WO2024067503A1 - 一种组合物以及包含其的有机电致发光器件 - Google Patents

一种组合物以及包含其的有机电致发光器件 Download PDF

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WO2024067503A1
WO2024067503A1 PCT/CN2023/121162 CN2023121162W WO2024067503A1 WO 2024067503 A1 WO2024067503 A1 WO 2024067503A1 CN 2023121162 W CN2023121162 W CN 2023121162W WO 2024067503 A1 WO2024067503 A1 WO 2024067503A1
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formula
compound represented
compound
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王占奇
李志强
陆金波
黄常刚
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阜阳欣奕华材料科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight

Definitions

  • the present application belongs to the technical field of organic electroluminescent materials, and in particular relates to a composition and an organic electroluminescent device comprising the composition.
  • OLED organic electroluminescent device
  • OLED technology Compared with other display technologies, OLED technology has outstanding advantages, such as low power consumption, fast response speed, easy bending, wide viewing angle, large-area display, full-color luminous, etc. It can be compatible with various existing standards and technologies to make low-cost light-emitting devices, showing broad application prospects in realizing color flat-panel displays.
  • OLED as a new display technology, has made great progress and has been widely used in the fields of flat-panel displays, flexible displays, solid-state lighting and vehicle-mounted displays.
  • OLED organic electroluminescence
  • the purpose of the present application is to provide a composition and an organic electroluminescent device comprising the same.
  • the composition by designing the specific components of the composition, a composition with excellent performance is obtained, and the composition is used as the material of the light-emitting layer of the organic electroluminescent device to prepare an organic electroluminescent device with excellent performance.
  • the present application provides a composition, comprising two compounds of formula I and one compound of formula II;
  • composition comprises one compound of formula I and two compounds of formula II;
  • Ar 21 and Ar 22 are each independently selected from a C6-C30 aryl group or a C6-C20 heteroaryl group;
  • Ar 23 is selected from any one of a single bond, a phenylene group or a biphenylene group;
  • the hydrogen atoms in the compound of formula I may be substituted by at least one of -F, -CN, C6-C20 aryl, C1-C6 alkyl or C1-C6 alkoxy;
  • the compound represented by formula I meets at least one of the following conditions:
  • the Ar 23 group is a phenylene group and/or a biphenylene group, and at least one hydrogen atom in the Ar 23 group is replaced by a deuterium atom;
  • the compound represented by formula II is obtained by fusing a group represented by formula IC with any two adjacent carbon atoms on ring E in the group represented by formula ID;
  • * indicates the fusion site
  • Ar 11 is selected from any one of a single bond, a phenylene group, a naphthylene group, and a biphenylene group;
  • R 101 and R 102 are each independently selected from H, C6-C30 aryl or C6-C20 heteroaryl;
  • X, Y, and Z are each independently selected from N or CR 304 , R 304 is selected from any one of H, phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, dibenzofuranyl, and dibenzothiophenyl, and at least one of X, Y, and Z is N;
  • X 1 is selected from O, S, wherein R 301 and R 302 are each independently selected from a C1-C5 alkyl group or a phenyl group, R 303 is selected from a phenyl group or a biphenyl group, and the dotted line indicates the connection site;
  • the hydrogen atoms in the compound represented by formula II may be substituted by at least one of -F, -CN, C6-C20 aryl, C1-C6 alkyl, and C1-C6 alkoxy;
  • the compound represented by formula II meets at least one of the following conditions:
  • R 304 is a deuterium atom
  • R 304 in the compound of formula II is selected from phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, dibenzofuranyl, and dibenzothienyl, at least one hydrogen atom in the phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, dibenzofuranyl, and dibenzothienyl is replaced by a deuterium atom;
  • composition having a specific composition is designed and further obtained by combining at least two specific compounds.
  • This composition is used as the material for the light-emitting layer of an organic electroluminescent device to prepare an organic electroluminescent device with excellent performance.
  • the C6 to C30 are selected from C6, C10, C12, C18, C24 or C30, etc.
  • the C6-C20 is selected from C6, C10, C12, C18 or C20.
  • the C1-C6 is selected from C1, C2, C3, C4, C5 or C6.
  • the C1-C5 are selected from C1, C2, C3, C4 or C5.
  • the composition includes two compounds represented by formula I and two compounds represented by formula II.
  • composition includes two compounds of formula I (denoted as compound 1-1 and compound 1-2) and a compound of formula II (denoted as compound 2-1), and the volume ratio of compound 1-1, compound 1-2, and compound 2-1 is 1:(1-2):(1-6), for example, it can be 1:1:1, 1:1:2, 1:1:3, 1:1:4, 1:2:1, 1:2:2, 1:2:3, 1:2:4, 1:2:5 or 1:2:6, etc.;
  • the composition includes a compound of formula I (denoted as compound 1-1) and two compounds of formula II (denoted as compound 2-1 and compound 2-2), and the volume ratio of compound 1-1, compound 2-1, and compound 2-2 is (1-6):(1-2):1, for example, it can be 1:1:1, 2:1:1, 3:1:1, 4:1:1, 1:2:1, 2:2:1, 3:2:1, 4:2:1, 5:2:1 or 6:2:1, etc.;
  • the composition includes two compounds of formula I (denoted as compound 1-1 and compound 1-2) and two compounds of formula II (denoted as compound 2-1 and compound 2-2), then the volume ratio of compound 1-1 to compound 1-2 is (2:8)-(8:2), for example, it can be 2:8, 3:7, 4:6, 5:5, 6:4, 7:3 or 8:2, the volume ratio of compound 2-1 to compound 2-2 is (2:8)-(8:2), for example, it can be 2:8, 3:7, 4:6, 5:5, 6:4, 7:3 or 8:2, and the ratio of the sum of the volumes of compound 1-1 and compound 1-2 to the sum of the volumes of compound 2-1 and compound 2-2 is (2:8)-(8:2), for example, it can be 2:8, 3:7, 4:6, 5:5, 6:4, 7:3 or 8:2, etc.
  • the compound represented by Formula I has a structure as represented by Formula I-1 or Formula I-2:
  • Ar 21 and Ar 22 have the same protection scope as above.
  • the compound represented by formula I meets condition (3) and/or condition (4).
  • the compound represented by Formula I has a structure represented by Formula I-1-D or Formula I-2-D:
  • Ar 21 and Ar 22 have the same protection scope as above, and Ar 21 and Ar 22 do not contain deuterium atoms.
  • (D) 4 represents the corresponding The four hydrogen atoms of are replaced by deuterium atoms.
  • (D) 3 indicates that the three hydrogen atoms on the corresponding benzene ring are replaced by deuterium atoms, and Ar 21 and Ar 22 do not contain deuterium atoms.
  • Ar 21 and Ar 22 are independently selected from any one of phenyl, biphenyl, naphthyl, fluorenyl, triphenylene, fluorenyl, dibenzofuranyl, dibenzothienyl, terphenyl or quaterphenyl, or a combination of at least two thereof.
  • R 101 and R 102 are each independently selected from any one of H, phenyl, naphthyl, triphenylene, fluoranthenyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, naphthyl, dibenzofuranyl, and dibenzothiophenyl.
  • the compound represented by formula I is selected from any one of the following substituted or unsubstituted compounds:
  • substitution means that the hydrogen atoms in the above compounds can each be independently replaced by a deuterium atom.
  • the compound represented by formula I is selected from any one of the following substituted or unsubstituted compounds H-1 to H-40, H-17o, and H-17m:
  • substitution means that the hydrogen atoms in the above compounds can each be independently replaced by a deuterium atom.
  • the compound represented by formula II is selected from any one of the following substituted or unsubstituted compounds:
  • substitution means that the hydrogen atoms in the above compounds can each be independently replaced by a deuterium atom.
  • the present application provides a compound, comprising the following compounds:
  • the compound is used to prepare the composition as described in the first aspect.
  • the present application provides an intermediate, which comprises the following compound:
  • the intermediate is used to prepare the compound represented by formula I in the composition described in the first aspect.
  • D in the above compounds and intermediates is a deuterium atom.
  • the present application provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode;
  • the material of the organic thin film layer includes the composition described in the first aspect.
  • the organic thin film layer includes a light-emitting layer, and the material of the light-emitting layer includes the composition as described in the first aspect.
  • the organic thin film layer includes a hole layer.
  • the hole layer includes an electron blocking layer
  • the material of the electron blocking layer includes a spirofluorene compound
  • the spirofluorene compound has a structure as shown in the following formula III:
  • X is selected from O or S
  • R 11 and R 21 are each independently selected from hydrogen, deuterium, fluorine, CN, substituted or unsubstituted C1-C20 (for example, C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18 or C20, etc.) linear or branched alkyl, substituted or unsubstituted C1-C20 (for example, C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18 or C20, etc.) alkoxy, substituted or unsubstituted C6-C40 (for example, C6, C8, C10, C12, C15, C18, C24, C30, C36 or C40, etc.) aryl;
  • C6-C40 for example, C6, C8, C10, C12, C15, C18, C24, C30, C36 or C40, etc.
  • Ar is selected from substituted or unsubstituted C6-C40 (e.g., C6, C8, C10, C12, C15, C18, C24, C30, C36 or C40, etc.) arylene;
  • Ar 1 and Ar 2 are each independently selected from substituted or unsubstituted C6-C40 (e.g., C6, C8, C10, C12, C15, C18, C24, C30, C36, or C40) aryl, substituted or unsubstituted C12-C40 (C12, C14, C16, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, or C40) oxaaryl, substituted or unsubstituted C12-C40 (C12, C14, C16, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, or C40) thiaaryl, and Ar 1 or Ar 2 is 2 , at least one of which is selected from any one of phenyl, naphthyl, triphenylene or fluoranthenyl; p is selected from 0 or 1; m and n are each independently
  • the oxygen heteroaryl group refers to a structure having an oxygen-containing five-membered heterocyclic ring formed by two aromatic rings connected by a single bond and bridged by an O atom.
  • two benzene rings are connected by a single bond to form biphenyl, and the carbon atoms on the two benzene rings constituting the biphenyl are simultaneously connected to O atoms to form dibenzofuran.
  • the sulfur heteroaryl group refers to a structure having a sulfur-containing five-membered heterocyclic ring formed by two aromatic rings connected by a single bond and bridged by an S atom.
  • two benzene rings are connected by a single bond to form biphenyl, and the carbon atoms on the two benzene rings constituting the biphenyl are simultaneously connected to S atoms to form dibenzothiophene.
  • the spirofluorene compound is selected from the compound shown in III-1 or the compound shown in III-2:
  • X and X1 are each independently selected from O or S;
  • R 11 , R 21 , and Ar have the same protection scope as above;
  • Ar 1 is selected from any one of phenyl, naphthyl, triphenylene or fluoranthenyl;
  • R 31 is selected from C1 to C20 (for example, C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18 or C20, etc.) straight or branched alkyl, C1-C20 (for example, C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18 or C20, etc.) alkoxy, C6-C40 (for example, C6, C8, C10, C12, C15, C18, C24, C30, C36 or C40, etc.) aryl;
  • R 41 and R 42 are each independently selected from C1-C20 (for example, C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18 or C20, etc.) straight chain or branched alkyl, C6-C40 (for example, C6, C8, C10, C12, C15, C18, C24, C30, C36 or C40, etc.) aryl, and R 41 and R 42 are independent of each other or connected to form a ring by a single bond.
  • C1-C20 for example, C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18 or C20, etc.
  • C6-C40 for example, C6, C8, C10, C12, C15, C18, C24, C30, C36 or C40, etc.
  • R 41 and R 42 are independent of each other or connected to form a ring by a single bond.
  • the spirofluorene compound is selected from any one of the following compounds 1-140 and compounds 1S-140S:
  • the compound 1S-140S is a compound 1-140 Replace with The dotted line indicates Connection site.
  • the present application provides a display device, comprising the organic electroluminescent device as described in the fourth aspect.
  • compositions with a specific composition are obtained.
  • This composition is used as the material for the light-emitting layer of an organic electroluminescent device to prepare an organic electroluminescent device with low driving voltage, high current efficiency and long life.
  • This synthesis example provides compound H-29-D and its synthesis method, the synthesis method is as follows:
  • the mass spectrometry detection of compound H-29-D was measured to be 730.40.
  • This synthesis example provides compound H-29-DE and its synthesis method, the synthesis method is as follows:
  • compound H-29-1 (3.9 g), palladium chloride (0.026 g), anhydrous nickel chloride (0.018 g), activated carbon (0.3 g), D 2 O (48 mL) and C 6 D 6 (120 mL) were added to a 500 mL autoclave, and hydrogen was introduced to a pressure of 0.02 MPa. The temperature was then raised to 90°C for reaction for 60 hours, and the temperature was lowered to room temperature, filtered, and separated.
  • the intermediate H-29-DE-1 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m/z) was measured to be 428.29.
  • the difference is that the compound H-29-1 is replaced by an equal amount of the intermediate H-29-DE-1, and the brominated deuterated biphenyl is replaced by an equal amount of bromobiphenyl to obtain the compound H-29-DE.
  • the compound H-29-DE was subjected to mass spectrometry detection: the mass-to-charge ratio (m/z) was measured to be 730.40.
  • This synthesis example also provides another synthesis method of compound H-29-DE, which is as follows:
  • intermediate H-29-DE-1 (4.3g) and 50mL of dry tetrahydrofuran, cool to -50°C, slowly drop 14mL of 1.6M butyl lithium n-hexane solution, after the addition, keep at -50°C for 30 minutes, slowly add 2g of methanol, warm to room temperature, add water and dichloromethane for separation, wash the organic layer with water, dry it with magnesium sulfate, and separate it by silica gel column chromatography to obtain intermediate H-29-DE-1H (3.6g).
  • the intermediate H-29-DE-1H was subjected to mass spectrometry detection, and the mass-to-charge ratio (m/z) was measured to be 426.28.
  • the difference is that the compound H-29-1 is replaced by an equal amount of H-29-DE-1H, and the brominated deuterated biphenyl is replaced by an equal amount of bromobiphenyl to obtain the compound H-29-DE.
  • the compound H-29-DE was subjected to mass spectrometry detection: the mass-to-charge ratio (m/z) was measured to be 730.40.
  • the device embodiment provides an organic electroluminescent device, and the composition provided in the present application is selected as the red light host material in the organic electroluminescent device.
  • the structure of the organic electroluminescent device is: ITO/HT-1 (20nm)/red light host material (35nm): Ir (piq) 3 [10%]/TPBI (10nm)/Alq3 (15nm)/LiF (0.5nm)/Al (150nm).
  • Ir (piq) 3 [10%] It refers to the doping ratio of the red light dye, that is, the volume ratio of the red light host material to Ir(piq)3 is 90:10.
  • the preparation process of organic electroluminescent device is as follows:
  • the glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;
  • the glass substrate with the anode is placed in a vacuum chamber, and the vacuum is evacuated to 1 ⁇ 10 -5 ⁇ 9 ⁇ 10 -4 Pa.
  • a hole transport layer HT-1 is vacuum-deposited on the anode layer film, with a deposition rate of 0.1 nm/s and a deposition film thickness of 20 nm.
  • the red light host material and the dye Ir(piq)3 are vacuum evaporated on the hole transport layer as the light-emitting layer of the organic electroluminescent device, the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 35nm; in this embodiment, if the red light host is two or more compounds, each compound is placed in a different evaporation source for heating, and the heating rate is controlled so that the volume ratio of each compound evaporated on the substrate is the same as the red light host material;
  • the electron transport layer TPBI and Alq 3 are vacuum-deposited on the light-emitting layer in sequence, with the evaporation rate of 0.1 nm/s and the thickness of the evaporated films being 10 nm and 15 nm respectively;
  • 0.5 nm of LiF and 150 nm of Al were vacuum-deposited on the electron transport layer as the electron injection layer and cathode.
  • Device Examples 2-15 respectively provide an organic electroluminescent device, which differs from Device Example 1 only in that the red light main material is different. If the red light main material is two or more compounds, each compound is placed in a different evaporation source for heating, and the heating rate is controlled so that the volume ratio of each compound evaporated onto the substrate is the same, as the red light main material (see Table 1 below for details). The other preparation steps and conditions are the same as those of Device Example 1.
  • Device comparison examples 1-3 respectively provide an organic electroluminescent device, which differs from device example 1 only in that the red light main material is different. If the red light main material is two or more compounds, each compound is placed in a different evaporation source for heating, and the heating rate is controlled so that the volume ratio of each compound evaporated onto the substrate is the same, as the red light main material (see Table 1 below for details). The other preparation steps and conditions are the same as those of device example 1.
  • the OLED-1000 multi-channel accelerated aging life and light color performance analysis system produced by Hangzhou Yuggling was used to test and measure the brightness, driving voltage, current efficiency, and life test LT90 of the prepared organic electroluminescent device.
  • life test LT90 refers to the time required for the brightness to decrease to 90% of the initial brightness at room temperature (25-27°C) while keeping the current density at the initial brightness unchanged (here 1000cd/ m2 ).
  • voltage, efficiency, and LT90 are all relative values. The test results are detailed in Table 1 below.
  • a specific composition is further composed of multiple components, and this composition is used as the material for the light-emitting layer of the organic electroluminescent device to prepare an organic electroluminescent device with low driving voltage, high current efficiency and long life.
  • the organic electroluminescent device prepared by adopting the multi-component composition in the present application has excellent comprehensive performance.
  • the present application uses the compound of formula I in which the hydrogen atom on the carbazole group is replaced by a deuterium atom as one of the components of the composition, which can further improve the life of the OLED device.
  • the performance of the prepared OLED device is better when the compound represented by formula I is selected, in which the hydrogen atom on the carbazole group is replaced by a deuterium atom and the benzene ring group (the substituent at the corresponding position of Ar 21 and Ar 22 ) does not contain a hydrogen atom.
  • the performance of the prepared OLED device is better when one of the two compounds conforming to the structure described in formula I does not contain a D atom.
  • the device embodiment provides an organic electroluminescent device, and the composition provided in the present application is selected as the red light host material in the organic electroluminescent device.
  • the structure of the organic electroluminescent device is: ITO/HT-1 (20nm)/electron blocking layer (5nm)/red light host material (35nm): Ir(piq)3[10%]/TPBI(10nm)/Alq3(15nm)/LiF(0.5nm)/Al(150nm).
  • Ir(piq)3[10%] refers to the doping ratio of the red light dye, that is, the volume ratio of the red light host material to Ir(piq)3 is 90:10.
  • the preparation process of organic electroluminescent device is as follows:
  • the glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment to completely remove the water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;
  • the glass substrate with the anode is placed in a vacuum chamber, and the vacuum is evacuated to 1 ⁇ 10 -5 ⁇ 9 ⁇ 10 -4 Pa.
  • a hole transport layer HT-1 is vacuum-deposited on the anode layer film, with a deposition rate of 0.1 nm/s and a deposition film thickness of 20 nm.
  • EB was vacuum-deposited on the hole transport layer as an electron blocking layer at a deposition rate of 0.1 nm/s and a deposition film thickness of 5 nm.
  • the red light host material and dye Ir(piq)3 are vacuum-deposited on the electron blocking layer as the light-emitting layer of the organic electroluminescent device.
  • the evaporation rate is 0.1nm/s and the total evaporation film thickness is 35nm.
  • the red light host is H-3, H-3-DE, E-1 and E-1D, placing each compound in a different evaporation source for heating, controlling the heating speed so that the volume ratio of each compound evaporated on the substrate is the same, as the red light main material.
  • the electron transport layer TPBI and Alq 3 are vacuum-deposited on the light-emitting layer in sequence, with the evaporation rate of 0.1 nm/s and the thickness of the evaporated films being 10 nm and 15 nm respectively;
  • 0.5 nm of LiF and 150 nm of Al were vacuum-deposited on the electron transport layer as the electron injection layer and cathode.
  • Device Example 17 provides an organic electroluminescent device, which differs from Device Example 16 only in that the electron blocking layer material is different (see Table 2 below for details), and the other preparation steps and conditions are the same as those of Device Example 16.

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Abstract

本申请提供一种组合物以及包含其的有机电致发光器件。所述组合物包括两种式I所示化合物和一种式II所示化合物；或者，所述组合物包括一种式I所示化合物和两种式II所示化合物；所述式II所示化合物由一个式I-C所示基团与式I-D所示基团中环E上任意相邻的两个碳原子稠合得到。本申请提供的组合物可作为有机电致发光器件的发光层材料，进而制备得到性能优异的有机电致发光器件。

Description

一种组合物以及包含其的有机电致发光器件
本申请要求在2022年9月30日提交中国专利局、申请号为202211215054.0的中国专利的优先权，以上申请的全部内容通过引用结合在本申请中。
技术领域
本申请属于有机电致发光材料技术领域，具体涉及一种组合物以及包含其的有机电致发光器件。
背景技术
有机电致发光现象早在1963年就已经被发现，但在当时并未引起人们的重视；直到1987年美国柯达公司Tang研究小组发表了以有机荧光材料和空穴材料制成直流低电压驱动的高亮度、高效率的薄膜型有机电致发光器件(OLED)后，该技术才重新得到关注，并开创了一个全新的研究领域。
OLED技术相较于其他显示技术具有突出的优势，如功耗低、响应速度快、易弯曲、视角广、可大面积显示、发光色彩全等，并可与现有的多种标准、技术兼容制成低成本的发光器件，在实现彩色平板显示方面展现出广阔的应用前景。在过去的数十年里，OLED作为一种新的显示技术已经获得了长足发展，在平板显示、柔性显示、固态照明和车载显示领域中获得了广泛应用。
当前，有机电致发光(OLED)已经成为主流的显示技术，相应的，各种新型的OLED材料也被开发。但是，其各种性能尚待提高，尤其在效率、寿命、电压等方面。因此，开发更多种类、性能更加完善的蓝光主体材料，以满足其在高性能OLED器件的使用需求，是本领域的研究重点。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
针对现有技术的不足，本申请的目的在于提供一种组合物以及包含其的有机电致发光器件。本申请中通过对组合物的具体组分进行设计，得到了性能优异的组合物，以此组合物作为有机电致发光器件发光层的材料，可制备得到的性能优异的有机电致发光器件。
为达此目的，本申请采用以下技术方案：
第一方面，本申请提供一种组合物，所述组合物包括两种式I所示化合物和一种式II所示化合物；
或者，所述组合物包括一种式I所示化合物和两种式II所示化合物；
所述式I所示化合物的结构式如下：
其中，Ar21、Ar22各自独立地选自C6～C30芳基或C6～C20杂芳基；
Ar23选自单键、亚苯基或亚联苯基中的任意一种；
式I所示化合物中的氢原子可以被-F、-CN、C6-C20芳基、C1-C6烷基或C1-C6烷氧基中的至少一种取代；
式I所示化合物符合如下条件中的至少一个：
(1)式I所示化合物中不含氘原子；
(2)式I所示化合物中两个咔唑基上连接的氢原子全部被氘原子替代；
(3)式I所示化合物中Ar21基团中至少一个氢原子被氘原子替代；
(4)式I所示化合物中Ar22基团中至少一个氢原子被氘原子替代；
(5)式I所示化合物中Ar23基团为亚苯基和/或亚联苯基，Ar23基团中至少一个氢原子被氘原子替代；
(6)式I所示化合物中的氢原子被C6-C20芳基取代，C6-C20芳基中至少一个氢原子被氘原子替代；
(7)式I所示化合物中的氢原子被C1-C6烷基和/或C1-C6烷氧基取代，C1-C6烷基和/或C1-C6烷氧基中氢原子全部被氘原子替代；
所述式II所示化合物由一个式I-C所示基团与式I-D所示基团中环E上任意相邻的两个碳原子稠合得到；
其中，*表示稠合位点；
Ar11选自单键、亚苯基、亚萘基、亚联苯基中的任意一种；
R101、R102各自独立地选自H、C6～C30芳基或C6～C20杂芳基；
X、Y、Z各自独立地选自N或者CR304，R304选自H、苯基、联苯基、萘基、9,9-二甲基芴基、二苯并呋喃基、二苯并噻吩基中的任意一种，且X、Y、Z中的至少一个为N；
X1选自O、S、其中R301、R302各自独立地选自C1-C5烷基或苯基，R303选自苯基或联苯基，虚线表示连接位点；
式II所示化合物中的氢原子可以被-F、-CN、C6～C20芳基、C1～C6烷基、C1～C6烷氧基中的至少一种取代；
式II所示化合物符合如下条件中的至少一个：
(a)式II所示化合物中不含氘原子；
(b)式II所示化合物中环F、环D、环E中至少一个环上的氢原子全部被氘原子替代；
(c)式II所示化合物中R101中至少一个氢原子被氘原子替代；
(d)式II所示化合物中R102中至少一个氢原子被氘原子替代；
(e)式II所示化合物中Ar11中至少一个氢原子被氘原子替代；
(f)式II所示化合物中R301和R302中的氢原子全部被氘原子替代；
(g)式II所示化合物中R303基团中至少一个氢原子被氘原子替代；
(h)式II所示化合物中R304为氘原子；
(i)式II所示化合物中R304选自苯基、联苯基、萘基、9,9-二甲基芴基、二苯并呋喃基、二苯并噻吩基时，苯基、联苯基、萘基、9,9-二甲基芴基、二苯并呋喃基、二苯并噻吩基中至少一个氢原子被氘原子替代；
(j)式II所示化合物中的氢原子被C6～C20芳基取代，C6～C20芳基中至少一个氢原子被氘原子替代；
(k)式II所示化合物中的氢原子被C1～C6烷基和/或C1～C6烷氧基取代，C1～C6烷基 和/或C1～C6烷氧基中氢原子全部被氘原子替代。
本申请中，通过对组合物的具体组成进行设计，进一步通过至少两种特定化合物的配合使用，得到了具有特定组成的组合物，以此组合物作为有机电致发光器件发光层的材料，可制备得到的性能优异的有机电致发光器件。
本申请中，所述C6～C30选自C6、C10、C12、C18、C24或C30等。
所述C6～C20选自C6、C10、C12、C18或C20等。
所述C1～C6选自C1、C2、C3、C4、C5或C6。
所述C1～C5选自C1、C2、C3、C4或C5。
以下作为本申请的可选技术方案，但不作为对本申请提供的技术方案的限制，通过以下可选的技术方案，可以更好的达到和实现本申请的目的和有益效果。
作为本申请的可选技术方案，所述组合物包括两种式I所示化合物和两种式II所示化合物。
需要说明的是，所述组合物包括两种式I所示化合物(记为化合物1-1和化合物1-2)和一种式II所示化合物(记为化合物2-1)，则化合物1-1、化合物1-2、化合物2-1的体积比为1:(1-2):(1-6)，例如可以是1:1:1、1:1:2、1:1:3、1:1:4、1:2:1、1:2:2、1:2:3、1:2:4、1:2:5或1:2:6等；
或者，所述组合物包括一种式I所示化合物(记为化合物1-1)和两种式II所示化合物(记为化合物2-1和化合物2-2)，则化合物1-1、化合物2-1、化合物2-2的体积比为(1-6):(1-2):1，例如可以是1:1:1、2:1:1、3:1:1、4:1:1、1:2:1、2:2:1、3:2:1、4:2:1、5:2:1或6:2:1等；
或者，所述组合物包括两种式I所示化合物(记为化合物1-1和化合物1-2)和两种式II所示化合物(记为化合物2-1和化合物2-2)，则化合物1-1、化合物1-2的体积比为(2:8)-(8:2)，例如可以是2:8、3:7、4:6、5:5、6:4、7:3或8:2等，化合物2-1、化合物2-2的体积比为(2:8)-(8:2)，例如可以是2:8、3:7、4:6、5:5、6:4、7:3或8:2等，并且化合物1-1、化合物1-2的体积之和与化合物2-1、化合物2-2的体积之和的比值(2:8)-(8:2)，例如可以是比可以为2:8、3:7、4:6、5:5、6:4、7:3或8:2等。在一个实施方式中，所述式I所示化合物具有如式I-1或式I-2所示结构：
其中，Ar21、Ar22具有与上述相同的保护范围。
作为本申请的可选技术方案，所述式I所示化合物符合条件(3)和/或条件(4)。
在一个实施方式中，所述式I所示化合物具有如式I-1-D或式I-2-D所示结构：
其中，Ar21、Ar22具有与上述相同的保护范围，且Ar21、Ar22中不含氘原子。
需要说明的是，式I-1-D所示化合物、式I-2-D所示化合物中，(D)4表示对应的苯环上 的四个氢原子均被氘原子取代，同理，(D)3表示对应的苯环上的三个氢原子均被氘原子取代，并且Ar21、Ar22均不含有氘原子。
作为本申请的可选技术方案，所述Ar21、Ar22各自独立地选自苯基、联苯基、萘基、芴基、三亚苯基、芴基、二苯并呋喃基、二苯并噻吩基、三联苯基或四联苯基中的任意一个或者至少两种的组合。
在一个实施方式中，所述R101、R102各自独立地选自H、苯基、萘基、三亚苯基、荧蒽基、芴基、蒽基、菲基、联苯基、萘基、二苯并呋喃基、二苯并噻吩基中的任意一种。
作为本申请的可选技术方案，所述式I所示化合物选自下述取代或未取代的化合物中的任意一种：

所述取代是指上述化合物中的氢原子各自独立地可以被氘原子取代。
在一个实施方式中，所述式I所示化合物选自下述取代或未取代的化合物H-1～H-40、H-17o、H-17m中的任意一种：


所述取代是指上述化合物中的氢原子各自独立地可以被氘原子取代。
作为本申请的可选技术方案，所述式II所示化合物选自下述取代或未取代的化合物中的任意一种：














所述取代是指上述化合物中的氢原子各自独立地可以被氘原子取代。
第二方面，本申请提供一种化合物，所述化合物包括如下化合物：
所述化合物用于制备如第一方面所述的组合物。
第三方面，本申请提供一种中间体，所述中间体包括如下化合物：
所述中间体用于制备如第一方面所述的组合物中的式I所示化合物。
需要说明的是，本申请中，对于式I所示化合物、式II所示化合物的制备方法不做任何特殊的限制，通过本领域常用的方法即可制备得到，示例性地可参考CN112996793A，CN112805277A、CN102212066A、CN114695764A中所述的制备方法。
同时需要说明的是，上述化合物和中间体中的D为氘原子。
第四方面，本申请提供一种有机电致发光器件，所述有机电致发光器件包括阳极、阴极以及设置于所述阳极和阴极之间的有机薄膜层；
所述有机薄膜层的材料包括如第一方面所述的组合物。
在一个实施方式中，所述有机薄膜层包括发光层，所述发光层的材料包括如第一方面所述的组合物。
在一个实施方式中，所述有机薄膜层包括空穴层。
在一个实施方式中，所述空穴层包括电子阻挡层，所述电子阻挡层的材料包括螺芴类化合物。
所述螺芴类化合物具体如下式III所示结构：
其中，X选自O或S；
R11、R21各自独立地选自氢、氘、氟、CN、取代或未取代的C1～C20(例如可以是C1、C2、C3、C4、C5、C7、C8、C9、C10、C13、C15、C18或C20等)直链或支链烷基、取代或未取代的C1～C20(例如可以是C1、C2、C3、C4、C5、C7、C8、C9、C10、C13、C15、C18或C20等)烷氧基、取代或未取代的C6～C40(例如可以是C6、C8、C10、C12、C15、C18、C24、C30、C36或C40等)芳基；
Ar选自取代或未取代的C6～C40(例如可以是C6、C8、C10、C12、C15、C18、C24、C30、C36或C40等)亚芳基；
Ar1、Ar2各自独立地选自取代或未取代的C6～C40(例如可以是C6、C8、C10、C12、C15、C18、C24、C30、C36或C40等)芳基、取代或未取代的C12～C40(C12、C14、C16、C18、C20、C23、C25、C27、C30、C32、C35、C37、C39或C40等)氧杂芳基、取代或未取代的C12～C40(C12、C14、C16、C18、C20、C23、C25、C27、C30、C32、C35、C37、C39或C40等)硫杂芳基，且Ar1或Ar2中至少一个选自苯基、萘基、三亚苯基或荧蒽基中的任意一种；p选自0或1；m、n各自独立地选自0～4的整数，例如可以是0、1、2、3、4。
需要说明的是，所述氧杂芳基是指通过单键相连的两个芳环通过O原子桥接，形成的具有含氧五元杂环的结构，例如两个苯环通过单键相连成联苯，组成联苯的两个苯环上的碳原子同时和O原子连接，形成二苯并呋喃。
所述硫杂芳基是指通过单键相连的两个芳环通过S原子桥接，形成的具有含硫五元杂环的结构，例如两个苯环通过单键相连成联苯，组成联苯的两个苯环上的碳原子同时和S原子连接，形成二苯并噻吩。
在一个实施方式中，所述螺芴类化合物选自III-1所示化合物或III-2所示化合物：
其中，X、X1各自独立地选自O或S；
R11、R21、Ar具有与上述相同的保护范围；
Ar1选自苯基、萘基、三亚苯基或荧蒽基中的任意一种；
R31选自C1～C20(例如可以是C1、C2、C3、C4、C5、C7、C8、C9、C10、C13、C15、 C18或C20等)直链或支链烷基、C1～C20(例如可以是C1、C2、C3、C4、C5、C7、C8、C9、C10、C13、C15、C18或C20等)烷氧基、C6～C40(例如可以是C6、C8、C10、C12、C15、C18、C24、C30、C36或C40等)芳基；
R41、R42各自独立地选自C1～C20(例如可以是C1、C2、C3、C4、C5、C7、C8、C9、C10、C13、C15、C18或C20等)直链或支链烷基、C6～C40(例如可以是C6、C8、C10、C12、C15、C18、C24、C30、C36或C40等)芳基，且R41和R42相互独立或通过单键连接成环。
在一个实施方式中，所述螺芴类化合物选自如下化合物1-140、化合物1S-140S中的任意一种：






所述化合物1S-140S是将化合物1-140中的替换为其中虚线表示 连接位点。
如化合物2的结构为则化合物2S的结构为：
第五方面，本申请提供一种显示装置，所述显示装置包括如第四方面所述的有机电致发光器件。
与现有技术相比，本申请具有以下有益效果：
通过对组合物的具体组分的设计，得到了具有特定组成的组合物，以此组合物作为有机电致发光器件发光层的材料，制备得到了驱动电压较低、电流效率较高、寿命较长的有机电致发光器件。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
为便于理解本申请，本申请列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
合成实施例1
本合成实施例提供化合物H-29-D及其合成方法，合成方法如下：
在氮气保护下，向250mL三口瓶中，加入100mL干燥的甲苯、中间体H-29-1(4.1g)、溴代的氘代联苯(5.2g)、Pd(dba)2(双二亚苄基丙酮钯，0.1g)、质量百分含量为10％的三叔丁基膦的甲苯溶液0.8g和叔丁醇钠(3.1g)，缓慢升温至回流反应8小时，降温至室温后加水分液，然后将有机层水洗至中性，用硫酸镁干燥，过滤除去硫酸镁后，浓缩至干，用硅胶柱层析分离，石油醚:二氯甲烷＝10:1(体积比)洗脱，得到6.0g化合物H-29-D。
对化合物H-29-D进行质谱检测：测得质荷比(m/z)为730.40。
合成实施例2
本合成实施例提供化合物H-29-DE及其合成方法，合成方法如下：
(1)H-29-DE-1的合成
在25℃下，向500mL高压釜内加入化合物H-29-1(3.9g)、氯化钯(0.026g)、无水氯化镍(0.018g)、活性炭(0.3g)、D2O(48mL)和C6D6(120mL)，并向其中通入氢气至压强为0.02MPa，然后升温到90℃反应60小时，降温至室温，过滤，分液，其中分液后的有机层用硫酸镁干燥后，短硅胶柱脱色，浓缩至干后，硅胶柱层析分离，石油醚：乙酸乙酯＝10:1(体积比)洗脱，得到中间体H-29-DE-1(3.2g)。
对中间体H-29-DE-1进行质谱检测，测得质荷比(m/z)为428.29。
(2)化合物H-29-DE的合成
参照H-29-D的合成方法，区别在于，将化合物H-29-1替换为等物质的量的中间体H-29-DE-1，将溴代的氘代联苯替换为等物质的量的溴代联苯，得到化合物H-29-DE。
对化合物H-29-DE进行质谱检测：测得质荷比(m/z)为730.40。
本合成实施例同时提供化合物H-29-DE的另一种合成方法，所述合成方法如下：
(1)中间体H-29-DE-1H的合成
向250mL三口瓶加入中间体H-29-DE-1(4.3g)、50mL干燥的四氢呋喃，降温至-50℃，缓慢滴加1.6M的丁基锂的正己烷溶液14mL，加毕后，于-50℃保温30分钟，缓慢加入2g甲醇，升温至室温，加水和二氯甲烷分液，有机层水洗，硫酸镁干燥后，硅胶柱层析分离，得到中间体H-29-DE-1H(3.6g)。
对中间体H-29-DE-1H进行质谱检测，测得质荷比(m/z)为426.28。
(2)化合物H-29-DE的合成
参照H-29-D的合成方法，区别在于，将化合物H-29-1替换为等物质的量的H-29-DE-1H，将溴代的氘代联苯替换为等物质的量的溴代联苯，得到化合物H-29-DE。
对化合物H-29-DE进行质谱检测：测得质荷比(m/z)为730.40。
其它未列明具体合成步骤的化合物，可以通过本领域公知常识，结合以上实施例制备。
下述器件实施例和器件对比例中使用的化合物的具体结构如下：
下述实施例中所采用的化合物的具体结构如下所示：

器件实施例1
本器件实施例提供一种有机电致发光器件，选用本申请提供的组合物作为有机电致发光器件中的红光主体材料。
所述有机电致发光器件的结构为：ITO/HT-1(20nm)/红光主体材料(35nm)：Ir(piq)3[10％]/TPBI(10nm)/Alq3(15nm)/LiF(0.5nm)/Al(150nm)。其中“Ir(piq)3[10％]” 是指红光染料的掺杂比例，即红光主体材料与Ir(piq)3的体积份比为90:10。
有机电致发光器件制备过程如下：
将涂布了ITO透明导电层的玻璃板在商用清洗剂中超声处理，在去离子水中冲洗，在丙酮：乙醇混合溶剂中超声除油，在洁净环境下烘烤至完全除去水份，用紫外光和臭氧清洗，并用低能阳离子束轰击表面；
把上述带有阳极的玻璃基片置于真空腔内，抽真空至1×10-5～9×10-4Pa，在上述阳极层膜上真空蒸镀空穴传输层HT-1，蒸镀速率为0.1nm/s，蒸镀膜厚为20nm；
在空穴传输层之上真空蒸镀红光主体材料和染料Ir(piq)3，作为有机电致发光器件的发光层，蒸镀速率为0.1nm/s，蒸镀总膜厚为35nm；此实施例中，如果红光主体为两种或者两种以上化合物时，则将各个化合物分别放置于不同的蒸发源中进行加热，控制加热速度，使得各个蒸镀到基板上的体积比例相同，作为红光主体材料；
在发光层之上依次真空蒸镀电子传输层TPBI和Alq3，其蒸镀速率均为0.1nm/s，蒸镀膜厚分别为10nm和15nm；
在电子传输层上真空蒸镀0.5nm的LiF，150nm的Al作为电子注入层和阴极。
器件实施例2-15
器件实施例2-15分别提供一种有机电致发光器件，与器件实施例1的区别仅在于，红光主体材料不同，如果红光主体为两种或者两种以上化合物时，则将各个化合物分别放置于不同的蒸发源中进行加热，控制加热速度，使得各个蒸镀到基板上的体积比例相同，作为红光主体材料(详见下表1)，其他制备步骤、条件与器件实施例1相同。
器件对比例1-3
器件对比实施例1-3分别提供一种有机电致发光器件，与器件实施例1的区别仅在于，红光主体材料不同，如果红光主体为两种或者两种以上化合物时，则将各个化合物分别放置于不同的蒸发源中进行加热，控制加热速度，使得各个蒸镀到基板上的体积比例为相同，作为红光主体材料(详见下表1)，其他制备步骤、条件与器件实施例1相同。
性能测试：
使用杭州远方生产的OLED-1000多通道加速老化寿命与光色性能分析系统测试测量了所制备有机电致发光器件的亮度、驱动电压、电流效率，以及寿命测试LT90。其中，寿命测试LT90是指在室温(25～27℃)，保持初始亮度下的电流密度不变(此处为1000cd/m2)，亮度降低为初始亮度90％所需要的时间。以下表格中，电压、效率、LT90均为相对值。测试结果详见下表1。
表1


注：表1中“/”表示不含该化合物。
由表1的内容可知，本申请中通过对组合物的具体组分的设计，进一步通过多组分组成特定组合物，以此组合物作为有机电致发光器件发光层的材料，制备得到了驱动电压较低、电流效率较高、寿命较长的有机电致发光器件。
由其通过器件实施例3与器件对比例1对比，器件实施例5和器件对比例2、器件对比例3对比，本申请中通过采用多组分组合物，制备得到的有机电致发光器件具有优异的综合性能。
器件实施例4与器件实施例15可知，组合含有4种成分时，制备得到的有机电致发光器件的综合性能更为优异。
通过器件实施例3和器件实施例4可知，本申请采用咔唑基上氢原子被氘原子取到后的式I所示化合物作为组合物的组分之一，可进一步提高OLED器件的寿命。
通过器件实施例9和器件实施例10可知，本申请采用式II所示化合物中Ar11相应位置的取代基为间苯二取代基，可进一步提高OLED器件的性能。且通过器件实施例9和器件实施例10可知，采用四组分组合物制备得到的OLED器件具有更高的电流效率，更长的寿命。
通过器件实施例11-13可知，选用中咔唑基上氢原子被氘原子取代，且苯环基团上(Ar21、Ar22相应位置的取代基)不含氢原子的式I所示化合物，制备得到的OLED器件的性能更为优异。并且，符合式I所述结构的两种化合物，其中一个不含有D原子时，制备得到的OLED器件的性能更好。
器件实施例16
本器件实施例提供一种有机电致发光器件，选用本申请提供的组合物作为有机电致发光器件中的红光主体材料。
所述有机电致发光器件的结构为：ITO/HT-1(20nm)/电子阻挡层(5nm)/红光主体材料(35nm)：Ir(piq)3[10％]/TPBI(10nm)/Alq3(15nm)/LiF(0.5nm)/Al(150nm)。其中“Ir(piq)3[10％]”是指红光染料的掺杂比例，即红光主体材料与Ir(piq)3的体积份比为90:10。
有机电致发光器件制备过程如下：
将涂布了ITO透明导电层的玻璃板在商用清洗剂中超声处理，在去离子水中冲洗，在丙酮：乙醇混合溶剂中超声除油，在洁净环境下烘烤至完全除去水份，用紫外光和臭氧清洗，并用低能阳离子束轰击表面；
把上述带有阳极的玻璃基片置于真空腔内，抽真空至1×10-5～9×10-4Pa，在上述阳极层膜上真空蒸镀空穴传输层HT-1，蒸镀速率为0.1nm/s，蒸镀膜厚为20nm；
在空穴传输层之上真空蒸镀EB作为电子阻挡层，蒸镀速率为0.1nm/s，蒸镀膜厚为5nm；
在电子阻挡层之上真空蒸镀红光主体材料和染料Ir(piq)3，作为有机电致发光器件的发光层，蒸镀速率为0.1nm/s，蒸镀总膜厚为35nm；此实施例中，红光主体为H-3、H-3-D-E、 E-1、E-1D，将各个化合物分别放置于不同的蒸发源中进行加热，控制加热速度，使得各个蒸镀到基板上的体积比例为相同，作为红光主体材料。
在发光层之上依次真空蒸镀电子传输层TPBI和Alq3，其蒸镀速率均为0.1nm/s，蒸镀膜厚分别为10nm和15nm；
在电子传输层上真空蒸镀0.5nm的LiF，150nm的Al作为电子注入层和阴极。
器件实施例17
器件实施例17提供一种有机电致发光器件，与器件实施例16的区别仅在于，电子阻挡层材料不同，(详见下表2)，其他制备步骤、条件与器件实施例16相同。
对器件实施例16-17提供的有机电致发光器件的性能进行测试，测试方法同上。测试结果详见下表2。
表2
由表2的内容可知，本申请中通过选用具有特定结构的螺芴类化合物作为电子阻挡层材料，配合本申请提供的组合物作为发光层材料，制备得到的有机电致发光器件具有更高的电流效率和更长的使用寿命。
申请人声明，本申请通过上述实施例来说明本申请的详细工艺流程，但本申请并不局限于上述详细工艺流程，即不意味着本申请必须依赖上述详细工艺流程才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。

Claims (10)

  1. 一种组合物，所述组合物包括两种式I所示化合物和一种式II所示化合物；
    或者，所述组合物包括一种式I所示化合物和两种式II所示化合物；
    所述式I所示化合物的结构式如下：
    其中，Ar21、Ar22各自独立地选自C6～C30芳基或C6～C20杂芳基；
    Ar23选自单键、亚苯基或亚联苯基中的任意一种；
    式I所示化合物中的氢原子可以被-F、-CN、C6-C20芳基、C1-C6烷基或C1-C6烷氧基中的至少一种取代；
    式I所示化合物符合如下条件中的至少一个：
    (1)式I所示化合物中不含氘原子；
    (2)式I所示化合物中两个咔唑基上连接的氢原子全部被氘原子替代；
    (3)式I所示化合物中Ar21基团中至少一个氢原子被氘原子替代；
    (4)式I所示化合物中Ar22基团中至少一个氢原子被氘原子替代；
    (5)式I所示化合物中Ar23基团为亚苯基和/或亚联苯基，Ar23基团中至少一个氢原子被氘原子替代；
    (6)式I所示化合物中的氢原子被C6-C20芳基取代，C6-C20芳基中至少一个氢原子被氘原子替代；
    (7)式I所示化合物中的氢原子被C1-C6烷基和/或C1-C6烷氧基取代，C1-C6烷基和/或C1-C6烷氧基中氢原子全部被氘原子替代；
    所述式II所示化合物由一个式I-C所示基团与式I-D所示基团中环E上任意相邻的两个碳原子稠合得到；
    其中，*表示稠合位点；
    Ar11选自单键、亚苯基、亚萘基、亚联苯基中的任意一种；
    R101、R102各自独立地选自H、C6～C30芳基或C6～C20杂芳基；
    X、Y、Z各自独立地选自N或者CR304，R304选自H、苯基、联苯基、萘基、9,9-二甲基芴基、二苯并呋喃基、二苯并噻吩基中的任意一种，且X、Y、Z中的至少一个为N；
    X1选自O、S、其中R301、R302各自独立地选自C1-C5烷基或苯基， R303选自苯基或联苯基，虚线表示连接位点；
    式II所示化合物中的氢原子可以被-F、-CN、C6～C20芳基、C1～C6烷基、C1～C6烷氧基中的至少一种取代；
    式II所示化合物符合如下条件中的至少一个：
    (a)式II所示化合物中不含氘原子；
    (b)式II所示化合物中环F、环D、环E中至少一个环上的氢原子全部被氘原子替代；
    (c)式II所示化合物中R101中至少一个氢原子被氘原子替代；
    (d)式II所示化合物中R102中至少一个氢原子被氘原子替代；
    (e)式II所示化合物中Ar11中至少一个氢原子被氘原子替代；
    (f)式II所示化合物中R301和R302中的氢原子全部被氘原子替代；
    (g)式II所示化合物中R303基团中至少一个氢原子被氘原子替代；
    (h)式II所示化合物中R304为氘原子；
    (i)式II所示化合物中R304选自苯基、联苯基、萘基、9,9-二甲基芴基、二苯并呋喃基、二苯并噻吩基时，苯基、联苯基、萘基、9,9-二甲基芴基、二苯并呋喃基、二苯并噻吩基中至少一个氢原子被氘原子替代；
    (j)式II所示化合物中的氢原子被C6～C20芳基取代，C6～C20芳基中至少一个氢原子被氘原子替代；
    (k)式II所示化合物中的氢原子被C1～C6烷基和/或C1～C6烷氧基取代，C1～C6烷基和/或C1～C6烷氧基中氢原子全部被氘原子替代。
  2. 根据权利要求1所述的组合物，其中，所述组合物包括两种式I所示化合物和两种式II所示化合物；
    可选地，所述式I所示化合物具有如式I-1或式I-2所示结构：
    其中，Ar21、Ar22具有与权利要求1相同的保护范围。
  3. 根据权利要求1或2所述的组合物，其中，所述式I所示化合物符合条件(3)和/或条件(4)；
    可选地，所述式I所示化合物具有如式I-1-D或式I-2-D所示结构：
    其中，Ar21、Ar22具有与权利要求1相同的保护范围，且Ar21、Ar22中不含氘原子。
  4. 根据权利要求1或2所述的组合物，其中，所述Ar21、Ar22各自独立地选自苯基、联苯基、萘基、芴基、三亚苯基、芴基、二苯并呋喃基、二苯并噻吩基、三联苯基或四联苯基中的任意一个或者至少两种的组合；
    可选地，所述R101、R102各自独立地选自H、苯基、萘基、三亚苯基、荧蒽基、芴基、 蒽基、菲基、联苯基、萘基、二苯并呋喃基、二苯并噻吩基中的任意一种。
  5. 根据权利要求1-4任一项所述的组合物，其中，所述式I所示化合物选自下述取代或未取代的化合物中的任意一种：

    所述取代是指上述化合物中的氢原子各自独立地可以被氘原子取代；
    可选地，所述式I所示化合物选自下述取代或未取代的化合物H-1～H-40、H-17o、H-17m中的任意一种：


    所述取代是指上述化合物中的氢原子各自独立地可以被氘原子取代。
  6. 根据权利要求1-5任一项所述的组合物，其中，所述式II所示化合物选自下述取代或未取代的化合物中的任意一种：












    所述取代是指上述化合物中的氢原子各自独立地可以被氘原子取代。
  7. 一种化合物，所述化合物包括如下化合物：
    所述化合物用于制备如权利要求1-6任一项所述的组合物。
  8. 一种中间体，所述中间体包括如下化合物：
    所述中间体用于制备如权利要求1-6任一项所述的组合物中的式I所示化合物。
  9. 一种有机电致发光器件，所述有机电致发光器件包括阳极、阴极以及设置于所述阳极和阴极之间的有机薄膜层；
    所述有机薄膜层的材料包括如权利要求1-6任一项所述的组合物；
    可选地，所述有机薄膜层包括发光层，所述发光层的材料包括如权利要求1-6任一项所述的组合物；
    可选地，所述有机薄膜层包括空穴层；
    可选地，所述空穴层包括电子阻挡层，所述电子阻挡层的材料包括螺芴类化合物；
    所述螺芴类化合物具体如下式III所示结构：
    其中，X选自O或S；
    R11、R21各自独立地选自氢、氘、氟、CN、取代或未取代的C1～C20直链或支链烷基、取代或未取代的C1～C20烷氧基、取代或未取代的C6～C40芳基；
    Ar选自取代或未取代的C6～C40亚芳基；
    Ar1、Ar2各自独立地选自取代或未取代的C6～C40芳基、取代或未取代的C12～C40氧杂芳基、取代或未取代的C12～C40硫杂芳基，且Ar1或Ar2中至少一个选自苯基、萘基、三亚苯基或荧蒽基中的任意一种；
    p选自0或1；
    m、n各自独立地选自0～4的整数。
  10. 一种显示装置，所述显示装置包括如权利要求9所述的有机电致发光器件。
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