A tertiary amine derivative and an organic electroluminescent device thereof

Abstract

The application provides a tertiary amine derivative, which is an arylamine compound in which a fused ring aryl group such as naphthalene or a fused ring heteroaryl group containing a nitrogen atom such as quinoline is combined to a benzonaphthofuran, a benzonaphthothiophene or the like through pyridine, pyrimidine, quinoline, isoquinoline or the like as a bridge, can have a wide band gap and a high refractive index, and can improve the absorption wavelength in the ultraviolet region, so that the organic electroluminescent element can have high efficiency and long service life when applied to a cover layer of an organic light emitting element; meanwhile, the tertiary amine derivative has a high glass transition temperature (T g ) and can prevent intermolecular recrystallization and maintain the stable state of the thin film when heat is generated during the driving process of the organic light emitting element, so that the external quantum efficiency is improved and the service life is significantly improved. The tertiary amine derivative and the organic electroluminescent element thereof have good application effect and industrialization prospect.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic materials technology, and in particular to a tertiary amine derivative and its organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) have the characteristics of high brightness, wide range of material selection, low driving voltage, and all-solid-state active light emission. They also have advantages such as high definition, wide viewing angle, and high-speed response for smooth animation display. They have broad application prospects in next-generation display and lighting products and have been a hot research area in the last ten years.

[0003] OLEDs generally consist of an anode, organic functional layers, and a metal cathode. The anode, serving as both the electrode and the light-emitting surface, must possess high electrical conductivity and high transmittance, typically using commercially available tin oxide (ITO). The organic functional layers generally include an electron transport layer (ETL), an emission layer (EML), and a hole transport layer (HTL). The cathode is usually made of a metal or metal alloy with a low work function. With increasing demands for enhanced functionality, various auxiliary functional structures have been added, such as an electron injection layer (ETL), an electron-blocking layer (EBL), a hole injection layer (HIL), a hole block layer (HBL), and a capping layer (CPL). Under the influence of an external electric field, holes generated at the anode and electrons generated at the cathode migrate toward the luminescent layer. Upon reaching the luminescent layer, holes and electrons recombine to generate excitons and release energy. The excitons migrate under the influence of the electric field, transferring energy to the luminescent material. Electrons in the molecules of the luminescent material transition from the ground state to the excited state. Since the excited state is unstable, when the excited electrons return to the ground state through radiation, light is emitted, which is called electroluminescence.

[0004] Although the internal quantum efficiency of OLEDs is now close to 100%, when light emitted from the light-emitting layer is incident on other films, total internal reflection occurs at the interfaces of the ITO thin film and the glass substrate, as well as at the interfaces of the glass substrate and air. The light emitted into the external space of the OLED device is mainly confined in the form of waveguides within the organic thin film, ITO thin film, and glass substrate. Ultimately, only about 20% of the photons reach the outside, while nearly 80% of the light cannot escape and is confined inside the device and dissipates as heat. Excessive heat accumulation can adversely affect the lifespan of other organic materials inside the device, greatly restricting the development and application of OLEDs. Therefore, how to improve the light extraction efficiency of OLEDs has become a research hotspot.

[0005] Currently, a key method to improve the light extraction efficiency of OLEDs is to add a light extraction layer, or capping material, to the cathode surface. This effectively reduces total internal reflection in OLED devices and improves light coupling efficiency. Organic materials used in the light extraction layer of OLED devices require high glass transition temperatures and molecular thermal stability, as well as low absorption and high refractive index in the visible light domain. Therefore, developing materials with high refractive index, excellent thin-film stability, and durability to improve the light extraction efficiency of OLEDs has become a pressing issue for those skilled in the art. Summary of the Invention

[0006] In view of the above-mentioned problems in the prior art, the purpose of this invention is to provide a tertiary amine derivative and its organic electroluminescent device, which can effectively improve the light extraction efficiency of OLED devices, thereby improving the luminous efficiency of OLED devices.

[0007] This invention provides a tertiary amine derivative, which is represented by chemical formula 1.

[0008]

[0009] X is selected from O or S;

[0010] The rings A and B are independently selected from one of an unsubstituted or substituted benzene ring or a substituted or unsubstituted naphthalene ring, and at least one of the rings A and B is not absent;

[0011] Ar1 and Ar2 are independently selected from one of substituted or unsubstituted C10-C30 fused-ring aryl groups and substituted or unsubstituted C6-C30 fused-ring heteroaryl groups;

[0012] The L1 is selected from one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted divalent C3-C12 cycloalkyl and C6-C30 aryl fused cycloalkyl, substituted or unsubstituted C3-C30 heteroarylene, or combinations thereof.

[0013] L2 and L3 are independently selected from the structures represented by chemical formula 2 or chemical formula 3.

[0014]

[0015] The Y is independently selected from N or CR2, and at least one Y is selected from N;

[0016] The L4 is selected from one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene, or a combination thereof;

[0017] R1 and R2 are independently selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or adjacent substituents can be linked to form a substituted or unsubstituted ring.

[0018] a1 is selected from 0, 1, 2, 3 or 4.

[0019] The present invention also provides an organic electroluminescent device comprising an anode, an organic layer, a cathode, and a capping layer, wherein the capping layer comprises at least one of the tertiary amine derivatives of the present invention.

[0020] The beneficial effects of this invention are:

[0021] This invention provides a tertiary amine derivative, which, as an aromatic amine compound with a fused-ring aryl group such as naphthalene or a nitrogen-containing fused-ring heteroaryl group such as quinoline, is bridging to groups such as benzonaphthofuran and benzonaphthothiophene via pyridine, pyrimidine, quinoline, or isoquinoline. This derivative can enhance the absorption wavelength in the ultraviolet region while maintaining a wide band gap and high refractive index, thereby achieving high-efficiency and long-life organic electroluminescent devices when used as a capping layer for organic light-emitting elements. Simultaneously, this tertiary amine derivative exhibits a high glass transition temperature (T0). g It can prevent recrystallization between molecules and maintain the stability of the film when heat is generated during the driving process of organic light-emitting elements, thereby improving external quantum efficiency and significantly improving service life.

[0022] In addition, adding low-refractive-index materials to the high-refractive-index capping layer can effectively reduce the total internal reflection effect in organic electroluminescent devices, improve optical coupling efficiency, and further improve the luminous efficiency of the device. Detailed implementation method:

[0023] The technical solutions of the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0024] 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.

[0025] In this invention, "*-" refers to the portion connected to another substituent.

[0026] In this invention, when the position of the substituent on the ring is not fixed, it means that it can be attached to any one of the corresponding optional sites on the ring.

[0027] For example, Can represent Can represent Can represent And so on.

[0028] The halogens described in this invention include fluorine, chlorine, bromine, and iodine.

[0029] In this invention, the alkyl group can be linear or branched, preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms. The alkyl group can be substituted or unsubstituted. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 2-ethylbutyl, 1-methylhexyl, n-octyl, etc., but are not limited thereto.

[0030] In this invention, the cycloalkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms. The cycloalkyl group may be substituted or unsubstituted. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, cycloheptyl, norbornelalkyl, adamantylalkyl, etc., but are not limited thereto.

[0031] In this invention, the aryl group can be monocyclic, polycyclic, or fused-ring, preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, even more preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The aryl group can be substituted or unsubstituted. When the aryl group is a monocyclic aryl group, specific examples include phenyl, but are not limited thereto; when the aryl group is a polycyclic aryl group, specific examples include biphenyl, terphenyl, etc., but are not limited thereto; when the aryl group is a fused-ring aryl group, specific examples include naphthyl, anthracene, phenanthrene, triphenylene, pyrene, perylene, indene, fluoranyl, fluorene, etc., but are not limited thereto.

[0032] In this invention, the heteroaryl group comprises one or more heteroatoms other than carbon. Specific heteroatoms may include those selected from O, S, N, Se, and Si, preferably having 3 to 30 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 7 carbon atoms. The heteroaryl group may be substituted or unsubstituted. The heteroaryl group may be monocyclic, polycyclic, or fused-ring. When the heteroaryl group is a monocyclic heteroaryl group, specific examples include thiophene, furanyl, pyrrole, imidazolyl, thiazolyl, pyridinyl, pyrimidinyl, triazine, triazolyl, pyridazinyl, diazolyl, oxazolyl, thiazolyl, etc., but are not limited thereto; when the heteroaryl group is a polycyclic heteroaryl group, specific examples include bipyridinyl, etc., but are not limited thereto; when the heteroaryl group is a fused-ring heteroaryl group, specific examples include... Examples include acridine, phenanthridine, phenazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, naphthidyl, pteridinyl, indolyl, inzolyl, carbazole, benzoxazolyl, benzoimidazolyl, benzothiazolyl, benzocarbazole, benzothiophene, benzofuranyl, phenothiazinyl, dibenzothiophene, dibenzofuranyl, azirmonyl, carbolinyl, phenantholinyl, etc., but are not limited to these.

[0033] In this invention, the term arylene refers to a divalent group obtained by removing two hydrogen atoms from the aromatic nucleus of an aryl group. The above description of aryl groups can be applied to arylene groups, except that arylene groups are divalent.

[0034] In this invention, the fused cycloalkyl and aryl group refers to the group obtained by removing two hydrogen atoms after fusion of cycloalkyl and aryl groups, preferably having 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 13 carbon atoms. Specific examples may include divalent benzocyclopropyl, divalent benzocyclobutyl, divalent benzocyclopentyl, divalent benzocyclohexyl, divalent benzocycloheptyl, divalent benzocyclopentenyl, divalent benzocyclohexenyl, divalent benzocycloheptenyl, divalent naphthocyclopentyl, divalent naphthocyclohexyl, etc., but are not limited thereto.

[0035] In this invention, the term "heteroaryl" refers to a divalent group obtained by removing two hydrogen atoms from an aromatic nucleus. The above description of heteroaryl can be applied to heteroaryl, except that heteroaryl is divalent.

[0036] In this invention, "substitution" refers to substitution by one or more of the following substituents: deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; preferably, it is selected from deuterium, halogen, cyano, C1-C4 alkyl, C3-C8 cycloalkyl, C6-C18 aryl, and C3-C15 heteroaryl. The position of the substituents is arbitrary, and when substituted by multiple substituents, the multiple substituents may be the same or different from each other; preferably, it refers to substitution by one or more of the following substituents: deuterium, halogen, cyano, methyl, and ethyl. Substituents include n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, adamantyl, norbornel, aniline, phenyl, tolyl, deuterated phenyl, biphenyl, deuterated biphenyl, naphthyl, deuterated naphthyl, anthracene, deuterated anthracene, phenanthrene, deuterated phenanthrene, triphenylene, pyridyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxolinyl, quinazolinyl, naphthidyl, pteridinyl, indolyl, inzolyl, benzimidazolyl, benzothiazolyl, benzothiophene, benzofuranyl, benzoxazolyl, phenothiazinyl, phenantholinyl, etc. The positions of the substituents are arbitrary. When substituted by multiple substituents, the multiple substituents may be the same or different from each other, or adjacent substituents may be connected to form substituted or unsubstituted rings.

[0037] The linking and ring formation described in this invention refers to two groups being linked together by chemical bonds and optionally aromatized. Examples are shown below:

[0038]

[0039] In this invention, the ring formed by the connection can be a five-membered ring, a six-membered ring, or a fused ring, examples of which include, but are not limited to, benzene, naphthalene, fluorene, cyclopentane, cyclohexane, cyclopentene, cyclohexene, cyclopentanone, cyclohexanone, phenanthrene, pyrene, pyridine, pyrimidine, quinoline, isoquinoline, or dibenzofuran, dibenzothiophene, etc.

[0040] This invention provides a tertiary amine derivative, characterized in that the tertiary amine derivative is represented by chemical formula 1.

[0041]

[0042] X is selected from O or S;

[0043] The rings A and B are independently selected from one of an unsubstituted or substituted benzene ring or a substituted or unsubstituted naphthalene ring, and at least one of the rings A and B is not absent;

[0044] Ar1 and Ar2 are independently selected from one of substituted or unsubstituted C10-C30 fused-ring aryl groups and substituted or unsubstituted C6-C30 fused-ring heteroaryl groups;

[0045] The L1 is selected from one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted divalent C3-C12 cycloalkyl and C6-C30 aryl fused cycloalkyl, substituted or unsubstituted C3-C30 heteroarylene, or combinations thereof.

[0046] L2 and L3 are independently selected from the structures represented by chemical formula 2 or chemical formula 3.

[0047]

[0048] The Y is independently selected from N or CR2, and at least one Y is selected from N;

[0049] The L4 is selected from one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene, or a combination thereof;

[0050] R1 and R2 are independently selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or adjacent substituents can be linked to form a substituted or unsubstituted ring.

[0051] a1 is selected from 0, 1, 2, 3 or 4.

[0052] Preferably, the tertiary amine derivative has one of the structures shown in chemical formulas 1-1 to 1-8.

[0053]

[0054]

[0055] The R1 is independently selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, and substituted or unsubstituted pyrimidinyl.

[0056] a1 is selected from 0, 1, 2, 3 or 4; a2 is selected from 0, 1 or 2; a3 is selected from 0, 1, 2 or 3.

[0057] Preferably, at least one of ring A and ring B is selected from substituted or unsubstituted benzene rings.

[0058] Preferably, L1 is independently selected from single bonds, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthraceneylene, substituted or unsubstituted phenanthylene, substituted or unsubstituted terphenylene, substituted or unsubstituted pyrene, substituted or unsubstituted benzocyclopentylene, substituted or unsubstituted benzocyclohexylene, substituted or unsubstituted pyridylene, substituted or unsubstituted pyrimidineene, substituted or unsubstituted pyrimidineene. The pyridyl group, substituted or unsubstituted pyridazinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted quinolineyl group, substituted or unsubstituted isoquinolineyl group, substituted or unsubstituted quinoazolineyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthidyl group, substituted or unsubstituted pteridyl group, substituted or unsubstituted acridineyl group, substituted or unsubstituted phenanthrinyl group, substituted or unsubstituted o-phenanthrolineyl group, or a combination thereof.

[0059] Preferably, chemical formulas 2 and 3 are independently selected from one of the following structures:

[0060]

[0061]

[0062] The R3 is independently selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl.

[0063] b1 is selected from 0, 1, 2 or 3; b2 is selected from 0, 1 or 2; b3 is selected from 0 or 1; b4 is selected from 0, 1, 2, 3 or 4.

[0064] Preferably, R3 is independently selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-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, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted pyridyl.

[0065] Preferably, chemical formulas 2 and 3 are independently selected from one of the following structures:

[0066]

[0067] Preferably, Ar1 and Ar2 are independently selected from the structures shown in chemical formulas I to VI.

[0068]

[0069] The Z is independently selected from N or CR4; the R4 is independently selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or two adjacent R4s may be connected to form an alicyclic or benzene ring.

[0070] Preferably, R4 is independently selected from one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-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, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, and substituted or unsubstituted quinoxalinyl.

[0071] Preferably, at most three Zs in the structures shown in chemical formulas I to VI are selected from N; more preferably, at most two Zs are selected from N; and most preferably, at most one Z is selected from N.

[0072] Preferably, Ar1 and Ar2 are independently selected from one of the following structures:

[0073]

[0074] Preferably, Ar1 and Ar2 are independently selected from one of the following structures:

[0075]

[0076] Most preferably, the chemical formula 1 is independently selected from one of the structures shown below.

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091] The above lists some specific structures of the tertiary amine derivatives of Formula 1 of the present invention, but the present invention is not limited to these listed chemical structures. Any derivative based on the tertiary amine derivative of Formula 1 with substituents as defined above should be included.

[0092] The tertiary amine derivative described in this invention can be prepared via the following synthetic route, but this invention is not limited thereto:

[0093]

[0094] Among them, Ar1~Ar2, L1~L3, R1, a1, ring A, and ring B are limited to the same limits as described above; Xa is selected from I, Br, and Cl;

[0095] The tertiary amine derivatives described in this invention involve the Suzuki reaction and the Buchwald reaction.

[0096] The present invention does not impose any particular restrictions on the source of the raw materials used in the above synthesis, and commercially available raw materials or preparation methods known to those skilled in the art can be used.

[0097] The present invention also provides an organic electroluminescent device, comprising an anode, an organic layer, a cathode, and a capping layer, wherein the capping layer comprises at least one of the tertiary amine derivatives described in the present invention.

[0098] Preferably, the coating layer of the present invention includes a first coating layer and a second coating layer, wherein the first coating layer includes at least one of the tertiary amine derivatives of the present invention, and the second coating layer contains inorganic materials.

[0099] Preferably, the first covering layer is located outside the cathode, and the second covering layer is located outside the first covering layer.

[0100] Preferably, the coating layer of the present invention includes a first coating layer and a second coating layer, wherein the first coating layer includes at least one of the tertiary amine derivatives of the present invention, and the second coating layer contains one of fluoride, oxide, nitride, and oxynitride.

[0101] Preferably, the coating layer of the present invention includes a first coating layer and a second coating layer, wherein the first coating layer includes at least one of the tertiary amine derivatives of the present invention, and the second coating layer contains a fluoride.

[0102] Preferably, the fluoride is selected from lithium fluoride, calcium fluoride, sodium fluoride, aluminum fluoride, magnesium fluoride, barium fluoride, yttrium fluoride, ytterbium fluoride, praseodymium fluoride, gadolinium fluoride, lanthanum fluoride, neodymium fluoride, cerium fluoride, and Na₅Al₃F₂. 14 At least one of Na3AlF6.

[0103] Preferably, the fluoride is selected from lithium fluoride.

[0104] The preferred structure of the organic electroluminescent device of the present invention is as follows:

[0105] Anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode / capping layer;

[0106] Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / electron transport layer / electron injection layer / cathode / capping layer;

[0107] Anode / hole injection layer / hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode / capping layer;

[0108] Anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode / capping layer;

[0109] Anode / hole injection layer / hole transport layer / light-emitting auxiliary layer / light-emitting layer / electron transport layer / electron injection layer / cathode / capping layer;

[0110] Anode / hole injection layer / hole transport layer / luminescent auxiliary layer / luminescent layer / hole blocking layer / electron transport layer / electron injection layer / cathode / capping layer;

[0111] Anode / hole injection layer / hole transport layer / light emission layer / electron transport layer / electron injection layer / cathode / first capping layer / second capping layer;

[0112] Anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode / first capping layer / second capping layer;

[0113] Anode / Hole injection layer / Hole transport layer / Light emission layer / Hole blocking layer / Electron transport layer / Electron injection layer / Cathode / First capping layer / Second capping layer;

[0114] Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode / first capping layer / second capping layer;

[0115] Anode / Hole injection layer / Hole transport layer / Light emission auxiliary layer / Light emission layer / Electron transport layer / Electron injection layer / Cathode / First capping layer / Second capping layer;

[0116] Anode / hole injection layer / hole transport layer / luminescent auxiliary layer / luminescent layer / hole blocking layer / electron transport layer / electron injection layer / cathode / first capping layer / second capping layer;

[0117] The structure of the organic electroluminescent device of the present invention is not limited to the above-described structure. If necessary, multiple organic layers can be omitted or included simultaneously. For example, an electron blocking layer can be provided between the hole transport layer and the light-emitting layer, and a hole blocking layer can also be provided between the electron transport layer and the light-emitting layer. Furthermore, organic layers with the same function can be made into a stacked structure of two or more layers, and each organic layer can contain one material or multiple materials.

[0118] The organic electroluminescent device of the present invention is typically formed on a substrate. The substrate can be used below the anode or above the cathode. The substrate is typically a glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. The substrate need not change during the formation of the electrodes or the organic layer; for example, substrates made of glass, plastic, polymer films, silicon, etc. When the substrate is opaque, the electrode opposite it is preferably transparent or translucent.

[0119] In the organic electroluminescent device of the present invention, the anode material preferably has good conductivity and stable chemical properties, and a suitable work function to reduce the injection barrier. Specific examples of anode materials that can be used in the present invention may include: monolayer metals, such as silver, aluminum, vanadium, chromium, copper, zinc, gold, etc., or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and combinations of metals and oxides, such as ITO-Ag-ITO, etc., but are not limited thereto. Preferably, the anode material of the present invention is selected from ITO, ITO-Ag-ITO, etc.

[0120] In the organic electroluminescent device described in this invention, hole injection not only increases charge injection between layers but also improves the efficiency and lifetime of the device. Specific examples of hole injection materials that can be used in this invention include: metal oxides such as silver oxide, vanadium oxide, tungsten oxide, copper oxide, and titanium oxide; phthalocyanine compounds; benzidine compounds; and phenazine compounds, such as copper phthalocyanine (CuPc), titanium phthalocyanine, N,N'-diphenyl-N,N'-di-[4-(N,N-diphenylamine)phenyl]benzidine (NPNPB), and N,N,N',N'-tetra(4-methoxyphenyl)benzidine. Aniline (MeO-TPD), diquinoxolino[2,3-a:2',3'-c]phenazine (HATNA), 4,4',4”-tris[2-naphthylphenylamino]triphenylamine (2T-NATA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzphenanthrene (HAT-CN), 4,4',4”-tris(N,N-diphenylamino)triphenylamine (TDATA), etc., but not limited thereto. Preferably, the hole injection material of the present invention is selected from copper phthalocyanine (CuPc), 4,4',4”-tris[2-naphthylphenylamino]triphenylamine (2T-NATA), 4,4',4”-tris(N,N-diphenylamino)triphenylamine (TDATA), etc.

[0121] In the organic electroluminescent device of the present invention, the main function of the hole transport material is to improve the balance between hole injection and transport in the device, thereby improving the device's efficiency and lifespan. Preferably, the material has excellent mobility, good film-forming properties, good heat resistance, and a suitable HOMO energy level. Specific examples of hole transport materials that can be used in this invention may include diphenylamine compounds, triphenylamine compounds, fluorene compounds, and carbazole compounds, such as N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), N,N'-di(naphthyl-1-yl)-N,N'-di(phenyl)-2,2'-dimethylbenzidine (α-NPD), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), 4-[1-[4-[di(4-methylphenyl)amino]phenyl]cyclohexyl]-N-(3-methylphenyl)-N-(4-methylphenyl)aniline (TAPC), etc., but are not limited thereto. Preferably, the hole transport material of the present invention is selected from N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), N,N'-di(naphthyl-1-yl)-N,N'-di(phenyl)-2,2'-dimethylbenzidine (α-NPD), 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC), etc.

[0122] The organic electroluminescent device described in this invention uses a light-emitting material with the following characteristics: good film-forming properties, good thermal stability, certain carrier transport capability, semiconductor properties, high conductivity, ability to conduct electrons or holes or both, and ability to match the corresponding electrode energy levels. Organic light-emitting materials can be classified into three categories according to their emission range: red light materials, green light materials, and blue light materials. Specific examples of red light materials that can be used in this invention include 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), 4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulonidin-9-enyl)-4H-pyran (DCJTB), bis(1-phenylisoquinoline)(acetylacetone)iridium(III))(Ir(piq)2(acac)), and octaethyl... PtOEP (platinum porphyrin), tris(dibenzoylmethane) mono(phenanthroline) europium(III) (Eu(dbm)3(Phen)), etc.; specific examples of green light materials may include tris(8-hydroxyquinoline)aluminum(III) (Alq3), coumarin 545T (C-525T), tris(2-phenylpyridine)iridium (Ir(ppy)3), di(2-phenylpyridine)iridium acetylacetonate (Ir(ppy)2(acac)), N,N'-dimethyl Quinacridone (DMQA), 5,12-diphenylnaphthonaphthalene (DPT), bis[2-(2-benzothiazolyl)phenol]zinc (Zn(BTZ)2), etc.; specific examples of blue light materials may include 9,10-di-(2-naphthyl)anthracene (ADN), 9-[4-(2-(7-(N,N-diphenylamino)-9,9-diethylfluorene-2-yl)vinyl)phenyl]-9-phenyl-fluorene (DPAFVF), 2,5,8,11-tetratert-butylperylene (T BPe), 4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl (DPAVBi), 4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl (DPAVB), bis(4,6-difluorophenylpyridine-C2,N)pyridinecarboxylic iridium (FIrpic), bis(2,4-difluorophenylpyridine)-tetra(1-pyrazolyl)boron(III) (Fir6), bis(2-hydroxyphenylpyridine)beryllium (Bepp2), etc.

[0123] In the organic electroluminescent device of the present invention, the hole blocking material is a material with strong hole blocking ability and suitable HOMO and LUMO energy levels. Specific examples of hole blocking materials that can be used in the present invention may include imidazole, triazole, phenanthroline derivatives, etc., such as 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), bis(2-methyl-8-hydroxyquinoline)(4-phenylphenol)aluminum(III) (BAlq), etc., but are not limited thereto. Preferably, the hole blocking material is selected from 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), bis(2-methyl-8-hydroxyquinoline)(4-phenylphenol)aluminum(III) (BAlq), etc.

[0124] In the organic electroluminescent device of the present invention, the electron transport material is a material that assists electrons in being injected from the cathode into the organic layer. Preferably, it is a material with high electron affinity, high electron mobility, good film-forming properties, good chemical stability, and thermal stability. Specific examples of electron transport materials that can be used in this invention may include imidazoles, triazoles, phenanthroline derivatives, quinolines, etc., such as 2,9-(dimethyl)-4,7-biphenyl-1,10-o-phenanthroline (BCP), 1,3,5-tris[(3-pyridyl)-phenyl]benzene (TmPyPB), 4,4'-bis(4,6-diphenyl-1,3,5-triazinyl)biphenyl (BTB), 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 2-(naphthyl-2-yl)-4,7-(diphenyl)-1,10-o-phenanthroline (HNBphen), 8-hydroxyquinoline-lithium, etc. (LiQ), but are not limited thereto. Preferably, the electron transport material of the present invention is selected from 1,3,5-tris(N-phenyl-2-benzimidazole)benzene (TPBi), tris(8-hydroxyquinoline)aluminum(III) (Alq3), 8-hydroxyquinoline-lithium (Liq), di(2-methyl-8-hydroxyquinoline)(4-phenylphenol)aluminum(III) (BAlq), etc., but is not limited thereto. Preferably, the electron transport material of the present invention is selected from 1,3,5-tris(1-phenyl-1H-benzimidazole-2-yl)benzene (TPBi), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 8-hydroxyquinoline-lithium, etc. (LiQ), etc.

[0125] In the organic electroluminescent device of the present invention, the role of the electron injection material is to improve the efficiency of electron injection from the cathode into the electron transport layer and the light-emitting layer. Preferably, it is a material with a small potential barrier to the adjacent organic transport material or host material. Examples of electron injection materials that can be used in the present invention include alkali gold compounds, such as lithium oxide (Li₂O), lithium boron oxide (LiBO₂), cesium carbonate (Cs₂CO₃), potassium silicate (K₂SiO₃), etc.; alkali metal fluorides, such as lithium fluoride (LiF), cesium fluoride (CsF), etc., but are not limited thereto. Preferably, the electron injection material of the present invention is selected from lithium fluoride (LiF), etc.

[0126] In the organic electroluminescent device of the present invention, the cathode material is preferably a low work function material with good electrical conductivity and chemical stability. Specific examples of cathode materials that can be used in the present invention include: metals such as aluminum, magnesium, silver, indium, tin, titanium, and their alloys; multilayer metal materials such as LiF / Al, Mg / Ag, Li / Al, LiO2 / Al, BaF2 / Al, etc., but are not limited thereto. Preferably, the cathode of the present invention is selected from a semi-transparent cathode, such as Ag or Mg-Ag alloys or thin Al.

[0127] In the organic electroluminescent device of the present invention, the first capping layer material is preferably a material with a high refractive index. Specific examples of the first capping layer material that can be used in the present invention include, in addition to the tertiary amine derivatives described herein, aryl amine derivatives, carbazole derivatives, benzimidazole derivatives, triazole derivatives, etc., but are not limited thereto. Preferably, the first capping layer material of the present invention is selected from the tertiary amine derivatives described herein.

[0128] In the organic electroluminescent device of the present invention, the second capping layer material is preferably a material with a low refractive index. Specific examples of the second capping layer materials that can be used in the present invention, besides fluorides, may also include other inorganic materials, such as silicon oxide, aluminum oxide, tungsten oxide, and Na₅Al₃F₂. 14 Materials such as Na3AlF6, but not limited to these, are preferred. The second coating material of the present invention is selected from the fluorides described in the present invention.

[0129] The present invention does not impose any special restrictions on the thickness of each organic layer of the organic electroluminescent device; thicknesses commonly used in the field can be adopted.

[0130] The organic electroluminescent device of the present invention can be made by one of the following methods: vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray coating, slot coating, and dip coating. In the present invention, vacuum evaporation is preferred.

[0131] The organic electroluminescent device described in this invention can be widely used in panel displays, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photosensitive materials or organic thin-film transistors, signs, signal lights and other fields.

[0132] The invention is explained in more detail through the following examples, but is not intended to limit the invention. Based on this description, those skilled in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the entire scope disclosed without inventive effort.

[0133] Preparation and characterization of compounds

[0134] Description of raw materials, reagents, and characterization equipment:

[0135] 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.

[0136] 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).

[0137] [Synthetic Example 1] Synthesis of intermediate c-20

[0138]

[0139] Under nitrogen protection, E-20 (23.77 mmol, 15.40 g), F-20 (82.00 mmol, 19.64 g), Pd(PPh3)4 (1.60 mmol, 1.85 g), K2CO3 (160.00 mmol, 22.11 g), 350 mL of toluene, and 150 mL of ethanol were added to a reaction flask. The mixture was stirred and heated under reflux for 4 hours. After the reaction was complete and cooled to room temperature, the filter cake was obtained by suction filtration and washed with ethanol. Finally, the filter cake was recrystallized from toluene / ethanol at a ratio of 4:1 to obtain intermediate c-20 (21.90 g, 83%); HPLC purity ≥99.76%. Mass spectrometry m / z: 329.0618 (theoretical value: 329.0607).

[0140] Following the method for intermediate c-20, by replacing raw material E with an equimolar amount of M and raw material F with an equimolar amount of N, the following intermediate a was synthesized:

[0141]

[0142] Following the method for intermediate c-20, by replacing raw material E with an equimolar amount of X and raw material F with an equimolar amount of N / Y, the following intermediate b is synthesized:

[0143]

[0144]

[0145] [Synthetic Example 2] Synthesis of Compound 20

[0146]

[0147] Preparation of intermediate A-20:

[0148] A-20 (72.00 mmol, 15.86 g), b-20 (70.00 mmol, 19.89 g), sodium tert-butoxide (105.00 mmol, 10.09 g), and 300 mL of toluene solvent were added sequentially to a reaction flask. The air was then purged three times with nitrogen. Pd₂(dba)₃ (0.70 mmol, 0.64 g) and tri-tert-butylphosphine (1.40 mmol, 0.28 g) were then added. The mixture was stirred at reflux under nitrogen protection for 4 h. After the reaction was complete, the mixture was cooled to room temperature. The reactants were filtered through diatomaceous earth, and the solvent was removed by vacuum distillation. The crude product was recrystallized from ethyl acetate to obtain intermediate A-20 (24.31 g, 82%); HPLC purity ≥99.73%. Mass spectrometry m / z: 423.1728 (theoretical value: 423.1735).

[0149] Preparation of compound 20:

[0150] Intermediate A-20 (52.00 mmol, 22.02 g), intermediate C-20 (50.00 mmol, 16.49 g), sodium tert-butoxide (75.00 mmol, 7.21 g), and 200 mL of DMF solvent were added sequentially to the reaction flask. The air was then purged three times with nitrogen. Pd2(dba)3 (0.50 mmol, 0.46 g) and tri-tert-butylphosphine (1.00 mmol, 0.20 g) were then added. The reaction was carried out under nitrogen protection and stirred at reflux temperature for 5.5 h. After the reaction was completed, the mixture was cooled to room temperature, and 200 mL of water was added. The mixture was extracted three times with 400 mL of ethyl acetate. The organic layer was washed with saturated brine and separated. The organic layer was then dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation. The crude product was purified by column chromatography to obtain compound 20 (26.88 g, 75%); HPLC purity ≥99.96%.

[0151] Mass spectrometry m / z: 716.2565 (theoretical value: 716.2576). Theoretical elemental content (%) C 51 H 32 N4O: C, 85.45; H, 4.50; N, 7.82. Measured elemental content (%): C, 85.47; H, 4.51; N, 7.81.

[0152] [Synthetic Example 3] Synthesis of Compound 25

[0153]

[0154] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-25, b-20 was replaced with an equimolar amount of b-25, and c-20 was replaced with an equimolar amount of c-25 to obtain compound 25 (23.74 g); HPLC purity ≥ 99.98%.

[0155] Mass spectrometry m / z: 641.2230 (theoretical value: 641.2216). Theoretical elemental content (%) C 44 H 27 N5O: C, 82.35; H, 4.24; N, 10.91. Measured elemental content (%): C, 82.36; H, 4.22; N, 10.93.

[0156] [Synthetic Example 4] Synthesis of Compound 48

[0157]

[0158] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-48, b-20 was replaced with an equimolar amount of b-48, and c-20 was replaced with an equimolar amount of c-48 to obtain compound 48 (27.75 g); HPLC purity ≥ 99.94%.

[0159] Mass spectrometry m / z: 739.2635 (theoretical value: 739.2624). Theoretical elemental content (%) C 54 H 33 N3O: C, 87.66; H, 4.50; N, 5.68. Measured elemental content (%): C, 87.69; H, 4.51; N, 5.66.

[0160] [Synthetic Example 5] Synthesis of Compound 57

[0161]

[0162] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-57, b-20 was replaced with an equimolar amount of b-57, and c-20 was replaced with an equimolar amount of c-57 to obtain compound 57 (24.95 g); HPLC purity ≥ 99.97%.

[0163] Mass spectrometry m / z: 639.2318 (theoretical value: 639.2311). Theoretical elemental content (%) C 46 H 29 N3O: C, 86.36; H, 4.57; N, 6.57. Measured elemental content (%): C, 86.38; H, 4.58; N, 6.56.

[0164] [Synthetic Example 6] Synthesis of Compound 71

[0165]

[0166] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-71, b-20 was replaced with an equimolar amount of b-71, and c-20 was replaced with an equimolar amount of c-57 to obtain compound 71 (25.18 g); HPLC purity ≥ 99.95%.

[0167] Mass spectrometry m / z: 689.2455 (theoretical value: 689.2467). Theoretical elemental content (%) C 50 H 31 N3O: C, 87.06; H, 4.53; N, 6.09. Measured elemental content (%): C, 87.07; H, 4.55; N, 6.05.

[0168] [Synthetic Example 7] Synthesis of Compound 107

[0169]

[0170] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-107, b-20 was replaced with an equimolar amount of b-107, and c-20 was replaced with an equimolar amount of c-57 to obtain compound 107 (24.83 g); HPLC purity ≥ 99.91%.

[0171] Mass spectrometry m / z: 689.2228 (theoretical value: 689.2216). Theoretical elemental content (%) C 48 H 27 N5O: C, 83.58; H, 3.95; N, 10.15. Measured elemental content (%): C, 83.56; H, 3.96; N, 10.17.

[0172] [Synthetic Example 8] Synthesis of Compound 178

[0173]

[0174] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-178, b-20 was replaced with an equimolar amount of b-178, and c-20 was replaced with an equimolar amount of c-57 to obtain compound 178 (24.71 g); HPLC purity ≥ 99.93%.

[0175] Mass spectrometry m / z: 641.2228 (theoretical value: 641.2216). Theoretical elemental content (%) C 44 H 27 N5O: C, 82.35; H, 4.24; N, 10.91. Measured elemental content (%): C, 82.38; H, 4.18; N, 10.95.

[0176] [Synthetic Example 9] Synthesis of Compound 206

[0177]

[0178] Following the preparation method of Synthesis Example 2, c-20 was replaced with an equimolar amount of c-206 to obtain compound 206 (24.95 g); HPLC purity ≥ 99.95%.

[0179] Mass spectrometry m / z: 639.2323 (theoretical value: 639.2311). Theoretical elemental content (%) C 46 H 29 N3O: C, 86.36; H, 4.57; N, 6.57. Measured elemental content (%): C, 86.38; H, 4.58; N, 6.55.

[0180] [Synthetic Example 10] Synthesis of Compound 210

[0181]

[0182] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-210, b-20 was replaced with an equimolar amount of b-210, and c-20 was replaced with an equimolar amount of c-206 to obtain compound 210 (25.17 g); HPLC purity ≥ 99.91%.

[0183] Mass spectrometry m / z: 653.3197 (theoretical value: 653.3189). Theoretical elemental content (%) C 46 H 15 D 14 N3O: C, 84.50; H, 6.63; N, 6.43. Measured elemental content (%): C, 84.51; H, 6.60; N, 6.42.

[0184] [Synthetic Example 11] Synthesis of Compound 215

[0185]

[0186] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-215, b-20 was replaced with an equimolar amount of b-215, and c-20 was replaced with an equimolar amount of c-206 to obtain compound 215 (31.67 g); HPLC purity ≥ 99.93%.

[0187] Mass spectrometry m / z: 891.3266 (theoretical value: 891.3250). Theoretical elemental content (%) C 66 H 41 N3O: C, 88.86; H, 4.63; N, 4.71. Measured elemental content (%): C, 88.87; H, 4.62; N, 4.73.

[0188] [Synthetic Example 12] Synthesis of Compound 220

[0189]

[0190] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-220, b-20 was replaced with an equimolar amount of b-220, and c-20 was replaced with an equimolar amount of c-206 to obtain compound 220 (24.07 g); HPLC purity ≥ 99.95%.

[0191] Mass spectrometry m / z: 641.2208 (theoretical value: 641.2216). Theoretical elemental content (%) C 44 H 27 N5O: C, 82.35; H, 4.24; N, 10.91. Measured elemental content (%): C, 82.38; H, 4.23; N, 10.95.

[0192] [Synthetic Example 13] Synthesis of Compound 223

[0193]

[0194] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-223, b-20 was replaced with an equimolar amount of b-223, and c-20 was replaced with an equimolar amount of c-206 to obtain compound 223 (29.75 g); HPLC purity ≥ 99.95%.

[0195] Mass spectrometry m / z: 803.3451 (theoretical value: 803.3469). Theoretical elemental content (%) C 56 H 25 D 10N5O: C, 83.66; H, 5.64; N, 8.71. Measured elemental content (%): C, 83.67; H, 5.65; N, 8.70.

[0196] [Synthetic Example 14] Synthesis of Compound 226

[0197]

[0198] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-226, b-20 was replaced with an equimolar amount of b-226, and c-20 was replaced with an equimolar amount of c-206 to obtain compound 226 (27.86 g); HPLC purity ≥ 99.97%.

[0199] Mass spectrometry m / z: 795.2762 (theoretical value: 795.2747). Theoretical elemental content (%) C 54 H 33 N7O: C, 81.49; H, 4.18; N, 12.32. Measured elemental content (%): C, 81.46; H, 4.16; N, 12.34.

[0200] [Synthetic Example 15] Synthesis of Compound 258

[0201]

[0202] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-258, b-20 was replaced with an equimolar amount of b-258, and c-20 was replaced with an equimolar amount of c-258 to obtain compound 258 (28.28 g); HPLC purity ≥ 99.93%.

[0203] Mass spectrometry m / z: 715.2633 (theoretical value: 715.2624). Theoretical elemental content (%) C 52 H 33 N3O: C, 87.25; H, 4.65; N, 5.87. Measured elemental content (%): C, 87.23; H, 4.64; N, 5.88.

[0204] [Synthetic Example 16] Synthesis of Compound 280

[0205]

[0206] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-280, b-20 was replaced with an equimolar amount of b-280, and c-20 was replaced with an equimolar amount of c-280 to obtain compound 280 (29.70 g); HPLC purity ≥ 99.96%.

[0207] Mass spectrometry m / z: 791.2947 (theoretical value: 791.2937). Theoretical elemental content (%) C 58 H 37 N3O: C, 87.96; H, 4.71; N, 5.31. Measured elemental content (%): C, 87.95; H, 4.72; N, 5.33.

[0208] [Synthetic Example 17] Synthesis of Compound 311

[0209]

[0210] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-311, b-20 was replaced with an equimolar amount of b-311, and c-20 was replaced with an equimolar amount of c-311 to obtain compound 311 (30.09 g); HPLC purity ≥ 99.98%.

[0211] Mass spectrometry m / z: 791.2951 (theoretical value: 791.2937). Theoretical elemental content (%) C 58 H 37 N3O: C, 87.96; H, 4.71; N, 5.31. Measured elemental content (%): C, 87.91; H, 4.73; N, 5.32.

[0212] [Synthetic Example 18] Synthesis of Compound 343

[0213]

[0214] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-343, b-20 was replaced with an equimolar amount of b-343, and C-20 was replaced with an equimolar amount of c-343 to obtain compound 343 (27.82 g); HPLC purity ≥ 99.92%.

[0215] Mass spectrometry m / z: 751.3575 (theoretical value: 751.3563). Theoretical elemental content (%) C 54 H 45 N3O: C, 86.25; H, 6.03; N, 5.59. Measured elemental content (%): C, 86.27; H, 6.01; N, 5.55.

[0216] [Synthetic Example 19] Synthesis of Compound 345

[0217]

[0218] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-345, b-20 was replaced with an equimolar amount of b-345, and c-20 was replaced with an equimolar amount of c-345 to obtain compound 345 (29.60 g); HPLC purity ≥ 99.95%.

[0219] Mass spectrometry m / z: 739.2638 (theoretical value: 739.2624). Theoretical elemental content (%) C 54 H 33 N3O: C, 87.66; H, 4.50; N, 5.68. Measured elemental content (%): C, 87.61; H, 4.51; N, 5.70.

[0220] [Synthetic Example 20] Synthesis of Compound 351

[0221]

[0222] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-351, b-20 was replaced with an equimolar amount of b-351, and c-20 was replaced with an equimolar amount of c-351 to obtain compound 351 (24.78 g); HPLC purity ≥ 99.93%.

[0223] Mass spectrometry m / z: 643.2128 (theoretical value: 643.2121). Theoretical elemental content (%) C 42 H 25 N7O: C, 78.37; H, 3.91; N, 15.23. Measured elemental content (%): C, 78.38; H, 3.95; N, 15.20.

[0224] [Synthetic Example 21] Synthesis of Compound 356

[0225]

[0226] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-258, b-20 was replaced with an equimolar amount of b-356, and c-20 was replaced with an equimolar amount of c-356 to obtain compound 356 (26.28 g); HPLC purity ≥ 99.91%.

[0227] Mass spectrometry m / z: 719.2888 (theoretical value: 719.2875). Theoretical elemental content (%) C 52 H 29 N3O: C, 86.76; H, 5.18; N, 5.84. Measured elemental content (%): C, 86.78; H, 5.17; N, 5.86.

[0228] [Synthetic Example 22] Synthesis of Compound 365

[0229]

[0230] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-365, b-20 was replaced with an equimolar amount of b-365, and c-20 was replaced with an equimolar amount of c-365 to obtain compound 365 (23.10 g); HPLC purity ≥ 99.95%.

[0231] Mass spectrometry m / z: 641.2230 (theoretical value: 641.2216). Theoretical elemental content (%) C 44 H 28 N5O: C, 82.35; H, 4.24; N, 10.91. Measured elemental content (%): C, 82.33; H, 4.25; N, 10.94.

[0232] [Synthetic Example 23] Synthesis of Compound 396

[0233]

[0234] Following the preparation method of Synthesis Example 2, b-20 was replaced with an equimolar amount of b-396, and c-20 was replaced with an equimolar amount of c-396 to obtain compound 396 (28.58 g); HPLC purity ≥ 99.93%.

[0235] Mass spectrometry m / z: 732.2360 (theoretical value: 732.2348). Theoretical elemental content (%) C 51 H 32 N4S: C, 83.58; H, 4.40; N, 7.64. Measured elemental content (%): C, 83.60; H, 4.38; N, 7.63.

[0236] [Synthetic Example 24] Synthesis of Compound 413

[0237]

[0238] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-413, b-20 was replaced with an equimolar amount of b-413, and c-20 was replaced with an equimolar amount of c-404 to obtain compound 413 (26.27 g); HPLC purity ≥ 99.96%.

[0239] Mass spectrometry m / z: 656.2047 (theoretical value: 656.2035). Theoretical elemental content (%) C 45 H 28 N4S: C, 82.29; H, 4.30; N, 8.53. Measured elemental content (%): C, 82.28; H, 4.33; N, 8.52.

[0240] [Synthetic Example 25] Synthesis of Compound 420

[0241]

[0242] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-420, b-20 was replaced with an equimolar amount of b-420, and c-20 was replaced with an equimolar amount of c-420 to obtain compound 420 (24.59 g); HPLC purity ≥ 99.95%.

[0243] Mass spectrometry m / z: 655.2095 (theoretical value: 655.2082). Theoretical elemental content (%) C 46 H 29 N3S: C, 84.25; H, 4.46; N, 6.41. Measured elemental content (%): C, 84.23; H, 4.47; N, 6.38.

[0244] [Synthetic Example 26] Synthesis of Compound 446

[0245]

[0246] Following the preparation method of Synthesis Example 2, a-20 was replaced with an equimolar amount of a-71, b-20 was replaced with an equimolar amount of b-446, and c-20 was replaced with an equimolar amount of c-446 to obtain compound 446 (26.46 g); HPLC purity ≥ 99.96%.

[0247] Mass spectrometry m / z: 755.2381 (theoretical value: 755.2395). Theoretical elemental content (%) C 54 H 33 N3S: C, 85.80; H, 4.40; N, 5.56. Measured elemental content (%): C, 85.82; H, 4.43; N, 5.53.

[0248] [Device Examples]

[0249] Clean the ITO / Ag / ITO glass substrate by ultrasonic cleaning twice with a 5% glass cleaning solution for 20 minutes each time, followed by ultrasonic cleaning twice with deionized water for 10 minutes each time. Then, ultrasonically clean with acetone and isoacetone for 20 minutes each time, and dry at 120°C.

[0250] Device Example 1: An organic electroluminescent device was fabricated using a vacuum evaporation method. A 60 nm thick 2-TNATN layer was vacuum-evaporated onto an ITO / Ag / ITO glass substrate serving as the anode as a hole injection layer. A 30 nm thick HTO1 layer was vacuum-evaporated onto the hole injection layer as a hole transport layer. A 30 nm thick Ir(piq)2(acac):26DCzPPy=5:95 layer was vacuum-evaporated onto the hole transport layer as a light-emitting layer. A 30 nm thick ETO1 layer was vacuum-evaporated onto the light-emitting layer as an electron transport layer. A 1 nm thick LiF layer was vacuum-evaporated onto the electron transport layer as an electron injection layer. An 18 nm thick Mg:Ag=9:1 layer was vacuum-evaporated onto the electron injection layer as a cathode. A 50 nm thick compound 20 of this invention was vacuum-evaporated onto the cathode as a first capping layer material. A 15 nm thick lithium fluoride layer was vacuum-evaporated onto the first capping layer as a second capping layer material.

[0251] The device structure of organic electroluminescent device 1 is as follows:

[0252] ITO / Ag / ITO / 2-TNATN(60nm) / HT01(30nm) / Ir(piq)2(acac):26DCzPPy=5:95(30nm) / ET01(30nm) / LiF(1n

[0253] m) / Mg:Ag(9:1)(18nm) / compound23(50nm) / LiF(15nm).

[0254]

[0255] Device Examples 2-25: Compound 20 of the present invention in Device Example 1 was replaced with compounds 25, 48, 57, 71, 107, 178, 206, 210, 215, 220, 223, 226, 258, 280, 311, 343, 345, 351, 356, 365, 396, 413, 420, and 434 as the first capping layer material, respectively. Otherwise, organic electroluminescent devices were prepared using the same steps as in Device Example 1.

[0256] Comparative Example 1: An organic electroluminescent device was prepared by vacuum evaporation. A 60 nm thick 2-TNATN layer was vacuum-evaporated onto an ITO / Ag / ITO glass substrate serving as the anode as a hole injection layer. A 30 nm thick HTO1 layer was vacuum-evaporated onto the hole injection layer as a hole transport layer. A 30 nm thick Ir(piq)2(acac):26DCzPPy=5:95 layer was vacuum-evaporated onto the hole transport layer as a light-emitting layer. A 30 nm thick ETO1 layer was vacuum-evaporated onto the light-emitting layer as an electron transport layer. A 1 nm thick LiF layer was vacuum-evaporated onto the electron transport layer as an electron injection layer. An 18 nm thick Mg:Ag=9:1 layer was vacuum-evaporated onto the electron injection layer as a cathode. A 65 nm thick compound 206 of this invention was vacuum-evaporated onto the cathode as a capping layer.

[0257] Comparative Examples 2-3: Compound 270 of the present invention and LiF were used to replace Compound 206 of the present invention in Comparative Example 1 as the capping material. Otherwise, the organic electroluminescent devices were prepared using the same steps as in Comparative Example 1.

[0258] Comparative Examples 4-7: Compounds CPO1, CPO2, CPO3, and CPO4 were used to replace compound 20 of the present invention in Device Example 1 as the first capping layer material. Otherwise, the organic electroluminescent device was prepared using the same steps as in Device Example 1.

[0259] A combined IVL testing system was used to test the luminous efficiency of organic light-emitting devices. The system consisted of testing software, a computer, a K2400 digital source meter manufactured by Keithley, USA, and a PR788 spectral scanning luminance meter manufactured by PhotoResearch, USA. The lifetime test was conducted using the McScience M6000 OLED lifetime test system in an atmospheric environment at room temperature.

[0260] Table 1 shows the luminescence characteristic test results of the organic electroluminescent devices prepared by the compounds prepared in the embodiments of the invention and the comparative compounds. [Table 1] Luminescence characteristic test of organic electroluminescent devices

[0261]

[0262]

[0263] The above embodiments illustrate that, compared with organic light-emitting devices with only one capping layer, organic electroluminescent devices with two capping layers have significantly improved luminous efficiency and lifetime. In addition, compared with organic electroluminescent devices using the compounds of the present invention, organic electroluminescent devices using the compounds of the present invention have significantly better efficiency and lifetime. The tertiary amine derivative of the present invention is a high-performance capping layer material.

[0264] Although this application discloses preferred embodiments as described above, it is not intended to limit the claims. Any person skilled in the art can make several possible changes and modifications without departing from the concept of this application. Therefore, the scope of protection of this application should be determined by the scope defined in the claims of this application.

Claims

1. A tertiary amine derivative, characterized in that, The tertiary amine derivative has one of the structures shown in chemical formulas 1-1 to 1-2. X is selected from O or S; R1 is independently selected from one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl; "substituted" means substituted by one or more of the following substituents: deuterium; a1 is selected from 0, 1, 2, 3 or 4; a2 is selected from 0, 1 or 2; a3 is selected from 0, 1, 2 or 3; Ar1 and Ar2 are independently selected from one of the following structures. The L1 is independently selected from a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted pyridylene group; the term "substituted" means substituted by one or more of the following substituents: deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; L2 and L3 are independently selected from one of the following structures. The R3 is independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C6 alkyl groups; the term "substituted" means substituted by one or more of the following substituents: deuterium; b1 is selected from 0, 1, 2 or 3; b2 is selected from 0, 1 or 2; b4 is selected from 0, 1, 2, 3 or 4.

2. The tertiary amine derivative according to claim 1, characterized in that, The L1 is independently selected from a single-bonded, substituted, or unsubstituted phenylene group.

3. The tertiary amine derivative according to claim 1, characterized in that, L2 and L3 are independently selected from one of the following structures. The R3 is independently selected from hydrogen and deuterium.

4. The tertiary amine derivative according to claim 1, characterized in that, Ar1 and Ar2 are independently selected from one of the following structures. 。 5. A tertiary amine derivative, characterized in that, The tertiary amine derivative is independently selected from one of the structures shown below. 。 6. An organic electroluminescent device, comprising an anode, an organic layer, a cathode, and a capping layer, characterized in that, The coating layer contains at least one of the tertiary amine derivatives according to any one of claims 1 to 5.

7. An organic electroluminescent device according to claim 6, characterized in that, The coating layer includes a first coating layer and a second coating layer, wherein the first coating layer contains at least one of the tertiary amine derivatives according to any one of claims 1 to 5, and the second coating layer contains a fluoride.

Images