WO2019206292A1 - 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 electroluminescent 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.

The organic electroluminescent device technology can be used for manufacturing new display products as well as for preparing new lighting products, and is expected to replace the existing liquid crystal display and fluorescent lighting, and has a wide application prospect. An organic electroluminescent device is used as a current device. When a voltage is applied to electrodes at both ends thereof and an electric field acts on the positive and negative charges in the organic layer functional material film layer, the positive and negative charges are further recombined in the organic light-emitting layer, that is, Electroluminescence.

Organic electroluminescent devices are generally multilayer in structure, and various auxiliary functional layers other than the luminescent layer also play a vital role in device performance. A reasonable device structure can effectively improve the performance of the device, and an electron injecting layer, an electron transporting layer, a hole blocking layer, an emitting layer, an electron blocking layer, a hole transporting layer, and a hole injecting layer are widely used to improve the performance of the device.

At present, research on improving the performance of organic electroluminescent devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and improving the service life of the device. In order to realize the continuous improvement of the performance of organic electroluminescent devices, not only the innovation of the structure and preparation process of organic electroluminescent devices, but also the continuous research and innovation of organic electroluminescent functional materials are required to produce higher performance organic electroluminescence. Luminous functional material.

The carriers (holes and electrons) in the organic electroluminescent device are respectively injected into the device by the two electrodes of the device under the driving of the electric field, and are combined to emit light in the luminescent layer. Hole transport materials used in existing organic electroluminescent devices are known, for example There is a large HOMO level difference between the HOMO level and the electron blocking layer material, and it is easy to form an accumulated charge at the material interface, which affects the lifetime of the OLED device.

In addition, in organic electroluminescent devices, not all of the energy levels of the materials are well matched, and the barrier between them severely hinders the effective injection of holes. A reasonable energy level structure facilitates the formation of a step barrier for the energy levels in each layer of the device, reduces the potential barrier of hole injection, and reduces the driving voltage of the device, thereby improving the luminous efficiency and lifetime of the device.

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

The present invention is directed to an organic electroluminescent 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 above the first electrode;

a light emitting layer over the hole transporting region, comprising a host material and a guest material;

An electron transport region located above the light emitting layer,

Wherein, the hole transporting region includes a hole injecting 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 first organic material has a HOMO level of from -5.2 eV to -5.6 eV, preferably from -5.3 eV to -5.5 eV, more preferably from -5.35 eV to -5.5 eV, and the HOMO level of the second organic material 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} |.

In an organic electroluminescent device comprising a hole transport layer comprising the first and second organic materials of the present invention, a HOMO of the first and second organic materials is defined, the level matching of the anode and the electron blocking The barrier between the layer interfaces is reduced, which facilitates the injection of holes from the anode into the electron blocking layer, improves the hole injection efficiency, reduces the driving voltage of the device, reduces the accumulated charge at the interface contact, and improves the device. 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 intermolecular interaction force, so that the film layer has higher stability, reduces the leakage current of the device, and improves the service life of the device.

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

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

Fig. 2 is a view schematically showing an energy transfer mechanism diagram of an organic electroluminescent device according to an embodiment of the present invention.

3 to 7 are schematic views showing a combination structure of light-emitting layers in an organic electroluminescence device comprising the hole transport layer of the present invention.

The invention is described in more detail hereinafter with reference to the accompanying drawings, but is not intended to limit the invention.

Any numerical range recited herein is intended to include all sub-ranges that have the For example, "1.0 to 10.0" means including all subranges (and 1.0 and 10.0) between the listed minimum value of 1.0 and the listed maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and equal to Or all subranges of values less than 10.0. Any of the maximum numerical limits set forth herein are meant to include all of the smaller numerical limits that are included herein, and any minimum numerical limitation listed herein is meant to include all of the greater numerical limitations included herein. The Applicant reserves the right to modify the present specification, including the claims, to clearly describe any sub-ranges that fall within the scope of the invention.

It is to be understood that the abbreviation "HT" as used herein means an organic material constituting a hole transporting layer, for example, HT-I means a first organic material, and HT-II means a second organic material.

In the figures, the dimensions of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "above" another layer or substrate, the layer or element can be directly over the other layer or substrate, or an intermediate layer can also be present. In addition, it will also be understood that when a layer is referred to as being "between" two layers, the layer may be the only layer between the two layers, or one or more intermediate layers may be present. The same reference numerals are used throughout the drawings to refer to the same elements.

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

Fig. 1 schematically shows a cross-sectional view of an organic electroluminescent device of one 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 transporting region A, a light emitting layer 6, an electron transporting region B, and a second electrode 10 in this order from bottom to top. The hole transporting region A includes a hole injecting layer 3, a hole transporting layer 4, and an electron blocking layer 5 in this order from bottom to top, and the electron transporting region B includes a hole blocking layer 7, an electron transporting layer 8, and electrons in order from bottom to top. Inject layer 9.

As the substrate of the organic electroluminescent device of the present invention, any substrate commonly used for an organic electroluminescence device 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 repellency, and the direction of use is different depending on the nature. 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 can 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 mixture of metals. The thickness of the first electrode layer depends on the material used, and is usually from 50 to 500 nm, preferably from 70 to 300 nm and more preferably from 100 to 200 nm.

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

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

Generally, an organic material having a p-type property, which is easily oxidized and electrochemically stabilized when it is oxidized, is mainly used as a hole injecting material or a hole transporting material. At the same time, an organic material having an n-type property, which is easily reduced and electrochemically stabilized when it is reduced, is used as an electron injecting material or an electron transporting material. As the light-emitting layer material, a material having both a p-type property and an n-type property is preferable, which is stable when it is oxidized and reduced, and preferably has a high luminescence for converting excitons into light when excitons are formed. Efficiency material.

The material of the hole injection layer is usually a material preferably having 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 formula (17), (18) or (19):

Wherein, in the 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 -G ₆ each independently represent hydrogen, nitrile group, halogen, amide group, alkoxy group, ester group, nitro group, CR ₁₁ , substituted or unsubstituted a C _6-30 aryl group, a 3 to 30 membered heteroaryl group, wherein R ₁₁ is a linear or branched C _1-20 alkyl group, provided that G ₁ -G _{6 are} not hydrogen at the same time;

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

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

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

The hole transport layer of the present invention may be disposed over 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, It is preferably from 30:70 to 70:30, based on the mass. Furthermore, the first organic material has a HOMO energy level of from -5.2 eV to -5.6 eV, preferably from -5.3 eV to -5.5 eV, more preferably from -5.35 eV to -5.5 eV, and the HOMO energy of the second organic material The grade 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} |.

2 is a view schematically showing an energy transfer mechanism of an organic electroluminescent device according to an embodiment of the present invention, wherein 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. The object, e represents the body of the luminescent layer, and f represents the electron transport layer.

In one embodiment, the absolute value of the difference between the HOMO levels of the second organic material and the electron blocking material is < 0.4 ev. A small 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 transport layer and further transported into the light emitting layer.

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

Wherein, in the general formula (1)

X, X ₁ are each independently selected from a single bond, a carbon atom, an 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, 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 halogen atom, a halogen atom, a halogen atom, a fluorine atom, a phosphoric acid or a salt thereof, a linear or branched C _1-20 alkyl-substituted alkyl group. a linear or branched C _1-20 alkyl substituted silylene group, an aryl group having 5 to 30 carbon atoms, a hetero atom having 5 to 30 carbon atoms and at least one selected from the group consisting of N, O and S a heteroaryl group, wherein in the case of the latter two, the group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a 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 ruthenium atom, a ruthenium atom, a ruthenium atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a linear or branched C _{1 - a 20} alkyl-substituted alkyl group, a linear or branched C _1-20 alkyl-substituted silylene group, an aryl group having 5 to 30 carbon atoms, having 5 to 30 carbon atoms, and at least one selected from N a heteroaryl heteroaryl group of 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, a C _6-20 aryl group, C _{a 5-20} heteroaryl substitution wherein two or more R ₆ groups may be attached to each other and may form a ring structure;

Ar ₁ , Ar ₂ , Ar ₃ , 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 straight chain or a branched chain. a C _1-20 alkyl-substituted silylene group, a heteroarylene group having 5 to 30 carbon atoms and at least one hetero atom 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, a C _5-20 heteroaryl group, wherein the Ar 1 , Ar 2 groups may also be joined 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 formula (4), the formula (5) or the formula (6), provided that R ₁ , R ₂ , R ₃ When it is different from R _{4 ,} it is a hydrogen atom;

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 group.} Alkyl-substituted silane group, C _6-20 aryl-substituted alkylene group, C _1-20 alkyl-substituted imido group, C _6-20 aryl-substituted imido group, C _5-20 heteroaryl group One of the substituted imido groups;

Y ₁ may represent N atom or CR identically or differently, wherein R may represent the same or different hydrogen atom, helium atom, rhodium atom, rhodium atom, fluorine atom, cyano group, phosphoric acid or a salt thereof, linear or branched a C _1-20 alkyl-substituted alkyl group, a linear or branched C _1-20 alkyl-substituted silane group, an aryl group having 5 to 30 carbon atoms, having 5 to 30 carbon atoms, and at least one selected a heteroaryl group derived from a hetero atom 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 group, a C _6-20 aryl group a C _5-20 heteroaryl group; wherein two or more R groups may be attached to each other and may form a ring structure;

R ₆ and R ₇ each independently represent a hydrogen atom, a halogen atom, a halogen atom, a halogen atom, a fluorine atom, a phosphoric acid or a salt thereof, a linear or branched C _1-20 alkyl group-substituted alkyl group, a straight chain or a branch. a C _1-20 alkyl-substituted silane group of a chain, 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, a structure represented by the formula (7) or the 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 substituted;

Among them, in the general formula (7):

Y ₂ may represent the N atom or CR ₁₀ identically or differently, wherein R ₁₀ may represent the same or differently a hydrogen atom, a halogen atom, a halogen atom, a halogen atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a linear chain or a branched C _1-20 alkyl-substituted alkyl group, a linear or branched C _1-20 alkyl-substituted silane group, an aryl group having 5 to 30 carbon atoms, having 5 to 30 carbon atoms, and at least a heteroaryl group selected from heteroatoms 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 group, C _6-20 Aryl, C _5-20 heteroaryl substituted;

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 group.} Alkyl-substituted silane group, C _6-20 aryl-substituted alkylene group, C _1-20 alkyl-substituted imido group, C _6-20 aryl-substituted imido group, C _5-20 heteroaryl group One of the substituted imido groups;

The general formula (7) is linked to the general formula (4) or the general formula (5) by a ring-and-loop method, and * is represented as a linking site. When connected, only two adjacent sites can be taken, and the general formula (7) and the pass are When the formula (4) or the formula (5) is connected in a loop, the linking 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, which may be Optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; R ₈ and R ₉ may also be bonded to form a ring;

In the general formula (2):

L ₁ , L ₂ , L ₃ each independently represent a single bond, an arylene group having 5 to 30 carbon atoms, a hetero atom having 5 to 30 carbon atoms and at least one hetero atom selected from N, O and S An aryl group, wherein in the case of the latter two, the group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; ₁ , L ₂ , L ₃ may be connected to each other and may 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, An imido group of 5 to 30 carbon atoms, which group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; Ar ₅ , Ar ₆ , Ar ₇ may be connected to each other two-two and may form a ring structure;

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

In the general formula (3):

D ₁ , D ₂ , D ₃ each independently represent a single bond, an arylene group having 5 to 30 carbon atoms, a hetero atom having 5 to 30 carbon atoms and at least one hetero atom selected from N, O and S An aryl group, wherein in the case of the latter two, the group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; ₁ , L ₂ , L ₃ may be connected to each other and may 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, An imino group of 5 to 30 carbon atoms, which group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; Ar ₈ , Ar ₉ , Ar ₁₀ may be connected to each other and may form a ring structure;

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

In a preferred embodiment of the invention, the formula (2) is represented by one of the formulae (9) to (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. Imino group, the group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, 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 invention, the formula (3) is represented by one of the formulae (13) to (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. Imino group, the group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group;

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 invention, the first organic material is selected from one of the following compounds:

In a preferred embodiment of the 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 from 1 × 10 ^-5 to 1 × 10 ^-2 cm ² /(V·s), preferably from 1 × 10 ^-4 to 1 × 10 ^-2 cm ² / (V·s) is more preferably 1 × 10 ^-4 to 1 × 10 ^-3 cm ² /(V·s).

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

The hole transport layer material of the present invention may have a thickness of from 1 to 200 nm, preferably from 10 to 100 nm.

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

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

The light emitting layer may be disposed over the hole transporting region. The material of the light-emitting layer is a material which can emit 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, bisstyrenebenzene derivatives, anthracene derivatives, oxazole derivatives, and polyparaphenylene derivatives. , but not limited to this. Further, 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 electroluminescent device of the present invention, a light-emitting layer material for an organic electroluminescence device which is known in the art may be used, and the host material may be, for example, a thiazole derivative or a benzene. And an imidazole derivative, a polydialkylfluorene derivative or 4,4'-bis(9-carbazolyl)biphenyl (CBP); the guest material may be, for example, quinacridone, coumarin, red fluorescent Alkene, anthracene and derivatives thereof, benzopyran derivatives, rhodamine derivatives or aminostyrene derivatives. In a preferred embodiment of the invention, the luminescent layer host material used is selected from the group consisting of one or more of EMH-1 to EMH-22 described below:

Furthermore, in order to improve the fluorescent or phosphorescent properties, the luminescent material may also comprise a phosphorescent or fluorescent material. Specific examples of the phosphorescent material include phosphorescent materials of metal complexes of ruthenium, platinum, and the like. For example, a green phosphorescent material such as Ir(ppy) ₃ [fac-tris(2-phenylpyridine)fluorene], a blue phosphorescent material such as FIrpic or FIr6, and a red phosphorescent material such as Btp2Ir (acac) can be used. For the fluorescent material, those commonly used in the art can be used. In a preferred embodiment of the invention, the luminescent 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 from 99:1 to 70:30, preferably from 99:1 to 85:15 and more preferably from 97:3 to 87:13, based on the mass. meter.

In addition, in order to obtain a highly efficient organic electroluminescent device, in addition to the fluorescent or phosphorescent host-guest material used above, the luminescent layer may be formed of another guest material or a plurality of guest materials, and the guest material may be simple. A fluorescent material, a delayed fluorescent (TADF) material or a phosphorescent material, or a combination of different fluorescent materials, TADF materials, and phosphorescent light, the light emitting layer may be a single light emitting layer material, or may be a composite light emitting layer stacked laterally or vertically. material. The light-emitting layers constituting the above organic electroluminescence device are exemplified by the following various structures:

(1) a single organic light-emitting layer material;

(2) any combination of a blue organic light-emitting layer material and a green, yellow or red light-emitting layer material, and without prior order, as shown in FIG. 3;

(3) any combination of the blue organic light-emitting layer material and the green, yellow or red light-emitting layer material, and without prior order, as shown in FIG. 4;

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

(5) any 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) A combination of any two 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.

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 light-emitting layer materials.

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

In order to adjust the effective binding of the carrier charge in the light-emitting layer, the film thickness of the light-emitting layer 6 constituting the OLED light-emitting body can be arbitrarily adjusted as needed, or the light-emitting layers which are not colorable can be alternately superimposed and combined as needed, and adjacent light can be emitted. A charge blocking layer or the like for different functional uses is added to the organic layer of the layer. Preferably, the light-emitting layer of the present invention may have a thickness of 5 to 60 nm, preferably 10 to 50 nm, more preferably 20 to 45 nm.

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

The hole blocking layer is a layer that blocks holes injected from the anode through the light emitting layer and enters the cathode, thereby extending the life of the device and improving the performance of the device. The hole blocking layer of the present invention may be disposed on the light emitting layer to the top. As the material of the hole blocking layer of the organic electroluminescent device of the present invention, a compound having a hole blocking function known in the art, for example, a phenanthroline derivative such as batholine (referred to as BCP), or aluminum can be used. (III) a metal complex of a hydroxyquinoline derivative such as bis(2-methyl-8-quinoline)-4-phenylphenolate (BAlq), various rare earth complexes, or an oxazole derivative, a triazole derivative, a triazine derivative, 9,9'-(5-(6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)-1, A pyrimidine derivative such as 3-phenylene) bis(9H-carbazole) (CAS No.: 1345338-69-3). The hole blocking layer of the present invention may have a thickness of 2 to 200 nm, preferably 5 to 150 nm, and more preferably 10 to 100 nm.

The electron transport layer can be disposed over the luminescent 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 transport layer of the organic electroluminescent device of the present invention, an electron transport layer material for an organic electroluminescence device known in the art, for example, a quinolinol derivative typified by Alq ₃ or BAlq can be used. Metal complexes, various metal complexes, triazole derivatives, 2,4-bis(9,9-dimethyl-9H-indol-2-yl)-6-(naphthalen-2-yl) a triazine derivative such as -1,3,5-triazine (CAS No.: 1459162-51-6), 2-(4-(9,10-di(naphthalen-2-yl)indol-2-yl)benzene Imidazole derivatives such as 1-phenyl-1H-benzo[d]imidazole (CAS No.: 561064-11-7, commonly known as LG201), triazine derivatives, oxadiazole derivatives, thiadiazole derivatives A carbodiimide derivative, a quinoxaline derivative, a phenanthroline derivative, a silicon-based compound derivative or the like. The electron transport layer of the present invention may have a thickness of 10 to 80 nm, preferably 20 to 60 nm, and more preferably 25 to 45 nm.

The electron injection layer may be disposed on the electron transport layer. The electron injecting layer material is generally a material preferably having a low work function such 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 art, for example, lithium; a lithium salt such as lithium quinolate, can be used. Lithium fluoride, lithium carbonate or lithium azide; or barium salt, barium fluoride, barium carbonate or barium azide. The electron injecting layer of the present invention may have a thickness of 0.1 to 5 nm, preferably 0.5 to 3 nm, and more preferably 0.8 to 1.5 nm.

The second electrode may be disposed over the electron transport region. The second electrode can 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 half When transmitting or reflecting the 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 a compound or mixture thereof.

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

In the case where the organic electroluminescent device is of the 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 of the 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 package structure. The package structure may be a protective structure for preventing foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The package structure may be, for example, a can, such as a glass jar or a metal can; or a film covering the entire surface of the organic layer.

In the process of preparing an organic electroluminescent device, the organic electroluminescent device of the present invention can be prepared, for example, 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. Also, the above 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 a spin coating method, a dip coating method, a jet printing method, a screen printing method, a spray method, and a roll coating method, but is not limited thereto. Vacuum evaporation means heating and plating a material onto a substrate in a vacuum environment. In the present invention, it is preferred to form the respective layers using a vacuum evaporation method.

In addition, it should be noted that the materials for forming the respective layers described in the present invention may be used as a single layer by separately forming a film, or may be formed as a single layer by mixing with other materials, or may be separately formed. The laminated structure between the layers of the film, the laminated structure between the layers after film formation after mixing, or the laminated structure of the layer formed separately and the layer formed by mixing.

In another aspect of the invention, a display is provided that includes one or more of the organic electroluminescent devices of the present invention, and where a plurality of devices are included, the devices are stacked in a lateral or longitudinal direction.

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

In another preferred embodiment, the display may comprise a device having a layer of organic luminescent material each having three colors of blue, green, red, and the device has a hole transport of the same film thickness but at least two combinations of materials thereof Floor. In yet another preferred embodiment, the display may comprise a device each having a layer of organic light-emitting material of three colors of blue, green, red, and the device has an empty film thickness and at least two combinations of materials thereof Hole transport layer.

It is to be understood that the exemplifications of the present invention are intended to be illustrative, and are not intended to be limiting. The features, characteristics, and/or elements described in connection with the specific embodiments may be used alone or in combination with the features, characteristics, and/or elements described in connection with the other embodiments, unless otherwise stated.

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

Example

The detection methods used in this article are as follows:

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

HOMO energy level: There are many methods or instruments for testing the HOMO energy level of organic optoelectronic materials, including CV (cyclic voltammetry), UPS (ultraviolet photoelectron spectroscopy), and AC series equipment manufactured by Riken Keiki 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. The HOMO 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 UPS method, AC method, IPS method, and fundamentally, all are measurement of ultraviolet photoelectron spectroscopy. Principle, in which UPS measurement requires not only ultra-high vacuum, but also expensive equipment, and there are large differences in data analysis results due to the difference in the person being measured and the instrument settings. In principle, the AC method requires the sample to be placed in an aerobic dry air environment. The oxygen element has a certain influence on the sample, and the data reproducibility and consistency are relatively poor. The IPS method measures the HOMO level and places the film material in In a vacuum environment, ultraviolet monochromatic light is directly applied to the surface of the sample, and the photoelectron current is measured to determine the magnitude of the HOMO level, 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 level of OLED materials. All HOMO energy levels of the materials involved in the present invention are measurement means of IPS. The specific measurement method is as follows:

Using a vacuum evaporation apparatus, the evaporation rate is controlled under a vacuum of 1.0E-5Pa.

The material is evaporated onto the ITO substrate to a film thickness of 60-80 nm, and then the HOMO level of the sample film is measured by using an IPS3 measuring device, and the measurement environment is a vacuum environment of 10-2 Pa or less;

Eg level: based on the UV spectrophotometric (UV absorption) baseline of the material single film and the rising side of the first absorption peak, the tangent line is calculated using the tangent and baseline intersection values.

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

Work function of the electrode material: It was tested in the atmospheric environment using a surface work function tester developed by Shanghai University.

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

Preparation of hole transport layer material

I. Preparation of the first organic material used:

Preparation of Compound HT1-1

In a 500 ml three-necked flask, 0.01 mol of the starting material I-1, 0.03 mol of the starting material II-1, 0.03 mol of sodium t-butoxide, 5 × 10 ^-5 mol of Pd ₂ (dba) ₃ and 5 × 10 ^{-5 were} placed under a nitrogen atmosphere. Mol tri-tert-butylphosphine was dissolved in 150 ml of toluene, heated to 100 ° C, refluxed for 24 hours, and the reaction was observed by TLC until the reaction was completed. It was naturally cooled to room temperature, filtered, and the filtrate was evaporated to dryness. The obtained material was purified through a silica gel column (petrole ether as eluent) to give the desired product with a purity of 99.6% and a yield of 70.4%.

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

ESI-MS (m/z) (M ⁺ ): calc.

Preparation of compound HTI-9

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

Elemental analysis structure (Molecular formula C ₅₄ H ₄₄ N ₂ ): Theory: C, 89.96; H, 6.15; N, 3.89; Tests: C, 89.97; H, 6.13; N, 3.90.

ESI-MS (m/z) (M ⁺ ): calc. 720.35.

Preparation of compound HTI-28

Under a nitrogen atmosphere, 0.01 mol of the starting material I-2 and 0.03 mol of the starting material II-3 were placed in 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 an aqueous Na ₂ CO ₃ solution (2M) was added. The mixture was stirred for 1 hour, then 1 × 10 ^-4 mol of Pd(PPh ₃ ) _{4 was added} , and the mixture was heated under reflux for 15 hours. The reaction was observed by TLC until the reaction was completed. It was naturally cooled, filtered, and the filtrate was evaporated to dryness. The obtained material was purified through a silica gel column ( petroleum ether as eluent) to give the desired product with a purity of 99.6% and a yield of 72.2%.

Elemental analysis structure (Molecular formula C ₄₂ H ₂₅ NO ₃ ): Theory: C, 85.26; H, 4.26; N, 2.37; Tests: C, 85.24; H, 4.24; N, 2.39.

ESI-MS (m/z) (M ⁺ ): calc. 591.

Preparation of compound HTI-41

Prepared according to the synthesis method of the compound HTI-1, except that the raw material III-4 was used instead of the raw material II-1, and the obtained target product had a purity of 99.5% and a yield of 68.8%.

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

ESI-MS (m/z) (M ⁺ ): calc.

Preparation of compound HTI-52

It was prepared according to the synthesis method of the compound HTI-1 except that the raw material III-5 was used instead of the raw material II-1, and the obtained target product had a purity of 99.8% and a yield of 72.9%.

Elemental analysis structure (Molecular formula C ₅₆ H ₄₀ N ₂ ): Theory: C, 90.78; H, 5.44; N, 3.78; </ RTI></RTI> C, 90.76; H, 5.45; N, 3.79.

ESI-MS (m/z) (M ⁺ ): s.

Preparation of compound HTI-57

In a 500 ml three-necked flask, 0.015 mol of the starting material I-3, 0.01 mol of the starting material II-6, 0.03 mol of sodium t-butoxide, 5 × 10 ^-5 mol of Pd ₂ (dba) ₃ and 5 × 10 ^{-5 were} placed under a nitrogen atmosphere. Mol tri-tert-butylphosphine was dissolved in 150 ml of toluene, heated to 100 ° C, refluxed for 24 hours, and the reaction was observed by TLC until the reaction was completed. It was naturally cooled to room temperature, filtered, and the filtrate was evaporated to dryness. The obtained material was purified through a silica gel column ( petroleum ether as eluent) to give the desired product, purity 99.7%, yield 77.5%.

Elemental analysis structure (Molecular formula C ₆₀ H ₄₄ N ₂ ): Theory: C, 90.87; H, 5.59; N, 3.53; </ RTI> C, 90.86; H, 5.58; N, 3.56.

ESI-MS (m/z) (M ⁺ ): calc. 792.

Preparation of compound HTI-63

Prepared according to the synthesis method of the compound HTI-57, except that the raw material I-4 was used instead of the raw material I-3, and the raw material II-7 was used instead of the raw material II-6, and the obtained target product had a purity of 99.9% and a yield of 73.9%.

Elemental analysis structure (Molecular formula C ₅₂ H ₃₇ N): Theory: C, 92.41; H, 5.52; N, 2.07; </ RTI> C, 92.42; H, 5.50; N, 2.08.

ESI-MS (m/z) (M ⁺ ): calc.

Preparation of compound HTI-72

Prepared according to the synthesis method of the compound HTI-57, except that the raw material I-5 was used instead of the raw material I-3, and the raw material II-7 was used instead of the raw material II-6, and the obtained target product had a purity of 99.6% and a yield of 72.6%.

Elemental analysis structure (Molecular formula C ₅₄ H ₃₉ N): Theory: C, 92.40; H, 5.60; N, 2.00; </ RTI> C, 92.38; H, 5.61; N, 2.01.

ESI-MS (m/z) (M ⁺ ): calc. 701.31.

Preparation of compound HTI-86

Prepared according to the synthesis method of the compound HTI-57, except that the raw material I-6 was used instead of the raw material I-3, and the raw material II-8 was used instead of the raw material II-6, and the obtained target product had a purity of 99.9% and a yield of 75.4%.

Elemental analysis structure (Molecular formula C ₅₂ H ₃₉ N): Theory: C, 92.13; H, 5.80; N, 2.07;

ESI-MS (m/z) (M ⁺ ): calc. 677.31.

Preparation of compound HTI-101

Prepared according to the synthesis method of the compound HTI-57, except that the raw material I-7 was used instead of the raw material I-3, and the raw material II-9 was used instead of the raw material II-6, and the obtained target product had a purity of 99.7% and a yield of 74.3%.

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

ESI-MS (m/z) (M ⁺ ): Theory: 731.32.

Preparation of compound HTI-114

Prepared according to the synthesis method of the compound HTI-57, except that the raw material I-8 was used instead of the raw material I-3, and the raw material II-7 was used instead of the raw material II-6, and the obtained target product had a purity of 99.6% and a yield of 77.6%.

Elemental analysis structure (Molecular formula C ₅₅ H ₄₃ N): Theory: C, 92.01; H, 6.04; N, 1.95; Tests: C, 92.02; H, 6.02; N, 1.96.

ESI-MS (m/z) (M ⁺ ): ???

Preparation of compound HTI-124

Prepared according to the synthesis method of the compound HTI-57, except that the raw material I-9 was used instead of the raw material I-3, and the raw material II-9 was used instead of the raw material II-6, and the obtained target product had a purity of 99.7% and a yield of 78.8%.

Elemental analysis structure (Molecular formula C ₅₄ H ₄₁ NO): Theory: C, 90.09; H, 5.74; N, 1.95; Tests: C, 90.07; H, 5.76; N, 1.97.

ESI-MS (m/z) (M ⁺ ): s.

Preparation of compound HTI-134

Prepared according to the synthesis method of the compound HTI-57, except that the raw material I-10 was used instead of the raw material I-3, and the raw material II-9 was used instead of the raw material II-6, and the obtained target product had a purity of 99.6% and a yield of 75.1%.

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

ESI-MS (m/z) (M ⁺ ): Found: 827.

Preparation of compound HTI-144

Prepared according to the synthesis method of the compound HTI-57, except that the raw material I-11 was used instead of the raw material I-3, and the raw material II-7 was used instead of the raw material II-6, and the obtained target product had a purity of 99.8% and a yield of 74.9%.

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

ESI-MS (m/z) (M ⁺ ): calc.

Preparation of compound HTI-162

Prepared according to the synthesis method of the compound HTI-57, except that the raw material I-12 was used instead of the raw material I-3, and the raw material II-9 was used instead of the raw material II-6, and the obtained target product had a purity of 99.7% and a yield of 75.7%.

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

ESI-MS (m/z) (M ⁺ ): Theory: 643.32.

Preparation of compound HTI-176

Prepared according to the synthesis method of the compound HTI-57, except that the raw material I-13 was used instead of the raw material I-3, and the raw material II-9 was used instead of the raw material II-6, and the obtained target product had a purity of 99.6% and a yield of 73.6%.

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

ESI-MS (m/z) (M ⁺ ): s.

II. Preparation of the second organic material used:

Preparation of compound HTII-7

In a 500 ml three-necked flask, 0.015 mol of the starting material IV-1, 0.01 mol of the starting material V-1, 0.03 mol of sodium t-butoxide, 5 × 10 ^-5 mol of Pd ₂ (dba) ₃ and 5 × 10 ^{-5 were} placed under a nitrogen atmosphere. Mol tri-tert-butyl phosphate. It was then dissolved by adding 150 ml of toluene, heated to 100 ° C, and refluxed for 24 hours. The reaction was observed by TLC until the reaction was completed. It was naturally cooled to room temperature, filtered, and the filtrate was evaporated to dryness. The obtained material was purified through a silica gel column (petrole ether as eluent) to give the desired product, purity 99.5%, yield 77.3%.

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

ESI-MS (m/z) (M ⁺ ): s.

Preparation of Compound HTII-21

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

Elemental analysis structure (Molecular formula C ₅₄ H ₃₉ N): Theory: C, 92.40; H, 5.60; N, 2.00; </ RTI></RTI> C, 92.41; H, 5.61; N, 1.98.

ESI-MS (m/z) (M ⁺ ): calc. 701.31.

Preparation of compound HTII-37

In a 500 ml three-necked flask, 0.03 mol of the starting material III-3, 0.01 mol of the starting material IV-4, 0.04 mol of sodium t-butoxide, 5 × 10 ^-5 mol of Pd ₂ (dba) ₃ and 5 × 10 ^{-5 were} placed under a nitrogen atmosphere. Mol tri-tert-butylphosphine was dissolved in 150 ml of toluene, heated to 100 ° C, refluxed for 24 hours, and the reaction was observed by TLC until the reaction was completed. It was naturally cooled to room temperature, filtered, and the filtrate was evaporated to dryness. The obtained material was purified through a silica gel column (petrole ether as eluent) to give the desired product, purity 99.7%, yield 74.6%.

Elemental analysis structure (Molecular formula C ₅₄ H ₃₅ NO ₂ ): Theory: C, 88.86; H, 4.83; N, 1.92; Tests: C, 88.85; H, 4.84; N, 1.91.

ESI-MS (m/z) (M ⁺ ): calc.

Preparation of compound HTII-41

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

Elemental analysis structure (Molecular formula C ₅₁ H ₃₇ NO): Theory: C, 90.10; H, 5.49; N, 2.06; </ RTI></RTI> C, 90.11; H, 5.47; N, 2.07.

ESI-MS (m/z) (M ⁺ ): calc.

Preparation of compound HTII-52

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

Elemental analysis structure (Molecular formula C ₅₄ H ₃₆ N ₂ O): Theory: C, 88.98; H, 4.98; N, 3.84; Tests: C, 88.96; H, 4.99; N, 3.85.

ESI-MS (m/z) (M ⁺ ): s.

Preparation of compound HTII-78

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

Elemental analysis structure (Molecular formula C ₅₂ H ₃₇ N): Theory: C, 92.41; H, 5.52; N, 2.07; </ RTI> C, 92.42; H, 5.53; N, 2.05.

ESI-MS (m/z) (M ⁺ ): calc.

Preparation of compound HTII-102

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

Elemental analysis structure (Molecular formula C ₄₉ H ₃₅ N): Theory: C, 92.41; H, 5.52; N, 2.07; </ RTI></RTI> C, 92.42; H, 5.53; N, 2.05.

ESI-MS (m/z) (M ⁺ ): calc. 637.28.

Preparation of compound HTII-132

Prepared according to the synthesis method of the compound HTII-7, except that the raw material III-8 was used instead of the raw material III-1, and the obtained target product had a purity of 99.7% and a yield of 75.6%.

Elemental analysis structure (Molecular formula C ₅₅ H ₄₁ NO): Theory: C, 90.25; H, 5.65; N, 1.91; Tests: C, 90.23; H, 5.66; N, 1.90.

ESI-MS (m/z) (M ⁺ ): Theory: 731.32, found 731.64.

Preparation of Compound HTII-148

Prepared according to the synthesis method of the compound HTII-7, except that the raw material III-9 was used instead of the raw material III-1, and the purity of the target product obtained by substituting the raw material IV-6 for the raw material IV-1 was 99.6%, and the yield was 73.8%.

Elemental analysis structure (Molecular formula C ₅₂ H ₃₉ NO): Theory: C, 90.01; H, 5.67; N, 2.02; </ RTI></RTI> C, 90.03; H, 5.64; N, 2.03.

ESI-MS (m/z) (M ⁺ ): calc.

Preparation of Compound HTII-164

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

Elemental analysis structure (Molecular formula C ₅₅ H ₄₃ N): Theory: C, 92.01; H, 6.04; N, 1.95; Tests: C, 92.02; H, 6.02; N, 1.96.

ESI-MS (m/z) (M ⁺ ): ???

Preparation of compound HTII-192

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

Elemental analysis structure (Molecular formula C ₅₄ H ₃₉ N): Theory: C, 92.40; H, 5.60; N, 2.00; </ RTI> C, 92.41; H, 5.58; N, 2.01.

ESI-MS (m/z) (M ⁺ ): calc. 701.31.

Preparation of compound HTII-232

Prepared according to the synthesis method of the compound HTII-7, except that the raw material III-12 was used instead of the raw material III-1, and the obtained target product had a purity of 99.7% and a yield of 73.3%.

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

ESI-MS (m/z) (M ⁺ ): Found: 827.

Preparation of Compound HTII-243

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

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

ESI-MS (m/z) (M ⁺ ): calc.

Preparation of Compound HTII-266

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

Elemental analysis structure (Molecular formula C ₄₅ H ₃₂ N ₂ O): Theory: C, 87.63; H, 5.23; N, 4.54; Tests: C, 87.61; H, 5.24; N, 4.55.

ESI-MS (m/z) (M ⁺ ): s.

Preparation of compound HTII-277

Prepared according to the synthesis method of the compound HTII-7, except that the raw material III-15 was used instead of the raw material III-1, and the raw material IV-10 was used instead of the raw material IV-1, and the obtained target product had a purity of 99.9% and a yield of 77.1%.

Elemental analysis structure (Molecular formula C ₄₆ H ₃₁ NO): Theory: C, 90.02; H, 5.09; N, 2.28; </ RTI></RTI></RTI> C, 90.01; H, 5.07; N, 2.29;

ESI-MS (m/z) (M ⁺ ): calc.

Preparation of compound HTII-314

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

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

ESI-MS (m/z) (M ⁺ ): calc. 629.24.

Preparation of Compound HTII-335

Prepared according to the synthesis method of the compound HTII-7, except that the raw material III-10 was used instead of the raw material III-1, and the raw material IV-12 was used instead of the raw material IV-1, and the obtained target product had a purity of 99.7% and a yield of 78.4%.

Elemental analysis structure (Molecular formula C ₄₉ H ₃₇ NO): Theory: C, 89.74; H, 5.69; N, 2.14; Tests: C, 89.74; H, 5.69; N, 2.14.

ESI-MS (m/z) (M ⁺ ): calc.

Table 1 shows the prepared first and second organic materials, the electron blocking layer material (EB1) adjacent thereto, the host materials (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 level.

Table 1

Material name	Tg (°C)	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 of Table 1, the HOMO energy level of the first organic material of the present invention is between -5.2 eV and -5.6 eV, and the HOMO energy level of the second organic material is between -5.4 eV and -5.9 eV, and | HOMO _{first organic material} | < | HOMO _{second organic material} |; and the absolute value of the difference between the HOMO levels of the second organic material and the electron blocking layer material is ≤ 0.4 ev.

Example 1

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

Controlling the evaporation rate of the second organic material 1 is

The hole transport layer material 1 of the present invention is obtained by co-mixing.

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

The 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

The 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

The hole transport layer material 4 was 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

The hole transport layer material 5 was 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 preparation 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 preparation 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 preparation 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 preparation 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 preparation 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 devices

It is to be noted that vacuum evaporation is performed under the following conditions: using a CIC vapor deposition apparatus (manufactured by Changzhou Industry Co., Ltd.), the vapor deposition rate is controlled under a vacuum of 1.0 E ^-5 Pa.

Device preparation example 1

Follow the process below:

a) using transparent glass as a substrate, coating thereon ITO having a thickness of 150 nm, as an anode layer, and then ultrasonically cleaning with deionized water, acetone, ethanol for 15 minutes, respectively, and then treating in a plasma cleaner for 2 minutes;

b) on the washed first electrode layer, HAT-CN is deposited by a vacuum evaporation method to a thickness of 10 nm, this layer serves as a hole injection layer;

c) on the hole injection layer, the hole transport layer material 1 obtained in Example 1 was prepared by vacuum evaporation to prepare a hole transport layer material having a thickness of 90 nm, the layer being a hole transport layer;

d) on the hole transport layer, EB1 is deposited by vacuum evaporation, the thickness is 20 nm, the layer is an electron blocking layer;

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

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

g) on the electron transport layer, vapor deposition of LiF by vacuum evaporation, the thickness is 1 nm, the layer is an electron injection layer;

h) On top of the electron injecting layer, Al is vacuum-evaporated to a thickness of 100 nm, and the layer is a second electrode layer.

Device Preparation Example 2-10

The procedure of Device Preparation Example 1 was carried out except that the hole transport layer materials 2-10 obtained in Examples 2 to 10 for preparing the hole transport layer material were respectively used in the step c).

Device Preparation Example 11

The procedure of Device Preparation Example 1 was carried out except that the film thickness of the hole transport layer in step c) was 160 nm; the host material in step e) was EMH-13, the guest material was EMD-8, and EMH-13 The mass ratio to EMD-8 was 90:10 and the thickness was 40 nm.

Device Preparation Example 12-13

The procedure of Device Preparation Example 11 was carried out except that the hole transport layer material 2-3 obtained in Example 2-3 for preparing a hole transport layer material was separately used in the step c).

Device Preparation Examples 14-20

The procedure of Device Preparation Example 11 was carried out except that the hole transport layer materials 12-18 obtained in Examples 12-18 for preparing the hole transport layer material were used in the step c).

Device Preparation Example 21

The procedure of Device Preparation Example 1 was carried out except that the film thickness of the hole transport layer in step c) was 50 nm; the host material in step e) was EMH-1, the guest material was EMD-1, and EMH-1 and The EMD-1 mass ratio was 95:5 and the thickness was 25 nm.

Device Preparation Examples 22-30

The procedure of Device Preparation Example 21 was carried out except that the hole transport layer materials 19-27 obtained in Examples 19-27 for preparing the hole transport layer material were respectively used in the step c).

Comparative Examples 1-10

The procedure of Device Preparation Example 1 was carried out except that only the first organic material or the second organic material listed in Table 2 below was used as the hole transport layer material.

Table 2:

Comparative Example 11-25

The procedure of Device Preparation Example 11 was carried out except that only the first organic material or the second organic material listed in Table 3 below was used as the hole transport layer material.

table 3:

Comparative Examples 26-38

The procedure of Device Preparation Example 21 was carried out except that only the first organic material or the second organic material listed in Table 4 below was used as the hole transport layer material.

Table 4:

Tables 5-7 show the performance results of the fabricated organic electroluminescent device at a current density of 10 mA/cm ² .

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

Note: * represents the 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 the OLED device life tester jointly researched by the owner of the invention and Shanghai University.

The notes also apply to Tables 6 and 7 below.

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

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

As can be seen from the results of Table 5, the driving voltages of the devices prepared in the device preparation examples 1 to 10 of the present invention were remarkably lowered as compared with Comparative Examples 1 to 10 in which the organic materials were used alone as the hole transport layer materials. And the luminance, the luminous efficiency (ie, current efficiency), and the lifetime are both significantly improved. As can be seen from the results of Table 6, the driving voltages of the devices prepared in the device preparation examples 11 to 20 of the present invention were also significantly lower than those of Comparative Examples 11 to 25, and the luminance and the luminous efficiency (i.e., current) were obtained. Both efficiency) and longevity are significantly improved. As can be seen from the results of Table 7, the driving voltages of the devices prepared in the device preparation examples 21 to 30 of the present invention were also significantly lower than those of Comparative Examples 26 to 38, and the luminance and the luminous efficiency (i.e., current) were obtained. Both efficiency) and longevity are significantly improved.

Finally, the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Modifications or equivalents of the technical solutions of the present invention are intended to be included within the scope of the claims of the present invention without departing from the spirit and scope of the invention.

Claims (12)

1. An organic electroluminescent 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 comprising:

   a hole transporting region located above the first electrode;

   a light emitting layer over the hole transporting region, comprising a host material and a guest material;

   An electron transport region located above the light emitting layer,

   Wherein, the hole transporting region includes a hole injecting 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 first organic material has a HOMO level of from -5.2 eV to -5.6 eV, preferably from -5.3 eV to -5.5 eV, more preferably from -5.35 eV to -5.5 eV, and the HOMO level of the second organic material 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} |.
2. The organic electroluminescent device according to claim 1, wherein an absolute value of a difference between HOMO levels of said second organic material and electron blocking layer material is ≤ 0.4 volt.
3. The organic electroluminescent device according to claim 1 or 2, wherein the ratio of the first and second organic materials is from 1:99 to 99:1, preferably from 10:90 to 90:10, 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 group consisting of the formula (1), the formula (2) or the formula (3) Either:

   

   Wherein, in the general formula (1)

   X, X ₁ are each independently selected from a single bond, a carbon atom, an 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, 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 halogen atom, a halogen atom, a halogen atom, a fluorine atom, a phosphoric acid or a salt thereof, a linear or branched C _1-20 alkyl-substituted alkyl group. a linear or branched C _1-20 alkyl-substituted silane group, an aryl group having 5 to 30 carbon atoms, a hetero atom having 5 to 30 carbon atoms and at least one selected from the group consisting of N, O and S a heteroaryl group, wherein in the case of the latter two, the group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a 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 ruthenium atom, a ruthenium atom, a ruthenium atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a linear or branched C _{1 - a 20} alkyl-substituted alkyl group, a linear or branched C _1-20 alkyl-substituted silane group, an aryl group having 5 to 30 carbon atoms, having 5 to 30 carbon atoms, and at least one selected from the group consisting of N, Heteroaryl heteroaryl groups of 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, a C _6-20 aryl group, a C ₅ group _{a -20heteroaryl} group, wherein two or more R ₆ groups are attached 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, 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, 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, a C _5-20 heteroaryl group, wherein the Ar ₁ and Ar ₂ groups may also be directly joined to form a ring or through C, O, S, and 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 formula (4), the formula (5) or the formula (6), provided that R ₁ , R ₂ , R ₃ When it is different from R _{4 ,} it is a hydrogen atom;

   

   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 group.} Alkyl-substituted silane group, C _6-20 aryl-substituted alkylene group, C _1-20 alkyl-substituted imido group, C _6-20 aryl-substituted imido group, C _5-20 heteroaryl group One of the substituted imido groups;

   Y ₁ may represent the N atom or CR ₇ identically or differently, wherein R ₇ may represent the same or different hydrogen atom, helium atom, germanium atom, germanium atom, fluorine atom, cyano group, phosphoric acid or a salt thereof, a straight chain or a branch. a C _1-20 alkyl-substituted alkyl group, a linear or branched C _1-20 alkyl-substituted silane group, an aryl group having 5 to 30 carbon atoms, having 5 to 30 carbon atoms, and at least one selected a heteroaryl group derived from a hetero atom 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 group, a C _6-20 aryl group a C _5-20 heteroaryl group; wherein two or more R ₇ groups may be attached to each other and may form a ring structure;

   R ₈ and R ₉ each independently represent a hydrogen atom, a halogen atom, a halogen atom, a halogen atom, a fluorine atom, a phosphoric acid or a salt thereof, a linear or branched C _1-20 alkyl group-substituted alkyl group, a straight chain or a branch. a C _1-20 alkyl-substituted silane group of a chain, 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, a structure represented by the formula (7) or the 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 substituted;

   

   Among them, in the general formula (7):

   Y ₂ may represent the N atom or CR ₁₄ identically or differently, wherein R ₁₄ may represent the same or differently a hydrogen atom, a halogen atom, a halogen atom, a halogen atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a linear chain or a branched C _1-20 alkyl-substituted alkyl group, a linear or branched C _1-20 alkyl-substituted silane group, an aryl group having 5 to 30 carbon atoms, having 5 to 30 carbon atoms, and at least a heteroaryl group selected from heteroatoms 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 group, C _6-20 Aryl, C _5-20 heteroaryl substituted; wherein two or more R ₁₂ groups may be attached 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 group.} Alkyl-substituted silylene group, C _6-20 aryl-substituted alkylene group, C _1-20 alkyl-substituted imido group, C _6-20 aryl-substituted imido group, C _5-20 heteroaryl One of the substituted imido groups;

   The general formula (7) is linked to the general formula (4) or the general formula (5) by a ring-and-loop method, and * is represented as a linking site. When connected, only two adjacent sites can be taken, and the general formula (7) and the pass are When the formula (4) or the formula (5) is connected in a loop, the linking 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, which may be Optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; R ₁₂ and R ₁₃ may also be bonded to form a ring;

   In the general formula (2):

   L ₁ , L ₂ , L ₃ each independently represent a single bond, an arylene group having 5 to 30 carbon atoms, a hetero atom having 5 to 30 carbon atoms and at least one hetero atom selected from N, O and S An aryl group, wherein in the case of the latter two, the group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; ₁ , L ₂ , L ₃ may be connected to each other and may 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, An imido group of 5 to 30 carbon atoms, which group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; Ar ₅ , Ar ₆ , Ar ₇ may be connected to each other two-two and may form a ring structure;

   Each of Ar ₅ , Ar ₆ and Ar ₇ may also be independently represented by one of the formula (4), the formula (5), and the formula (6), wherein the groups X ₂ and X _{3 in} the formula are 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 , D ₃ each independently represent a single bond, an arylene group having 5 to 30 carbon atoms, a hetero atom having 5 to 30 carbon atoms and at least one hetero atom selected from N, O and S An aryl group, wherein in the case of the latter two, the group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group; ₁ , D ₂ , D ₃ may be connected to each other and may 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 hetero atom having 5 to 30 carbon atoms and at least one hetero atom selected from N, O and S An aryl group, an imido group of 5 to 30 carbon atoms, which group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group ; Ar ₈ , Ar ₉ , Ar ₁₀ may be connected to each other and may form a ring structure;

   At least one of Ar ₈ , Ar ₉ and Ar ₁₀ is one of the formula (4), the formula (5), and the formula (6); wherein the group X ₂ , X ₃ , Y ₁ on the formula And R ₈ , R ₉ , R ₁₀ , R ₁₁ and * each have the meanings as described above.
5. The organic electroluminescent device according to claim 4, wherein the formula (2) is represented by one of the formulae (9) to (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. Imino group, the group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, 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 as set forth in claim 4.
6. The organic electroluminescent device according to claim 4 or 5, wherein the general formula (3) is represented by one of the general formulae (13) to (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. Imino group, the group may be optionally substituted by a linear or branched C _1-20 alkyl group, a C _6-20 aryl group, a C _5-20 heteroaryl group;

   And D ₁ -D ₃ , R ₆ -R ₉ , Y ₁ and X ₂ -X ₃ all have the meanings as set forth in claim 4.
7. The organic electroluminescent device according to any one of claims 1 to 4, 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 to 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, wherein the first organic material and the second organic material of the hole transport layer are mixed and used for electroluminescent device fabrication. It is also possible to mix during the production of the organic electroluminescent device.
10. The organic electroluminescent device according to any one of claims 1 to 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 electroluminescent devices according to any of claims 1-10; and in the case of comprising a plurality of devices, the devices are combined laterally or vertically.
12. The display according to claim 11, wherein said display comprises one or more combinations of devices each having a layer of organic light-emitting materials of three colors of blue, green, and red, said devices each having 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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