WO2021135261A1 - 一种芳胺类化合物及其在光电器件中的应用 - Google Patents

一种芳胺类化合物及其在光电器件中的应用 Download PDF

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WO2021135261A1
WO2021135261A1 PCT/CN2020/109402 CN2020109402W WO2021135261A1 WO 2021135261 A1 WO2021135261 A1 WO 2021135261A1 CN 2020109402 W CN2020109402 W CN 2020109402W WO 2021135261 A1 WO2021135261 A1 WO 2021135261A1
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compound
aromatic amine
present
optoelectronic device
formula
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王鹏
王一鸣
魏月芳
张静
袁艺
雷鸣
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Zhejiang University
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Definitions

  • the invention belongs to the technical field of organic semiconductors, and specifically relates to an aromatic amine compound and its application in optoelectronic devices.
  • Solid-state electronics based on inorganic semiconductors has undergone decades of development, which has reduced the size of microelectronic components to micrometers and sub-micrometers, and it is difficult to further improve integration. For this reason, people have proposed to realize the control of electron movement in an organic molecular area, and even develop to control the photon process, so that molecular aggregates form special devices, thus opening up a way to further improve integration.
  • the electronic properties, conduction mechanism, and impurity effects of organic semiconductors are different from traditional inorganic semiconductors. Revealing the relationship between the chemical structure and physical properties of organic semiconductors, researching and preparing model devices, not only has important scientific significance, but also has huge application prospects.
  • OPCs organic photoconductors
  • OLED organic electroluminescent diodes
  • OCV organic photovoltaic cells
  • OFETs Effect transistors
  • Organic semiconductors have shown complementary properties to inorganic semiconductors in several aspects, mainly in: on the basis of the basic properties of semiconductor materials, organic molecules have much more flexible Van der Waals interactions, making organic semiconductor devices more flexible It is possible to use a flexible plastic film or metal foil, which effectively overcomes the shortcomings of brittle and hard inorganic semiconductor devices caused by covalent bonding between adjacent atoms; organic semiconductors also have good solubility, high transparency, and Adjust the photoelectric performance, potential biocompatibility and other advantages through molecular tailoring.
  • the carrier generation function is often separated from the transport function. Specifically, the material is layered into a film on the device, so that each layer is in an independent and optimal state.
  • organic hole transport materials OHTMs
  • OHTs organic hole transport materials
  • the organic hole transport material usually uses 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene ( spiro-OMeTAD), which has a low glass transition temperature and is easy to crystallize under heating conditions, resulting in poor thermal stability of devices based on this material. Therefore, the development of new low-cost, high-stability organic semiconductor materials is of great significance for improving device performance, improving working stability, and accelerating the pace of commercialization.
  • spiro-OMeTAD 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene
  • the technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide an aromatic amine compound and its application in optoelectronic devices.
  • the solution of the present invention is:
  • An aromatic amine compound is provided, which is composed of N,N-dialkyldicarbazolamine functional group modified with a ⁇ unit with a larger conjugated system, and its chemical structure is as any one of formulas (1) to (112) Kind of shows:
  • R is a C1-C3 alkyl group.
  • the present invention further provides a preparation method of the aforementioned aromatic amine compound, which includes the following steps:
  • the compound containing ⁇ -conjugated unit and N,N-dimethyldicarbazolamine, tris(dibenzylideneacetone)dipalladium, and tri-tert-butyl tetrafluoroborate Phosphine and sodium tert-butoxide were added to toluene together; under the protection of nitrogen, heated to 120°C while stirring, and reacted for 12 hours; allowed to stand and cool to room temperature, filtered off the organic solvent to obtain the crude product; purified by column chromatography to obtain Aromatic amine compounds.
  • the compound containing ⁇ -conjugated unit is any one of the following: 5,9-dibromodinaphthofuran, 5,9-dibromodinaphthothiophene, 3,9-dibromo Dioxaanthanthrene, 3,6,11,14-tetrachlorodibenzophenone, 2,7,10,15-tetrachlorotetrao-phenylene or 18,23-dibromodiaphthylene Furopyrrole.
  • the present invention further provides another preparation method of aromatic amine compounds, including the following steps:
  • the compound containing ⁇ -conjugated unit, 3,4-ethylenedioxythiophenemethylcarbazole triarylamine borate, palladium acetate, tri-tert-butyl phosphine tetrafluoroborate and Potassium phosphate is added to the mixed solvent of dioxane and water.
  • the volume ratio of dioxane to water in the mixed solvent is 5:1; under the protection of argon, it is heated to 100°C while stirring, and reacted for 6 hours. ; Standing and cooling to room temperature, adding deionized water, and extracting and separating with dichloromethane, retaining the organic phase to obtain the crude product; purified by column chromatography to obtain aromatic amine compounds.
  • the compound containing ⁇ -conjugated unit is any one of the following: 5,9-dibromodinaphthofuran, 5,9-dibromodinaphthothiophene, 3,9-dibromo Dioxaanthanthrene, 3,6,11,14-tetrachlorodibenzophenone, 2,7,10,15-tetrachlorotetrao-phenylene or 18,23-dibromodiaphthylene Furopyrrole.
  • the present invention further provides an application method of aromatic amine compounds, which are used as organic hole transport materials to prepare optoelectronic devices.
  • the present invention designs and synthesizes a class of aromatic amine compounds by using N,N-dialkyldicarbazolamine functional groups to modify the ⁇ unit with a larger conjugated system.
  • the semiconductor material provided by the invention has high glass transition temperature, high solubility, good film-forming properties, and high thermal stability of film morphology, and can be used as a hole transport material in optoelectronic devices to achieve excellent thermal stability .
  • the compound of the present invention has simple preparation process, readily available raw materials, low price, and is very suitable for industrial production.
  • the compound of the present invention has a high glass transition temperature and good thermal stability, which is beneficial to prolong the working life of the optoelectronic device.
  • the compound of the present invention has high solubility and can form an amorphous film of good quality, which is beneficial for application in optoelectronic devices; the high photoelectric conversion efficiency of the device indicates that the compound of the present invention is a hole transport material with excellent performance. .
  • Figure 1 is the glass transition temperature of the compound of the present invention measured by differential scanning calorimetry.
  • Figure 2 is a graph showing the stability data of perovskite solar cells made of the compound of the present invention as hole transport materials under the dark conditions of 85°C (the abscissa refers to the battery aging time, and the ordinate refers to the retention rate of photoelectric conversion efficiency) .
  • the preparation method of compound H6 is the same as that of Example 1, except that 18,23-dibromobis-naphthofuropyrrole is used in place of 5,9-dibromo-dinaphthofuran to obtain compound H6 (85% yield ).
  • the preparation method of compound H12 is the same as that of Example 7, except that 18,23-dibromobis-naphthofuropyrrole is used instead of 5,9-dibromodinopyrrole to obtain compound H12 (50% yield ).
  • the preparation methods of the products of structural formulas (13) to (68) can refer to the preparation process of compound H1 in Example 1.
  • the preparation methods of the products of structural formulas (69) to (112) can refer to the preparation process of compound H7 in Example 7.
  • Example 13 Example 14
  • Example 15 The application method and effect of the compound synthesized by the present invention as a hole transport layer material in an optoelectronic device will be described in detail below through Example 13, Example 14, and Example 15.
  • the compound of the present invention is used as a hole transport material for perovskite solar cells:
  • the perovskite solar cells prepared by using the compounds of the present invention as the hole transport layer respectively include: FTO glass substrate, dense TiO 2 layer, porous TiO 2 layer, perovskite layer, hole transport layer and metal electrode, Among them, the FTO glass substrate is composed of a glass substrate and an FTO cathode (fluorine-doped tin oxide glass electrode).
  • the dense TiO 2 layer and the porous TiO 2 layer serve as the TiO 2 electron transport layer, and the perovskite layer serves as the light absorption layer.
  • the perovskite layer was prepared by a two-step spin coating process.
  • the two-step spin coating was rotated at 2000 rpm for 10 s and at 5000 rpm for 30 s.
  • the chlorobenzene anti-solvent was added dropwise; then, the substrate After drying at 120°C for 1 hour, the required perovskite layer is prepared;

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Abstract

本发明涉及有机半导体技术领域，旨在提供一种芳胺类化合物及其在光电器件中的应用。该化合物是由N,N-二烷基二咔唑胺功能基修饰具有较大共轭体系的π单元构成。本发明提供的半导体材料玻璃化转变温度较高，溶解度较高，成膜性好，薄膜形貌的热稳定性较高，可作为空穴传输材料应用于光电器件中，实现优异的热稳定性。该化合物制备工艺简单，原料易得，价格低廉，非常适宜工业化生产。玻璃化转变温度高，热稳定性好，有利于延长光电器件的工作寿命。溶解度高，可以形成质量优良的无定形膜，有利于应用在光电器件中；器件的光电转换效率高，是性能优良的空穴传输材料。

Description

一种芳胺类化合物及其在光电器件中的应用 技术领域
本发明属于有机半导体技术领域，具体涉及一种芳胺类化合物及其在光电器件中的应用。
背景技术
以无机半导体为材料基础的固体电子学经历了数十年发展，已使微电子元件尺寸降到了微米和亚微米，再进一步提高集成遇到了困难。为此，人们提出了在一个有机分子区域内实现对电子运动的控制，甚至发展到对光子过程进行控制，使分子聚集体构成特殊器件的设想，从而开辟了一条进一步提高集成的途径。有机半导体的电子性质、导电机理和杂质影响不同于传统无机半导体，揭示有机半导体中化学结构和物理性能的关系、研究和制备模型器件，不仅具有重要的科学意义，而且有着巨大的应用前景。
近年来，有机半导体材料的发展极为迅速，在光电及电子组件的应用极为广泛，目前已应用于有机光电导体(OPCs)、有机电致发光二极管(OLED)、有机光伏电池(OPV)、有机场效应晶体管(OFETs)、光折射全息摄像等诸多领域。有机半导体在若干方面已经表现出与无机半导体互补的性能，主要表现在：在具有半导体材料的基本性能的基础上，有机分子之间具有灵活得多的范德华相互作用，使有机半导体器件制备在柔韧性的塑料薄膜或者金属箔片上成为可能，有效地克服了由于相邻原子间以共价键连接给无机半导体器件带来的脆而硬的缺点；有机半导体还具有溶解性好、透明度高、可通过分子剪裁调控光电性能、潜在的生物相容性等优势。
在目前所制备的有机光电器件中，常将载流子产生功能与传输功能分开，具体在器件上是将材料分层成膜，让每一层都处于独立而最佳的状态。其中，有机空穴传输材料(OHTMs)在有机光电器件中起着非常重要的作用。
现有技术中，有机空穴传输材料通常采用2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴(spiro-OMeTAD)，其玻璃化转变温度较低，在加热条件下容易结晶，从而导致基于该材料的器件热稳定性差。因此，发展新型低成本、高稳定性的有机半导体材料对于提高器件性能，提升工作稳定性，以及加快商业化步伐都具有重要的意义。
发明内容
本发明要解决的技术问题是，克服现有技术中的不足，提供一种芳胺类化合物及其在光电器件中的应用。
为解决技术问题，本发明的解决方案是：
提供一种芳胺类化合物，是由N,N-二烷基二咔唑胺功能基修饰具有较大共轭体系的π单元构成，其化学结构式如式(1)～(112)中任意一种所示：
Figure PCTCN2020109402-appb-000001
Figure PCTCN2020109402-appb-000002
Figure PCTCN2020109402-appb-000003
Figure PCTCN2020109402-appb-000004
Figure PCTCN2020109402-appb-000005
Figure PCTCN2020109402-appb-000006
Figure PCTCN2020109402-appb-000007
Figure PCTCN2020109402-appb-000008
Figure PCTCN2020109402-appb-000009
Figure PCTCN2020109402-appb-000010
Figure PCTCN2020109402-appb-000011
Figure PCTCN2020109402-appb-000012
各式中，R为C1～C3的烷基。
本发明进一步提供了前述芳胺类化合物的制备方法，包括以下步骤：
按摩尔比1∶5∶0.2∶0.4∶15将含π共轭单元化合物与N,N-二甲基二咔唑胺、三(二亚苄基丙酮)二钯、四氟硼酸三叔丁基膦和叔丁醇钠一起加入到甲苯中；在氮气的保护下，边搅拌边加热到120℃，反应12h；静置冷却至室温，滤除有机溶剂得到产物粗品；经过柱层析提纯，得到芳胺类化合物。
本发明中，所述含π共轭单元化合物是下述的任意一种：5,9-二溴代二萘并呋喃、5,9-二溴代二萘并噻吩、3,9-二溴代二氧杂蒽嵌蒽、3,6,11,14-四氯代二苯并屈、2,7,10,15-四氯代四邻亚苯或18,23-二溴代双二萘并呋喃并吡咯。
本发明进一步提供了另一种芳胺类化合物的制备方法，包括以下步骤：
在干燥的三口圆底烧瓶中，将3,4-乙烯二氧噻吩甲基咔唑三芳胺溶于超干四氢呋喃中，并降温至-78℃；在氩气的保护下，用针头将1.5倍当量的正丁基锂的己烷溶液缓慢加入上述溶液，搅拌半小时；随后，用注射器将2倍当量的异丙醇频哪醇硼酸酯加入上述体系，将体系缓慢升至室温并搅拌2小时；反应结束后，加入去离子水，并用二氯甲烷萃取分液，保留有机相；经过柱层析提纯后，得到中间体3,4-乙烯二氧噻吩甲基咔唑三芳胺硼酸酯；
按摩尔比1:5:0.08:0.08:10将含π共轭单元化合物、3,4-乙烯二氧噻吩甲基咔唑三芳胺硼酸酯、醋酸钯、四氟硼酸三叔丁基膦和磷酸钾一起加入到二氧六环和水的混合溶剂中，混合溶剂中二氧六环与水的体积比为5:1；在氩气的保护下，边搅拌边加热到100℃，反应6h；静置冷却至室温，加入去离子水，并用二氯甲烷萃取分液，保留有机相，得到产物粗品；经过柱层析提纯，得到芳胺类化合物。
本发明中，所述含π共轭单元化合物是下述的任意一种：5,9-二溴代二萘并呋喃、5,9-二溴代二萘并噻吩、3,9-二溴代二氧杂蒽嵌蒽、3,6,11,14-四氯代二苯并屈、2,7,10,15-四氯代四邻亚苯或18,23-二溴代双二萘并呋喃并吡咯。
本发明进一步提供了芳胺类化合物的应用方法，是将其作为有机空穴传输材料用于制备光电器件。
发明原理简述：
本发明通过采用N,N-二烷基二咔唑胺功能基修饰具有较大共轭体系的π单元，设计合成了一类芳胺类化合物。本发明提供的半导体材料玻璃化转变温度较高，溶解度较高，成膜性好，薄膜形貌的热稳定性较高，可作为空穴传输材料应用于光电器件中，实现优异的热稳定性。
与现有技术相比，本发明的有益效果是：
(1)本发明的化合物，制备工艺简单，原料易得，价格低廉，非常适宜工业化生产。
(2)本发明的化合物，玻璃化转变温度高，热稳定性好，有利于延长光电器件的工作寿命。
(3)本发明的化合物，溶解度高，可以形成质量优良的无定形膜，有利于应用在光电器件中；器件的光电转换效率高，说明本发明所述的化合物是性能优良的空穴传输材料。
附图说明
图1是以差示扫描量热法测得的本发明化合物的玻璃化转变温度。
图2是以本发明化合物为空穴传输材料制成的钙钛矿太阳电池在85℃暗处条件下老化的稳定性数据图(横坐标指电池老化时间，纵坐标指光电转换效率保有率)。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
为了使本发明的目的、技术方案及优点更加清楚明白，结合以下附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
更换不同的π共轭单元，通过修饰N,N-二甲基二咔唑胺取代基，可以分别得到如下化合物；所采用的π共轭单元，以及合成得到的对应化合物H1～H12 如下表所示：
Figure PCTCN2020109402-appb-000013
Figure PCTCN2020109402-appb-000014
Figure PCTCN2020109402-appb-000015
实施例1
化合物H1的合成：
按摩尔比1∶5∶0.2∶0.4∶15将5,9-二溴代二萘并呋喃与N,N-二甲基二咔唑胺、三(二亚苄基丙酮)二钯、四氟硼酸三叔丁基膦和叔丁醇钠一起加入到甲苯中；在氮气的保护下，边搅拌边加热到120℃，反应12h；静置冷却至室温，滤除有机溶剂得到产物粗品；经过柱层析提纯，得到化合物H1(90％产率)。 1H NMR(600MHz,THF-d 8)δ:9.21(d,J＝8.5Hz,2H),8.51(d,J＝8.6Hz,2H),7.89–7.79(m,8H),7.65(t,J＝7.6Hz,2H),7.56(s,2H),7.35(ddt,J＝15.4,8.2,7.7Hz,18H),7.00(t,J＝7.5Hz,4H),3.82ppm(d,J＝4.9Hz,6H). 13C NMR(150MHz,THF-d 8)δ:156.15,147.45,144.18,142.81,138.57,130.79,129.76,127.81,127.03,126.87,126.48,125.25,124.73,123.83,123.76,121.28,119.33,117.67,116.02,112.67,110.20,109.37,29.29ppm.HR-MS(MALDI-TOF)m/z(分子式C 72H 50N 6O)理论值:1014.4046，实测值:1014.4041。
所得化合物H1的化学结构式如式(1)所示。
实施例2
化合物H2的合成：
化合物H2的制备方法同实施例1，不同之处在于用5,9-二溴代二萘并噻吩替换5,9-二溴代二萘并呋喃，得到化合物H2(87％产率)。 1H NMR(600MHz,THF-d 8)δ:8.94(d,J＝8.5Hz,2H),8.45(d,J＝8.4Hz,2H),7.87(dd,J＝7.3,5.0Hz,8H),7.65(s,2H),7.55–7.23(m,18H),7.02(t,J＝7.4Hz,4H),3.85ppm(s,12H). 13C NMR(150MHz,THF-d 8)δ:146.69,144.36,143.04,139.93,138.86,132.53,130.86,129.85,127.60,127.41,126.72,126.21,125.82,124.99,124.33,124.00,121.53,120.18,119.58,116.57,110.46,109.60,29.52ppm.HR-MS(MALDI-TOF)m/z(分子式C 72H 50N 6S)理论值:1030.3818，实测值:1030.3812。
所得化合物H2的化学结构式如式(2)所示。
实施例3
化合物H3的合成：
化合物H3的制备方法同实施例1，不同之处在于用3,9-二溴代二氧杂蒽嵌蒽替换5,9-二溴代二萘并呋喃，得到化合物H3(70％产率)。 1H NMR(600MHz,THF-d 8)δ:7.87(d,J＝7.7Hz,4H),7.77(d,J＝2.0Hz,4H),7.50(d,J＝9.4Hz,2H),7.44–7.32(m,12H),7.23(dd,J＝8.7,2.2Hz,4H),7.07–7.01(m,4H),6.89(d,J＝8.3Hz,2H),6.78(d,J＝9.4Hz,2H),6.66ppm(d,J＝8.3Hz,2H). 13C NMR(150MHz,THF-d 8)δ:150.14,145.53,143.36,142.70,142.10,140.85,138.32,134.99,128.68,126.34,125.73,124.57,123.70,123.67,123.33,121.13,119.20,117.66,115.29,110.35,109.99,109.25,30.69ppm.HR-MS(MALDI-TOF)m/z(分子式C 72H 48N 6O 2)理论值:1028.3839，实测值:1028.3833。
所得化合物H3的化学结构式如式(3)所示。
实施例4
化合物H4的合成：
化合物H4的制备方法同实施例1，不同之处在于用3,6,11,14-四氯代二苯并屈替换5,9-二溴代二萘并呋喃，得到化合物H4(74％产率)。 1H NMR(600MHz,THF-d 8)δ:8.27(d,J＝2.3Hz,4H),8.19(d,J＝9.0Hz,4H),7.80(dd,J＝4.9,2.9Hz,16H),7.39–7.29(m,16H),7.23(d,J＝8.7Hz,8H),7.20–7.09(m,12H),7.04–6.95(m,8H),3.70ppm(s,24H). 13C NMR(150MHz,THF-d 8)δ:147.41,141.60,141.01,137.67,129.74,125.19,125.04,124.16,123.54,123.43,122.69,122.28,120.16,119.24,118.20,117.68,116.71,109.13,108.23,28.18ppm.HR-MS(MALDI-TOF)m/z(分子式C 130H 92N 12)理论值:1821.7601，实测值:1821.7596。
所得化合物H4的化学结构式如式(4)所示。
实施例5
化合物H5的合成：
化合物H5的制备方法同实施例1，不同之处在于用2,7,10,15-四氯代四邻亚苯替换5,9-二溴代二萘并呋喃，得到化合物H5(75％产率)。 1H NMR(600MHz,THF-d 8)δ:7.92(s,8H),7.88(d,J＝7.7,8H),7.37(d,J＝8.2,8H),7.35–7.16(m,24H),6.97(t,J＝7.4,8H),6.92(s,4H),6.87–6.66(m,8H),3.81ppm(s,24H). 13C NMR(150MHz,THF-d 8)δ:148.58,141.60,140.59,137.77,130.98,128.87,125.28,124.74,123.63,122.51,120.24,120.16,119.75,118.33,117.91,117.60,109.06,108.12,27.96ppm.HR-MS(MALDI-TOF)m/z(分子式C 128H 92N 12)理论值:1797.7601，实测值:1797.7596。
所得化合物H5的化学结构式如式(5)所示。
实施例6
化合物H6的合成：
化合物H6的制备方法同实施例1，不同之处在于用18,23-二溴代双二萘并呋喃并吡咯替换5,9-二溴代二萘并呋喃，得到化合物H6(85％产率)。 1H NMR(600MHz,THF-d 8)δ:12.40(s,1H),9.28(d,J＝8.0Hz,2H),9.22(d,J＝8.4Hz,2H),8.79(d,J＝8.0Hz,2H),8.51(d,J＝8.3Hz,2H),8.03(s,2H),7.83(dd,J＝12.1,4.6Hz,8H),7.73–7.55(m,6H),7.45–7.18(m,18H),6.97(t,J＝6.8Hz,4H),3.74ppm(s,12H). 13C NMR(150MHz,THF-d 8)δ:158.82,154.57,148.71,147.47,146.07,141.55,140.00,133.88,131.43,130.78,130.29,129.76,129.68,129.30,128.61,128.51,127.99,127.13,127.09,126.45,125.07,124.62,122.54,122.37,118.53,118.43,117.78,113.36,112.62,83.02,82.80,82.58,32.63ppm.HR-MS(MALDI-TOF)m/z(分子式C 92H 59N 7O 2)理论值:1293.4730，实测值:1293.4725。
所得化合物H6的化学结构式如式(6)所示。
实施例7
化合物H7的合成：
在干燥的三口圆底烧瓶中，将3,4-乙烯二氧噻吩甲基咔唑三芳胺溶于超干四氢呋喃中，并降温至-78℃；在氩气的保护下，用针头将1.5倍当量的正丁基锂的己烷溶液缓慢加入上述溶液，搅拌半小时；随后，用注射器将2倍当量的异丙醇频哪醇硼酸酯加入上述体系，将体系缓慢升至室温并搅拌2小时；反应结束后，加入去离子水，并用二氯甲 烷萃取分液，保留有机相；经过柱层析提纯后，得到中间体3,4-乙烯二氧噻吩甲基咔唑三芳胺硼酸酯；
按摩尔比1:5:0.08:0.08:10将5,9-二溴代二萘并呋喃、3,4-乙烯二氧噻吩甲基咔唑三芳胺硼酸酯、醋酸钯、四氟硼酸三叔丁基膦和磷酸钾一起加入到二氧六环和水的混合溶剂中，二氧六环与水的体积比为5:1；在氩气的保护下，边搅拌边加热到100℃，反应6h；静置冷却至室温，加入去离子水，并用二氯甲烷萃取分液，保留有机相，得到产物粗品；经过柱层析提纯，得到化合物H7(60％产率)。 1H NMR(600MHz,THF-d 8)δ:9.21(d,J＝8.4Hz,2H),8.42(d,J＝8.5Hz,2H),8.00(d,J＝1.7Hz,4H),7.99–7.93(m,6H),7.76(t,J＝7.6Hz,2H),7.63(d,J＝8.7Hz,4H),7.61–7.54(m,2H),7.44(t,J＝8.6Hz,8H),7.38(t,J＝7.5Hz,8H),7.09(t,J＝7.4Hz,4H),7.03(d,J＝8.8Hz,4H),4.36(d,J＝2.4Hz,4H),4.27(d,J＝2.1Hz,4H),3.87ppm(s,12H). 13C NMR(150MHz,THF-d 8)δ:155.01,149.89,142.69,141.30,140.60,139.14,138.20,131.94,130.92,129.84,129.73,129.35,129.20,127.58,127.11,126.52,125.79,125.50,124.74,123.63,121.20,120.59,119.94,119.45,119.01,118.63,115.64,111.44,110.27,109.41,65.72,65.54,29.23ppm.HR-MS(MALDI-TOF)m/z(分子式C 96H 66N 6O 5S 2)理论值:1446.4536，实测值:1446.4531。
所得化合物H7的化学结构式如式(7)所示。
实施例8
化合物H8的合成：
化合物H8的制备方法同实施例7，不同之处在于用5,9-二溴代二萘并噻吩替换5,9-二溴代二萘并呋喃，得到化合物H8(60％产率)。 1H NMR(600MHz,THF-d 8)δ:8.94–8.86(m,2H),8.40–8.31(m,2H),8.13(s,2H),8.00(d,J＝1.9Hz,4H),7.96(d,J＝7.8Hz,4H),7.66–7.60(m,4H),7.56(dd,J＝9.3,5.0Hz,4H),7.44(dd,J＝8.4,5.1Hz,8H),7.42–7.32(m,8H),7.14–7.05(m,4H),7.02(t,J＝5.7Hz,4H),4.41–4.22(m,8H),3.87ppm(s,12H). 13C NMR(150MHz,THF-d 8)δ:148.85,141.77,141.69,140.31,139.50,138.14,137.21,130.81,130.68,130.05,129.91,127.64,126.53,125.89,125.47,125.16,124.76,124.65,124.59,123.75,122.76,122.65,120.18,119.60,118.41,117.87,117.61,110.38,109.20,108.35,64.71,64.50,28.18ppm.HR-MS(MALDI-TOF)m/z(分子式C 96H 66N 6O 4S 3)理论值:1463.4341，实测值:1463.4345。
所得化合物H8的化学结构式如式(8)所示。
实施例9
化合物H9的合成：
化合物H9的制备方法同实施例7，不同之处在于用3,9-二溴代二氧杂蒽嵌蒽替换5,9-二溴代二萘并呋喃，得到化合物H9(45％产率)。 1H NMR(600MHz,THF-d 8)δ:8.36(d,J＝7.8Hz,4H),7.87–7.85(m,4H),7.70(d,J＝7.5Hz,4H),7.42–7.37(m,16H),7.24(dd,J＝8.3,5.2Hz,4H),7.14(s,4H),7.03(d,J＝7.8Hz,2H),6.99(d,J＝9.0Hz,4H),6.54(d,J＝7.2Hz,2H),4.28(d,J＝5.0Hz,4H),4.27(d,J＝3.5Hz,4H),3.82ppm(s,12H). 13C NMR(150MHz,THF-d 8)δ:158.57,148.69,148.51,148.52,145.96,144.34,134.88,132.97,131.11,129.92,128.42,128.16,126.83,125.49,125.18,123.25,122.44,121.78,121.47,119.82,115.33,114.19,114.07,113.74,113.72,111.08,110.49,109.67,109.26,103.33,65.21,65.28,29.90ppm.HR-MS(MALDI-TOF)m/z(分子式C 96H 64N 6O 6S 2)理论值:1461.4362，实测值:1461.4357。
所得化合物H9的化学结构式如式(9)所示。
实施例10
化合物H10的合成：
化合物H10的制备方法同实施例7，不同之处在于用3,6,11,14-四氯代二苯并屈替换5,9-二溴代二萘并呋喃，得到化合物H10(42％产率)。 1H NMR(600MHz,THF-d 8)δ:9.26(s,4H),8.59(d,J＝5.0Hz,4H),8.01(d,J＝5.1Hz,4H),7.95(s,8H),7.75(d,J＝5.0Hz,8H),7.45(t,J＝9.9Hz,8H),7.42–7.18(m,32H),7.00(t,J＝4.8Hz,8H),6.89(t,J＝6.5Hz,8H),4.14(s,16H),3.76ppm(s,24H). 13C NMR(150MHz,THF-d 8)δ:148.60,141.62,140.38,139.55,138.00,137.78,131.53,130.59,129.27,128.86,126.59,125.37,124.73,124.57,124.17,123.65,123.36,122.64,120.27,119.80,118.38,117.49,116.38,113.49,109.18,108.24,64.59,64.44,28.12ppm.HR-MS(MALDI-TOF)m/z(分子式C 178H 124N 12O 8S 4)理论值:2685.8581，实测值:2685.8576。
所得化合物H10的化学结构式如式(10)所示。
实施例11
化合物H11的合成：
化合物H11的制备方法同实施例7，不同之处在于用2,7,10,15-四氯代四邻亚苯替换5,9-二溴代二萘并呋喃，得到化合物H11(48％产率)。 1H NMR(600MHz,THF-d 8)δ:8.36(d,J＝9.0Hz,8H),7.77–7.60(m,20H),7.42–7.37(m,32H),7.24(dd,J＝7.6,4.5Hz,8H),7.14(s,8H),6.99(d,J＝8.8Hz,8H),4.28(s,16H),3.77ppm(s,24H). 13C NMR(150MHz,THF-d 8)δ:148.69,148.55,145.97,138.61 135.83,134.83,133.78,129.56,129.07,128.53,128.40,128.18,127.53,126.92,123.21,121.73,121.47,119.87,116.53,114.17, 114.08,113.79,112.37,111.06,109.66,109.21,65.35,65.22,29.90ppm.HR-MS(MALDI-TOF)m/z(分子式C 176H 124N 12O 8S 4)理论值:2661.8581，实测值:2661.8576。
所得化合物H11的化学结构式如式(11)所示。
实施例12
化合物H12的合成：
化合物H12的制备方法同实施例7，不同之处在于用18,23-二溴代双二萘并呋喃并吡咯替换5,9-二溴代二萘并呋喃，得到化合物H12(50％产率)。 1H NMR(600MHz,THF-d 8)δ:12.50(s,1H),9.37(d,J＝8.1Hz,2H),9.28(d,J＝8.4Hz,2H),8.89(d,J＝7.9Hz,2H),8.41(d,J＝8.2Hz,2H),8.38(s,2H),8.00(d,J＝1.3Hz,4H),7.92(d,J＝7.8Hz,4H),7.85–7.72(m,8H),7.65(d,J＝8.8Hz,4H),7.62–7.56(m,4H),7.43–7.32(m,12H),7.09–7.00(m,8H),4.37(d,J＝5.0Hz,4H),4.29(d,J＝3.5Hz,4H),3.82ppm(s,12H). 13C NMR(150MHz,THF-d 8)δ:154.30,151.33,151.26,150.98,142.81,141.60,140.74,140.69,139.21,137.10,136.87,136.39,136.34,129.69,129.24,129.18,128.28,127.62,127.43,126.57,126.31,125.93,125.22,124.89,123.80,121.70,121.44,121.36,121.28,119.56,118.84,118.62,114.25,113.95,113.91,112.25,112.12,110.33,109.45,106.57,65.89,65.66,29.30ppm.HR-MS(MALDI-TOF)m/z(分子式C 116H 75N 7O 6S 2)理论值:1726.5254，实测值:1726.5249。
所得化合物H12的化学结构式如式(12)所示。
以上是本发明所述芳胺类化合物制备方法的示例。除上述12种产品外，结构式(13)至(68)的产品制备方法可参考实施例1中化合物H1的制备过程。结构式(69)至(112)的产品制备方法可参考实施例7中化合物H7的制备过程。本领域技术人员可根据结构式中π共轭单元的变化情况，利用其掌握的知识技能在现有技术中选择相应的反应原料。鉴于该部分内容已有上述实施例作为示例，本发明不再赘述。
以下通过实施例13、实施例14、实施例15详细说明本发明合成的化合物在光电器件中作为空穴传输层材料的应用方法及效果。
实施例13
本发明的化合物作为空穴传输材料，应用于钙钛矿太阳电池：
将本发明所述的化合物分别作为空穴传输层制备的钙钛矿太阳电池，包括：FTO玻璃基片、致密TiO 2层、多孔TiO 2层、钙钛矿层、空穴传输层和金属电极，其中，FTO玻璃基片由玻璃基片和FTO阴极(氟掺杂氧化锡玻璃电极)组成，致密TiO 2层和多孔TiO 2层作为TiO 2电子传输层，钙钛矿层作为吸光层。
实施例14
钙钛矿太阳电池的制备：
1)清洗：首先用洗涤剂清洗FTO玻璃基片的表面附着的灰尘等污染物，然后分别用水、丙酮和乙醇超声以除去有机污染物，洗净的FTO玻璃基片用氮气吹干，即可得到表面干净的透明导电衬底，再用紫外线-臭氧处理30min，保证其表面干净、清洁；
2)制备致密TiO 2层：在450℃的条件下，按体积比为1∶9将双(乙酰丙酮基)二异丙基钛酸酯溶于乙醇中，将溶液通过喷雾热解沉积在干净的FTO玻璃基片上，冷却室温后，得到TiO 2/FTO基底；
3)制备多孔TiO 2层：在上述得到的TiO 2/FTO基底上旋涂TiO 2浆料和乙醇配成的悬浊液(TiO 2浆料与乙醇的质量比为1∶6)，然后100℃下干燥10min，在450℃下灼烧30min，形成多孔TiO 2层；
4)制备钙钛矿层：由FAI、PbI 2、MABr和PbBr 2、CsI混合于DMF:DMSO＝4:1(v:v)中得到的(FAPbI 3) 0.875(MAPbBr 3) 0.075(CsPbI 3) 0.05(PbI 2) 0.03前驱溶液，前驱溶液中FAI浓度为1.19mol/L，PbI 2浓度为1.30mol/L，MABr浓度为0.14mol/L，PbBr 2浓度为0.14mol/L，CsI浓度为0.07mol/L。通过两步旋涂步骤制备钙钛矿层，两步旋涂分别以2000rpm速度转动10s和以5000rpm速度转动30s，在第二次旋涂过程的最后15s中滴加氯苯反溶剂；随后，基片在120℃条件下烘干1h后制得所需钙钛矿层；
5)制备空穴传输层：将520mg/mL的LiTFSI的乙腈溶液和TBP加入氯苯中，得到浓度分别为20mmol/L和132mmol/L的混合溶液，将含N,N-二烷基二咔唑胺取代基的化合物加入上述混合溶液中，配制成浓度为30mmol/L溶液，然后将溶液以4000rpm的速度旋涂20s沉积到钙钛矿层上；
6)置于真空蒸镀室，通过真空蒸镀法将金属电极蒸镀到空穴传输层表面，制得钙钛矿太阳电池。
实施例15
利用本发明的化合物作空穴传输材料所制备的钙钛矿太阳电池的光电效率：
化合物 光电转换效率
H1 21.3％
H2 21.2％
H3 20.8％
H4 20.0％
H5 20.6％
H6 21.9％
H7 21.7％
H8 21.5％
H9 20.3％
H10 20.7％
H11 19.9％
H12 21.0％
以上所述，仅是本发明的较佳实施例，并非对本发明作任何形式上的限制，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，依据本发明的技术实质，对以上实施例所作的任何简单的修改、等同替换与改进等，均仍属于本发明技术方案的保护范围之内。

Claims (6)

  1. 一种芳胺类化合物，其特征在于，是由N,N-二烷基二咔唑胺功能基修饰具有较大共轭体系的π单元构成，其化学结构式如式(1)～(112)中任意一种所示：
    Figure PCTCN2020109402-appb-100001
    Figure PCTCN2020109402-appb-100002
    Figure PCTCN2020109402-appb-100003
    Figure PCTCN2020109402-appb-100004
    Figure PCTCN2020109402-appb-100005
    Figure PCTCN2020109402-appb-100006
    Figure PCTCN2020109402-appb-100007
    Figure PCTCN2020109402-appb-100008
    Figure PCTCN2020109402-appb-100009
    Figure PCTCN2020109402-appb-100010
    Figure PCTCN2020109402-appb-100011
    Figure PCTCN2020109402-appb-100012
    各式中，R为C1～C3的烷基。
  2. 权利要求1所述芳胺类化合物的制备方法，其特征在于，包括以下步骤：
    按摩尔比1∶5∶0.2∶0.4∶15将含π共轭单元化合物与N,N-二甲基二咔唑胺、三(二亚苄基丙酮)二钯、四氟硼酸三叔丁基膦和叔丁醇钠一起加入到甲苯中；在氮气的保护下，边搅拌边加热到120℃，反应12h；静置冷却至室温，滤除有机溶剂得到产物粗品；经过柱层析提纯，得到芳胺类化合物。
  3. 根据权利要求2所述的方法，其特征在于，所述含π共轭单元化合物是下述的任意一种：5,9-二溴代二萘并呋喃、5,9-二溴代二萘并噻吩、3,9-二溴代二氧杂蒽嵌蒽、3,6,11,14-四氯代二苯并屈、2,7,10,15-四氯代四邻亚苯或18,23-二溴代双二萘并呋喃并吡咯。
  4. 权利要求1所述芳胺类化合物的制备方法，其特征在于，包括以下步骤：
    在干燥的三口圆底烧瓶中，将3,4-乙烯二氧噻吩甲基咔唑三芳胺溶于超干四氢呋喃中，并降温至-78℃；在氩气的保护下，用针头将1.5倍当量的正丁基锂的己烷溶液缓慢加入上述溶液，搅拌半小时；随后，用注射器将2倍当量的异丙醇频哪醇硼酸酯加入上述体系，将体系缓慢升至室温并搅拌2小时；反应结束后，加入去离子水，并用二氯甲烷萃取分液，保留有机相；经过柱层析提纯后，得到中间体3,4-乙烯二氧噻吩甲基咔唑三芳胺硼酸酯；
    按摩尔比1:5:0.08:0.08:10将含π共轭单元化合物、3,4-乙烯二氧噻吩甲基咔唑三芳胺硼酸酯、醋酸钯、四氟硼酸三叔丁基膦和磷酸钾一起加入到二氧六环和水的混合溶剂中，混合溶剂中二氧六环与水的体积比为5:1；在氩气的保护下，边搅拌边加热到100℃，反应6h；静置冷却至室温，加入去离子水，并用二氯甲烷萃取分液，保留有机相，得到产物粗品；经过柱层析提纯，得到芳胺类化合物。
  5. 根据权利要求4所述的方法，其特征在于，所述含π共轭单元化合物是下述的任意一种：5,9-二溴代二萘并呋喃、5,9-二溴代二萘并噻吩、3,9-二溴代二氧杂蒽嵌蒽、3,6,11,14-四氯代二苯并屈、2,7,10,15-四氯代四邻亚苯或18,23-二溴代双二萘并呋喃并吡咯。
  6. 权利要求1所述芳胺类化合物的应用方法，其特征在于，是将其作为有机空穴传输材料用于制备光电器件。
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