1-20 Alkyl substituted silylene, C _6-20 aryl substituted alkylene, C _1-20 alkyl substituted imine, C _6-20 aryl substituted imine, C _5-20 heteroaryl One of a group-substituted imine group;

   The general formula (7) is connected to the general formula (4) or the general formula (5) by a ring method, and * is indicated as a connection site. When connected, only two adjacent sites can be taken. When formula (4) or formula (5) is cyclically linked, the connection site Y _{1 is} represented as a carbon atom;

   In the general formula (8):

   R ₁₂ and R ₁₃ each independently represent an aryl group having 5 to 30 carbon atoms, a heteroaryl group having 5 to 30 carbon atoms, and at least one hetero atom selected from N, O, and S, and the group may be Optionally substituted by straight or branched C _1-20 alkyl, C _6-20 aryl, C _5-20 heteroaryl; R ₁₂ , R ₁₃ may also be linked to form a ring;

   In the general formula (2):

   L ₁ , L ₂ , and L ₃ each independently represent a single bond, an arylene group having 5 to 30 carbon atoms, a sub-heterocycle having 5 to 30 carbon atoms, and at least one hetero atom selected from N, O, and S Aryl, where in the case of the latter two, the group may be optionally substituted with a linear or branched C _1-20 alkyl group, C _6-20 aryl group, C _5-20 heteroaryl group; L _1. L ₂ and L ₃ can be connected to each other and form a ring structure;

   Ar ₅ , Ar ₆ , and Ar ₇ each independently represent an arylene group having 5 to 30 carbon atoms, a heteroarylene group having 5 to 30 carbon atoms, and at least one hetero atom selected from N, O, and S, Imine having 5 to 30 carbon atoms, said group may be optionally substituted by straight or branched C _1-20 alkyl, C _6-20 aryl, C _5-20 heteroaryl; Ar ₅ , Ar ₆ , Ar ₇ can be connected to each other and can form a ring structure;

   Ar ₅ , Ar ₆ , and Ar ₇ can also be independently represented as one of the general formula (4), the general formula (5), and the general formula (6), wherein the groups X ₂ , X ₃ , Y ₁ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and * have the meanings as described above;

   In the general formula (3):

   D ₁ , D ₂ , and D ₃ each independently represent a single bond, an arylene group having 5 to 30 carbon atoms, a sub-heterocycle having 5 to 30 carbon atoms, and at least one hetero atom selected from N, O, and S Aryl, where in the case of the latter two, the group may be optionally substituted with a linear or branched C _1-20 alkyl, C _6-20 aryl, C _5-20 heteroaryl; D _1. D ₂ and D ₃ can be connected to each other and form a ring structure;

   Ar ₈ , Ar ₉ , and Ar ₁₀ each independently represent a hydrogen atom, an arylene group having 5 to 30 carbon atoms, a sub-heterocycle having 5 to 30 carbon atoms, and at least one hetero atom selected from N, O, and S Aryl, imine having 5 to 30 carbon atoms, said group may be optionally substituted with straight or branched C _1-20 alkyl, C _6-20 aryl, C _5-20 heteroaryl ; Ar ₈ , Ar ₉ , Ar ₁₀ can be connected to each other and can form a ring structure;

   At least one of Ar ₈ , Ar ₉ , and Ar ₁₀ is one of the general formula (4), the general formula (5), and the general formula (6); wherein the groups on the general formula are X ₂ , X ₃ , and Y ₁ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and * each have the meanings described above.
5. The organic electroluminescent device according to claim 4, wherein the general formula (2) is represented as one of the general formula (9) to the general formula (12):

   

   among them

   Ar ₅ to Ar ₇ represent an arylene group having 5 to 30 carbon atoms, a heteroarylene group having 5 to 30 carbon atoms and at least one hetero atom selected from N, O, and S, and 5 to 30 carbon atoms An imino group, the group may be optionally substituted with a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, and a C _5-20 heteroaryl group;

   And, L ₁ -L ₃ , R ₆ -R ₉ , Y ₁ and X ₂ -X ₃ all have the meanings described in claim 4.
6. The organic electroluminescent device according to claim 4 or 5, wherein the general formula (3) is represented as one of the general formula (13) to the general formula (16):

   

   among them

   Ar ₈ and Ar ₁₀ represent an arylene group having 5 to 30 carbon atoms, a heteroarylene group having 5 to 30 carbon atoms and at least one hetero atom selected from N, O, and S, and 5 to 30 carbon atoms An imino group, the group may be optionally substituted with a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; and

   And D ₁ -D ₃ , R ₆ -R ₉ , Y ₁ and X ₂ -X ₃ all have the meanings described in claim 4.
7. The organic electroluminescent device according to any one of claims 1-6, wherein the first organic material of the hole transport layer is selected from one of the following compounds:

   

   

   

   
8. The organic electroluminescent device according to any one of claims 1-6, wherein the second organic material of the hole transport layer is selected from one of the following compounds:

   

   

   

   

   

   
9. The organic electroluminescent device according to any one of claims 1 to 8, characterized in that the first organic material and the second organic material of the hole transporting layer can be mixed and used for manufacturing an electroluminescent device, They can also be mixed during the fabrication of organic electroluminescent devices.
10. The organic electroluminescent device according to any one of claims 1-9, wherein the device comprises one or more combinations of blue, green, red, or yellow organic light emitting material layers; different organic light emitting material layers Horizontal or vertical overlay combination.
11. A display comprising one or more organic electroluminescence devices according to any one of claims 1 to 10; and in a case where a plurality of devices are included, the devices are stacked in a horizontal or vertical combination.
12. The display according to claim 11, wherein the display comprises one or more combinations of devices each having an organic light emitting material layer of three colors of blue, green, and red, and each of the devices has the same or Hole transport layers of different film thicknesses, and the materials of the hole transport layers are the same or different.

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