Compound, Organic Electroluminescence Device, and Display Device

Abstract

The present invention provides compounds, organic electroluminescent devices, and displays, which have the structure shown in Formula I and include a substituent Ar at the 1-position of the naphthalene ring. 2 By introducing (I), not only can the degree of steric hindrance at the ortho position be adjusted, but also the twist of the molecule can be effectively controlled to reduce the crystallinity of the molecule; then, by introducing an arylamine group at the 2-position and introducing a tri-substituted structure on the arylamine group, the molecular conformation can be effectively controlled and the molecular bulk density can be increased, so that the designed material can meet the requirements of device materials. The compound of the present invention can be applied to organic electroluminescent devices, and especially when used as an electron barrier layer, it can improve the luminous efficiency, reduce the starting voltage, and extend the life of the device. JPEG2023528214000254.jpg51118

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and specifically to compounds, organic electroluminescent devices and display devices.

Background Art

[0002] In recent years, optoelectronic devices based on organic materials have become increasingly popular. Organic materials are very suitable for manufacturing on flexible substrates due to their inherent flexibility, and can design and produce beautiful and cool optoelectronic products according to demand, with advantages that inorganic materials cannot compare with. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field-effect transistors, organic solar cells, organic sensors, etc. Among them, OLEDs have developed particularly rapidly and are already commercially used in the field of information display. OLEDs can provide three colors of high-chroma red, green, and blue, and full-color display devices made using them have advantages such as not requiring an additional backlight, having vivid colors, being light and thin, and being flexible.

[0003] The core of an OLED device is a thin-film structure containing multiple organic functional materials. Common functional organic materials include hole injection materials, hole transport materials, hole barrier materials, electron injection materials, electron transport materials, electron barrier materials, and light-emitting host materials and light-emitting guests (dyes), etc. When energized, electrons and holes are respectively injected, transported to the light-emitting region, and excitons are generated by recombination here, emitting light.

[0004] A variety of organic materials have been developed, which, when combined with various peculiar device structures, can enhance the carrier mobility, adjust the carrier balance, break through the electroluminescence efficiency, and delay the decay of the device. For quantum mechanical reasons, general fluorescent emitters mainly utilize singlet excitons generated when electrons and holes combine, and are still widely applied to various OLED products at present. Metal complexes such as iridium complexes that emit light by simultaneously utilizing triplet excitons and singlet excitons are called phosphorescent emitters, and their energy conversion efficiency can be increased by four times compared with conventional fluorescent emitters. Thermally activated delayed fluorescence (TADF) technology can effectively utilize triplet excitons to achieve high luminous efficiency even without adopting metal complexes by promoting the conversion of triplet excitons to singlet excitons. Thermally activated sensitized fluorescence (TASF) technology adopts materials with TADF properties, and the emitter is sensitized by the method of energy transfer, which can also achieve high luminous efficiency.

[0005] With the commercialization of OLED products, the requirements for the performance of such products are becoming increasingly high. The currently used OLED materials and device structures cannot completely solve the problems in various aspects such as the efficiency, lifespan, and cost of OLED products. Therefore, in order to develop more types and higher-performance OLED devices, it is urgent to develop organic electroluminescence materials that can improve the luminous efficiency of the device, reduce the driving voltage, and extend the lifespan.

Summary of the Invention

Problems to be Solved by the Invention

[0006] The main object of the present invention is to provide a novel organic electroluminescence material, and to provide a compound, an organic electroluminescence device, and a display device for improving the luminous efficiency of the OLED device. One of the objects of the present invention is to provide a compound that can improve the luminous efficiency of the device, reduce the driving voltage, and extend the lifespan when used in an organic electroluminescence device.

Means for Solving the Problem

[0007] To achieve this object, the present invention provides a compound having a structure represented by Formula I.

Chemical Formula

[0008] The aforementioned "substituted or unsubstituted" group may be substituted with one substituent or may be substituted with a plurality of substituents. When there are a plurality of substituents, different substituents may be used. In the present invention, even when the same expression is used, the meaning is the same, and since the range of the substituents is as described above, it will not be described in detail.

[0009] In the present invention, the expression of chemical elements also includes the concept of isotopes having the same chemical properties. For example, hydrogen (H) includes 1 H (protium or called H), 2 H (deuterium or called D), etc., and carbon (C) includes 12 C, 13 C, etc. In the present invention, the heteroatom of heteroaryl is usually selected from N, O, S. In the present invention, the expression method of the ring structure depicted with "-" means that the connecting site is at any position on this ring structure where a bond can be formed.

[0010] The aforementioned C1-C20 linear alkyls are preferably C1-C10 linear alkyls, more preferably C1-C6 linear alkyls, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, n-pentyl, n-heptyl, n-nonyl, n-decyl, etc. The aforementioned C3-C20 cyclic alkyls are preferably cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0011] The aforementioned substituted or unsubstituted C6-C30 aryls, preferably C6-C20 aryls, preferably, the aryl is a group selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthracyl, phenanthrenyl, indenyl, fluorenyl and derivatives thereof, fluoranthenyl, triphenylene, pyrenyl, perylenyl, chrysenyl, and tetracenyl. The biphenyl is selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl, the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, and m-terphenyl-2-yl, the naphthyl includes 1-naphthyl or 2-naphthyl, the anthracyl is selected from the group consisting of 1-anthracyl, 2-anthracyl, and 9-anthracyl, the fluorenyl is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl, the fluorenyl derivative is selected from the group consisting of 9,9'-dimethylfluorene, 9,9'-spirobisfluorene, and benzofluorene, the pyrenyl is selected from the group consisting of 1-pyrenyl, 2-pyrenyl, and 4-pyrenyl, and the tetracenyl is selected from the group consisting of 1-tetracenyl, 2-tetracenyl, and 9-tetracenyl.

[0012] The aforementioned substituted or unsubstituted C3-C30 heteroaryl, preferably C4-C20 heteroaryl, preferably, the heteroaryl is furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and derivatives thereof, wherein, the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, or indolocarbazole.

[0013] In the present invention, the symbols of the substitution sites on the naphthalene ring are as follows.

Chemical formula

[0014] In the compound structure of the present invention, by introducing a substituent Ar at the 1-position of the naphthalene ring, not only can the steric hindrance at the 1-position be adjusted, but also the torsion of the molecule can be effectively adjusted to reduce the crystallinity of the molecule. Next, an arylamine group is substituted at the 2-position, and a trisubstituted structure 2 is introduced on the arylamine group, thereby effectively adjusting the steric structure of the molecule and increasing the bulk density of the molecule, so that the designed material can meet the requirements for the material of the device.

Chemical formula

[0015] Ar 1 Ar 2 R 1 ~R 4 etc., an optimal effect can be obtained. When this material is applied to an organic electroluminescence device, especially when used as an electron barrier layer, the luminous efficiency can be improved, the turn-on voltage can be reduced, and the lifetime of the device can be extended. In addition, the compounds of the present invention are easy to implement in the manufacturing process, the raw materials are easily available, and they are suitable for scale-up.

[0016] Preferably, the above-mentioned L 2 is selected from a single bond, a substituted or unsubstituted C6-C20 arylene, or a substituted or unsubstituted C3-C20 heteroarylene, and preferably is a single bond or phenylene. Preferably, the above-mentioned Ar 2 is selected from a substituted or unsubstituted C6-C20 aryl or a substituted or unsubstituted C3-C20 heteroaryl.

[0017] Preferably, the above-mentioned Ar 2 is any one selected from a substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo[9,9-dimethylfluorenyl], benzospirofluorenyl.

[0018] Preferably, the above-mentioned Ar 2 is any one selected from a substituted or unsubstituted group as follows.

Chemical formula

[0019] Preferably, the above-mentioned L 2 is a single bond, and the above-mentioned Ar 2 is selected from a substituted or unsubstituted C10-C30 condensed-ring aryl or a substituted or unsubstituted C6-C30 condensed-ring heteroaryl.

[0020] Preferably, the above-mentioned L 2 is a single bond, and the above-mentioned Ar 2is any one selected from substituted or unsubstituted naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo(9,9-dimethylfluorenyl), benzospirofluorenyl.

[0021] Preferably, the said L 2 is a single bond, and the said Ar 2 is any one selected from substituted or unsubstituted following groups.

Chemical formula

[0022] Preferably, the said L 2 is phenylene, and the said Ar 2 is selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl. Preferably, the said L 2 is phenylene, and the said Ar 2 is any one selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo(9,9-dimethylfluorenyl), benzospirofluorenyl.

[0023] Preferably, the said L 2 is phenylene, and the said Ar 2 is any one selected from substituted or unsubstituted following groups.

Chemical formula

[0024] Preferably, the said R 1 , R 2 and R 3 are each independently one selected from methyl, ethyl or phenyl. Preferably, the said R 1 , R 2 and R 3 are all methyl.

[0025] Preferably, the said L 1 is one selected from substituted or unsubstituted phenylene, biphenylene, naphthalene, dibenzofurylidene, dibenzothienylidene, 9,9 - dimethylfluorenylidene.

[0026] Preferably, the said L 1 is any one selected from substituted or unsubstituted groups shown below. [Chemical formula] (Here, the dashed line represents the connecting hand of the group.) Preferably, the said m is 0.

[0027] Preferably, the said compound has any one of the structures shown in the following P1 - P777. [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0028] Another object of the present invention is to provide the use of the compound described in one of the objects in an organic electroluminescence device. Preferably, the compound is used as a material for an electron barrier layer in the organic electroluminescence device.

[0029] A further object of the present invention is to provide an organic electroluminescence device having a first electrode, a second electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein at least one of the compounds described in one of the objects is contained in the organic layer.

[0030] The organic electroluminescence device containing the compound of formula I according to the present invention has a driving voltage as low as 3.8 V or less and a current efficiency as high as 18.2 cd / A or more when the luminance reaches 3000 cd / m 2 . Preferably, the organic layer includes an electron barrier layer, and at least one of the compounds described in one of the objects is contained in the electron barrier layer.

[0031] The compound of the present invention can be applied to other types of organic electronic devices including organic field effect transistors, organic thin film solar cells, information labels, electronic artificial skin sheets, sheet scanners, or electronic papers in addition to organic electroluminescence devices.

[0032] Specifically, another technical solution of the present invention includes a substrate, an anode layer, a plurality of light-emitting functional layers, and a cathode layer sequentially formed on the substrate. The light-emitting functional layer includes at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron barrier layer, and an electron transport layer, and provides an organic electroluminescence device in which at least one of the aforementioned compounds is contained in the electron barrier layer.

[0033] The OLED includes a first electrode, a second electrode, and an organic material layer located between the electrodes. This organic material layer may be further divided into a plurality of regions. For example, this organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region. In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is made of glass or polymer material that has mechanical strength, thermal stability, waterproofness, and excellent transparency. Further, thin film transistors (TFTs) may be attached on the substrate for display.

[0034] The first electrode may be formed by sputtering or depositing a material for the first electrode on the substrate. When the first electrode is an anode, oxide transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), and any combination thereof may be used. When the first electrode is a cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and any combination thereof may be used.

[0035] The organic material layer may be formed on the electrode by methods such as vacuum thermal evaporation, spin coating, printing, etc. The compounds used as the organic material layer may be organic small molecules, organic macromolecules, polymers, and combinations thereof.

[0036] The hole transport region is located between the anode and the light-emitting layer. The hole transport region may be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one kind of compound and a single-layer hole transport layer containing multiple kinds of compounds. The hole transport region may also be a multilayer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron barrier layer (EBL). The electron barrier layer employs the compound represented by Formula I of the present invention.

[0037] The material of the hole transport region may be selected from phthalocyanine derivatives such as CuPc, conductive polymers, or polymers containing conductive dopants such as poly(phenylene ethylene), polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), arylamine derivatives such as the compounds shown in HT-1 to HT-34 below; or any combination thereof, but is not limited thereto.

Chemical formula

Chemical formula

[0038] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of multiple kinds of compounds. For example, the hole injection layer may use one or more of the compounds among the aforementioned HT-1 to HT-34, or one or more of the compounds among the following HI-1 to HI-3. It may also use a material obtained by doping one or more of the compounds among the following HI-1 to HI-3 into one or more of the compounds among HT-1 to HT-34.

Chemical formula

[0039] The light-emitting layer may contain a light-emitting dye (i.e., dopant) capable of emitting spectra of various wavelengths, and may also contain a host material. The light-emitting layer may be a single-color light-emitting layer that emits a single color such as red, green, or blue. Multiple types of single-color light-emitting layers of different colors may be two-dimensionally arranged according to a pixel pattern, or may be deposited to form a color light-emitting layer. When light-emitting layers of different colors are deposited, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may also be a single color light-emitting layer capable of simultaneously emitting different colors such as red, green, and blue.

[0040] Depending on the technology, the material of the light-emitting layer may adopt various materials such as a fluorescent electroluminescence material, a phosphorescent electroluminescence material, and a thermally activated delayed fluorescence emitting material. In an OLED device, one light-emitting technology may be used, or a combination of multiple types of light-emitting technologies may be used. These light-emitting materials classified by technology may emit light of the same color or light of different colors.

[0041] In one aspect of the present invention, the light-emitting layer adopts a fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer may be one or a combination of multiple types selected from the following BFH-1 to BFH-17, but is not limited thereto.

Chemical formula

[0042] In one aspect of the present invention, the light-emitting layer adopts a fluorescent electroluminescence technology. The fluorescent dopant of the light-emitting layer may be one or a combination of multiple types selected from the following BFD-1 to BFD-12, but is not limited thereto.

Chemical formula

[0043] In one aspect of the present invention, the light-emitting layer employs phosphorescent electroluminescence technology. The host material of the light-emitting layer may be one or a combination of more than one selected from GPH-1 to GPH-80, but is not limited thereto.

Chemical formula

Chemical formula

Chemical formula

[0044] In one aspect of the present invention, the light-emitting layer employs phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer may be one or a combination of more than one selected from the following GPD-1 to GPD-47, but is not limited thereto.

Chemical formula

Chemical formula

[0045] In one aspect of the present invention, the light-emitting layer employs phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer may be one or a combination of more than one selected from the following RPD-1 to RPD-28, but is not limited thereto.

Chemical formula

[0046] In one aspect of the present invention, the light-emitting layer employs phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer may be one or a combination of more than one selected from the following YPD-1 to YPD-11, but is not limited thereto.

Chemical formula

[0047] In one aspect of the present invention, the light-emitting layer employs thermally activated delayed fluorescence (TADF) emission technology. The fluorescent dopant in the light-emitting layer may be one or a combination of more than one selected from the following TDE-1 to TDE-39, but is not limited thereto.

Chemical formula

Chemical formula

[0048] In one aspect of the present invention, the light-emitting layer employs thermally activated delayed fluorescence (TADF) emission technology. The host material of the light-emitting layer may be one or a combination of more than one selected from TDH1 to TDH24, but is not limited thereto.

Chemical formula

Chemical formula

[0049] The OLED organic material layer may include an electron transport region between the light-emitting layer and the cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole barrier layer (HBL).

[0050] In one aspect of the present invention, the material of the electron transport layer may be one or a combination of more than one selected from the following ET-1 to ET-57, but is not limited thereto.

Chemical formula

Chemical formula

Chemical formula

[0051] The device may further include an electron injection layer located between the electron transport layer and the cathode. The material of the electron injection layer may include one or a combination of more than one of LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, or Ca, but is not limited thereto.

[0052] Compared with the prior art, the above-mentioned solution of the present invention has the following beneficial effects. In the compound structure of the present invention, by introducing a substituent Ar at the 1-position of the naphthalene ring 2 not only can the steric hindrance at the ortho position be adjusted, but also the twist of the molecule can be effectively regulated to reduce the crystallinity of the molecule. Next, an arylamine group is substituted at the 2-position, and by introducing a trisubstituted structure on the arylamine group, the steric structure of the molecule can be effectively regulated, and the bulk density of the molecule can be increased. Thereby, the designed material can meet the requirements for the material of the device.

[0053] In the present invention, the naphthalene ring parent nucleus structure is substituted at both the 1-position and the 2-position, and combined with substituents such as Ar 1 Ar 2 R 1 ~R 4 etc., the optimal effect can be obtained. This material is adapted to an organic electroluminescence device, and especially when used as an electron barrier layer, it can improve the light emission efficiency, reduce the turn-on voltage, and extend the life of the device. In addition, the compound of the present invention is easy to implement in the manufacturing process, the raw materials are easy to obtain, and it is suitable for scale-up. The organic electroluminescence device containing the compound of formula I according to the present invention has a driving voltage as low as 3.8 V or less and a current efficiency as high as 18.2 cd / A or more when the luminance reaches 3000 cd / m 2 .

[0054] In some other preferred embodiments of the present invention, an organic electroluminescence device with improved optoelectronic performance is provided. The organic electroluminescence device includes an anode layer, a cathode layer, and an organic layer provided between the anode layer and the cathode layer. The organic layer includes a light-emitting layer, and a host material and a dopant material are contained in the light-emitting layer. The host material includes a first host material and a second host material, and the first host material has a structure represented by the aforementioned formula I.

Chemical formula

[0055] The aforementioned "substituted or unsubstituted" group may be substituted with one substituent or a plurality of substituents. When there are a plurality of substituents, different substituents may be used. In the present invention, even when the same expression is used, the meaning is the same, and since the range of substituents is as described above, it will not be described in detail.)

[0056] In the present invention, the expression of chemical elements also includes the concept of isotopes having the same chemical properties. For example, hydrogen (H) includes 1 H (protium or called H), 2 H (deuterium or called D), etc., and carbon (C) includes 12 C, 13 C, etc.) In the present invention, the heteroatom of heteroaryl is usually selected from N, O, and S.) In the present invention, the expression method of the ring structure depicted with "-" means that the bonding site is at any position on this ring structure where bond formation is possible.)

[0057] The above-mentioned C1-C20 linear alkyls are preferably C1-C10 linear alkyls, more preferably C1-C6 linear alkyls, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, n-pentyl, n-heptyl, n-nonyl, n-decyl, and the like. The above-mentioned C3-C20 cyclic alkyls are preferably cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0058] The above-mentioned substituted or unsubstituted C6-C30 aryl (arylene), preferably C6-C20 aryl (arylene), preferably, the aryl is a group selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthracyl, phenanthrenyl, indenyl, fluorenyl and derivatives thereof, fluoranthenyl, triphenylene, pyrenyl, perylenyl, chrysenyl, and tetracenyl. The biphenyl is selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl, the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, and m-terphenyl-2-yl, the naphthyl includes 1-naphthyl or 2-naphthyl, the anthracyl is selected from the group consisting of 1-anthracyl, 2-anthracyl, and 9-anthracyl, the fluorenyl is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl, the fluorenyl derivative is selected from the group consisting of 9,9-dimethylfluorene, 9,9-spirobifluorene, and benzofluorene, the pyrenyl is selected from the group consisting of 1-pyrenyl, 2-pyrenyl, and 4-pyrenyl, and the tetracenyl is selected from the group consisting of 1-tetracenyl, 2-tetracenyl, and 9-tetracenyl.

[0059] In the present invention, the aryl includes monocyclic aryl and condensed-ring aryl, and the heteroaryl also includes monocyclic heteroaryl and condensed-ring heteroaryl. The aforementioned substituted or unsubstituted C3-C30 heteroaryl (heteroarylene), preferably C4-C20 heteroaryl (heteroarylene), preferably, the heteroaryl is furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and derivatives thereof, wherein, the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, or indolocarbazole. The aforementioned C6-C30 arylamino is a group linking aryl and amino, and the linking bond may be on the amino or on the aryl, and the same applies to C3-C30 heteroarylamino.

[0060] The aforementioned preferred embodiment provides an organic electroluminescence device using a double host light-emitting layer, wherein, the first host material adopts the compound shown in formula I, this compound has high hole mobility and appropriate energy levels, and by adjusting the carrier distribution inside the light-emitting layer, the recombination region of carriers is adjusted, and moreover, it has a high spatial deposition structure, when used as one of the two hosts, in combination with the second host material, accurately adjusts the carrier distribution inside the light-emitting layer, improves the light extraction efficiency of the organic electroluminescence device, and improves the optoelectronic performance of the device.

[0061] Preferably, in formula I, the Ar 1 is any one selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo-9,9-dimethylfluorenyl, benzospirofluorenyl. And / or, in formula I, the Ar 2is any one selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo[9,9-dimethylfluorenyl], benzospirofluorenyl, and is preferably substituted or unsubstituted naphthyl.

[0062] Preferably, the aforementioned Ar 2 is any one selected from substituted or unsubstituted following groups. [Chemical formula] (Here, the dashed line represents the connecting bond of the group.)

[0063] Preferably, in formula I, the aforementioned R 1 , R 2 and R 3 are each independently one selected from methyl, ethyl or phenyl, and preferably all are methyl. Preferably, in formula I, the aforementioned L 1 is any one selected from substituted or unsubstituted phenylene, biphenylene, naphthalene, dibenzofurylidene, dibenzothienylidene, 9,9-dimethylfluorenylidene. Preferably, in formula I, the aforementioned L 2 is one selected from a single bond, substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene, and is preferably a single bond or phenylene.

[0064] Preferably, the first host material is any one selected from the aforementioned Compound P1 to Compound P777 or a combination of at least two of them. Preferably, the mass ratio of the first host material to the second host material is 0.01:1 to 1.5:1, for example, 0.05:1, 0.1:1, 0.2:1, 1:0.3, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1.0, 1.1:1, 1.2:1, 1.3:1, 1.4:1, etc., and preferably 0.1:1 to 1:1. In the present invention, preferably, the mass ratio of the first host material (i.e., the compound of Formula I) to the second host material is 0.01:1 to 1.5:1. Within the aforementioned range, the optoelectronic performance of the device is optimized. If the addition amount of the compound of Formula I is too large, the voltage of the device will increase and the efficiency of the device will decrease. If the addition amount is too small, there will be no obvious increase in the efficiency of the device.

[0065] Preferably, the HOMO energy level of the second host material is -5.3 eV to -5.7 eV, for example, -5.4 eV, -5.5 eV, -5.6 eV, etc., and / or the LUMO energy level of the second host material is -2.3 eV to -2.6 eV, for example, -2.4 eV, -2.5 eV, etc. Preferably, the HOMO energy level of the second host material is -5.3 eV to -5.7 eV, and the LUMO energy level is -2.3 eV to -2.6 eV.

[0066] In the present invention, preferably, the second host material has the aforementioned specific HOMO energy level and LUMO energy level. Thereby, it can be combined well with the first host material to more accurately adjust the carrier distribution inside the light-emitting layer, further improve the light extraction efficiency of the organic electroluminescence device, and improve the efficiency of the device.

[0067] Preferably, the second host material is any one or at least two combinations selected from the following compounds PH-1 to compound PH-85.

Chemical formula

Chemical formula

Chem.

Chem.

[0068] Preferably, the thickness of the light-emitting layer is 10 to 65 nm, for example, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, etc., and preferably 15 to 55 nm.

[0069] Based on the specific substance composition of the light-emitting layer in the foregoing preferred embodiment, the preferred thickness of the light-emitting layer of the present invention is 10 to 65 nm. Within this thickness range, the efficiency of the device is further improved. If the thickness is too small, color shift of the device occurs and the efficiency decreases. If the thickness is too large, the voltage of the device increases and the efficiency decreases. In the present invention, the first host material and the second host material may be co-evaporated or premixed to obtain the light-emitting layer, but are not limited to co-evaporation or premixing.

[0070] Preferably, the organic layer further includes any one or at least two combinations of a hole injection layer, a hole transport layer, an electron barrier layer, an electron transport layer, or an electron injection layer. The organic layer of the OLED may be further divided into a plurality of regions. For example, this organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region.

[0071] In a specific embodiment, a substrate may be used under the first electrode or on the second electrode. All substrates are made of glass or polymer materials having mechanical strength, thermal stability, water resistance, and excellent transparency. Further, a thin film transistor (TFT) may be attached on the substrate for display.

[0072] The first electrode may be formed by sputtering or depositing a material for the first electrode on a substrate. When the first electrode is an anode, oxide transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), etc. and any combination thereof may be used. When the first electrode is a cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), etc. and any combination thereof may be used.

[0073] The organic material layer may be formed on the electrode by methods such as vacuum thermal evaporation, spin coating, printing, etc. The compounds used as the organic material layer may be organic small molecules, organic macromolecules, polymers, and combinations thereof.

[0074] The hole transport region is located between the anode and the light-emitting layer. The hole transport region may be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one kind of compound and a single-layer hole transport layer containing multiple kinds of compounds. The hole transport region may also be a multilayer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL). The HIL is located between the anode and the HTL, and the EBL is located between the HTL and the light-emitting layer.

[0075] The materials in the hole transport region may be selected from phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopant materials such as poly(phenylene ethylene), polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), arylamine derivatives shown in HT-1 to HT-51 below (wherein HT-1 to HT-34 are as described above, and the structures of HT-35 to HT-51 are as follows); or any combination thereof, but not limited thereto. [Chemical formula]

[0076] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of multiple compounds. For example, the hole injection layer may use one or more compounds among the aforementioned HT-1 to HT-51, or one or more compounds among the aforementioned HI-1 to HI-3, or may adopt a material obtained by doping one or more compounds among HT-1 to HT-51 with one or more compounds among HI-1 to HI-3.

[0077] The light-emitting layer contains a light-emitting dye (i.e., dopant) capable of emitting spectra of various wavelengths, and may also contain a host material at the same time. The light-emitting layer may be a single-color light-emitting layer that emits a single color such as red, green, or blue. Multiple single-color light-emitting layers of different colors may be arranged two-dimensionally according to a pixel pattern, or stacked to form a color light-emitting layer. When light-emitting layers of different colors are stacked, they may be spaced apart from each other or connected to each other. The light-emitting layer may also be a single color light-emitting layer capable of emitting different colors such as red, green, and blue simultaneously.

[0078] Depending on the technology, various materials such as phosphorescent electroluminescent materials may be adopted for the light-emitting layer material. In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescent technology. The phosphorescent doping material of the light-emitting layer may be one or a combination of more than one selected from the aforementioned GPD-1 to GPD-47, but is not limited thereto. In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescent technology. The phosphorescent doping material of the light-emitting layer may be one or a combination of more than one selected from the aforementioned RPD-1 to RPD-28, but is not limited thereto. In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescent technology. The phosphorescent doping material of the light-emitting layer may be one or a combination of more than one selected from the aforementioned YPD-1 to YPD-11, but is not limited thereto.

[0079] The OLED organic material layer may further include an electron transport region between the light-emitting layer and the cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one kind of compound and a single-layer electron transport layer containing multiple kinds of compounds. The electron transport region may also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole barrier layer (HBL).

[0080] In one aspect of the present invention, the material of the electron transport layer may be one or a combination of more than one selected from the aforementioned ET-1 to ET-57 and the following ET-58 to ET-73, but is not limited thereto.

Chemical formula

[0081] The device may further include an electron injection layer located between the electron transport layer and the cathode. The material of the electron injection layer may include one or a combination of more than one of LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg, Yb, but is not limited thereto.

[0082] In another embodiment of the present invention, there is provided a display device including the organic electroluminescence device described in one of the objects. The foregoing preferred embodiment provides an organic electroluminescence device using a double host light-emitting layer, wherein the first host material employs a compound represented by Formula I. Compared with the prior art, this compound has high hole mobility and appropriate energy levels, and by adjusting the carrier distribution inside the light-emitting layer, it can regulate the carrier recombination region. Moreover, it has a high spatial deposition structure. When used as one of the two hosts, in combination with the second host material, it can accurately adjust the carrier distribution inside the light-emitting layer, improve the light extraction efficiency of the organic electroluminescence device, and improve the optoelectronic performance of the device. The organic electroluminescence devices according to the foregoing preferred embodiments all have a current efficiency of 11.7 cd / A or more, most reach 15 cd / A or more, and can reach 17 cd / A or more at the highest.

[0083] According to another aspect of the present invention, there is provided an organic electroluminescence device. The organic electroluminescence device has high efficiency. The organic electroluminescence device includes an anode layer, a cathode layer, and an organic layer provided between the anode layer and the cathode layer.

[0084] The organic layer contains Compound I and Compound II.

Chemical formula

[0085] Said compound II has a structure represented by formula (3).

Chemical formula

[0086] The aforementioned "substituted or unsubstituted" group may be substituted with one substituent or may be substituted with a plurality of substituents. When there are a plurality of substituents, different substituents may be used. In the present invention, when the same expression is used, the meaning is the same, and since the range of the substituents is as described above, it will not be described in detail.

[0087] In the present invention, the representation of chemical elements also includes the concept of isotopes having the same chemical properties. For example, hydrogen (H) includes 1 H (protium or called H), 2 H (deuterium or called D), etc., and carbon (C) includes 12 C, 13 C, etc. In the present invention, the heteroatoms of heteroaryl are usually selected from N, O, and S. In the present invention, the representation method of the ring structure with "-" drawn means that the connecting site is at any position on this ring structure where a bond can be formed.

[0088] The aforementioned C1-C20 linear alkyl is preferably C1-C10 linear alkyl, more preferably C1-C6 linear alkyl. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, n-pentyl, n-heptyl, n-nonyl, n-decyl, etc. can be mentioned. The aforementioned C3-C20 cyclic alkyl is preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

[0089] The aforementioned substituted or unsubstituted C6-C30 aryl(arylene), preferably C6-C20 aryl, preferably, the aryl is a group selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthracyl, phenanthrenyl, indenyl, fluorenyl and their derivatives, fluoranthenyl, triphenylene, pyrenyl, perylenyl, chrysenyl and tetracenyl. The biphenyl is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl, the terphenyl is selected from p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl, the naphthyl includes 1-naphthyl or 2-naphthyl, the anthracyl is selected from the group consisting of 1-anthracyl, 2-anthracyl and 9-anthracyl, the fluorenyl is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl, the fluorenyl derivative is one of the group consisting of 9,9'-dimethylfluorene, 9,9'-spirobisfluorene and benzofluorene, the pyrenyl is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl, and the tetracenyl is selected from the group consisting of 1-tetracenyl, 2-tetracenyl and 9-tetracenyl.

[0090] In the present invention, the aryl includes monocyclic aryl and condensed-ring aryl, and the heteroaryl also includes monocyclic heteroaryl and condensed-ring heteroaryl. The aforementioned substituted or unsubstituted C3-C30 heteroaryl(heteroarylene), preferably C4-C20 heteroaryl, preferably, the heteroaryl is furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and their derivatives, where the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, or indolocarbazole.

[0091] The aforementioned C6-C30 arylamino is a group connecting aryl and amino, and the connecting bond may be on the amino or on the aryl. The same applies to C3-C30 heteroarylamino.

[0092] In this example, both Compound I and Compound II are used as materials for the organic layer. By adjusting the carrier distribution inside the light-emitting layer, Compound I can regulate the recombination region of carriers, and moreover, it has a high spatial deposition structure. On the other hand, Compound II has excellent planar expansion characteristics of molecules, can accelerate the hole transport, improve the hole mobility, and has a high triplet energy level, capable of blocking excessive excitons. When both are used in combination, the efficiency of the device can be effectively improved.

[0093] Preferably, the Compound I has any one of the structures shown in the aforementioned P1-P777. Preferably, the Compound II has any one of the structures shown in A1-A291.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0094] Preferably, the organic layer includes a light-emitting layer and an electron barrier layer. Preferably, the light-emitting layer contains Compound I, and the electron barrier layer contains Compound II. Preferably, the light-emitting layer contains Compound II, and the electron barrier layer contains Compound I.

[0095] In one preferred technical solution of the present invention, using one of Compound I and Compound II as the material of the light-emitting layer and the other as the material of the electron barrier layer is because both of these two materials have hole-transporting properties. By being used as the materials of the electron barrier layer and the light-emitting layer respectively, the balance of the influence due to the relatively fast electron transport is achieved, the position of the recombination center is made the center of the light-emitting layer, and the efficiency of the device is further improved.

[0096] Preferably, the light-emitting layer contains a first host material, a second host material, and a dopant material. The first host material is Compound I, and the electron barrier layer contains Compound II, or the first host material is Compound II, and the electron barrier layer contains Compound I.

[0097] Furthermore, in the present invention, preferably, Compound I or Compound II is used as one of the host materials of the double-host light-emitting layer. Thereby, the carrier distribution inside the light-emitting layer is adjusted better, the recombination region of the carriers is regulated, and moreover, such a compound has a high spatial deposition structure. When used as one of the two hosts, the light extraction efficiency is improved. By combining with other host materials, the efficiency under low gray levels is further improved, the degree of roll-off of the efficiency of the device is reduced, and the efficiency of the device can be further improved.

[0098] In one preferred embodiment, the mass ratio of the first host material to the second host material is 0.01:1 to 1.5:1, such as 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1, etc., preferably 0.1:1 to 1:1.

[0099] In a further preferred technical solution of the present invention, the addition amount of Compound I or Compound II in the double host light-emitting layer is within the aforementioned specific range. Within this range, the efficiency of the device is further improved. If the addition amount is too high, the hole transport is too fast, which will instead disrupt the balance inside the device. If the addition amount is too low, the adjustment effect cannot be obtained. Preferably, the second host material contains a phosphorescent material.

[0100] Preferably, the thickness of the aforementioned double host light-emitting layer is 10 to 60 nm, such as 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, etc., preferably 20 to 50 nm.

[0101] In the present invention, preferably, the thickness of the light-emitting layer containing Compound I or Compound II is 10 to 60 nm. Within this thickness range, the efficiency of the device is further improved. If the thickness is too small, the internal excitons cannot be sufficiently recombined. If the thickness is too large, the hole and electron transport processes are too long, and the internal loss also increases, both of which will lead to a decrease in efficiency.

[0102] Preferably, the thickness of the electron barrier layer is 2 to 100 nm, such as 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, etc., preferably 3 to 90 nm.

[0103] In the present invention, preferably, the thickness of the electron barrier layer containing Compound I or Compound II is 2 to 100 nm. Within this thickness range, the efficiency of the device is further improved. If the thickness is too small, internal excitons cannot be sufficiently recombined. If the thickness is too large, the hole and electron transport processes are too long, and the internal loss also increases, both cases leading to a decrease in efficiency. Preferably, the organic layer further includes a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer.

[0104] Preferably, in Compound I, the Ar 1 is any one selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo-9,9-dimethylfluorenyl, benzospirofluorenyl. Preferably, in Compound I, the Ar 2 is any one selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo-9,9-dimethylfluorenyl, benzospirofluorenyl, and is preferably substituted or unsubstituted naphthyl.

[0105] Preferably, the Ar 2 is any one selected from the following substituted or unsubstituted groups.

Chemical formula

[0106] Preferably, in Compound I, the R 1 , R 2 and R 3is independently one selected from methyl, ethyl or phenyl, preferably all methyl. Preferably, in Compound I, said L 1 is one selected from substituted or unsubstituted phenylene, biphenylene, naphthalene, dibenzofurylidene, dibenzothienylidene, 9,9-dimethylfluorenylidene. Preferably, in Compound I, said L 2 is one selected from a single bond, substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene, preferably a single bond or phenylene.

[0107] Preferably, said Compound II is a compound in which at least one Rx is substituted at any substitutable position in the structure represented by formula (3-1).

Chemical formula

[0108] Preferably, said Rx is any one selected from the following groups.

Chemical formula

[0109] Preferably, said Ar 3 ~Ar 5 are each independently any one selected from substituted or unsubstituted following groups.

Chemical formula

[0110] Preferably, said L 3 and L 4 are each independently selected from a single bond, phenylene or naphthalene, preferably a single bond. Preferably, said L 5 is a single bond.

[0111] The OLED includes a first electrode, a second electrode, and an organic material layer located between the electrodes. This organic material may be divided into a plurality of regions. For example, this organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region.

[0112] In a specific embodiment, a substrate may be used under the first electrode or on the second electrode. The substrate is made of glass or polymer materials that all have mechanical strength, thermal stability, waterproofness, and excellent transparency. Furthermore, a thin film transistor (TFT) may be attached to the substrate for a display.

[0113] The first electrode may be formed by sputtering or depositing a material for the first electrode on the substrate. When the first electrode is an anode, oxide transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), etc. and any combination thereof may be used. When the first electrode is a cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), etc. and any combination thereof may be used.

[0114] The organic material layer may be formed on the electrode by methods such as vacuum thermal evaporation, spin coating, printing, etc. The compounds used as the organic material layer may be organic small molecules, organic macromolecules, polymers, and combinations thereof.

[0115] The hole transport region is located between the anode and the light-emitting layer. The hole transport region may be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one kind of compound and a single-layer hole transport layer containing a plurality of kinds of compounds. The hole transport region may also be a multilayer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL). The HIL is located between the anode and the HTL, and the EBL is located between the HTL and the light-emitting layer.

[0116] The material of the hole transport region may be selected from phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing a conductive dopant such as poly(phenylene ethylene), polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), arylamine derivatives such as the compounds shown in HT-1 to HT-51 above; or any combination thereof, but is not limited thereto.

[0117] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of multiple compounds. For example, the hole injection layer may employ one or more of the compounds of HT-1 to HT-51 above, or one or more of the compounds of HI-1 to HI-3 above, or a material in which one or more of the compounds of HI-1 to HI-3 above are doped into one or more of the compounds of HT-1 to HT-51.

[0118] The light-emitting layer contains a light-emitting dye (i.e., dopant) that can emit spectra of various wavelengths and may also contain a host material. The light-emitting layer may be a single-color light-emitting layer that emits a single color such as red, green, or blue. Multiple single-color light-emitting layers of different colors may be arranged two-dimensionally according to a pixel pattern or deposited to form a color light-emitting layer. When light-emitting layers of different colors are deposited, they may be spaced apart from each other or connected to each other. The light-emitting layer may also be a single color light-emitting layer that can emit different colors such as red, green, and blue simultaneously.

[0119] According to the technology, the material of the light-emitting layer may adopt a phosphorescent electroluminescence material. In an OLED device, one light-emitting technology may be used, or a combination of multiple different light-emitting technologies may be adopted. These light-emitting materials classified by the technology may emit light of the same color or different colors.

[0120] In one aspect of the present invention, the second host material of the light-emitting layer is a phosphorescent material, and the phosphorescent material may be one or a combination of more than one selected from PH-1 to PH-86, but is not limited thereto.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0121] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer may be one or a combination of more than one selected from the aforementioned GPD-1 to GPD-47, but is limited thereto. In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer may be one or a combination of more than one selected from the aforementioned RPD-1 to RPD-28, but is limited thereto. In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer may be one or a combination of more than one selected from the aforementioned YPD-1 to YPD-11, but is limited thereto.

[0122] In one aspect of the present invention, the light-emitting layer adopts thermally activated delayed fluorescence emission technology. The host material of the light-emitting layer may be one or a combination of more than one selected from the aforementioned PH-1 to PH-86, but is not limited thereto.

[0123] In one aspect of the present invention, the electron blocking layer (EBL) is located between the hole transport layer and the light-emitting layer. The electron blocking layer may employ one or a combination of more than one compound contained in the aforementioned Compound I and Compound II, but is not limited thereto.

[0124] The OLED organic material layer may further include an electron transport region between the light-emitting layer and the cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an electron injection layer (EIL) and an electron transport layer (ETL).

[0125] In one aspect of the present invention, the material of the electron transport layer may be one or a combination of more than one selected from the aforementioned ET-1 to ET-65, but is not limited thereto.

[0126] The device may further include an electron injection layer located between the electron transport layer and the cathode. The material of the electron injection layer may include one or a combination of more than one of LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg, Yb, but is not limited thereto.

[0127] Another embodiment of the present invention provides a display device including the organic electroluminescence device described in one of the objectives.

[0128] Compared with the prior art, the above preferred embodiments of the present invention have the following beneficial effects. The present invention uses both Compound I and Compound II as materials for the organic layer. Compound I adjusts the carrier distribution inside the light-emitting layer to regulate the recombination region of carriers, and moreover, has a high spatial deposition structure. On the other hand, Compound II has excellent molecular planar expansion characteristics, accelerates hole transport, improves hole mobility, and has a high triplet energy level, capable of blocking excessive excitons. When both are used in combination, the efficiency of the device can be effectively improved.

Brief Description of the Drawings

[0129] The drawings of the specification that form part of this application are provided to further understand the present invention. The exemplary embodiments and their descriptions of the present invention interpret the present invention and do not unduly limit the present invention. The drawings are as follows.

Figure 1

Modes for Carrying Out the Invention

[0130] Unless there is no contradiction, the examples and the features of the examples in this application may be combined with each other. Hereinafter, the present invention will be described in detail with reference to the examples.

[0131] The typical synthetic route of the Compound I of the present invention is as follows.

Chemical Formula

[0132] More specifically, the following synthesis examples of the present invention exemplarily provide specific synthesis methods of representative compounds. Solvents and reagents used in the following synthesis examples, such as 3-bromo-9,9-dimethylfluorene, 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride, tris(dibenzylideneacetone)dipalladium(0), toluene, methanol, ethanol, tri-t-butylphosphine, potassium t-butoxide / sodium t-butoxide and other chemical reagents may all be commercially available or customized as chemical industrial products in China. For example, they may be purchased from Sinopharm Chemical Reagent Co., Ltd., Sigma-Aldrich, or Bailingwei Reagent Co., Ltd. Intermediates M1 to M7 are customized by reagent companies. Also, those skilled in the art may synthesize them by known methods.

[0133] Synthesis Example 1: Synthesis of Compound P1

Chemical formula

[0134] In a 1000 mL one-necked flask, add M1 - 123 g (50 mmol), 4-bromo-t-butylbenzene 11 g (50 mmol), tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3) 0.9 g (1 mmol), tri-t-butylphosphine ((t-Bu)3P) 0.5 mL, toluene 500 mL, and sodium t-butoxide (NaOBu-t) 14.4 g (150 mmol). Perform vacuum suction to conduct nitrogen substitution three times, heat to 110 °C, and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution by liquid separation, concentrate the organic phase, add methanol, stir for 1 h, and perform suction filtration to obtain light yellow powder P1. Theoretical value of M / Z: 593; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 594.

[0135] Synthesis Example 2: Synthesis of Compound P2

Chemical formula

[0136] Synthesis Example 3: Synthesis of Compound P5

Chemical formula

[0137] Synthesis Example 4: Synthesis of Compound P6

Chemical formula

[0138] Synthesis Example 5: Synthesis of Compound P7

Chemical formula

[0139] In a 1000 mL one-necked flask, add 29 g (50 mmol) of M1-2, 11 g (50 mmol) of 4-bromo-t-butylbenzene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3), 0.5 mL of tri-t-butylphosphine ((t-Bu)3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium t-butoxide (NaOBu-t). Perform vacuum suction to conduct nitrogen replacement three times, heat to 110 °C, and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution by liquid separation, concentrate the organic phase, add methanol, stir for 1 h, and perform suction filtration to obtain pale yellow powder P7. Theoretical value of M / Z: 717; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 718.

[0140] Synthesis Example 6: Synthesis of Compound P15

Chemical formula

[0141] Into a 1000 mL one-necked flask, add 25.5 g (50 mmol) of M1-3, 11 g (50 mmol) of 4-bromo-t-butylbenzene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3), 0.5 mL of tri-t-butylphosphine ((t-Bu)3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium t-butoxide (NaOBu-t). Perform vacuum suction to conduct nitrogen substitution three times, heat to 110 °C, and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution by liquid separation, concentrate the organic phase, add methanol, stir for 1 h, and perform suction filtration to obtain light yellow powder P15. Theoretical value of M / Z: 643; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 644.

[0142] Synthesis Example 7: Synthesis of Compound P37 [Chemical formula] Into a 1000 mL one-necked flask, add M2 16 g (50 mmol), 3-bromo-9,9-dimethylfluorene 13.5 g (50 mmol), tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3) 0.9 g (1 mmol), IPr.HCl 0.5 g, toluene 500 mL, and sodium t-butoxide (NaOBu-t) 14.4 g (150 mmol). Perform vacuum suction to conduct nitrogen substitution three times, heat to 90 °C and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution by liquid separation, concentrate the organic phase, add methanol and stir for 1 h, and perform suction filtration to obtain pale yellow powder M2-1.

[0143] Into a 1000 mL one-necked flask, add M2-1 26 g (50 mmol), 4-bromo-t-butylbenzene 11 g (50 mmol), tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3) 0.9 g (1 mmol), tri-t-butylphosphine ((t-Bu)3P) 0.5 mL, toluene 500 mL, and sodium t-butoxide (NaOBu-t) 14.4 g (150 mmol). Perform vacuum suction to conduct nitrogen substitution three times, heat to 110 °C and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution by liquid separation, concentrate the organic phase, add methanol and stir for 1 h, and perform suction filtration to obtain pale yellow powder P37. Theoretical value of M / Z: 649; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 650.

[0144] Synthesis Example 8: Synthesis of Compound P38

Chemical formula

[0145] Synthesis Example 9: Synthesis of Compound P74

Chemical formula

[0146] Into a 1000 mL one-necked flask, add M3-125 g (50 mmol), 4-bromo-4'-t-butylbiphenyl 14.5 g (50 mmol), tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3) 0.9 g (1 mmol), tri-t-butylphosphine ((t-Bu)3P) 0.5 mL, toluene 500 mL, and sodium t-butoxide (NaOBu-t) 14.4 g (150 mmol). Perform vacuum suction and nitrogen replacement three times, heat to 110 °C and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, add methanol and stir for 1 h, and perform suction filtration to obtain pale yellow powder P74. Theoretical value of M / Z: 709; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 710.

[0147] Synthesis Example 10: Synthesis of Compound P253

Chemical formula

[0148] Into a 1000 mL one-necked flask, add M4 - 126.5 g (50 mmol), 4-bromo-t-butylbenzene 11 g (50 mmol), tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3) 0.9 g (1 mmol), tri-t-butylphosphine ((t-Bu)3P) 0.5 mL, toluene 500 mL, and sodium t-butoxide (NaOBu-t) 14.4 g (150 mmol). Perform vacuum suction to carry out nitrogen substitution three times, heat to 110 °C, and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, add methanol, stir for 1 h, and perform suction filtration to obtain light yellow powder P253. Theoretical value of M / Z: 659; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 660.

[0149] Synthesis Example 11: Synthesis of Compound P284

Chemical formula

[0150] Synthesis Example 12: Synthesis of Compound P375

Chemical formula

[0151] Into a 1000 mL one-necked flask, add 25 g (approx. 50 mmol) of M5-1, 14.5 g (50 mmol) of 2-phenyl-4-bromo-t-butylbenzene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3), 0.5 mL of tri-t-butylphosphine ((t-Bu)3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium t-butoxide (NaOBu-t). Perform vacuum suction to conduct nitrogen replacement three times, heat up to 110 °C, and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution by liquid separation, concentrate the organic phase, add methanol, stir for 1 h, and perform suction filtration to obtain pale yellow powder P375. Theoretical value of M / Z: 695; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 696.

[0152] Synthesis Example 13: Synthesis of Compound P322

Chemical formula

[0153] In a 1000 mL one-necked flask, add 26.5 g (50 mmol) of M7-1, 14 g (50 mmol) of 1-(4-bromophenyl)-1,1-dimethyl-1-phenylmethane, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3), 0.5 mL of tri-t-butylphosphine ((t-Bu)3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium t-butoxide (NaOBu-t). Perform vacuum suction to conduct nitrogen replacement three times, heat to 110 °C, and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution by liquid separation, concentrate the organic phase, add methanol, stir for 1 h, and perform suction filtration to obtain light yellow powder P322. Theoretical value of M / Z: 721; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 722.

[0154] Synthesis Example 14: Synthesis of Compound P323

Chemical formula

[0155] Into a 1000 mL one-necked flask, add 29 g (50 mmol) of M7-2, 12.7 g (50 mmol) of 1-(4-bromophenyl)-1,1,1-triethylmethane, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3), 0.5 mL of tri-tert-butylphosphine ((t-Bu)3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t). Perform vacuum suction to conduct nitrogen substitution three times, heat to 110 °C, and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution by liquid separation, concentrate the organic phase, add methanol, stir for 1 h, and perform suction filtration to obtain pale yellow powder P323. Theoretical value of M / Z: 751; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 752.

[0156] Synthesis Example 15: Synthesis of Compound P20

Chemical formula

[0157] Synthesis Example 16: Synthesis of Compound P628

Chemical formula

[0158] Into a 1000 mL one-necked flask, add M1 - 425.5 g (50 mmol), 2-bromo-5-t-butylbiphenyl 14.5 g (50 mmol), tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3) 0.9 g (1 mmol), tri-t-butylphosphine ((t-Bu)3P) 0.5 mL, toluene 500 mL, and sodium t-butoxide (NaOBu-t) 14.4 g (150 mmol). Perform vacuum suction to conduct nitrogen substitution three times, heat to 110 °C, and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, add methanol, stir for 1 h, and perform suction filtration to obtain pale yellow powder P628. Theoretical value of M / Z: 719; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 720.

[0159] Synthesis Example 17: Synthesis of Compound P613

Chemical formula

[0160] Into a 1000 mL single-necked flask, add M1-522 g (50 mmol), 4-bromo-t-butylbenzene 11 g (50 mmol), tris(dibenzylideneacetone)dipalladium (i.e., Pd2(dba)3) 0.9 g (1 mmol), tri-t-butylphosphine ((t-Bu)3P) 0.5 mL, toluene 500 mL, and sodium t-butoxide (NaOBu-t) 14.4 g (150 mmol). Perform vacuum suction to conduct nitrogen replacement three times, heat to 110 °C, and react for 5 h. When the reaction is completed, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, add methanol, stir for 1 h, and perform suction filtration to obtain pale yellow powder P613. Theoretical value of M / Z: 567; Measured value of M / Z by ZAB-HS type mass spectrometer (manufactured by Micromass, UK): 568.

[0161] Synthesis Example 18: Synthesis of Compound P602

Chemical formula

[0162] Example 1 This example provides an organic electroluminescence device, and its manufacturing is specifically shown as follows. A glass plate coated with an ITO transparent conductive layer (as an anode) was ultrasonically treated with an industrial cleaning agent, rinsed in deionized water, degreased ultrasonically in an acetone:ethanol mixed solvent, baked in a clean environment until the moisture was completely removed, cleaned with ultraviolet light and ozone, and a low-energy cation beam was made to impinge on the surface. The aforementioned glass substrate with an anode was placed in a vacuum chamber and evacuated to less than 1 × 10 -5 Pa. HI-3 was vacuum-evaporated as a hole injection layer on the aforementioned anode layer film at a deposition rate of 0.1 nm / s and a deposited film thickness of 10 nm. HT-4 was vacuum-evaporated as a hole transport layer of the device on the hole injection layer at a deposition rate of 0.1 nm / s and a total deposited film thickness of 80 nm. Compound P1 was vacuum-evaporated as a material for the electron barrier layer of the device on the hole transport layer at a deposition rate of 0.1 nm / s and a total deposited film thickness of 80 nm. An emission layer containing a host material and a dye material of the device was vacuum-evaporated by a multi-source co-evaporation method on the electron barrier layer. The deposition rate of the host material GPH-59 was adjusted to 0.1 nm / s, the deposition rate of the dye RPD-8 was set at a ratio of 3% of the host material, and the total deposited film thickness was 30 nm. The material ET-46 of the electron transport layer of the device was vacuum-evaporated on the emission layer at a deposition rate of 0.1 nm / s and a total deposited film thickness of 30 nm. LiF with a thickness of 0.5 nm was vacuum-evaporated as an electron injection layer on the electron transport layer (ETL), and an Al layer with a thickness of 150 nm was vacuum-evaporated as the cathode of the device.

[0163] The manufacturing processes of the organic electroluminescence devices according to Examples 2 to 18 and Comparative Examples 1 to 6 were the same as those of Example 1, except that the material compound P1 of the electron barrier layer was changed to the compounds described in Table 1, respectively.

[0164] The structures of the materials of the electron barrier layers of Comparative Examples 1 to 6 are shown below.

Chemical formula

[0165] For the organic electroluminescence device manufactured by the foregoing process, the performance was measured as follows. At the same luminance, using a Digital SourceMeter (Keithley 2400), a luminance meter (ST-86LA type luminance meter, Beijing Normal University Optoelectronic Instrument Factory), and a luminance meter, the driving voltage and current efficiency of the organic electroluminescence devices manufactured in Examples 1 to 18 and Comparative Examples 1 to 6 were measured. Specifically, the voltage was increased at a rate of 0.1 V / s, and while measuring the driving voltage, which is the voltage when the luminance of the organic electroluminescence device reached 3000 cd / m 2 ², the current density at this time was measured, and the ratio of luminance to current density was taken as the current efficiency. The test results are shown in Table 1.

[0166]

Table 1

[0167] It is obvious from the data in Table 1 that when the compound of the present invention is used as the material of the electron barrier layer of the organic electroluminescence device, when the luminance of the device reaches 3000 cd / m 2 ², the driving voltage is as low as 3.8 V or less, and the current efficiency is as high as 18.2 cd / A or more. Thus, the driving voltage is effectively improved and the current efficiency is enhanced. Therefore, the compound of the present invention is a material for the electron barrier layer with excellent performance.

[0168] In the compound R-1 of Comparative Example 1, compared with the compound P602 of Example 18, there is no substitution at the 1-position of naphthalene in the structure of the compound R-1, and the 4-position is substituted with a benzene ring, which is different. When this compound is used as a material for the electron barrier layer of an organic electroluminescence device, the driving voltage of the device is 5.3 V, and the current efficiency is 11 cd / A. The turn-on voltage and current efficiency of this compound are inferior to those of P602, which is considered to be due to the fact that the compound P602 has better spatial deposition and improved hole transport performance.

[0169] In the compound R-2 of Comparative Example 2, arylamine group substitution occurs at the 1-position of the naphthalene ring, benzene ring substitution occurs at the 2- and 3-positions, and no substituent with a t-butyl structure is included. When this compound is used as a material for the electron barrier layer of an organic electroluminescence device, the driving voltage of the device is 5.8 V, and the current efficiency is 10.1 cd / A. From this, the effect is clearly inferior to that of Examples 1-18.

[0170] In the compound R-3 of Comparative Example 3, compared with the compound P1 of Example 1, the difference is that there is no t-butyl substitution at the 4-position of the phenyl group linked to N. When this compound is used as a material for the electron barrier layer of an organic electroluminescence device, the driving voltage of the device is 3.3 V, and the current efficiency is 19 cd / A. The current efficiency of this compound is inferior to that of P1, which is considered to be due to the fact that the t-butyl group at the 4-position of the compound P1 provides a higher electron-donating ability, the molecular spatial deposition structure is improved, and the hole transport performance of the material is effectively improved.

[0171] In the compound R-4 of Comparative Example 4, compared with the compound P2 of Example 2, the difference is that there is no t-butyl substitution on the biphenyl side linked to N in the molecule. When this compound is used as a material for the electron barrier layer of an organic electroluminescence device, the driving voltage of the device is 3.1 V and the current efficiency is 19.3 cd / A. The current efficiency of this compound is inferior to that of P2, which is considered to be due to the fact that the t-butyl group at the 4-position of the compound P2 provides an electron-donating ability, improves the molecular spatial deposition structure, and effectively improves the hole-transporting performance of the material.

[0172] In the compound R-5 of Comparative Example 5, compared with the compound P5 of Example 3, the difference is that there is no t-butyl substitution at the 4-position of the biphenyl linked to N. When this compound is used as a material for the electron barrier layer of an organic electroluminescence device, the driving voltage of the device is 3.4 V and the current efficiency is 18.5 cd / A. The current efficiency of this compound is inferior to that of P5, which is considered to be due to the fact that the t-butyl group at the 4-position of the compound P5 provides a high electron-donating ability, improves the molecular spatial deposition structure, and effectively improves the hole-transporting performance of the material.

[0173] In the compound R-6 of Comparative Example 6, compared with the compound P6 of Example 4, the difference is that there is no t-butyl substitution at the terminal of the 2-phenylbiphenyl linked to nitrogen in the molecule. When this compound is used as a material for the electron barrier layer of an organic electroluminescence device, the driving voltage of the device is 3.5 V and the current efficiency is 17.8 cd / A. The current efficiency of this compound is inferior to that of P6, which is considered to be due to the fact that the t-butyl group of the compound P6 provides an electron-donating ability, improves the molecular spatial deposition structure, and effectively improves the hole-transporting performance of the material.

[0174] From the above, in the compound according to the present invention, the substitution at the 1-position of the naphthalene ring with Ar 2 substitution, the substitution of the 2-position with an arylamine substitution, and the substitution of the t-butyl structure substituent are clearly factors that can impart excellent performance when this compound is used in an organic electroluminescence device.

[0175] Example 19 This example provides an organic electroluminescence device, and its structure includes, as shown in FIG. 1, a glass substrate 1 with an anode, a hole injection layer 2, a hole transport layer 3, an electron barrier layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, a cathode layer 8, and an external power source 9.

[0176] The manufacturing method of the aforementioned organic electroluminescence device is shown below. The glass plate coated with the ITO transparent conductive layer was ultrasonically treated with a commercial cleaning agent, rinsed in deionized water, degreased ultrasonically in an acetone:ethanol mixed solvent, baked in a clean environment until the moisture was completely removed, washed with ultraviolet light and ozone, and a low-energy cation beam was made to collide with the surface. The aforementioned glass substrate with an anode was placed in a vacuum chamber and evacuated to less than 1×10 -5 Pa. On the aforementioned anode layer film, a 10-nm mixture of HT-4:HI-3 (97 / 3, w / w) as a hole injection layer, a 60-nm compound HT-4 as a hole transport layer, a 5-nm compound HT-48 as an electron barrier layer, a 40-nm ternary mixture of PH-34:P1:RPD-10 (100:30:3, w / w / w) as a light-emitting layer, a 5-nm ET-23 as a hole barrier layer, a 25-nm mixture of compound ET-69:ET-57 (50 / 50, w / w) as an electron transport layer, a 1-nm LiF as an electron injection layer, and a 150-nm metal aluminum as a cathode were sequentially vacuum thermally evaporated. The total evaporation rate of all organic layers and LiF was 0.1 nm / second, and the evaporation rate of the metal electrode was 1 nm / second. Here, "97 / 3, w / w" represents a mass ratio of 97:3.

[0177] The differences between Examples 19 to 42, Comparative Examples 7 to 8 and Example 19 are shown in Table 3 respectively, and all parts not described in Table 3 are the same as those in Example 19.

[0178] Performance test (1) The HOMO energy level and LUMO energy level of the second host material used in the aforementioned examples and comparative examples are shown in Table 2.

[0179]

Table 2

[0180] (2) At the same luminance, the current efficiency of the organic electroluminescence devices manufactured according to the examples and comparative examples was measured. Specifically, the voltage was increased at a rate of 0.1 V / s, and when the luminance of the organic electroluminescence device reached 3000 cd / m 2 , the current density was measured, and the ratio of the luminance to the current density was defined as the current efficiency. The test results are shown in Table 3.

[0181]

Table 3

[0182] Comparative Example 7 is a single host device, and the mass ratio of PH-34 to RPD-10 is 130:3. Comparative Example 8 is also a single host device, and the mass ratio of P1 to RPD-10 is 130:3.

[0183] From Table 3, it was found that the organic electroluminescence device including the double host light-emitting layer according to the present invention has excellent optoelectronic performance, and all of them have a current efficiency of 11.7 cd / A or more, and most of them can reach 15 cd / A or more, and the highest can reach 17 cd / A or more. In Comparative Examples 7 and 8 using a single host device, the effect was clearly reduced compared to the present invention.

[0184] From the comparison of Examples 19, 22 to 27, when the mass ratio of the first host material to the second host material is 0.01:1 to 1.5:1 (Examples 19, 22 to 27), the efficiency of the device is further improved, and particularly when it is 0.1:1 to 1:1 (Examples 19, 24 and 25), it was found that the effect is the highest.

[0185] From the comparison of Examples 19, 28 to 33, when the thickness of the double host light-emitting layer is 10 to 65 nm (Examples 19, 28 to 31), the efficiency of the device is further improved. In particular, when the thickness is in the range of 15 to 55 nm (Examples 19, 30 and 31), it was found that the effect is the highest. From the comparison of Example 19 and Example 34, it was found that when the second host material satisfies specific LUMO energy level and HOMO energy level (Example 19), it is advantageous for further improvement of the device efficiency. In the following examples, the synthesis method of Compound I is as described above, and the synthesis method of Compound II refers to the Chinese patent application with publication number CN110950762A (application number 201910857132.9).

[0186] Example 43 This example provides an organic electroluminescence device, and its structure includes, as shown in FIG. 1, a glass substrate 1 with an anode, a hole injection layer 2, a hole transport layer 3, an electron barrier layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, a cathode layer 8, and an external power source 9.

[0187] The manufacturing method of the aforementioned organic electroluminescence device is shown below. The glass plate coated with the ITO transparent conductive layer was ultrasonically treated with a commercial cleaning agent, rinsed in deionized water, degreased ultrasonically in an acetone:ethanol mixed solvent, baked in a clean environment until the moisture was completely removed, washed with ultraviolet light and ozone, and a low-energy cation beam was made to impinge on the surface. The aforementioned glass substrate with an anode was placed in a vacuum chamber, and 1×10 -5Vacuum suction was performed until it was less than Pa, and on the aforementioned anode layer film, a 10-nm HT-4:HI-3 (97 / 3, w / w) mixture as a hole injection layer, a 60-nm compound HT-4 as a hole transport layer, a 60-nm compound A1 as an electron barrier layer, a 30-nm compound PH86:P1:RPD-10 (1:0.01:0.05, w / w / w) ternary mixture as a light-emitting layer (here, PH86 and P1 are host materials), a 25-nm compound ET-61:ET-57 (50 / 50, w / w) mixture as an electron transport layer, a 1-nm LiF as an electron injection layer, and a 150-nm metal aluminum as a cathode were sequentially vacuum thermally evaporated. The total evaporation rate of all organic layers and LiF was 0.1 nm / second, and the evaporation rate of the metal electrode was 1 nm / second.

[0188] The differences between Examples 44 to 68, Comparative Examples 9 to 12 and Example 43 are all shown in Table 4, and the parts not described in Table 4 are the same as those in Example 43.

[0189] Performance test At the same luminance, the external quantum efficiency (EQE, %) of the organic electroluminescence devices manufactured according to the examples and comparative examples was measured, and the required luminance was 3000 cd / m 2 It was.

[0190]

Table 4

[0191] As can be seen from Table 4, in the present invention, by using Compound I and Compound II in an organic electroluminescence device, the external quantum efficiency is effectively improved, the device performance is improved, and as a result, the energy consumption of the device is reduced, and characteristics such as luminance are excellent. Therefore, these compounds are materials for an electron barrier layer and a light-emitting layer with excellent performance, and the external quantum efficiency of the device reaches 19%.

[0192] In Comparative Example 10, compared with Example 56, only the material of the electron barrier layer was different in that it was HT5, and its external quantum efficiency was clearly lower than that of Example 14. In Comparative Example 11, compared with Example 45, only the material of the electron barrier layer was different in that it was HT5, and its external quantum efficiency was clearly lower than that of Example 45. In Comparative Example 4, compared with Example 45, only the host materials were different in that they were PH86 and HT-10, and its external quantum efficiency was clearly lower than that of Example 45. From the above results, in the present invention, it was shown that by combining Compound I and Compound II, the efficiency of the device was effectively improved, and any replacement would result in a decrease in efficiency.

[0193] As can be seen from the comparison between Example 45 and Example 57, and between Example 56 and Example 58, when Compound I or Compound II was used in the double host light-emitting layer, the efficiency of the device (Example 45, Example 56) was further improved, and when used alone, the effect was deteriorated (Example 57, Example 58).

[0194] As can be seen from the comparison between Examples 43 to 47, 59 and 60, when the mass ratio of the first host material to the second host material was 0.01:1 to 1.5:1 (Examples 43 to 47), the external quantum efficiency was further improved. When the addition amount was too low (Example 59) or too high (Example 60), a decrease in efficiency was observed.

[0195] As can be seen from the comparison between Examples 45, 48 to 51 and Examples 61, 62, by setting the thickness of the light-emitting layer to 10 to 60 nm (Examples 45, 48 to 51), the external quantum efficiency of the device was further improved. When the thickness was too small (Example 61) or too large (Example 62), a decrease in efficiency was observed.

[0196] As can be seen from the comparison between Examples 45, 52 to 55 and Examples 63, 64, by setting the thickness of the electron barrier layer to 2 to 100 nm (Examples 45, 52 to 55), the external quantum efficiency of the device was further improved. When the thickness was too small (Example 63) or too large (Example 64), a decrease in efficiency was observed.

[0197] The above are only preferred embodiments of the present invention and do not limit the present invention. As will be apparent to those skilled in the art, various modifications and changes are possible to the present invention. All modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and principle of the present invention shall be included in the patent scope of the present invention.

Explanation of Reference Numerals

[0198] 1 Glass substrate with anode 2 Hole injection layer 3 Hole transport layer 4 Electron barrier layer 5 Light-emitting layer 6 Electron transport layer 7 Electron injection layer 8 Cathode layer 9 External power source

Claims

1. A compound characterized by having the structure shown in Formula I. 【Chemical 1】 (In formula I, the Ar １ and Ar ２ are each independently selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl, In Formula I, the aforementioned L １ is selected from substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C3-C30 heteroarylene, In Formula I, said L ２ is one selected from a single bond, a substituted or unsubstituted C6-C30 arylene, or a substituted or unsubstituted C3-C30 heteroarylene, In formula I, said R １ , R ２ and R ３ are independently selected from substituted or unsubstituted C1-C20 chain alkyl and unsubstituted C6-C30 aryl, In Formula I, m is 0, Ar １ 、Ar ２ 、L １ 、L2, the substituting group is, respectively, independently, one kind or at least a combination of two kinds selected from halogen, C1-C10 linear alkyl, C3-C10 cyclic alkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, C6-C30 monocyclic aryl, C10-C30 condensed ring aryl, C3-C30 monocyclic heteroaryl, C6-C30 condensed ring heteroaryl.

2. The above-mentioned L ２ The compound according to claim 1, wherein the above-mentioned L is one selected from a single bond, a substituted or unsubstituted C6-C20 arylene or a substituted or unsubstituted C3-C20 heteroarylene.

3. The compound according to Claim 1, wherein L2 is a single bond or phenylene.

4. Said Ar ２ The compound according to claim 1, wherein said Ar is selected from substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C3-C20 heteroaryl.

5. Said Ar ２ is any one selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo[9,9-dimethylfluorenyl], benzospirofluorenyl, and the compound according to claim 1, characterized in that it is any one of them.

6. The Ar ２ is any one selected from the following substituted or unsubstituted groups, and the compound according to claim 1, characterized in that. [Chemical Formula 2] (Here, the dashed line represents the connecting bond of the group.)

7. The aforementioned L ２ is a single bond, and the aforementioned Ar ２ is selected from a substituted or unsubstituted C10-C30 fused-ring aryl or a substituted or unsubstituted C6-C30 fused-ring heteroaryl. The compound according to claim 1, characterized in that.

8. The L ２ is a single bond, and the Ar ２ is any one selected from substituted or unsubstituted naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo(9,9-dimethylfluorenyl), benzospirofluorenyl, and the compound according to claim 1, characterized in that it is such a compound.

9. The L ２ is a single bond, and the Ar ２ is any one selected from the following substituted or unsubstituted groups, and the compound according to claim 1 is characterized in that [Chemical Formula 3] (Here, the dashed line represents the connecting bond of the group.)

10. Said L ２ is phenylene, and said Ar ２ is selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl. The compound according to claim 1, characterized in that.

11. The L ２ is phenylene, and the Ar ２ is any one selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo-9,9-dimethylfluorenyl, benzospirofluorenyl, and the compound according to claim 1, characterized in that it is any one of them.

12. The L ２ is phenylene, and the Ar ２ is any one selected from the following substituted or unsubstituted groups, the compound according to claim 1, characterized in that. 【Chemical Formula 4】 (Here, the dashed line represents the connecting bond of the group.)

13. Said R １ , R ２ and R ３ is independently one selected from methyl, ethyl or phenyl, and the compound according to any one of claims 1 to 12, characterized in that.

14. Said R １ , R ２ and R ３ The compound according to any one of claims 1 to 12, wherein all of them are methyl.

15. The above-mentioned L １ is one selected from substituted or unsubstituted phenylene, biphenylene, naphthalene, dibenzofurylidene, dibenzothienylidene, 9,9-dimethylfluorenylidene, and the compound according to any one of claims 1 to 12, characterized in that.

16. The aforementioned L １ is any one selected from the following substituted or unsubstituted groups, and the compound according to any one of claims 1 to 12, characterized in that. [Chemical Formula 5] (Here, the dashed line represents the connecting bond of the group.)

17. The compound according to Claim 1, characterized by having any one of the structures shown in P1 to P777. 【Chemical Formula 6-1】 ​ 【Chemical Formula 6-3】 【Chemical Formula 6-4】 【Chemical Formula 6-5】 【Chemical Formula 6-6】 【Chemical Formula 6-7】 【Chemical Formula 6-8】 [[Chemical 6-9]] 【Chemical Formula 6-10】 【Chemical Formula 6-11】 【Chemical Formula 6-12】 【Chemical Formula 6-13】 【Chemical Formula 6-14】 【Chemical Formula 6-15】 [Chemical Formula 6-16] ​ [Chemical Formula 6-18] 【Chemical Formula 6-19】 [[Chemical Formula 6-20]] 【Chemical Formula 6-21】 ​ ​ 【Chemical Formula 6-24】 【Chemical Formula 6-25】 【Chemical Formula 6-26】 ​ 【Chemical Formula 6-28】 【Chemical Formula 6-29】 【Chemical Formula 6-30】 ​ 【Chemical Formula 6-32】 【Chemical Formula 6-33】 【Chemical Formula 6-34】 【Chemical Formula 6-35】 【Chemical Formula 6-36】 [Chemical Formula 6-37] 【Chemical Formula 6-38】 【Chemical Formula 6-39】 【Chemical Formula 6-40】 【Chemical Formula 6-41】 【Chemical Formula 6-42】 【Chemical Formula 6-43】 【Chemical Formula 6-44】 【Chemical Formula 6-45】 【Chemical Formula 6-46】 【Chemical Formula 6-47】 【Chemical Formula 6-48】 【Chemical Formula 6-49】 【Chemical Formula 6-50】 【Chemical Formula 6-51】 【Chemical Formula 6-52】 【Chemical Formula 6-53】 【Chemical Formula 6-54】 【Chemical Formula 6-55】 【Chemical Formula 6-56】 【Chemical Formula 6-57】 【Chemical Formula 6-58】 【Chemical Formula 6-59】 【Chemical Formula 6-60】 【Chemical Formula 6-61】 ​

18. An organic electroluminescence device having a first electrode, a second electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the organic layer contains at least one compound according to any one of Claims 1 to 17.

19. The organic electroluminescence device according to Claim 18, wherein the organic layer includes an electron barrier layer, and the electron barrier layer contains at least one compound according to any one of Claims 1 to 17.

20. The first electrode is an anode layer, the second electrode is a cathode layer, the organic layer includes a light-emitting layer, the light-emitting layer contains a host material and a dopant material, the host material includes a first host material and a second host material, and the first host material is the compound according to Claim 1. The organic electroluminescence device according to Claim 18.

21. In formula I, said Ar １ is any one selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo[9,9-dimethylfluorenyl], benzospirofluorenyl, and / or In formula I, the above-mentioned Ar ２ is any one selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracyl, dibenzofuryl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo(9,9-dimethylfluorenyl), benzospirofluorenyl, and the organic electroluminescence device according to claim 20, characterized in that it is any one of them.

22. The organic electroluminescence device according to Claim 20, wherein Ar2 is a substituted or unsubstituted naphthyl.

23. In Formula I, R1, R2, and R3 are each independently selected from methyl, ethyl, or phenyl. The organic electroluminescence device according to any one of Claims 20 to 22.

24. In Formula I, R1, R2, and R3 are each independently methyl. The organic electroluminescence device according to any one of Claims 20 to 22.

25. The organic electroluminescence device according to any one of claims 20 to 22, wherein the first host material is any one selected from the compounds described in claim 17 or a combination of at least two thereof.

26. The organic electroluminescence device according to any one of claims 20 to 24, wherein the mass ratio of the first host material to the second host material is 0.01:1 to 1.5:

1.

27. The organic electroluminescence device according to any one of claims 20 to 24, wherein the mass ratio of the first host material to the second host material is 0.1:1 to 1:

1.

28. The HOMO energy level of the second host material is -5.3 eV to -5.7 eV, and / or The organic electroluminescence device according to any one of claims 20 to 27, wherein the LUMO energy level of the second host material is -2.3 eV to -2.6 eV.

29. The organic electroluminescence device according to any one of claims 20 to 27, wherein the HOMO energy level of the second host material is -5.3 eV to -5.7 eV and the LUMO energy level is -2.3 eV to -2.6 eV.

30. The organic electroluminescence device according to any one of claims 20 to 29, wherein the second host material is any one selected from the following compounds PH-1 to PH-85 or a combination of at least two thereof. 【Chemical Formula 7-1】 【Chemical Formula 7-2】 【Chemical Formula 7-3】 【Chemical Formula 7-4】

31. The organic electroluminescence device according to any one of claims 20 to 30, wherein the thickness of the light-emitting layer is 10 to 65 nm.

32. The organic electroluminescence device according to any one of claims 20 to 30, wherein the thickness of the light-emitting layer is 15 to 55 nm.

33. The organic layer further includes any one or a combination of at least two of a hole injection layer, a hole transport layer, an electron barrier layer, an electron transport layer, or an electron injection layer, and the hole injection layer, the hole transport layer, the electron barrier layer, the light-emitting layer, the electron transport layer, and the electron injection layer are sequentially provided in the direction from the anode layer to the cathode layer. The organic electroluminescence device according to any one of claims 20 to 32.

34. The first electrode is an anode layer, the second electrode is a cathode layer, the organic layer contains Compound I and Compound II, and Compound I is the compound described in Claim 1. The organic electroluminescence device according to Claim 18, wherein Compound II has a structure represented by Formula (3). 【Chemical 8】 (where r is an integer from 0 to 6. Said Ar ３ to Ar ５ are independently selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl, The foregoing L ３ to L ５ is each independently any one selected from a single bond, a substituted or unsubstituted C6-C30 arylene, and a substituted or unsubstituted C3-C30 heteroarylene; Said R ５ is independently any one selected from substituted or unsubstituted C1-C20 linear alkyl, substituted or unsubstituted C3-C20 cyclic alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, y is an integer from 1 to 15, Rx is a substituent at any substitutable position, and at least one Rx is selected from substituted or unsubstituted C3-C20 cyclic alkyls. In the formula (I) and the formula (3), Ar １ ~Ar ５ , L １ ~L ５ , R １ , R ２ , R ３ , R ４ , R ５ and Rx, the substituting group is independently one or at least two combinations selected from halogen, C1-C10 linear alkyl, C3-C10 cyclic alkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 condensed ring aryl, C3-C30 monocyclic heteroaryl, C6-C30 condensed ring heteroaryl. )

35. The organic electroluminescence device according to Claim 34, wherein Compound I is any one of the compounds described in Claim 17.

36. The organic electroluminescence device according to Claim 32, wherein Compound II has any one of the structures represented by A1 to A291. 【Chemical Formula 9-1】 【Chemical Formula 9-2】 【Chemical Formula 9-3】 【Chemical Formula 9-4】 【Chemical Formula 9-5】 【Chemical Formula 9-6】 【Chemical Formula 9-7】 【Chemical Formula 9-8】 【Chemical Formula 9-9】 【Chemical Formula 9-10】 【Chemical Formula 9-11】 【Chemical Formula 9-12】 【Chemical Formula 9-13】 【Chemical Formula 9-14】 【Chemical Formula 9-15】 【Chemical Formula 9-16】 【Chemical Formula 9-17】 【Chemical Formula 9-18】 【Chemical Formula 9-19】 【Chemical Formula 9-20】 【Chemical Formula 9-21】 【Chemical Formula 9-22】 【Chemical Formula 9-23】 【Chemical Formula 9-24】 [Chemical Formula 9-25]

37. In the direction from the cathode layer to the anode layer, the organic layer sequentially includes a light-emitting layer and an electron barrier layer. Compound I is contained in the light-emitting layer, and Compound II is contained in the electron barrier layer, or The organic electroluminescence device according to Claim 34, wherein Compound II is contained in the light-emitting layer, and Compound I is contained in the electron barrier layer.

38. The light-emitting layer contains a first host material, a second host material, and a doping material. The first host material is Compound I, and Compound II is contained in the electron barrier layer, or the first host material is Compound II, and Compound I is contained in the electron barrier layer. The organic electroluminescence device according to Claim 37.

39. The organic electroluminescence device according to Claim 38, wherein the mass ratio of the first host material to the second host material is 0.01:1 to 1.5:

1.

40. The organic electroluminescence device according to Claim 38, wherein the mass ratio of the first host material to the second host material is 0.1:1 to 1:

1.

41. The organic electroluminescence device according to Claim 37, wherein the thickness of the light-emitting layer is 10 to 60 nm.

42. The organic electroluminescence device according to claim 37, wherein the thickness of the light-emitting layer is 20 to 50 nm.

43. The organic electroluminescence device according to claim 38, wherein the thickness of the electron barrier layer is 2 to 100 nm.

44. The organic electroluminescence device according to claim 38, wherein the thickness of the electron barrier layer is 3 to 90 nm.

45. The organic layer further includes a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer. In the direction from the anode layer to the cathode layer, the organic layer sequentially includes the hole injection layer, the hole transport layer, the electron barrier layer, the light-emitting layer, the electron transport layer, and the electron injection layer. The organic electroluminescence device according to claim 38.

46. A display device comprising the organic electroluminescence device according to any one of claims 20 to 33 or any one of claims 36 to 45.

Images