CN114989022A - Compound containing triarylamine and phenanthrene structure and application thereof - Google Patents

Compound containing triarylamine and phenanthrene structure and application thereof Download PDF

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CN114989022A
CN114989022A CN202110228807.0A CN202110228807A CN114989022A CN 114989022 A CN114989022 A CN 114989022A CN 202110228807 A CN202110228807 A CN 202110228807A CN 114989022 A CN114989022 A CN 114989022A
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吴秀芹
尚书夏
谢丹丹
李崇
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention discloses a compound containing triarylamine and phenanthrene structures and application thereof, belonging to the technical field of semiconductors. The structure of the compound containing triarylamine and phenanthrene structures is shown in a general formula (1), and the compound is applied to an organic electroluminescent device, has strong hole injection transmission capability and proper energy level, can effectively transmit and inject holes into a light-emitting layer, and can realize high-efficiency light emission of the organic electroluminescent device under low driving voltage.

Description

Compound containing triarylamine and phenanthrene structure and application thereof
Technical Field
The invention relates to the technical field of semiconductors, in particular to a compound containing triarylamine and phenanthrene structures and application thereof.
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 in an organic light emitting layer to emit light. 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 view of the above problems in the prior art, the applicant of the present invention provides a compound containing triarylamine and phenanthrene structures and applications thereof. The compound contains phenanthryl and triarylamine structures, and has excellent hole transport capacity, film phase stability and weather resistance. When the triarylamine and the phenanthrene compound are used to form a hole injection and transport material of an organic electroluminescent device, the device performance can be improved, such as device efficiency improvement, drive voltage reduction, and lifetime extension.
The technical scheme of the invention is as follows:
a compound containing triarylamine and phenanthrene structures, wherein the structure of the compound is shown as a general formula (1):
Figure BDA0002957994500000011
in the general formula (1), L, L 1 、L 2 Each independently represents a single bond, phenylene, naphthylene, biphenylene, furylene, benzofuranylene or dibenzofuranylene;
R 1 、R 2 each independently represents substituted or unsubstituted C 6 -C 30 One of an aryl, a substituted or unsubstituted 5-to 30-membered heteroaryl containing one or more heteroatoms;
r represents phenyl, naphthyl, biphenyl, furyl, benzofuryl or dibenzofuryl;
for takingThe substituent of the substituent group is selected from deuterium, tritium and C 1-10 Alkyl of (C) 6 -C 30 One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is an oxygen, sulfur or nitrogen atom.
In a preferred embodiment, the R group 1 、R 2 Each independently represents one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted benzodioxin, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted piperonyl, substituted or unsubstituted indenyl, and substituted or unsubstituted carbazolyl;
the substituent group used for the substituent group is one or more of deuterium, tritium, methyl, tert-butyl, adamantyl, phenyl, naphthyl, biphenyl, carbazolyl, benzofuranyl, dibenzofuranyl, fluorenyl, phenanthryl, pyrenyl, acenaphthenyl and piperonyl.
In a preferred embodiment, R represents phenyl, R 2 Represented as biphenyl or phenyl.
In a preferred embodiment, R represents phenyl, R represents 1 And R 2 The same is true.
Preferably, the specific structure of the compound is any one of the following structures:
Figure BDA0002957994500000021
Figure BDA0002957994500000031
Figure BDA0002957994500000041
Figure BDA0002957994500000051
Figure BDA0002957994500000061
Figure BDA0002957994500000071
Figure BDA0002957994500000081
Figure BDA0002957994500000091
Figure BDA0002957994500000101
an organic electroluminescent device comprises an anode, a hole transport region, a luminescent region, an electron transport region and a cathode, wherein the hole transport region contains the compound containing triarylamine and phenanthrene structures.
In a preferred scheme, the hole transport region sequentially comprises a hole injection layer, a hole transport layer and an electron blocking layer; the hole injection layer and the hole transmission layer both comprise the compound containing triarylamine and phenanthrene structures; preferably, the hole injection layer is a mixed film layer of the compound containing the triarylamine and phenanthrene structures and the P-type doping material.
In a preferred embodiment, the light-emitting region includes a host material and a guest material, where the host material includes an anthracene group and the guest material is a fluorescent material;
preferably, the electron transport region comprises a nitrogen heterocyclic compound represented by the following general formula (3):
Figure BDA0002957994500000102
in the general formula (3), Ar 1 、Ar 2 、Ar 3 Independently of one another, as substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C containing one or more hetero atoms 5 -C 30 One of heterocyclic groups;
L 1 selected from single bond, substituted or unsubstituted C 6 -C 30 Arylene, substituted or unsubstituted C containing one or more hetero atoms 5 -C 30 One of a heterocyclylene group;
each of said heteroatoms is independently selected from N, O or S; n represents 1 or 2;
X 1 、X 2 、X 3 independently of one another, N or CH, X 1 、X 2 、X 3 Represents N.
Preferably, the electron transport region comprises an electron transport layer and an electron injection layer, wherein the electron transport layer comprises the nitrogen heterocyclic compound; the electron injection layer is made of an N-type metal material.
Preferably, the nitrogen heterocyclic compound has a structure of any one of the following compounds:
Figure BDA0002957994500000111
preferably, the electron transport region comprises an electron transport layer and an electron injection layer, wherein the electron transport layer comprises the nitrogen heterocyclic compound; the electron injection layer is made of an N-type metal material.
The beneficial technical effects of the invention are as follows:
the triarylamine and phenanthrene compound has a higher glass transition temperature, excellent film phase stability and excellent high-temperature weather resistance, so that the device is prevented from being aged or crystallized due to heat generated in the lighting process.
The compound has smaller reforming energy (energy generated by molecular configuration change and environmental polarization caused by electronic state change), so that the compound has higher mobility, thereby having excellent hole transport performance, and can obviously reduce the voltage of the device when being applied to an OLED device.
The compound provided by the invention has a proper HOMO energy level, can form a stable CT complex with a P doping material under a low doping proportion, further improves the hole injection efficiency, and reduces the risk of Cross-talk (red, green and blue pixels are subjected to color crosstalk due to different starting voltages of the red, green and blue pixels, wherein the starting voltage of the blue pixel is highest, and when the blue pixel is lighted, the risk of lighting an adjacent pixel point is caused).
In addition, the triarylamine and phenanthrene compound is combined with the nitrogen heterocyclic electronic transmission material, so that electrons and holes are in an optimal balance state, and the triarylamine and phenanthrene compound has higher efficiency and excellent service life, particularly high-temperature service life of devices.
Drawings
FIG. 1 is a schematic cross-sectional view of an organic electroluminescent device according to the present invention.
In the figure: 1 is a substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, 10 is a cathode layer, and 11 is a CPL layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In the present invention, unless otherwise stated, all operations are carried out at room temperature under normal pressure.
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 the present invention, when a layer or element is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or intervening layers may also be present. Further, it will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present. Like reference numerals refer to like elements throughout.
In the present invention, when describing electrodes and organic electroluminescent devices, and other structures, "upper", "lower", "top", and "bottom" and the like used to indicate orientation only indicate orientation in a certain specific state, and do not mean that the related structures can exist only in the orientation; conversely, if the structure is repositioned, e.g., inverted, the orientation of the structure is changed accordingly. Specifically, in the present invention, the "bottom" side of the electrode refers to the side of the electrode that is closer to the substrate during fabrication, while the opposite side that is further from the substrate is the "top" side.
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 "C 6 -C 30 Aryl "refers to 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.
In this specification, the term 5 to 30 membered heteroaryl refers to a saturated, partially saturated or fully unsaturated cyclic group 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.
In the present specification, the substituted or unsubstituted fluorenyl group means a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, and a substituted or unsubstituted spirofluorenyl group.
More precisely, substituted or unsubstituted C 6 -C 30 Aryl and/or substituted or unsubstituted 5-to 30-membered heteroaryl means substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted tetracenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted metaterphenylyl, substituted or unsubstituted heteroarylphenyl
Figure BDA0002957994500000131
A group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted pyridyl group, a substituted or substituted pyridyl group, a substituted or unsubstituted pyridyl group, a substituted or substituted pyridyl group, a substituted or substituted pyridyl group, or substituted orA triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, Substituted or unsubstituted phenoxazinyl, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, combinations thereof or fused rings of combinations of the foregoing, but are not limited thereto.
In the present specification, substituted or unsubstituted C 6 -C 30 Arylene or substituted or unsubstituted C 5 -C 30 Heteroarylene refers to a substituted or unsubstituted C as defined above and having two linking groups 6 -C 30 Aryl or substituted or unsubstituted C 5 -C 30 Heteroaryl groups, such as substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted tetracylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted isophthalyltriphenylene, substituted or unsubstituted naphthylene
Figure BDA0002957994500000132
A group, a substituted or unsubstituted triphenylene methylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanylene groupA thienyl group, a substituted or unsubstituted pyrrolylene group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolylene group, a substituted or unsubstituted oxazolylene group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolylene group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted triazinylene group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenylene group, a substituted or unsubstituted benzimidazolylene group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted quinazolinylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted naphthyrylene group, Substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted fluorenylidene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, combinations thereof or fused rings of combinations of the foregoing, but not limited thereto.
In this specification, the hole characteristics refer to characteristics that are capable of supplying electrons when an electric field is applied and holes formed in the anode are easily injected into and transported in the light emitting layer due to the conductive characteristics according to the Highest Occupied Molecular Orbital (HOMO) level.
In this specification, the electron characteristics refer to characteristics that are capable of accepting electrons when an electric field is applied and electrons formed in the cathode are easily injected into and transported in the light-emitting layer due to the conductive characteristics according to the Lowest Unoccupied Molecular Orbital (LUMO) level.
Organic electroluminescent device
The invention provides an organic electroluminescent device using a compound containing triarylamine and phenanthrene structure of general formula (1).
In an 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.
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 differs 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 of a conductor having a high work function to aid hole injection, and may be, for example, a metal such as nickel, platinum, copper, zinc, silver, or an alloy thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and metal oxides, such as ZnO with Al or ITO with Ag; conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1, 2-dioxy) thiophene), and polyaniline, but are not limited thereto. The thickness of the anode depends on the material used, and is generally 50-500nm, preferably 70-300nm, and more preferably 100-200nm, and ITO and Ag, which are combinations of metals and metal oxides, are preferably used in the present invention.
Cathode electrode
The cathode may be made of a conductor having a lower work function to aid in electron injection, and may be, for example, a metal or alloy thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, aluminum, silver, tin, and combinations thereof; materials of multilayer structure, e.g. LiF/Al, Li 2 O/Al and BaF 2 But not limited thereto,/Ca. The thickness of the cathode depends on the material used, and is typically 10-50nm, preferably 15 to 20 nm.
Light emitting region
In the present invention, the light emitting region may be disposed between the anode and the cathode, and 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. The host material may be, for example, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or 4,4' -bis (9-Carbazolyl) Biphenyl (CBP). As the host material, a compound containing an anthracene group can be used. The guest material may be, for example, quinacridone, coumarin, rubrene, perylene and derivatives thereof, 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 region.
In a preferred embodiment of the present invention, two host material compounds are contained in the light emitting region, and the two host material compounds form an exciplex.
In a preferred embodiment of the invention, the host material of the light-emitting region used is selected from one or more of the following compounds BH-1-BH-11:
Figure BDA0002957994500000141
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. Specific examples of the phosphorescent guest material include metal complexes of iridium, platinum, and the like, and for the fluorescent guest material, those generally used in the art may be used. In a preferred embodiment of the present invention, the guest material of the luminescent film layer used is selected from one of the following compounds BD-1 to BD-10:
Figure BDA0002957994500000142
Figure BDA0002957994500000151
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.
The thickness of the light emitting region may be 10-50nm, preferably 15-30nm, 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 hole transport layer, and an electron blocking layer.
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 0.4 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, specific examples of the host organic material include: metalloporphyrin, oligothiophene, arylamine organic materials, hexanitrile hexaazatriphenylene, quinacridone organic materials, perylene organic materials, anthraquinone, polyaniline and polythiophene conductive polymers; but is not limited thereto. Preferably, the host organic material is an arylamine-based organic material.
Preferably, the P-type doping material is a compound having charge conductivity selected from the group consisting of: quinone derivatives 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 HI1 to HI 8:
Figure BDA0002957994500000152
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.
In a preferred embodiment of the present invention, the hole injection layer is a mixed film layer of an arylamine compound and a P-type dopant material, and the arylamine compound is an arylamine compound of the general formula (1).
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 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 as the hole injection layer.
The thickness of the hole transport layer of the present invention may be 80-200nm, preferably 100-150nm, but the thickness is not limited to this range.
Electron blocking layer
In the organic electroluminescent device of the present invention, the electron blocking layer may be disposed between the hole transport layer and the light emitting layer, and particularly, contacts the light emitting layer. The electron blocking layer is disposed to contact the light emitting layer, and thus, hole transfer at the interface of the light emitting layer and the hole transport layer can be precisely controlled. In one embodiment of the present invention, the electron blocking layer material is selected from carbazole-based aromatic amine derivatives. The thickness of the electron blocking layer may be 5 to 20nm, preferably 8 to 15nm, but the thickness is not limited to this range.
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 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. 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 used 3 Metal complexes of hydroxyquinoline derivatives represented by BAlq and 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, and the like.
In a preferred organic electroluminescent device of the present invention, the electron transporting region comprises a nitrogen heterocyclic compound represented by the following general formula (3):
Figure BDA0002957994500000171
in the general formula (3), Ar 1 、Ar 2 、Ar 3 Independently of one another, as substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C containing one or more hetero atoms 5 -C 30 One of heteroaryl;
L 1 selected from single bond, substituted or unsubstituted C 6 -C 30 Arylene, substituted or unsubstituted C containing one or more hetero atoms 5 -C 30 One of heteroarylenes;
the heteroatom is N, O or S; n represents 1 or 2;
X 1 、X 2 、X 3 independently of one another, N or CH, X 1 、X 2 、X 3 Represents N.
Preferably, the nitrogen heterocyclic compound of the general formula (3) is represented by the general formula (3-1):
Figure BDA0002957994500000172
wherein Ar is 1 、Ar 2 、Ar 3 、X 1 、X 2 、X 3 、L 1 Each as defined above.
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 BDA0002957994500000173
Figure BDA0002957994500000181
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:
Figure BDA0002957994500000182
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.
Cover 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 cathode 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 or metal can; or a thin film covering the entire surface of the organic layer.
Hereinafter, an organic electroluminescent device according to an embodiment of the present invention is described.
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. It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
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.
Exemplary embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purposes of limitation. In some instances, features, characteristics and/or elements described in connection with a particular embodiment may be used alone or in combination with features, characteristics and/or elements described in connection with other embodiments, unless specifically indicated otherwise, as will be apparent to one of ordinary skill in the art upon submission of the present application. Accordingly, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
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.
Example 1: synthesis of Compound 7
Figure BDA0002957994500000191
A250 ml three-necked flask was charged with 0.012mol of A1 as a starting material, 0.01mol of B1 as a starting material, 0.03mol of potassium tert-butoxide, and 1X 10 under a nitrogen atmosphere -4 mol tris (dibenzylideneacetone) dipalladium Pd 2 (dba) 3 ，1×10 -4 mol triphenylphosphine, 150ml toluene, heated to refluxSamples were taken from the plates for 12 hours, indicating complete reaction. Naturally cooling, filtering, rotatably evaporating the filtrate, and passing through a silica gel column (silica gel 100-200 meshes, and the eluent is chloroform: n-hexane-1: 2 (volume ratio)) to obtain the compound 7. Elemental analysis Structure (molecular formula C) 50 H 35 N): the analysis found value is: c, 92.40; h, 5.49; and N, 2.17. LC-MS ([ M + H)] + ): found 650.33.
Example 2: synthesis of Compound 18
Figure BDA0002957994500000192
A250 ml three-necked flask was charged with 0.01mol of C1 as a starting material, 0.01mol of D1 as a starting material, 0.03mol of potassium tert-butoxide, and 1X 10 under a nitrogen atmosphere -4 mol tris (dibenzylideneacetone) dipalladium Pd 2 (dba) 3 ，1×10 -4 mol triphenylphosphine, 150ml toluene, heated to reflux for 12 hours, and a sample of the plaque taken, indicating completion of the reaction. Naturally cooling, filtering, rotatably evaporating the filtrate, and passing through a silica gel column (silica gel 100-200 meshes, and the eluent is chloroform: n-hexane-1: 2 (volume ratio)) to obtain an intermediate 1. Elemental analysis Structure (molecular formula C) 24 H 19 N)；LC-MS([M+H] + ): found 322.21.
A250 ml three-necked flask was charged with 0.012mol of A1 as a starting material, 0.01mol of 1 as an intermediate, 0.03mol of potassium tert-butoxide, and 1X 10 in the presence of nitrogen gas -4 mol tris (dibenzylideneacetone) dipalladium Pd 2 (dba) 3 ，1×10 -4 mol triphenylphosphine, 150ml toluene, heated to reflux for 12 hours, and a sample of the plaque taken, indicating completion of the reaction. Naturally cooling, filtering, rotatably evaporating the filtrate, and passing through a silica gel column (silica gel 100-200 meshes, and the eluent is chloroform: n-hexane-1: 2 (volume ratio)) to obtain the compound 18. Elemental analysis Structure (molecular formula C) 44 H 31 N): the analysis found value is: c, 92.10; h, 5.47; and N, 2.41. LC-MS ([ M + H)] + ): found 574.27.
The following compounds were prepared in the same manner as in example 1 or 2, and the synthetic raw materials are shown in table 1 below. The synthesis of the material of the present invention is referred to patent CN 110577511A.
For structural analysis of the compounds prepared in the examples, the molecular weights were measured by LC-MS as shown in table 1:
TABLE 1
Figure BDA0002957994500000201
Figure BDA0002957994500000211
Detection method
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 carried out by an ionization energy test system (IPS-3) and the test was carried out in a vacuum 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 the Fluorolog-3 series fluorescence spectrometer from Horiba.
The results of the physical property tests are shown in Table 2.
TABLE 2
Figure BDA0002957994500000221
As can be seen from the data in table 2 above, the compound of the present invention has a suitable HOMO level, a higher hole mobility, and a wider band gap (Eg), and can realize an organic electroluminescent device having 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 BDA0002957994500000222
comparative device example 1
The organic electroluminescent device was prepared as follows:
a) using transparent glass as a substrate, a substrate layer 1, washing an anode layer 2(Ag (100nm)) thereon, namely sequentially performing alkali washing, pure water washing and drying, and then performing ultraviolet-ozone washing to remove organic residues on the surface of the anode layer;
b) on the anode layer 2 after washing, HT1 and HI1 with the film thickness of 10nm are evaporated as a hole injection layer 3 by a vacuum evaporation device, and the mass ratio of HT1 to HI1 is 97: 3;
c) evaporating a hole transport layer 4 on the hole injection layer 3 in a vacuum evaporation mode, wherein the material of the hole transport layer is a compound HT1, and the thickness is 117 nm;
d) evaporating an electron blocking layer 5 on the hole transport layer 4 in a vacuum evaporation mode, wherein the electron blocking layer is made of a compound EB-1, and the thickness of the electron blocking layer is 10 nm;
e) evaporating a light-emitting layer 6 on the electron blocking layer 5 in a vacuum evaporation mode, wherein the light-emitting layer 6 is made of a host material BH-1 and a guest material BD-1, the mass ratio of the host material to the guest material is 97:3, and the thickness is 20 nm;
f) continuing to vapor-deposit HB1 as a hole blocking layer 7 on the light-emitting layer 6, wherein the vapor-deposition film thickness is 8 nm;
g) evaporating ET1 and LiQ on the hole blocking layer 7 in a vacuum evaporation mode, wherein the mass ratio of ET1 to LiQ is 1:1, the thickness is 30nm, and the layer serves as an electron transport layer 8;
h) evaporating LiF on the electron transport layer 8 in a vacuum evaporation mode, wherein the thickness of the LiF is 1nm, and the layer is an electron injection layer 9;
i) an Mg: Ag (mass ratio 1:9) electrode layer with a thickness of 16nm is vacuum-evaporated on the electron injection layer 9, and the layer is a cathode layer 10;
j) above the cathode layer 10, CPL material CPL-1 is vacuum-evaporated to a thickness of 70nm, which is a CPL layer 11.
Device comparative examples 2 to 3 the process of device comparative example 1 was carried out, except that the organic materials in steps b)/c) were respectively replaced with the organic materials shown in table 3. Device comparative examples 4 to 6 were conducted in the same manner as in device comparative example 1 except that the organic materials in b)/c)/g) were respectively replaced with the organic materials shown in table 3. Device preparation examples 1 to 17 were conducted in the same manner as in comparative device example 1 except that the organic materials in steps b)/c) were respectively replaced with organic materials as shown in table 3. Device preparation examples 18 to 34 were conducted in the same manner as in comparative device 1 except that the organic materials in b)/c)/g) were respectively replaced with the organic materials shown in Table 3.
TABLE 3
Figure BDA0002957994500000231
Figure BDA0002957994500000241
In the table above, taking example 1 as an example, "7: HI1 (3% 10 nm)" in the second column table indicates that the materials used for the hole injection layer are compound (7) and P-type dopant material HI1, 3% refers to the weight ratio of the materials used for the P-type dopant material HI1 for the hole injection layer: 10nm indicates the thickness of the layer; "7 (117 nm)" in the third table indicates that the material used is compound (7) and that the layer thickness is 117 nm. And so on in other tables.
After the OLED light-emitting device was prepared as described above, the cathode and the anode were connected by a known drive circuit, and various properties of the device were measured.
The device measurement performance results of examples 1 to 34 and comparative examples 1 to 6 are shown in table 4.
TABLE 4
Figure BDA0002957994500000251
Note: voltage, Current efficiency and color coordinates were measured using an IVL (Current-Voltage-Brightness) test System (Fund scientific instruments, Suzhou) at a current density of 10mA/cm 2 (ii) a The life test system is an EAS-62C type OLED device life tester of Japan System research company; LT95 refers to the time it takes for the device brightness to decay to 95% at a particular brightness; the test temperature for high temperature lifetime is 85 deg.c and LT80 refers to the time it takes for the device brightness to decay to 80% at a particular brightness.
As can be seen from table 4, the results of comparative examples 1 to 3 and device examples 1 to 17, the use of triarylamine and phenanthrene compounds of the present invention as hole injection and hole transport layer materials effectively reduced device voltage and improved device lifetime due to higher carrier transport rate.
As can be seen from the results of comparative examples 4 to 6 and device examples 18 to 34 in table 4, the triarylamine and phenanthrene compounds of the present invention, when used in combination with a specific electron transport layer material, effectively improve the efficiency and lifetime of the device.
The compound contains a phenanthryl group, so that the glass transition temperature of the material can be effectively improved, and the group has high heat-resistant stability, so that the compound has excellent film phase stability and evaporation stability, the interface stability of a device under a high-temperature condition is effectively improved, and the device has excellent high-temperature service life.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A compound containing triarylamine and phenanthrene structures is characterized in that the structure of the compound is shown as a general formula (1):
Figure FDA0002957994490000011
in the general formula (1), L, L 1 、L 2 Each independently represents a single bond, phenylene, naphthylene, biphenylene, furylene, benzofuranylene or dibenzofuranylene;
R 1 、R 2 each independently represents substituted or unsubstituted C 6 -C 30 One of an aryl, a substituted or unsubstituted 5-to 30-membered heteroaryl containing one or more heteroatoms;
r represents phenyl, naphthyl, biphenyl, furyl, benzofuryl or dibenzofuryl;
the substituents for the substituent groups are optionally selected from deuterium, tritium, C 1-10 Alkyl of (C) 6 -C 30 One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is an oxygen, sulfur or nitrogen atom.
2. A compound containing triarylamine and phenanthrene structures according to claim 1, wherein R is selected from the group consisting of 1 、R 2 Each independently represents one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted benzodioxin, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted piperonyl, substituted or unsubstituted indenyl, and substituted or unsubstituted carbazolyl;
the substituent group used for the substituent group is one or more of deuterium, tritium, methyl, tert-butyl, adamantyl, phenyl, naphthyl, biphenyl, carbazolyl, benzofuranyl, dibenzofuranyl, fluorenyl, phenanthryl, pyrenyl, acenaphthenyl and piperonyl.
3. A compound containing triarylamine and phenanthrene structures according to claim 1Wherein R represents a phenyl group, R 2 Represented as biphenyl or phenyl.
4. A compound containing triarylamine and phenanthrene structures as claimed in claim 1, wherein R represents phenyl, and R represents 1 And R 2 The same is true.
5. A compound containing triarylamine and phenanthrene structures according to claim 1, wherein the specific structure of the compound is any one of the following structures:
Figure FDA0002957994490000012
Figure FDA0002957994490000021
Figure FDA0002957994490000031
Figure FDA0002957994490000041
Figure FDA0002957994490000051
Figure FDA0002957994490000061
Figure FDA0002957994490000071
Figure FDA0002957994490000081
Figure FDA0002957994490000091
Figure FDA0002957994490000101
6. an organic electroluminescent device comprising an anode, a hole transporting region, a light-emitting region, an electron transporting region and a cathode, wherein the hole transporting region comprises a compound containing a triarylamine and a phenanthrene structure as claimed in any one of claims 1 to 5.
7. The organic electroluminescent device according to claim 6, wherein the hole transport region comprises a hole injection layer, a hole transport layer and an electron blocking layer in this order; the hole injection layer and the hole transport layer both comprise the compound containing triarylamine and phenanthrene structures in any one of claims 1-5; preferably, the hole injection layer is a mixed film layer of the compound containing triarylamine and phenanthrene structures and the P-type doping material, which is described in any one of claims 1 to 5.
8. The organic electroluminescent device according to claim 6, wherein the light-emitting region comprises a host material and a guest material, wherein the host material comprises an anthracene group and the guest material is a fluorescent material.
9. The organic electroluminescent device according to claim 6, wherein the electron transport region comprises a nitrogen heterocyclic compound represented by the following general formula (3):
Figure FDA0002957994490000102
in the general formula (3), Ar 1 、Ar 2 、Ar 3 Independently of one another, as substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C containing one or more hetero atoms 5 -C 30 One of heteroaryl;
L 1 selected from single bond, substituted or unsubstituted C 6 -C 30 Arylene, substituted or unsubstituted C containing one or more hetero atoms 5 -C 30 One of heteroarylenes;
each of said heteroatoms is independently selected from N, O or S; n represents 1 or 2;
X 1 、X 2 、X 3 independently of one another, N or CH, X 1 、X 2 、X 3 Represents N.
10. The organic electroluminescent device according to claim 6, 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 according to claim 9; the electron injection layer is made of an N-type metal material.
CN202110228807.0A 2021-03-02 2021-03-02 Compound containing triarylamine and phenanthrene structure and application thereof Pending CN114989022A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115557921A (en) * 2022-12-02 2023-01-03 吉林奥来德光电材料股份有限公司 Cap layer material, preparation method, organic electroluminescent device and display device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115557921A (en) * 2022-12-02 2023-01-03 吉林奥来德光电材料股份有限公司 Cap layer material, preparation method, organic electroluminescent device and display device

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