WO2020220399A1 - 电致发光材料、电致发光材料的制备方法及发光器件 - Google Patents

电致发光材料、电致发光材料的制备方法及发光器件 Download PDF

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WO2020220399A1
WO2020220399A1 PCT/CN2019/086776 CN2019086776W WO2020220399A1 WO 2020220399 A1 WO2020220399 A1 WO 2020220399A1 CN 2019086776 W CN2019086776 W CN 2019086776W WO 2020220399 A1 WO2020220399 A1 WO 2020220399A1
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reactant
electroluminescent material
structural formula
preparing
material according
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汪亚民
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武汉华星光电半导体显示技术有限公司
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Priority to US16/607,626 priority Critical patent/US11424413B2/en
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Definitions

  • This application relates to the field of display, in particular to an electroluminescent material, a preparation method of the electroluminescent material, and a light-emitting device.
  • Organic Light Emitting Diode (Organic Light Emitting Diode) has self-luminous characteristics, and the materials that dominate its luminescence are mainly electroluminescent materials.
  • the low luminous efficiency of current electroluminescent materials often leads to organic light emitting diodes. Therefore, it is necessary to provide an electroluminescent material with high luminous efficiency, a preparation method of the electroluminescent material, and a light emitting device.
  • This application provides an electroluminescent material with high electroluminescence efficiency, a preparation method of the electroluminescent material, and a light-emitting device.
  • This application provides an electroluminescent material, the structural formula of the electroluminescent material is R 3 -R 2 -R 1 -R 2 -R 3 , wherein the R 1 is a carbazole group, and the R1
  • the structural formula is One of the R 2 is a fluorene group, and the structural formula of R 2 is One of the R 3 is a pyridine group, and the structural formula of R 3 is In one of them, the X 1 may be one of H, alkyl, alkoxy and heteroalkyl, and the X 2 is one of H, alkyl, alkoxy, and heteroalkyl.
  • This application also provides a preparation method of electroluminescent material, including:
  • a first reactant and a second reactant are provided, and the first reactant and the second reactant react to form a first intermediate product, wherein the first reactant is a compound including a carbazole group R 1 ,
  • the second reactant is a compound including a fluorene group R 2
  • the structure of the first intermediate product is R 2 -R 1 -R 2
  • the structural formula of R1 is One of the structural formula of R 2 is Said X 1 is one of H, alkyl, alkoxy and heteroalkyl, and said X 2 is one of hydrogen, alkyl, alkoxy and heteroalkyl;
  • a third reactant is provided, the first intermediate product and the third reactant react to form the electroluminescent material, and the structural formula of the electroluminescent material is R 3 -R 2 -R 1 -R 2- R 3 , wherein the third reactant is a compound including a pyridine group R 3 , and the structural formula of R 3 is One of them.
  • the molar amount of the first reactant and the second reactant in the reaction between the first reactant and the second reactant to form a first intermediate product, the molar amount of the first reactant and the second
  • the corresponding relationship between the molar amounts of the reactants is that the first reactant of 1 millimoles-6 millimoles corresponds to the second reactant of 4 millimoles-30 millimoles.
  • the first reactant and the second reactant are reacted in a first solvent to form a first intermediate product
  • the first solvent includes toluene, tetrahydrofuran, ethanol, ethylene , Perchloroethylene, trichloroethylene, acetone, ethylene glycol ether and triethanolamine one or a combination of several.
  • the first solvent has a first additive
  • the first additive includes sodium isopropoxide, 1,1'-bis(diphenylphosphine)ferrocene , Palladium acetate, palladium chloride, [1,1'-bis(diphenylphosphorus) ferrocene] palladium dichloride, tetratriphenylphosphonium palladium, bistriphenylphosphorus palladium dichloride, three (two One or more of benzalacetone) dipalladium, allyl palladium chloride (II) dimer, potassium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide, sodium tert-butoxide and sodium bicarbonate The combination.
  • the first solvent includes toluene
  • the first additive includes sodium isopropoxide, 1,1'-bis(diphenylphosphine)ferrocene and palladium acetate .
  • the molar amount of sodium isopropoxide, the molar amount of 1,1'-bis(diphenylphosphine) ferrocene and the molar amount of palladium acetate in the first additive 1 millimole-13 millimole of sodium isopropoxide corresponds to 0.1 millimole-5 millimole of 1,1'-bis(diphenylphosphine)ferrocene and 0.01 millimole-0.06 millimole Palladium acetate.
  • the molar amount of the first intermediate product is The corresponding relationship of the molar amount of the third reactant is that the first intermediate product of 0.3 mmol to 12 mmol corresponds to the third reactant of 0.1 mmol to 5.9 mmol.
  • the first intermediate product and the third reactant are reacted in a second solvent to form the electroluminescent material
  • the second solvent includes toluene, One or a combination of tetrahydrofuran, ethanol, ethylene, perchloroethylene, trichloroethylene, acetone, ethylene glycol ether and triethanolamine.
  • the second solvent has a second additive
  • the second additive includes palladium tetrakistriphenylphosphorus, sodium isopropoxide, 1,1'-bis(two Phenylphosphine) ferrocene, palladium acetate, palladium chloride, [1,1'-bis(diphenylphosphorus)ferrocene] palladium dichloride, tetrakistriphenylphosphorus palladium, bistriphenylphosphorus Palladium chloride, tris(dibenzylideneacetone) dipalladium, allylpalladium(II) chloride dimer, potassium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide, sodium tert-butoxide, and sodium bicarbonate One or a combination of several.
  • the second solvent includes toluene
  • the second additive includes potassium carbonate aqueous solution and palladium tetrakistriphenylphosphorus.
  • the first reactant and the second reactant react to form a first intermediate product
  • the reaction temperature is 90 degrees Celsius -120 degrees Celsius.
  • the first reactant and the second reactant react to form a first intermediate product
  • the reaction time is 9 hours-36 hours.
  • the reaction temperature It is 90 degrees Celsius -120 degrees Celsius.
  • the reaction time is It is 9 hours-36 hours.
  • the structural formula of the first reactant is One of them.
  • the structural formula of the second reactant is Of one, wherein said X 3 as a F., Cl, Br and I, the X 4 is F, one kind of Cl, Br and I is.
  • the third reactant is R 3 -Y
  • the Y is a boronic acid pinacol ester group or a boronic acid group.
  • the application provides a light emitting device, including:
  • a substrate substrate layer the substrate layer includes a substrate and an anode layer, the anode layer is disposed on the substrate;
  • a hole injection layer, the hole injection layer is disposed on the anode layer;
  • a hole transport layer, the hole transport layer is disposed on the hole injection layer;
  • a light-emitting layer, the light-emitting layer is disposed on the hole transport layer;
  • An electron transport layer, the electron transport layer is disposed on the light-emitting layer
  • An electron injection layer is disposed on the electron transport layer;
  • a cathode layer, the cathode layer is disposed on the electron transport layer;
  • the light-emitting layer includes the electroluminescent material, the structural formula of the electroluminescent material is R 3 -R 2 -R 1 -R 2 -R 3 , wherein the R 1 is a carbazole group, and the The structural formula of R1 is One of the R 2 is a fluorene group, and the structural formula of R 2 is One of the R 3 is a pyridine group, and the structural formula of R 3 is In one of them, the X 1 may be one of H, alkyl, alkoxy and heteroalkyl, and the X 2 is one of H, alkyl, alkoxy, and heteroalkyl.
  • This application provides an electroluminescent material, a preparation method of an electroluminescent material, and a light-emitting device, by selecting a fluorenyl group with good planarity and strong visible ⁇ - ⁇ * absorption as a ⁇ -based system, and introducing a carbazole
  • the compound of the group is used as the electron donor and the compound including the pyridine group is used as the electron acceptor, realizing a kind of electroluminescent material capable of emitting blue light and having high electroluminescence efficiency, the preparation method of the electroluminescent material and Light-emitting device.
  • FIG. 1 is a schematic diagram of the structure of the light emitting device provided by this application.
  • Fig. 2 is an electroluminescence spectrum diagram of the light-emitting device provided by the application when the driving voltage is 4V.
  • Fig. 3 is an electroluminescence spectrum diagram of the light-emitting device provided by the application when the driving voltage is 5V.
  • Fig. 4 is an electroluminescence spectrum diagram of the light-emitting device provided by the application when the driving voltage is 6V.
  • Fig. 5 is an electroluminescence spectrum diagram of the light-emitting device provided by the application when the driving voltage is 7V.
  • Fig. 6 is an electroluminescence spectrum diagram of the light emitting device provided by the application when the driving voltage is 8V.
  • the structural formula of the electroluminescent material is R 3 -R 2 -R 1 -R 2 -R 3 , wherein the R 1 is a carbazole group, and the structural formula of R 1 is One of the R 2 is a fluorene group, and the structural formula of R 2 is One of the R 3 is a pyridine group, and the structural formula of R 3 is In one of them, the X 1 may be one of H, alkyl, alkoxy and heteroalkyl, and the X 2 is one of H, alkyl, alkoxy, and heteroalkyl.
  • the electroluminescent material is a deep blue luminescent material.
  • This application also proposes a method for preparing the electroluminescent material.
  • the preparation method of the electroluminescent material includes:
  • A. Provide a first reactant and a second reactant, the first reactant and the second reactant react to form a first intermediate product, wherein the first reactant includes a carbazole group R 1
  • the second reactant is a compound including a fluorene group R 2
  • the first intermediate product has the formula R 2 -R 1 -R 2 , wherein the structural formula of R 1 is One of the structural formula of R 2 is Said X 1 is one of H, alkyl, alkoxy and heteroalkyl, and said X 2 is one of hydrogen, alkyl, alkoxy and heteroalkyl.
  • the first reactant is a compound including a carbazole group R 1 .
  • the structural formula of the first reactant may be One of the others.
  • the second reactant is a compound including a fluorene group R 2 .
  • the structural formula of the second reactant can be One kind, and the like, wherein the X 3 may be one F, Cl, Br and I, and the like, the X 4 may be one F, Cl, Br and I, and the like.
  • the first reactant can be expressed as HR 1 -H
  • the second reactant can be expressed as X 3 -R 2 -X 4 , wherein the stability of the X 3 -R bond is greater than or equal to the stability of the X 4 -R bond Sex.
  • the general reaction formula of the first reactant and the second reactant to generate the first intermediate product may be:
  • the first intermediate product can be expressed as X 3 -R 2 -R 1 -R 2 -X 3 .
  • the corresponding relationship between the molar amount of the first reactant and the molar amount of the second reactant is 1 millimolar- 6 millimoles of the first reactant corresponds to 4 millimoles to 30 millimoles of the second reactant.
  • the corresponding relationship between the molar amount of the first reactant and the molar amount of the second reactant may be 1 millimolar of the first reactant corresponding to 4 millimoles of the second reactant.
  • the corresponding relationship between the molar amount of the first reactant and the molar amount of the second reactant may also be 3 moles of the first reactant corresponding to 10 moles of the second reactant.
  • the first reactant and the second reactant are reacted in a first solvent to form a first intermediate product.
  • the first solvent includes toluene, tetrahydrofuran, ethanol, ethylene, perchloroethylene, trichloroethylene, acetone, ethylene ethyl One or a combination of glycol ether and triethanolamine.
  • the first solvent has a first additive, and the first additive includes sodium isopropoxide, 1,1'-bis(diphenylphosphine) ferrocene, palladium acetate, palladium chloride, [1,1' -Bis(diphenylphosphorus)ferrocene]palladium dichloride, tetrakistriphenylphosphonium palladium, bistriphenylphosphorus palladium dichloride, tris(dibenzylideneacetone)dipalladium, allyl chloride One or a combination of palladium(II) dimer, potassium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide, sodium tert-butoxide, and sodium bicarbonate.
  • the first additive includes sodium isopropoxide, 1,1'-bis(diphenylphosphine) ferrocene, palladium acetate, palladium chloride, [1,1' -Bis(diphenylphosphorus)ferrocene
  • the first reactant may be The second reactant can be any reactant.
  • reaction equation of the first intermediate product by reacting the first reactant and the second reactant may be:
  • the structural formula of the electroluminescent material is R 3 -R 2 -R 1 -R 2 -R 3 , wherein the third reactant is a compound including a pyridine group R 3 , and the structural formula of R 3 is One of
  • the third reactant is a compound including a pyridine group R3.
  • the structural formula of the third reactant can be One of the others.
  • the first intermediate product can be expressed as X 3 -R 2 -R 1 -R 2 -X 3 .
  • the third reactant can be represented as R 3 -Y.
  • the Y is a boronic acid pinacol ester group or a boronic acid group.
  • the general reaction formula of the reaction between the first intermediate product and the third reactant to produce the electroluminescent material is:
  • the corresponding relationship between the molar amount of the first intermediate product and the molar amount of the third reactant is 0.3 millimetres.
  • the first intermediate product at -12 mM corresponds to the third reactant at 0.1-5.9 mM.
  • the corresponding relationship between the molar amount of the first intermediate product and the molar amount of the third reactant may be 1 millimole of the first intermediate product corresponding to 1 millimole of the third reactant.
  • the corresponding relationship between the molar amount of the first intermediate product and the molar amount of the third reactant may also be 3 moles of the first intermediate product corresponding to 5 moles of the third reactant.
  • the first intermediate product and the third reactant react in a second solvent to produce the electroluminescent material
  • the second solvent includes toluene, tetrahydrofuran, ethanol, ethylene, perchloroethylene, and trichloroethylene , Acetone, ethylene glycol ether and triethanolamine one or a combination of several.
  • the second solvent has a second additive, and the second additive includes palladium tetrakistriphenylphosphorus, sodium isopropoxide, 1,1'-bis(diphenylphosphine) ferrocene, palladium acetate, chlorinated Palladium, [1,1'-bis(diphenylphosphorus)ferrocene]palladium dichloride, tetrakistriphenylphosphonium palladium, bistriphenylphosphorus palladium dichloride, tris(dibenzylidene acetone) two One or a combination of palladium, allyl palladium chloride (II) dimer, potassium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide, sodium tert-butoxide, and sodium bicarbonate.
  • II allyl palladium chloride
  • the structural formula of the electroluminescent material is R 3 -R 2 -R 1 -R 2 -R 3 , wherein the structural formula of R1 is One of the structural formula of R 2 is X 1 is one of H, alkyl, alkoxy and heteroalkyl, and X 2 is one of hydrogen, alkyl, alkoxy and heteroalkyl,
  • the structural formula of R 3 is One of them.
  • the first intermediate product may be The third reactant may be any reactant.
  • reaction equation of the first intermediate product and the third reactant to generate the electroluminescent material is:
  • the mixture can be cooled to room temperature first, the reaction solution is poured into water, and the extraction solvent is used for extraction 2 to 5 times, the organic layer is taken and dried with Na 2 SO 4 , and the water is suspended and evaporated. Chromatography to obtain solid powder, that is, the electroluminescent material.
  • the extraction solvent may be one or a combination of several kinds of ether, dichloromethane, trichloromethane and tetrahydrofuran.
  • the light emitting device 100 includes a base substrate layer 11, a hole injection layer 12, a hole transport layer 13, a light emitting layer 14, an electron transport layer 15, an electron injection layer 16 and a cathode layer 17.
  • the base substrate layer 11 includes a substrate 111 and an anode layer 112.
  • the substrate 111 may be a glass substrate or a transparent plastic substrate.
  • the anode layer 112 is disposed on the substrate 111.
  • the anode layer 112 may be indium tin oxide material.
  • the hole injection layer 12 is disposed on the anode layer 112.
  • the hole transport layer 13 is disposed on the hole injection layer 12.
  • the light-emitting layer 14 is disposed on the hole transport layer 13.
  • the light-emitting layer 14 includes the electroluminescent material.
  • the structural formula of the electroluminescent material is R 3 -R 2 -R 1 -R 2 -R 3 , wherein the R 1 is a carbazole group, and the structural formula of R 1 is One of the R 2 is a fluorene group, and the structural formula of R 2 is One of the R 3 is a pyridine group, and the structural formula of R 3 is In one of them, the X 1 may be one of H, alkyl, alkoxy and heteroalkyl, and the X 2 is one of H, alkyl, alkoxy, and heteroalkyl.
  • the electron transport layer 15 is disposed on the light-emitting layer 14.
  • the electron injection layer 16 is disposed on the cathode layer 17.
  • the cathode layer 17 is disposed on the electron injection layer 16.
  • the cathode layer 17 may be a lithium fluoride/aluminum material.
  • Figures 2-6 are electroluminescence spectra of the light-emitting devices provided by this application when the driving voltages are 4V, 5V, 6V, 7V, and 8V. Under different driving voltages, the maximum emission peak positions of the electroluminescent material of the light-emitting layer 14 are all located near 456 nm-480 nm.
  • the electroluminescent material is a deep blue luminescent material. Measure the electroluminescent material with a steady-state/transient fluorescence spectrometer The fluorescence quantum yield is 96.5%.
  • This application provides an electroluminescent material, a preparation method of an electroluminescent material, and a light-emitting device, by selecting a fluorenyl group with good planarity and strong visible ⁇ - ⁇ * absorption as a ⁇ -based system, and introducing a carbazole
  • the compound of the group is used as the electron donor and the compound including the pyridine group is used as the electron acceptor, realizing a kind of electroluminescent material capable of emitting blue light and having high electroluminescence efficiency, the preparation method of the electroluminescent material and Light-emitting device.

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Abstract

本申请提供一种电致发光材料、电致发光材料的制备方法及发光器件，通过选用具有良好的平面性和强烈的可见π-π*吸收的芴基作为π基体系，同时引入包括咔唑基团的化合物作为电子给体和包括吡啶基团的化合物作为电子受体，实现了一种能发出的蓝光的、具有电致发光效率高的电致发光材料、电致发光材料的制备方法及发光器件。

Description

电致发光材料、电致发光材料的制备方法及发光器件 技术领域
本申请涉及显示领域，具体涉及一种电致发光材料、电致发光材料的制备方法及发光器件。
背景技术
在现有技术中，有机发光二极管(Organic Light Emitting Diode)具有自发光特性，主导其发光的材料主要为电致发光材料，但是，当前的电致发光材料的发光效率低，往往导致有机发光二极管的失效，因此，有必要提供一种发光效率高的电致发光材料、电致发光材料的制备方法及发光器件。
技术问题
本申请提供一种具有电致发光效率高的电致发光材料、电致发光材料的制备方法及发光器件。
技术解决方案
本申请提供一种电致发光材料，所述电致发光材料的结构式为R 3-R 2-R 1-R 2-R 3，其中，所述R 1为咔唑基团，所述R1的结构式为
Figure PCTCN2019086776-appb-000001
Figure PCTCN2019086776-appb-000002
中的一种，所述R 2为芴基团，所述R 2的结构式为
Figure PCTCN2019086776-appb-000003
Figure PCTCN2019086776-appb-000004
中的一种，所述R 3为吡啶基团，所述R 3的结构式为
Figure PCTCN2019086776-appb-000005
中的一种，所述X 1可以为H、烷基、烷氧基和杂烷基中的一种，所述X 2为H、烷基、烷氧基和杂烷基中的一种。
本申请还提供一种电致发光材料的制备方法，包括：
提供第一反应物和第二反应物，所述第一反应物和所述第二反应物进行反应生成第一中间产物，其中，所述第一反应物为包括咔唑基团R 1的化合物，所述第二反应物为包括芴基团R 2的化合物，所述第一中间产物的结式为R 2-R 1-R 2，其中，所述R1的结构式为
Figure PCTCN2019086776-appb-000006
Figure PCTCN2019086776-appb-000007
中的一种，所述R 2的结构式为
Figure PCTCN2019086776-appb-000008
Figure PCTCN2019086776-appb-000009
中的一种，所述X 1为H、烷基、烷氧基和杂烷基中的一种，所述X 2为氢基、烷基、烷氧基和杂烷基中的一种；
提供第三反应物，所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料，所述电致发光材料的结构式为R 3-R 2-R 1-R 2-R 3，其中，所述第三反应物为包括吡啶基团R 3的化合物，所述R 3的结构式为
Figure PCTCN2019086776-appb-000010
Figure PCTCN2019086776-appb-000011
中的一种。
在所述的电致发光材料的制备方法中，在所述第一反应物和所述第二反应物进行反应生成第一中间产物中，所述第一反应物的摩尔量和所述第二反应物的摩尔量的对应关系为1毫摩-6毫摩的所述第一反应物对应4毫摩-30毫摩的所述第二反应物。
在所述的电致发光材料的制备方法中，所述第一反应物和第二反应物在第一溶剂中进行反应生成第一中间产物，所述第一溶剂包括甲苯、四氢呋喃、乙醇、乙烯、全氯乙烯、三氯乙烯、丙酮、乙烯乙二醇醚和三乙醇胺中的一种或几种的组合。
在所述的电致发光材料的制备方法中，所述第一溶剂中具有第一添加剂，所述第一添加剂包括异丙醇钠、1,1'-双(二苯基膦)二茂铁、醋酸钯、氯化钯、[1,1'-双(二苯基磷)二茂铁]二氯化钯、四三苯基磷钯、双三苯基磷二氯化钯、三(二亚苄基丙酮)二钯、烯丙基氯化钯(II)二聚体、碳酸钾、碳酸铯、氢氧化钾、氢氧化钠、叔丁醇钠和碳酸氢钠中的一种或几种的组合。
在所述的电致发光材料的制备方法中，所述第一溶剂包括甲苯，所述第一添加剂包括异丙醇钠、1,1'-双(二苯基膦)二茂铁和醋酸钯。
在所述的电致发光材料的制备方法中，所述第一添加剂中异丙醇钠的摩尔量、1,1'-双(二苯基膦)二茂铁的摩尔量和醋酸钯的摩尔量的对应关系为：1毫摩-13毫摩的异丙醇钠对应0.1毫摩-5毫摩的1,1'-双(二苯基膦)二茂铁和0.01毫摩-0.06毫摩的醋酸钯。
在所述的电致发光材料的制备方法中，在所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料中，所述第一中间产物的摩尔量和所述第三反应物的摩尔量的对应关 系为0.3毫摩-12毫摩的所述第一中间产物对应0.1毫摩-5.9毫摩的所述第三反应物。
在所述的电致发光材料的制备方法中，所述第一中间产物和所述第三反应物在第二溶剂中进行反应生成所述电致发光材料中，所述第二溶剂包括甲苯、四氢呋喃、乙醇、乙烯、全氯乙烯、三氯乙烯、丙酮、乙烯乙二醇醚和三乙醇胺中的一种或几种的组合。
在所述的电致发光材料的制备方法中，所述第二溶剂中具有第二添加剂，所述第二添加剂包括四三苯基磷钯、异丙醇钠、1,1'-双(二苯基膦)二茂铁、醋酸钯、氯化钯、[1,1'-双(二苯基磷)二茂铁]二氯化钯、四三苯基磷钯、双三苯基磷二氯化钯、三(二亚苄基丙酮)二钯、烯丙基氯化钯(II)二聚体、碳酸钾、碳酸铯、氢氧化钾、氢氧化钠、叔丁醇钠和碳酸氢钠中的一种或几种的组合。
在所述的电致发光材料的制备方法中，所述第二溶剂包括甲苯，所述第二添加剂包括碳酸钾水溶液和四三苯基磷钯。
在所述的电致发光材料的制备方法中，在所述提供第一反应物和第二反应物，所述第一反应物和所述第二反应物进行反应生成第一中间产物的步骤中，反应温度为90摄氏度-120摄氏度。
在所述的电致发光材料的制备方法中，在所述提供第一反应物和第二反应物，所述第一反应物和所述第二反应物进行反应生成第一中间产物的步骤中，反应时间为9小时-36小时。
在所述的电致发光材料的制备方法中，在所述提供第三反应物，所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料的步骤中，反应温度为90摄氏度-120摄氏度。
在所述的电致发光材料的制备方法中，在所述提供第三反应物，所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料的步骤中，反应时间为9小时-36小时。
在所述的电致发光材料的制备方法中，所述第一反应物的结构式为
Figure PCTCN2019086776-appb-000012
Figure PCTCN2019086776-appb-000013
中的一种。
在所述的电致发光材料的制备方法中，所述第二反应物的结构式为
Figure PCTCN2019086776-appb-000014
Figure PCTCN2019086776-appb-000015
中的一种，其中，所述X 3为F，Cl，Br和I中的一种，所述X 4为F，Cl，Br和I中的一种。
在所述的电致发光材料的制备方法中，所述第三反应物为R 3-Y，所述Y为硼酸频哪醇酯基或者硼酸基。
本申请提供一种发光器件，包括：
衬底基板层，所述衬底层包括基板和阳极层，所述阳极层设置于所述基板上；
空穴注入层，所述空穴注入层设置于所述阳极层上；
空穴传输层，所述空穴传输层设置于所述空穴注入层上；
发光层，所述发光层设置于所述空穴传输层上；
电子传输层，所述电子传输层设置于所述发光层上；
电子注入层，所述电子注入层设置于所述电子传输层上；
阴极层，所述阴极层设置于所述电子传输层上；
所述发光层包括所述电致发光材料，所述电致发光材料的结构式为R 3-R 2-R 1-R 2-R 3，其中，所述R 1为咔唑基团，所述R1的结构式为
Figure PCTCN2019086776-appb-000016
Figure PCTCN2019086776-appb-000017
中的一种，所述R 2为芴基团，所述R 2的结构式为
Figure PCTCN2019086776-appb-000018
Figure PCTCN2019086776-appb-000019
中的一种，所述R 3为吡啶基团，所述R 3的结构式为
Figure PCTCN2019086776-appb-000020
中的一种，所述X 1可以为H、烷基、烷氧基和杂烷基中的一种，所述X 2为H、烷基、烷氧基和杂烷基中的一种。
有益效果
本申请提供一种电致发光材料、电致发光材料的制备方法及发光器件，通过选用具有良好的平面性和强烈的可见π-π*吸收的芴基作为π基体系，同时引入包括咔唑基团的化合物作为电子给体和包括吡啶基团的化合物作为电子受体，实现了一种能发出的蓝光的、具有电致发光效率高的电致发光材料、电致发光材料的制备方法及发光器件。
附图说明
为了更清楚地说明本申请中的技术方案，下面将对实施方式描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施方式，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请所提供的发光器件的结构示意图。
图2为申请所提供的发光器件在驱动电压为4V时的电致发光光谱图。
图3为申请所提供的发光器件在驱动电压为5V时的电致发光光谱图。
图4为申请所提供的发光器件在驱动电压为6V时的电致发光光谱图。
图5为申请所提供的发光器件在驱动电压为7V时的电致发光光谱图。
图6为申请所提供的发光器件在驱动电压为8V时的电致发光光谱图。
本发明的实施方式
下面将结合本申请实施方式中的附图，对本申请中的技术方案进行清楚、完整地描述。显然，所描述的实施方式仅仅是本申请一部分实施方式，而不是全部的实施方式。基于本申请中的实施方式，本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，都属于本申请保护的范围。
本申请提供一种电致发光材料。所述电致发光材料的结构式为R 3-R 2-R 1-R 2-R 3，其中，所述R 1为咔唑基团，所述R1的结构式为
Figure PCTCN2019086776-appb-000021
Figure PCTCN2019086776-appb-000022
中的一种，所述R 2为芴基团，所述R 2的结构式为
Figure PCTCN2019086776-appb-000023
中的一种，所述R 3为吡啶基团，所述R 3的结构式为
Figure PCTCN2019086776-appb-000024
Figure PCTCN2019086776-appb-000025
中的一种，所述X 1可以为H、烷基、烷氧基和杂烷基中的一种，所述X 2为H、烷基、烷氧基和杂烷基中的一种。所述电致发光材料属 于深蓝色发光材料。
本申请还提出一种电致发光材料的制备方法。所述电致发光材料的制备方法包括：
A、提供第一反应物和第二反应物，所述第一反应物和所述第二反应物进行反应生成第一中间产物，其中，所述第一反应物为包括咔唑基团R 1的化合物，所述第二反应物为包括芴基团R 2的化合物，所述第一中间产物的结式为R 2-R 1-R 2，其中，所述R 1的结构式为
Figure PCTCN2019086776-appb-000026
Figure PCTCN2019086776-appb-000027
中的一种，所述R 2的结构式为
Figure PCTCN2019086776-appb-000028
Figure PCTCN2019086776-appb-000029
中的一种，所述X 1为H、烷基、烷氧基和杂烷基中的一种，所述X 2为氢基、烷基、烷氧基和杂烷基中的一种。
所述第一反应物为包括咔唑基团R 1的化合物。所述第一反应物的结构式可以为
Figure PCTCN2019086776-appb-000030
Figure PCTCN2019086776-appb-000031
等中的一种。
所述第二反应物为包括芴基团R 2的化合物。所述第二反应物的结构式可以为
Figure PCTCN2019086776-appb-000032
Figure PCTCN2019086776-appb-000033
等中的一种，其中，所述X 3可以为F，Cl，Br和I等中的一种，所述X 4可以为F，Cl，Br和I等中的一种。
所述第一反应物可以表示为H-R 1-H，所述第二反应物可以表示为X 3-R 2-X 4，其中X 3-R键的稳定性大于等于X 4-R键的稳定性。
所述第一反应物和第二反应物进行反应生成第一中间产物的反应通式可以为：
H-R 1-H+X 3-R 2-X 4→X 3-R 2-R 1-R 2-X 3
所述第一中间产物可以表示为X 3-R 2-R 1-R 2-X 3。
在所述第一反应物和所述第二反应物进行反应生成第一中间产物中，所述第一反应物的摩尔量和所述第二反应物的摩尔量的对应关系为1毫摩-6毫摩的所述第一反应物对应4毫摩-30毫摩的所述第二反应物。具体的，所述第一反应物的摩尔量和第二反应物的摩尔量的对应关系可以为1毫摩的所述第一反应物对应4毫摩的所述第二反应物。所述第一反应物的摩尔量和第二反应物的摩尔量的对应关系还可以为3摩尔的所述第一反应物对应10摩尔的所述第二反应物。
所述第一反应物和第二反应物在第一溶剂中进行反应生成第一中间产物，所述第一溶剂包括甲苯、四氢呋喃、乙醇、乙烯、全氯乙烯、三氯乙烯、丙酮、乙烯乙二醇醚和三乙醇胺中的一种或几种的组合。
所述第一溶剂中具有第一添加剂，所述第一添加剂包括异丙醇钠、1,1'-双(二苯基膦)二茂铁、醋酸钯、氯化钯、[1,1'-双(二苯基磷)二茂铁]二氯化钯、四三苯基磷钯、双三苯基磷二氯化钯、三(二亚苄基丙酮)二钯、烯丙基氯化钯(II)二聚体、碳酸钾、碳酸铯、氢氧化钾、氢氧化钠、叔丁醇钠和碳酸氢钠中的一种或几种的组合。
在一种实施例中，所述第一反应物可以为
Figure PCTCN2019086776-appb-000034
所述第二反应物可以为
Figure PCTCN2019086776-appb-000035
在一种实施例中，所述第一反应物和所述第二反应物进行反应生成第一中间产物的反应方程式可以为：
Figure PCTCN2019086776-appb-000036
在实际操作中，在容器中加入1毫摩-6毫摩的所述第一反应物
Figure PCTCN2019086776-appb-000037
4毫摩-30毫摩的所述第二反应物
Figure PCTCN2019086776-appb-000038
1毫升-30毫升的甲苯和1毫摩-13毫摩的异丙醇钠，在氩气氛围下加入0.1毫摩-5毫摩的1,1'-双(二苯基膦)二茂铁和0.01毫摩-0.06毫摩的醋酸钯，在90摄氏度-120摄氏度反应9小时-36小时，得到包括所述第一中间产物的混合物，然后分离提纯，得到所述第一中间产物
Figure PCTCN2019086776-appb-000039
B、提供第三反应物，所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料，所述电致发光材料的结构式为R 3-R 2-R 1-R 2-R 3，其中，所述第三反应物为包括吡啶基团R 3的化合物，所述R 3的结构式为
Figure PCTCN2019086776-appb-000040
Figure PCTCN2019086776-appb-000041
中的一种
所述第三反应物为包括吡啶基团R3的化合物。所述第三反应物的结构式可以为
Figure PCTCN2019086776-appb-000042
Figure PCTCN2019086776-appb-000043
等中的一种。
所述第一中间产物可以表示为X 3-R 2-R 1-R 2-X 3。所述第三反应物可以表示为R 3-Y。所述Y为硼酸频哪醇酯基或者硼酸基。
所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料的反应通式为：
X 3-R 2-R 1-R 2-X 3+R 3-Y→R 3-R 2-R 1-R 2-R 3
在所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料中，所述第一中间产物的摩尔量和所述第三反应物的摩尔量的对应关系为0.3毫摩-12毫摩的所述第一中间产物对应0.1毫摩-5.9毫摩的所述第三反应物。具体的，所述第一中间产物的摩尔量和所述第三反应物的摩尔量的对应关系可以为1毫摩的所述第一中间产物对应1毫摩的所述第三反应物。所述第一中间产物的摩尔量和所述第三反应物的摩尔量的对应关系还可以为3摩尔的所述第一中间产物对应5摩尔的所述第三反应物。
所述第一中间产物和所述第三反应物在第二溶剂中进行反应生成所述电致发光材料中，所述第二溶剂包括甲苯、四氢呋喃、乙醇、乙烯、全氯乙烯、三氯乙烯、丙酮、乙烯乙二醇醚和三乙醇胺中的一种或几种的组合。
所述第二溶剂中具有第二添加剂，所述第二添加剂包括四三苯基磷钯、异丙醇钠、1,1'-双(二苯基膦)二茂铁、醋酸钯、氯化钯、[1,1'-双(二苯基磷)二茂铁]二氯化钯、四三苯基磷钯、双三苯基磷二氯化钯、三(二亚苄基丙酮)二钯、烯丙基氯化钯(II)二聚体、碳酸钾、碳酸铯、氢氧化钾、氢氧化钠、叔丁醇钠和碳酸氢钠中的一种或几种的组合。
所述电致发光材料的结构式为R 3-R 2-R 1-R 2-R 3，其中，所述R1的结构式为
Figure PCTCN2019086776-appb-000044
Figure PCTCN2019086776-appb-000045
中的一种，所述R 2的结构式为
Figure PCTCN2019086776-appb-000046
Figure PCTCN2019086776-appb-000047
中的一种，所述X 1为H、烷基、烷氧基和杂烷基中的一种，所述X 2为氢基、烷基、烷氧基和杂烷基中的一种，所述R 3的结 构式为
Figure PCTCN2019086776-appb-000048
中的一种。
在一种实施方式中，所述第一中间产物可以为
Figure PCTCN2019086776-appb-000049
所述第三反应物可以为
Figure PCTCN2019086776-appb-000050
所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料的反应方程式为：
Figure PCTCN2019086776-appb-000051
在实际操作中，在容器中加入0.3毫摩-12毫摩的所述第一中间产物
Figure PCTCN2019086776-appb-000052
0.1毫摩-5.9毫摩的所述第三反应物
Figure PCTCN2019086776-appb-000053
加入适量甲苯和碳酸钾水溶液，在氩气氛围下分两次共加入0.001毫摩-0.99毫摩的四三苯基磷钯，在90摄氏度-120摄氏度反应9小时-36小时，得到包括所述电致发光材料的混合物，然后分离提纯，得到所述电致发光材料
Figure PCTCN2019086776-appb-000054
在分离提纯中，可以先将混合物冷却至室温，将反应液倒入水中，采用萃取溶剂萃取2次-5次，取用有机层并用Na 2SO 4干燥，悬蒸出水，采用层析柱进行层析，得固体粉末，也即所述电致发光材料。
所述萃取溶剂可以为乙醚、二氯甲烷、三氯甲烷和四氢呋喃中的一种或几可达种的组合。所述层析柱的配比可以为二氯甲烷的体积：正己烷的体积＝1:0.5-1:10。
请参阅图1，本申请提供一种发光器件100。所述发光器件100包括衬底基板层11、空穴注入层12、空穴传输层13、发光层14、电子传输层15、电子注入层16和阴极层17。
所述衬底基板层11包括基板111和阳极层112。所述基板111可以是玻璃基板或透明塑料基板。所述阳极层112设置于所述基板111上。所述阳极层112可以是氧化铟锡材料。所述空穴注入层12设置于所述阳极层112上。所述空穴传输层13设置于所述空穴注入层12上。所述发光层14设置于所述空穴传输层13上。所述发光层14包括所述电致发光材料。所述电致发光材料的结构式为R 3-R 2-R 1-R 2-R 3，其中，所述R 1为咔唑基团，所述R1的结构式为
Figure PCTCN2019086776-appb-000055
Figure PCTCN2019086776-appb-000056
中的一种，所述R 2为芴基团，所述R 2的结构式为
Figure PCTCN2019086776-appb-000057
Figure PCTCN2019086776-appb-000058
中的一种，所述R 3为吡啶基团，所述R 3的结构式为
Figure PCTCN2019086776-appb-000059
中的一种，所述X 1可以为H、烷基、烷氧基和杂烷基中的一种，所述X 2为H、烷基、烷氧基和杂烷基中的一种。
所述电子传输层15设置于所述发光层14上。所述电子注入层16设置于所述阴极层17上。所述阴极层17设置于电子注入层16上。所述阴极层17可以是氟化锂/铝材料。
请参阅图2-6，图2-6为本申请所提供的发光器件在驱动电压分别为4V、5V、6V、7V和8V时的电致发光光谱图。在不同驱动电压下，所述发光层14的所述电致发光材料的最大发射峰位均位于456nm-480nm附近。所述电致发光材料属于深蓝色发光材料。采用稳态/瞬态荧光光谱仪器测得所述电致发光材料
Figure PCTCN2019086776-appb-000060
的荧光量子产率为96.5％。
本申请提供一种电致发光材料、电致发光材料的制备方法及发光器件，通过选用具有良好的平面性和强烈的可见π-π*吸收的芴基作为π基体系，同时引入包括咔唑基团的化合物作为电子给体和包括吡啶基团的化合物作为电子受体，实现了一种能发出的蓝光的、具有电致发光效率高的电致发光材料、电致发光材料的制备方法及发光器件。
以上对本申请实施方式提供了详细介绍，本文中应用了具体个例对本申请的原理及实施方式进行了阐述，以上实施方式的说明只是用于帮助理解本申请。同时，对于本领域的技术人员，依据本申请的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本申请的限制。

Claims (19)

  1. 一种电致发光材料，其中，所述电致发光材料的结构式为R 3-R 2-R 1-R 2-R 3，其中，所述R 1为咔唑基团，所述R1的结构式为
    Figure PCTCN2019086776-appb-100001
    Figure PCTCN2019086776-appb-100002
    中的一种，所述R 2为芴基团，所述R 2的结构式为
    Figure PCTCN2019086776-appb-100003
    Figure PCTCN2019086776-appb-100004
    中的一种，所述R 3为吡啶基团，所述R 3的结构式为
    Figure PCTCN2019086776-appb-100005
    中的一种，所述X 1可以为H、烷基、烷氧基和杂烷基中的一种，所述X 2为H、烷基、烷氧 基和杂烷基中的一种。
  2. 一种电致发光材料的制备方法，其中，包括：
    提供第一反应物和第二反应物，所述第一反应物和所述第二反应物进行反应生成第一中间产物，其中，所述第一反应物为包括咔唑基团R 1的化合物，所述第二反应物为包括芴基团R 2的化合物，其中，所述R 1的结构式为
    Figure PCTCN2019086776-appb-100006
    Figure PCTCN2019086776-appb-100007
    中的一种，所述R 2的结构式为
    Figure PCTCN2019086776-appb-100008
    Figure PCTCN2019086776-appb-100009
    中的一种，所述X 1为H、烷基、烷氧基和杂烷基中的一种，所述X 2为氢基、烷基、烷氧基和杂烷基中的一种；
    提供第三反应物，所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料，所述电致发光材料的结构式为R 3-R 2-R 1-R 2-R 3，其中，所述第三反 应物为包括吡啶基团R 3的化合物，所述R 3的结构式为
    Figure PCTCN2019086776-appb-100010
    Figure PCTCN2019086776-appb-100011
    中的一种。
  3. 如权利要求2所述的电致发光材料的制备方法，其中，在所述第一反应物和所述第二反应物进行反应生成第一中间产物中，所述第一反应物的摩尔量和所述第二反应物的摩尔量的对应关系为1毫摩-6毫摩的所述第一反应物对应4毫摩-30毫摩的所述第二反应物。
  4. 如权利要求2所述的电致发光材料的制备方法，其中，所述第一反应物和第二反应物在第一溶剂中进行反应生成第一中间产物，所述第一溶剂包括甲苯、四氢呋喃、乙醇、乙烯、全氯乙烯、三氯乙烯、丙酮、乙烯乙二醇醚和三乙醇胺中的一种或几种的组合。
  5. 如权利要求4所述的电致发光材料的制备方法，其中，所述第一溶剂中具有第一添加剂，所述第一添加剂包括异丙醇钠、1,1'-双(二苯基膦)二茂铁、醋酸钯、氯化钯、[1,1'-双(二苯基磷)二茂铁]二氯化钯、四三苯基磷钯、双三苯基磷二氯化钯、三(二亚苄基丙酮)二钯、烯丙基氯化钯(II)二聚体、碳酸钾、碳酸铯、氢氧化钾、氢氧化钠、叔丁醇钠和碳酸氢钠中的一种或几种的组合。
  6. 如权利要求5所述的电致发光材料的制备方法，其中，所述第一溶剂包括甲苯，所述第一添加剂包括异丙醇钠、1,1'-双(二苯基膦)二茂铁和醋酸钯。
  7. 如权利要求6所述的电致发光材料的制备方法，其中，所述第一添加剂中异丙醇钠的摩尔量、1,1'-双(二苯基膦)二茂铁的摩尔量和醋酸钯的摩尔量的对应关系为：1毫摩-13毫摩的异丙醇钠对应0.1毫摩-5毫摩的1,1'-双(二苯基膦)二茂铁和0.01毫摩-0.06毫摩的醋酸钯。
  8. 如权利要求2所述的电致发光材料的制备方法，其中，在所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料中，所述第一中间产物的摩尔量和所述第三反应物的摩尔量的对应关系为0.3毫摩-12毫摩的所述第一中间产物对应0.1毫摩-5.9毫摩的所述第三反应物。
  9. 如权利要求2所述的电致发光材料的制备方法，其中，所述第一中间产物和所述第三反应物在第二溶剂中进行反应生成所述电致发光材料中，所述第二溶剂包括甲苯、四氢呋喃、乙醇、乙烯、全氯乙烯、三氯乙烯、丙酮、乙烯乙二醇醚和三乙醇胺中的一种或几种的组合。
  10. 如权利要求9所述的电致发光材料的制备方法，其中，所述第二溶剂中具有第二添加剂，所述第二添加剂包括四三苯基磷钯、异丙醇钠、1,1'-双(二苯基膦)二茂铁、醋酸钯、氯化钯、[1,1'-双(二苯基磷)二茂铁]二氯化钯、四三苯基磷钯、双三苯基磷二氯化钯、三(二亚苄基丙酮)二钯、烯丙基氯化钯(II)二聚体、碳酸钾、碳酸铯、氢氧化钾、氢氧化钠、叔丁醇钠和碳酸氢钠中的一种或几种的组合。
  11. 如权利要求9所述的电致发光材料的制备方法，其中，所述第二溶剂包括甲苯，所述第二添加剂包括碳酸钾水溶液和四三苯基磷钯。
  12. 如权利要求2所述的电致发光材料的制备方法，其中，在所述提供第一反应物和第二反应物，所述第一反应物和所述第二反应物进行反应生成第一中间产物的步骤中，反应温度为90摄氏度-120摄氏度。
  13. 如权利要求12所述的电致发光材料的制备方法，其中，在所述提供第一反应物和第二反应物，所述第一反应物和所述第二反应物进行反应生成第一中间产物的步骤中，反应时间为9小时-36小时。
  14. 如权利要求2所述的电致发光材料的制备方法，其中，在所述提供第三反应物，所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料的步骤中，反应温度为90摄氏度-120摄氏度。
  15. 如权利要求14所述的电致发光材料的制备方法，其中，在所述提供第三反应物，所述第一中间产物和所述第三反应物进行反应生成所述电致发光材料的步骤中，反应时间为9小时-36小时。
  16. 如权利要求2所述的电致发光材料的制备方法，其中，所述第一反应物的结构式为
    Figure PCTCN2019086776-appb-100012
    Figure PCTCN2019086776-appb-100013
    中的一种。
  17. 如权利要求2所述的电致发光材料的制备方法，其中，所述第二反应物的结构式为
    Figure PCTCN2019086776-appb-100014
    Figure PCTCN2019086776-appb-100015
    中的一种，其中，所述X3为F，Cl，Br和I中的一种，所述X 4为F，Cl，Br和I中的一种。
  18. 如权利要求2所述的电致发光材料的制备方法，其中，所述第三反应物为R 3-Y，所述Y为硼酸频哪醇酯基或者硼酸基。
  19. 一种发光器件，其中，包括：
    衬底基板层，所述衬底层包括基板和阳极层，所述阳极层设置于所述基板上；
    空穴注入层，所述空穴注入层设置于所述阳极层上；
    空穴传输层，所述空穴传输层设置于所述空穴注入层上；
    发光层，所述发光层设置于所述空穴传输层上；
    电子传输层，所述电子传输层设置于所述发光层上；
    电子注入层，所述电子注入层设置于所述电子传输层上；
    阴极层，所述阴极层设置于所述电子传输层上；
    所述发光层包括所述电致发光材料，所述电致发光材料的结构式为R 3-R 2-R 1-R 2-R 3，其中，所述R 1为咔唑基团，所述R1的结构式为
    Figure PCTCN2019086776-appb-100016
    Figure PCTCN2019086776-appb-100017
    中的一种，所述R 2为芴基团，所述R 2的结构式为
    Figure PCTCN2019086776-appb-100018
    Figure PCTCN2019086776-appb-100019
    中的一种，所述R 3为吡啶基团，所述R 3的结构式为
    Figure PCTCN2019086776-appb-100020
    中的一种，所述X 1可以为H、烷基、烷氧基和杂烷基中的一种，所述X 2为H、烷基、烷氧基和杂烷基中的一种。
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