A compound and its application, and an organic electroluminescent device containing the same

Abstract

The present invention relates to a novel compound and its application, and an organic electroluminescent device comprising the compound. The compound has the structure of the following formula (1): wherein: L 1 is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; Ar 1 One selected from substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups. When the compound of the present invention is used as a host material in an OLED device, it exhibits excellent device performance and stability. The present invention also protects an organic electroluminescent device using the compound of the general formula.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescence, and in particular to a novel compound and application thereof, and an organic electroluminescence device containing the compound. Background Art

[0002] In recent years, optoelectronic devices based on organic materials have become increasingly popular. The inherent flexibility of organic materials makes them very suitable for manufacturing on flexible substrates. Beautiful and cool optoelectronic products can be designed and produced according to demand, gaining unparalleled advantages over inorganic materials. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field-effect transistors, organic photovoltaic cells, organic sensors, etc. Among them, OLED has developed particularly rapidly and has achieved commercial success in the field of information display. OLED can provide highly saturated red, green, and blue colors. Full-color display devices made of OLEDs do not require additional backlight sources and have the advantages of brilliant colors, lightness, thinness, and softness.

[0003] The core of OLED devices is a thin film structure containing a variety of organic functional materials. Common functionalized organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, luminescent host materials and luminescent guest (dyes), etc. When power is turned on, electrons and holes are injected and transported to the luminescent area respectively and recombine there, thereby generating excitons and emitting light.

[0004] People have developed a variety of organic materials that can improve carrier mobility, regulate carrier balance, break through electroluminescence efficiency, and delay device attenuation. For quantum mechanical reasons, common fluorescent luminescent bodies mainly use singlet excitons generated when electrons and voids combine to emit light, and are still widely used in various OLED products. Some metal complexes, such as iridium complexes, can simultaneously use triplet excitons and singlet excitons to emit light, and are called phosphorescent luminescent bodies. Their energy conversion efficiency can be increased by up to four times that of traditional fluorescent luminescent bodies. Thermally excited delayed fluorescence (TADF) technology promotes the transformation of triplet excitons to singlet excitons. Without the use of metal complexes, triplet excitons can still be effectively utilized to achieve higher luminescence efficiency. Thermally excited sensitized fluorescence (TASF) technology uses materials with TADF properties to sensitize luminescent bodies through energy transfer, which can also achieve higher luminescence efficiency.

[0005] As OLED products gradually enter the market, people have higher and higher requirements for the performance of such products. The currently used OLED materials and device structures cannot completely solve the problems of OLED product efficiency, life span, cost, etc. Through careful thinking and continuous experiments, the researchers of the present invention have discovered an ingenious molecular design scheme, which is described in detail below. Surprisingly, the compounds disclosed in the present invention are very suitable for application in OLED and improve the performance of the device. Summary of the invention

[0006] The purpose of the present invention is to design a compound with a condensed ring and carbazole structure, and through the selection of substituents and substitution positions, ensure that the compound has a larger conjugated plane, stronger transmission ability and better film morphology, thereby obtaining a new light-emitting layer main material with good thermal stability and optical stability and good transmission performance.

[0007] The present invention provides a compound represented by the following general formula (1):

[0008]

[0009] Where: L 1 One selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0010] Ar 1 One selected from substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C3-C30 heteroaryl groups;

[0011] X 1 ~X 14 Separately, CR 1 , the R 1 is independently selected from one of hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0012] More preferably, in formula (1), L 1 For a single key.

[0013] Further preferably, in formula (1), Ar 1 One selected from a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C2-C30 electron-withdrawing heteroaryl group.

[0014] Still further preferably, the Ar 1A substituted or unsubstituted group selected from the following groups: phenyl, naphthyl, biphenyl, terphenyl, triphenylene, fluorenyl, carbazolyl, phenanthryl, dibenzofuranyl, dibenzothiophenyl, pyridyl, pyrimidinyl, triazine, quinolyl, quinazolinyl, quinoxalinyl, phenanthroline;

[0015] Further preferably, in formula (1), the X 7 and X 8 The CR 1 In, R 1 One independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 electron-donating heteroaryl group;

[0016] Still further preferably, in formula (1), the X 7 and X 8 Selected from CR 1 In, R 1 A substituted or unsubstituted group selected from the following groups: an arylamine group, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a triphenylene group, a fluorenyl group, a carbazolyl group, a phenanthryl group, a dibenzofuranyl group, and a dibenzothiophenyl group;

[0017] In the present invention, C6 to C30 in the substituted or unsubstituted C6 to C30 aryl group represents the number of carbon atoms in the group. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms in the substituent.

[0018] In the present invention, the expression of chemical elements includes the concept of isotopes with the same chemical properties. For example, the expression "hydrogen" also includes the concepts of "deuterium" and "tritium" with the same chemical properties.

[0019] The substituted or unsubstituted C6-C30 aryl group preferably has 6-20 backbone carbon atoms, and the aryl group is preferably phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene, pyrenyl, peryl, The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group is 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl. ; The fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetraphenyl group is selected from the group consisting of 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl.

[0020] As a substituted or unsubstituted C6~C30 heteroaryl group, it is preferred to have 6-20 backbone carbon atoms, and the heteroaryl group is preferably furyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazole and derivatives thereof, wherein the carbazole derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolecarbazole.

[0021] As preferred structures of the compounds involved in the present invention, the following compounds with structures represented by C1 to C306 can be cited, but are not limited to these compounds:

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036] DETAILED DESCRIPTION

[0037] The specific preparation method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the preparation method of the present invention is not limited to these synthesis examples.

[0038] Various chemicals used in the present invention, such as petroleum ether, ethyl acetate, sodium sulfate, toluene, tetrahydrofuran, dichloromethane, acetic acid, potassium phosphate, sodium tert-butoxide and other basic chemical raw materials, were purchased from Shanghai Titan Technology Co., Ltd. and Xilong Chemical Co., Ltd., and other intermediates were obtained by customization. The mass spectrometer used to determine the following compounds was a ZAB-HS mass spectrometer (manufactured by Micromass, UK).

[0039] The synthesis method of the compound of the present invention is briefly described below.

[0040] Representative synthetic routes:

[0041]

[0042] By replacing different Br-L-Ar 1 Different target compounds can be obtained.

[0043] Synthesis Example 1

[0044] Synthesis of compound C1:

[0045]

[0046] In a 500ml single-mouth bottle, add 15g (31.94mmol) of intermediate compound C, 6.2g (38.33mmol) of bromobenzene, 292.52mg (391.44umol) of tris (dibenzylideneacetone) dipalladium (i.e. Pd2(dba)3), 262.28mg (638.88umol) of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml of toluene (Toluene), 4.6g (47.92mmol) of sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen three times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C1. M / Z theoretical value: 545, M / Z measured value: 546.

[0047] Synthesis Example 2

[0048] Synthesis of compound C2

[0049]

[0050] In a 500ml single-mouth bottle, add 15g (31.94mmol) of intermediate C, 10.47g (38.33mmol) of 2-bromo-9,9-dimethylfluorene, 292.52mg (391.44umol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd2(dba)3), 262.28mg (638.88umol) of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml of toluene (Toluene), 4.6g (47.92mmol) of sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen 3 times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C2. M / Z theoretical value: 661, M / Z measured value: 662.

[0051] Synthesis Example 3

[0052] Synthesis of compound C3

[0053]

[0054] In a 500ml single-mouth bottle, add 15g (31.94mmol) of intermediate compound C, 8.94g (38.33mmol) of 4-bromobiphenyl, 292.52mg (391.44umol) of tris (dibenzylideneacetone) dipalladium (i.e. Pd2(dba)3), 262.28mg (638.88umol) of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml of toluene (Toluene), 4.6g (47.92mmol) of sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen three times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C3. M / Z theoretical value: 621, M / Z measured value: 622.

[0055] Synthesis Example 4

[0056] Synthesis of compound C21

[0057]

[0058] In a 500ml single-mouth bottle, add 15g (31.94mmol) of intermediate compound C, 12.39g (38.33mmol) of 2-(4-bromophenyl) dibenzofuran, 292.52mg (391.44umol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd2(dba)3), 262.28mg (638.88umol) of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml of toluene (Toluene), 4.6g (47.92mmol) of sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen three times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C21. M / Z theoretical value: 711, M / Z measured value: 712.

[0059] Synthesis Example 5

[0060] Synthesis of compound C38

[0061]

[0062] In a 500ml single-mouth bottle, add 15g (31.94mmol) of intermediate compound C, 12.39g (38.33mmol) of 2-bromonaphthalene, 292.52mg (391.44umol) of tris (dibenzylideneacetone) dipalladium (i.e. Pd2(dba)3), 262.28mg (638.88umol) of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml of toluene (Toluene), 4.6g (47.92mmol) of sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen three times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C38. M / Z theoretical value: 595, M / Z measured value: 596.

[0063] Synthesis Example 6

[0064] Synthesis of compound C82

[0065]

[0066] In a 500ml single-mouth bottle, add 15g (28.87mmol) of intermediate compound a, 9.46g (34.64mmol) of 2-bromo-9,9-dimethylfluorene, 264.34mg (288.67umol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd2(dba)3), 237.01mg (577.33umol) of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml of toluene (Toluene), 4.16g (43.30mmol) of sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen three times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C82. M / Z theoretical value: 711, M / Z measured value: 712.

[0067] Synthesis Example 7

[0068] Synthesis of compound C83

[0069]

[0070] In a 500ml single-mouth bottle, add 15g (28.87mmol) of intermediate compound a, 8.07g (34.64mmol) of 4-bromobiphenyl, 264.34mg (288.67umol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd2(dba)3), 237.01mg (577.33umol) of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml of toluene (Toluene), 4.16g (43.30mmol) of sodium tert-butoxide (NaOBu-t), evacuate and replace nitrogen three times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C83. M / Z theoretical value: 671, M / Z measured value: 672.

[0071] Synthesis Example 8

[0072] Synthesis of compound C90

[0073]

[0074] In a 500ml single-mouth bottle, add 15g (28.87mmol) of intermediate compound a, 8.56g (34.64mmol) of 4-bromodibenzofuran, 264.34mg (288.67umol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd2(dba)3), 237.01mg (577.33umol) of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml of toluene (Toluene), 4.16g (43.30mmol) of sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen three times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C90. M / Z theoretical value: 685, M / Z measured value: 686.

[0075] Synthesis Example 9

[0076] Synthesis of compound C121

[0077]

[0078] In a 500ml single-mouth bottle, add 16g (50mmol) intermediate compound B, 8g (50mmol) bromobenzene, 230.57mg (251.79umol) tris (dibenzylideneacetone) dipalladium (i.e. Pd2(dba)3), 206.74mg (503.58umol) 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml toluene (Toluene), 15g (150mmol) sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen 3 times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C121. M / Z theoretical value: 393, M / Z measured value: 394.

[0079] Synthesis Example 10

[0080] Synthesis of compound C215

[0081]

[0082] In a 500ml single-mouth bottle, add 16g (50mmol) of intermediate compound D, 14g (50mmol) of Z-1 and 1.7g of 60% NaH. After the addition, heat to 100°C in a nitrogen atmosphere and react for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C215. M / Z theoretical value: 548, M / Z measured value: 549.

[0083] Synthesis Example 11

[0084] Synthesis of compound C223

[0085]

[0086] In a 500ml single-mouth bottle, add 16g (50mmol) intermediate compound D, 20.5g (50mmol) Z-2, 230.57mg (251.79umol) tris (dibenzylideneacetone) dipalladium (i.e. Pd2(dba)3), 206.74mg (503.58umol) 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml toluene (Toluene), 3.63g (37.77mmol) sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen 3 times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C223. M / Z theoretical value: 648, M / Z measured value: 649.

[0087] Synthesis Example 12

[0088] Synthesis of compound C245

[0089]

[0090] In a 500ml single-mouth bottle, add 28g (50mmol) of intermediate compound E, 14g (50mmol) of Z-1 and 1.7g of 60% NaH. After the addition, heat to 100°C in a nitrogen atmosphere and react for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C245. Theoretical M / Z value: 789, M / Z measured value: 790.

[0091] Synthesis Example 13

[0092] Synthesis of compound C271

[0093]

[0094] In a 500ml single-mouth bottle, add 28g (50mmol) intermediate compound E, 19.5g (50mmol) Z-3, 230.57mg (251.79umol) tris (dibenzylideneacetone) dipalladium (i.e. Pd2(dba)3), 206.74mg (503.58umol) 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml toluene (Toluene), 3.63g (37.77mmol) sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen 3 times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C271. M / Z theoretical value: 865, M / Z measured value: 866.

[0095] Synthesis Example 14

[0096] Synthesis of compound C278

[0097]

[0098] In a 500ml single-mouth bottle, add 23.5g (50mmol) intermediate compound F, 19.5g (50mmol) Z-3, 230.57mg (251.79umol) tris (dibenzylideneacetone) dipalladium (i.e. Pd2(dba)3), 206.74mg (503.58umol) 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (i.e. sphos), 300ml toluene (Toluene), 3.63g (37.77mmol) sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen 3 times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C278. M / Z theoretical value: 776, M / Z measured value: 777.

[0099] Synthesis Example 15

[0100] Synthesis of compound C283

[0101]

[0102] In a 500ml single-mouth bottle, add 15.5g (50mmol) of intermediate compound D, 12g (50mmol) of Z-4 and 1.7g of 60% NaH. After the addition, heat to 100°C in a nitrogen atmosphere and react for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C283. M / Z theoretical value: 521, M / Z measured value: 522.

[0103] Synthesis Example 16

[0104] Synthesis of compound C301

[0105]

[0106] In a 500ml single-mouth bottle, add 16g (50mmol) intermediate compound D, 20g (50mmol) Z-5, 230.57mg (251.79umol) tris (dibenzylideneacetone) dipalladium (i.e. Pd2 (dba) 3), 206.74mg (503.58umol) 2-dicyclohexylphosphine-2', 6'-dimethoxybiphenyl (i.e. sphos), 300ml toluene (Toluene), 3.63g (37.77mmol) sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen 3 times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C301. M / Z theoretical value: 647, M / Z measured value: 648.

[0107] Synthesis Example 17

[0108] Synthesis of compound C306

[0109]

[0110] In a 500ml single-mouth bottle, add 23.5g (50mmol) intermediate compound G, 24.3g (50mmol) Z-6, 230.57mg (251.79umol) tris (dibenzylideneacetone) dipalladium (i.e. Pd2 (dba) 3), 206.74mg (503.58umol) 2-dicyclohexylphosphine-2', 6'-dimethoxybiphenyl (i.e. sphos), 300ml toluene (Toluene), 3.63g (37.77mmol) sodium tert-butoxide (NaOBu-t), vacuum and replace nitrogen 3 times, and heat the reaction to 110°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, and perform silica gel column chromatography to obtain compound C306. M / Z theoretical value: 875, M / Z measured value: 876.

[0111] Device Embodiment

[0112] OLED includes a first electrode, a second electrode, and an organic material layer between the electrodes. The organic material can be divided into multiple regions. For example, the organic material layer can include a hole transport region, a light emitting layer, and an electron transport region.

[0113] In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) may also be provided on the substrate used as a display.

[0114] The first electrode can be formed by sputtering or depositing the material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO) and any combination thereof can be used. When the first electrode is used as a cathode, a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and any combination thereof can be used.

[0115] The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, etc. The compound used as the organic material layer can be organic small molecules, organic macromolecules and polymers, and combinations thereof.

[0116] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a hole transport layer (HTL) of a single-layer structure, including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multi-layer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0117] The hole transport material and electron blocking material in the hole transport zone are selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives such as the compounds shown in HT-1 to HT-34 below; or any combination thereof.

[0118]

[0119]

[0120] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of HT-1 to HT-34, or one or more compounds of HI-1 to HI-3 described below; or one or more compounds of HT-1 to HT-34 can be doped with one or more compounds of HI-1 to HI-3 described below.

[0121]

[0122] The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a host material (Host). The light-emitting layer can be a monochrome light-emitting layer that emits a single color such as red, green, and blue. A plurality of monochrome light-emitting layers of different colors can be arranged in a plane according to a pixel pattern, or they can be stacked together to form a color light-emitting layer. When light-emitting layers of different colors are stacked together, they can be separated from each other or connected to each other. The light-emitting layer can also be a single color light-emitting layer that can simultaneously emit different colors such as red, green, and blue.

[0123] According to different technologies, the light-emitting layer material can be made of different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescent materials. In an OLED device, a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used. These different light-emitting materials classified by technology can emit light of the same color or different colors.

[0124] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The main material of the light-emitting layer is selected from, but not limited to, a combination of one or more compounds represented by formula (1) of the present invention; or selected from, but not limited to, a combination of one or more compounds represented by formula (1) of the present invention and one or more of GPH-1 to GPH-80.

[0125]

[0126]

[0127]

[0128]

[0129] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of GPD-1 to GPD-47 listed below.

[0130]

[0131]

[0132] Where D is deuterium.

[0133] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of RPD-1 to RPD-28 listed below.

[0134]

[0135] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of YPD-1 to YPD-11 listed below.

[0136]

[0137] The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0138] In one aspect of the present invention, the electron transport layer material can be selected from, but not limited to, one or more combinations of ET-1 to ET-57 listed below.

[0139]

[0140]

[0141]

[0142] The device may also include an electron injection layer located between the electron transport layer and the cathode. The electron injection layer material includes but is not limited to one or more combinations of the following: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca.

[0143] Compared with the prior art, the present invention has the following beneficial effects:

[0144] The compounds in the present invention have a specific inwardly twisted condensed ring and carbazole structure, which enables the series of compounds to obtain good triplet energy levels; secondly, the inwardly twisted structure can effectively control the crystallization properties of the material, which is extremely beneficial to the stability of the amorphous film prepared later in the device, and effectively improves the stability of the device prepared therefrom.

[0145] Example 1

[0146] The preparation process of the organic electroluminescent device in this embodiment is as follows:

[0147] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment to completely remove the water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0148] Place the glass substrate with the anode in a vacuum chamber and evacuate to a vacuum of <1×10 -5 , vacuum evaporating HI-3 on the above anode layer as a hole injection layer, the evaporation rate is 0.1nm / s, and the evaporation film thickness is 10nm;

[0149] HT-4 was vacuum-deposited on the hole injection layer as the hole transport layer of the device, with a deposition rate of 0.1 nm / s and a total deposition thickness of 80 nm.

[0150] On top of the hole transport layer, HT-14 was vacuum-deposited as the electron blocking layer of the device, with a deposition rate of 0.1 nm / s and a total deposition film thickness of 80 nm.

[0151] The light-emitting layer of the device is vacuum-evaporated on the electron blocking layer. The light-emitting layer includes a main material and a dye material. The evaporation rate of the main material C1:GPH-59 (ratio is 2:6) is adjusted to 0.1nm / s by a multi-source co-evaporation method. The evaporation rate of the dye RPD-8 is set at 3% ratio. The total film thickness of the evaporation is 30nm, and the mass ratio of the main material: dye RPD-8 is 97:3.

[0152] On the light-emitting layer, the electron transport layer material ET-46 of the device is vacuum-deposited at a ratio of 50% and ET-57 at a ratio of 50%, with a deposition rate of 0.1 nm / s and a total deposition film thickness of 30 nm;

[0153] LiF with a thickness of 0.5 nm was vacuum evaporated on the electron transport layer (ETL) as an electron injection layer, and an Al layer with a thickness of 150 nm was used as the cathode of the device.

[0154] Example 2

[0155] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 1, except that the compound C1 is replaced by the compound C2.

[0156] Example 3

[0157] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 1, except that the compound C1 is replaced by the compound C3.

[0158] Example 4

[0159] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 1, except that the compound C1 is replaced by the compound C21.

[0160] Example 5

[0161] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 1, except that compound C1 is replaced by compound C38.

[0162] Example 6

[0163] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 1, except that compound C1 is replaced by compound C82.

[0164] Example 7

[0165] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 1, except that compound C1 is replaced by compound C83.

[0166] Example 8

[0167] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 1, except that the compound C1 is replaced by the compound C90.

[0168] Example 9

[0169] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 1, except that compound C1 is replaced by compound C164.

[0170] Comparative Example 1

[0171] In this comparative example, the preparation process of the organic electroluminescent device is the same as that in Example 1, except that compound C1 is replaced by compound I(a) in the prior art as the main material, and the structure of I(a) is as follows.

[0172]

[0173] The organic electroluminescent devices prepared in Examples 1-9 and Comparative Example 1 were subjected to the following performance tests:

[0174] At the same brightness, a digital source meter and a brightness meter were used to measure the driving voltage and current efficiency of the organic electroluminescent devices prepared in Examples 1-9 and Comparative Example 1, as well as the device life. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 5000 cd / m 2 The voltage at which the light is on is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the life test of LT95 is as follows: use a brightness meter at 5000cd / m 2 At the same brightness, the current is kept constant and the brightness of the organic electroluminescent device is measured to drop to 4750cd / m 2 The time is in hours. The measurement results are shown in Table 1.

[0175] Table 1:

[0176]

[0177] It can be seen from the results in Table 1 that the turn-on voltage of the compound C121 of the present invention is greatly reduced compared with the comparative example 1, and the current efficiency and life are improved; in the present invention, other embodiments all show better turn-on voltage and life and better photoelectric performance.

[0178] Example 10

[0179] The preparation process of the organic electroluminescent device in this embodiment is as follows:

[0180] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment to completely remove the water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0181] Place the glass substrate with the anode in a vacuum chamber and evacuate to a vacuum of <1×10 -5 , vacuum evaporating HI-3 on the above anode layer as a hole injection layer, the evaporation rate is 0.1nm / s, and the evaporation film thickness is 10nm;

[0182] HT-4 was vacuum-deposited on the hole injection layer as the hole transport layer of the device, with a deposition rate of 0.1 nm / s and a total deposition thickness of 80 nm.

[0183] On top of the hole transport layer, HT-14 was vacuum-deposited as the electron blocking layer of the device, with a deposition rate of 0.1 nm / s and a total deposition film thickness of 80 nm.

[0184] The light-emitting layer of the device is vacuum-evaporated on the electron blocking layer. The light-emitting layer includes a main material and a dye material. The evaporation rate of the main material C215 is adjusted to 0.1nm / s, and the evaporation rate of the dye RPD-8 is set at 3% by using a multi-source co-evaporation method. The total evaporation film thickness is 30nm.

[0185] The electron transport layer material ET-46 of the device is vacuum-deposited on the light-emitting layer at a ratio of 50% and ET-57 at a ratio of 50%. The evaporation rate is 0.1 nm / s and the total film thickness is 30 nm.

[0186] LiF with a thickness of 0.5 nm was vacuum evaporated on the electron transport layer (ETL) as an electron injection layer, and an Al layer with a thickness of 150 nm was used as the cathode of the device.

[0187] Embodiment 11

[0188] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 10, except that compound C215 is replaced by compound C223 as the main material.

[0189] Example 12

[0190] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 10, except that compound C215 is replaced by compound C245 as the main material.

[0191] Example 13

[0192] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 10, except that compound C215 is replaced by compound C271 as the main material.

[0193] Embodiment 14

[0194] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 10, except that compound C215 is replaced by compound C278 as the main material.

[0195] Embodiment 15

[0196] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 10, except that compound C215 is replaced by compound C283 as the main material.

[0197] Example 16

[0198] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 10, except that compound C215 is replaced by compound C301 as the main material.

[0199] Embodiment 17

[0200] The preparation process of the organic electroluminescent device in this embodiment is the same as that in Embodiment 10, except that compound C215 is replaced by compound C306 as the main material.

[0201] Comparative Example 2

[0202] In this comparative example, the preparation process of the organic electroluminescent device is the same as that in Example 10, except that compound C215 is replaced by compound I(b) in the prior art as the main material, and the structure of I(b) is as follows.

[0203]

[0204] The organic electroluminescent devices prepared in Examples 10-14 and Comparative Example 2 were subjected to the following performance tests:

[0205] At the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices prepared in Examples 10-14 and Comparative Example 2, as well as the device life, were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 5000 cd / m 2 The voltage at which the light is on is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the life test of LT95 is as follows: use a brightness meter at 5000cd / m 2 At the same brightness, the current is kept constant and the brightness of the organic electroluminescent device is measured to drop to 4750cd / m 2 The time is in hours. The measurement results are shown in Table 1.

[0206] Table 2:

[0207]

[0208] It can be seen from the results in Table 2 that the compound C215 of the present invention has a lower starting voltage, better current efficiency and life compared with comparative example 2; in the present invention, other embodiments all show better turn-on voltage and life.

[0209] From the above results, it can be seen that the device prepared with the above compounds as the main material of the light-emitting layer has the characteristics of low starting voltage, high performance and long life. This may be attributed to the fact that the material designed in this patent has a better spatial stacking morphology compared with the comparative material. This stacking can not only improve the film exciton transport performance, but also obtain a more stable film morphology, which is beneficial to improving the stability of the material. In short, this type of material is a main material with good performance.

[0210] Although the present invention has been described in conjunction with the embodiments, the present invention is not limited to the above embodiments. It should be understood that under the guidance of the concept of the present invention, those skilled in the art may make various modifications and improvements. The appended claims summarize the scope of the present invention.

[0211] 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 compound of the general formula, as shown in the following formula (1): in: L 1 One selected from a single bond, a C6-C30 arylene group, and a C3-C30 heteroarylene group; Ar 1 A substituted or unsubstituted group selected from the following groups: phenyl, naphthyl, biphenyl, terphenyl, triphenylene, fluorenyl, carbazolyl, phenanthryl, dibenzofuranyl, dibenzothiophenyl, pyridyl, pyrimidinyl, triazine, quinolyl, quinazolinyl, quinoxalinyl, phenanthroline; X 1 ~X 14 CR 1 , the R 1 is independently selected from one of hydrogen, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; When the above-mentioned groups have substituents, the substituents are selected from one of C1-C10 alkyl groups, C6-C30 monocyclic aromatic hydrocarbon or condensed aromatic hydrocarbon groups, and C3-C30 monocyclic heteroaromatic hydrocarbon or condensed heteroaromatic hydrocarbon groups.

2. The compound of the general formula according to claim 1, wherein in formula (1), L 1 For a single key.

3. The compound of the general formula according to claim 1, wherein in formula (1), X 7 and X 8 The CR 1 In, R 1 Independently selected from a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C3-C30 electron-donating heteroaryl group.

4. The compound of the general formula according to claim 1, wherein in formula (1), X 7 and X 8 The CR 1 In, R 1 One selected from the following substituted or unsubstituted groups: arylamine, phenyl, naphthyl, biphenyl, terphenyl, triphenylene, fluorenyl, carbazolyl, phenanthryl, dibenzofuranyl, dibenzothiophenyl.

5. The compound of the general formula according to claim 1 is selected from the following specific structural compounds:

6. Use of the compound according to any one of claims 1 to 5 as a main material of a light-emitting layer in an organic electroluminescent device.

7. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers inserted between the first electrode and the second electrode, characterized in that: The organic layer comprises a light-emitting layer, and the light-emitting layer comprises at least one compound according to any one of claims 1 to 5.

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