Laminated organic light-emitting device

Abstract

The invention relates to the technical field of display, in particular to a laminated organic light-emitting device. The invention provides a laminated organic light-emitting device. The laminated organic light-emitting device comprises a first electrode, a first organic layer, a first light-emitting auxiliary layer, a first light-emitting layer, a connecting layer, a second light-emitting auxiliary layer, a second light-emitting layer, a third light-emitting layer, a second organic layer and a second electrode which are sequentially connected in series, wherein the first light-emitting auxiliary layer comprises a compound with a structure as shown in a formula (1); the current efficiency and the service life of the laminated organic light-emitting device can be effectively improved by arranging the specific laminated structure, particularly arranging the first light-emitting auxiliary layer and limiting the material of the first light-emitting auxiliary layer.

Description

Technical Field

[0001] The invention relates to the field of display technology, and in particular to a laminated organic electroluminescent device. Background Art

[0002] Organic electroluminescent devices (OLEDs) convert electrical energy into light by applying power to organic electroluminescent materials, and generally include an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of an organic EL device may include a hole injection layer, a hole transport layer, a hole auxiliary layer, a luminescent auxiliary layer, an electron blocking layer, a luminescent layer (containing a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. The materials used in the organic layer may be divided into hole injection materials, hole transport materials, hole auxiliary materials, luminescent auxiliary materials, electron blocking materials, luminescent materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, and the like depending on their functions. In an organic EL device, holes from the anode and electrons from the cathode are injected into the luminescent layer by applying a voltage, and excitons with high energy are generated by the recombination of holes and electrons, and light is emitted when the excitons re-transition to the ground state.

[0003] In the related art, the core of conventional stacked organic electroluminescent devices is a blue-yellow-red light-emitting structure or a blue-yellow-red-blue light-emitting structure (where blue and yellow-red refer to the blue light-emitting layer and the yellow-red light-emitting layer, respectively); however, conventional structures are prone to light emission deviations; and it is not difficult to see from conventional stacked organic electroluminescent devices that the blue light-emitting layer structure is crucial. In the related art, due to the lack of a corresponding light-emitting auxiliary layer or the selection of light-emitting auxiliary layer materials, the excitons often transfer energy to the hole transport layer in the form of carriers, and the potential barrier between the hole transport layer and the main material is too high, thereby affecting the luminescence efficiency of the device and even affecting the life of the device; therefore, how to set the structure of the stacked organic electroluminescent device and how to set the blue light-emitting auxiliary layer to match other stacked structures in the device are problems that need to be solved urgently. Summary of the invention

[0004] The purpose of the present invention is to overcome the structural defects of the stacked organic electroluminescent device in the related art and the difficulty of the blue light emitting auxiliary layer to match other stacked structural defects, which in turn cause the low current efficiency and short life of the stacked organic electroluminescent device, severely limiting the application of the stacked organic electroluminescent device, thereby providing a stacked organic electroluminescent device.

[0005] Definitions of substituent terms in this invention:

[0006] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0007] As used in the present invention, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0008] As used in the present invention, the term "C3-C30 cycloalkyl" refers to a group derived from a monocyclic hydrocarbon or a polycyclic hydrocarbon having 1 to 30 ring main chain carbon atoms, and the cycloalkane may include cyclopropyl, cyclobutyl, adamantyl, and the like.

[0009] In the present invention, aryl and arylene groups include monocyclic, polycyclic or condensed-ring aromatic groups, the rings may be interrupted by short non-aromatic units, and may contain spiro structures. Aryl groups include but are not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc., and arylene groups include but are not limited to phenylene, biphenylene, terphenylene, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc.

[0010] In the present invention, heteroaryl and heteroarylide include monocyclic, polycyclic or condensed ring heteroaryl, and the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen and sulfur. Heteroaryl includes, but is not limited to, furanyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzo thiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof; heteroarylene includes but is not limited to furanyl, phenylene thio, pyrroleyl yl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, benzofuranyl, benzothiophenylene, isobenzofuranyl, dibenzofuranyl, dibenzothiophenylene, benzimidazolyl, oxazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, acridinyl, and derivatives thereof.

[0011] As used in the present invention, the term "substituted" refers to a hydrogen atom in a compound being replaced by another substituent. The position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. When two or more substituents are present, the two or more substituents may be the same or different.

[0012] As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium and tritium.

[0013] In the present invention, the range of the number of carbon atoms is defined in the definition of the group, and the number of carbon atoms is any integer within the defined range. For example, C6-C30 aromatic group, the number of carbon atoms representing the aromatic group can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25 or 30, etc.

[0014] The scheme adopted by the present invention is as follows:

[0015] The present invention provides a stacked organic electroluminescent device, comprising a first electrode, a first organic layer, a first light-emitting auxiliary layer, a first light-emitting layer, a connecting layer, a second light-emitting auxiliary layer, a second light-emitting layer, a third light-emitting layer, a second organic layer, and a second electrode connected in series in sequence; wherein the first light-emitting auxiliary layer comprises a compound having the following structure (1):

[0016]

[0017] In formula (1), L 1 -L 3 Each is independently selected from a substituted or unsubstituted non-fused C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0018] Ar 1 -Ar 3 Each is independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C60 arylamine group, a substituted or unsubstituted C3-C60 heteroarylamine group, and a substituted or unsubstituted C3-C30 heteroaryl group;

[0019] The substituents in the substituted C6-C30 arylene group, substituted C3-C30 heteroarylene group, substituted C6-C30 aryl group, substituted C6-C60 aromatic amine group, substituted C3-C60 heteroaromatic amine group and substituted C3-C30 heteroaromatic group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl group, C3-C30 cycloalkyl group, C6-C30 aryl group, C3-C30 heteroaromatic group, C6-C60 aromatic amine group and C3-C60 heteroaromatic amine group.

[0020] Preferably, in the formula (1), L 1 -L3 Each is independently selected from a substituted or unsubstituted non-fused C6-C30 arylene group;

[0021] Wherein, the substituent in the substituted non-fused C6-C30 arylene group is selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 arylamine, and C3-C30 heteroarylamine;

[0022] Preferably, Ar 1 -Ar 3 Each is independently selected from a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group;

[0023] Wherein, the substituents in the substituted C6-C60 aryl group and the substituted C3-C30 heteroaryl group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 arylamine, and C3-C30 heteroarylamine;

[0024] Preferably, L 1 -L 3 Each independently selected from phenylene, biphenylene;

[0025] Ar 1 -Ar 3 Each is independently selected from substituted or unsubstituted C6-C18 aryl, C3-C18 heteroaryl;

[0026] Preferably, the substituents in the substituted C6-C18 aryl group and the substituted C3-C18 heteroarylamine group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 aromatic amine and C3-C30 heteroaromatic amine.

[0027] Preferably, the formula (1) is selected from one of the following structures of formula 1-1 to formula 1-10:

[0028]

[0029] Among them, Ar 1 -Ar 3 The definition of is as above.

[0030] Preferably, in the formula (1), Ar 1 -Ar 3Each is independently selected from a substituted or unsubstituted B group; the B group includes: phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthene, triphenylene, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranyl, naphthobenzofuranyl, dinaphthofuranyl, dibenzothienyl, naphthobenzothienyl, carbazolyl, phenylcarbazolyl, benzomethylcarbazolyl, dibenzocarbazolyl, phenyloxazolyl;

[0031] Wherein, the substituent of the substituted B group is selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 aromatic amine, and C3-C30 heteroaromatic amine.

[0032] Preferably, the structure of formula (1) is represented by any one of the following B-1 to B-130:

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] Preferably, the first light-emitting layer is a blue light-emitting layer;

[0040] And / or, the second light-emitting layer is a red light-emitting layer;

[0041] And / or, the third light-emitting layer is a green light-emitting layer.

[0042] Preferably, the connection layer includes an n-type charge generation layer and a p-type charge generation layer which are sequentially connected.

[0043] Preferably, the n-type charge generation layer is selected from at least one of PTCBI, PTCDA, and ET-1;

[0044] And / or, the p-type charge generation layer is selected from one or a combination of at least two of NPB, B-NPB, TPD, Spiro-TPD, NATA, 1T-NATA, 2T-NATA, BPD, TAPC, m-MTDATA, HAT-CN, TCTA, MTDAB, NDP-9, HT.

[0045] For example, it should be noted that the above materials are as follows:

[0046]

[0047]

[0048] Preferably, the first organic layer comprises a hole injection layer and a first hole transport layer connected in sequence;

[0049] and / or, the second organic layer comprises a hole blocking layer, an electron transport layer and an electron injection layer connected in sequence;

[0050] And / or, the device further includes a second hole transport layer between the connecting layer and the second light-emitting auxiliary layer.

[0051] Further preferably, the first organic layer comprises a hole injection layer, a first hole transport layer, and an electron blocking layer connected in sequence;

[0052] Preferably, the first electrode is an anode;

[0053] Preferably, the second electrode is a cathode.

[0054] Preferably, the stacked organic electroluminescent device includes an anode, a hole injection layer, a first hole transport layer, a first light-emitting auxiliary layer, a first light-emitting layer, an n-type charge generation layer, a p-type charge generation layer, a second hole transport layer, a second light-emitting auxiliary layer, a second light-emitting layer, a third light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode connected in series in sequence.

[0055] It should be noted that when manufacturing a laminated organic electroluminescent device, a transparent substrate is usually used. The present invention does not impose any special restrictions on the substrate, which is formed of conventional materials. For example, optional examples include: glass or polymer materials, wherein the polymer material can be cellulose ester, polyamide, polycarbonate, polyester, polystyrene, polyolefin, polysulfone, polyethersulfone, polyetherketone, polyetherimide, polyethylene oxide, norbornene resin, etc. When a polymer material is used, the substrate can be rigid or flexible.

[0056] In the present invention, the visible light transmittance of the substrate is at least greater than 80%, preferably greater than 86%.

[0057] The anode and cathode used in the present disclosure mean electrodes used in a stacked organic electroluminescent device.

[0058] As the anode material, it is generally preferred to use a material with a large work function so that holes can be smoothly injected into the organic material layer. Specific examples of anode materials include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline; etc., but are not limited thereto.

[0059] As the cathode material, it is generally preferred to use a material having a small work function so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; multilayer structure materials such as LiF / Al or LiO2 / Al; etc., but are not limited thereto.

[0060] Hole injection layer

[0061] If necessary, the stacked organic electroluminescent device according to the present disclosure may further include a hole injection layer on the anode.

[0062] The hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound that has the ability to transport holes, has the effect of injecting holes in the anode and has an excellent hole injection effect on the light-emitting layer or the light-emitting material, prevents the excitons generated in the light-emitting layer from moving to the electron injection layer or the electron injection material, and is excellent in the ability to form a thin film. In addition, it is preferred that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer.

[0063] Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

[0064] Hole transport layer

[0065] If necessary, the stacked organic electroluminescent device according to the present disclosure may include a hole transport layer on the anode (or on the hole injection layer if the hole injection layer is present).

[0066] The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer. The hole transport material is suitably a material having a large hole mobility that can receive injection of holes from the anode or the hole injection layer and transfer the holes to the light-emitting layer. Specific examples of the hole transport material include organic materials based on arylamine, conductive polymers, block copolymers having both conjugated and non-conjugated parts, etc., but are not limited thereto.

[0067] Light-emitting auxiliary layer

[0068] The stacked organic electroluminescent device according to the present disclosure includes a light-emitting auxiliary layer on a hole transport layer,

[0069] The light-emitting auxiliary layer improves light-emitting efficiency by enhancing hole injection characteristics and electron blocking characteristics for blocking electrons injected from the cathode to increase the recombination probability of holes and electrons, and by confining excitons generated in the light-emitting layer.

[0070] Electron blocking layer

[0071] If necessary, the stacked organic electroluminescent device according to the present disclosure includes an electron blocking layer on the light emitting auxiliary layer.

[0072] The electron blocking layer means a layer disposed between the light-emitting auxiliary layer and the light-emitting layer to prevent the electrons injected by the cathode from transferring to the light-emitting auxiliary layer without recombining in the light-emitting layer, which can also be called an electron blocking layer or an electron suppression layer. The electron blocking layer is preferably a material having a smaller electron affinity than the electron transport layer.

[0073] Luminescent layer

[0074] The light-emitting layer used in the present disclosure is a layer that can emit light in the visible light region by combining holes and electrons transmitted from the anode and the cathode. Generally, the light-emitting layer includes a host material and a dopant material, and in the present disclosure, includes a first light-emitting layer, a second light-emitting layer, and a third light-emitting layer, wherein each light-emitting layer includes a host material and a corresponding guest material, and the type of the guest material can be selected, which can be a fluorescent material or a phosphorescent material. The amount of the guest material is preferably 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, further preferably 1 to 30% by mass, further preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.

[0075] It can be understood that in the present application, the host material and the guest material in the first light-emitting layer, the second light-emitting layer, and the third light-emitting layer are all conventional materials in the prior art.

[0076] The fluorescent guest materials that can be used in the present invention may include: fused polycyclic aromatic derivatives, styrylamine derivatives, fused ring amine derivatives, boron-containing compounds, pyrrole derivatives, indole derivatives, carbazole derivatives, etc., but are not limited thereto.

[0077] Phosphorescent guest materials that can be used in the present invention may include heavy metal complexes, phosphorescent rare earth metal complexes, etc., but are not limited thereto. Heavy metal complexes include, for example, iridium complexes, platinum complexes, osmium complexes, etc.; rare earth metal complexes include, for example, terbium complexes, europium complexes, etc., but are not limited thereto.

[0078] Hole blocking layer

[0079] If necessary, the stacked organic electroluminescent device according to the present disclosure may include a hole blocking layer on the light-emitting layer. The hole blocking layer is a layer that is disposed between the electron transport layer and the light-emitting layer to prevent the holes injected by the anode from being transferred to the electron transport layer without being recombined in the light-emitting layer, and may also be referred to as a hole suppression layer or a hole blocking layer. The hole blocking layer is preferably a material with high ionization energy.

[0080] Electron transport layer

[0081] If necessary, the stacked organic electroluminescent device according to the present disclosure may include an electron transport layer on the light-emitting layer. The electron transport layer is a layer that receives electrons from the cathode or the electron injection layer formed on the cathode and transports the electrons to the light-emitting layer and inhibits the transfer of holes from the light-emitting layer, and the electron transport material is appropriately a material that can well receive the injection of electrons from the cathode and transfer the electrons to the light-emitting layer, and has a large electron mobility.

[0082] Specific examples of electron transport materials include: Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavone-metal complexes, etc., but are not limited thereto. The electron transport layer can be used together with any desired cathode material as used according to conventional techniques. In particular, suitable examples of cathode materials are typical materials with a small work function, followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

[0083] Electron injection layer

[0084] If necessary, the stacked organic electroluminescent device according to the present disclosure may further include an electron injection layer on the light-emitting layer (or on the electron transport layer if the electron transport layer exists).

[0085] The electron injection layer is a layer that injects electrons from the electrode, and is preferably a compound that has the ability to transport electrons, has the effect of injecting electrons from the cathode and the excellent effect of injecting electrons into the light-emitting layer or the light-emitting material, prevents the excitons generated by the light-emitting layer from moving to the hole injection layer, and is also excellent in the ability to form a thin film.

[0086] Specific examples of the electron injection layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, azole, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenyl methane, anthrone, etc., and derivatives thereof; metal complex compounds; nitrogen-containing 5-membered ring derivatives; etc., but are not limited thereto.

[0087] Examples of metal complex compounds include 8-hydroxyquinoline lithium, bis(8-hydroxyquinoline) zinc, bis(8-hydroxyquinoline) copper, bis(8-hydroxyquinoline) manganese, tris(8-hydroxyquinoline) aluminum, tris(2-methyl-8-hydroxyquinoline) aluminum, tris(8-hydroxyquinoline) gallium, bis(10-hydroxybenzo[h]quinoline) beryllium, bis(10-hydroxybenzo[h]quinoline) zinc, bis(2-methyl-8-quinoline) gallium chloride, bis(2-methyl-8-quinoline)(o-cresol) gallium, bis(2-methyl-8-quinoline)(1-naphthol) aluminum, bis(2-methyl-8-quinoline)(2-naphthol) gallium, and the like, but are not limited thereto.

[0088] Another aspect of the present invention provides a display device, comprising the stacked organic electroluminescent device as described above.

[0089] Beneficial effects of the present invention:

[0090] The present invention provides a stacked organic electroluminescent device, comprising a first electrode, a first organic layer, a first light-emitting auxiliary layer, a first light-emitting layer, a connecting layer, a second light-emitting auxiliary layer, a second light-emitting layer, a third light-emitting layer, a second organic layer, and a second electrode, which are sequentially connected in series; wherein the first light-emitting auxiliary layer comprises a compound having a structure as shown in formula (1); the present invention sets a specific stacked structure, especially sets a first light-emitting auxiliary layer and limits its material, so that the first light-emitting auxiliary layer and the corresponding light-emitting layer energy level are more matched, which can reduce the potential barrier between the hole transport layer and the main material, efficiently transport holes to the main material for recombination with electrons, thereby improving the matching degree with the main material; and can block electrons transmitted from the cathode direction, avoiding electrons entering the hole transport layer to cause non-radiative decay transition or entering the anode to cause leakage current, thereby improving the recombination efficiency of electrons and holes; thereby effectively improving the current efficiency and life of the stacked organic electroluminescent device.

[0091] Furthermore, in the stacked organic electroluminescent device provided by the present invention, the first light-emitting layer is a blue light-emitting layer; the second light-emitting layer is a red light-emitting layer; and the third light-emitting layer is a green light-emitting layer; the blue-red-green light-emitting structure combined with the first light-emitting auxiliary layer having a specific material can make the light emission of the stacked organic electroluminescent device relatively stable, and can emit white light with stable chromaticity. BRIEF DESCRIPTION OF THE DRAWINGS

[0092] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0093] Figure 1 It is a structural diagram of a stacked organic electroluminescent device in a device embodiment of the present invention;

[0094] Among them: 1-substrate; 2-anode; 3-hole injection layer; 4-first hole transport layer; 5-first luminescent auxiliary layer; 6-first luminescent layer; 7-n-type charge generation layer; 8-p-type charge generation layer; 9-second hole transport layer, 10-second luminescent auxiliary layer; 11-second luminescent layer; 12-third luminescent layer; 13-hole blocking layer; 14-electron transport layer; 15-electron injection layer; 16-cathode. DETAILED DESCRIPTION

[0095] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0096] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0097] Example 1

[0098] This embodiment provides a method for preparing compound B-1, comprising the following steps:

[0099]

[0100] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A1 (yield 85%).

[0101] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material A1 (1.1 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and then purify the crude product by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-1 (yield 65%).

[0102] Elemental analysis: C 48 H 33 N; Calculated value: C, 92.42; H, 5.33; N, 2.25; Found: C, 92.41; H, 5.34; N, 2.25; HRMS (ESI) m / z [M+H] + : Theoretical value: 623.80; measured value: 624.83.

[0103] Example 2

[0104] This embodiment provides a method for preparing compound B-2, comprising the following steps:

[0105]

[0106] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A2 (yield 83%).

[0107] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material A2 (1.1 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and the crude product is purified by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-2 (yield 61%).

[0108] Elemental analysis: C 52 H 33 NO2; Theoretical value: C, 88.74; H, 4.73; N, 1.99; O, 4.55; Found value: C, 88.71; H, 4.75; N, 1.99; HRMS (ESI) m / z [M+H] + : Theoretical value: 703.84; measured value: 704.89.

[0109] Example 3

[0110] This embodiment provides a method for preparing compound B-4, comprising the following steps:

[0111]

[0112] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A4 (yield 87%).

[0113] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material B (1 mmol), raw material A4 (1.1 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and then purify the crude product by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-4 (yield 70%).

[0114] Elemental analysis: C 50 H 33 NS; theoretical value: C, 88.33; H, 4.89; N, 2.06; S, 4.72; found value: C, 88.36; H, 4.88; N, 2.05; S, 4.71; HRMS (ESI) m / z [M+H] + : Theoretical value: 679.88; measured value: 680.82.

[0115] Example 4

[0116] This embodiment provides a method for preparing compound B-7, comprising the following steps:

[0117]

[0118] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A7 (yield 78%).

[0119] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material B (1 mmol), raw material A7 (1.1 mmol), tri(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and the crude product is purified by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-7 (yield 67%).

[0120] Elemental analysis: C 44 H 31 N; Calculated value: C, 92.11; H, 5.45; N, 2.44; Found: C, 92.14; H, 5.44; N, 2.42; HRMS (ESI) m / z [M+H] + : Theoretical value: 573.74; measured value: 574.78.

[0121] Example 5

[0122] This embodiment provides a method for preparing compound B-19, comprising the following steps:

[0123]

[0124] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A19 (yield 86%).

[0125] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material B (1 mmol), raw material A19 (1.1 mmol), tri(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and then purify the crude product by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-19 (yield 70%).

[0126] Elemental analysis: C 50 H 33 NO; Calculated: C, 90.47; H, 5.01; N, 2.11; O, 2.41; Found: C, 90.45; H, 5.02; N, 2.09; HRMS (ESI) m / z [M+H] + : Theoretical value: 663.82; measured value: 664.87.

[0127] Example 6

[0128] This embodiment provides a method for preparing compound B-23, comprising the following steps:

[0129]

[0130] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A23 (yield 84%).

[0131] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material B (1 mmol), raw material A23 (1.1 mmol), tri(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and then purify the crude product by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-23 (yield 63%).

[0132] Elemental analysis: C 46 H 26 D5NO; theoretical value: C, 89.29; H, 5.86; N, 2.26; O, 2.59; found value: C, 89.26; H, 5.87; N, 2.28; HRMS (ESI) m / z [M+H] + : Theoretical value: 618.79; measured value: 619.72.

[0133] Example 7

[0134] This embodiment provides a method for preparing compound B-26, comprising the following steps:

[0135]

[0136] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A26 (yield 85%).

[0137] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material B (1 mmol), raw material A26 (1.1 mmol), tri(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and then purify the crude product by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-26 (yield 67%).

[0138] Elemental analysis: C 59 H 39 N; Calculated value: C, 93.00; H, 5.16; N, 1.84; Found: C, 93.03; H, 5.15; N, 1.82; HRMS (ESI) m / z [M+H] + : Theoretical value: 761.97; measured value: 762.91.

[0139] Example 8

[0140] This embodiment provides a method for preparing compound B-43, comprising the following steps:

[0141]

[0142] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A43 (yield 81%).

[0143] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material B (1 mmol), raw material A43 (1.1 mmol), tri(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and then purify the crude product by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-43 (yield 65%).

[0144] Elemental analysis: C 54 H 37 N; Calculated value: C, 92.67; H, 5.33; N, 2.00; Found: C, 92.63; H, 5.35; N, 2.02; HRMS (ESI) m / z [M+H] + : Theoretical value: 699.90; measured value: 700.93.

[0145] Example 9

[0146] This embodiment provides a method for preparing compound B-55, comprising the following steps:

[0147]

[0148] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A55 (yield 82%).

[0149] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material B (1 mmol), raw material A55 (1.1 mmol), tri(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, raise the temperature to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and then purify the crude product by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-55 (yield 67%).

[0150] Elemental analysis: C 54 H 37 N; Calculated value: C, 92.67; H, 5.33; N, 2.00; Found: C, 92.63; H, 5.35; N, 2.02; HRMS (ESI) m / z [M+H] + : Theoretical value: 699.90; measured value: 700.93.

[0151] Example 10

[0152] This embodiment provides a method for preparing compound B-79, comprising the following steps:

[0153]

[0154] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A79 (yield 79%).

[0155] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material B (1 mmol), raw material A79 (1.1 mmol), tri(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and then purify the crude product by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-79 (yield 63%).

[0156] Elemental analysis: C 54 H 37 N; Calculated value: C, 92.67; H, 5.33; N, 2.00; Found: C, 92.63; H, 5.35; N, 2.02; HRMS (ESI) m / z [M+H] + : Theoretical value: 699.90; measured value: 700.93.

[0157] Embodiment 11

[0158] This embodiment provides a method for preparing compound B-90, comprising the following steps:

[0159]

[0160] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A90 (yield 88%).

[0161] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material B (1 mmol), raw material A90 (1.1 mmol), tri(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and then purify the crude product by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-90 (yield 71%).

[0162] Elemental analysis: C 58 H 39 NO; Calculated: C, 90.95; H, 5.13; N, 1.83; O, 2.09; Found: C, 90.91; H, 5.15; N, 1.85; HRMS (ESI) m / z [M+H] + : Theoretical value: 765.96; measured value: 766.91.

[0163] Example 12

[0164] This example provides a method for preparing compound B-103, comprising the following steps:

[0165]

[0166] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material R (1 mmol), raw material S (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate A103 (yield 81%).

[0167] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add raw material B (1 mmol), raw material A103 (1.1 mmol), tri(dibenzylideneacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), toluene (10 mL) in sequence, heat to 110 degrees Celsius and react for 5 hours. After the reaction, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and then purify the crude product by recrystallization with toluene and tetrahydrofuran twice to obtain compound B-103 (yield 66%).

[0168] Elemental analysis: C 58 H 37 NO2; Theoretical value: C, 89.32; H, 4.78; N, 1.80; O, 4.10; Found: C, 89.35; H, 4.76; N, 1.79; HRMS (ESI) m / z [M+H] + : Theoretical value: 779.94; measured value: 780.96.

[0169] Device Example 1

[0170] The present device embodiment provides a stacked organic electroluminescent device, such as Figure 1As shown, it includes a substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4, a first luminescent auxiliary layer 5, a first luminescent layer 6, an n-type charge generation layer 7, a p-type charge generation layer 8, a second hole transport layer 9, a second luminescent auxiliary layer 10, a second luminescent layer 11, a third luminescent layer 12, a hole blocking layer 13, an electron transport layer 14, an electron injection layer 15, and a cathode 16, which are sequentially stacked and arranged in series. The device structure is: an anode (indium tin oxide (ITO) coated glass substrate) a hole injection layer ( HIL) / first hole transport layer (HTL) / first light-emitting auxiliary layer (prime) / first light-emitting layer (EML-1) / n-type charge generation layer (n-CGL) / p-type charge generation layer (p-CGL) / second hole transport layer (HTL) / second light-emitting auxiliary layer (prime) / second light-emitting layer (EML-2) / third light-emitting layer (EML-3) / hole blocking layer (HBL) / electron transport layer (ETL) / electron injection layer (EIL) / thick cathode (Al).

[0171] The materials for manufacturing the stacked organic electroluminescent device are as follows:

[0172]

[0173]

[0174] The preparation of the above-mentioned stacked organic electroluminescent device comprises the following steps:

[0175] 1) Substrate cleaning:

[0176] The glass substrate coated with transparent ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10wt%, triethanolamine ≤ 1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (the volume ratio of acetone to ethanol is 1:1), baked in a clean environment until the moisture is completely removed, and then cleaned with ultraviolet light and ozone.

[0177] 2) Preparation of organic layer:

[0178] Transfer the ITO transparent substrate to the evaporation equipment and evacuate to 1×10 -6 Up to 2×10 -4Pa, sequentially depositing hole injection layer (HIL) / first hole transport layer (HTL) / first luminescent auxiliary layer (prime) / first luminescent layer (EML-1) / n-type charge generation layer (n-CGL) / p-type charge generation layer (p-CGL) / second hole transport layer (HTL) / second luminescent auxiliary layer (prime) / second luminescent layer (EML-2) / third luminescent layer (EML-3) / hole blocking layer (HBL) / electron transport layer (ETL) / electron injection layer (EIL) / thick cathode (Al) on the anode film;

[0179] in:

[0180] The materials of the hole injection layer 3 (HIL) are NDP-9 and HT, with a mass ratio of 3:97, a thickness of 10 nm, and a total evaporation rate of 0.1 nm / s;

[0181] The material of the first hole transport layer 4 (HTL) is HT, the thickness is 30 nm, and the total evaporation rate is 0.1 nm / s;

[0182] The first light-emitting auxiliary layer 5 is a compound B-1 prepared as shown in Example 1, with a thickness of 5 nm and a total evaporation rate of 0.1 nm / s;

[0183] The first light-emitting layer 6 is a blue light-emitting layer, which is vacuum-evaporated in a co-evaporation manner, and includes a host material and a guest material, wherein the host material is D, the guest material is E, the mass ratio of the host material to the guest material is 98:2, the total thickness is 20 mm, and the total evaporation rate is 0.1 nm / s;

[0184] The materials of the n-type charge generation layer 7 (CGL-n) are ET-1 and Yb, with a mass ratio of 1:1, a thickness of 30 nm, and a total evaporation rate of 0.1 nm / s;

[0185] The material of the p-type charge generation layer 8 (CGL-p) is NDP-9 and HT, with a mass ratio of 1:9, a thickness of 10 nm, and a total evaporation rate of 0.1 nm / s;

[0186] The material of the second hole transport layer 9 (HTL) is HT, the thickness is 30 nm, and the total evaporation rate is 0.1 nm / s;

[0187] The material of the second light-emitting auxiliary layer 10 is GP, the thickness is 10 mm, and the total evaporation rate is 0.1 nm / s;

[0188] The second light-emitting layer 11 is a red light-emitting layer, which is vacuum-evaporated in a co-evaporation manner, and includes a host material and a guest material, wherein the host material is CBP, the guest material is (piq)2Ir(acac), the mass ratio of the host material to the guest material is 95:5, the total thickness is 10 mm, and the total evaporation rate is 0.1 nm / s;

[0189] The third light-emitting layer 12 is a green light-emitting layer, which is vacuum-evaporated in a co-evaporation manner, and includes a host material and a guest material, wherein the host material is GH, the guest material is GD-1, the mass ratio of the host material to the guest material is 90:10, the total thickness is 20 mm, and the total evaporation rate is 0.1 nm / s;

[0190] The material of the hole blocking layer 13 (HBL) is HB-1, the thickness is 5 nm, and the total evaporation rate is 0.1 nm / s;

[0191] The material of the electron transport layer 14 (ETL) is a binary mixture of ET-1 and LiQ co-evaporated in a mass ratio of 1:1, with a thickness of 30 nm and a total evaporation rate of 0.1 nm / s;

[0192] The material of the electron injection layer 15 (EIL) is Yb, the thickness is 1 nm, and the total evaporation rate is 0.1 nm / s;

[0193] The cathode 16 is aluminum with a thickness of 100 nm and a deposition rate of 1 nm / s.

[0194] Device Example 2

[0195] The difference between the device embodiment 1 and the device embodiment 2 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-2 prepared as shown in the embodiment 2.

[0196] Device Example 3

[0197] The difference between the device embodiment 1 and the device embodiment 2 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-4 prepared as shown in the embodiment 3.

[0198] Device Example 4

[0199] The difference between the device embodiment 1 and the device embodiment 2 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-7 prepared as shown in the embodiment 4.

[0200] Device Example 5

[0201] The difference between the device embodiment 1 and the device embodiment 1 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-19 prepared as shown in the embodiment 5.

[0202] Device Example 6

[0203] The difference between the device embodiment 1 and the device embodiment 2 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-23 prepared as shown in the embodiment 6.

[0204] Device Example 7

[0205] The difference between the device embodiment 1 and the device embodiment 2 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-26 prepared as shown in the embodiment 7.

[0206] Device Example 8

[0207] The difference between the device embodiment 1 and the device embodiment 2 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-43 prepared as shown in the embodiment 8.

[0208] Device Example 9

[0209] The difference between the device embodiment 1 and the device embodiment 1 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-55 prepared as shown in the embodiment 9.

[0210] Device Example 10

[0211] The difference between the device embodiment 1 and the device embodiment 1 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-79 prepared as shown in the embodiment 10.

[0212] Device Example 11

[0213] The difference between the device embodiment 1 and the device embodiment 1 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-90 prepared as shown in the embodiment 11.

[0214] Device Example 12

[0215] The difference between the device embodiment 1 and the device embodiment 2 is that the material of the first light-emitting auxiliary layer 5 is changed to the compound B-103 prepared as shown in the embodiment 12.

[0216] Device Comparative Example 1

[0217] The device comparative example is different from the device embodiment 1 in that the first light-emitting auxiliary layer 5 is not provided.

[0218] Device Comparison Example 2

[0219] The difference between the device comparative example and the device embodiment 1 is that the material of the first light-emitting auxiliary layer 5 is changed to a compound having the following structure:

[0220]

[0221] Device Comparison Example 3

[0222] The difference between the device comparative example and the device embodiment 1 is that the material of the first light-emitting auxiliary layer 5 is changed to a compound having the following structure:

[0223]

[0224] The difference between the device comparative example and the device embodiment 1 is that the second light-emitting layer is changed to a yellow light-emitting layer, and its main structure is shown in the following structure, and the guest material is 15% Ir(ppy)3 and 1% Ir(mdq)2(acac); the material of the third light-emitting layer is changed to the material used for the second light-emitting layer in the device embodiment 1, that is, the red light-emitting layer.

[0225]

[0226] Test Case

[0227] The organic electroluminescent devices obtained from device examples 1 to 12 and comparative examples 1 to 4 in the device examples were tested.

[0228] Instruments: The current, voltage, brightness and other characteristics of the device are tested synchronously using a PR 650 spectrum scanning brightness meter and a Keithley K2400 digital source meter system;

[0229] Test conditions: Photoelectric characteristics test conditions: Current density is 10mA / cm2.

[0230] Life test: The current density is 50 mA / cm2, and the time (in hours) when the device brightness drops to 95% of the original brightness is recorded.

[0231] The device performance test results are shown in Table 1:

[0232] Table 1

[0233]

[0234]

[0235] As shown in the above table, compared with the device comparative example 1 in which the first light-emitting auxiliary layer is not added, the performance of the device structure of the present application is significantly improved. Compared with the traditional blue-yellow-red structure in the device comparative example 4, in the devices provided by the device embodiments 1 to 12 of the present application, the first light-emitting auxiliary layer is more matched with the energy level of the corresponding light-emitting layer, which can reduce the potential barrier between the hole transport layer and the main material, and efficiently transport holes to the main material to recombine with electrons, thereby improving the matching degree with the main material; and can block electrons transmitted from the cathode direction, preventing electrons from entering the hole transport layer to cause non-radiative decay transitions or entering the anode to cause leakage current, thereby improving the recombination efficiency of electrons and holes, so that the device emits white light with a purer color point, and will not be biased towards red and green;

[0236] Compared with the device comparison example 2 in which the three aromatic groups of the triarylamine group are changed to heteroaryl groups, the organic compound of the present application fixes the three aromatic groups in the triarylamine group. The fixation of the three aromatic groups makes the entire compound have a hyperconjugation effect, which can improve the hole mobility of the compound, thereby improving the device efficiency; at the same time, the compound has a certain steric hindrance, which can inhibit the intermolecular force to a certain extent, can form a better amorphous film, and improve the device life.

[0237] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A stacked organic electroluminescent device, characterized in that: It includes a first electrode, a first organic layer, a first light-emitting auxiliary layer, a first light-emitting layer, a connecting layer, a second light-emitting auxiliary layer, a second light-emitting layer, a third light-emitting layer, a second organic layer, and a second electrode connected in series in sequence; Wherein, the first light-emitting auxiliary layer comprises a compound having the following structure: In formula (1), L 1 -L 3 Each is independently selected from a substituted or unsubstituted non-fused C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; Ar 1 -Ar 3 Each is independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C60 arylamine group, a substituted or unsubstituted C3-C60 heteroarylamine group, and a substituted or unsubstituted C3-C30 heteroaryl group; The substituents in the substituted C6-C30 arylene group, substituted C3-C30 heteroarylene group, substituted C6-C30 aryl group, substituted C6-C60 aromatic amine group, substituted C3-C60 heteroaromatic amine group and substituted C3-C30 heteroaromatic group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl group, C3-C30 cycloalkyl group, C6-C30 aryl group, C3-C30 heteroaromatic group, C6-C60 aromatic amine group and C3-C60 heteroaromatic amine group.

2. The stacked organic electroluminescent device according to claim 1, characterized in that: In the formula (1), L 1 -L 3 Each is independently selected from a substituted or unsubstituted non-fused C6-C30 arylene group; Wherein, the substituent in the substituted non-fused C6-C30 arylene group is selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 arylamine, and C3-C30 heteroarylamine; Preferably, Ar 1 -Ar 3 Each is independently selected from a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group; Wherein, the substituents in the substituted C6-C60 aryl group and the substituted C3-C30 heteroaryl group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 arylamine, and C3-C30 heteroarylamine; Preferably, L 1 -L 3 Each independently selected from phenylene, biphenylene; Ar 1 -Ar 3 Each is independently selected from substituted or unsubstituted C6-C18 aryl, C3-C18 heteroaryl; Preferably, the substituents in the substituted C6-C18 aryl group and the substituted C3-C18 heteroarylamine group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 aromatic amine and C3-C30 heteroaromatic amine.

3. The stacked organic electroluminescent device according to claim 1 or 2, characterized in that: The formula (1) is selected from one of the following structures: Among them, Ar 1 -Ar 3 The definition is the same as that of claim 1.

4. The stacked organic electroluminescent device according to any one of claims 1 to 3, characterized in that: In the formula (1), Ar 1 -Ar 3 Each is independently selected from a substituted or unsubstituted B group; the B group includes: phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluoranthene, triphenylene, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranyl, naphthobenzofuranyl, dinaphthofuranyl, dibenzothienyl, naphthobenzothienyl, carbazolyl, phenylcarbazolyl, benzomethylcarbazolyl, dibenzocarbazolyl, phenyloxazolyl; Wherein, the substituent of the substituted B group is selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 aromatic amine, and C3-C30 heteroaromatic amine.

5. The stacked organic electroluminescent device according to any one of claims 1 to 3, characterized in that: The structure of formula (1) is represented by any one of the following B-1 to B-130: 。 6. The stacked organic electroluminescent device according to any one of claims 1 to 5, characterized in that: The first light-emitting layer is a blue light-emitting layer; And / or, the second light-emitting layer is a red light-emitting layer; And / or, the third light-emitting layer is a green light-emitting layer.

7. The stacked organic electroluminescent device according to any one of claims 1 to 6, characterized in that: The connection layer shown includes an n-type charge generation layer and a p-type charge generation layer which are sequentially connected.

8. The stacked organic electroluminescent device according to any one of claims 1 to 7, characterized in that: The n-type charge generation layer is selected from at least one of PTCBI, PTCDA, and ET-1; And / or, the p-type charge generation layer is selected from one or a combination of at least two of NPB, B-NPB, TPD, Spiro-TPD, NATA, 1T-NATA, 2T-NATA, BPD, TAPC, m-MTDATA, HAT-CN, TCTA, MTDAB, NDP-9, HT.

9. The stacked organic electroluminescent device according to any one of claims 1 to 8, characterized in that: The first organic layer includes a hole injection layer and a first hole transport layer connected in sequence; and / or, the second organic layer comprises a hole blocking layer, an electron transport layer and an electron injection layer connected in sequence; And / or, the stacked organic electroluminescent device further includes a second hole transport layer between the connecting layer and the second light-emitting auxiliary layer.

10. A display device comprising the stacked organic electroluminescent device according to any one of claims 1 to 9.

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