CN112079767A - Aromatic amine compound and organic electroluminescent device comprising same - Google Patents

Aromatic amine compound and organic electroluminescent device comprising same Download PDF

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CN112079767A
CN112079767A CN202010924055.7A CN202010924055A CN112079767A CN 112079767 A CN112079767 A CN 112079767A CN 202010924055 A CN202010924055 A CN 202010924055A CN 112079767 A CN112079767 A CN 112079767A
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hole transport
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CN112079767B (en
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王芳
张兆超
李崇
崔明
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Jiangsu Sunera Technology Co Ltd
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Abstract

The application relates to a novel arylamine compound, wherein arylamine is used as a basic skeleton, carbazole is connected to a meta position relative to a nitrogen atom on a benzene ring connected with the nitrogen atom in the arylamine, and an aryl group is connected to a para position relative to the nitrogen atom on the benzene ring. In addition, the application also relates to the application of the novel arylamine compound as a hole transport material in an organic electroluminescent device, the organic electroluminescent device containing the arylamine compound and a display device comprising the luminescent device.

Description

Aromatic amine compound and organic electroluminescent device comprising same
Technical Field
The invention relates to the technical field of semiconductors, in particular to a novel arylamine compound, application of the novel arylamine compound as a hole transport material in an organic electroluminescent device, the organic electroluminescent device containing the arylamine compound and a display device containing the luminescent device.
Background
Carriers (holes and electrons) in an organic electroluminescent device (OLED) are injected into the device from two electrodes of the device respectively under the driving of an electric field, and meet recombination to emit light in an organic light emitting layer. High performance organic electroluminescent devices require various organic functional materials to have good photoelectric properties. For example, as a charge transport material, it is required to have good carrier mobility. The hole injection layer material and the hole transport layer material used in the existing organic electroluminescent device have relatively weak injection and transport characteristics, and the hole injection and transport rate is not matched with the electron injection and transport rate, so that the composite region has large deviation, and the stability of the device is not facilitated. In addition, reasonable energy level matching between the hole injection layer material and the hole transport layer material is an important factor for improving the efficiency and the service life of the device, and therefore, how to adjust the balance between holes and electrons and adjust the recombination region is an important subject in the field.
Blue organic electroluminescent devices are always soft ribs in the development of full-color OLEDs, and the efficiency, the service life and other properties of blue light devices are difficult to be comprehensively improved at present, so that how to improve the properties of the blue light devices is still a crucial problem and challenge in the field. Most of blue host materials currently used in the market are electron-biased hosts, and therefore, in order to adjust the carrier balance of the light-emitting layer, a hole-transporting material is required to have excellent hole-transporting performance. The better the hole injection and transmission, the more the composite region will shift to the side far away from the electron blocking layer, so as to far away from the interface to emit light, thus improving the performance of the device and prolonging the service life. Therefore, the hole transport region material is required to have high hole injection property, high hole mobility, high electron blocking property, and high electron weatherability.
Since the hole transport material has a thick film thickness, the heat resistance and amorphousness of the material have a crucial influence on the lifetime of the device. Materials with poor heat resistance are easy to decompose in the evaporation process, pollute the evaporation cavity and damage the service life of devices; the material with poor film phase stability can crystallize in the use process of the device, and the service life of the device is reduced. Therefore, the hole transport material is required to have high film phase stability and decomposition temperature during use. However, the development of materials for stable and effective organic material layers for organic electroluminescent devices has not been sufficiently realized. Therefore, there is a continuous need to develop a new material to better meet the performance requirements of the organic electroluminescent device.
Disclosure of Invention
In order to solve the problems, the organic electroluminescent device is made of materials with excellent hole and electron injection/transmission performance, film stability and weather resistance, so that the organic electroluminescent device is beneficial to improving the recombination efficiency of electrons and holes and the utilization rate of excitons, and the obtained device has high efficiency and long service life.
Therefore, the inventor has developed a novel aromatic amine compound, wherein aromatic amine is used as a basic skeleton, carbazole is connected to a meta position relative to a nitrogen atom on one benzene ring connected with the nitrogen atom in the aromatic amine, and an aryl group is connected to a para position relative to the nitrogen atom on the benzene ring, and the connection mode enables the compound disclosed by the invention to have excellent hole migration capability, film phase stability and weather resistance. Further, the present inventors have found that when a hole transport material of an organic electroluminescent device is formed by using a novel aromatic amine-based compound, effects such as improvement in device efficiency and prolongation of lifetime can be exhibited.
It is therefore an object of the present invention to provide a novel aromatic amine compound having the following general formula (1):
Figure BDA0002667716130000021
wherein
R1An aryl group having 6 to 30 ring-constituting carbon atoms, which is substituted or unsubstituted;
R2represents hydrogen atom, deuterium atom, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted 5-30-membered heteroaryl containing one or more heteroatoms, wherein the heteroatoms are one or more selected from oxygen atom, sulfur atom or nitrogen atom;
R3represents substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, or substituted or unsubstituted 5-30-membered heteroaryl containing one or more heteroatoms, wherein the heteroatoms are selected from one or more of oxygen atoms, sulfur atoms or nitrogen atoms;
wherein R is5Represented by phenyl, naphthyl or biphenyl;
R4independently represent hydrogen atom, deuterium atom, aryl with 6-30 ring carbon atoms and 5-30 membered heteroaryl, wherein the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom; and R is4The connection mode with the general formula (1) includes two modes of ring merging and substitution;
L1、L2each independently represents a direct bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group;
the substituent is optionally selected from deuterium atom, phenyl, naphthyl, biphenyl, benzofuranyl or dibenzofuranyl.
It is another object of the present invention to provide the use of the amine compounds of formula (1) as hole transport materials in organic electroluminescent devices, preferably to provide the use of said compounds in blue organic electroluminescent devices.
It is another object of the present invention to provide an organic electroluminescent device having improved luminous efficiency and lifespan, which comprises an anode, a hole transporting region, a light emitting region, an electron transporting region, and a cathode in this order, wherein the hole transporting region comprises the arylamine-based compound of the general formula (1) according to the present invention.
It is also an object of the present invention to provide a full color display apparatus including three pixels of red, green and blue, the full color display apparatus including the organic electroluminescent device of the present invention. Preferably, the present invention also provides a blue display device comprising the compound of the present invention as a hole transport material. Preferably, the invention also provides a full-color display device comprising three pixels of red, green and blue, wherein the full-color display device comprises a red organic electroluminescent device, a blue organic electroluminescent device and a green organic electroluminescent device, and the devices of the three pixels of red, green and blue have a common hole injection layer and a first hole transport layer. Preferably, the present invention further provides a full-color display device including three red, green and blue pixels, wherein the devices of the three red, green and blue pixels have a common hole injection layer and a first hole transport layer, and the second hole transport layer of the device of the blue pixel is a common layer.
Advantageous effects
According to the arylamine compound, arylamine is used as a basic skeleton, carbazole is connected to a position which is meta relative to a nitrogen atom and is on a benzene ring connected with the nitrogen atom in the arylamine, and an aryl group is connected to a position which is para relative to the nitrogen atom and is on the benzene ring.
The compound and P doping of the invention can more easily form a stable electron transfer state (CT state), so that a hole injection layer and an anode interface form good ohmic contact, which is beneficial to forming space charge limited current, promoting the injection of carriers, improving the exciton concentration of a light-emitting layer and further improving the efficiency of a device.
Compared with the hole transport material commonly used in the industry at present, the compound provided by the invention has a relatively deep HOMO energy level, so that the injection barrier between the hole transport material and the main body material is reduced, a space charge limited current region can be reached under a lower driving voltage, and the efficiency of the device is effectively improved.
The compounds 18-22 of the published patent application CN110903276A have a structure similar to that of the present application, but differ from that of the present application in the presence or absence of dimethylfluorenyl group. The inventors of the present application have found that, unexpectedly, what appears to be just one linking group difference can have a large impact on the overall performance of the material. The inventors of the present application found that when the compound of the present invention containing no dimethylfluorenyl group is used as a hole transport material, the current efficiency and the like of the prepared device are improved, and LT95 and the high temperature lifetime are significantly improved.
In published patent application CN 107652223a, compounds 11 and 23 disclose the same bonding methods as the carbazole of the present invention, except that the carbazole group is bonded to the para position of the aromatic amine with respect to the nitrogen atom, which is highly effective. However, unexpectedly, the inventors of the present application found that when the carbazole group is not attached at the position para to the nitrogen atom in the arylamine compound of the present invention, the arylamine compound is used as a hole transport material to produce an organic electroluminescent device, so that the device achieves better current efficiency and high-temperature lifetime.
In addition, the arylamine compound has excellent film phase stability and high weather resistance, so that the interface stability is good, cracking caused by high electron concentration is avoided, and the arylamine compound also has excellent high-temperature weather resistance, so that the device is prevented from being aged due to heat generated in the lighting process of the device.
In addition, the arylamine compound is combined with the nitrogen heterocyclic electron transport material, so that electrons and holes are in an optimal balance state, and the arylamine compound has higher efficiency and excellent service life, particularly the high-temperature service life of a device.
Drawings
Fig. 1 schematically shows a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
1 represents an anode; 10 denotes a hole transport region, 2 denotes a hole injection layer, 3 denotes a first hole transport layer, and 4 denotes a second hole transport layer; 5 denotes a light emitting region; 20 denotes an electron transport region, 6 denotes an electron transport layer, and 7 denotes an electron injection layer; 8 is represented as a cathode; 9 denotes a cover layer; and 30 an organic light emitting diode.
In the drawings, the thickness of layers, films, substrates, regions, etc. are exaggerated for clarity. Like reference numerals refer to like elements throughout the specification.
Detailed Description
Definition of
In the present invention, unless otherwise specified, HOMO means the highest occupied orbital of a molecule, and LUMO means the lowest unoccupied orbital of a molecule. In addition, the "difference in HOMO energy levels" and "difference in LUMO energy levels" referred to in the present specification mean a difference in absolute value of each energy value. Further, in the present invention, HOMO and LUMO energy levels are expressed in absolute values, and the comparison between the energy levels is also a comparison of the magnitude of the absolute values thereof, and those skilled in the art know that the larger the absolute value of an energy level is, the lower the energy of the energy level is.
In this specification, the term "substituted" means that one or more hydrogen atoms on the designated atom or group are replaced with the designated group, provided that the designated atom's normal valency is not exceeded in the present case.
In this specification, the term "C6-C30Aryl "or" aryl having 6 to 30 ring carbon atoms "refers to a monovalent group of a fully unsaturated monocyclic, polycyclic or fused polycyclic (i.e., rings sharing a pair of adjacent carbon atoms) system having 6 to 30 ring carbon atoms, examples of which include, but are not limited to, phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, biphenylyl, terphenyl, m-terphenyl, anthryl, pyrenyl, terphenyl, p-terphenyl, m-terphenyl, anthryl, phenanthryl, and the like,
Figure BDA0002667716130000032
A group derived from a biphenylene group, a perylene group, an indenyl group, a triphenylene group, a fluorene group, a fluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, a group in which a phenyl group and a spirobifluorenyl group are condensed,
Figure BDA0002667716130000031
And the like. "C6-C30Arylene "is a divalent group of a fully unsaturated monocyclic, polycyclic or fused polycyclic (i.e., rings that share a pair of adjacent carbon atoms) system having 6 to 30 ring carbon atoms, examples of which include, but are not limited to, divalent groups of the above groups.
In this specification, the term "C5-C30Heterocyclyl "refers to a monovalent group of saturated, partially saturated, or fully unsaturated rings having 5 to 30 ring carbon atoms and containing at least one heteroatom selected from N, O and S, including but not limited to heteroaryl, heterocycloalkyl, fused rings, or combinations thereof. When the heterocyclyl is a fused ring, each or all of the rings of the heterocyclyl may contain at least one heteroatom. Said C is5-C30Examples of heterocyclic groups include, but are not limited to, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothienyl, benzimidazolyl, indolyl, quinolyl, isoquinolyl, quinazolinyl, quinolinyl, naphthyridinyl, benzoxazinyl, benzothiazinyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, dibenzothienyl, carbazolyl, phenylfuranyl, dibenzofuranyl, N-phenylcarbazolyl, N-naphthylcarbazolyl, N-biphenylcarbazolyl, N-bithenylcarbazolyl, N-phenylcarbazolyl, 9-diphenylfluorenyl, dimethylfluorenyl, fluorenyl, triazolyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, benzoxazinyl, dibenzothienyl, carbazolyl, carboxalyl, carbo,
Figure BDA0002667716130000041
Figure BDA0002667716130000042
And the like. "C5-C30The "heterocyclylene group" is a divalent group of a saturated, partially saturated or fully unsaturated ring having 5 to 30 ring carbon atoms and containing at least one heteroatom selected from N, O and S, and examples thereof include, but are not limited to, divalent groups of the above groups.
"5-30 membered heteroaryl" means an aromatic monovalent group having 5 to 29 ring carbon atoms and at least one heteroatom selected from N, O and S, examples of which include, but are not limited to, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothienyl, benzimidazolyl, indolyl, quinolyl, isoquinolyl, quinazolinyl, quinolyl, naphthyridinyl, benzoxazinyl, benzothiazinyl, acridinyl, phenazinyl, phenothiazinyl, oxarphinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, and the like.
C6-C30Aryl or aryl having 6 to 30 ring-forming carbon atoms and C6-C30Arylene group "," C5-C30Heterocyclic group "," C5-C30Heterocyclylene "," 5-to 30-membered heteroaryl "may be unsubstituted or may be substituted with: deuterium, phenyl, biphenyl, naphthyl, benzofuranyl, dibenzofuranyl, and the like.
Arylamine compounds of general formula (1)
The invention provides an arylamine compound shown as a general formula (1):
Figure BDA0002667716130000043
wherein
L1、L2、R1、R2、R3、R4、R5As defined above.
In a preferred embodiment of the present invention, in the general formula (1),
R2represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted benzofuranyl group;
R3represented by a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl groupSubstituted or unsubstituted terphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted benzofuranyl;
the substituent is optionally selected from deuterium atom, phenyl, naphthyl, benzofuranyl or dibenzofuranyl;
R1represented by phenyl, naphthyl, biphenyl or terphenyl;
L1、L2represented as a direct bond or phenylene.
In another preferred embodiment of the present invention, in the general formula (1),
R2represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted benzofuranyl group;
R3represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted benzofuranyl group; the substituent is selected from deuterium atom, phenyl, naphthyl or dibenzofuranyl;
L1、L2represented as a direct bond or phenylene.
In a preferred embodiment of the present invention, in the general formula (1),
R4is represented by phenyl, and R4The connection mode with the general formula (1) is ring-merging connection.
In a further preferred embodiment of the present invention, in the general formula (1)
R4Is represented by benzofuranyl, and R4The connection mode with the general formula (1) is ring-merging connection.
Preferred specific examples of the aromatic amine-based compound of the present invention include, but are not limited to, the following compounds:
Figure BDA0002667716130000051
Figure BDA0002667716130000061
Figure BDA0002667716130000071
Figure BDA0002667716130000081
Figure BDA0002667716130000091
in a more preferred embodiment of the present invention, the aniline compound may be selected from any one of the following compounds: (H1) (H3), (H5), (H8), (H17), (H22), (H24), (H30), (H43), (H57), (H63), (H69), (H79), (H87), (H89), (H91), (H97), (H107), (H109), (H118), and (H114).
Organic electroluminescent device
The invention provides an organic electroluminescent device containing an arylamine compound of a general formula (1).
The organic electroluminescent device may be any element that converts electrical energy into light energy or converts light energy into electrical energy without particular limitation, and may be, for example, an organic light emitting diode. Herein, the organic light emitting diode is described as one example of the organic electroluminescent device (but the present invention is not limited thereto), and may be applied to other organic electroluminescent devices in the same manner.
In one exemplary embodiment of the present invention, an organic electroluminescent device may include an anode, a hole transport region, a light emitting region, an electron transport region, and a cathode. In addition to using the aromatic amine-based compound of the present invention in the organic electroluminescent device, the organic electroluminescent device can be prepared by conventional methods and materials for preparing organic electroluminescent devices.
The organic electroluminescent device of the present invention may be a bottom emission organic electroluminescent device, a top emission organic electroluminescent device, and a stacked organic electroluminescent device, which is not particularly limited.
In the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices may also be used. Examples thereof are transparent substrates such as glass or transparent plastic substrates; opaque substrates, such as silicon substrates; a flexible Polyimide (PI) film substrate. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, water resistance. The direction of use varies depending on the nature of the substrate. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.
Anode
Preferably, the anode may be formed on the substrate. In the present invention, the anode and the cathode are opposed to each other. The anode may be made using materials conventionally used in the art. Preferably, the anode may be made of a conductor having a high work function to aid hole injection, such as a metal, metal oxide and/or conductive polymer. Specifically, the anode may be, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, silver, or an alloy thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals with metal oxides, e.g. ZnO with Al or SnO2And Sb, or ITO and Ag; conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1, 2-dioxy) thiophene) (PEDOT), polypyrrole, and polyaniline, or combinations of the above materials, but are not limited thereto. The thickness of the anode depends on the material used and is typically 50-500nm, preferably 70-300nm, and more preferably 100-200 nm.
Cathode electrode
The cathode may be made using materials conventionally used in the art. Preferably, the cathode may be made of a conductor having a low work function to aid in electron injection, and may be, for example, a metal oxide, and/or a conductive polymer. In particular, the cathode may be, for example, goldMetals or alloys thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, and combinations thereof; materials of multilayer structure, e.g. LiF/Al, Li2O/Al, LiF/Ca and BaF2Ca, or a combination of the above materials, but not limited thereto. The thickness of the cathode depends on the material used and is generally from 10 to 50nm, preferably from 15 to 20 nm.
Light emitting area
In the present invention, the light emitting region includes a light emitting layer, which may be disposed between an anode and a cathode, wherein the light emitting layer may include at least one host material and at least one guest material. As the host material and the guest material of the light emitting region of the organic electroluminescent device of the present invention, light emitting layer materials for organic electroluminescent devices known in the art can be used. According to one embodiment of the present application, the compound of the present invention can be used for organic electroluminescent devices of blue, red, yellow and other colors, wherein blue organic electroluminescent devices are preferred, and thus, according to the present invention, the light emitting layer material can be a blue light emitting layer material, a red light emitting layer material, a yellow light emitting layer material and other colors of light emitting layer materials. In a preferred embodiment of the present application, the host material may be a blue light emitting material, such as a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or 4,4' -bis (9-Carbazolyl) Biphenyl (CBP). Preferably, the host material may comprise anthracene groups. The guest material may be, for example, perylene and its derivatives, benzopyran derivatives, rhodamine derivatives, or aminostyrene derivatives.
In a preferred embodiment of the present invention, one or two host material compounds are contained in the light-emitting layer.
In a preferred embodiment of the present invention, two host material compounds are contained in the light-emitting layer, and the two host material compounds form an exciplex.
In a preferred embodiment of the present invention, the host material of the light emitting region used is selected from one or more of the following compounds BH1-BH 6:
Figure BDA0002667716130000101
in the present invention, the light emitting region may include a phosphorescent or fluorescent guest material to improve the fluorescent or phosphorescent characteristics of the organic electroluminescent device. The guest material may use those conventionally used in the art according to the present invention. Preferably, specific examples of the phosphorescent guest material include metal complexes of iridium, platinum, and the like. For example, Ir (ppy)3[ fac-tris (2-phenylpyridine) iridium]And the like, blue phosphorescent materials such as FIrpic and FIr6, and red phosphorescent materials such as Btp2Ir (acac). In a preferred embodiment of the present invention, the guest materials of the light-emitting layer used are those suitable for co-formulation with a blue light-emitting material, preferably selected from one of the following compounds BD-1 to BD-13:
Figure BDA0002667716130000111
in the light emitting region of the present invention, the ratio of the host material to the guest material is used in a range of 99:1 to 70:30, preferably 99:1 to 85:15 and more preferably 97:3 to 87:13 by mass.
In the light emitting region of the present invention, a host material may also be mixed with a small amount of a dopant to produce a material that emits light, which may be an organic compound or a metal complex such as Al that emits fluorescence by singlet excitation; or a material such as a metal complex that emits light by multiple-state excitation into a triplet state or more. The dopant may be, for example, an inorganic compound, an organic compound, or an organic/inorganic compound, and one or more species thereof may be used.
The thickness of the light emitting region of the present invention may be 10 to 50nm, preferably 15 to 30nm, but the thickness is not limited to this range.
Hole transport region
In the organic electroluminescent device of the present invention, a hole transport region is provided between the anode and the light emitting region, and includes a hole injection layer, a first hole transport layer, and a second hole transport layer. According to the present invention, the hole transporting region uses the arylamine-based compound of the present invention.
Hole injection layer
The hole injection material used in the hole injection layer (also referred to as an anode interface buffer layer) is a material that can sufficiently accept holes from the anode at a low voltage, and the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is preferably a value between the work function of the anode material and the HOMO of the adjacent organic material layer. In a preferred embodiment of the present invention, the hole injection layer is a mixed film layer of a host organic material and a P-type dopant material. In order to smoothly inject holes from the anode into the organic film layer, the HOMO level of the host organic material must have a certain characteristic with the P-type dopant material, so that the generation of a charge transfer state between the host material and the dopant material is expected, and ohmic contact between the hole injection layer and the anode is realized, thereby realizing efficient injection of holes from the electrode to the hole injection layer. This feature is summarized as: the difference between the HOMO energy level of the host material and the LUMO energy level of the P-type doping material is less than or equal to 0.5 eV. Therefore, for hole-type host materials with different HOMO levels, different P-type doping materials need to be selected to match with the hole-type host materials, so that ohmic contact of an interface can be realized, and the hole injection effect is improved.
Preferably, the hole injection host organic material is selected from the aromatic amine-based compounds of the present invention as described previously.
Preferably, the P-type doping material is a compound having charge conductivity selected from the group consisting of: quinone derivatives such as Tetracyanoquinodimethane (TCNQ) and 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinodimethane (F4-TCNQ); or hexaazatriphenylene derivatives, such as 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN); or a cyclopropane derivative, such as 4,4',4 "- ((1E,1' E, 1" E) -cyclopropane-1, 2, 3-trimethylenetri (cyanoformylidene)) tris (2,3,5, 6-tetrafluorobenzyl); or metal oxides such as tungsten oxide and molybdenum oxide, but not limited thereto.
In a preferred embodiment of the present invention, the P-type doping material used is selected from any one of the following compounds HI-1 to HI-10:
Figure BDA0002667716130000121
in one embodiment of the invention, the ratio of host organic material to P-type dopant material used is 99:1 to 95:5, preferably 99:1 to 97:3, by mass.
The thickness of the hole injection layer of the present invention may be 5 to 20nm, preferably 8 to 15nm, but the thickness is not limited to this range.
Hole transport layer
In the organic electroluminescent device of the present invention, the hole transport layer may be disposed on the hole injection layer. The hole transport layer includes a first hole transport layer and a second hole transport layer. The hole transport material is suitably a material having a high hole mobility, which can accept holes from the anode or the hole injection layer and transport the holes into the light-emitting layer. Specific examples thereof include: aromatic amine-based organic materials, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like, but are not limited thereto.
In a preferred embodiment, the hole transport layer comprises the same aromatic amine-based compound of the present invention as the hole injection layer host organic material. In another preferred embodiment, the first hole transport layer material and the hole injection layer host organic material are the same and are the aromatic amine compounds of the present invention. In a more preferred embodiment, the first hole transport layer comprises or consists of the aromatic amine-based compound of the present invention. In a preferred embodiment, the second hole transport layer has a different organic compound than the first hole transport layer. In another preferred embodiment, the second hole transport layer is composed of a carbazole-based aromatic amine derivative. Preferably, the compound of the second hole transport layer may be
Figure BDA0002667716130000131
Figure BDA0002667716130000132
In a preferred embodiment, both the hole injection layer and the first hole transport layer are composed of materials conventionally used in the art for this purpose, and the second hole transport layer comprises or consists of the aromatic amine-based compound of the present invention. In a preferred embodiment, the first hole transport layer material is the same as the hole injection layer host organic material and is the arylamine compound of the present invention, and the second hole transport layer comprises or consists of the arylamine compound of the present invention.
The thickness of the hole transport layer of the present invention (the sum of the thicknesses of the first hole transport layer and the second hole transport layer) may be 80 to 200nm, preferably 100-150nm, but the thickness is not limited to this range. Preferably, the thickness of the first hole transport layer may be 100-150nm, preferably 115-125 nm; the thickness of the second hole transport layer is 5 to 50nm, preferably 5 to 20nm, more preferably 5 to 10 nm.
The invention does not deny the substrate collocation principle of the traditional hole materials, but further superposes the physical parameters screened by the traditional materials, namely, the influence effects of HOMO energy level, carrier mobility, film phase stability, heat resistance stability of the materials and the like on the hole injection efficiency of the organic electroluminescent device are acknowledged. On the basis, the material screening conditions are further increased, and the material selection accuracy for preparing the high-performance organic electroluminescent device is improved by selecting more excellent organic electroluminescent materials for matching the device.
Electron transport region
In the organic electroluminescent device of the present invention, the electron transport region is disposed between the light emitting region and the cathode, and includes an electron transport layer and an electron injection layer, but is not limited thereto.
Electron injection layer
The electron injection layer may be disposed between the electron transport layer and the cathode. The electron injection layer material is generally a material conventionally used in the art, preferably having a low work function, so that electrons are easily injected into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material of the organic electroluminescent device of the present invention, electron injection layer materials for organic electroluminescent devices known in the art, for example, lithium; lithium salts such as lithium 8-hydroxyquinoline, lithium fluoride, lithium carbonate or lithium azide; or cesium salts, cesium fluoride, cesium carbonate or cesium azide. The thickness of the electron injection layer of the present invention may be 0.1 to 5nm, preferably 0.5 to 3nm, and more preferably 0.8 to 1.5nm, but the thickness is not limited to this range.
Electron transport layer
The electron transport layer may be disposed over the light emitting film layer or, if present, the hole blocking layer. The electron transport layer material is a material that easily receives electrons of the cathode and transfers the received electrons to the light emitting layer. Heterocyclic nitrogen-based materials with 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 organic electroluminescent devices known in the art, for example, in Alq, can be used3And metal complexes of hydroxyquinoline derivatives represented by LiQ, various rare earth metal complexes, triazole derivatives, triazine derivatives such as 2, 4-bis (9, 9-dimethyl-9H-fluoren-2-yl) -6- (naphthalen-2-yl) -1,3, 5-triazine (CAS number: 1459162-51-6), 2- (4- (9, 10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d]Imidazole derivatives such as imidazole (CAS number: 561064-11-7, commonly known as LG201), oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silicon-based compound derivatives, and the like. Alq3And the LiQ structural formula is as follows:
Figure BDA0002667716130000141
in a preferred organic electroluminescent device of the invention, the electron transport layer comprises or consists of a nitrogen heterocyclic derivative of the general formula (a):
Figure BDA0002667716130000142
wherein
Ar1、Ar2And Ar3Represent, independently of one another: substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing one or more hetero atoms5-C30Heterocyclyl, said heteroatoms being independently from each other selected from N, O or S; preferably phenyl, pyridyl, carbazolyl, dimethylfluorenyl, biphenyl, dibenzofuranyl, triphenylenyl, phenanthrenyl, naphthyl, 1-phenylbenzimidazol-2-yl, isoquinolinyl,
Figure BDA0002667716130000143
Figure BDA0002667716130000144
L represents a single bond, substituted or unsubstituted C6-C30Arylene radical, substituted or unsubstituted C containing one or more hetero atoms5-C30(ii) heterocyclylene, each of said heteroatoms being independently selected from N, O or S; preferably a single bond, phenylene, biphenylene, phenylenephenylene pyridyl;
n represents 1 or 2, preferably 1;
X1、X2、X3independently of one another, N or CH, with the proviso that X1、X2、X3At least one group in (a) represents N.
In a preferred embodiment of the present invention, the electron transport layer comprises any one of the compounds selected from the group consisting of:
Figure BDA0002667716130000145
Figure BDA0002667716130000151
in a more preferred embodiment of the present invention, the electron transport layer comprises any one of the compounds selected from the group consisting of: (E2) (E5), (E12), (E16) or (E23).
In a preferred embodiment of the present invention, the electron transport layer comprises, in addition to the compound of the formula (A), other compounds conventionally used in electron transport layers, for example, Alq3LiQ is preferred. In a more preferred embodiment of the present invention, the electron transport layer is composed of one of the compounds of the general formula (a) and one of the other compounds conventionally used for electron transport layers, preferably LiQ.
The thickness of the electron transport layer of the present invention may be 10 to 80nm, preferably 20 to 60nm, and more preferably 25 to 45nm, but the thickness is not limited to this range.
Covering layer
In order to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., a CPL layer, also referred to as a capping layer) may be added on the electrode on the light extraction side of the device. According to the principle of optical absorption and refraction, the CPL cover layer material should have a higher refractive index as well as a better refractive index, and the absorption coefficient should be smaller as well. Any material known in the art may be used as the CPL layer material, such as Alq3, or N4, N4' -diphenyl-N4, N4' -bis (9-phenyl-3-carbazolyl) biphenyl-4, 4' -diamine. The CPL capping layer is typically 5-300nm, preferably 20-100nm and more preferably 40-80nm thick.
The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layers of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer. The present invention also relates to a method of preparing an organic electroluminescent device comprising sequentially laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer and a cathode, and optionally a capping layer, on a substrate. In this regard, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, LITI, or the like may be used, but are not limited thereto. In the present invention, it is preferable that the respective layers are formed by a vacuum evaporation method. The individual process conditions in the vacuum evaporation process can be routinely selected by the person skilled in the art according to the actual requirements.
The material for forming each layer according to the present invention may be used as a single layer by forming a film alone, may be used as a single layer by forming a film in admixture with another material, or may be used as a laminated structure of layers formed alone, layers formed in admixture with each other, or a laminated structure of layers formed alone and layers formed in admixture with each other.
The invention also relates to a full-color display device, in particular a flat panel display device, having three pixels of red, green and blue, comprising the organic electroluminescent device of the invention. The display device may further include at least one thin film transistor. The thin film transistor may include a gate electrode, source and drain electrodes, a gate insulating layer, and an active layer, wherein one of the source and drain electrodes may be electrically connected to an anode of the organic electroluminescent device. The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor, or an oxide semiconductor, but is not limited thereto.
The following examples are intended to better illustrate the invention, but the scope of the invention is not limited thereto.
Examples
Unless otherwise indicated, various materials used in the following examples and comparative examples are commercially available or may be obtained by methods known to those skilled in the art.
I. Preparation of the Compounds of the invention
Example 1: compound H1
Figure BDA0002667716130000161
Adding 0.01mol of raw material A, 0.012mol of raw material B, 0.02mol of sodium carbonate and 150ml of toluene into a three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 1 multiplied by 10-4mol tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) The reaction was heated to 105 ℃ and refluxed for 24 hours, and the reaction was complete when the sample was taken and no bromide remained. Then naturally cooling to room temperature, filtering, and performing reduced pressure rotary evaporation on the filtrate (-0.09MPa, 85 ℃), passing through a neutral silica gel column(silica gel 100 mesh, eluent: chloroform: n-hexane ═ 1:2 (volume ratio)) to give intermediate M. Elemental analysis Structure (molecular formula C)24H15BrClN): test values are: c, 66.60; h, 3.45; br, 18.49; cl, 8.18; and N, 3.27. MS: found 431.37.
Adding 0.01mol of intermediate M, 0.012mol of raw material B, 0.02mol of sodium carbonate and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 1X 10-4mol tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) The reaction was heated to 105 ℃ and refluxed for 24 hours, and a sample was taken from the plate to show that no bromide remained and the reaction was complete. Naturally cooling to room temperature, filtering, carrying out reduced pressure rotary evaporation on the filtrate (-0.09MPa, 85 ℃), and passing through a neutral silica gel column (silica gel 100 meshes and 200 meshes, eluent: chloroform: n-hexane: 1:2 (volume ratio)) to obtain an intermediate P. Elemental analysis Structure (molecular formula C)30H20ClN): test values are: c83.83; h4.66; cl, 8.28; and (3) N3.24. MS: found 429.49.
A250 ml three-necked flask was charged with 0.01mol of the raw material D, 0.012mol of the intermediate P, 0.03mol of potassium tert-butoxide, and 1X 10 under a nitrogen atmosphere-4mol tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3)、1×10-4mol triphenylphosphine, 150ml toluene, heated to reflux for 12 hours, and a sample of the dot plate showed complete reaction. Naturally cooling, filtering, rotatably evaporating the filtrate, and passing through a silica gel column (silica gel 100-200 meshes, eluent: chloroform: n-hexane: 1:2 (volume ratio)) to obtain the target compound 1. Elemental analysis Structure (molecular formula C)54H38N2): test values are: c, 90.75; h, 5.38; and N, 3.87. MS: found 714.41.
Nuclear magnetic characterization:1H NMR(400MHz,Chloroform-d)8.10–7.97(m,1H),7.85–7.74(m,1H),7.66–7.53(m,9H),7.53–7.43(m,7H),7.43–7.27(m,13H),7.26–7.18(m,2H),7.14–7.07(m,4H),7.01(dd,1H).
the following compounds were prepared in a similar manner to example 1, starting with the synthetic materials shown in Table 1 below, and nuclear magnetic characterization shown in tables 1-1 below. The synthesis of the hole transport layer material used in the present invention refers to patent CN110577511A, and the raw materials used are provided by the energy conservation in the middle.
TABLE 1
Figure BDA0002667716130000171
Figure BDA0002667716130000181
Figure BDA0002667716130000191
Figure BDA0002667716130000201
TABLE 1-1
Figure BDA0002667716130000202
Figure BDA0002667716130000211
Compound testing
Glass transition temperature Tg: measured by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter, Nachi company, Germany), the rate of temperature rise was 10 ℃/min.
HOMO energy level: the test was conducted by an ionization energy test system (IPS3) and was conducted in an atmospheric environment.
Eg energy level: based on the ultraviolet spectrophotometry (UV absorption) baseline of the material single film and the ascending side of the first absorption peak, a tangent is taken, and the numerical value of the intersection point of the tangent and the baseline is calculated.
Hole mobility: the material was fabricated into a single charge device and measured by space charge (induced) limited current method (SCLC).
Triplet energy level T1: the material was dissolved in toluene solution and tested by Hitachi F4600 fluorescence spectrometer.
The results of the physical property tests are shown in Table 2. HT3 and HT4 structural formulas are shown below.
TABLE 2
Figure BDA0002667716130000212
As is clear from the data in Table 2 above, the HOMO energy level of the compound of the present invention is 5.3-6.0eV, preferably 5.5-5.7eV, and more preferably 5.54-5.63 eV; tg of 130-160 ℃, preferably 135-150 ℃; the Eg level is 3.0-3.5eV, preferably 3.0-3.3 eV; hole mobility of 6.1-8.9cm2V.s, preferably 6.15-8.8cm2V · s; t1 is 2.4-2.6eV, preferably 2.45-2.55 eV. From the above, the compound of the present invention has a suitable HOMO level, a higher glass transition temperature Tg, a higher hole mobility and a wider band gap (Eg), and is suitable for use as a hole transport material in an organic electroluminescent device, so that the organic electroluminescent device has high efficiency, low voltage and long lifetime.
Preparation of organic electroluminescent device
The molecular structural formula of the materials involved in the following preparation is as follows:
Figure BDA0002667716130000221
device preparation examples
The compounds of the present invention are used below as an example of a top-emitting organic electroluminescent device, but the present application is not limited thereto.
Comparative example 1
The organic electroluminescent device was prepared as follows:
a) using transparent glass as a substrate, washing an anode layer (ITO (15nm)/Ag (150nm)/ITO (15nm)) on the substrate, respectively ultrasonically cleaning the anode layer for 15 minutes by using deionized water, acetone and ethanol, and then treating the anode layer for 2 minutes in a plasma cleaner;
b) after washingOn the anode layer, a hole transport material HT1 and a P-type dopant material HI1 were placed in two evaporation sources under a vacuum of 1.0E-5The vapor deposition rate of a compound HT1 under Pa pressure is controlled to be
Figure BDA0002667716130000222
Controlling the evaporation rate of the P-type doping material HI1 to be
Figure BDA0002667716130000223
Co-evaporating to form a hole injection layer with the thickness of 10 nm;
c) evaporating a first hole transport layer on the hole injection layer in a vacuum evaporation mode, wherein the hole transport layer is made of a compound HT1 and has the thickness of 120 nm;
d) evaporating a second hole transport layer B-1 on the first hole transport layer in a vacuum evaporation mode, wherein the thickness of the second hole transport layer B-1 is 10 nm;
e) evaporating a luminescent layer material on the second hole transport layer in a vacuum evaporation mode, wherein the host material is BH1, the guest material is BD1, the mass ratio is 97:3, and the thickness is 20 nm;
f) on the light-emitting layer, ET1 and LiQ were evaporated by vacuum evaporation, ET1: the LiQ mass ratio is 50:50, the thickness is 30nm, and the layer is used as an electron transport layer;
g) evaporating LiF on the electron transport layer in a vacuum evaporation mode, wherein the thickness of the LiF is 1nm, and the LiF is an electron injection layer;
h) vacuum evaporating an Mg: Ag (1:1) electrode layer with the thickness of 16nm on the electron injection layer, wherein the layer is a cathode layer;
i) CPL material CPL-1 is evaporated in vacuum on the cathode layer, and the thickness is 70 nm.
Comparative examples 2 to 22
The organic materials in steps b), c), d), f) were replaced with the organic materials shown in table 3, respectively, according to the method of device preparation example 1, wherein the proportions of ET1: LiQ, E2: LiQ, E5: LiQ, E12: LiQ, E16: LiQ, E23: LiQ were all 50: 50.
Examples 1 to 122
The procedure of device preparation example 1 was followed, except that the organic materials in steps b), c), d), f) were respectively replaced with organic materials as shown in table 3, wherein the proportions of ET1: LiQ, E2: LiQ, E5: LiQ, E12: LiQ, E16: LiQ, E23: LiQ were all 50: 50.
TABLE 3
Figure BDA0002667716130000231
Figure BDA0002667716130000241
Figure BDA0002667716130000251
Figure BDA0002667716130000261
Figure BDA0002667716130000271
After the OLED light-emitting device was prepared as described above, the cathode and the anode were connected by a known driving circuit, and various properties of the device were measured. The device measurement performance results of examples 1 to 122 and comparative examples 1 to 22 are shown in table 4.
TABLE 4
Figure BDA0002667716130000272
Figure BDA0002667716130000281
Figure BDA0002667716130000291
Figure BDA0002667716130000301
Note: LT95 refers to the time it takes for the device luminance to decay to 95% of the original luminance at a luminance of 1500 nits;
voltage, current efficiency and color coordinates were tested using the IVL (current-voltage-brightness) test system (frastd scientific instruments, su);
the life test system is an EAS-62C type OLED life test system of Japan scientific research Co.
The high-temperature service life means that the brightness of the device is 10mA/cm at the temperature of 80 DEG C2In this case, the time taken for the luminance of the device to decay to 80% of the original luminance.
As can be seen from the results of table 4, the organic electroluminescent device (hereinafter referred to as an invention device) prepared using the arylamine-based compound of the present invention containing no fluorene group and no carbazole group at a position para to the nitrogen atom as the organic host material of the hole injection layer and simultaneously as the hole transport layer material has a comparable voltage as compared to the organic electroluminescent device (hereinafter referred to as a comparative device) prepared using other substances as the hole injection layer and simultaneously as the hole transport layer material, while the invention device has unexpected technical effects in terms of current efficiency, high temperature lifetime, LT 95. Specifically, under the same conditions, the current efficiency of the inventive device (about 159-169cd/A) is higher than that of the comparative device (about 147-156cd/A), and is improved by more than about 4%; in the LT95 aspect, the inventive device (about 310-360Hr) far exceeds the comparative device (about 265-285Hr), and is improved by more than 10%; in terms of high temperature lifetime (LT80), the inventive device (about 900-. It can be seen that under the same conditions, the inventive device achieved better current efficiency, LT95, and high temperature lifetime than the comparative device with comparable drive voltages, which would not be expected by one skilled in the art.
In addition, in the inventive examples, compared with the devices obtained by matching the electron transport layer compound ET1 (examples 1-63), the devices obtained by matching the electron transport layer compounds E2, E5, E12, E16, E23 (examples 63-113) had current efficiencies comparable to those of the devices obtained by matching the electron transport layer compounds E2, E5, E12, E16, E23, but had better LT95 (311-.

Claims (10)

1. An arylamine compound has the following general formula (1):
Figure FDA0002667716120000011
wherein
R1An aryl group having 6 to 30 ring-constituting carbon atoms, which is substituted or unsubstituted;
R2represents hydrogen atom, deuterium atom, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted 5-30-membered heteroaryl containing one or more heteroatoms, wherein the heteroatoms are one or more selected from oxygen atom, sulfur atom or nitrogen atom;
R3represents substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, or substituted or unsubstituted 5-30-membered heteroaryl containing one or more heteroatoms, wherein the heteroatoms are selected from one or more of oxygen atoms, sulfur atoms or nitrogen atoms;
R5represented by phenyl, naphthyl or biphenyl;
R4represents hydrogen atom, deuterium atom, aryl with 6-30 ring carbon atoms and 5-30-membered heteroaryl, wherein the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom; and R is4The connection mode with the general formula (1) includes two modes of ring merging and substitution;
L1、L2each independently represents a direct bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene groupSubstituted or unsubstituted terphenylene;
the substituent is optionally selected from deuterium atom, phenyl, naphthyl, biphenyl, benzofuranyl or dibenzofuranyl.
2. The aromatic amine compound according to claim 1, wherein
L1、L2Represented by a direct bond or a phenylene group,
R2represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted benzofuranyl group;
R3represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted benzofuranyl group;
the substituent is selected from deuterium atom, phenyl, naphthyl or dibenzofuranyl;
R1expressed as phenyl, naphthyl, biphenylyl or terphenyl, preferably phenyl.
3. The aromatic amine-based compound according to claim 1 or 2,
wherein R is4Is represented by phenyl, and R4The connection mode with the general formula (1) is ring-merging connection.
4. The aromatic amine-based compound according to claim 1 or 2,
wherein R is4Is represented by benzofuranyl, and R4The connection mode with the general formula (1) is ring-merging connection.
5. The aromatic amine-based compound according to any one of claims 1 to 4, which is selected from any one of the following compounds;
Figure FDA0002667716120000012
Figure FDA0002667716120000021
Figure FDA0002667716120000031
Figure FDA0002667716120000041
Figure FDA0002667716120000051
Figure FDA0002667716120000061
6. an organic electroluminescent device comprising an anode, a hole transport region, a light emitting region, an electron transport region and a cathode in this order, wherein the hole transport region comprises the arylamine-based compound of any one of claims 1 to 5, preferably the organic electroluminescent device is a blue organic electroluminescent device; preferably, the hole transport region comprises a hole injection layer, a first hole transport layer and a second hole transport layer, more preferably, the first hole transport layer and the hole injection layer comprise the arylamine-based compound of any one of claims 1 to 5; more preferably, the first hole transport layer is composed of the arylamine compound described in any one of claims 1 to 5, and the hole injection layer is composed of the arylamine compound described in any one of claims 1 to 5 and other doping materials conventionally used for the hole injection layer; advantageously, the hole injection layer and the first hole transport layer consist of conventional materials for hole injection layers and first hole transport layers, the second hole transport layer consists of an arylamine-based compound as claimed in any of claims 1 to 5, more advantageously the first hole transport layer and the second hole transport layer consist of an arylamine-based compound as claimed in any of claims 1 to 5, and the hole injection layer consists of an arylamine-based compound as claimed in any of claims 1 to 5 and further of other doping materials conventionally used for hole injection layers.
7. The organic electroluminescent device according to claim 5, wherein the electron transport region comprises a nitrogen heterocyclic compound represented by the following general formula (A):
Figure FDA0002667716120000062
wherein
Ar1、Ar2And Ar3Independently of one another, represents substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing one or more hetero atoms5-C30Heterocyclyl, said heteroatoms being independently from each other selected from N, O or S; l represents a single bond, substituted or unsubstituted C6-C30Arylene, substituted or unsubstituted C containing one or more hetero atoms5-C30(ii) heterocyclylene, each of said heteroatoms being independently selected from N, O or S;
n represents 1 or 2, preferably 1;
X1、X2、X3independently of one another, N or CH, with the proviso that X1、X2、X3At least one group in (a) represents N.
8. The organic electroluminescent device according to claim 7, wherein the electron transport region comprises an electron transport layer and an electron injection layer, wherein the electron transport layer comprises the nitrogen heterocyclic compound of the general formula (A) according to claim 8, and the electron injection layer is an N-type metal material.
9. Use of the arylamine compounds according to any one of claims 1 to 5 as hole transport materials in organic electroluminescent devices.
10. A display device comprising the organic electroluminescent device according to any one of claims 6 to 8.
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