Organic electroluminescent device and use thereof

Abstract

Disclosed are an organic electroluminescent device and a use thereof. The organic electroluminescent device comprises an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode. The organic thin film layer comprises a light-emitting layer. A doped material of the light-emitting layer comprises any one or a combination of at least two of compounds represented by formula I. The organic electroluminescent device involved in the present application shows excellent performance, which is mainly reflected in the advantages of high electroluminescent efficiency, low device efficiency roll-off, good stability and the like of the device.

Description

Organic electroluminescent device and its application Technical Field

[0001] The embodiments of the present application relate to the field of organic electroluminescence technology, for example, an organic electroluminescent device and its application. Background Art

[0002] Organic optoelectronic materials (OEM) are a class of organic materials with properties such as the generation, conversion, and transmission of photons and electrons. Currently, the controllable optoelectronic properties of OEM materials have been applied to organic light-emitting diodes (OLEDs), organic solar cells (OPVs), organic field-effect transistors (OFETs), and even organic lasers. In recent years, OLEDs have become a very popular new type of flat-panel display product both domestically and internationally. OLED displays feature self-luminescence, wide viewing angles, short response times, high luminous efficiency, a wide color gamut, low operating voltage, thin panels, the ability to produce large, flexible panels, and low cost, earning them the reputation of being the star flat-panel display product of the 21st century.

[0003] The history of organic electroluminescence can be traced back to the report by Bernanose et al. in 1953 (Holst GA, Kster T, Voges E, et al. FLOX - an oxygen-flux-measuring system using a phase-modulation method to evaluate the oxygen-dependent fluorescence lifetime, Science Direct. Sensors and Actuators B: Chemical, 1995, 29, 213.). About 10 years later, in 1963, Pope et al. of New York University applied voltage to anthracene crystals and observed the fluorescence emission of anthracene (M. Pope, H. Kallmann and P. Magnante, Electroluminescence in Organic Crystals, J. Chem. Phys., 1963, 38, 2042). In 1987, CW Tang et al. from Kodak Company in the United States used ultra-thin film technology to prepare a light-emitting device with aromatic amines with good hole transport performance as the hole transport layer, an aluminum complex of 8-hydroxyquinoline as the light-emitting layer, and indium tin oxide (ITO) thin film and metal alloy as the anode and cathode respectively. The device achieved a brightness of up to 1000 cd / m at a driving voltage of 10V. 2Green light emission was achieved with a device efficiency of 1.5 lm / W (CW Tang and SAVan Slyke, Organic electroluminescent diodes, Appl. Phys. Lett., 1987, 51, 913). This breakthrough led to a rapid and in-depth development of organic electroluminescence research worldwide. In 1990, Burroughes et al. at the University of Cambridge proposed the first light-emitting diode based on a polymer (PPV). They showed that PPV could be used as a highly fluorescent emitting material in a single-layer device, with a high luminous efficiency (Burroughes JH et al., Light-emitting diodes based on conjugated polymers, Nature, 1990, 347, 539). In 1998, Baldo and Forrest et al. from Princeton University reported the first electroluminescent phosphorescent device, which in principle can have an internal quantum yield of 100% (MA Baldo, DFO' Brienetal., Highly efficient phosphorescent emission from organic electroluminescent devices, Nature, 1998, 395, 151). However, on the one hand, phosphorescent materials generally use precious metals such as iridium and platinum, which are expensive. On the other hand, for deep blue light phosphorescent materials, there are still problems such as chemical instability and large efficiency roll-off of the device at high current density. Therefore, it is extremely important to develop an OLED device that uses inexpensive and stable organic small molecule materials and can achieve high-efficiency light emission.

[0004] In 2012, the Adachi research group at Kyushu University reported highly efficient all-fluorescent OLED devices based on the thermally activated delayed fluorescence (TADF) mechanism (Uoyama H, Goushi K, Shizu K, et al. Highly efficient organic light-emitting diodes from delayed fluorescence, Nature, 2012, 492(7428): 234-238.). When the energy difference between the Sl and T1 levels of a molecule is sufficiently small, triplet excitons can absorb thermal energy, return to the singlet state through a RISC process, and then emit fluorescence. The device's internal quantum efficiency (IQE) can theoretically reach 100%, and its external quantum efficiency (EQE) can even reach 30%, comparable to that of phosphorescent devices. Research on TADF materials, as next-generation luminescent materials, is rapidly developing.

[0005] TADF molecules are mainly doped as guest materials in wide bandgap host materials to achieve highly efficient thermally activated delayed fluorescence (Q. Zhang, J. Li, K. Shizu, et al. Design of Efficient Thermally Activated Delayed Fluorescence Materials for Pure Blue Organic Light Emitting Diodes, J. Am. Chem. Soc. 2012, 134, 14706; H. Uoyama, K. Goushi, K. Shizu, H. Nomura, C. Adachi, Highly efficient organic light-emitting diodes from delayed fluorescence, Nature, 2012, 492, 234; T. Nishimoto, T. Yasuda, et al., A six-carbazole-decorated cyclophosphazene as a host with high triplet energy to realize efficient delayed-fluorescence OLEDs, Mater. Horiz., 2014, 1, 264). Different from the localized (LE) state luminescence of traditional fluorescent molecules, TADF luminescent materials undergo a reverse intersystem crossing process from the triplet excited state to the singlet excited state during the luminescence process. Therefore, the delayed fluorescence excited state lifetime of TADF luminescent materials is long. This excited state characteristic often leads to a serious efficiency roll-off of TADF electroluminescent devices, that is, the device shows a high electroluminescent efficiency at low brightness, and the device brightness exceeds 100 cd / m 2 The efficiency will drop rapidly, especially when the device brightness exceeds 1000cd / m 2 The efficiency will decrease faster.

[0006] Therefore, it is desired in the art to develop an electroluminescent device with high luminous efficiency at high brightness and a long lifespan.

[0007] Summary of the Invention

[0008] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0009] The embodiments of the present application provide an organic electroluminescent device and its application.

[0010] In one aspect, an embodiment of the present application provides an organic electroluminescent device, comprising an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode, wherein the organic thin film layer comprises a light-emitting layer, and a dopant material of the light-emitting layer comprises any one or a combination of at least two of the compounds represented by Formula I:

[0011] where R 1 and R 2 are independently hydrogen, deuterium, C1-C 16 Alkyl, C1~C 16 Alkoxy, C3-C 18 Cycloalkyl, C6~C 24 Aryl, C6~C 24 Heteroaryl, one or more R a Substituted C6~C 18 aryl;

[0012] R a Each time it appears, it is independently C1~C 12 Alkyl, C1~C 12 Alkoxy, C3-C 12 Cycloalkyl, C6~C 18 Aryl, one or more R b Substituted C6~C 18 aryl;

[0013] R b Each time it appears, it is independently C1~C 12 Alkyl, C1~C 12 Alkoxy, C3-C 12 Cycloalkyl, C6~C 18 Aryl.

[0014] R 3 and R 4 Independently C1~C 12 Alkyl, C1~C 12 Alkoxy, C3-C 12 Cycloalkyl, C6~C 18 Aryl, C6~C 18 Heteroaryl.

[0015] Preferably, the R 1 and R 2 Independently selected from hydrogen, methyl, ethyl, Phenyl, 3,5-dimethylphenyl, 2-methyl-phenyl, 4-methyl-phenyl, 3-methyl-phenyl, The wavy line represents the attachment site of the group.

[0016] Preferably, the R 3 and R4 independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, biphenyl, 3,5-dimethylphenyl, pyridyl, In any of the above, the wavy line represents the attachment site of the group.

[0017] Preferably, the doping material of the light-emitting layer includes any one or a combination of at least two of the following compounds BN-1 to BN-633:

[0018] Preferably, the light-emitting layer further comprises a host material, and the host material comprises any one or a combination of at least two of the carbazole or carbidine compounds represented by the following formulas (H-1) to (H-6):

[0019] wherein X1, Y1 and Z1 are CH or N, and at most one of X1, Y1 and Z1 is N;

[0020] where R 1H and R 2H Independently any of the following groups:

[0021] wherein X1, Y1 and Z1 are CH or N, and at most one of X1, Y1 and Z1 is N;

[0022] where R aH and R bH are independently H, C1-C20 Alkyl, C1-C 20 Alkoxy, C6-C 20 Aryl, C1-C 20 Alkyl-substituted C6-C 20 Aryl or C1-C 20 Alkoxy-substituted C6-C 20 Aryl group, * represents the attachment site of the group.

[0023] Preferably, the weight percentage of the doping material in the light-emitting layer is 0.3-30.0wt% (for example, 0.3wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt% or 30wt%), and the weight percentage of the main material is 99.7-70.0wt% (for example, 99.7wt%, 98wt%, 95wt%, 90wt%, 85wt%, 80wt%, 75wt% or 70wt%).

[0024] Preferably, the light-emitting layer contains 0.3-30.0 wt% (for example, 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%) of any one of the compounds shown in Formula I as a doping material, and the remaining 99.7-70.0 wt% (for example, 99.7 wt%, 98 wt%, 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt% or 70 wt%) of the components are main materials composed of 1-2 compounds having structures of Formula (H-1) to Formula (H-6).

[0025] Preferably, the light-emitting layer contains 0.3-30.0 wt% (for example, 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%) of any one of compounds BN-1 to BN-633 as a doping material, and the remaining 99.7-70.0 wt% (for example, 99.7 wt%, 98 wt%, 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt% or 70 wt%) of the components are main materials composed of 1-2 compounds having structures of formula (H-1) to (H-6).

[0026] Preferably, the main material contains two compounds having structures of formula (H-1) to formula (H-6), and the weight ratio of the two compounds is 1:5 to 5:1; for example, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, etc.

[0027] Preferably, the host material in the light-emitting layer is any one or a combination of at least two of compounds H1-1 to H1-427:

[0028] Preferably, the host material of the light-emitting layer is one or two of compounds H1-1 to H1-427.

[0029] Preferably, the light-emitting layer contains 0.3-30.0 wt% (for example, 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%) of any one of the compounds shown in Formula I as a doping material, and the remaining 99.7-70.0 wt% (for example, 99.7 wt%, 98 wt%, 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt% or 70 wt%) of the component is a main material composed of one or two compounds of compounds H1-1 to H1-427.

[0030] Preferably, the light-emitting layer contains 0.3-30.0 wt% (for example, 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%) of any one of compounds BN-1 to BN-633 as a doping material, and the remaining 99.7-70.0 wt% (for example, 99.7 wt%, 98 wt%, 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt% or 70 wt%) of the component is a main material composed of one or two compounds of compounds H1-1 to H1-427.

[0031] Preferably, the light-emitting layer further comprises an IrPPy3 phosphorescent material as a sensitizer.

[0032] Preferably, the light-emitting layer contains 0.3-10.0 wt% (e.g., 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt% or 10 wt%) of any one of the compounds shown in Formula I as a doping material, 94.7-65.0 wt% (e.g., 93 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt% or 65 wt%) of a host material consisting of one or two of the carbazole or carbidine compounds shown in Formula (H-1) to Formula (H-6), and 5.0-25.0 wt% (e.g., 8 wt%, 10 wt%, 15 wt%, 20 wt% or 25 wt%) of IrPPy3 as a sensitizer.

[0033] Preferably, the light-emitting layer contains 0.3-10.0 wt% (e.g., 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt% or 10 wt%) of any one of compounds BN-1 to BN-633 as a doping material, 94.7-65.0 wt% (e.g., 93 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt% or 65 wt%) of a host material consisting of one or two of the carbazole or carbidine compounds represented by formula (H-1) to formula (H-6), and 5.0-25.0 wt% (e.g., 8 wt%, 10 wt%, 15 wt%, 20 wt% or 25 wt%) of IrPPy3 as a sensitizer.

[0034] Preferably, the light-emitting layer contains 0.3-10.0 wt% of any one of compounds BN-1 to BN-633 as a doping material, 94.7-65.0 wt% of a host material consisting of one or two of compounds H1-1 to H1-427, and 5.0-25.0 wt% of IrPPy3 as a sensitizer.

[0035] Preferably, the host material in the light-emitting layer is any one or a combination of at least two of the compounds having the structure represented by formula Trz1-A, formula Trz2-A, formula Trz3-A, formula Trz4-A, formula Trz5-A or formula Trz6-A:

[0036] where R 1a 、R 1b 、R 2a 、R 2b 、R 3a and R 3b One or two of them are independently R Tz , the rest are the same or different and are independently hydrogen, deuterium, C1-C8 alkyl, C1-C8 alkoxy, C6-C 18 Aryl, C1-C8 alkyl substituted C6-C 18C6-C8 substituted aryl or C1-C8 alkoxy 18 Aryl; R Tz is any one of the substituent groups shown below:

[0037] The asterisk represents the attachment site of the group.

[0038] Preferably, the doping material in the light-emitting layer is any one of the compounds shown in Formula I, and the host material is any one of the compounds shown in Formulas TRZ-1 to TRZ-82:

[0039] Preferably, the doping material in the light-emitting layer is any one of the compounds represented by formulas BN-1 to BN-633, and the host material is any one of the compounds represented by formulas TRZ-1 to TRZ-82.

[0040] Preferably, the light-emitting layer contains 0.3-30.0 wt% (for example, 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%) of any one of the light-emitting compounds shown in Formula I, and the remaining 99.7-70.0 wt% (for example, 99.7 wt%, 98 wt%, 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt% or 70 wt%) of the component is any one of compounds TRZ-1 to TRZ-82.

[0041] Preferably, the light-emitting layer contains 0.3-30.0 wt% (e.g., 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%) of any one of compounds BN-1 to BN-633 as a doping material, and 99.7-70.0 wt% (e.g., 99.7 wt%, 98 wt%, 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt% or 70 wt%) of any one of compounds TRZ-1 to TRZ-82 as a host material.

[0042] Preferably, the doping material in the light-emitting layer is any one of the compounds represented by Formula I; the main material is any one of the compounds represented by Formula Trz1-A, Formula Trz2-A, Formula Trz3-A, Formula Trz4-A, Formula Trz5-A or Formula Trz6-A, and the sensitizer is IrPPy3 phosphorescent material.

[0043] Preferably, the doping material in the light-emitting layer is any one of the compounds represented by Formula I; the host material is any one of the compounds represented by Formula TRZ-1 to Formula TRZ-82, and the sensitizer is an IrPPy3 phosphorescent material.

[0044] Preferably, the light-emitting layer contains 0.3-10.0 wt% (e.g., 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt% or 10 wt%) of any one of the compounds represented by Formula I as a doping material, 94.7-65.0 wt% (e.g., 94 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt% or 65 wt%) of a host material composed of any one of the compounds having a structure represented by Formula Trz1-A, Formula Trz2-A, Formula Trz3-A, Formula Trz4-A, Formula Trz5-A or Formula Trz6-A, and 5.0%-25.0% (e.g., 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt% or 25 wt%) of IrPPy3 as a sensitizer.

[0045] Preferably, the light-emitting layer contains 0.3-10.0 wt% (e.g., 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt% or 10 wt%) of any one of compounds BN-1 to BN-633 as a doping material, 94.7-65.0 wt% (e.g., 94 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt% or 65 wt%) of a main material composed of any one of the compounds having a structure represented by formula Trz1-A, formula Trz2-A, formula Trz3-A, formula Trz4-A, formula Trz5-A or formula Trz6-A, and 5.0%-25.0% (e.g., 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt% or 25 wt%) of IrPPy3 as a sensitizer.

[0046] Preferably, the light-emitting layer contains 0.3-10.0 wt% (e.g., 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt% or 10 wt%) of any one of the compounds shown in Formula I as a doping material, 94.7-65.0 wt% (e.g., 94 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt% or 65 wt%) of a host material composed of any one of the compounds having the structures of Formulas TRZ-1 to TRZ-82, and 5.0%-25.0% (e.g., 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt% or 25 wt%) of IrPPy3 as a sensitizer.

[0047] Preferably, the light-emitting layer contains 0.3-10.0 wt% (e.g., 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt% or 10 wt%) of any one of compounds BN-1 to BN-462 as a doping material, 94.7-65.0 wt% (e.g., 94 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt% or 65 wt%) of a host material composed of any one of compounds having structures of formula TRZ-1 to TRZ-82, and 5.0%-25.0% (e.g., 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt% or 25 wt%) of IrPPy3 as a sensitizer.

[0048] Preferably, the main material in the light-emitting layer is composed of any one of the compounds represented by formula (H-1) to formula (H-6) and any one of the compounds having the structure represented by formula Trz1-A, formula Trz2-A, formula Trz3-A, formula Trz4-A, formula Trz5-A or formula Trz6-A.

[0049] Preferably, the doping material in the light-emitting layer is any one of the compounds shown in Formula I; the host material is composed of one of compounds H1-1 to H1-427 and any one of the compounds shown in Formulas TRZ-1 to TRZ-82.

[0050] Preferably, the light-emitting layer contains 0.3-10.0 wt% (e.g., 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt% or 10 wt%) of any one of the compounds represented by Formula I as a doping material, 99.7-90.0 wt% (e.g., 99.7 wt%, 98 wt%, 95 wt% or 90 wt%) of one of the compounds H1-1 to H1-427 and a host material composed of any one of the compounds represented by Formulas TRZ-1 to TRZ-82. Preferably, the weight ratio of the two components in the host material is 1:9 to 9:1, for example, 1:9, 1:8, 1:6, 1:5, 1:3, 1:1, 2:1, 4:1, 5:1, 7:1, 8:1 or 9:1.

[0051] Preferably, the light-emitting layer contains 0.3-10.0 wt% (e.g., 0.3 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt% or 10 wt%) of any one of compounds BN-1 to BN-633 as a doping material, 99.7-90.0 wt% (e.g., 99.7 wt%, 98 wt%, 95 wt% or 90 wt%) of one of compounds H1-1 to H1-427 and a host material composed of any one of the compounds represented by formulas TRZ-1 to TRZ-82; preferably, the weight ratio of the two components in the host material is 1:9 to 9:1, for example, 1:9, 1:8, 1:6, 1:5, 1:3, 1:1, 2:1, 4:1, 5:1, 7:1, 8:1 or 9:1.

[0052] In the present application, the organic thin film layer in the organic electroluminescent device further includes at least one layer of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0053] In the present application, the organic electroluminescent device is composed of any of the following stacked structures, but is not limited thereto:

[0054] (1) Anode / HTL / Emitting Layer / Cathode

[0055] (2) Anode / HOL injection layer / HOL transport layer / Emitting layer / Cathode

[0056] (3) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / cathode

[0057] (4) Anode / HTL / Luminescent Layer / Electron Transport Layer / Cathode

[0058] (5) Anode / HTL / Luminescent Layer / Electron Transport Layer / Electron Injection Layer / Cathode

[0059] (6) Anode / HOL injection layer / HOL transport layer / Luminescent layer / Electron transport layer / Cathode

[0060] (7) Anode / Hole Injection Layer / Hole Transport Layer / Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode

[0061] (8) Anode / Hole Injection Layer / Hole Transport Layer / Electron Blocking Layer / Emitting Layer / Electron Transport Layer / Cathode

[0062] (9) Anode / HOL injection layer / HOL transport layer / Electron blocking layer / Emission layer / Electron transport layer / Electron injection layer / Cathode

[0063] (10) Anode / hole transport layer / electron blocking layer / light-emitting layer / electron transport layer / cathode

[0064] (11) Anode / HTL / Electron Blocking Layer / Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode

[0065] (12) Anode / HTL / Emitting layer / HTL / Electron transport layer / Cathode

[0066] (13) Anode / HTL / Emitting Layer / HTL / Electron Transport Layer / Electron Injection Layer / Cathode

[0067] (14) Anode / hole injection layer / hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

[0068] (15) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0069] On the other hand, an embodiment of the present application provides a use of the organic electroluminescent device as described above in an organic electroluminescent display or an organic electroluminescent lighting source.

[0070] Terminology

[0071] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0072] As used herein, the terms "comprising" or "including" may be open, semi-closed, or closed. In other words, the terms also include "consisting essentially of" or "consisting of."

[0073] The section headings used in this specification are for organizational purposes only and should not be construed as limitations on the subject matter described. All documents or portions of documents cited in this application, including but not limited to patents, patent applications, articles, books, manuals, and papers, are incorporated herein by reference in their entirety.

[0074] Unless otherwise specified, all technical and scientific terms used herein have the standard meanings in the art to which the claimed subject matter belongs. If there are multiple definitions for a term, the definition herein shall prevail.

[0075] It should be understood that singular forms used in this application, such as "a", include plural references unless otherwise specified. In addition, the term "comprising" is an open limitation rather than a closed limitation, that is, it includes the content specified in this application, but does not exclude other aspects.

[0076] Unless otherwise stated, this application adopts traditional methods of mass spectrometry and elemental analysis, and each step and condition can refer to conventional operating steps and conditions in the art.

[0077] Unless otherwise indicated, this application employs standard nomenclature and standard laboratory procedures and techniques in analytical chemistry, synthetic organic chemistry, and optics. In some cases, standard techniques are used for chemical syntheses, chemical analyses, and light-emitting device performance testing.

[0078] In this application, unless otherwise specified, the number of "substituted" can be one or more; when "plural," it means two or more, for example, 2, 3, or 4. Furthermore, when the number of "substituted" is multiple, the "substituted" can be the same or different. In this application, the position of "substituted" can be any position unless otherwise specified.

[0079] Without violating the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present application.

[0080] The reagents and raw materials used in this application are commercially available.

[0081] Compared with the related art, the embodiments of the present application have the following beneficial effects:

[0082] The organic electroluminescent devices involved in the embodiments of the present application show excellent performance, which is mainly reflected in the advantages of high electroluminescent efficiency, small device efficiency roll-off, and good stability.

[0083] Still other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] The accompanying drawings are used to provide a further understanding of the technical solution of this article and constitute a part of the specification. Together with the embodiments of this application, they are used to explain the technical solution of this article and do not constitute a limitation on the technical solution of this article.

[0085] Figure 1 is a schematic structural diagram of a vacuum-evaporated organic electroluminescent device provided in an embodiment of the present application, wherein 1 is an ITO anode, 2 is a hole transport layer 1, 3 is a hole transport layer 2, 4 is a light-emitting layer, 5 is an electron transport layer, 6 is an electron injection layer, and 7 is a metal cathode.

[0086] FIG2 is an electroluminescence spectrum diagram of the electroluminescent device in device examples 1-2 provided in this application.

[0087] FIG3 is an electroluminescence spectrum diagram of the electroluminescent devices in device examples 1-9 provided in this application.

[0088] FIG4 is an electroluminescence spectrum diagram of the electroluminescent device in device examples 1-20 provided in this application. DETAILED DESCRIPTION

[0089] The technical solution of the present application is further described below through specific implementation methods. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0090] Compound Preparation Examples

[0091] Preparation of raw materials

[0092] The synthesis of the compounds described in this application has a unified raw material: 1-bromo-3-chloro-2,4,5-trifluoroiodobenzene, and the specific synthesis method is as follows:

[0093] 1-Bromo-3-chloro-2,4,5-trifluorobenzene (24.5 g, 0.1 mol) was dissolved in 1.0 L of tetrahydrofuran and added dropwise at -60°C under nitrogen. LDA solution (55.0 mL, 2 M) was then added dropwise. After 1 hour, 27.9 g (0.11 mol) of iodine in 200 mL of tetrahydrofuran was added dropwise. The mixture was slowly warmed to room temperature and stirred overnight. The mixture was washed with sodium thiosulfate solution and dichloromethane. The organic phase was concentrated and purified by column chromatography (eluent: petroleum ether) to obtain 30.8 g of a brown oil with an 83.0% yield. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 371.70 [M]+ (calcd: 371.78). Elemental analysis calculated values: C, 19.41; Br, 21.52; Cl, ​​9.55; F, 15.35; I, 34.18. Found value: C, 19.45.

[0094] The specific synthetic route of compound BN-245 described in this application is as follows:

[0095] The BN-245 synthesis process is described as follows:

[0096] Synthesis and Characterization of Compound BN-3-A: 1-Bromo-3-chloro-2,4,5-trifluoroiodobenzene (1.86 g, 5.00 mmol), phenylboronic acid (1.34 g, 11.00 mmol), and potassium carbonate (2.28 g, 16.50 mmol) were dissolved in a mixture of THF and water (32 mL:8 mL). Pd(PPh3)4 (0.29 g, 0.25 mmol) was added under nitrogen, and the mixture was heated under reflux with stirring for 12 hours. After completion of the reaction, the mixture was washed with dichloromethane and water. The organic phase was concentrated and purified by column chromatography to obtain 1.22 g of a white solid (Compound BN-245-A) in a yield of 76.6%. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 318.03 [M] + (calculated: 318.04). Elemental analysis calculated for C, 67.83; H, 3.16; Cl: 11.12; F, 17.88. Found: C, 67.93; H, 3.15.

[0097] Synthesis and Characterization of Compound BN-245-B: Compound BN-3-A (1.59 g, 5.00 mmol), 3,6-di-tert-butylcarbazole (4.61 g, 16.50 mmol), and cesium carbonate (6.52 g, 20.00 mmol) were dissolved in 50.0 mL of DMF and incubated at 120°C under nitrogen for 8 hours. After the reaction was completed, the system was returned to room temperature and the reaction solution was poured into ice water. After filtration, the filter cake was recrystallized from dichloromethane / ethanol to obtain 5.02 g of a white solid (compound BN-245-B) in a yield of 91.5%. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 1095.65 [M] + (calculated: 1095.62). Elemental analysis calculated for C, 85.40; H, 7.53; Cl: 3.23; N, 3.83. Found: C, 85.50; H, 7.35; N, 3.87.

[0098] Synthesis and Characterization of Compound BN-245: Compound BN-245-B (5.04 g, 4.59 mmol) was dissolved in 50 mL of tert-butylbenzene. Tert-butyllithium (4.6 mL, 1.2 M) was added dropwise at 0°C under nitrogen. The temperature was raised to 70°C and maintained for 2 hours. BBr3 (2.30 g, 9.18 mmol) was then added dropwise at 0°C. The mixture was slowly returned to room temperature and stirred for 1 hour. DIEA (1.18 g, 9.18 mmol) was then added dropwise at 0°C. The reaction system was heated to 120°C and maintained for 6 hours. After completion of the reaction, the reaction was quenched with 10 mL of methanol and washed with dichloromethane and water. The organic phase was concentrated and purified by column chromatography to obtain 1.22 g of a yellow solid (compound BN-409) in a 24.8% yield. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 1069.69 [M] + (calculated: 1069.64). Elemental analysis calculated for C, 87.53; H, 7.53; B, 1.01 N, 3.93. Found: C, 87.51; H, 7.53; N, 3.95.

[0099] The specific synthetic route of the compound BN-409 described in this application is as follows:

[0100] The BN-409 synthesis process is described as follows:

[0101] Synthesis and Characterization of Compound BN-409-A: 1-Bromo-3-chloro-2,4,5-trifluoroiodobenzene (2.97 g, 8.00 mmol), 3,5-dimethylphenylboronic acid (1.44 g, 9.60 mmol), and potassium carbonate (1.66 g, 12.00 mmol) were dissolved in a mixture of 24 mL of toluene and 6 mL of water. Pd(PPh3)4 (0.46 g, 0.40 mmol) was added under nitrogen, and the mixture was heated under reflux for 12 hours. After completion of the reaction, the mixture was washed with dichloromethane / water, and the organic phase was concentrated and purified by column chromatography to obtain 2.95 g of a white solid (Compound BN-409-A) in a yield of 92.7%. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 350.02 [M] + (calculated: 349.95). Elemental analysis calculated for C, 48.10; H, 2.60; Br, 22.85; Cl: 10.14; F, 16.30. Found: C, 48.13; H, 2.65.

[0102] Synthesis and Characterization of Compound BN-409-B: Compound BN-522-A (1.75 g, 5.00 mmol), phenylboronic acid (0.73 g, 6.00 mmol), and potassium carbonate (1.04 g, 7.50 mmol) were dissolved in a mixture of 20 mL of toluene and 5 mL of water. Pd(PPh3)4 (0.46 g, 0.40 mmol) was added under nitrogen, and the mixture was heated under reflux for 12 hours. After completion of the reaction, the mixture was washed with dichloromethane / water, and the organic phase was concentrated and purified by column chromatography to obtain 1.66 g of a white solid (compound BN-409-B) in a yield of 96.0%. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 346.08 [M] + (calculated: 346.07). Elemental analysis calculated for C, 69.27; H, 4.07; Cl: 10.22; F, 16.44. Found: C, 69.23; H, 4.05.

[0103] Synthesis and Characterization of Compound BN-409-C: Compound BN-409-B (1.73 g, 5.00 mmol), 3,6-diphenylcarbazole (1.76 g, 5.50 mmol), and cesium carbonate (2.44 g, 7.50 mmol) were dissolved in 50.0 mL of DMF and incubated at 120°C under nitrogen for 6 hours. After completion of the reaction, the mixture was washed with dichloromethane / water. The organic phase was concentrated and purified by column chromatography to yield 2.20 g of a white solid (compound BN-409-C) in a 68.1% yield. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 645.24 [M]+ (calculated: 645.20). Elemental analysis calculated for C, 81.79; H, 4.68; Cl: 5.49; F, 5.88; N, 2.17. Found: C, 81.73; H, 4.65; N, 2.18.

[0104] Synthesis and Characterization of Compound BN-409-D: Compound BN-409-C (1.94 g, 3.00 mmol), 3,6-di-tert-butylcarbazole (1.84 g, 6.60 mmol), and cesium carbonate (3.22 g, 9.90 mmol) were dissolved in 50.0 mL of DMF and incubated at 120°C under nitrogen for 12 hours. After completion of the reaction, the reaction system was cooled to room temperature and poured into 200.0 mL of ice water. The precipitated solid was filtered under reduced pressure, and the filter cake was recrystallized from dichloromethane / ethanol to obtain 3.27 g of a white solid (Compound BN-409-D) in a 93.6% yield. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 1163.54 [M] + (calculated: 1163.59). Elemental analysis calculated for C, 86.60; H, 6.75; Cl: 3.04; N, 3.61. Found: C, 86.73; H, 6.75; N, 3.58.

[0105] Synthesis and Characterization of Compound BN-409: The synthesis of Compound BN-409 was similar to that of Compound BN-245, except that Compound BN-409-D (5.35 g, 4.59 mmol) was used instead of Compound BN-245-C. The remaining raw material amounts and synthetic procedures were the same. After final column chromatography, 1.57 g of a yellow solid (Compound BN-409) was obtained in a 30.0% yield. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 1138.65 [M]+ (calcd: 1138.62). Elemental analysis calculated: C, 88.63; H, 6.73; B: 0.95; N, 3.69. Found: C, 88.65; H, 6.74; N, 3.65.

[0106] The specific synthetic route of the compound BN-609 described in this application is as follows:

[0107] The synthesis process of BN-609 is described as follows:

[0108] Synthesis and Characterization of Compound BN-609-A: The synthesis of Compound BN-609-A was similar to that of Compound BN-409-A, except that phenylboronic acid (1.17 g, 9.60 mmol) was used instead of 3,5-dimethylphenylboronic acid. The amounts of other reactants and reaction conditions were the same. Column chromatography yielded 1.49 g of a white solid (Compound BN-609-A) in 92.7% yield. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 321.95 [M]+ (calcd: 321.92). Elemental analysis: Calcd: C, 44.83; H, 1.57; Br, 24.85; Cl: 11.03; F, 17.73. Found: C, 44.83; H, 1.55.

[0109] Synthesis and Characterization of Compound BN-609-B: The synthesis of Compound BN-609-B was similar to that of Compound BN-409-B, except that Compound BN-609-A (1.61 g, 5.00 mmol) and 3,5-diphenylphenylboronic acid (1.64 g, 6.00 mmol) were used in place of Compound BN-409-A. The amounts of other reactants and reaction conditions were the same. Column chromatography yielded 2.08 g of a white solid (Compound BN-609-B) in 88.5% yield. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 470.08 [M]+ (calcd: 470.10). Elemental analysis: Calcd: C, 76.52; H, 3.85; Cl: 7.53; F, 12.10. Found: C, 76.53; H, 3.85.

[0110] Synthesis and Characterization of Compound BN-609-C: The synthesis of Compound BN-609-C was similar to that of Compound BN-409-C, except that Compound BN-609-B (2.35 g, 5.00 mmol) was used instead of Compound BN-409-B, and Compound 3,6-bis(4-tert-butylphenyl)carbazole (2.37 g, 5.5 mmol) was used instead of Compound 3,6-diphenylcarbazole. The amounts of other reactants and reaction conditions were the same. After column chromatography, 3.10 g of a white solid (Compound BN-609-C) was obtained in a 70.3% yield. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 881.34 [M]+ (calculated: 881.36). Elemental analysis calculated for C, 84.38; H, 5.71; Cl: 4.02; F, 4.31; N, 1.59. Found: C, 84.33; H, 5.75; N, 1.58.

[0111] Synthesis and Characterization of Compound BN-609-D: The synthesis of Compound BN-609-D was similar to that of Compound BN-409-D, except that Compound BN-609-C (2.64 g, 3.00 mmol) was used in place of Compound BN-409-C. The amounts of other reactants and reaction conditions were the same. Recrystallization yielded 3.47 g of a white solid (Compound BN-609-D) in 82.6% yield. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 1400.54 [M]+ (calcd: 1400.75). Elemental analysis: Calcd: C, 87.42; H, 7.05; Cl: 2.53; N, 3.00. Found: C, 87.43; H, 7.15; N, 3.08.

[0112] Synthesis and Characterization of Compound BN-609: The synthesis of Compound BN-609 was similar to that of Compound BN-245, except that Compound BN-609-D (6.43 g, 4.59 mmol) was used instead of Compound BN-245-C. The remaining raw material amounts and synthetic procedures were the same. After final column chromatography, 1.79 g of a yellow solid (Compound BN-609) was obtained in a 28.4% yield. Mass spectrometry and elemental analysis confirmed the product as the desired product. MALDI-TOF MS: m / z: 1374.75 [M]+ (calcd: 1374.77). Elemental analysis calculated: C, 89.12; H, 7.04; B: 0.79; N, 3.06. Found: C, 89.17; H, 7.07; N, 3.09.

[0113] Other compounds can be synthesized using the same or similar synthetic routes as above, and their structures have been verified by mass spectrometry and elemental analysis.

[0114] Electroluminescent device embodiments

[0115] Some representative examples of electroluminescent devices are given below. The molecular structures of some materials involved in the device examples and comparative examples are as follows:

[0116] The following is an example of an electroluminescent device prepared using the materials of the present application. The specific device preparation process is as follows:

[0117] Organic electroluminescent device preparation process:

[0118] The device results are shown in FIG1 , where 1 is an ITO anode, 2 is a hole transport layer 1, 3 is a hole transport layer 2, 4 is a light-emitting layer, 5 is an electron transport layer, 6 is an electron injection layer, and 7 is a metal cathode.

[0119] The preparation process is as follows:

[0120] (1) Substrate treatment: Transparent ITO glass was used as the substrate material for device preparation. It was first ultrasonically treated with 5% ITO solution for 30 minutes, then ultrasonically cleaned with distilled water (twice), acetone (twice), and isopropyl alcohol (twice). Finally, the ITO glass was stored in isopropyl alcohol. Before each use, the surface of the ITO glass was carefully wiped with acetone cotton balls and isopropyl alcohol cotton balls, rinsed with isopropyl alcohol, dried, and then plasma treated for 5 minutes before use. The device was prepared by combining spin coating and vacuum evaporation technology.

[0121] (2) Preparation of hole injection layer and hole transport layer: The hole transport layer was prepared by evaporation process. When the vacuum degree of vacuum evaporation system reached 5×10 -4 Pa below, the deposition rate was measured by the film thickness meter. The organic hole transport layer was deposited on the surface of the ITO electrode in sequence using the vacuum evaporation process. The deposition rate of the hole transport material was

[0122] (3) Preparation of the luminescent layer: The luminescent layer was prepared by evaporation process. When the vacuum degree of the vacuum evaporation system reached 5×10 -4 Pa below, the deposition rate was measured by the film thickness meter. The light-emitting layer was deposited on the hole transport layer in sequence using a vacuum evaporation process. The deposition rate of the light-emitting layer material was

[0123] (4) Preparation of electron transport layer, electron injection layer and metal electrode: The electron transport layer, electron injection layer and metal electrode are prepared by evaporation process. When the vacuum degree of vacuum evaporation system reaches 5×10 -4 When the thickness is below Pa, the deposition begins, and the deposition rate is measured by a film thickness meter. The organic electron transport layer, the LiF electron injection layer, and the metal Al electrode are sequentially deposited on the light-emitting layer using a vacuum deposition process (see the following embodiment for the specific device structure). The deposition rate of the organic material is The deposition rate of LiF is The deposition rate of Al is

[0124] Device Examples 1-n (n=1-35)

[0125] In the organic electroluminescent devices of device examples 1-n (n=1-35) (structure shown in FIG1 ), TAPC is used as the hole transport layer 1, TCTA is used as the hole transport layer 2, H1-32 is used as the host material in the light-emitting layer, BN-m (m represents the last digit of the light-emitting material code used in the device example) is used as the dopant light-emitting material (doping concentration is 1 wt%), TRZ-8 is used as the electron transport material, LiF is used as the electron injection layer, and Al is used as the metal cathode. The structure of the organic electroluminescent device of the effect example is [ITO / TAPC (50 nm) / TCTA (5 nm) / 99 wt% H1-32 + 1 wt% BN-m (30 nm) / TRZ-8 (30 nm) / LiF (1 nm) / Al (100 nm)].

[0126] The performance data of the device embodiment are shown in Table 1. The device life (T95, hours) in Table 1 refers to the device initial brightness of 1000 cd / m 2 When the brightness of the device drops to 95% of the initial brightness (i.e. the brightness of the device drops to 950cd / m 2 Comparative Example D1-n (n=1-10)

[0127] In the organic electroluminescent device of device comparative example D1 (structure shown in FIG1 ), TAPC is used as the hole transport layer 1, TCTA is used as the hole transport layer 2, H1-32 is used as the host material in the light-emitting layer, Rn (n=1-10) is used as the doped light-emitting material (doping concentration is 1 wt%), TRZ-8 is used as the electron transport material, LiF is used as the electron injection layer, and Al is used as the metal cathode. The structure of the organic electroluminescent device of the effect example is [ITO / TAPC (50 nm) / TCTA (5 nm) / 99 wt% H1-32 + 1 wt% Rn (30 nm) / TRZ-8 (30 nm) / LiF (1 nm) / Al (100 nm)].

[0128] The performance data of the device comparison are shown in Table D1. The device life (T95, hours) in Table D1 refers to the device initial brightness of 1000 cd / m 2 When the brightness of the device drops to 95% of the initial brightness (i.e. the brightness of the device drops to 950cd / m 2 The time required for

[0129] Table 1

[0130] Table D1

[0131] From the comparison between Table 1 and Table D1, it can be seen that the maximum external quantum efficiency of the organic electroluminescent device of the present application is more than 36%, 1000 cd / m 2 The electroluminescent external quantum efficiency reaches more than 24% under the bright conditions, and the device life is as high as more than 537 hours, which is significantly better than the device performance of the comparative example.

[0132] The electroluminescence spectra of the devices were measured using a Konica Minolta CS2000 and a Keithley 2400 current source meter. Figure 2 shows the electroluminescence spectrum of the electroluminescent device in Device Example 1-2, with an emission peak at 519 nm and a half-width at half maximum of 36 nm. Figure 3 shows the electroluminescence spectrum of the electroluminescent device in Device Example 1-9, with an emission peak at 526 nm and a half-width at half maximum of 35 nm. Figure 4 shows the electroluminescence spectrum of the electroluminescent device in Device Example 1-20, with an emission peak at 535 nm and a half-width at half maximum of 36 nm.

[0133] Device Example 2-n (n=1-35)

[0134] In the organic electroluminescent device of device example 2-n (n=1-35) (structure shown in FIG1 ), TAPC is used as the hole transport layer 1, TCTA is used as the hole transport layer 2, H1-32 is used as the host material in the light-emitting layer, IrPPy3 is used as the sensitizer, BN-m (m represents the last digit of the light-emitting material code used in the device example) is used as the doping light-emitting material (doping concentration is 1 wt%), TRZ-8 is used as the electron transport material, LiF is used as the electron injection layer, and Al is used as the metal cathode. The structure of the organic electroluminescent device of the effect example is [ITO / TAPC (50 nm) / TCTA (5 nm) / 84 wt% H1-32 + 15 wt% IrPPy3 + 1 wt% BN-m (30 nm) / TRZ-8 (30 nm) / LiF (1 nm) / Al (100 nm)].

[0135] The performance data of the device embodiment are shown in Table 2. The device life (T95, hours) in Table 2 refers to the device initial brightness of 1000 cd / m 2 When the brightness of the device drops to 95% of the initial brightness (i.e. the brightness of the device drops to 950cd / m 2 The time required for

[0136] Comparative device example D2-n (n=1-10)

[0137] In the organic electroluminescent device of device comparative example D2-n (structure shown in FIG1 ), TAPC is used as the hole transport layer 1, TCTA is used as the hole transport layer 2, H1-32 is used as the host material in the light-emitting layer, IrPPy3 is used as the sensitizer, Rn (n=1-10) is used as the doped light-emitting material (doping concentration is 1 wt%), TRZ-8 is used as the electron transport material, LiF is used as the electron injection layer, and Al is used as the metal cathode. The structure of the organic electroluminescent device of the effect example is [ITO / TAPC (50 nm) / TCTA (5 nm) / 84 wt% H-48 + 15 wt% IrPPy3 + 1 wt% Rn (30 nm) / TRZ-8 (30 nm) / LiF (1 nm) / Al (100 nm)].

[0138] The performance data of the device comparison are shown in Table D2. The device life (T95, hours) in Table D2 refers to the device initial brightness of 1000 cd / m 2 When the brightness of the device drops to 95% of the initial brightness (i.e. the brightness of the device drops to 950cd / m 2 The time required for

[0139] Table 2

[0140] Table D2

[0141] From the comparison between Table 2 and Table D2, it can be seen that the maximum external quantum efficiency of the organic electroluminescent device of the present application is more than 36%, 1000 cd / m 2 The electroluminescent external quantum efficiency reaches more than 27.7% under the bright condition, and the device life is as high as more than 670 hours, which is significantly better than the device performance of the comparative example.

[0142] Device Example 3-n (n=1-35)

[0143] In the organic electroluminescent device of Device Example 3 (structure shown in FIG1 ), TAPC is used as the hole transport layer 1, TCTA is used as the hole transport layer 2, TRZ-81 is used as the host material in the light-emitting layer, BN-m (m represents the last digit of the light-emitting material code used in the device example) (doping concentration is 1 wt%), TRZ-8 is used as the electron transport material, LiF is used as the electron injection layer, and Al is used as the metal cathode. The structure of the organic electroluminescent device of the effect example is [ITO / TAPC (50 nm) / TCTA (5 nm) / 99 wt% TRZ-81 + 1 wt% BN-Y (30 nm) / TRZ-8 (30 nm) / LiF (1 nm) / Al (100 nm)].

[0144] The performance data of the device embodiment are shown in Table 3. The device life (T95, hours) in Table 3 refers to the device initial brightness of 1000 cd / m 2 When the brightness of the device drops to 95% of the initial brightness (i.e. the brightness of the device drops to 950cd / m 2 The time required for

[0145] Comparative device example D3-n (n=1-10)

[0146] In the organic electroluminescent device of comparative device example D3-n (n=1-10) (structure shown in FIG1 ), TAPC is used as the hole transport layer 1, TCTA is used as the hole transport layer 2, TRZ-81 is used as the host material in the light-emitting layer, R-10 (n=1-8) is used as the doped light-emitting material (doping concentration is 1 wt%), TRZ-8 is used as the electron transport material, LiF is used as the electron injection layer, and Al is used as the metal cathode. The structure of the organic electroluminescent device of the effect example is [ITO / TAPC (50 nm) / TCTA (5 nm) / 99 wt% TRZ-81 + 1 wt% Rn (30 nm) / TRZ-8 (30 nm) / LiF (1 nm) / Al (100 nm)].

[0147] The performance data of the device comparison are shown in Table D3. The device life (T95, hours) in Table D3 refers to the device initial brightness of 1000 cd / m 2 When the brightness of the device drops to 95% of the initial brightness (i.e. the brightness of the device drops to 950cd / m 2 The time required for

[0148] Table 3

[0149] Table D3

[0150] From the comparison between Table 3 and Table D3, it can be seen that the maximum external quantum efficiency of the organic electroluminescent device of the present application reaches more than 36%, 1000 cd / m 2 The electroluminescent external quantum efficiency reaches more than 25% under the bright conditions, and the device life is as high as more than 570 hours, which is significantly better than the device performance of the comparative example.

[0151] Device Example 4-n (n=1-35)

[0152] In the organic electroluminescent device of device example 4-n (n=1-35) (structure shown in FIG1 ), TAPC is used as the hole transport layer 1, TCTA is used as the hole transport layer 2, TRZ-81 is used as the host material in the light-emitting layer, IrPPy3 is used as the sensitizer, BN-m (m represents the last digit of the light-emitting material code used in the device example) (doping concentration is 1 wt%), TRZ-8 is used as the electron transport material, LiF is used as the electron injection layer, and Al is used as the metal cathode. The structure of the organic electroluminescent device of the effect example is [ITO / TAPC (50 nm) / TCTA (5 nm) / 84 wt% TRZ-84 + 15 wt% IrPPy3 + 1 wt% BN-m (30 nm) / TRZ-8 (30 nm) / LiF (1 nm) / Al (100 nm)].

[0153] The performance data of the device embodiment are shown in Table 4. The device life (T95, hours) in Table 4 refers to the device initial brightness of 1000 cd / m 2 When the brightness of the device drops to 95% of the initial brightness (i.e. the brightness of the device drops to 950cd / m 2 Comparative Example D4-n (n=1-10)

[0154] In the organic electroluminescent device of device comparative example D4-n (n=1-10) (structure shown in FIG1 ), TAPC is used as the hole transport layer 1, TCTA is used as the hole transport layer 2, TRZ-81 is used as the host material in the light-emitting layer, IrPPy3 is used as the sensitizer, Rn (n=1-10) is used as the doped light-emitting material (doping concentration is 1 wt%), TRZ-8 is used as the electron transport material, LiF is used as the electron injection layer, and Al is used as the metal cathode. The structure of the organic electroluminescent device of the effect example is [ITO / TAPC (50 nm) / TCTA (5 nm) / 84 wt% TRZ-81+15 wt% IrPPy3+1 wt% Rn (30 nm) / TRZ-8 (30 nm) / LiF (1 nm) / Al (100 nm)].

[0155] The performance data of the device comparison are shown in Table D4. The device life (T95, hours) in Table D4 refers to the device initial brightness of 1000 cd / m 2 When the brightness of the device drops to 95% of the initial brightness (i.e. the brightness of the device drops to 950cd / m 2 The time required for

[0156] Table 4

[0157] Table D4

[0158] From the comparison between Table 4 and Table D4, it can be seen that the maximum external quantum efficiency of the organic electroluminescent device of the present application reaches more than 36%, 1000 cd / m 2 The electroluminescent external quantum efficiency reaches more than 27% under the bright conditions, and the device life is as high as more than 370 hours, which is significantly better than the device performance of the comparative example.

[0159] Device Example 5-n (n=1-35)

[0160] In the organic electroluminescent device of device example 5-n (n=1-35) (structure shown in FIG1 ), TAPC is used as the hole transport layer 1, TCTA is used as the hole transport layer 2, H1-32 and TRZ-81 (weight ratio of 1:1) are used as host materials in the light-emitting layer, BN-m (m represents the last digit of the light-emitting material code used in the device example) (doping concentration is 1 wt%), TRZ-8 is used as an electron transport material, LiF is used as the electron injection layer, and Al is used as the metal cathode. The structure of the organic electroluminescent device of the effect example is [ITO / TAPC (50 nm) / TCTA (5 nm) / 44.5 wt% H1-32 + 44.5 wt% TRZ-84 + 1 wt% BN-m (30 nm) / TRZ-8 (30 nm) / LiF (1 nm) / Al (100 nm)].

[0161] The performance data of the device embodiment are shown in Table 5. The device life (T95, hours) in Table 5 refers to the device initial brightness of 1000 cd / m 2 When the brightness of the device drops to 95% of the initial brightness (i.e. the brightness of the device drops to 950cd / m 2 The time required for

[0162] Comparative device example D5-n (n=1-10)

[0163] In the organic electroluminescent device of device comparative example D5-n (n=1-10) (structure shown in FIG1 ), TAPC is used as the hole transport layer 1, TCTA is used as the hole transport layer 2, H1-32 and TRZ-81 (weight ratio of 1:1) are used as the host material in the light-emitting layer, Rn (n=1-10) is used as the doping light-emitting material (doping concentration is 1 wt%), TRZ-8 is used as the electron transport material, LiF is used as the electron injection layer, and Al is used as the metal cathode. The structure of the organic electroluminescent device of the effect example is [ITO / TAPC (50 nm) / TCTA (5 nm) / 44.5 wt% H1-32 + 44.5 wt% TRZ-84 + 1 wt% Rn (30 nm) / TRZ-8 (30 nm) / LiF (1 nm) / Al (100 nm)].

[0164] The performance data of the device comparison are shown in Table D5. The device life (T95, hours) in Table D5 refers to the device initial brightness of 1000 cd / m 2 When the brightness of the device drops to 95% of the initial brightness (i.e. the brightness of the device drops to 950cd / m 2 The time required for

[0165] Table 5

[0166] Table D5

[0167] From the comparison between Table 5 and Table D5, it can be seen that the maximum external quantum efficiency of the organic electroluminescent device of the present application is more than 36%, 1000 cd / m 2 The electroluminescent external quantum efficiency reaches more than 26% under the bright conditions, and the device life is as high as more than 770 hours, which is significantly better than the device performance of the comparative example.

[0168] The applicant declares that while the present application uses the above-mentioned embodiments to illustrate the organic electroluminescent device and its applications, the present application is not limited to the above-mentioned embodiments, and does not necessarily rely on the above-mentioned embodiments for implementation. Persons skilled in the art should understand that any improvements to the present application, equivalent substitutions for the raw materials used in the present application, addition of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present application.

Claims

1. An organic electroluminescent device, wherein: The organic electroluminescent device comprises an anode, a cathode and an organic thin film layer disposed between the anode and the cathode, wherein the organic thin film layer comprises a light-emitting layer, and the doping material of the light-emitting layer comprises any one or a combination of at least two of the compounds shown in Formula I: Where R 1 and R 2 are independently hydrogen, deuterium, C1~C 16 Alkyl, C1~C 16 Alkoxy, C3-C 18 Cycloalkyl, C6~C 24 Aryl, C6~C 24 Heteroaryl, one or more R a Substituted C6~C 18 Aryl; R a Each time it appears, it is independently C1~C 12 Alkyl, C1~C 12 Alkoxy, C3-C 12 Cycloalkyl, C6~C 18 Aryl, one or more R b Substituted C6~C 18 Aryl; R b Each time it appears, it is independently C1~C 12 Alkyl, C1~C 12 Alkoxy, C3-C 12 Cycloalkyl, C6~C 18 Aryl. R 3 and R 4 Independently C1~C 12 Alkyl, C1~C 12 Alkoxy, C3-C 12 Cycloalkyl, C6~C 18 Aryl, C6~C 18 Heteroaryl.

2. The organic electroluminescent device according to claim 1, wherein: The R 1 and R 2 are independently selected from hydrogen, methyl, ethyl, Phenyl, 3,5-dimethylphenyl, 2-methyl-phenyl, 4-methyl-phenyl, 3-methyl-phenyl, The wavy line represents the attachment site of the group.

3. The organic electroluminescent device according to claim 1 or 2, wherein: The R 3 and R 4 independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, biphenyl, 3,5-dimethylphenyl, pyridyl, In any of the above, the wavy line represents the attachment site of the group.

4. The organic electroluminescent device according to any one of claims 1 to 3, wherein: The doping material of the light-emitting layer includes any one or a combination of at least two of the following compounds BN-1 to BN-633:

5. The organic electroluminescent device according to any one of claims 1 to 4, wherein: The light-emitting layer further includes a host material, and the host material includes any one or a combination of at least two of the carbazole or carbazole compounds shown in the following formula (H-1) to formula (H-6): wherein X1, Y1 and Z1 are CH or N, and at most one of X1, Y1 and Z1 is N; Where R 1H and R 2H Independently any of the following groups: wherein X1, Y1 and Z1 are CH or N, and at most one of X1, Y1 and Z1 is N; Where R aH and R bH are independently H, C1-C 20 Alkyl, C1-C 20 Alkoxy, C6-C 20 Aryl, C1-C 20 Alkyl-substituted C6-C 20 Aryl or C1-C 20 Alkoxy substituted C6-C 20 Aryl, * represents the attachment site of the group; Preferably, the weight percentage of the doping material in the light-emitting layer is 0.3-30.0wt%, and the weight percentage of the host material is 99.7-70.0wt%; Preferably, the light-emitting layer contains 0.3-30.0 wt% of any one of the compounds shown in Formula I as a doping material, and the remaining 99.7-70.0 wt% of the components are a host material composed of 1-2 compounds having structures of Formula (H-1) to Formula (H-6); Preferably, the light-emitting layer contains 0.3-30.0 wt% of any one of compounds BN-1 to BN-462 as a doping material, and the remaining 99.7-70.0 wt% of the components are a host material composed of 1-2 compounds having structures of formula (H-1) to formula (H-6); Preferably, the host material contains two compounds having structures of formula (H-1) to (H-6), and the weight ratio of the two compounds is 1:5 to 5:

1.

6. The organic electroluminescent device according to claim 5, wherein: The host material in the light-emitting layer is any one or a combination of at least two of compounds H1-1 to H1-427:

7. The organic electroluminescent device according to any one of claims 1 to 6, wherein: The host material of the light-emitting layer is one or two of compounds H1-1 to H1-427; Preferably, the light-emitting layer contains 0.3-30.0 wt% of any one of the compounds shown in Formula I as a doping material, and the remaining 99.7-70.0 wt% of the components are a host material composed of one or two compounds from Compounds H1-1 to H1-427; Preferably, the light-emitting layer contains 0.3-30.0 wt % of any one of compounds BN-1 to BN-633 as a doping material, and the remaining 99.7-70.0 wt % is a host material composed of one or two compounds of compounds H1-1 to H1-427. Preferably, the light-emitting layer further comprises an IrPPy3 phosphorescent material as a sensitizer; Preferably, the light-emitting layer contains 0.3-10.0 wt % of any one of the compounds shown in Formula I as a doping material, 94.7-65.0 wt % of a host material consisting of one or two of the carbazole or carbidine compounds shown in Formula (H-1) to Formula (H-6), and 5.0-25.0 wt % of IrPPy3 as a sensitizer; Preferably, the light-emitting layer contains 0.3-10.0 wt % of any one of compounds BN-1 to BN-633 as a doping material, 94.7-65.0 wt % of a host material consisting of one or two of the carbazole or carbazole compounds represented by formula (H-1) to formula (H-6), and 5.0-25.0 wt % of IrPPy3 as a sensitizer; Preferably, the light-emitting layer contains 0.3-10.0 wt % of any one of compounds BN-1 to BN-633 as a doping material, 94.7-65.0 wt % of a host material consisting of one or two of compounds H1-1 to H1-427, and 5.0-25.0 wt % of IrPPy3 as a sensitizer.

8. The organic electroluminescent device according to any one of claims 1 to 7, wherein: The host material in the light-emitting layer is any one or a combination of at least two of the compounds having the structure shown in formula Trz1-A, formula Trz2-A, formula Trz3-A, formula Trz4-A, formula Trz5-A or formula Trz6-A: Where R 1a , R 1b , R 2a , R 2b , R 3a and R 3b One or two of them are independently R Tz , the rest are the same or different and are independently hydrogen, deuterium, C1-C8 alkyl, C1-C8 alkoxy, C6-C 18 Aryl, C1-C8 alkyl substituted C6-C 18 C6-C8 substituted aryl or C1-C8 alkoxy 18 The aryl group; R Tz is any one of the substituent groups shown below: The asterisk represents the attachment point of the group.

9. The organic electroluminescent device according to any one of claims 1 to 8, wherein: The doping material in the light-emitting layer is any one of the compounds shown in Formula I, and the main material is any one of the compounds shown in Formulas TRZ-1 to TRZ-82:

10. The organic electroluminescent device according to any one of claims 1 to 9, wherein: The doping material in the light-emitting layer is any one of the compounds of formula BN-1 to BN-633, and the main material is any one of the compounds of formula TRZ-1 to TRZ-82; Preferably, the light-emitting layer contains 0.3-30.0 wt% of any light-emitting compound as shown in Formula I, and the remaining 99.7-70.0 wt% of the components are any one of compounds TRZ-1 to TRZ-82; Preferably, the light-emitting layer contains 0.3-30.0 wt% of any one of compounds BN-1 to BN-633 as a doping material, and 99.7-70.0 wt% of any one of compounds TRZ-1 to TRZ-82 as a host material; Preferably, the doping material in the light-emitting layer is any one of the compounds shown in Formula I; the main material is any one of the compounds shown in Formula Trz1-A, Formula Trz2-A, Formula Trz3-A, Formula Trz4-A, Formula Trz5-A or Formula Trz6-A, and the sensitizer is IrPPy3 phosphorescent material; Preferably, the doping material in the light-emitting layer is any one of the compounds shown in Formula I; the host material is any one of the compounds shown in Formula TRZ-1 to Formula TRZ-82, and the sensitizer is IrPPy3 phosphorescent material; Preferably, the light-emitting layer contains 0.3-10.0 wt% of any one of the compounds shown in formula I as a doping material, 94.7-65.0 wt% of a host material composed of any one of the compounds having a structure shown in formula Trz1-A, Trz2-A, Trz3-A, Trz4-A, Trz5-A or Trz6-A, and 5.0%-25.0% of IrPPy3 as a sensitizer; Preferably, the light-emitting layer contains 0.3-10.0 wt% of any one of compounds BN-1 to BN-633 as a doping material, 94.7-65.0 wt% of the component is a host material composed of any one of the compounds having a structure represented by formula Trz1-A, formula Trz2-A, formula Trz3-A, formula Trz4-A, formula Trz5-A or formula Trz6-A, and 5.0%-25.0% of IrPPy3 as a sensitizer; Preferably, the light-emitting layer contains 0.3-10.0 wt% of any one of the compounds shown in formula I as a doping material, 94.7-65.0 wt% of a host material composed of any one of the compounds having structures of formulas TRZ-1 to TRZ-82, and 5.0%-25.0% of IrPPy3 as a sensitizer; Preferably, the light-emitting layer contains 0.3-10.0 wt% of any one of compounds BN-1 to BN-633 as a dopant. A hetero material, a main material composed of 94.7-65.0 wt % of any one compound having a structure of formula TRZ-1 to formula TRZ-82 and 5.0%-25.0% of IrPPy3 as a sensitizer; Preferably, the host material in the light-emitting layer is composed of any one of the compounds represented by formula (H-1) to formula (H-6) and any one of the compounds represented by formula Trz1-A, formula Trz2-A, formula Trz3-A, formula Trz4-A, formula Trz5-A or formula Trz6-A; Preferably, the doping material in the light-emitting layer is any one of the compounds shown in Formula I; the main material is composed of one of the compounds H1-1 to H1-427 and any one of the compounds shown in Formulas TRZ-1 to TRZ-82; Preferably, the light-emitting layer contains 0.3-10.0 wt% of any one of the compounds represented by formula I as a doping material, 99.7-90.0 wt% of one of the compounds H1-1 to H1-427 and a host material composed of any one of the compounds represented by formulas TRZ-1 to TRZ-82; Preferably, the light-emitting layer contains 0.3-10.0 wt% of any one of compounds BN-1 to BN-633 as a doping material, 99.7-90.0 wt% of one of compounds H1-1 to H1-427 and a host material composed of any one of the compounds represented by formulas TRZ-1 to TRZ-82.

11. The organic electroluminescent device according to any one of claims 1 to 10, wherein: The organic thin film layer in the organic electroluminescent device further comprises at least one layer of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer.

12. Use of the organic electroluminescent device according to any one of claims 1 to 11 in an organic electroluminescent display or an organic electroluminescent lighting source.

Images