A top-emission organic electroluminescent device and applications thereof

Abstract

The top-emitting organic electroluminescent device has good stability and good luminescent performance, specifically has long service life and high luminescent efficiency. This is because the azoxazole compound molecules used in the cover layer of the device have asymmetry, are not easy to crystallize in a thin film state, have good thermal stability and film forming property, and when applied to the organic electroluminescent device, the service life of the device can be improved. In addition, the compound also has a high refractive index, when applied to the cover layer of the organic electroluminescent device, the total reflection phenomenon of the light in the device can be effectively avoided, the light extraction efficiency of the device is improved, and the luminescent efficiency of the device is further improved. In summary, the top-emitting organic electroluminescent device provided by the application has obvious advantages, can realize high luminescent efficiency and long service life, and has good application effect and industrialization prospect.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescence technology, specifically to a top-emitting organic electroluminescent device and its applications. Background Technology

[0002] Organic light-emitting diodes (OLEDs) have become the most promising replacement for liquid crystal displays due to their advantages such as low energy consumption, self-emission, wide viewing angle, low cost, wide temperature range, fast response speed, continuously adjustable emission color, flexible display capability, and relatively simple manufacturing process. The electroluminescence process of an OLED is an energy transfer process that converts electrical energy into light energy. In this process, a voltage is applied across the two ends of the OLED. The electric field generated by this voltage causes electrons to be injected from the cathode into the electron transport layer, while holes are injected from the anode into the hole transport layer. These two types of charge carriers migrate into the light-emitting layer and recombine to form excitons, which then emit light through radiative recombination.

[0003] Organic light-emitting devices (OLEDs) can be classified into two structures based on the direction of light emission: bottom-emitting and top-emitting. Since top-emitting devices emit light from the top, they are unaffected by the bottom driving panel, effectively increasing the aperture ratio and facilitating integration with the bottom driving circuitry. Furthermore, top-emitting devices offer advantages such as improved efficiency, narrower spectral density, and enhanced color purity, making them a promising area for future development.

[0004] The light extraction efficiency of a device is a crucial factor limiting its external quantum efficiency and thus its performance. For top-emitting devices, this efficiency can theoretically reach 100%. However, due to total internal reflection between multiple organic thin films, light is confined within the organic layers and lost, reducing the light extraction efficiency and resulting in lower luminous efficiency, which significantly hinders the development of OLEDs. Therefore, improving the light extraction efficiency of OLEDs has become a hot research topic. Currently, one method to improve light extraction efficiency is to introduce a capping layer into the traditional device structure, which can improve the luminous efficiency of organic electroluminescent devices to some extent. Therefore, in-depth research on organic electroluminescent devices with capping layers to further improve their performance is of great significance. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, the present invention aims to provide a top-emitting organic electroluminescent device, comprising a substrate, an anode, an organic functional layer, a cathode, and a capping layer, wherein the capping layer comprises an organic compound based on a aziroxazole structure, the structure of which is shown in general formula 1.

[0006]

[0007] X is selected from O, S, or NR. a The R a It is selected from any one of substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0008] The Y is independently selected from N or CR. b And at least one Y is selected from N; the R b Selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or any adjacent R b The links form substituted or unsubstituted rings;

[0009] The R is independently selected from any one of the following: linking bond, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl.

[0010] The Ar is independently selected from any one of the following C6-C30 aryl groups, substituted or unsubstituted pyridyl groups, substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted pyridazinyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, substituted or unsubstituted quinazolinyl groups, substituted or unsubstituted quinoxalinyl groups, substituted or unsubstituted o-phenanthrolineyl groups, substituted or unsubstituted benzoxazolyl groups, substituted or unsubstituted benzothiazolyl groups, substituted or unsubstituted benzimidazolyl groups, substituted or unsubstituted dibenzofuranyl groups, substituted or unsubstituted dibenzothiophenyl groups, substituted or unsubstituted carbazoleyl groups, substituted or unsubstituted benzodibenzofuranyl groups, substituted or unsubstituted benzodibenzothiophenyl groups, and substituted or unsubstituted benzocarbazoleyl groups;

[0011] The Z independent selection is from CR d Or N, and at least one Z is selected from N; the R d It is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornel, and substituted or unsubstituted phenyl.

[0012] The L is independently selected from any one of single-bonded, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C3-C30 heteroaryl groups;

[0013] The m is selected from 1, 2, or 3; the n is selected from 0, 1, or 2;

[0014] The substituent group in "substituted or unsubstituted" is selected from one or more of the following groups: deuterium, halogen atom, cyano, trifluoromethyl, amino, nitro, C1-C25 alkyl, C3-C25 cycloalkyl, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidinyl, and pyrimidinyl; the phenyl, biphenyl, terphenyl, naphthyl, pyridyl, and pyrimidinyl may be further substituted by deuterium, halogen atom, trifluoromethyl, cyano, C1-C12 alkyl, and C3-C12 cycloalkyl; in the case of substitution by multiple substituents, the multiple substituents may be the same or different from each other, or adjacent substituents may bond to form any one of substituted or unsubstituted benzene ring, substituted or unsubstituted naphthyl ring, substituted or unsubstituted five-membered ring, and substituted or unsubstituted six-membered ring.

[0015] Beneficial effects:

[0016] The top-emitting organic light-emitting device of the present invention exhibits good stability and excellent light-emitting performance, specifically a long lifespan and high luminous efficiency. This is because the aziroxazole compound used in the capping layer of the device has asymmetric molecules, is not easily crystallized in the thin film state, and possesses good thermal stability and film-forming properties. Its application in organic light-emitting devices enables a long device lifespan. Furthermore, this compound also has a high refractive index; when applied to the capping layer of organic light-emitting devices, it effectively avoids total internal reflection of light within the device, improving the light extraction efficiency and thus enhancing the luminous efficiency. Detailed Implementation

[0017] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. After reading the present invention, any modifications of the present invention in various equivalent forms by those skilled in the art will fall within the scope of protection claimed in this application.

[0018] In the compounds of the present invention, any atom not specified as a particular isotope is included as any stable isotope of that atom, and includes atoms at both their natural and non-natural isotopic abundances.

[0019] In this invention, when the position of the substituent on the ring is not fixed, it means that it can be attached to any of the corresponding optional sites on the ring. For example, Can represent And so on.

[0020] The halogens mentioned in this invention refer to fluorine, chlorine, bromine, and iodine.

[0021] The "*" on the substituent group in this invention indicates a linking site.

[0022] The alkyl group described in this invention refers to a monovalent group formed by removing one hydrogen atom from an alkane molecule. The alkyl group preferably has C1 to C25 carbon atoms, more preferably C1 to C18, further preferably C1 to C12, and particularly preferably C1 to C6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, isohexyl, 3-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 3,3-dimethylpentane, 2,3-dimethylpentane, etc.

[0023] The cycloalkyl group described in this invention refers to a monovalent group formed by removing one hydrogen atom from a cycloalkane molecule. The cycloalkyl group preferably has 3 to 25 carbon atoms, more preferably 3 to 18, further preferably 3 to 12, and particularly preferably 3 to 6. Specific examples of the cycloalkyl group include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, camphenyl, norbornyl, etc.

[0024] The aryl group described in this invention refers to a monovalent group formed by removing one hydrogen atom from the aromatic carbon atom of an aromatic hydrocarbon molecule. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 25, further preferably 6 to 18, and most preferably 6 to 12. Specific examples of the aryl group include, but are not limited to, phenyl, biphenyl, terphenyl, tetraphenyl, naphthyl, phenanthryl, anthracene, triphenylene, pyrene, peryl, fluoranyl, and fluorene.

[0025] The heteroaryl group described in this invention refers to a monovalent group in which at least one aromatic carbon atom is replaced by a heteroatom. The heteroatom includes, but is not limited to, O, S, N, Si, B, P, etc. The number of carbon atoms in the heteroaryl group is preferably C3 to C30, more preferably C3 to C25, particularly preferably C3 to C18, and most preferably C3 to C12. Specific examples of the heteroaryl group include, but are not limited to, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, carbazoyl, benzocarbazoyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxazolyl, quinazolinyl, benzoxazolyl, benzothiazoyl, benzimidazolyl, N-heterobenzoxazolyl, N-heterobenzothiazoyl, N-heterobenzimidazolyl, etc.

[0026] The arylene group described in this invention refers to a divalent group formed by removing two hydrogen atoms from the aromatic carbon atom in an aromatic hydrocarbon molecule. The arylene group preferably has C6 to C30 carbon atoms, more preferably C6 to C25, further preferably C6 to C18, and most preferably C6 to C12. Specific examples of the arylene group include, but are not limited to, phenylene, biphenylene, terphenylene, tetraphenylene, naphthylene, phenanthrene, anthracene, triphenylene, pyrene, and perylene.

[0027] The heteroarylene group refers to a divalent group in which at least one carbon atom of the arylene group is replaced by a heteroatom. The heteroatom includes, but is not limited to, O, S, N, Si, B, P, etc. The number of carbon atoms in the heteroarylene group is preferably C3–C30, more preferably C3–C25, further preferably C3–C18, and most preferably C3–C12. Specific examples of the heteroarylene group include, but are not limited to, pyridinyl, pyrimidinyl, triazineyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinoxalinyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophene, and benzodibenzothiophene.

[0028] In this invention, "substituted..." refers to the group being monosubstituted or polysubstituted by a substituent group independently selected from, but not limited to, deuterium, halogen, cyano, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amino, etc. Preferably, the substituent group is deuterium, halogen, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, etc. The following groups can be monosubstituted or polysubstituted: camphenic, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, benzo[a]phenanthrene, perylene, pyrene, benzyl, tolyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, diphenylamino, dimethylamino, carbazole, 9-phenylcarbazole, acridine, furanyl, thiophene, benzofuranyl, benzothiophene, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothiophene, phenothiazinyl, phenothiazinyl, indole, etc. Furthermore, the above substituents can also be monosubstituted or polysubstituted by deuterium, halogen, cyano, alkyl, cycloalkyl, aryl, etc.

[0029] The cyclic structure formed by bonding as described in this invention refers to two groups being linked together by chemical bonds and optionally aromatized. Examples are shown below:

[0030]

[0031] In this invention, the ring formed by the connection can be a five-membered ring, a six-membered ring, or a fused ring, such as benzene, naphthalene, fluorene, cyclopentene, cyclohexene, cyclopentane, cyclohexane, cyclohexane, benzobenzene, quinoline, isoquinoline, dibenzothiophene, phenanthrene, or pyrene, but is not limited thereto.

[0032] This invention provides a top-emitting organic electroluminescent device, comprising a substrate, an anode, an organic functional layer, a cathode, and a capping layer. The capping layer contains an organic compound based on a aziroxazole structure, the structure of which is shown in general formula 1.

[0033]

[0034] X is selected from O, S, or NR. a The R a It is selected from any one of substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0035] The Y is independently selected from N or CR. b And at least one Y is selected from N; the R b Selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or any adjacent R b The links form substituted or unsubstituted rings;

[0036] The R is independently selected from any one of the following: linking bond, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl.

[0037] The Ar is independently selected from any one of the following C6-C30 aryl groups, substituted or unsubstituted pyridyl groups, substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted pyridazinyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, substituted or unsubstituted quinazolinyl groups, substituted or unsubstituted quinoxalinyl groups, substituted or unsubstituted o-phenanthrolineyl groups, substituted or unsubstituted benzoxazolyl groups, substituted or unsubstituted benzothiazolyl groups, substituted or unsubstituted benzimidazolyl groups, substituted or unsubstituted dibenzofuranyl groups, substituted or unsubstituted dibenzothiophenyl groups, substituted or unsubstituted carbazoleyl groups, substituted or unsubstituted benzodibenzofuranyl groups, substituted or unsubstituted benzodibenzothiophenyl groups, and substituted or unsubstituted benzocarbazoleyl groups;

[0038] The Z independent selection is from CR d Or N, and at least one Z is selected from N; the R d It is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornel, and substituted or unsubstituted phenyl.

[0039] The L is independently selected from any one of single-bonded, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C3-C30 heteroaryl groups;

[0040] The m is selected from 1, 2, or 3; the n is selected from 0, 1, or 2;

[0041] The substituent group in "substituted or unsubstituted" is selected from one or more of the following groups: deuterium, halogen atom, cyano, trifluoromethyl, amino, nitro, C1-C25 alkyl, C3-C25 cycloalkyl, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidinyl, and pyrimidinyl; the phenyl, biphenyl, terphenyl, naphthyl, pyridyl, and pyrimidinyl may be further substituted by deuterium, halogen atom, trifluoromethyl, cyano, C1-C12 alkyl, and C3-C12 cycloalkyl; in the case of substitution by multiple substituents, the multiple substituents may be the same or different from each other, or adjacent substituents may bond to form any one of substituted or unsubstituted benzene ring, substituted or unsubstituted naphthyl ring, substituted or unsubstituted five-membered ring, and substituted or unsubstituted six-membered ring.

[0042] Preferably, m+n≥3.

[0043] More preferably, m+n=3.

[0044] Preferably, the general formula 1 is selected from any one of the structures 1 to 3 shown below.

[0045]

[0046] Preferably, the Selected from any one of the following groups,

[0047]

[0048] More preferably, the Selected from any one of the following groups,

[0049]

[0050]

[0051] Preferably, the Selected from any one of the following groups,

[0052]

[0053] The R b The group is independently selected from hydrogen, deuterium, halogen, cyano, or substituted or unsubstituted groups of the following: methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclohexyl, adamantyl, norbornel, camphenyl, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl; the substituent may be selected from deuterium, cyano, trifluoromethyl, halogen, isopropyl, tert-butyl, phenyl, naphthyl, and when substituted by multiple substituents, the substituents may be the same or different from each other; or any adjacent R b They can be linked together to form any one of a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring.

[0054] Preferably, the Ar group is independently selected from any one of the following groups:

[0055]

[0056]

[0057]

[0058] The above-mentioned groups may be substituted or unsubstituted by one or more substituents selected from deuterium, cyano, halogen, substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclohexyl, adamantyl, norbornel, camphenyl, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidinyl, triazine, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl; the substituents in "substituted or unsubstituted" may be selected from one or more of deuterium, cyano, trifluoromethyl, halogen, isopropyl, tert-butyl, phenyl, naphthyl, and in the case of being substituted by multiple substituents, the multiple substituents may be the same as or different from each other.

[0059] Preferably, L is independently selected from any of the following groups, whether single-bonded, substituted, or unsubstituted: phenylene, biphenylene, naphthylene, anthraceneylene, phenanthrene, triphenylene, pyridylene, pyrimidinylene, quinolinylene, isoquinolinylene, quinoxalinylene, quinoxalinylene, or combinations thereof. When substituted by multiple substituents, the multiple substituents may be the same or different from each other, or any adjacent substituents may be connected to form any of the following: a substituted or unsubstituted five-membered ring or a substituted or unsubstituted six-membered ring.

[0060] Preferably, the L is independently selected from single bonds or groups shown below, or combinations thereof.

[0061]

[0062] Most preferably, the general formula 1 is selected from any of the following structures.

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] The organic layer of the organic electroluminescent device of the present invention may include one or more of the functional layers described below: hole injection layer, hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, electron transport layer, and electron injection layer, but is not limited thereto. Any functional layer having hole injection and / or transport properties or having electron injection and / or transport properties should be included. Each functional layer may be composed of a single thin film or multiple thin films, and each thin film may contain one material or multiple materials.

[0086] Preferably, the organic light-emitting functional layer further includes a combination of at least two of the following: a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0087] This invention does not particularly limit the materials of the thin films in the organic electroluminescent device; substances known in the art can be used. The following describes the materials of each organic functional layer and the electrode materials on both sides of the device:

[0088] The substrate serves as the connection point between the organic electroluminescent device and the external circuit. It is preferably made of a material with good stability. Commonly used substrate materials include glass, resin, silicon, and metal foil, but are not limited to these.

[0089] The anode material has a high work function and can be selected from one or more of the following materials: metal oxides, metals, metal alloys, polymers, etc. Specific examples include, but are not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), zinc aluminum oxide (AZO), indium oxide, zinc oxide, Ag, Au, Al, Cu, Ni, Mo, Ti, Zn, Pd, Pt, polypyrrole, etc.

[0090] Hole injection materials possess excellent hole-accepting capabilities and can be selected from one or more of the following materials: metal oxides such as molybdenum oxide, silver oxide, vanadium oxide, tungsten oxide, ruthenium oxide, nickel oxide, copper oxide, titanium oxide, and aluminum oxide; low-molecular-weight organic compounds such as phthalocyanine compounds, aromatic amine derivatives, and conjugated organic materials containing polycyanides; and polymers. Specific examples include, but are not limited to, molybdenum trioxide, vanadium pentoxide, nickel oxide, copper oxide, titanium dioxide, aluminum oxide, copper phthalocyanine (II) (CuPc), titanium phthalocyanine (TiOPC), 4,4'4"-tris(N,N-diphenylamino)triphenylamine (NATA), N4,N4,N4',N4'-tetra(4-methoxyphenyl)-[1,1'-biphenyl]-4,4'-diamine (MeO-TPD), and N,N'-di[4-di( [m-Tolyl)aminophenyl]-N,N'-diphenylbenzidine (abbreviated as DNTPD), 7,7,8,8-tetracyano-p-benzodiquinone dimethyl methyl ether (abbreviated as TCNQ), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (abbreviated as F4-TCNQ), pyrazolo[2,3-F][1,10]phenanthroline-2,3-dionitrile (abbreviated as PPDN), 1,4,5,8,9,11-hexaazabenzonitrile (abbreviated as HAT-CN), etc.

[0091] Hole transport materials are preferably materials with excellent hole transport performance and HOMO energy levels that match the corresponding anode materials. One or more of the following materials can be selected: aromatic amine derivatives, pyrazoline compounds, carbazole derivatives, hydrazone compounds, styrene compounds, butadiene compounds, polymers, etc. Specific examples include, but are not limited to, 4,4',4”-tris(N,N-diphenylamino)triphenylamine (abbreviated as TDATA), 4,4',4”-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviated as MTDATA), N,N'-diphenyl-N,N'-diphenanthrene-9-yl-4,4'-biphenyldiamine (abbreviated as PPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (abbreviated as NPB), 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (abbreviated as TAPC), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (abbreviated as TPD), and 4,4',4”-tris(carbazole-9-yl)triphenylamine (abbreviated as TCTA), etc.

[0092] Luminescent materials can be divided into host materials and guest materials. The host material can be one or more of the following materials: aluminum complexes, zinc complexes and other metal complexes, fluorene derivatives, anthracene derivatives, carbazole derivatives, etc. Specific examples include, but are not limited to, tris(8-hydroxyquinoline)aluminum(III) (abbreviated as Alq3), zinc 8-hydroxyquinoline (abbreviated as Znq2), 2,7-bis[9,9-bis(4-methylphenyl)fluorene-2-yl]-9,9-bis(4-methylphenyl)fluorene (abbreviated as TDAF), 9,10-bis(2-naphthyl)anthracene (abbreviated as ADN), 9-(1-naphthyl)-10-[4-(2-naphthyl)phenyl]anthracene, 1,3,5-tris(9-carbazole)benzene (abbreviated as TCP), 9,9'-(1,3-phenyl)bis-9H-carbazole (abbreviated as MCP), 4,4'-bis(9-carbazole)biphenyl (abbreviated as CBP), and 4,4',4”-tris(carbazole-9-yl)triphenylamine (abbreviated as TCTA), etc.

[0093] The guest material can be selected from one or more of the following materials: pyrene derivatives, anthracene derivatives, fluorene derivatives, perylene derivatives, styrene-based amine derivatives, coumarin dyes, quinacrine copper derivatives, polycyclic aromatic hydrocarbons, diamine anthracene derivatives, carbazole derivatives, metal complexes, etc. Specific examples include, but are not limited to, 9,10-di-(2-naphthyl)anthracene (ADN), 2-methyl-9,10-di-2-naphthylanthracene (MADN), 2,5,8,11-tetra-tert-butylperylene (TBPe), 4,4'-bis[4-(diphenylamino)styrene]biphenyl (BDAVBi), 4,4'-bis[4-(di-p-tolylamino)styrene]biphenyl (DPAVBi), bis(4,6-difluorophenylpyridine-C2,N)pyridinecarboxyiridium (FIrpic), bis(2,4-difluorophenylpyridine)-tetra(1-pyrazolyl)iridium borate (III) (abbreviated as Fir6), coumarin 6 (abbreviated as C-6), N,N'-dimethylquinacridone (abbreviated as DMQA), tris(8-hydroxyquinoline)aluminum(III) (abbreviated as Alq3), tris(2-phenylpyridine)iridium (abbreviated as Ir(ppy)3), di(2-phenylpyridine)iridium acetylacetonate (abbreviated as Ir(ppy)2(acac)), 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (abbreviated as DCM), di(1-phenylisoquinoline)(acetylacetonone)iridium(III) (abbreviated as Ir(piq)2(acac)), etc.

[0094] Electron transport materials are preferably those with strong electron-withdrawing ability and low HOMO and LUMO energy levels. They can be selected from one or more of the following materials: aluminum complexes, beryllium complexes, zinc complexes, oxazole derivatives, imidazole derivatives, triazole derivatives, phenanthroline derivatives, pyridine derivatives, polymers, etc. Specific examples include, but are not limited to, tris(8-hydroxyquinoline)aluminum(III) (Alq3), bis(10-hydroxybenzo[h]quinoline)beryllium (Bepq2), bis(2-methyl-8-hydroxyquinoline)(4-phenylphenol)aluminum(III) (BAlq), bis(8-hydroxyquinoline)zinc(II) (Znq), 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), and 1,3,5-tris(N-phenyl-2-phenylene) Imidazole benzene (TPBi), 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 2,9-di(naphthyl-2-yl)-4,7-diphenyl-1,10-phenanthroline (NBphen), 3,3'-[5'-[3-(3-pyridyl)phenyl] (TmPyPB), 1,3,5-tris(4-pyridin-3-ylphenyl)benzene (TpPyPB), etc.

[0095] The electron injection material is preferably a material with a small potential barrier to the adjacent organic transport material or host material. One or more of the following materials can be selected: alkali metals, alkaline earth metals, or compounds containing alkali metals or alkaline earth metals, including but not limited to magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, magnesium fluoride, calcium fluoride, lithium oxide, cesium carbonate, lithium metaborate, potassium silicate, lithium acetate, sodium acetate, rubidium acetate, potassium acetate, cesium acetate, lithium tetra(8-hydroxyquinoline)boron, lithium 8-hydroxyquinoline, etc.

[0096] The cathode material is preferably a low work function material that promotes electron injection into the organic layer. It can be one or more of the following materials: main group metals, alkali metals, alkaline earth metals, transition metals, lanthanides, and other metals or alloys. Specific examples include, but are not limited to, Al, In, Li, Mg, Ca, Ag, Ti, Sm, Mg / Ag, Li / Al, LiO2 / Al, LiF / Ca, LiF / Al, BaF2 / Ca, etc.

[0097] The coating material can be selected from one or more of the following materials: metal compounds, aromatic amine derivatives, carbazole derivatives, or the aromatic amine derivatives described in this invention. Specific examples include, but are not limited to, tris(8-hydroxyquinoline)aluminum(III) (abbreviated as Alq3), magnesium oxide, zinc selenide, zinc sulfide, tin oxide, molybdenum oxide, N,N'-di(naphthyl-1-yl)-N,N'-di(phenyl)-2,2'-dimethylbenzidine (abbreviated as α-NPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (abbreviated as NPB), 4,4'-di(9-carbazole)biphenyl (abbreviated as CBP), etc. Preferably, it is an organic compound based on an oxazole structure as described in Formula 1 of this invention.

[0098] There are no particular limitations on the preparation method of each thin film in the organic electroluminescent device of the present invention. Vacuum evaporation, sputtering, spin coating, spraying, screen printing, laser transfer, etc. can be used, but are not limited to these methods.

[0099] The organic electroluminescent device of this invention is mainly used in the field of information display technology. It is widely used in various information displays, such as tablet computers, flat-screen TVs, mobile phones, smartwatches, digital cameras, VR, in-vehicle systems, wearable devices, etc.

[0100] Preferably, a display device includes the top-emitting organic electroluminescent device described in this invention.

[0101] Synthesis Examples

[0102] There are no particular limitations on the preparation method of the azaoxazole structures of general formula 1 of this invention, and conventional methods well known to those skilled in the art can be used. For example, carbon-carbon coupling reaction, carbon-nitrogen coupling reaction, etc. The following are synthetic routes for compounds of general formula 1 of this invention when m=3 and n=0, but this invention is not limited to this route, and other compounds can also be prepared by referring to this method.

[0103] (1) When three When they are the same,

[0104]

[0105] (2) When two When they are the same,

[0106]

[0107] (3) When three When they are all different,

[0108]

[0109] Each X1 may be the same or different, and is selected from Cl, Br, and I;

[0110] Raw materials and reagents: This invention does not impose any particular limitations on the raw materials or reagents used in the following synthesis examples. They can be commercially available products or prepared using methods well-known to those skilled in the art. All raw materials and reagents used in this invention are of reagent purity.

[0111] Instruments: G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer (Waters Corporation, UK); Vario ELcube organic elemental analyzer (Elementar Corporation, Germany); Bruker-510 nuclear magnetic resonance spectrometer (Bruker Corporation, Germany).

[0112] Synthesis Example 1: Preparation of Compound 7

[0113]

[0114] Preparation of intermediate A-7:

[0115] Under nitrogen protection, a-7 (22.51 g, 110.00 mmol), pinacol diborate (27.93 g, 110.00 mmol), potassium carbonate (30.41 g, 220.00 mmol), and 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.80 g, 1.10 mmol) were added to N,N-dimethylformamide (600 mL). The mixture of the above reactants was heated under reflux for 3 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. After standing and separation, the organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The obtained solid was recrystallized from ethyl acetate to give intermediate A-7 (26.71 g, yield 82%); HPLC purity ≥99.78%. Mass spectrometry m / z: 296.1345 (theoretical value: 296.1332).

[0116] Preparation of intermediate I-7:

[0117] Under nitrogen protection, intermediates D-7 (11.34 g, 50.00 mmol), A-7 (14.81 g, 50.00 mmol), tetrakis(triphenylphosphine)palladium (0.58 g, 0.50 mmol), potassium carbonate (13.82 g, 100.00 mmol), 180 mL toluene, 60 mL ethanol, and 60 mL water were added sequentially to a reaction flask. The mixture was stirred and the reaction system was heated under reflux for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a filter cake, and washed with ethanol. Finally, the filter cake was recrystallized from toluene:ethanol = 20:3 to obtain intermediate I-7 (12.33 g, yield 78%); HPLC purity ≥99.80%. Mass spectrometry m / z: 314.9952 (theoretical value: 314.9966).

[0118] Preparation of compound 7:

[0119] Under nitrogen protection, I-7 (9.48 g, 30.00 mmol), B-7 (19.81 g, 60.00 mmol), tris(benzylacetone)palladium (0.27 g, 0.30 mmol), tri-tert-butylphosphine (0.20 g, 1.00 mmol), potassium carbonate (8.29 g, 60.00 mmol), 150 mL toluene, 50 mL ethanol, and 50 mL water were added sequentially to a reaction flask. The mixture was stirred and refluxed for 5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a filter cake, washed with ethanol, and finally recrystallized from toluene to give compound 7 (14.27 g, yield 73%), with an HPLC purity ≥99.95%. Mass spectrometry m / z: 651.2324 (theoretical value: 651.2311). Theoretical elemental content (%) C 47 H 29 N3O: C, 86.61; H, 4.49; N, 6.45. Measured elemental content (%): C, 86.65; H, 4.44; N, 6.47.

[0120] Synthesis Example 2: Preparation of Compound 15

[0121]

[0122] According to the preparation method in Synthesis Example 1, a-7 was replaced with an equimolar amount of a-15, A-7 was replaced with an equimolar amount of A-15, and B-7 was replaced with an equimolar amount of B-15 to obtain compound 15 (15.32 g); HPLC purity ≥ 99.98%. Mass spectrometry m / z: 689.3419 (theoretical value: 689.3406). Theoretical elemental content (%) C 49 H 43N3O: C, 85.31; H, 6.28; N, 6.09. Measured elemental content (%): C, 85.36; H, 6.23; N, 6.05.

[0123] Synthesis Example 3: Preparation of Compound 34

[0124]

[0125] Preparation of intermediate A-34:

[0126] Following the preparation method of intermediate A-7 in Synthesis Example 1, a-7 was replaced with an equimolar amount of a-34 to obtain intermediate A-34 (18.78 g), with an HPLC purity ≥99.77%. Mass spectrometry m / z: 323.1425 (theoretical value: 323.1441).

[0127] Preparation of intermediate I-34:

[0128] Under nitrogen protection, D-34 (22.28 g, 70.00 mmol), intermediate B-34 (23.12 g, 70.00 mmol), tetrakis(triphenylphosphine)palladium (0.81 g, 0.70 mmol), sodium carbonate (14.84 g, 140.00 mmol), 240 mL toluene, 80 mL ethanol, and 80 mL water were added sequentially to a reaction flask. The mixture was stirred and refluxed for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a filter cake, and washed with ethanol. Finally, the filter cake was crystallized with toluene:ethanol = 20:3 to obtain intermediate I-34 (21.55 g, yield 78%), with an HPLC purity ≥99.80%. Mass spectrometry m / z: 392.9907 (theoretical value: 392.9920).

[0129] Preparation of intermediate II-34:

[0130] Under nitrogen protection, intermediates I-34 (19.73 g, 50.00 mmol), A-34 (16.16 g, 50.00 mmol), tetrakis(triphenylphosphine)palladium (0.58 g, 0.50 mmol), potassium carbonate (13.82 g, 100.00 mmol), 180 mL toluene, 60 mL ethanol, and 60 mL water were added sequentially to a reaction flask. The mixture was stirred and the reaction system was heated under reflux for 4.5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a filter cake, and washed with ethanol. Finally, the filter cake was recrystallized from toluene:ethanol = 10:1 to obtain intermediate II-34 (19.16 g, yield 75%) with HPLC purity ≥99.84%. Mass spectrometry m / z: 510.1260 (theoretical value: 510.1247).

[0131] Preparation of compound 34:

[0132] Under nitrogen protection, II-34 (15.33 g, 30.00 mmol), C-34 (10.33 g, 30.00 mmol), tris(benzylacetone)palladium (0.27 g, 0.30 mmol), tri-tert-butylphosphine (0.20 g, 1.00 mmol), potassium carbonate (8.29 g, 60.00 mmol), 120 mL toluene, 40 mL ethanol, and 40 mL water were added sequentially to a reaction flask. The mixture was stirred and refluxed for 5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a filter cake, washed with ethanol, and finally recrystallized from toluene to give compound 34 (14.76 g, yield 71%), with an HPLC purity ≥99.92%. Mass spectrometry m / z: 692.2226 (theoretical value: 692.2212). Theoretical elemental content (%) C 48 H 28 N4O2: C, 83.22; H, 4.07; N, 8.09. Measured elemental content (%): C, 83.26; H, 4.03; N, 8.05.

[0133] Synthesis Example 4: Preparation of Compound 58

[0134]

[0135] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-58, D-7 with an equimolar amount of D-58, A-7 with an equimolar amount of B-58, and B-7 with an equimolar amount of A-58, yielding compound 58 (13.94 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 627.2524 (theoretical value: 627.2510). Theoretical elemental content (%) C 41 H 17 D8N5O2: C, 78.45; H, 5.30; N, 11.16. Measured elemental content (%): C, 78.42; H, 5.35; N, 11.11.

[0136] Synthesis Example 5: Preparation of Compound 59

[0137]

[0138] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-59, A-7 was replaced with an equimolar amount of B-59, and B-7 was replaced with an equimolar amount of A-59 to obtain compound 59 (14.84 g); HPLC purity ≥ 99.94%. Mass spectrometry m / z: 677.2776 (theoretical value: 677.2791). Theoretical elemental content (%) C 45 H 35N5O2: C, 79.74; H, 5.21; N, 10.33. Measured elemental content (%): C, 79.70; H, 5.26; N, 10.36.

[0139] Synthesis Example 6: Preparation of Compound 60

[0140]

[0141] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-60, D-7 with an equimolar amount of D-60, A-7 with an equimolar amount of B-60, and B-7 with an equimolar amount of A-60, yielding compound 60 (14.55 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 673.2178 (theoretical value: 673.2195). Theoretical elemental content (%) C 43 H 23 D2N7O2: C, 76.66; H, 4.04; N, 14.55. Measured elemental content (%): C, 76.62; H, 4.09; N, 14.50.

[0142] Synthesis Example 7: Preparation of Compound 70

[0143]

[0144] Preparation of intermediate a-70:

[0145] Under nitrogen protection, M-70 (34.78 g, 130.00 mmol), N-70 (31.99 g, 130.00 mmol), tetrakis(triphenylphosphine)palladium (1.50 g, 1.30 mmol), potassium acetate (25.52 g, 260.00 mmol), 450 mL toluene, 150 mL ethanol, and 150 mL water were added sequentially to a reaction flask. The mixture was stirred and refluxed for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a filter cake, and washed with ethanol. Finally, the filter cake was recrystallized from toluene:ethanol = 5:1 to obtain intermediate a-70 (33.90 g, yield 85%); HPLC purity ≥99.78%. Mass spectrometry m / z: 306.0573 (theoretical value: 306.0560).

[0146] The remaining steps followed the preparation method of Synthesis Example 1, except that a-7 was replaced with an equimolar amount of a-70, D-7 with an equimolar amount of D-58, A-7 with an equimolar amount of B-70, and B-7 with an equimolar amount of A-70, yielding compound 70 (17.81 g); HPLC purity ≥ 99.93%. Mass spectrometry m / z: 835.2571 (theoretical value: 835.2583). Theoretical elemental content (%) C 57 H33 N5O3: C, 81.90; H, 3.98; N, 8.38. Measured elemental content (%): C, 81.95; H, 3.95; N, 8.34.

[0147] Synthesis Example 8: Preparation of Compound 95

[0148]

[0149] Preparation of intermediate A-95:

[0150] According to the preparation method in Synthesis Example 1, a-7 was replaced with an equimolar amount of a-95 to obtain intermediate A-95 (29.06 g); HPLC purity ≥99.88%. Mass spectrometry m / z: 322.1727 (theoretical value: 322.1710).

[0151] Preparation of compound 95:

[0152] Under nitrogen protection, D-95 (9.47 g, 30.00 mmol), intermediate A-95 (29.00 g, 90.00 mmol), tris(benzylacetone)palladium (0.27 g, 0.30 mmol), tri-tert-butylphosphine (0.20 g, 1.00 mmol), potassium carbonate (8.29 g, 60.00 mmol), 200 mL toluene, 75 mL ethanol, and 75 mL water were added sequentially to a reaction flask. The mixture was stirred and refluxed for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a filter cake, washed with ethanol, and finally recrystallized from toluene to obtain compound 95 (14.49 g, yield 73%). HPLC purity ≥99.95%. Mass spectrometry m / z: 661.1843 (theoretical value: 661.1862). Theoretical elemental content (%) C 41 H 23 N7O3: C, 74.42; H, 3.50; N, 14.82. Measured elemental content (%): C, 74.47; H, 3.53; N, 14.80.

[0153] Synthesis Example 9: Preparation of Compound 100

[0154]

[0155] According to the preparation method in Synthesis Example 8, a-95 was replaced with an equimolar amount of a-100, and A-95 was replaced with an equimolar amount of A-100 to obtain compound 100 (17.54 g); HPLC purity ≥ 99.93%. Mass spectrometry m / z: 811.2345 (theoretical value: 811.2332). Theoretical elemental content (%) C 53 H 29N7O3: C, 78.41; H, 3.60; N, 12.08. Measured elemental content (%): C, 78.45; H, 3.65; N, 12.04.

[0156] Synthesis Example 10: Preparation of Compound 123

[0157]

[0158] According to the preparation method in Synthesis Example 3, a-34 was replaced with an equimolar amount of a-123, B-34 with an equimolar amount of B-123, A-34 with an equimolar amount of C-123, and C-34 with an equimolar amount of A-123, yielding compound 123 (15.63 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 733.2540 (theoretical value: 733.2552). Theoretical elemental content (%) C 52 H 35 N3S: C, 85.10; H, 4.81; N, 5.73. Measured elemental content (%): C, 85.15; H, 4.85; N, 5.70.

[0159] Synthetic Example 11: Preparation of Compound 173

[0160]

[0161] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-173, A-7 was replaced with an equimolar amount of B-173, and B-7 was replaced with an equimolar amount of A-173 to obtain compound 173 (15.94 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 727.1878 (theoretical value: 727.1864). Theoretical elemental content (%) C 47 H 29 N5S2: C, 77.50; H, 4.06; N, 9.65. Measured elemental content (%): C, 77.55; H, 4.02; N, 9.62.

[0162] Synthesis Example 12: Preparation of Compound 241

[0163]

[0164] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-241, A-7 was replaced with an equimolar amount of A-241, and B-7 was replaced with an equimolar amount of A-59 to obtain compound 241 (15.71 g); HPLC purity ≥ 99.92%. Mass spectrometry m / z: 737.2273 (theoretical value: 737.2288). Theoretical elemental content (%) C 46 H 27N9O2: C, 74.89; H, 3.69; N, 17.09. Measured elemental content (%): C, 74.84; H, 3.65; N, 17.14.

[0165] Synthetic Example 13: Preparation of Compound 255

[0166]

[0167] According to the preparation method in Synthesis Example 3, a-34 was replaced with an equimolar amount of a-255, D-34 with an equimolar amount of D-255, B-34 with an equimolar amount of B-255, A-34 with an equimolar amount of C-255, and C-34 with an equimolar amount of A-255, yielding compound 255 (13.84 g); HPLC purity ≥ 99.91%. Mass spectrometry m / z: 640.3028 (theoretical value: 640.3016). Theoretical elemental content (%) C 44 H 16 D 12 N4O: C, 82.47; H, 6.29; N, 8.74. Measured elemental content (%): C, 82.44; H, 6.24; N, 8.79.

[0168] Synthesis Example 14: Preparation of Compound 258

[0169]

[0170] According to the preparation method in Synthesis Example 3, a-34 was replaced with an equimolar amount of a-258, D-34 with an equimolar amount of D-258, B-34 with an equimolar amount of B-258, A-34 with an equimolar amount of C-258, and C-34 with an equimolar amount of A-258, yielding compound 258 (16.10 g); HPLC purity ≥99.94%. Mass spectrometry m / z: 755.2671 (theoretical value: 755.2685). Theoretical elemental content (%) C 53 H 33 N5O: C, 84.22; H, 4.40; N, 9.27. Measured elemental content (%): C, 84.26; H, 4.45; N, 9.22.

[0171] Synthesis Example 15: Compound 261

[0172]

[0173] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-261, D-7 with an equimolar amount of D-261, A-7 with an equimolar amount of A-261, and B-7 with an equimolar amount of B-261, yielding compound 261 (13.29 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 606.1678 (theoretical value: 606.1692). Theoretical elemental content (%) C 40 H 22 N4O3: C, 79.20; H, 3.66; N, 9.24. Measured elemental content (%): C, 79.25; H, 3.61; N, 9.28.

[0174] Synthesis Example 16: Preparation of Compound 268

[0175]

[0176] Preparation of intermediate a-268:

[0177] According to the preparation method of intermediate a-70 in Synthesis Example 7, M-70 was replaced with an equimolar amount of M-268 and N-70 was replaced with an equimolar amount of N-268 to obtain intermediate a-268 (34.29 g); HPLC purity ≥99.77%. Mass spectrometry m / z: 306.0576 (theoretical value: 306.0560).

[0178] The remaining steps followed the preparation method of Synthesis Example 1, except that a-7 was replaced with an equimolar amount of a-268, D-7 with an equimolar amount of D-268, A-7 with an equimolar amount of A-268, and B-7 with an equimolar amount of B-268, yielding compound 268 (15.18 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 702.2438 (theoretical value: 702.2420). Theoretical elemental content (%) C 50 H 30 N4O: C, 85.45; H, 4.30; N, 7.97. Measured elemental content (%): C, 85.49; H, 4.35; N, 7.92.

[0179] Synthesis Example 17: Preparation of Compound 278

[0180]

[0181] According to the preparation method in Synthesis Example 1, a-7 was replaced with an equimolar amount of a-278, D-7 with an equimolar amount of D-261, A-7 with an equimolar amount of A-278, and B-7 with an equimolar amount of B-278, yielding compound 278 (13.26 g); HPLC purity ≥ 99.92%. Mass spectrometry m / z: 605.1978 (theoretical value: 605.1964). Theoretical elemental content (%) C 39 H 23 N7O: C, 77.34; H, 3.83; N, 16.19. Measured elemental content (%): C, 77.30; H, 3.88; N, 16.15.

[0182] Synthesis Example 18: Preparation of Compound 293

[0183]

[0184] According to the preparation method in Synthesis Example 1, a-7 was replaced with an equimolar amount of a-293, D-7 with an equimolar amount of D-268, A-7 with an equimolar amount of B-34, and B-7 with an equimolar amount of A-293, yielding compound 293 (14.69 g); HPLC purity ≥ 99.93%. Mass spectrometry m / z: 670.2104 (theoretical value: 670.2117). Theoretical elemental content (%) C 44 H 26 N6O2: C, 78.79; H, 3.91; N, 12.53. Measured elemental content (%): C, 78.74; H, 3.95; N, 12.58.

[0185] Synthesis Example 19: Preparation of Compound 300

[0186]

[0187] According to the preparation method in Synthesis Example 1, a-7 was replaced with an equimolar amount of a-59, D-7 with an equimolar amount of D-268, A-7 with an equimolar amount of B-300, and B-7 with an equimolar amount of A-59, yielding compound 300 (15.14 g); HPLC purity ≥ 99.95%. Mass spectrometry m / z: 700.1696 (theoretical value: 700.1681). Theoretical elemental content (%) C 44 H 24 N6O2S: C, 75.41; H, 3.45; N, 11.99. Measured elemental content (%): C, 75.46; H, 3.48; N, 11.94.

[0188] Synthesis Example 20: Preparation of Compound 327

[0189]

[0190] According to the preparation method in Synthesis Example 8, a-95 was replaced with an equimolar amount of a-327, D-95 was replaced with an equimolar amount of D-327, and A-95 was replaced with an equimolar amount of A-327 to obtain compound 327 (13.98 g); HPLC purity ≥99.98%. Mass spectrometry m / z: 665.1661 (theoretical value: 665.1672). Theoretical elemental content (%) C 37 H 19 N 11 O3: C, 66.76; H, 2.88; N, 23.15. Measured element content (%): C, 66.71; H, 2.85; N, 23.19.

[0191] Synthesis Example 21: Preparation of Compound 399

[0192]

[0193] According to the preparation method in Synthesis Example 8, a-95 was replaced with an equimolar amount of a-399, D-95 was replaced with an equimolar amount of D-327, and A-95 was replaced with an equimolar amount of A-399 to obtain compound 399 (15.14 g); HPLC purity ≥99.96%. Mass spectrometry m / z: 710.1114 (theoretical value: 710.1130). Theoretical elemental content (%) C 40 H 22 N8S3: C, 67.59; H, 3.12; N, 15.76. Measured elemental content (%): C, 67.54; H, 3.15; N, 15.71.

[0194] Synthesis Example 22: Preparation of Compound 469

[0195]

[0196] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-95, D-7 with an equimolar amount of D-469, A-7 with an equimolar amount of A-95, and B-7 with an equimolar amount of B-34, yielding compound 469 (15.09 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 679.2388 (theoretical value: 679.2372). Theoretical elemental content (%) C 47 H 29 N5O: C, 83.04; H, 4.30; N, 10.30. Measured elemental content (%): C, 83.00; H, 4.33; N, 10.35.

[0197] Synthesis Example 23: Preparation of Compound 472

[0198]

[0199] According to the preparation method in Synthesis Example 1, a-7 was replaced with an equimolar amount of a-293, D-7 with an equimolar amount of D-469, A-7 with an equimolar amount of A-293, and B-7 with an equimolar amount of B-472, yielding compound 472 (15.29 g); HPLC purity ≥ 99.94%. Mass spectrometry m / z: 707.1945 (theoretical value: 707.1957). Theoretical elemental content (%) C 47 H 25 N5O3: C, 79.76; H, 3.56; N, 9.90. Measured elemental content (%): C, 79.71; H, 3.52; N, 9.95.

[0200] Synthesis Example 24: Preparation of Compound 476

[0201]

[0202] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-476, D-7 with an equimolar amount of D-469, A-7 with an equimolar amount of A-476, and B-7 with an equimolar amount of B-476, yielding compound 476 (13.98 g); HPLC purity ≥ 99.91%. Mass spectrometry m / z: 629.2233 (theoretical value: 629.2216). Theoretical elemental content (%) C 43 H 27 N5O: C, 82.02; H, 4.32; N, 11.12. Measured elemental content (%): C, 82.06; H, 4.30; N, 11.17.

[0203] Synthesis Example 25: Preparation of Compound 500

[0204]

[0205] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-95, D-7 with an equimolar amount of D-469, A-7 with an equimolar amount of B-500, and B-7 with an equimolar amount of A-95, yielding compound 500 (13.04 g); HPLC purity ≥ 99.93%. Mass spectrometry m / z: 595.1743 (theoretical value: 595.1757). Theoretical elemental content (%) C 37 H 21 N7O2: C, 74.61; H, 3.55; N, 16.46. Measured elemental content (%): C, 74.65; H, 3.50; N, 16.49.

[0206] Synthesis Example 26: Preparation of Compound 504

[0207]

[0208] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-504, D-7 with an equimolar amount of D-469, A-7 with an equimolar amount of B-504, and B-7 with an equimolar amount of A-504, yielding compound 504 (14.51 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 662.1803 (theoretical value: 662.1815). Theoretical elemental content (%) C 40 H 22 N8O3: C, 72.50; H, 3.35; N, 16.91. Measured elemental content (%): C, 72.54; H, 3.30; N, 16.96.

[0209] Synthesis Example 27: Preparation of Compound 510

[0210]

[0211] According to the preparation method in Synthesis Example 1, a-7 was replaced with an equimolar amount of a-510, D-7 with an equimolar amount of D-469, A-7 with an equimolar amount of B-510, and B-7 with an equimolar amount of A-510, yielding compound 510 (15.11 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 699.1891 (theoretical value: 699.1880). Theoretical elemental content (%) C 41 H 21 N 11 O2: C, 70.38; H, 3.03; N, 22.02. Measured elemental content (%): C, 70.34; H, 3.00; N, 22.07.

[0212] Synthesis Example 28: Preparation of Compound 522

[0213]

[0214] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-522, D-7 with an equimolar amount of D-469, A-7 with an equimolar amount of B-522, and B-7 with an equimolar amount of A-522, yielding compound 522 (14.49 g); HPLC purity ≥ 99.94%. Mass spectrometry m / z: 670.1878 (theoretical value: 670.1866). Theoretical elemental content (%) C 42 H 22N8O2: C, 75.22; H, 3.31; N, 16.71. Measured elemental content (%): C, 75.20; H, 3.33; N, 16.76.

[0215] Synthesis Example 29: Preparation of Compound 532

[0216]

[0217] Preparation of intermediate a-532:

[0218] According to the preparation method of intermediate a-70 in Synthesis Example 7, M-70 was replaced with an equimolar amount of M-532 to obtain intermediate a-532 (34.34 g), with HPLC purity ≥99.74%. Mass spectrometry m / z: 310.0828 (theoretical value: 310.0811).

[0219] The remaining steps followed the preparation method of compound 95 in Synthesis Example 8, except that a-95 was replaced with an equimolar amount of a-532, D-95 with an equimolar amount of D-532, and A-95 with an equimolar amount of A-532, yielding compound 532 (19.26 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 903.3441 (theoretical value: 903.3460). Theoretical elemental content (%) C 57 H 21 D 12 N9O3: C, 75.73; H, 5.02; N, 13.94. Measured elemental content (%): C, 75.70; H, 5.07; N, 13.91.

[0220] Synthesis Example 30: Preparation of Compound 537

[0221]

[0222] According to the preparation method in Synthesis Example 8, a-95 was replaced with an equimolar amount of a-537, D-95 with an equimolar amount of D-532, and A-95 with an equimolar amount of A-537 to obtain compound 537 (13.94 g); HPLC purity ≥99.92%. Mass spectrometry m / z: 663.1778 (theoretical value: 663.1767). Theoretical elemental content (%) C 39 H 21 N9O3: C, 70.58; H, 3.19; N, 19.00; . Measured elemental content (%): C, 70.55; H, 3.15; N, 19.05.

[0223] Synthesis Example 31: Preparation of Compound 545

[0224]

[0225] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-545, D-7 with an equimolar amount of D-469, A-7 with an equimolar amount of A-545, and B-7 with an equimolar amount of B-545, yielding compound 545 (13.20 g); HPLC purity ≥ 99.98%. Mass spectrometry m / z: 619.1815 (theoretical value: 619.1831). Theoretical elemental content (%) C 41 H 25 N5S: C, 79.46; H, 4.07; N, 11.30. Measured elemental content (%): C, 79.42; H, 4.02; N, 11.35.

[0226] Synthesis Example 32: Preparation of Compound 576

[0227]

[0228] According to the preparation method in Example 1, a-7 was replaced with an equimolar amount of a-576, D-7 with an equimolar amount of D-469, A-7 with an equimolar amount of B-576, and B-7 with an equimolar amount of A-576, yielding compound 576 (16.05 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 742.1736 (theoretical value: 742.1722). Theoretical elemental content (%) C 45 H 26 N8S2: C, 72.76; H, 3.53; N, 15.08. Measured elemental content (%): C, 72.71; H, 3.58; N, 15.04.

[0229] Device Examples

[0230] In this invention, all organic materials are sublimated, with a purity of over 99.99%. The device is fabricated using a vacuum evaporation system, where it is continuously evaporated under uninterrupted vacuum conditions.

[0231] A combined IVL testing system was used to test the luminous efficiency of organic light-emitting elements (OLEDs), comprising testing software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectral scanning luminance meter. Lifetime testing was performed using the McScience M6000 OLED lifetime testing system. The testing environment was atmospheric, at room temperature.

[0232] Comparative Example 1: Fabrication of Comparative Organic Electroluminescent Device 1

[0233] Substrate processing: ITO / Ag / ITO glass was used as the substrate material. The substrate was first ultrasonically washed twice in distilled water for 20 minutes each time, then ultrasonically washed for 20 minutes in acetone solution, then ultrasonically washed for 20 minutes in isoacetone solution, and then ultrasonically washed twice in distilled water for 10 minutes each time. Finally, it was dried at 120°C and then transferred to a vacuum evaporation machine for later use.

[0234] The following organic functional layer materials were sequentially vacuum-deposited on the substrate: a) NTNPB as a hole injection layer with a deposition thickness of 50 nm; b) β-NPB as a hole transport layer with a deposition thickness of 75 nm; c) Ir(piq)3 and TCTA as light-emitting layers with a mass ratio of 5:95 and a deposition thickness of 30 nm; d) BmPyPhB as an electron transport layer with a deposition thickness of 25 nm; e) LiF as an electron injection layer with a deposition thickness of 0.5 nm; f) Mg and Ag as cathodes with a mass ratio of 9:1 and a deposition thickness of 13 nm; g) Compound A as a capping layer with a deposition thickness of 80 nm.

[0235] Comparative Examples 2-3: Fabrication of Comparative Organic Electroluminescent Devices 2-3

[0236] According to the preparation method of Comparative Example 1, compound A in the capping layer was replaced with compound B and compound C, respectively, to obtain comparative organic electroluminescent devices 2-3.

[0237] Application Examples 1-32: Fabrication of Organic Electroluminescent Devices 1-32

[0238] According to the preparation method of Comparative Example 1, the compound A in the capping layer was replaced with compound 7, compound 15, compound 34, compound 58, compound 59, compound 60, compound 70, compound 95, compound 100, compound 123, compound 173, compound 241, compound 255, compound 258, compound 261, compound 268, compound 278, compound 293, compound 300, compound 327, compound 399, compound 469, compound 472, compound 476, compound 500, compound 504, compound 510, compound 522, compound 532, compound 537, compound 545, and compound 576, respectively, to obtain organic electroluminescent devices 1 to 32.

[0239] The structural formulas of the materials used in the above embodiments are as follows:

[0240]

[0241] The luminescence characteristic test results of the above embodiments are shown in the table below:

[0242] Table 1. Test data on the luminescence characteristics of organic electroluminescent devices.

[0243]

[0244]

[0245] Note: T97 refers to a current density of 10 mA / cm². 2 Under these conditions, the time it takes for the device brightness to decay to 97%.

[0246] As can be seen from Table 1, the organic electroluminescent devices 1-32 of the present invention have a longer service life compared with the comparative organic electroluminescent devices 1-3. This indicates that the compound shown in Formula 1 of the present invention has better stability and can maintain a stable thin film state for a longer period of time. In addition, the device of the present invention also has higher luminous efficiency, which indicates that the compound shown in Formula 1 of the present invention can more effectively couple out the light trapped in the device, thereby improving the luminous efficiency of the organic electroluminescent device.

[0247] It should be noted that the present invention has been described in detail through the above embodiments, but the present invention is not limited to the above embodiments. It should also be noted that, without departing from the principles of the present invention, those skilled in the art can make various forms or details to the present invention, and these modifications also fall within the protection scope of the present invention.

Claims

1. A top-emitting organic electroluminescent device, characterized in that, It includes a substrate, an anode, an organic functional layer, a cathode, and a capping layer, wherein the capping layer comprises an organic compound based on a aziroxazole structure, the structure of which is shown in general formula 1. The Selected from any one of the following groups, The Selected from any one of the following groups, The R b Independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted groups of one or more of the following: methyl, ethyl, propyl, butyl, phenyl, naphthyl; substituents selected from one or more of deuterium, cyano, trifluoromethyl, halogen, isopropyl, tert-butyl, wherein, in the case of multiple substituents, the substituents are identical or different from each other; or any adjacent R b They connect to form substituted or unsubstituted benzene rings; X is selected from O, S, or NR. a The R a Selected from any one of the aryl groups of C6 to C12, whether substituted or unsubstituted; The Ar group is independently selected from any one of the following groups. The above-mentioned groups may be substituted or unsubstituted by one or more substituents selected from deuterium, cyano, halogen, substituted or unsubstituted groups of the following: methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclohexyl, adamantyl, norbornyl, camphenyl, phenyl; the substituents in "substituted or unsubstituted" may be selected from one or more of deuterium, cyano, trifluoromethyl, halogen, isopropyl, tert-butyl, and in the case of being substituted by multiple substituents, the multiple substituents may be the same as or different from each other; Alternatively, the Ar group can be independently selected from any one of substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiopheneyl; the substituent group in the "substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiopheneyl" group can be selected from one or more of the following groups: deuterium or any one of C1 to C6 alkyl groups; in the case of being substituted by multiple substituents, the multiple substituents may be the same or different from each other, or adjacent substituents may bond to form a substituted or unsubstituted benzene ring; The L is independently selected from any one of the following groups, which are single-bonded, substituted or unsubstituted: phenylene, biphenylene, naphthylene, pyridylene, pyrimidinylene, quinolineylene, and isoquinolineylene, and when substituted by multiple substituents, the multiple substituents may be the same or different from each other; The m is selected from 1, 2, or 3; the n is selected from 0, 1, or 2; and m + n = 3. The substituted or unsubstituted group in the term "substituted or unsubstituted" is selected from one or more of the following groups: deuterium, halogen atom, cyano, trifluoromethyl, C1-C6 alkyl; in the case of being substituted by multiple substituents, the multiple substituents may be the same or different from each other.

2. The top-emitting organic electroluminescent device according to claim 1, characterized in that, The general formula 1 is selected from any one of the structures 1 to 3 shown below. 。 3. A top-emitting organic electroluminescent device according to claim 1, characterized in that, The Selected from any one of the following groups, The R b The independent group is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted of one or more of the following: methyl, ethyl, propyl, butyl, phenyl; the substituent is selected from one or more of deuterium, cyano, trifluoromethyl, halogen, isopropyl, tert-butyl, and in the case of being substituted by multiple substituents, the multiple substituents may be the same as or different from each other.

4. A top-emitting organic light-emitting device according to claim 1, characterized in that, The Ar group is independently selected from any one of the following groups. The above-mentioned group may be substituted or unsubstituted by one or more substituents selected from deuterium, cyano, halogen, substituted or unsubstituted groups: methyl, ethyl, propyl, butyl; the substituents in "substituted or unsubstituted" may be selected from one or more substituents selected from deuterium, cyano, trifluoromethyl, halogen, isopropyl, tert-butyl, and in the case of being substituted by multiple substituents, the multiple substituents may be the same as or different from each other.

5. A top-emitting organic electroluminescent device according to claim 1, characterized in that, The L is independently selected from any one of single bonds or groups shown below, or combinations thereof. 。 6. A top-emitting organic electroluminescent device, characterized in that, It includes a substrate, an anode, an organic functional layer, a cathode, and a capping layer, wherein the capping layer comprises an organic compound based on a azaoxazole structure, and the organic compound based on the azaoxazole structure is selected from any of the structures shown below. 。 7. The top-emitting organic electroluminescent device according to claim 1 or 6, characterized in that, The organic light-emitting functional layer further includes a combination of at least two of the following: a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

8. A display device, characterized in that, Including claim 1 The top-emitting organic electroluminescent device described in any one of the 7.

Images