WO2024055195A1 - High-efficiency organic electroluminescent device and preparation method therefor - Google Patents

High-efficiency organic electroluminescent device and preparation method therefor Download PDF

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WO2024055195A1
WO2024055195A1 PCT/CN2022/118714 CN2022118714W WO2024055195A1 WO 2024055195 A1 WO2024055195 A1 WO 2024055195A1 CN 2022118714 W CN2022118714 W CN 2022118714W WO 2024055195 A1 WO2024055195 A1 WO 2024055195A1
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organic electroluminescent
layer
electroluminescent device
compound
formula
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PCT/CN2022/118714
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French (fr)
Chinese (zh)
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唐建新
谢凤鸣
李昊泽
李艳青
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苏州大学
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Priority to PCT/CN2022/118714 priority Critical patent/WO2024055195A1/en
Publication of WO2024055195A1 publication Critical patent/WO2024055195A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof

Definitions

  • the present invention relates to an organic electroluminescent device, which has a novel structure of luminescent material.
  • Organic Light Emitting Diodes are current-driven light-emitting devices that use organic materials as active materials. They have a sandwich-like structure, including positive and negative electrode film layers and sandwiched between the electrode film layers. Organic functional materials.
  • OLED light-emitting devices with lower driving voltage, better luminous efficiency, and longer device service life, and to continuously improve the performance of OLED devices, it is not only necessary to innovate the structure and manufacturing process of OLED devices, but also to improve the optoelectronics in OLED devices.
  • Functional materials are constantly researched and innovated to prepare functional materials with higher performance. Different from inorganic materials, organic materials have the characteristics of low synthesis cost, adjustable functions, flexibility, and good film-forming properties.
  • devices based on organic materials usually have simple manufacturing processes, are easy to prepare in large areas, are environmentally friendly, and can adopt thin film preparation methods with lower operating temperatures. Therefore, they have the advantage of low manufacturing cost, have huge application potential and have caused a lot of development in the past 30 years. It has received extensive attention and research from domestic and foreign scholars. At present, lighting devices and display devices based on OLEDs light-emitting technology have been commercialized. However, the luminescent performance brought by the luminescent layer materials of existing light-emitting devices still needs to be improved.
  • the purpose of the present invention is to provide an electroluminescent device that adopts a new thermally activated delayed fluorescent material, thereby having excellent luminescence performance, while being able to achieve high efficiency and low roll-off, which will bring huge benefits. Application prospects and economic value.
  • an organic electroluminescent device including an anode, a cathode, and a luminescent layer inserted between the anode and the cathode.
  • the luminescent layer includes a compound of the formula I structure.
  • R′ and R′′ are selected from one of the following substituted or unsubstituted groups: C1 to C10 alkyl, C6 to C30 monocyclic aromatic hydrocarbons or condensed ring aromatic hydrocarbons, C5 ⁇ C30 monocyclic heteroaromatic hydrocarbons or condensed ring heteroaromatic hydrocarbons.
  • the substituent is selected from one of deuterium, trifluoromethyl, cyano group, halogen, C1-C10 alkyl or cycloalkyl group, C6-C30 aryl group, and C3-C30 heteroaryl group.
  • Heteroatoms in the present invention generally refer to atoms or atomic groups selected from N, O, S, P, Si and Se, with N, O and S being preferred.
  • the organic electroluminescent device of the present invention includes an anode, a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a light emitting layer (EML), a hole blocking layer (HBL), and an electron transport layer. (ETL), electron injection layer (EIL), cathode; the specific preparation process of each layer of the organic electroluminescent device is conventional technology and is prepared by vacuum evaporation method.
  • the present invention is an organic electroluminescent device based on the compound of the above formula I structure.
  • indium tin oxide ITO
  • HIL hole injection layer
  • TAPC 4,4'-(cyclohexane-1,1-diyl)bis (N,N-di-p-tolylaniline)
  • HTL hole transport layer
  • TCTA 4,4′,4′′-tris(carbazol-9-yl)triphenylamine
  • mCBP electron/exciton blocking layer
  • the compound of formula I is used as the guest material doping2,8 - Bis(diphenylphosphoryl)dibenzo[B,D]furan (PPF) host material is used together
  • the invention discloses the application of the above-mentioned organic electroluminescent device in preparing an organic electroluminescent device.
  • the present invention uses new organic compounds to prepare organic electroluminescent devices, as luminescent layer materials, preferably as luminescent dyes and/or sensitizers; the prepared OLED devices have low turn-on voltage, high luminous efficiency, high color purity and better service life.
  • Figure 1 is the specific chemical structural formula of the compound of formula I of the present invention.
  • Figure 2 is the specific chemical structural formula of the compound of formula I of the present invention.
  • Figure 3 is the specific chemical structural formula of the compound of formula I of the present invention.
  • Figure 4 is the specific chemical structural formula of the compound of formula I of the present invention.
  • Figure 5 is a device efficiency diagram of device D1 prepared in an embodiment of the present invention.
  • Figure 6 is an electroluminescence spectrum chart of the device D1 prepared in the embodiment of the present invention.
  • Figure 7 is a hydrogen spectrum of compound 2PXZ2TRZ prepared in the embodiment of the present invention.
  • Figure 8 is the mass spectrum of compound 2PXZ2TRZ prepared in the embodiment of the present invention.
  • the present invention uses the compound of the formula I structure as the luminescent layer or doping material of the luminescent layer of the device, so that the OLED device has low turn-on voltage, high luminous efficiency, high color purity and better service life.
  • R′ and R′′ are selected from one of the following substituted or unsubstituted groups: C1 to C10 alkyl, C6 to C30 monocyclic aromatic hydrocarbons or condensed ring aromatic hydrocarbons, C5 ⁇ C30 monocyclic heteroaromatic hydrocarbons or condensed ring heteroaromatic hydrocarbons.
  • the substituent is selected from one of deuterium, trifluoromethyl, cyano group, halogen, C1-C10 alkyl or cycloalkyl group, C6-C30 aryl group, and C3-C30 heteroaryl group.
  • Heteroatoms in the present invention generally refer to atoms or atomic groups selected from N, O, S, P, Si and Se, with N, O and S being preferred.
  • the present invention discloses a preparation method of the compound of the above formula I structure, and the schematic diagram is as follows: .
  • the substituents are the same as those of the compound of formula I above, and Y is halogen, such as Cl, Br or I.
  • the invention discloses a new structure compound as a guest material doped with a host material as a luminescent layer, or directly as a luminescent layer, used to prepare an organic electroluminescent device; further, when the compound is used as a guest material and doped with a host material as a luminescent layer,
  • the doping concentration of the compound is 15-25 wt%, preferably 20 wt%. Doping concentration refers to the percentage of the guest material that accounts for the mass sum of the guest material and the host material.
  • ITO indium tin oxide
  • HIL hole injection layer
  • TAPC 4,4'-(cyclohexane-1,1-diyl)bis(N,N-di-p-tolylaniline)
  • HTL hole transport layer
  • TCTA 4,4′,4′′-tris(carbazol-9-yl)triphenylamine
  • EBL electron blocking layer
  • EBL electron blocking layer
  • the compound as the guest material is prepared as follows.
  • n-butyllithium (2.0 M, 3.00 ml) was added dropwise to a low-temperature (-78°C) solution of raw material A1 (1.00g, 1.67 mmol) in tetrahydrofuran, and stirred at -78°C for 1 hour.
  • raw material B1 (2.40 g, 4.92 mmol) dissolved in tetrahydrofuran solution, then stir at room temperature for 12 hours, then remove the solvent under reduced pressure, then add acetic acid (40 ml) and hydrochloric acid (36%, 1 ml), at 120
  • the reaction was carried out for 15 hours at °C. After the reaction was completed, the reaction solution was poured into water and filtered under reduced pressure.
  • Figure 7 is the hydrogen spectrum of compound 2PXZ2TRZ;
  • Figure 8 is the mass spectrum of compound 2PXZ2TRZ.
  • the by-product 2PXZTRZ (0.35 g, yield: 21%) was also obtained as a white powder.
  • MALDI-TOF-MS result molecular ion peak 988.945.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention relates to a high-efficiency organic electroluminescent device and a preparation method therefor. A hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode are sequentially prepared on an anode, such that an organic electroluminescent device is obtained, wherein the light-emitting layer comprises a compound of the structure as shown in formula I. In the present invention, a new thermally activated delayed fluorescent material is used, such that excellent light emission performance is achieved, and high-efficiency low-roll-off can be achieved, thereby having wide application prospects and a high economic value.

Description

一种高效率有机电致发光器件及其制备方法A high-efficiency organic electroluminescent device and its preparation method 技术领域Technical field
本发明涉及一种有机电致发光器件，其具有新型结构的发光材料。The present invention relates to an organic electroluminescent device, which has a novel structure of luminescent material.
背景技术Background technique
有机发光二极管(Organic Light Emitting Diodes，简称OLED)是一种以有机材料作为活性材料的电流驱动式发光器件，具有类三明治结构的器件，包括正负电极膜层及夹在电极膜层之间的有机功能材料。为了制备驱动电压更低、发光效率更好、器件使用寿命更长的OLED发光器件，实现OLED器件的性能不断提升，不仅需要对OLED器件结构和制作工艺进行创新，更需要对OLED器件中的光电功能材料不断研究和创新，以制备出具有更高性能的功能材料。与无机材料不同，有机材料具有合成成本低、功能可调、可柔性、以及成膜性好的特点。而且基于有机材料的器件通常制作工艺简单，易于大面积制备，环境友好，可采用操作温度较低的薄膜制备方法，因此具有制作成本低的优点，具有巨大的应用潜力并在过去的30年引起国内外学者的广泛关注与研究。 目前基于OLEDs发光技术的照明器件和显示器件已经商业化。但是现有发光器件的发光层材料带来的发光性能还需要改善。Organic Light Emitting Diodes (OLED for short) are current-driven light-emitting devices that use organic materials as active materials. They have a sandwich-like structure, including positive and negative electrode film layers and sandwiched between the electrode film layers. Organic functional materials. In order to prepare OLED light-emitting devices with lower driving voltage, better luminous efficiency, and longer device service life, and to continuously improve the performance of OLED devices, it is not only necessary to innovate the structure and manufacturing process of OLED devices, but also to improve the optoelectronics in OLED devices. Functional materials are constantly researched and innovated to prepare functional materials with higher performance. Different from inorganic materials, organic materials have the characteristics of low synthesis cost, adjustable functions, flexibility, and good film-forming properties. Moreover, devices based on organic materials usually have simple manufacturing processes, are easy to prepare in large areas, are environmentally friendly, and can adopt thin film preparation methods with lower operating temperatures. Therefore, they have the advantage of low manufacturing cost, have huge application potential and have caused a lot of development in the past 30 years. It has received extensive attention and research from domestic and foreign scholars. At present, lighting devices and display devices based on OLEDs light-emitting technology have been commercialized. However, the luminescent performance brought by the luminescent layer materials of existing light-emitting devices still needs to be improved.
技术问题technical problem
为了解决上述技术问题，本发明的目的在于提供一种电致发光器件，采用新的热激活延迟荧光材料，从而具有优异的发光性能，同时能够实现高效率低滚降，将会带来巨大的应用前景和经济价值。In order to solve the above technical problems, the purpose of the present invention is to provide an electroluminescent device that adopts a new thermally activated delayed fluorescent material, thereby having excellent luminescence performance, while being able to achieve high efficiency and low roll-off, which will bring huge benefits. Application prospects and economic value.
技术解决方案Technical solutions
本发明采用如下技术方案：一种有机电致发光器件，包括阳极、阴极和***所述阳极、阴极之间的发光层，所述发光层包括式Ⅰ结构的化合物。The present invention adopts the following technical solution: an organic electroluminescent device, including an anode, a cathode, and a luminescent layer inserted between the anode and the cathode. The luminescent layer includes a compound of the formula I structure.
。 .
式中： R 1、R 2、R 3和R 4独立的选自下述基团中的一种：氢、甲基、叔丁基、环己烷基、苯基、4-叔丁基苯基、二苯胺基、含氮芳环（比如咔唑基等）；X 1和/或X 2未取代，或者，X 1、X 2独立的选自单键、双键、O、S、S(＝O) 2、CR′R″或Se；X 1和/或X 2未取代是指X 1和/或X 2不存在；A选自C6～C60的芳胺或杂芳基。 In the formula: R 1 , R 2 , R 3 and R 4 are independently selected from one of the following groups: hydrogen, methyl, tert-butyl, cyclohexyl, phenyl, 4-tert-butylbenzene group, diphenylamine group, nitrogen-containing aromatic ring (such as carbazolyl group, etc.); X 1 and/or X 2 are unsubstituted, or X 1 and X 2 are independently selected from single bonds, double bonds, O, S, S (=O) 2 , CR′R″ or Se; X 1 and/or X 2 are unsubstituted, which means that X 1 and/or X 2 do not exist; A is selected from C6 to C60 arylamine or heteroaryl.
进一步的，CR′R″中，R′和R″选自取代或未取代的下述基团中的一种：C1～C10的烷基、C6～C30的单环芳烃或稠环芳烃、C5～C30的单环杂芳烃或稠环杂芳烃。优选的，取代基选自氘、三氟甲基、氰基、卤素、C1-C10的烷基或环烷基、C6-C30的芳基、C3-C30的杂芳基中的一种。Further, in CR′R″, R′ and R″ are selected from one of the following substituted or unsubstituted groups: C1 to C10 alkyl, C6 to C30 monocyclic aromatic hydrocarbons or condensed ring aromatic hydrocarbons, C5 ~C30 monocyclic heteroaromatic hydrocarbons or condensed ring heteroaromatic hydrocarbons. Preferably, the substituent is selected from one of deuterium, trifluoromethyl, cyano group, halogen, C1-C10 alkyl or cycloalkyl group, C6-C30 aryl group, and C3-C30 heteroaryl group.
本发明中的杂原子，通常指选自N、O、S、P、Si和Se中的原子或原子团，优选N、O和S。Heteroatoms in the present invention generally refer to atoms or atomic groups selected from N, O, S, P, Si and Se, with N, O and S being preferred.
本发明有机电致发光器件包括阳极、空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、发光层(EML)、空穴阻挡层（HBL）、电子传输层(ETL)、电子注入层(EIL)、阴极；有机电致发光器件各层具体的制备工艺为常规技术，采用真空蒸镀法制备。优选的，本发明基于上述式Ⅰ结构化合物的有机电致发光器件，具体结构为：氧化铟锡(ITO)用作阳极、双吡嗪并[2,3-f:2',3'-h]喹喔啉-2,3,6,7,10,11-己腈(HATCN)用作空穴注入层(HIL)、4,4'-(环己烷-1,1-二基)双(N,N-二-对甲苯基苯胺)(TAPC)用作空穴传输层(HTL)、4,4′,4”-三(咔唑-9-基)三苯胺(TCTA)和3,3′-二(9H-咔唑-9-基)-1,1′-联苯（mCBP）用作电子/激子阻挡层(EBL)、式Ⅰ结构的化合物作客体材料掺杂2,8-双(二苯基磷酰基)二苯并[B,D]呋喃(PPF)主体材料共同用作发光层(EML)或者式Ⅰ结构的化合物作发光层(EML)、2,8-双(二苯基磷酰基)二苯并[B,D]呋喃(PPF)用作空穴阻挡层（HBL）、4,6-双(3,5-二(吡啶-3-基)苯基)-2-甲基嘧啶(TmPyPB)用作电子传输层(ETL)、八羟基喹啉锂(Liq)用作电子注入层(EIL)、铝(Al)用作阴极；有机电致发光器件各层规格为常规设计，比如为：ITO/HATCN (10 nm)/TAPC (40 nm)/TCTA (10 nm)/mCBP (8 nm)/PPF:客体材料(20 wt%) (20 nm)/PPF (8 nm)TmPyPB (40 nm)/Liq (3 nm)/Al (100 nm)。具体的制备工艺为常规技术，采用真空蒸镀法制备。The organic electroluminescent device of the present invention includes an anode, a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a light emitting layer (EML), a hole blocking layer (HBL), and an electron transport layer. (ETL), electron injection layer (EIL), cathode; the specific preparation process of each layer of the organic electroluminescent device is conventional technology and is prepared by vacuum evaporation method. Preferably, the present invention is an organic electroluminescent device based on the compound of the above formula I structure. The specific structure is: indium tin oxide (ITO) is used as the anode, bipyrazino[2,3-f:2',3'-h ] Quinoxaline-2,3,6,7,10,11-hexanenitrile (HATCN) is used as the hole injection layer (HIL), 4,4'-(cyclohexane-1,1-diyl)bis (N,N-di-p-tolylaniline) (TAPC) is used as the hole transport layer (HTL), 4,4′,4″-tris(carbazol-9-yl)triphenylamine (TCTA) and 3, 3′-Bis(9H-carbazol-9-yl)-1,1′-biphenyl (mCBP) is used as the electron/exciton blocking layer (EBL), and the compound of formula I is used as the guest material doping2,8 - Bis(diphenylphosphoryl)dibenzo[B,D]furan (PPF) host material is used together as the luminescent layer (EML) or the compound of the formula I structure is used as the luminescent layer (EML), 2,8-bis( Diphenylphosphoryl)dibenzo[B,D]furan (PPF) was used as hole blocking layer (HBL), 4,6-bis(3,5-bis(pyridin-3-yl)phenyl)- 2-Methylpyrimidine (TmPyPB) is used as the electron transport layer (ETL), lithium octahydroxyquinolate (Liq) is used as the electron injection layer (EIL), and aluminum (Al) is used as the cathode; specifications for each layer of the organic electroluminescent device For conventional designs, such as: ITO/HATCN (10 nm)/TAPC (40 nm)/TCTA (10 nm)/mCBP (8 nm)/PPF:guest material (20 wt%) (20 nm)/PPF (8 nm)TmPyPB (40 nm)/Liq (3 nm)/Al (100 nm). The specific preparation process is conventional technology and is prepared by vacuum evaporation method.
本发明公开了上述有机电致发光器件在制备有机电致发光装置中的应用。The invention discloses the application of the above-mentioned organic electroluminescent device in preparing an organic electroluminescent device.
有益效果beneficial effects
本发明采用新的有机化合物制备有机电致发光器件，作为发光层材料，优选作为发光染料和/或敏化剂；制备的OLED器件具有低开启电压、高发光效率、高色纯度和更优的使用寿命。The present invention uses new organic compounds to prepare organic electroluminescent devices, as luminescent layer materials, preferably as luminescent dyes and/or sensitizers; the prepared OLED devices have low turn-on voltage, high luminous efficiency, high color purity and better service life.
附图说明Description of drawings
图1为本发明式Ⅰ结构的化合物的具体化学结构式。Figure 1 is the specific chemical structural formula of the compound of formula I of the present invention.
图2为本发明式Ⅰ结构的化合物的具体化学结构式。Figure 2 is the specific chemical structural formula of the compound of formula I of the present invention.
图3为本发明式Ⅰ结构的化合物的具体化学结构式。Figure 3 is the specific chemical structural formula of the compound of formula I of the present invention.
图4为本发明式Ⅰ结构的化合物的具体化学结构式。Figure 4 is the specific chemical structural formula of the compound of formula I of the present invention.
图5为本发明实施例制备的器件D1的器件效率图。Figure 5 is a device efficiency diagram of device D1 prepared in an embodiment of the present invention.
图6为本发明实施例制备的器件D1的电致发光光谱图。Figure 6 is an electroluminescence spectrum chart of the device D1 prepared in the embodiment of the present invention.
图7为本发明实施例制备的化合物2PXZ2TRZ的氢谱。Figure 7 is a hydrogen spectrum of compound 2PXZ2TRZ prepared in the embodiment of the present invention.
图8为本发明实施例制备的化合物2PXZ2TRZ的质谱。Figure 8 is the mass spectrum of compound 2PXZ2TRZ prepared in the embodiment of the present invention.
本发明的实施方式Embodiments of the invention
本发明以式Ⅰ结构的化合物作为器件的发光层或发光层掺杂材料，使得OLED器件具有低开启电压、高发光效率、高色纯度和更优的使用寿命。The present invention uses the compound of the formula I structure as the luminescent layer or doping material of the luminescent layer of the device, so that the OLED device has low turn-on voltage, high luminous efficiency, high color purity and better service life.
。 .
式中： R 1、R 2、R 3和R 4独立的选自下述基团中的一种：氢、甲基、叔丁基、环己烷基、苯基、4-叔丁基苯基、二苯胺基、含氮芳环（比如咔唑基等）；X 1和/或X 2未取代，或者，X 1、X 2独立的选自单键、双键、O、S、S(＝O) 2、CR′R″或Se；X 1和/或X 2未取代是指X 1和/或X 2不存在；A选自C6～C60的芳胺或杂芳基。 In the formula: R 1 , R 2 , R 3 and R 4 are independently selected from one of the following groups: hydrogen, methyl, tert-butyl, cyclohexyl, phenyl, 4-tert-butylbenzene group, diphenylamine group, nitrogen-containing aromatic ring (such as carbazolyl group, etc.); X 1 and/or X 2 are unsubstituted, or X 1 and X 2 are independently selected from single bonds, double bonds, O, S, S (=O) 2 , CR′R″ or Se; X 1 and/or X 2 are unsubstituted, which means that X 1 and/or X 2 do not exist; A is selected from C6 to C60 arylamine or heteroaryl.
进一步的，CR′R″中，R′和R″选自取代或未取代的下述基团中的一种：C1～C10的烷基、C6～C30的单环芳烃或稠环芳烃、C5～C30的单环杂芳烃或稠环杂芳烃。优选的，取代基选自氘、三氟甲基、氰基、卤素、C1-C10的烷基或环烷基、C6-C30的芳基、C3-C30的杂芳基中的一种。Further, in CR′R″, R′ and R″ are selected from one of the following substituted or unsubstituted groups: C1 to C10 alkyl, C6 to C30 monocyclic aromatic hydrocarbons or condensed ring aromatic hydrocarbons, C5 ~C30 monocyclic heteroaromatic hydrocarbons or condensed ring heteroaromatic hydrocarbons. Preferably, the substituent is selected from one of deuterium, trifluoromethyl, cyano group, halogen, C1-C10 alkyl or cycloalkyl group, C6-C30 aryl group, and C3-C30 heteroaryl group.
本发明中的杂原子，通常指选自N、O、S、P、Si和Se中的原子或原子团，优选N、O和S。Heteroatoms in the present invention generally refer to atoms or atomic groups selected from N, O, S, P, Si and Se, with N, O and S being preferred.
本发明公开了上述式Ⅰ结构的化合物的制备方法，示意如下： 。 The present invention discloses a preparation method of the compound of the above formula I structure, and the schematic diagram is as follows: .
原料中，取代基与上述式Ⅰ结构的化合物的取代基一样，Y为卤素，比如Cl，Br或I。In the raw materials, the substituents are the same as those of the compound of formula I above, and Y is halogen, such as Cl, Br or I.
本发明式Ⅰ结构的化合物的具体化学结构式见图1至图4。The specific chemical structural formulas of the compounds of formula I of the present invention are shown in Figures 1 to 4.
下面将以多个合成实施例为例来详述本发明的上述新化合物的具体制备方法，但本发明的制备方法并不限于这些合成实施例。本发明所有原料都是现有产品，具体制备方以及测试方法为常规技术，比如真空蒸镀，真空度≤2×10 -4 Pa，功能层沉积速率为2 Å/s，主体材料的沉积速率为1 Å/s，Liq层沉积速率为0.1 Å/s，Al的沉积速率8 Å/s。本发明的创造性在于提供新的化合物掺杂主体材料作为有机电致发光器件的发光层。对所制作的有机电致发光器件施加直流电流，使用PhotoResearch PR655亮度计来评价发光性能；使用电脑控制的Keithley 2400型数字源表测量电流-电压特性。所述有机电致发光器件的发光性质是在外加直流电压变化的情况下进行测定的。 The specific preparation method of the above-mentioned new compound of the present invention will be described in detail below using multiple synthetic examples as examples, but the preparation method of the present invention is not limited to these synthetic examples. All raw materials of the present invention are existing products, and the specific preparation methods and testing methods are conventional technologies, such as vacuum evaporation, vacuum degree ≤ 2×10 -4 Pa, functional layer deposition rate 2 Å/s, and main material deposition rate is 1 Å/s, the Liq layer deposition rate is 0.1 Å/s, and the Al deposition rate is 8 Å/s. The creativity of the present invention lies in providing a new compound-doped host material as the light-emitting layer of an organic electroluminescent device. DC current was applied to the produced organic electroluminescent device, and the luminescence performance was evaluated using a PhotoResearch PR655 luminance meter; the current-voltage characteristics were measured using a computer-controlled Keithley 2400 digital source meter. The luminescent properties of the organic electroluminescent device are measured under changes in applied DC voltage.
本发明公开了新结构化合物作为客体材料掺杂主体材料作为发光层，或者直接作为发光层，用于制备有机电致发光器件；进一步的，化合物作为客体材料掺杂主体材料共同作为发光层时，所述化合物的掺杂浓度为15～25 wt%，优选20 wt%。掺杂浓度指客体材料占客体材料与主体材料质量和的百分数。The invention discloses a new structure compound as a guest material doped with a host material as a luminescent layer, or directly as a luminescent layer, used to prepare an organic electroluminescent device; further, when the compound is used as a guest material and doped with a host material as a luminescent layer, The doping concentration of the compound is 15-25 wt%, preferably 20 wt%. Doping concentration refers to the percentage of the guest material that accounts for the mass sum of the guest material and the host material.
实施例一。Example 1.
有机电致发光器件，具体结构为：氧化铟锡(ITO)用作阳极、双吡嗪并[2,3-f:2',3'-h]喹喔啉-2,3,6,7,10,11-己腈(HATCN)用作空穴注入层(HIL)、4,4'-(环己烷-1,1-二基)双(N,N-二-对甲苯基苯胺)(TAPC)用作空穴传输层(HTL)、4,4′,4”-三(咔唑-9-基)三苯胺(TCTA)和3,3′-二(9H-咔唑-9-基)-1,1′-联苯（mCBP）用作电子阻挡层(EBL)、化合物作客体材料掺杂2,8-双(二苯基磷酰基)二苯并[B,D]呋喃(PPF)主体材料共同用作发光层(EML)、2,8-双(二苯基磷酰基)二苯并[B,D]呋喃(PPF)用作空穴阻挡层（HBL）、4,6-双(3,5-二(吡啶-3-基)苯基)-2-甲基嘧啶(TmPyPB)用作电子传输层(ETL)、八羟基喹啉锂(Liq)用作电子注入层(EIL)、铝(Al)用作阴极；有机电致发光器件各层规格为：ITO/HATCN (10 nm)/TAPC (40 nm)/TCTA (10 nm)/mCBP (8 nm)/PPF:客体材料(20 wt%) (20 nm)/PPF (8 nm)TmPyPB (40 nm)/Liq (3 nm)/Al (100 nm)。具体的制备工艺为常规技术，采用真空蒸镀法制备。Organic electroluminescent device, the specific structure is: indium tin oxide (ITO) is used as the anode, bipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7 ,10,11-hexanenitrile (HATCN) is used as the hole injection layer (HIL), 4,4'-(cyclohexane-1,1-diyl)bis(N,N-di-p-tolylaniline) (TAPC) is used as the hole transport layer (HTL), 4,4′,4″-tris(carbazol-9-yl)triphenylamine (TCTA) and 3,3′-bis(9H-carbazole-9- (mCBP) is used as the electron blocking layer (EBL), and the compound is used as the guest material doped with 2,8-bis(diphenylphosphoryl)dibenzo[B,D]furan ( PPF) host material is used together as the emissive layer (EML), 2,8-bis(diphenylphosphoryl)dibenzo[B,D]furan (PPF) is used as the hole blocking layer (HBL), 4,6 -Bis(3,5-di(pyridin-3-yl)phenyl)-2-methylpyrimidine (TmPyPB) is used as the electron transport layer (ETL), lithium octahydroxyquinolate (Liq) is used as the electron injection layer ( EIL) and aluminum (Al) are used as cathodes; the specifications of each layer of the organic electroluminescent device are: ITO/HATCN (10 nm)/TAPC (40 nm)/TCTA (10 nm)/mCBP (8 nm)/PPF:guest material (20 wt%) (20 nm)/PPF (8 nm)TmPyPB (40 nm)/Liq (3 nm)/Al (100 nm). The specific preparation process is conventional technology and is prepared by vacuum evaporation method.
[0049]  基于上述各个化合物的有机电致发光器件的具体性能数据详见表1，具体测试方法为现有技术。The specific performance data of the organic electroluminescent device based on the above-mentioned compounds are detailed in Table 1, and the specific test method is the prior art.
。 .
以上实验数据表明，本发明提供的新型TADF材料应用到有机电致发光器件中后，在实现器件具有高发光效率和低效率滚降的良好性能的同时，还实现了电致发光器件的超高亮度。因此，本发明的这类新型化合物是性能良好的有机发光功能材料，有望推广商业化应用。图5为器件D1的器件效率图；图6为器件D1的电致发光光谱图。The above experimental data shows that after the new TADF material provided by the present invention is applied to an organic electroluminescent device, it not only achieves the good performance of the device with high luminous efficiency and low efficiency roll-off, but also achieves ultra-high performance of the electroluminescent device. brightness. Therefore, the novel compounds of the present invention are organic light-emitting functional materials with good performance and are expected to be promoted for commercial application. Figure 5 is the device efficiency diagram of device D1; Figure 6 is the electroluminescence spectrum diagram of device D1.
作为客体材料的化合物的制备方法如下。The compound as the guest material is prepared as follows.
合成例一 化合物的2PXZ2TRZ合成。Synthesis Example 1 Synthesis of compound 2PXZ2TRZ.
。 .
在氮气氛围下，将正丁基锂（2.0 M，3.00毫升）滴加到原料A1（1.00克，1.67毫摩尔）的四氢呋喃低温（-78 ℃）溶液中，在-78 ℃下搅拌1小时后，加入溶于四氢呋喃溶液的原料B1（2.40克，4.92毫摩尔），然后于室温搅拌12小时，再减压除去溶剂，然后加入醋酸（40毫升）和盐酸（36%，1毫升），在120 ℃下反应15小时，反应完成后将反应液倒入水中减压抽滤，滤渣通过硅胶柱色谱法提纯（展开剂为二氯甲烷∶石油醚＝1:1，v/v），得化合物2PXZ2TRZ（1.26克，产量：55%），白色粉末，为主产物，MALDI-TOF-MS结果：分子离子峰1378.797。图7为化合物2PXZ2TRZ的氢谱；图8为化合物2PXZ2TRZ的质谱。还得到副产物2PXZTRZ（0.35克，产量：21%），白色粉末，MALDI-TOF-MS结果：分子离子峰988.945。Under a nitrogen atmosphere, n-butyllithium (2.0 M, 3.00 ml) was added dropwise to a low-temperature (-78°C) solution of raw material A1 (1.00g, 1.67 mmol) in tetrahydrofuran, and stirred at -78°C for 1 hour. , add raw material B1 (2.40 g, 4.92 mmol) dissolved in tetrahydrofuran solution, then stir at room temperature for 12 hours, then remove the solvent under reduced pressure, then add acetic acid (40 ml) and hydrochloric acid (36%, 1 ml), at 120 The reaction was carried out for 15 hours at ℃. After the reaction was completed, the reaction solution was poured into water and filtered under reduced pressure. The filter residue was purified by silica gel column chromatography (the developing agent was dichloromethane: petroleum ether = 1:1, v/v) to obtain compound 2PXZ2TRZ. (1.26 g, yield: 55%), white powder, main product, MALDI-TOF-MS result: molecular ion peak 1378.797. Figure 7 is the hydrogen spectrum of compound 2PXZ2TRZ; Figure 8 is the mass spectrum of compound 2PXZ2TRZ. The by-product 2PXZTRZ (0.35 g, yield: 21%) was also obtained as a white powder. MALDI-TOF-MS result: molecular ion peak 988.945.
在合成例一的基础上，更换原料，可以得到其他化合物；反应如下。On the basis of Synthesis Example 1, other compounds can be obtained by changing the raw materials; the reaction is as follows.
。 .
尽管结合实施例对本发明进行了说明，但本发明并不局限于上述实施例，应当理解，在本发明构思的引导下，本领域技术人员可进行各种修改和改进，所有这些修改和改进都应属于本发明所附权利要求的保护范围。Although the present invention has been described in conjunction with the embodiments, the present invention is not limited to the above-mentioned embodiments. It should be understood that under the guidance of the concept of the present invention, those skilled in the art can make various modifications and improvements, all of which are It should fall within the protection scope of the appended claims of the present invention.

Claims (10)

  1. 一种有机电致发光器件，包括阳极、阴极和***所述阳极、阴极之间的发光层，其特征在于，所述发光层包括式Ⅰ结构的化合物：An organic electroluminescent device, including an anode, a cathode and a luminescent layer inserted between the anode and the cathode, characterized in that the luminescent layer includes a compound of formula I:
    式中： R 1、R 2、R 3和R 4独立的选自下述基团中的一种：氢、甲基、叔丁基、环己烷基、苯基、4-叔丁基苯基、二苯胺基、含氮芳环；X 1和/或X 2未取代，或者，X 1、X 2独立的选自单键、双键、O、S、S(＝O) 2、CR′R″或Se；X 1和/或X 2未取代是指X 1和/或X 2不存在；A选自C6～C60的芳胺或杂芳基。 In the formula: R 1 , R 2 , R 3 and R 4 are independently selected from one of the following groups: hydrogen, methyl, tert-butyl, cyclohexyl, phenyl, 4-tert-butylbenzene group , diphenylamine group, nitrogen-containing aromatic ring; X 1 and/or X 2 are unsubstituted, or X 1 and ' R ' or Se ;
  2. 根据权利要求1所述有机电致发光器件，其特征在于，所述有机电致发光器件包括阳极、空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层、阴极。The organic electroluminescent device according to claim 1, characterized in that the organic electroluminescent device includes an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer layer, electron injection layer, cathode.
  3. 根据权利要求2所述有机电致发光器件，其特征在于，有机电致发光器件各层采用真空蒸镀法制备。The organic electroluminescent device according to claim 2, characterized in that each layer of the organic electroluminescent device is prepared by a vacuum evaporation method.
  4. 根据权利要求1所述有机电致发光器件，其特征在于，发光层为式Ⅰ结构的化合物。The organic electroluminescent device according to claim 1, characterized in that the light-emitting layer is a compound of formula I.
  5. 根据权利要求1所述有机电致发光器件，其特征在于，式Ⅰ结构的化合物掺杂主体材料作为发光层。The organic electroluminescent device according to claim 1, characterized in that the compound of the formula I structure is doped with the host material as the light-emitting layer.
  6. 根据权利要求5所述有机电致发光器件，其特征在于，式Ⅰ结构化合物的掺杂浓度为15～25 wt%。The organic electroluminescent device according to claim 5, characterized in that the doping concentration of the compound of formula I is 15 to 25 wt%.
  7. 根据权利要求1所述有机电致发光器件，其特征在于，CR′R″中，R′和R″独立的选自取代或未取代的下述基团中的一种：C1～C10的烷基、C6～C30的单环芳烃或稠环芳烃、C5～C30的单环杂芳烃或稠环杂芳烃。The organic electroluminescent device according to claim 1, characterized in that in CR′R″, R′ and R″ are independently selected from one of the following substituted or unsubstituted groups: alkane of C1 to C10. base, C6 to C30 monocyclic aromatic hydrocarbons or condensed ring aromatic hydrocarbons, C5 to C30 monocyclic heteroaromatic hydrocarbons or condensed ring heteroaromatic hydrocarbons.
  8. 权利要求1所述有机电致发光器件的制备方法，其特征在于，在阳极上依次制备空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层、阴极，得到有机电致发光器件。The method for preparing an organic electroluminescent device according to claim 1, characterized in that a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron transport layer and an electron transport layer are sequentially prepared on the anode. Inject the layer and cathode to obtain an organic electroluminescent device.
  9. 一种有机电致发光装置，其特征在于，包括权利要求1所述有机电致发光器件。An organic electroluminescent device, characterized by comprising the organic electroluminescent device according to claim 1.
  10. 权利要求1所述有机电致发光器件在制备有机电致发光装置中的应用。Application of the organic electroluminescent device according to claim 1 in the preparation of organic electroluminescent devices.
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