An organic electroluminescent compound and an organic electroluminescent device

Abstract

This invention relates to an organic light-emitting compound and an organic electroluminescent device. The compound has a structure represented by F-L-Ar, where L has the structure shown in Formula 1 and F has the structure shown in Formula 2. The compound of this invention can be used as the host material for the light-emitting layer of an organic electroluminescent device, exhibiting significantly reduced evaporation temperature and better thermal stability, effectively reducing energy consumption and facilitating the device fabrication process. Furthermore, it can effectively improve device efficiency, reduce the device driving voltage, and provide better device performance.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescence technology, and more specifically to an organic electroluminescent compound and an organic electroluminescent device containing the same. Background Technology

[0002] Organic electronic devices include, but are not limited to, the following types: organic light-emitting diodes (OLEDs), organic field-effect transistors (O-FETs), organic light-emitting transistors (OLETs), organic photovoltaic devices (COPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photosensors, organic field-effect devices (OFQDs), light-emitting electrochemical cells (LEGS), organic laser diodes, and organic plasma light-emitting devices.

[0003] In 1987, Tang and Van Slyke of Eastman Kodak reported a bilayer organic electroluminescent device comprising an arylamine hole transport layer and a tri-8-hydroxyquinoline aluminum layer as both an electron transport layer and a light-emitting layer (Applied Physics Letters, 1987, 51(12): 913-915). Once a bias voltage was applied to the device, green light was emitted. This invention laid the foundation for the development of modern organic light-emitting diodes (OLEDs). State-of-the-art OLEDs can include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light-emitting layers between the cathode and anode. Because OLEDs are self-emissive solid-state devices, they offer enormous potential for display and lighting applications. Furthermore, the inherent properties of organic materials, such as their flexibility, make them well-suited for specialized applications, such as in the fabrication of flexible substrates.

[0004] OLEDs can be categorized into three different types based on their light-emitting mechanism. The OLED invented by Tang and Van Slyke is a fluorescent OLED. It uses only singlet state emission. The triplet state generated in the device is wasted through non-radiative decay channels. Therefore, the internal quantum efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation hindered the commercialization of OLEDs. In 1997, Forrest and Thompson reported phosphorescent OLEDs, which use triplet emission from complexed heavy metals as the emitter. Therefore, both singlet and triplet states can be harvested, achieving 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributed to the commercialization of active-matrix OLEDs (AMOLEDs). Recently, Adachi achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. These emitters have small singlet-triple state gaps, making it possible for excitons to return from the doublet state to the singlet state. In TADF devices, triplet excitons can generate singlet excitons through reverse intersystem crossing, resulting in high IQE. OLEDs can also be classified into small-molecule and polymer OLEDs based on the form of the materials used. Small molecules refer to any organic or organometallic material that is not a polymer. Small molecules can have large molecular weights, provided they have a precise structure. Dendritic polymers with well-defined structures are considered small molecules. Polymer OLEDs include conjugated polymers and non-conjugated polymers with side-chain luminescent groups. Small-molecule OLEDs can become polymer OLEDs if post-polymerization occurs during manufacturing. Various OLED manufacturing methods exist. Small-molecule OLEDs are typically manufactured via vacuum thermal evaporation. Polymer OLEDs are manufactured using solution methods such as spin coating, inkjet printing, and nozzle printing. Small-molecule OLEDs can also be manufactured using solution methods if the material can be dissolved or dispersed in a solvent. The emission color of an OLED can be achieved through the design of the luminescent material structure. OLEDs can include one or more luminescent layers to achieve a desired spectrum. Green, yellow, and red OLEDs using phosphorescent materials have been successfully commercialized. Blue phosphorescent devices still suffer from problems such as blue unsaturation, short device lifetime, and high operating voltage. Commercial full-color OLED displays typically employ a hybrid strategy, using blue fluorescence and phosphorescent yellow, or red and green. Currently, the rapid decrease in efficiency of phosphorescent OLEDs at high brightness remains a problem. Furthermore, a more saturated emission spectrum, higher efficiency, and longer device lifetime are desired.

[0005] Currently reported main materials still have room for improvement. To meet the industry's ever-increasing demands, especially for higher device efficiency, longer device lifespan, and lower drive voltage, new materials still require further research and development. Summary of the Invention

[0006] The purpose of this invention is to provide a compound formed by Y-shaped aryl or heteroaryl bonds, which can be used as the host material in organic electroluminescent devices. The organic electroluminescent devices prepared by this invention have significantly reduced evaporation temperature, higher device efficiency, better thermal stability, and can effectively reduce energy consumption, which is more conducive to the device fabrication process. In addition, it can also reduce the device driving voltage and provide better device performance.

[0007] In a first aspect, the present invention provides an organic light-emitting compound having an FL-Ar structure, wherein L has a structure represented by Formula 1:

[0008]

[0009] In Formula 1, ring 1 and ring 2 are selected from carbon rings having 5-18 carbon atoms or heterocycles having 3-18 carbon atoms each time they appear; wherein A can be arbitrarily chosen as a carbon atom or a nitrogen atom;

[0010] R X Each occurrence, whether identical or different, indicates monosubstitution, polysubstitution, or no substitution;

[0011] F has a structure represented by Equation 2:

[0012]

[0013] In Formula 2, rings A, B, and C are selected from carbon rings having 5-18 carbon atoms or heterocarbon rings having 3-18 carbon atoms each time they appear;

[0014] R Y Each occurrence, whether identical or different, indicates monosubstitution, polysubstitution, or no substitution;

[0015] Y 1 Y 2 Each occurrence is selected from NR, either identically or differently. N or CR Y ;

[0016] Ar has the structure represented by Equation 3, which is as follows:

[0017]

[0018] In Equation 3, Z 1 To Z 5 Each occurrence is selected from NR, either identically or differently. N or CR a R b ;

[0019] In equations 1 to 3, R X RY R N R a and R b Each time it appears, it is selected from the group consisting of the following, either identically or differently: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-20 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted aralkyl groups having 7-30 carbon atoms, substituted or unsubstituted alkoxy groups having 1-20 carbon atoms, substituted or unsubstituted aroxy groups having 6-30 carbon atoms, substituted or unsubstituted alkenyl groups having 2-20 carbon atoms, substituted or unsubstituted alkynyl groups having 2-20 carbon atoms, substituted or Unsubstituted aryl groups having 6-30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3-30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3-20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6-20 carbon atoms, substituted or unsubstituted amino, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphinyl, and combinations thereof having 0-20 carbon atoms; wherein the substituents used for substitution are selected from hydrogen, deuterium, halogen, alkyl groups having 1-10 carbon atoms, cycloalkyl groups having 3-10 carbon atoms, aryl groups having 6-20 carbon atoms, or heteroaryl groups having 3-20 carbon atoms;

[0020] Adjacent substituent R X R Y R N R a and R b Any two or more can be arbitrarily connected to form a ring;

[0021] The asterisk (*) indicates the location where F and L bonds are formed. This indicates the location where L and Ar are bonded.

[0022] According to some embodiments of the present invention, in Formula 1, ring 1 and ring 2 are each independently selected from an alicyclic ring having 5-12 carbon atoms, an aromatic ring having 6-12 carbon atoms, or a heteroaromatic ring having 3-12 carbon atoms. In some specific embodiments, ring 1 and ring 2 are each independently selected from a 5-membered carbon ring, a benzene ring, a naphthalene ring, a 5-membered heteroaromatic ring, a 6-membered heteroaromatic ring, a benzo5-membered heteroaromatic ring, or a fused ring formed by a 5-membered heteroaromatic ring and a 6-membered heteroaromatic ring, wherein the heteroatom in the heteroaromatic ring is selected from N, O, S, Se, and Si.

[0023] In some embodiments, the L is selected each time it appears from a structure represented by Equations 1-1 to 1-5:

[0024]

[0025] Among them, X 1 To X 6 Each occurrence is selected from NR, either identically or differently. N or CR X R X The definition is the same as in equation 1;

[0026] Each time X appears, select from O, S, Se, NR. N ,CR a R b and SiR a R b The group formed, R N ,R a and R b The definition is the same as in equation 3.

[0027] Preferably, in formulas 1-1 to 1-5, R N ,R a and R b Each time it appears, it is selected from the group consisting of the same or different elements: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-10 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted aralkyl groups having 7-20 carbon atoms, substituted or unsubstituted alkoxy groups having 1-10 carbon atoms, substituted or unsubstituted aroxy groups having 6-30 carbon atoms, substituted or unsubstituted... Alkenyl groups with 2-10 carbon atoms, substituted or unsubstituted alkynyl groups with 2-10 carbon atoms, substituted or unsubstituted aryl groups with 6-20 carbon atoms, substituted or unsubstituted heteroaryl groups with 3-20 carbon atoms, substituted or unsubstituted alkylsilyl groups with 3-10 carbon atoms, substituted or unsubstituted arylsilyl groups with 6-20 carbon atoms, substituted or unsubstituted amino, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphinyl, and combinations thereof with 0-10 carbon atoms; adjacent substituents R a and R b They can be arbitrarily connected to form a loop.

[0028] In some preferred embodiments, L is selected from the structure shown in Equation 1-1 or Equation 1-5 each time it appears. In some specific embodiments, in Equation 1-1 or Equation 1-5, X 1 To X 6 Each time it appears, it is selected from CR in the same or different ways. X X is selected from CR a R b R X Ra and R b The definition is the same as above.

[0029] According to a preferred embodiment of the present invention, in formulas 1-1 to 1-5, R X R N R a and R b Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl having 1-10 carbon atoms, haloalkyl having 1-10 carbon atoms, or aryl having 6-18 carbon atoms, preferably hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, trifluoromethyl, phenyl, naphthyl, and biphenyl.

[0030] In some specific embodiments, the structure of L is one of the structures shown below, numbered L-1 to L-39; or, the structure of L is the structure obtained by partially or completely replacing the hydrogen in any of the structures shown below, numbered L-1 to L-39, with deuterium as a substitute; wherein the structures corresponding to numbers L-1 to L-39 are as follows:

[0031]

[0032] In some embodiments, in Formula 2, rings A, B, and C are each independently selected from alicyclic rings having 5-18 carbon atoms, aromatic rings having 6-18 carbon atoms, or heteroaromatic rings having 3-18 carbon atoms. In some preferred embodiments, rings A, B, and C are each independently selected from 5-membered carbon rings, benzene rings, naphthalene rings, 5-membered heteroaromatic rings, 6-membered heteroaromatic rings, fused rings formed by a 5-membered heteroaromatic ring and a benzene ring, or fused rings formed by a 5-membered carbon ring and a benzene ring, wherein the heteroatom in the heteroaromatic ring is selected from N, O, S, Se, and Si.

[0033] In some implementations, F is selected from the structures represented by equations 2-1 to 2-12 each time it appears:

[0034]

[0035]

[0036] Among them, Y 1 To Y 15 Each occurrence is selected from NR, either identically or differently. N or CR Y R Y The definition is the same as in equation 2;

[0037] Y is selected from O, S, Se, NR N ,CR a R b and SiR a Rb R N R a and R b The definition is the same as in equation 3.

[0038] In some preferred embodiments, in formulas 2-1 to 2-12, Y 1 and Y 2 Each independently selected from CR Y R Y The definition is the same as in equation 2.

[0039] In some preferred embodiments, in formulas 2-1 to 2-12, R Y R N R a and R b Each time it appears, it is selected from the group consisting of the same or different groups of the following: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-10 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted aralkyl groups having 7-10 carbon atoms, substituted or unsubstituted alkoxy groups having 1-10 carbon atoms, substituted or unsubstituted aroxy groups having 6-20 carbon atoms, substituted or unsubstituted... Alkenyl groups having 2-10 carbon atoms, substituted or unsubstituted alkynyl groups having 2-10 carbon atoms, substituted or unsubstituted aryl groups having 6-20 carbon atoms, substituted or unsubstituted heteroaryl groups having 3-20 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3-10 carbon atoms, substituted or unsubstituted arylsilyl groups having 6-20 carbon atoms, and substituted or unsubstituted amino, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphinyl, and combinations thereof having 0-10 carbon atoms. Adjacent substituents R a and R b Optional linkages can form 3-15 membered rings, such as benzene rings or naphthalene rings.

[0040] In some preferred embodiments, F is selected from the structure shown in Formula 2-1. In some specific embodiments, Y 1 To Y 13 Same or different, and each independently selected from CR Y R Y The definition is the same as above.

[0041] In some preferred embodiments, in formulas 2-1 to 2-12, R YIt is selected from the group consisting of: hydrogen, deuterium, halogen, alkyl having 1-10 carbon atoms, haloalkyl having 1-10 carbon atoms, alkenyl having 1-10 carbon atoms, or aryl having 6-18 carbon atoms, preferably hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert-butyl, trifluoromethyl, vinyl, propenyl, phenyl, naphthyl, and biphenyl.

[0042] In some preferred embodiments, in formulas 2-1 to 2-12, R N R a and R b Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl having 1-10 carbon atoms, haloalkyl having 1-10 carbon atoms, or aryl having 6-18 carbon atoms, preferably hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert-butyl, trifluoromethyl, phenyl, naphthyl, and biphenyl.

[0043] In some embodiments, the structure of F in the compound is one of the structures shown below, numbered F-1 to F-143, or a structure obtained by partially or completely replacing the hydrogen in any of the structures shown below, numbered F-1 to F-143 with deuterium; wherein the structures corresponding to numbers F-1 to F-143 are as follows:

[0044]

[0045]

[0046]

[0047]

[0048]

[0049] In some embodiments, Ar, each time it appears in the compound, is selected from structures represented by formulas 3-1 to 3-8:

[0050]

[0051] Among them, Z 1 To Z 5 Each time it appears, it is selected from CR. a R b R a and R b The definition is the same as in formula 3, with adjacent substituents R a and R b They can be optionally connected to form saturated or unsaturated 3-15 member rings.

[0052] In some preferred embodiments, Ar is selected from the structure shown in Formula 3-1 each time it appears.

[0053] In some preferred embodiments, in formulas 3-1 to 3-8, R a and R b Each of the following is independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl group having 1-10 carbon atoms, substituted or unsubstituted alkenyl group having 1-10 carbon atoms, substituted or unsubstituted aryl group having 6-18 carbon atoms, substituted or unsubstituted heteroaryl group having 3-18 carbon atoms, mercapto or hydroxyl group, wherein the substituent is selected from deuterium, halogen, alkyl group having 1-5 carbon atoms, aryl group having 6-15 carbon atoms or heteroaryl group having 3-15 carbon atoms.

[0054] In some preferred embodiments, in formulas 3-1 to 3-8, R a and R b Each is independently selected from the group consisting of: hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert-butyl, trifluoromethyl, substituted or unsubstituted vinyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted triazine, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazoleyl, mercapto, or hydroxyl, wherein the substituent used for the substitution is selected from deuterium, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl, benzofuranyl, benzothiophenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, or carbazoleyl.

[0055] In some specific embodiments, the structure of Ar is one of the structures shown in Ar-1 to Ar-108, or a structure obtained by partially or completely replacing the hydrogen in any of the structures shown in Ar-1 to Ar-108 with deuterium; wherein the structures corresponding to Ar-1 to Ar-108 are as follows:

[0056]

[0057]

[0058]

[0059]

[0060] In some preferred embodiments, in formulas 1 to 3, 1-1 to 1-5, 2-1 to 2-12 and 3-1 to 3-8 above, R X R Y RN R a and R b Each time it appears, it is selected from the group consisting of, in the same or different ways, hydrogen, deuterium, halogen, substituted or unsubstituted heteroalkyl groups having 1-20 carbon atoms, substituted or unsubstituted heterocyclic alkyl groups having 3-20 carbon atoms, substituted or unsubstituted aralkyl groups having 7-30 carbon atoms, substituted or unsubstituted alkoxy groups having 1-20 carbon atoms, substituted or unsubstituted aryloxy groups having 6-30 carbon atoms, substituted or unsubstituted alkenyl groups having 2-20 carbon atoms, substituted or unsubstituted aryl groups having 6-30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3-30 carbon atoms, substituted or unsubstituted amino, acyl, carbonyl, carboxylic acid, ester, cyano, isocyanate, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0061] Preferably, R X R Y R N R a and R b At least one of them is selected from deuterium, substituted or unsubstituted aryl group having 6-30 carbon atoms, or substituted or unsubstituted heteroaryl group having 3-30 carbon atoms.

[0062] More preferably, R X R Y R N R a and R b At least one of them is selected from deuterium, phenyl, biphenyl, naphthyl or pyridyl.

[0063] In some embodiments, the compound has an FL-Ar structure, wherein F is selected from the group consisting of the structures numbered F-1 to F-143 above, L is selected from the group consisting of the structures numbered L-1 to L-39 above, and Ar is selected from the group consisting of the structures numbered Ar-1 to Ar-108 above; optionally, the hydrogen in the compounds numbered F-1 to F-143, L-1 to L-39, and Ar-1 to Ar-108 is partially or completely replaced by deuterium.

[0064] In some specific embodiments, the compound is selected from the compounds corresponding to numbers C1 to C1533, or the compound obtained by partially or completely replacing the hydrogen in any of the structures corresponding to numbers C1 to C1533 with deuterium. The compounds shown in numbers C1 to C1533 have an FL-Ar structure, wherein F, L, and Ar correspond to the structures in Table 1 below.

[0065] Table 1

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083] Secondly, the present invention provides the application of the above-mentioned organic light-emitting compounds in the preparation of organic electroluminescent devices.

[0084] Preferably, the compound is used as the host material of the light-emitting layer in an organic electroluminescent device.

[0085] Thirdly, the present invention provides an organic electroluminescent device, including a light-emitting layer, wherein the main material of the light-emitting layer contains the compound described in the first aspect.

[0086] Preferably, the organic electroluminescent device comprises: an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode. In some embodiments, the light-emitting layer further comprises a dopant. In some embodiments, the dopant included in the organic electroluminescent device of the present invention may be at least one phosphorescent or fluorescent dopant, preferably a phosphorescent dopant. The phosphorescent dopant material is not particularly limited, but may preferably be selected from metallized complexes of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably from ortho-metallized complexes of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably from ortho-metallized iridium complexes. In some embodiments, the doping concentration (mass percentage) of the dopant relative to the host material in the light-emitting layer is 1 wt% to 20 wt%, preferably 1 wt% to 10 wt%, more preferably 2 wt% to 8 wt%.

[0087] Preferably, the organic electroluminescent device further includes one or more of the following: a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0088] Fourthly, the present invention provides a display device comprising the organic light-emitting compound described in the first aspect of the present invention or the organic electroluminescent device described in the third aspect of the present invention.

[0089] The beneficial effects of this invention are as follows: The organic light-emitting compounds disclosed in this invention have a structure composed of aryl or heteroaryl bonds linked in a "Y" shape, and can be used as the host material in electroluminescent devices. This compound connects hole transport units and electron transport units in a "Y" shape, giving these compound molecules a unique spatial structure that brings unexpected effects. This novel compound exhibits significantly reduced evaporation temperature, effectively improves device efficiency, has better thermal stability, and effectively reduces energy consumption, which is beneficial to the device fabrication process. Furthermore, it provides better device performance. Attached Figure Description

[0090] Figure 1 This is a schematic diagram of an organic light-emitting device according to a specific embodiment of the present invention.

[0091] Figure 2 This is a schematic diagram of an organic light-emitting device according to another specific embodiment of the present invention.

[0092] The attached figures are labeled as follows:

[0093] 100, First organic light-emitting device; 101, Substrate; 102, Encapsulation layer; 110, Anode; 120, Hole injection layer; 130, Hole transport layer; 140, Electron blocking layer; 150, Light-emitting layer; 160, Hole blocking layer; 170, Electron transport layer; 180, Electron injection layer; 190, Cathode; 200, Second organic light-emitting device. Detailed Implementation

[0094] OLEDs can be manufactured on various substrates, such as glass, plastic, and metal. Figure 1 A first organic light-emitting device 100 of the present invention is illustrated schematically and non-limitingly. The figures are not necessarily drawn to scale, and some layer structures may be omitted as needed. Device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light-emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. Device 100 can be manufactured by sequentially depositing the described layers. The properties and functions of each layer, as well as exemplary materials, are described in more detail in columns 6-10 of U.S. Patent 7,279,704B2, the entire contents of which are incorporated herein by reference.

[0095] Each of these layers has numerous examples. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. An example of a host material is disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes are disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. These cathodes comprise composite cathodes having a thin metal layer, such as Mg:Ag, overlaid with a transparent, conductive, sputter-deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are also incorporated herein by reference in their entirety. Examples of implanted layers are provided in U.S. Patent Application Publication No. 2004 / 0174H6, which is also incorporated herein by reference in its entirety.

[0096] The description of the protective layer was found in application for disclosure No. 2004 / 0174H6.

[0097] The layered structure described above is provided through non-limiting embodiments. The functionality of an OLED can be achieved by combining the various layers described above, or some layers can be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of multiple materials can be used to achieve optimal performance. Any functional layer may include several sublayers. For example, a light-emitting layer may have two different light-emitting materials to achieve a desired emission spectrum.

[0098] In one embodiment, an OLED can be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may include one or more layers.

[0099] OLEDs also require an encapsulation layer, such as Figure 2 The second organic light-emitting device 200 of the present invention is shown schematically and non-limitingly, and is related to... Figure 1 The difference lies in the fact that an encapsulation layer 102 may also be included above the cathode 190 to protect against harmful substances from the environment, such as moisture and oxygen. Any material capable of providing encapsulation can be used as the encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly on the outside of the OLED device. Multilayer thin-film encapsulation is described in US Patent 7,968,146B2.

[0100] The description is provided in [the original text], and its entire content is incorporated herein by reference.

[0101] Devices manufactured according to embodiments of the present invention can be incorporated into a variety of consumer products having one or more electronic component modules (or units). Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, smartphones, tablet computers, phablets, wearable devices, smartwatches, laptop computers, digital cameras, portable camcorders, viewfinders, microdisplays, 3D displays, vehicle displays, and taillights.

[0102] The materials and structures described in this article can also be used in other organic electronic devices listed above.

[0103] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. When the first layer is described as being "disposed" on the second layer, the first layer is positioned further from the substrate. Unless it is specified that the first layer "contacts" the second layer, other layers may exist between the first and second layers. For example, even if various organic layers exist between the cathode and anode, the cathode may still be described as being "disposed" on the anode.

[0104] As used herein, “solution-handleable” means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0105] When a ligand is believed to directly contribute to the photosensitivity of the emitting material, the ligand can be called "photosensitive." When a ligand is believed not to contribute to the photosensitivity of the emitting material, the ligand can be called "auxiliary," but auxiliary ligands can alter the properties of photosensitivity ligands.

[0106] It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistical limit through delayed fluorescence. Delayed fluorescence can generally be divided into two types: p-type delayed fluorescence and E-type delayed fluorescence. p-type delayed fluorescence is generated by triplet-triplet annihilation (TTA).

[0107] On the other hand, E-type delayed fluorescence does not depend on the collision of two triplet states, but rather on the transition between triplet and singlet excited states. Compounds capable of producing E-type delayed fluorescence need to have a very small singlet-triple gap to facilitate the transition between energy states. Thermal energy can activate the transition from triplet to singlet. This type of delayed fluorescence is also called thermally activated delayed fluorescence (TADF). A significant characteristic of TADF is that the delayed component increases with increasing temperature. If the reverse system crossover (RISC) rate is fast enough to minimize the nonradiative decay from the triplet state, the fraction of singlet excited states that are refilled can reach 75%. The total singlet fraction can be 100%, far exceeding the 25% spin statistics of electrogenerated excitons.

[0108] E-type delayed fluorescence can be observed in excited complex systems or single compounds. Unbound by theory, it is believed that E-type delayed fluorescence requires the luminescent material to have a small singlet-triple bandgap (ΔE). S-T Organic, nonmetallic donor-acceptor luminescent materials may be able to achieve this. The emission of these materials is typically characterized as donor-acceptor charge transfer (CT) emission. Spatial separation of the HOMO and LUMO in these donor-acceptor compounds usually produces small ΔE. S-T These states can include CT states. Typically, donor-acceptor luminescent materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) with an electron acceptor moiety (e.g., an N-containing six-membered aromatic ring).

[0109] Definition of the term "substituent group"

[0110] The halogens or halides described in this invention include fluorine, chlorine, bromine, and iodine.

[0111] The alkyl groups described in this invention include straight-chain and branched alkyl groups. The alkyl group can be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, and 3-methylpentyl. Furthermore, the alkyl group may optionally be substituted. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, and n-hexyl are preferred. Furthermore, the alkyl group may optionally be substituted.

[0112] The cycloalkyl group described in this invention comprises a cyclic alkyl group. The cycloalkyl group can be a cycloalkyl group having 3 to 20 carbon atoms, preferably a cycloalkyl group having 4 to 10 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, etc. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and 4,4-dimethylcyclohexyl are preferred. Furthermore, the cycloalkyl group may optionally be substituted.

[0113] The heteroalkyl group described in this invention comprises one or more carbon atoms in an alkyl chain that are replaced by heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, selenium, phosphorus, silicon, germanium, and boron atoms. The heteroalkyl group can be a heteroalkyl group having 1 to 20 carbon atoms, preferably a heteroalkyl group having 1 to 10 carbon atoms, and more preferably a heteroalkyl group having 1 to 6 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminolactone, dimethylaminomethyl, trimethylsilyl, dimethylethylsilyl, dimethylisolactone, tert-butyldimethylsilyl, triethylsilyl, triisolactone, trimethylsilylmethyl, trimethylsilylethyl, and trimethylsilylisolactone. Additionally, the heteroalkyl group may optionally be substituted.

[0114] The alkenyl groups described in this invention encompass straight-chain, branched, and cyclic olefinic groups. Alkenyl groups can be alkenyl groups containing 2 to 20 carbon atoms, preferably alkenyl groups having 2 to 10 carbon atoms. Examples of alkenyl groups include vinyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptanetrienyl, cyclooctenyl, cyclooctatetraenyl, and norbornyl. In addition, the alkenyl group can be optionally substituted.

[0115] The alkynyl group described in this invention encompasses straight-chain alkynyl groups. The alkynyl group can be an alkynyl group containing 2 to 20 carbon atoms, preferably an alkynyl group having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3,3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3,3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl, etc. Among the above, ethynyl, propynyl, propynyl, butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, and phenylethynyl are preferred. Furthermore, the alkynyl group can be optionally substituted.

[0116] The aryl or aromatic group described in this invention considers both non-fused and fused systems. The aryl group can be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthyl, anthracene, ferroyl, phenanthryl, fluorenyl, pyrene, etc. The aryl group can be substituted with phenyl, peryl, and azulel, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorenyl, and naphthyl. Additionally, the aryl group may be optionally substituted. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4”-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesitylene, and m-tetraphenyl. Additionally, the aryl group may be optionally substituted.

[0117] The heterocyclic groups or heterocycles described in this invention are considered to be non-aromatic cyclic groups. Non-aromatic heterocyclic groups include saturated heterocyclic groups having 3-20 ring atoms and unsaturated non-aromatic heterocyclic groups having 3-20 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen, oxygen, sulfur, selenium, silicon, phosphorus, germanium, and boron atoms. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen, silicon, or sulfur. Examples of non-aromatic heterocyclic groups include ethylene oxide, oxadiazolyl, tetrahydrofuranyl, tetrahydropyranyl, dioxapentaneyl, dioxahexacycloyl, acridineyl, dihydropyrroleyl, tetrahydropyrroleyl, piperidinyl, oxazolidinyl, morpholinyl, piperazineyl, oxadiazonyl heptadienyl, thioheptadienyl, azaheptadienyl, and tetrahydrothiorroleyl. Furthermore, the heterocyclic group may optionally be substituted.

[0118] The heteroaryl group described in this invention may comprise non-fused and fused heteroaryl groups with 1 to 5 heteroatoms, wherein at least one heteroatom is selected from the group consisting of nitrogen, oxygen, sulfur, selenium, silicon, phosphorus, germanium, and boron atoms. Isoaryl also refers to heteroaryl. The heteroaryl group may be a heteroaryl group having 3 to 30 carbon atoms, preferably a heteroaryl group having 3 to 20 carbon atoms, and more preferably a heteroaryl group having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazol, pyridine, pyrazine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzoisoxazole, benzothiazole, quinoline, iso Quinoline, cyclophosphine, quinazolin, quinoxaline, naphthidine, phthalazine, pteridine, guarbenzine, acridine, phenazine, phenothiazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, selenobenzodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, boronazole and its aza analogues. Additionally, the heteroaryl group may optionally be substituted.

[0119] The alkoxy group described in this invention is represented by -O-alkyl, -O-cycloalkyl, -O-heteroalkyl, or -O-heterocyclic groups. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl, and heterocyclic groups are the same as described above. The alkoxy group can be an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, cyclopropyloxy, cyclobutyloxy, cyclopentoxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy, and ethoxymethyloxy. Additionally, the alkoxy group may optionally be substituted.

[0120] The aryloxy group described in this invention is represented by -O-aryl or -O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. The aryloxy group can be an aryloxy group having 6 to 30 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenyloxy groups. Furthermore, the aryloxy group may optionally be substituted.

[0121] The aralkyl group described in this invention encompasses aryl-substituted alkyl groups. The aralkyl group can be an aralkyl group having 7 to 30 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 13 carbon atoms. Examples of aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α-naphthylmethyl, 1-α-naphthylethyl, 2-α-naphthylethyl, 1-α-naphthylisopropyl, 2-α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthyl-ethyl, 2-β-naphthyl-ethyl, 1-β-naphthylisopropyl, 2-β-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl The compounds include alkyl groups, such as o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl, and 1-chloro-2-phenylisopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, and 2-phenylisopropyl are preferred. Additionally, the alkyl group may optionally be substituted.

[0122] The alkylsilyl group described in this invention encompasses alkyl-substituted silyl groups. The alkylsilyl group can be an alkylsilyl group having 3-20 carbon atoms, preferably an alkylsilyl group having 3 to 10 carbon atoms. Examples of alkylsilyl groups include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tritert-butylsilyl, triisobutylsilyl, dimethyltert-butylsilyl, and methylditert-butylsilyl. Furthermore, the alkylsilyl group may optionally be substituted.

[0123] The arylsilyl group described in this invention encompasses at least one aryl-substituted silane group. The arylsilyl group can be an arylsilyl group having 6-30 carbon atoms, preferably an arylsilyl group having 8-20 carbon atoms. Examples of arylsilyl groups include triphenylsilyl, phenyldiphenylsilyl, diphenylbiphenylsilyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyltert-butylsilyl, tri-tert-butylsilyl, dimethyltert-butylsilyl, and methyldi-tert-butylsilyl. Furthermore, the arylsilyl group may optionally be substituted.

[0124] In this invention, the term "aza" in azadibenzofuran, azadibenzothiophene, etc., refers to the substitution of one or more CH groups in the corresponding aromatic fragment by a nitrogen atom. For example, azatriphenylene includes dibenzo[f,h]quinoline, dibenzo[f,h]quinoline, and other analogs having two or more nitrogen atoms in the ring system. Other nitrogen analogs of the aforementioned aza derivatives will readily conceive of those skilled in the art, and all such analogs are identified as being included in the terminology used herein.

[0125] In this disclosure, unless otherwise defined, when any of the terms consisting of the group consisting of alkyl, cycloalkyl, heteroalkyl, substituted heterocyclic, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alksilyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphinyl, refers to any one of the following groups: alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alksilyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl, and phosphinyl, which may be one or more groups selected from deuterium, halogen, unsubstituted alkyl having 1-20 carbon atoms. The substituted group comprises cycloalkyl groups having 3-20 carbon atoms, unsubstituted heteroalkyl groups having 1-20 carbon atoms, unsubstituted heterocyclic groups having 3-20 carbon atoms, unsubstituted aralkyl groups having 7-30 carbon atoms, unsubstituted alkoxy groups having 1-20 carbon atoms, unsubstituted aroxy groups having 6-30 carbon atoms, unsubstituted alkenyl groups having 2-20 carbon atoms, unsubstituted alkynyl groups having 2-20 carbon atoms, unsubstituted aryl groups having 6-30 carbon atoms, unsubstituted heteroaryl groups having 3-30 carbon atoms, unsubstituted alkylsilyl groups having 3-20 carbon atoms, unsubstituted arylsilyl groups having 6-20 carbon atoms, and unsubstituted amino, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphin, and combinations thereof having 0-20 carbon atoms.

[0126] It should be understood that when a molecular segment is described as a substituent or otherwise attached to another part, its name may be written according to whether it is a segment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or attaching segments are considered equivalent.

[0127] In the compounds mentioned in this disclosure, hydrogen atoms can be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. Substitution with other stable isotopes in the compounds is likely preferred due to their ability to enhance device efficiency and stability.

[0128] In the compounds mentioned in this disclosure, multiple substitution refers to the range including disubstitution, up to the maximum number of available substitutions. When a substituent in a compound mentioned in this disclosure represents multiple substitution (including disubstitution, trisubstitution, tetrasubstitution, etc.), it means that the substituent can be present at multiple available substitution positions on its linkage structure. The substituent present at multiple available substitution positions can be the same structure or different structures.

[0129] In the compounds mentioned in this disclosure, unless explicitly specified, for example, that adjacent substituents can optionally connect to form a ring, adjacent substituents in the compounds cannot connect to form a ring. In the compounds mentioned in this disclosure, the optional connection of adjacent substituents to form a ring includes both cases where adjacent substituents can connect to form a ring and cases where adjacent substituents do not connect to form a ring. When adjacent substituents can optionally connect to form a ring, the resulting ring can be a monocyclic or polycyclic ring, and can be an alicyclic, heterocyclic, aromatic, or heteroaromatic ring. In this context, adjacent substituents can refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

[0130] The statement that adjacent substituents can optionally connect to form a ring is also intended to be understood as referring to two substituents bonded to the same carbon atom connecting to each other via chemical bonds to form a ring, as exemplified by the following formula:

[0131]

[0132] The statement that adjacent substituents can optionally link to form a ring is also intended to be understood as referring to two substituents bonded to carbon atoms directly bonded to each other forming a ring through chemical bonds, as exemplified by the following formula:

[0133]

[0134] Furthermore, the statement that adjacent substituents can optionally connect to form a ring is also intended to mean that, in the case where one of the two substituents bonded to the carbon atom directly bonded to each other represents hydrogen, the second substituent bonds at the position where the hydrogen atom is bonded, thereby forming a ring. This is illustrated by the following example:

[0135]

[0136] The materials described in this invention for specific layers in organic light-emitting devices can be used in combination with a variety of other materials present in the device. These combinations of materials are described in detail in paragraphs 0132-0161 of U.S. Patent Application US2016 / 0359122M, the entire contents of which are incorporated herein by reference. The materials described or mentioned herein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0137] Materials described herein for use in specific layers in organic light-emitting devices can be used in combination with a variety of other materials present in said devices. For example, the compounds disclosed herein can be used in combination with a variety of host layers, delivery layers, barrier layers, injection layers, electrodes, and other possible layers. These combinations of materials are described in detail in paragraphs 0080-0101 of U.S. Patent Application US2015 / 0349273M, the entire contents of which are incorporated herein by reference. The materials described or mentioned herein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0138] In the examples of material synthesis, unless otherwise stated, all reactions were carried out under nitrogen protection. All reaction solvents were anhydrous and used as is from commercial sources. The synthesized products were structurally confirmed and characterized using one or more instruments conventional in the art (including but not limited to Agilent liquid chromatographs, liquid chromatography-mass spectrometers, gas chromatography-mass spectrometers, differential scanning calorimeters, fluorescence spectrophotometers, electrochemical workstations, sublimation apparatuses, etc.) in methods well known to those skilled in the art. In the examples of devices, the characteristics of the devices were also tested using conventional instruments in the art (including but not limited to vapor deposition machines manufactured by Nanjing Institute of Microelectronics, optical testing systems and lifetime testing systems manufactured by Suzhou Fushida, ellipsometers manufactured by Wuhan Yiguang Technology, etc.) in methods well known to those skilled in the art. Since those skilled in the art are familiar with the use of the above-mentioned equipment, testing methods, and other related content, and can obtain the inherent data of the samples definitively and unaffected, the above-mentioned related content will not be elaborated further in this patent.

[0139] Material synthesis examples:

[0140] The preparation methods of the compounds of this invention are not limited. Typical but not limited examples are the following compounds, whose synthetic routes and preparation methods are as follows:

[0141] Synthesis Example 1: Synthesis of Compound C97

[0142] Synthesis of intermediate 1:

[0143]

[0144] In a dry three-necked flask under nitrogen protection, carbazole (16.72 g, 0.1 mol), o-fluorophenylboronic acid (35 g, 0.25 mol), cesium carbonate (97.7 g, 0.3 mol), and 200 mL of N,N-dimethylacetamide were added sequentially. The mixture was heated to 175 °C and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and a suitable amount of dilute hydrochloric acid was added to neutralize the solution. The mixture was extracted with ethyl acetate, washed three times with saturated sodium chloride solution, and washed once with water. The organic phase was separated, dried over anhydrous magnesium sulfate, concentrated, and separated by column chromatography to obtain solid 1 (17 g, yield 60%).

[0145] Synthesis of intermediate 2:

[0146]

[0147] Compound 1 (31.57 g, 0.11 mol), 3-bromo-2-chloronitrobenzene (23.6 g, 0.1 mol), tetrakis(triphenylphosphine)palladium (3.5 g, 3 mmol), sodium carbonate (26.5 g, 0.25 mol), 320 mL toluene, 160 mL ethanol, and 160 mL water were added to a 2 L three-necked flask and stirred at 110 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic phase was dried over magnesium sulfate and dissolved. Purification by column chromatography yielded compound 2 (25.9 g, 65% yield).

[0148] Synthesis of intermediate 3:

[0149]

[0150] Compound 2 (39.9 g, 0.1 mol), palladium(II) acetate (2.25 g, 0.01 mol), tricyclohexylphosphine tetrafluoroborate (7.36 g, 0.02 mol), cesium carbonate (97.7 g, 0.3 mol), and 400 mL of o-xylene were placed in a 1 L three-necked flask under a nitrogen atmosphere and stirred under reflux for 12 hours. After the reaction was complete, the mixture was extracted with water and ethyl acetate. The extracted organic layer was dried over magnesium sulfate and dissolved. Column chromatography was used to purify the mixture to obtain compound 3 (32.6 g, yield: 90%).

[0151] Synthesis of intermediate 4:

[0152]

[0153] Compound 3 (36.23 g, 0.1 mol) and 400 mL of triphenylphosphine (131.1 g, 0.5 mol) and o-dichlorobenzene were placed in a 1 L three-necked flask and stirred at 150 °C for 6 hours. After the reaction was complete, the solvent was removed by vacuum distillation. The mixture was extracted with water and ethyl acetate, and the organic phase was dried over magnesium sulfate and dissolved. Column chromatography was used to purify compound 4 (23.13 g, yield: 70%).

[0154] Synthesis of intermediate 5:

[0155]

[0156] In a 250 mL dry three-necked flask, 1-bromo-8-chloronaphthalene (5 g, 20.66 mmol), pinacol diboronate (6.3 g, 24.79 mmol), potassium acetate (4.05 g, 41.32 mmol), and Pd(dppf)Cl2 (0.190 g, 0.26 mmol) were added. Nitrogen gas was purged three times. 50 mL of 1,4-dioxane was added to the reaction flask, and the reaction was allowed to proceed for 12 h. Ethyl acetate and water were added to extract the reaction solution, followed by solvent removal. The mixture was then slurried in heptane for 2 h and filtered to obtain intermediate 5 (4.4 g, yield 73.8%).

[0157] Synthesis of intermediate 6:

[0158]

[0159] Under nitrogen atmosphere, intermediate 5 (5.2 g, 18.02 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.38 g, 16.38 mmol), potassium carbonate (6.78 g, 49.14 mmol), and tetraphenylphosphine palladium (0.9 g, 0.8 mmol) were added sequentially to a three-necked flask. Dioxane (50 mL) and water (25 mL) were then added. The reaction was carried out at approximately 110 °C for 12 hours. After cooling to room temperature, ethyl acetate and water were added to extract the reaction solution. The organic phase was washed with water until neutral, dried, and then dissolved. After stirring in heptane for 2 hours, the mixture was filtered to obtain white intermediate 6 (3.7 g, 52% yield).

[0160] C97 synthesis:

[0161]

[0162] Under a nitrogen atmosphere, intermediate 6 (3.42 g, 8.68 mmol), intermediate 4 (3.01 g, 9.12 mmol), dipalladium (0.46 g, 0.8 mmol), sodium tert-butoxide (1.25 g, 13.02 mmol), and tritert-butylphosphine tetrafluoroborate (5.036 g, 17.36 mmol), and xylene (70 mL) were added sequentially to a three-necked flask. The reaction was carried out at approximately 140 °C for 18 hours. After cooling to room temperature, ethyl acetate and water were added to extract the reaction solution. The organic phase was desolvated, and column chromatography yielded a bright yellow solid C97 (2.5 g, yield 42%).

[0163] 1 H NMR (400MHz, CDCl3) δ=8.45–8.36(m,4H),8.21–8.12(m,2H),8.11–8.01(m,2H),7.86– 7.76(m,3H),7.71(dd,J=11.0,6.7,1.2Hz,2H),7.67–7.42(m,13H),7.40–7.28(m,3H).

[0164] MS = 687.8.

[0165] Synthesis Example 2: Compound C98

[0166]

[0167] 2-chloro-4,6-diphenyl-1,3,5-triazine was replaced with 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine. With a suitable material ratio selected, the other raw materials and steps were the same as in Synthesis Example 1, yielding 3.14 g of yellow solid C98, with a yield of 45%.

[0168] 1 H NMR (400MHz, CDCl3) δ=8.44–8.38(m,2H),8.21–8.12(m,2H),8.11–8.01(m,2H),8.00–7.94(m,2H),7.86–7.76(m,3H ),7.74–7.67(m,4H),7.67–7.58(m,2H),7.62–7.55(m,4H),7.55–7.41(m,8H),7.41–7.34(m,2H),7.34–7.28(m,2H).

[0169] MS = 763.8.

[0170] Synthesis Example 3: Compound C103

[0171]

[0172] 2-Chloro-4,6-diphenyl-1,3,5-triazine was replaced with 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine. A suitable material ratio was selected, and other raw materials and steps were the same as in Synthesis Example 1, yielding 2.48 g of yellow solid C103, with a yield of 35%.

[0173] 1 H NMR (400MHz, CDCl3) δ=8.44–8.38(m,2H),8.21–8.12(m,2H),8.11–7.95(m,3H),7.87–7.76(m,4H),7 .71(d,J=6.7Hz,2H),7.64(d,J=2.3Hz,2H),7.63–7.55(m,4H),7.55–7.42(m,8H),7.40–7.28(m,4H).

[0174] MS = 777.9.

[0175] Synthesis Example 4: Compound C107

[0176]

[0177] 2-Chloro-4,6-diphenyl-1,3,5-triazine was replaced with 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-(naphth-2-yl)-1,3,5-triazine. With appropriate material ratios selected, and other raw materials and steps being the same as in Synthesis Example 1, 3.39 g of yellow solid C107 was obtained, with a yield of 45%.

[0178] 1 H NMR (400MHz, CDCl3) δ=8.87(t,J=1.9Hz,1H),8.36(d,J=1.9Hz,1H),8.21–8.12(m,2H),8.11–7.95(m,5 H),7.93–7.86(m,1H),7.86–7.76(m,4H),7.71(d,J=6.7Hz,2H),7.67–7.42(m,13H),7.40–7.28(m,4H).

[0179] MS = 827.8.

[0180] Synthesis Example 5: Compound C1283

[0181]

[0182] Synthesis steps:

[0183]

[0184] By replacing 1-bromo-8-chloronaphthalene with 1-chlorocarbazole, selecting an appropriate material ratio, and referring to the synthesis example 1 (see above formula) for other raw materials and steps, 2.58 g of yellow solid C1283 was obtained, with a yield of 39%.

[0185] 1 H NMR (400MHz, CDCl3) δ=8.37–8.31(m,4H),8.19(d,J=3.4Hz,3H),7.78–7.65(m,6 H),7.58–7.49(m,4H),7.53–7.45(m,6H),7.48–7.35(m,4H),7.38–7.28(m,3H).

[0186] MS = 726.7.

[0187] Those skilled in the art should understand that the above preparation method is merely an exemplary example, and they can obtain other compound structures of the present invention by improving it.

[0188] Device Example 1

[0189] First, the glass substrate, which has a 120 nm thick indium tin oxide (ITO) anode, is cleaned and then treated with UV ozone and oxygen plasma. After treatment, the substrate is dried in a nitrogen-filled glove box to remove moisture, and then mounted on a substrate holder and placed in a vacuum chamber. The organic layer specified below is applied at a vacuum degree of approximately 10... -8 In the case of Torr, The deposition rate is achieved sequentially on the ITO anode via thermal vacuum. Simultaneously, the deposited compounds HT and NDP-9 are used as a hole injection layer (HIL), with a thickness of [missing information]. Compound HT is used as a hole transport layer (HTL) with a thickness of [missing information]. Compound EB is used as an electron blocking layer (EBL) with a thickness of [missing information]. Then, the compound C97 of this invention, as the main component, and the compound RD, as a dopant, are co-deposited as an emissive layer (EML) with a thickness of [thickness missing]. Compound HB was used as the hole blocking layer (HBL), with a thickness of [missing information]. On the hole-blocking layer, compound ET and 8-hydroxyquinoline-lithium (Liq) are co-deposited as an electron transport layer (ETL) with a thickness of [missing information]. Finally, vapor deposition Thick 8-hydroxyquinoline-lithium (Liq) was used as the electron injection layer (EIL) and deposited by evaporation. Aluminum was used as the cathode. The device was then transferred back to the glove box and sealed with a glass cover to complete the device.

[0190] Device Example 2

[0191] The implementation method of Device Example 2 is the same as that of Device Example 1, except that the compound C97 of the present invention is replaced by the compound C98 of the present invention as the main body in the light-emitting layer (EML).

[0192] Device Example 3

[0193] The implementation method of Device Example 3 is the same as that of Device Example 1, except that the compound C103 of the present invention is used instead of the compound C97 of the present invention as the main body in the light-emitting layer (EML).

[0194] Device Example 4

[0195] The implementation method of Device Example 4 is the same as that of Device Example 1, except that Compound C107 of the present invention is used instead of Compound C97 of the present invention as the main body in the light-emitting layer (EML).

[0196] Device Example 5

[0197] The implementation method of Device Example 5 is the same as that of Device Example 1, except that the compound C1283 of the present invention is used instead of the compound C97 of the present invention as the main body in the light-emitting layer (EML).

[0198] Device Comparison Example 1

[0199] The implementation of Comparative Example 1 is the same as that of Example 1, except that compound A is used instead of compound C97 of the present invention as the main component in the light-emitting layer (EML).

[0200] Device Comparison Example 2

[0201] The implementation of Comparative Example 2 is the same as that of Example 1, except that compound B is used instead of compound C97 of the present invention as the main component in the light-emitting layer (EML).

[0202] Device Comparison Example 3

[0203] The implementation of Comparative Example 3 is the same as that of Example 1, except that compound C is used instead of compound C97 of the present invention as the main body in the light-emitting layer (EML).

[0204] During the experiment, the vapor deposition temperature of compounds C97, C98, C103, C107, and C1283 was significantly lower than that of compounds A, B, and C. The specific results are shown in Table 2.

[0205] Table 2 Comparison of Evaporation Temperatures for Materials

[0206] Material Number Evaporation temperature / ℃ C97 172 C98 178 C103 181 C107 192 C1283 175 Compound A 224 Compound B 215 Compound C 231

[0207] The detailed device layer structure and thickness are shown in Table 3 below. The layers used are made of more than one material, and are obtained by doping different compounds in the weight ratios specified herein.

[0208] Table 3 Device structures of the device embodiments and comparative examples

[0209]

[0210] The material structure used in the device is shown below:

[0211]

[0212]

[0213] Table 4 lists the values ​​at 10 mA / cm 2 Under the conditions, the measured current efficiency (CE) and maximum wavelength (λ) max ) and external quantum efficiency (EQE). To better illustrate the data comparison, the CE and EQE data of Comparative Example 2 were set to 100%. The CE and EQE data of Examples 1, 2, 3, 4, 5, Comparative Example 1 and Comparative Example 3 were all converted relative to the corresponding data of Comparative Example 2. The relevant data and conversion results are shown in Table 4.

[0214] Table 4 Device Data

[0215]

[0216] Discussion: As shown in Table 4, the maximum wavelength of the comparative examples and the embodiment remained essentially unchanged. At 10 mA / cm² 2 The EQE of Examples 1, 2, 3, 4, and 5, measured at current densities, was increased by 7%, 6%, 1%, 3%, and 6%, respectively, compared to the EQE of Comparative Example 1; the CE of Examples 1, 2, 3, 4, and 5 was increased by 10%, 8%, 1%, 5%, and 8%, respectively, compared to Comparative Example 1; at 10 mA / cm 2 The EQE of Examples 1, 2, 3, 4, and 5, measured at current densities, was increased by 10%, 9%, 4%, 6%, and 9%, respectively, compared to Comparative Example 3; the CE of Examples 1, 2, 3, 4, and 5 was increased by 12%, 10%, 3%, 7%, and 10%, respectively, compared to Comparative Example 3, showing a significant improvement; at 10 mA / cm²... 2The EQE of Examples 1, 2, 3, 4, and 5, measured at current density, was increased by 17%, 16%, 11%, 13%, and 16%, respectively, compared to Comparative Example 2. The CE of Examples 1, 2, 3, 4, and 5 was increased by 17%, 15%, 8%, 12%, and 15%, respectively, compared to Comparative Example 2, showing a more significant improvement. The data indicate that the examples exhibit superior luminous efficiency compared to the comparative examples. Specifically, the compounds of this invention, which are hole transport units with a double α-position naphthalene or carbazole linking a fused macrocyclic structure to an electron transport unit with a triazine or similar structure, exhibit different device performance than Comparative Examples A, B, and C due to the change in the linking fragments. Unexpectedly, this results in excellent device performance, leading to higher current efficiency and external quantum efficiency, and a significant improvement in device performance. This demonstrates the unique advantages of the compounds of this invention.

[0217] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. Therefore, as will be apparent to those skilled in the art, the claimed invention may include variations of the specific embodiments and preferred embodiments described herein. Many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. It should be understood that various theories regarding why the invention works are not intended to be limiting.

Claims

1. An organic electroluminescent compound having a structure represented by FL-Ar, wherein, L is selected from the structures shown in L-1, L-2, L-3, and L-38, or L is selected from the structures shown in L-1, L-2, L-3, and L-38 where the hydrogen is partially or completely replaced by deuterium. F is selected from the structures shown in F-1, F-57 to F-69, or F is selected from the structures shown in F-1, F-57 to F-69 where the hydrogen is partially or completely replaced by deuterium. Ar is selected from the structures shown in Ar-97 to Ar-108, or Ar is selected from the structures shown in Ar-97 to Ar-108 where the hydrogen is partially or completely replaced by deuterium:

2. The compound according to claim 1, characterized in that, The compounds are selected from compounds corresponding to C97 to C108, C164 to C176, C1251, C1252, C1283, C1381 to C1391, and C1447 to C1459, or compounds obtained by partially or completely replacing hydrogen with deuterium in any of the compounds corresponding to C97 to C108, C164 to C176, C1251, C1252, C1283, C1381 to C1391, and C1447 to C1459; the F, L, and Ar in the compounds shown in C97 to C108, C164 to C176, C1251, C1252, C1283, C1381 to C1391, and C1447 to C1459 correspond to the following structures respectively: The structures shown in F-1, F-57 to F-69 are defined as in claim 1, the structures shown in L-1, L-2, L-3 and L-38 are defined as in claim 1, and the structures shown in Ar-97 to Ar-108 are defined as in claim 1.

3. The use of the compound according to any one of claims 1-2 in the preparation of organic electroluminescent devices.

4. The application according to claim 3, characterized in that, The compound is used as the host material for the light-emitting layer in organic electroluminescent devices.

5. An organic electroluminescent device, comprising a light-emitting layer, wherein the bulk material of the light-emitting layer contains a compound according to any one of claims 1-2.

6. The organic electroluminescent device according to claim 5, characterized in that, The organic electroluminescent device includes: an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode.

7. The organic electroluminescent device according to claim 5, characterized in that, The organic electroluminescent device further includes one or more of the following: a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

8. A display component comprising the organic electroluminescent device according to any one of claims 5 to 7.

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