WO2020182070A1 - 一种以含有芘或者氮杂芘的三芳胺为核心的化合物及其应用 - Google Patents

一种以含有芘或者氮杂芘的三芳胺为核心的化合物及其应用 Download PDF

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WO2020182070A1
WO2020182070A1 PCT/CN2020/078130 CN2020078130W WO2020182070A1 WO 2020182070 A1 WO2020182070 A1 WO 2020182070A1 CN 2020078130 W CN2020078130 W CN 2020078130W WO 2020182070 A1 WO2020182070 A1 WO 2020182070A1
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张小庆
唐丹丹
吴秀芹
谢丹丹
王芳
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江苏三月光电科技有限公司
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Definitions

  • the present invention relates to the technical field of semiconductor materials, in particular to a compound with triarylamine containing pyrene or azapyrene as the core and its application in organic electroluminescence devices.
  • OLED display technology has been applied in smart phones, tablet computers and other fields, and will further expand to large-size applications such as TVs.
  • OLED devices have performance such as luminous efficiency and service life It needs further improvement.
  • Current research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and increasing the service life of the device.
  • OLED optoelectronic functional materials are required to create higher-performance OLED functional materials.
  • OLED optoelectronic functional materials used in OLED devices can be divided into two categories in terms of usage, namely charge injection and transport materials and light-emitting materials. Further, charge injection and transport materials can also be divided into electron injection and transport materials, electron blocking materials, hole injection and transport materials, and hole blocking materials, and luminescent materials can also be divided into host luminescent materials and doped materials.
  • organic functional materials are required to have good optoelectronic properties.
  • a charge transport material it is required to have good carrier mobility, high glass transition temperature, etc., as the main body of the light-emitting layer
  • the material has good bipolarity, appropriate HOMO/LUMO energy levels, etc.
  • the OLED photoelectric functional material film layer constituting the OLED device includes at least two or more layers, and the OLED device structure used in industry includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron transport Layers, electron injection layers and other film layers, that is to say, the optoelectronic functional materials used in OLED devices include at least hole injection materials, hole transport materials, luminescent materials, electron transport materials, etc.
  • the material types and matching forms are rich And diversity.
  • the optoelectronic functional materials used have strong selectivity, and the performance of the same material in devices with different structures may be completely different.
  • the applicant of the present invention provides a compound with a triarylamine containing pyrene or azapyrene as the core and its application.
  • the compound of the present invention takes triarylamine containing pyrene or azapyrene as the core, has high glass transition temperature, molecular thermal stability, and suitable HOMO energy level. Through device structure optimization, it can effectively improve the photoelectric performance of OLED devices and The lifetime of OLED devices.
  • the technical scheme of the present invention is as follows: a compound with a triarylamine containing pyrene or azapyrene as the core, and the structure of the compound is as shown in general formula (1):
  • n represents the number 0 or 1;
  • n When n is expressed as the number 0, it means that L 1 and L 2 are directly connected;
  • L 1 , L 2 , and L 3 each independently represent a single bond, phenylene or naphthylene;
  • Each occurrence of Y that is the same or different is represented by CR or a nitrogen atom, where each occurrence of R is the same or different and is represented by a hydrogen atom, a deuterium atom, a substituted or unsubstituted C 1-10 alkyl group, a substituted or unsubstituted C6-30 aryl or substituted or unsubstituted C 3-30 heteroaryl;
  • Ar 1 represents phenyl or naphthyl
  • Ar 2 represents a substituted or unsubstituted C 6-30 aryl group
  • Ar 3 is expressed as the structure shown in general formula (2)
  • X is represented by -O-, -S-, -C(R 1 )(R 2 )- or -N(R 3 )-;
  • Each occurrence of Z that is the same or different is represented as CR, carbon atom or nitrogen atom, and Z connected to other groups is represented as a carbon atom, wherein each occurrence of R that is the same or different is represented as hydrogen atom, deuterium atom, substitution or Unsubstituted C 1-10 alkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 heteroaryl;
  • R1, R2 and R3 are each independently represented by a C 1-10 alkyl group, a substituted or unsubstituted C 6-30 aryl group, a substituted or unsubstituted C 3-30 heteroaryl group; and R1 and R2 can be Mutually bond to form a ring;
  • the substituent when each of the above groups is substituted is selected from one or more of fluorine atom, cyano group, phenyl group, biphenyl group, naphthyl group, furyl group, carbazolyl group, thienyl group or pyridyl group;
  • the heteroatom in the heteroaryl group is selected from one or more of N, O or S.
  • At least one Y in the general formula (1) represents a nitrogen atom.
  • At least one Z in the general formula (2) represents a nitrogen atom.
  • R is preferably hydrogen, deuterium, methyl, isopropyl, tert-butyl, cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl
  • R is preferably hydrogen, deuterium, methyl, isopropyl, tert-butyl, cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl
  • R1 ⁇ R3 are independently selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted One of biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl;
  • the substituent when each of the above groups is substituted is selected from one or more of fluorine atom, cyano group, phenyl group, biphenyl group, naphthyl group, furyl group, carbazolyl group, thienyl group or pyridyl group.
  • the compound is represented by general formula (1-1), general formula (1-2), general formula (1-3), general formula (1-4), general formula (1-5), general formula (1-6), any of the structures shown in general formula (1-7) or general formula (1-8);
  • the general formula (1) is any one of the following specific compounds:
  • An organic electroluminescence device has multiple organic thin film layers between the anode and the cathode, and at least one organic thin film layer contains the triarylamine containing pyrene or azapyrene as the core Compound.
  • the multi-layer organic film layer includes an electron blocking layer and/or hole transport layer, and the electron blocking layer and/or hole transport layer contains the triarylamine containing pyrene or azapyrene. Amine-based compound.
  • a display element containing the organic electroluminescence device is a display element containing the organic electroluminescence device.
  • the C 1-20 alkyl group of the present invention is preferably the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 1-methylpropyl, tert-butyl, N-pentyl, isopentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-methylpentyl, 2-methyl Pentyl, 3-methylpentyl, 4-methylpentyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl.
  • a heteroaryl group is a monocyclic or bicyclic aromatic heterocycle (heteroaromatic), which contains up to four identical or different ring heteroatoms selected from N, O and S, and passes through the ring
  • the carbon atom or, if appropriate, is connected via a ring nitrogen atom, preferably the following groups: furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, quinolinyl, thiazolyl, oxazolyl, isoxazolyl, iso Thiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl.
  • the group may be mono-substituted or multi-substituted, unless otherwise specified.
  • the compound of the present invention takes the triarylamine containing pyrene or azapyrene as the core, is connected to the electron-donating group, has a higher hole mobility, and is used as a material for the hole transport layer of an OLED light-emitting device, which can improve excitation
  • the recombination efficiency of electrons in the light-emitting layer improves the energy utilization rate, thereby improving the luminous efficiency of the device.
  • the compound of the present invention makes the distribution of electrons and holes in the light-emitting layer more balanced, improves hole injection and transport performance at a proper HOMO energy level, and acts as an electron barrier at a proper LUMO energy level. It can improve the recombination efficiency of excitons in the light-emitting layer; it can effectively improve the exciton utilization rate, reduce the device voltage, and improve the current efficiency and lifetime of the device.
  • the compound of the invention has good application effects in OLED light-emitting devices and has a good industrialization prospect.
  • Figure 1 is a schematic diagram of the structure of the materials listed in the present invention applied to OLED devices;
  • 1 is a transparent substrate layer
  • 2 is an ITO anode layer
  • 3 is a hole injection layer
  • 4 is a hole transport layer
  • 5 is an electron blocking layer
  • 6 is a light-emitting layer
  • 7 is an electron transport layer
  • 8 is an electron injection Layers
  • 9 is the cathode layer
  • 10 is the CPL layer.
  • Fig. 2 is a curve of the current efficiency of the device of the present invention with temperature.
  • Figure 3 is the UV absorption spectrum of compound 274 of the present invention.
  • Figure 4 is the UV absorption spectrum of compound 426 of the present invention.
  • reactant A-1 The synthesis steps of reactant A-1 are:
  • the above halogenated compounds can be synthesized through 1-2 steps of Suzuki coupling reaction of aryl halides and phenylboronic acid.
  • the organic compound of the present invention is used in a light-emitting device, and can be used as an electron blocking layer or hole transport layer material.
  • compound (003) compound (013), compound (016), compound (037), compound (045), compound (057), compound (064), compound (081), compound (082), compound (099) of the present invention ), compound (142), compound (151), compound (159), compound (201), compound (218), compound (229), compound (237), compound (248), compound (274), compound (276) ), compound (300), compound (312), compound (334), compound (346), compound (347), compound (371), compound (379), compound (414), compound (426), compound (437) ), compound (444), compound (452), compound (468), compound (477), compound (486) and compound (496) were tested for thermal performance, Eg, HOMO energy level, and hole mobility, respectively. The results As shown in table 2.
  • the glass transition temperature Tg is measured by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter from Netzsch, Germany), and the heating rate is 10°C/min; the thermal weight loss temperature Td is the temperature at which weight loss is 1% in a nitrogen atmosphere. The measurement was carried out on the TGA-50H thermogravimetric analyzer of Shimadzu Corporation, and the nitrogen flow rate was 20 mL/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy test system (IPS3), and the test was in an atmospheric environment.
  • Hole mobility The material is made into a single-charge device and measured by the SCLC method.
  • the organic compound of the present invention has a high glass transition temperature, can improve the phase stability of the material film, and further increase the service life of the device; it has a high T1 energy level, which can block the energy loss of the light-emitting layer, thereby improving the device Luminous efficiency; a suitable HOMO energy level can solve the problem of carrier injection, reduce device voltage, and a higher band gap (Eg) ensures that the material does not absorb in the visible light range. Therefore, after the pyrene-containing compound of the present invention is applied to different functional layers of an OLED device, the luminous efficiency and service life of the device can be effectively improved.
  • Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10nm) / hole transport layer 4 (compound (003), thickness 60 nm) / electron blocking layer 5 (EB-1, thickness 20 nm )/Light-emitting layer 6 (GH1, GH2 and GD-1 are mixed according to the weight ratio of 45:45:10, thickness 40nm)/Hole blocking/electron transport layer 7 (ET-1 and Liq, according to the weight of 1:1 Ratio mixing, thickness 40nm)/electron injection layer 8 (LiF, thickness 1nm)/cathode layer 9 (Mg and Ag, mixing in a weight ratio of 9:1, thickness 15nm)/CPL layer 10 (compound CP-1, The thickness is 70nm).
  • the transparent substrate layer 1 is a transparent PI film
  • the ITO anode layer 2 (film thickness is 150nm) is washed, that is, alkaline washing, pure water washing, drying, and ultraviolet-ozone washing to remove the transparency. Organic residues on the surface of ITO.
  • HAT-CN with a film thickness of 10 nm was deposited and used as the hole injection layer 3 using a vacuum vapor deposition device.
  • compound (003) with a thickness of 60 nm was deposited as the hole transport layer 4.
  • EB-1 with a thickness of 20 nm was deposited as the electron blocking layer 5.
  • the light-emitting layer 6 of the OLED light-emitting device is fabricated. Its structure includes GH-1 and GH-2 used in the OLED light-emitting layer 6 as host materials, GD-1 as the doping material, and the doping material The doping ratio is 10% by weight, and the film thickness of the light-emitting layer is 40 nm.
  • the electron transport layer materials are ET-1 and Liq.
  • the vacuum evaporation film thickness of the material is 40 nm, and this layer is the hole blocking/electron transport layer 7.
  • a lithium fluoride (LiF) layer with a thickness of 1 nm was formed by a vacuum evaporation device, and this layer is the electron injection layer 8.
  • a Mg:Ag electrode layer with a film thickness of 15 nm was formed by a vacuum evaporation device, and this layer was used as the cathode layer 9.
  • 70 nm of CP-1 was vacuum deposited as the CPL layer 10.
  • the organic light-emitting device of the present invention has a greater improvement in efficiency and life span compared to OLED devices of known materials.
  • the efficiency of the OLED device prepared by the material of the present invention is relatively stable when working at low temperature.
  • the device examples 1, 18, 26, 35 and device comparative example 1 were tested for efficiency in the range of -10 to 80°C. The results are shown in the table 5 and Figure 2.
  • device embodiments 1, 18, 26, and 35 are device structures with the materials of the present invention and known materials. Compared with the device comparative example 1, not only the low temperature efficiency is higher, but also the temperature rise In the high process, the efficiency rises steadily.

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Abstract

本发明公开了一种以含有芘或者氮杂芘的三芳胺为核心的化合物及其应用，本发明提供的有机化合物的结构如通式(1)所示。本发明提供的化合物具有较高的玻璃化转变温度和分子热稳定性、合适的HOMO和LUMO能级、高的空穴迁移率，通过器件结构优化，可有效提升OLED器件的光电性能以及OLED器件的寿命。

Description

一种以含有芘或者氮杂芘的三芳胺为核心的化合物及其应用 技术领域
本发明涉及半导体材料技术领域，尤其是涉及一种以含有芘或者氮杂芘的三芳胺为核心的化合物及其在有机电致发光器件上的应用。
背景技术
当前，OLED显示技术已经在智能手机，平板电脑等领域获得应用，进一步还将向电视等大尺寸应用领域扩展，但是，和实际的产品应用要求相比，OLED器件的发光效率和使用寿命等性能还需要进一步提升。目前对OLED发光器件提高性能的研究包括：降低器件的驱动电压、提高器件的发光效率、提高器件的使用寿命等。为了实现OLED器件的性能的不断提升，不但需要从OLED器件结构和制作工艺的创新，更需要OLED光电功能材料不断研究和创新，创制出更高性能的OLED功能材料。
应用于OLED器件的OLED光电功能材料从用途上可划分为两大类，分别为电荷注入传输材料和发光材料。进一步，还可将电荷注入传输材料分为电子注入传输材料、电子阻挡材料、空穴注入传输材料和空穴阻挡材料，还可以将发光材料分为主体发光材料和掺杂材料。
为了制作高性能的OLED发光器件，要求各种有机功能材料具备良好的光电性能，譬如，作为电荷传输材料，要求具有良好的载流子迁移率，高玻璃化转化温度等，作为发光层的主体材料具有良好双极性，适当的HOMO/LUMO能阶等。
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构，产业上应用的OLED器件结构则包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层等多种膜层，也就是说应用于OLED器件的光电功能材料至少包括空穴注入材料、空穴传输材料、发光材料、电子传输材料等，材料类型和搭配形式具有丰富性和多样性的特点。另外，对于不同结构的OLED器件搭配而言，所使用的光电功能材料具有较强的选择性，相同的材料在不同结构器件中的性能表现也可能完全迥异。
因此，针对当前OLED器件的产业应用要求以及OLED器件的不同功能膜层，器件的光电特性需求，必须选择更适合、性能更高的OLED功能材料或材料组合，才能实现器件的高效率、长寿命和低电压的综合特性。就当前的OLED显示照明产业的实际需求而言，目前OLED材料的发展还远远不够，落后于面板制造企业的要求，作为材料企业开发更高性能的有机功能材料显得尤为重要。
发明内容
针对现有技术存在的上述问题，本发明申请人提供了一种以含有芘或者氮杂芘的三芳胺为核心的化合物及其应用。本发明化合物以含有芘或者氮杂芘的三芳胺为核心，具有较高的玻璃化转变温度和分子热稳定性，合适的HOMO能级，通过器件结构优化，可有效提升OLED器件的光电性能以及OLED器件的寿命。
本发明的技术方案如下：一种以含有芘或者氮杂芘的三芳胺为核心的化合物，所述化合物的结构如通式(1)所示：
Figure PCTCN2020078130-appb-000001
通式(1)中，，n表示为数字0或1；
n表示为数字0时，意味着L 1和L 2直接相连；
L 1、L 2、L 3各自独立的表示为单键、亚苯基或亚萘基；
Y每次出现相同或不同的表示为C-R或氮原子，其中，R每次出现相同或不同的表示为氢原子、氘原子、取代或未取代的C 1-10烷基、取代或未取代的C6-30芳基或者取代或未取代的C 3-30杂芳基；
Ar 1表示为苯基或萘基；
Ar 2表示为取代或未取代的C 6-30芳基；
Ar 3表示为通式(2)所示结构
Figure PCTCN2020078130-appb-000002
所述通式(2)中，X表示为-O-、-S-、-C(R 1)(R 2)-或-N(R 3)-；
Z每次出现相同或不同的表示为C-R、碳原子或氮原子，与其它基团相连的Z表示为碳原子，其中，R每次出现相同或不同的表示为氢原子、氘原子、取代或未取代的C 1-10烷基、取代或未取代的C 6-30芳基或取代或未取代的C 3-30杂芳基；
所述R1、R2以及R3各自独立的表示为C 1-10的烷基、取代或未取代的C 6-30芳基、取代或未取代的C 3-30杂芳基；且R1与R2可相互键结成环；
上述各基团被取代时的取代基选自氟原子、氰基、苯基、联苯基、萘基、呋喃基、咔唑基、噻吩基或吡啶基中的一种或多种；
所述杂芳基中的杂原子选自N、O或S中的一种或多种。
进一步，所述通式(1)中至少有一个Y表示为氮原子。
进一步，所述通式(2)中至少有一个Z表示为氮原子。
进一步的，所述R优选氢、氘、甲基、异丙基、叔丁基、环己基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的吡啶基中的一种；
其中R1～R3各自独立的任选自甲基、乙基、丙基、异丙基、丁基、叔丁基、戊基、己基、环己基、取代或未取代的苯基、取代或未取代联苯基、取代或未取代的萘基、取代或未取代的吡啶基中的一种；
上述各基团被取代时的取代基选自氟原子、氰基、苯基、联苯基、萘基、呋喃基、咔唑基、噻吩基或吡啶基中的一种或多种。
优选方案，所述化合物表示为通式(1-1)、通式(1-2)、通式(1-3)、通式(1-4)、通式(1-5)、通式(1-6)、通式(1-7)或通式(1-8)所示结构中任一种；
Figure PCTCN2020078130-appb-000003
优选方案，所述通式(1)为下列具体化合物中的任一种：
Figure PCTCN2020078130-appb-000004
Figure PCTCN2020078130-appb-000005
Figure PCTCN2020078130-appb-000006
Figure PCTCN2020078130-appb-000007
一种有机电致发光器件，所述有机电致发光器件的阳极与阴极之间具有多层有机薄膜层，至少一层有机薄膜层含有所述以含有芘或者氮杂芘的三芳胺为核心的化合物。
作为本发明的进一步改进，所述多层有机薄膜层包括电子阻挡层和/或空穴传输层，所述电子阻挡层和/或空穴传输层含有所述以含有芘或者氮杂芘的三芳胺为核心的化合物。
一种显示元件，所述显示元件含有所述的有机电致发光器件。
另外说明，本发明申请C 1-20烷基优选下列基团：甲基、乙基、正丙基、异丙基、正丁基、异丁基、1-甲基丙基、叔丁基、正戊基、异戊基、1-乙基丙基、1-甲基丁基、2-甲基丁基、3-甲基丁基、正己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基。
在本发明的上下文中，杂芳基为单环或双环芳族杂环(杂芳族)，其含有最多达四个选自N、O和S的相同或不同的环杂原子，并且经由环碳原子或如果合适，经由环氮原子连接，优选下列基团：呋喃基、吡咯基、噻吩基、吡唑基、咪唑基、喹啉基、噻唑基、噁唑基、异噁唑基、异噻唑基、三唑基、噁二唑基、噻二唑基、四唑基、吡啶基、嘧啶基、哒嗪基、吡嗪基和三嗪基。
当本发明化合物中的基团被取代时，所述基团可被单取代或多取代，除非另有说明。
与现有技术相比，本发明有益的技术效果在于：
(1)本发明的化合物以含有芘或者氮杂芘的三芳胺为核心，连接给电子基团，具有较高的空穴迁移率，作为OLED发光器件的空穴传输层的材料，可提高激子在发光层中的复合效率，提高能量利用率，从而提高器件发光效率。
(2)本发明的化合物使得电子和空穴在发光层的分布更加平衡，在恰当的HOMO能级下，提升了空穴注入和传输性能；在合适的LUMO能级下，又起到了电子阻挡的作用，提升激子在发光层中的复合效率；可有效提高激子利用率，降低器件电压，提高器件的电流效率和寿命。本发明的化合物在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。
附图说明
图1为本发明所列举的材料应用于OLED器件的结构示意图；
图中，1为透明基板层，2为ITO阳极层，3为空穴注入层，4、空穴传输层，5为电子阻挡层，6为发光层，7为电子传输层，8为电子注入层，9为阴极层，10为CPL层。
图2为本发明器件的电流效率随温度的变化曲线。
图3为本发明化合物274的UV吸收光谱；
图4为本发明化合物426的UV吸收光谱。
具体实施方式
下面结合附图和实施例，对本发明进行具体描述。
下述实施例中所有反应物均采购于烟台万润精细化工股份有限公司。
实施例1 化合物003的合成：
Figure PCTCN2020078130-appb-000008
将0.01mol反应物A-1和0.012mol反应物B-1溶解于150mL甲苯中，加入0.015mol的叔丁醇钾，0.001molCuI，在氮气的氛围下120℃反应24小时，取样点板，待反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到化合物1，收率79.5％，HPLC纯度99.65％；元素分析结构(C 67H 47N) 理论值：C,92.91；H,5.47；N,1.62；测试值：C,92.90；H,5.46；N,1.64。HRMS(EI)：理论值为865.3709，实测值为865.3722。
其中反应物A-1的合成步骤为：
Figure PCTCN2020078130-appb-000009
将0.01mol的1-芘硼酸与0.012mol的卤代化合物加至150mL的甲苯：乙醇＝2:1的混合溶剂中，加入0.02mol的碳酸钾，除氧后加入0.0002mol Pd(PPh 3) 4，在氮气的氛围下110℃反应24小时，取样点板，待反应物反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到反应物A-1；HPLC纯度98.97％，收率74.5％；元素分析结构(C 34H 21Br)理论值：C,80.16；H,4.16；Br,15.68；测试值：C,80.19；H,4.15；Br,15.66。HRMS(EI)：理论值：508.0827，实测值：508.0809。
上述卤代化合物可通过芳基卤代物与苯基硼酸的铃木偶联反应1-2步合成得到。
重复实施例1制备过程合成以下化合物；反应条件相同，不同之处在于使用下表1中所列出的反应物A和反应物B；
表1
Figure PCTCN2020078130-appb-000010
Figure PCTCN2020078130-appb-000011
Figure PCTCN2020078130-appb-000012
本发明的有机化合物在发光器件中使用，可以作为电子阻挡层或空穴传输层材料使用。对本发明化合物(003)、化合物(013)、化合物(016)、化合物(037)、化合物(045)、化合物(057)、化合物(064)、 化合物(081)、化合物(082)、化合物(099)、化合物(142)、化合物(151)、化合物(159)、化合物(201)、化合物(218)、化合物(229)、化合物(237)、化合物(248)、化合物(274)、化合物(276)、化合物(300)、化合物(312)、化合物(334)、化合物(346)、化合物(347)、化合物(371)、化合物(379)、化合物(414)、化合物(426)、化合物(437)、化合物(444)、化合物(452)、化合物(468)、化合物(477)、化合物(486)和化合物(496)分别进行热性能、Eg、HOMO能级以及空穴迁移率的检测，结果如表2所示。
表2
Figure PCTCN2020078130-appb-000013
Figure PCTCN2020078130-appb-000014
注：玻璃化温度Tg由示差扫描量热法(DSC，德国耐驰公司DSC204F1示差扫描量热仪)测定，升温速率10℃/min；热失重温度Td是在氮气气氛中失重1％的温度，在日本岛津公司的TGA-50H热重分析仪上进行测定，氮气流量为20mL/min；最高占据分子轨道HOMO能级是由电离能量测试系统(IPS3)测试，测试为大气环境。空穴迁移率：将材料制作成单电荷器件，用SCLC方法测定。使用Gaussian16，采用TD-FDT算法优化几何结构，6-31G(d)基组，B3lyp泛函，进行HOMO、LUMO能级计算，Eg＝|HOMO-LUMO|；Eg实测通过紫外光谱进行测试；
由上表数据可知，本发明的有机化合物具有高的玻璃转化温度，可提高材料膜相态稳定性，进一步提高器件使用寿命；具有高的T1能级，可以阻挡发光层能量损失，从而提升器件发光效率；合适的HOMO能级可以解决载流子的注入问题，可降低器件电压，较高的带隙宽度(Eg)，保证材料在可见光领域范围内没有吸收。因此，本发明含芘的化合物在应用于OLED器件的不同功能层后，可有效提高器件的发光效率及使用寿命。
以下通过器件实施例1-36和器件比较例1详细说明本发明合成的化合物在器件中作为空穴传输材料的应用效果。器件实施例2-36以及器件比较例1与器件实施例1相比，所述器件的制作工艺完全相同，并且采用了相同的基板材料和电极材料，电极材料的膜厚也保持一致，所不同的是器件中空穴传输层材料发生了改变。器件叠层结构如表3所示，各器件的性能测试结果见表4和表5。
器件实施例1
透明基板层1/ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(化合物(003)，厚度60nm)/电子阻挡层5(EB-1，厚度20nm)/发光层6(GH1、GH2和GD-1按照45:45:10的重量比混掺，厚度40nm)/空穴阻挡/电子传输层7(ET-1和Liq，按照1:1的重量比混掺，厚度40nm)/电子注入层8(LiF，厚度1nm)/阴极层9(Mg和Ag，按照9:1的重量比混掺，厚度15nm)/CPL层10(化合物CP-1，厚度70nm)。
具体制备过程如下：
如图1所示，透明基板层1为透明PI膜，对ITO阳极层2(膜厚为150nm)进行洗涤，即依次进行碱洗涤、纯水洗涤、干燥，再进行紫外线-臭氧洗涤以清除透明ITO表面的有机残留物。在进行了上述洗涤之后的ITO阳极层2上，利用真空蒸镀装置，蒸镀膜厚为10nm的HAT-CN作为空穴注入层3使用。接着蒸镀60nm厚度的化合物(003)作为空穴传输层4。随后蒸镀20nm厚度的EB-1作为电子阻挡层5。上述空穴传输材料蒸镀结束后，制作OLED发光器件的发光层6，其结构包括OLED发光层6所使用GH-1、GH-2作为主体材料，GD-1作为掺杂材料，掺杂材料掺杂比例为10％重量比，发光层膜厚为40nm。在上述发光层6之后，继续真空蒸镀电子传输层材料为ET-1和Liq。该材料的真空蒸镀膜厚为40nm，此层为空穴阻挡/电子传输层7。在空穴阻挡/电子传输层7上，通过真空蒸镀装置，制作膜厚为1nm的氟化锂(LiF)层，此层为电子注入层8。在电子注入层8上，通过真空蒸镀装置，制作膜厚为15nm的Mg：Ag电极层，此层为阴极层9使用。在阴极层9上，真空蒸镀70nm的CP-1，作为CPL层10。如上所述地完成OLED发光器件后，用公知的驱动电路将阳极和阴极连接起来，测量器件的电流效率以及器件的寿命。
按照上述步骤完成电致发光器件的制作后，测量器件的效率数据和光衰寿命，其结果见表4所示。相关材料的分子结构式如下所示：
Figure PCTCN2020078130-appb-000015
表3
Figure PCTCN2020078130-appb-000016
Figure PCTCN2020078130-appb-000017
Figure PCTCN2020078130-appb-000018
各器件实施例和器件比较例1的效率和寿命数据见表4所示。
表4
编号 电流效率(cd/A) 色彩 LT97寿命(Hr)@5000nits
器件实施例1 121.5 绿光 114.7
器件实施例2 121.5 绿光 123.4
器件实施例3 124.3 绿光 112.7
器件实施例4 120.7 绿光 111.0
器件实施例5 121.5 绿光 110.1
器件实施例6 121.5 绿光 114.9
器件实施例7 124.5 绿光 123.2
器件实施例8 118.6 绿光 125.8
器件实施例9 121.5 绿光 112.3
器件实施例10 119.8 绿光 122.0
器件实施例11 118.6 绿光 110.1
器件实施例12 119.6 绿光 113.2
器件实施例13 119.4 绿光 116.1
器件实施例14 123.4 绿光 128.8
器件实施例15 123.6 绿光 128.9
器件实施例16 118.3 绿光 123.1
器件实施例17 125.8 绿光 117.6
器件实施例18 119.4 绿光 127.8
器件实施例19 118.2 绿光 132.6
器件实施例20 118.8 绿光 126.5
器件实施例21 118.7 绿光 132.5
器件实施例22 123.8 绿光 132.3
器件实施例23 118.1 绿光 113.7
器件实施例24 125.2 绿光 135.0
器件实施例25 125.5 绿光 115.5
器件实施例26 121.9 绿光 130.0
器件实施例27 124.5 绿光 114.6
器件实施例28 119.3 绿光 113.1
器件实施例29 121.4 绿光 124.6
器件实施例30 123.5 绿光 110.9
器件实施例31 120 绿光 113.3
器件实施例32 122.3 绿光 117.8
器件实施例33 120.1 绿光 120.3
器件实施例34 122.5 绿光 130.4
器件实施例35 120 绿光 117.8
器件实施例36 119.1 绿光 118.9
比较例1 116 绿光 80.5
由表4的器件数据结果可以看出，本发明的有机发光器件无论是效率还是寿命均相对于已知材料的OLED器件获得较大的提升。
进一步的本发明材料制备的OLED器件在低温下工作时效率也比较稳定，将器件实施例1、18、26、35和器件比较例1在-10～80℃区间进行效率测试，所得结果如表5和图2所示。
表5
Figure PCTCN2020078130-appb-000019
从表5和图2的数据可知，器件实施例1、18、26、35为本发明材料和已知材料搭配的器件结构，与器件比较例1相比，不仅低温效率高，而且在温度升高过程中，效率平稳升高。

Claims (9)

  1. 一种以含有芘或者氮杂芘的三芳胺为核心的化合物，其特征在于，所述化合物的结构如通式(1)所示：
    Figure PCTCN2020078130-appb-100001
    通式(1)中，n表示为数字0或1；
    L 1、L 2、L 3各自独立的表示为单键、亚苯基或亚萘基；
    Ar 1表示为苯基或萘基；
    Ar 2表示为取代或未取代的C 6-30芳基；
    Ar 3表示为通式(2)所示结构
    Figure PCTCN2020078130-appb-100002
    所述通式(2)中，X表示为-O-、-S-、-C(R 1)(R 2)-或-N(R 3)-；
    Y每次出现相同或不同的表示为C-R或氮原子；
    Z每次出现相同或不同的表示为C-R、碳原子或氮原子，与其它基团相连的Z表示为碳原子；
    所述R每次出现相同或不同的表示为氢原子、氘原子、取代或未取代的C1-10烷基、取代或未取代的C6-30芳基或者取代或未取代的C3-30杂芳基；
    所述R 1、R 2以及R 3各自独立的表示为C 1-10的烷基、取代或未取代的C 6-30芳基、取代或未取代的C 3-30杂芳基；且R 1与R 2可相互键结成环；
    上述各基团被取代时的取代基选自氟原子、氰基、苯基、联苯基、萘基、呋喃基、咔唑基、噻吩基或吡啶基中的一种或多种；
    所述杂芳基中的杂原子选自N、O或S中的一种或多种。
  2. 根据权利要求1所述的化合物，其特征在于，所述通式(1)中至少有一个Y表示为氮原子。
  3. 根据权利要求1或2所述的化合物，其特征在于，所述通式(2)中至少有一个Z表示为氮原子。
  4. 根据权利要求1所述的化合物，其特征在于，所述R优选氢、氘、甲基、异丙基、叔丁基、环己基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的吡啶基中的一种；
    其中R 1～R 3各自独立的任选自甲基、乙基、丙基、异丙基、丁基、叔丁基、戊基、己基、环己基、取代或未取代的苯基、取代或未取代联苯基、取代或未取代的萘基、取代或未取代的吡啶基中的一种；
    上述各基团被取代时的取代基选自氟原子、氰基、苯基、联苯基、萘基、呋喃基、咔唑基、噻吩基或吡啶基中的一种或多种。
  5. 根据权利要求1所述的化合物，其特征在于，所述化合物表示为通式(1-1)、通式(1-2)、通式(1-3)、通式(1-4)、通式(1-5)、通式(1-6)、通式(1-7)或通式(1-8)所示结构中任一种；
    Figure PCTCN2020078130-appb-100003
  6. 根据权利要求1所述以含有芘或者氮杂芘的三芳胺为核心的化合物，其特征在于，所述通式(1)为下列具体化合物中的任一种：
    Figure PCTCN2020078130-appb-100004
    Figure PCTCN2020078130-appb-100005
    Figure PCTCN2020078130-appb-100006
    Figure PCTCN2020078130-appb-100007
    Figure PCTCN2020078130-appb-100008
  7. 一种有机电致发光器件，所述有机电致发光器件的阳极与阴极之间具有多层有机薄膜层，其特征在于，至少一层有机薄膜层含有权利要求1～6任一项所述以含有芘或者氮杂芘的三芳胺为核心的化合物。
  8. 根据权利要求7所述有机电致发光器件，其特征在于，所述多层有机薄膜层包括电子阻挡层和/或空穴传输层，所述电子阻挡层和/或空穴传输层含有权利要求1～6任一项所述以含有芘或者氮杂芘的三芳胺为核心的化合物。
  9. 一种显示元件，其特征在于，所述显示元件含有权利要求7或8任一项所述的有机电致发光器件。
PCT/CN2020/078130 2019-03-08 2020-03-06 一种以含有芘或者氮杂芘的三芳胺为核心的化合物及其应用 WO2020182070A1 (zh)

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