CN117603135A - 含吡啶二羧基自组装空穴传输材料、合成方法及作为光电器件的应用 - Google Patents
含吡啶二羧基自组装空穴传输材料、合成方法及作为光电器件的应用 Download PDFInfo
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- CN117603135A CN117603135A CN202311756903.8A CN202311756903A CN117603135A CN 117603135 A CN117603135 A CN 117603135A CN 202311756903 A CN202311756903 A CN 202311756903A CN 117603135 A CN117603135 A CN 117603135A
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Abstract
本发明属于有机半导体光电技术领域，具体涉及一种含吡啶二羧基自组装空穴传输材料、合成方法及作为光电器件的应用。本发明提供了一种吡啶二羧基为锚定基团，通过自组装单分子层策略，在分子结构中引入桥连单元和空穴传输单元，从而得到含吡啶二羧基的空穴传输材料，可以解决现有技术中具有锚定基团的有机小分子面临着稳定性差以及器件性能不佳等技术问题。本发明所述空穴传输材料中吡啶二羧基的引入，能够提升光电器件的效率，延长其使用寿命，包括钙钛矿太阳能电池、钙钛矿发光二极管，以及量子点发光二极管等等。
Description
技术领域
本发明属于有机半导体技术领域，具体涉及一种含吡啶二羧基自组装空穴传输材料、合成方法及应用。
背景技术
有机半导体材料由于具备溶液可加工、成本低廉、材料合成简单、结构/种类多样、性能可调控、易于制备大面积及柔性光电子器件等独特的优势，而受到产学研界的广泛关注，在新一代高性能超低成本光伏发电、平板显示、生物传感和柔性可穿戴器件等领域显现出广阔的应用前景。2024年全球半导体产业景气度将逐步复苏，重新进入稳步增长的发展态势。根据Gartner、IDC、WSTS等全球市场机构预测的数据，2024年全球半导体产业增速将超过两位数，平均预测增速在13％-15％左右，规模超过6000亿美元。有机空穴传输材料作为新型光电子器件的重要组成部分，承担着器件中空穴的收集与传输和电子的阻挡，对器件的光电转化效率和稳定性起着至关重要的作用。
近年来，单分子自组装(SAM)空穴传输材料由于原材料价格低、合成路线简单、分子结构确定、可使用绿色醇类溶剂加工，与基底的结合力强、耐溶剂性好、容易通过化学修饰调整能级，尤其是其分子自组装方法可以灵活有效地制造出具有可控表面特性和形状的样品。自组装可以在溶液中或固体表面上进行，分子或颗粒等材料的聚集在界面上进行结构调整，最终形成稳定的薄膜。因此，自组装空穴传材料在光电中起到了关键的作用，使用含有锚定基团的有机小分子制备空穴传输层已被证明具有优异的电荷选择能力(EnergyEnviron.Sci.,2019,12,230-237)。但是目前发展的具有锚定基团的有机小分子空穴传输材料面临着稳定性较差以及器件性能不佳等问题。
发明内容
本发明的目的在于克服现有技术的不足，提供一种空穴传输性好、界面钝化能力强，适用于大规模应用的自组装单分子层空穴传输材料。
为了达到上述目的，本发明提供了一种含吡啶二羧基的空穴传输材料，具有如下式(I)所示的化学通式：
式中，R1-R2独立地选自为氢、卤素、烷氧基、硫代烷氧基、三氟甲基、Cl-C6烷基中任一种或两种，且Rl-R2可以为不同的取代位置或不同取代数目；L表示为单键、苯基、噻吩、呋喃、联苯；X表示为空、单键、氧、硫、羰基、磺酰基、碳二甲基、氮甲基、硅二甲基。
进一步，式(I)为如下化合物i到viii中的任意一种：
其中，R1、R2取代基独立地是-H、-F、-Cl、-Br、-I、-OCH3、-SCH3、-CH3、-CH2CH3、-CF3中任一种或两种，且Rl和R2可以是不同的取代位置或不同取代数目；L表示为单键、苯基、噻吩、呋喃、联苯。
更进一步，R1、R2取代基为-H或-OCH3，且Rl和R2在相同的对位取代位置；L为单键、苯基。
本发明所述的一种含吡啶二羧基自组装空穴传输材料的合成方法，包括：
S1、将4-羟基吡啶-2,6-二羧酸与三氯氧磷氯化，并与叔丁醇(TBA)在4-二甲氨基吡啶(DMAP)和二氯甲烷(DCM)的混合溶液中进行酯化反应，制备中间体1的步骤，
S2、将中间体1与芳胺化合物在四氢呋喃(THF)和氢化钠(NaH)的混合溶液中进行偶联反应，并在盐酸体系中发生水解反应，制备含吡啶二羧基的空穴传输材料，
进一步的，步骤(S1)中，4-羟基吡啶-2,6-二羧酸、三氯氧磷、叔丁醇和4-二甲氨基吡啶的摩尔比为1:2～3:2～3:0.05～0.1；酯化反应温度为80～100℃，酯化反应时间为12～24h。
进一步的，步骤(S2)中，中间体1、芳胺化合物和氢化钠的摩尔比为1:1～1.5:1～1.2；偶联反应温度为40～50℃，偶联反应时间为24～48h。
本发明所述的一种含吡啶二羧基自组装空穴传输材料的合成方法，包括：
(a)将4-羟基吡啶-2,6-二羧酸与三氯氧磷氯化，并与叔丁醇(TBA)在4-二甲氨基吡啶(DMAP)和二氯甲烷(DCM)的混合溶液中进行酯化反应，制备中间体1的步骤，
(b)将中间体1和联硼酸频那醇酯在醋酸钾和四氢呋喃(THF)的混合溶液中，通过三(二亚苄基丙酮)钯和2-二环己基磷-2′,4′,6′-三异丙基联苯催化偶联反应，制备中间体2的步骤，
(c)将中间体2和溴代芳烃在磷酸钾和四氢呋喃的混合溶液中，通过醋酸钯和X-phos进行催化偶联反应，制备含吡啶二羧基的空穴传输材料的步骤，
进一步的，步骤(a)中，4-羟基吡啶-2,6-二羧酸、三氯氧磷、叔丁醇和4-二甲氨基吡啶的摩尔比为1:2～3:2～3:0.05～0.1；酯化反应温度为80～100℃，酯化反应时间为12～24h。
进一步的，步骤(b)中，中间体1、联硼酸频那醇酯、醋酸钾、三(二亚苄基丙酮)钯和2-二环己基磷-2′,4′,6′-三异丙基联苯的摩尔比为1:1～1.5:1～3:0.02～0.03:0.04～0.06；偶联反应温度为50～60℃，偶联反应时间为8～12h。
进一步的，步骤(c)中，中间体2、溴代芳烃、磷酸钾、醋酸钯和2-二环己基磷-2′,4′,6′-三异丙基联苯的摩尔比为1:1～1.5:1～3:0.02～0.03:0.04～0.06；偶联反应温度为50～60℃，偶联反应时间为12～24h。
本发明的另一目的在于光电器件应用，所述的光电器件至少包括依次设置的透明导电氧化物衬底、空穴传输层、光吸收层、电子传输层和电极层；或者，包括依次设置的透明导电氧化物衬底、空穴传输层、发光层、电子传输层和电极层；其中，所述的透明导电氧化物电极层上设置有金属背电极；所述的空穴传输层为上述的含有如通式(I)所示的吡啶二羧基自组装空穴传输材料。
可选地，所述的有机空穴传输层通过将含有通式(I)所示的吡啶二羧基自组装空穴传输材料溶解于醇类溶剂中制成浓度为1～10mg/mL的溶液，再涂覆在透明导电氧化物衬底上得到。
与现有技术相比，本发明的有益效果在于：
(1)吡啶羧基的引入，大幅度提高有机空穴传输材料的稳定性，包括光稳定性、热稳定性、氧化还原稳定性等，有益于器件工作状态下的长期稳定。
(2)吡啶羧基的引入，能够调节材料的前线轨道能级，使其与活性层材料能级更加匹配，提高界面载流子注入与提取效率，提升器件性能。
(3)吡啶羧基的引入，能够钝化界面的结构缺陷，延长活性层中的载流子寿命，提升光电器件的开路电压和填充因子。
(4)吡啶羧基的引入，由于吡啶羧基的疏水性，一方面可以降低水分对活性层的侵蚀，另一方面可以降低活性层的组分扩散，这两方面有助于提升光电器件的稳定性，延长电池的寿命。
附图说明
图1为本发明的光电器件结构示意图；
图2为采用本发明提供的化合物1～3作为空穴传输材料制备的钙钛矿电池的J/V曲线图；
图3为采用本发明提供的化合物4～6作为空穴传输材料制备的钙钛矿电池的J/V曲线图；
图4为采用本发明提供的化合物7～9作为空穴传输材料制备的钙钛矿电池的J/V曲线图；
图5为采用本发明提供的化合物10～12作为空穴传输材料制备的钙钛矿电池的J/V曲线图；
图6为采用本发明提供的化合物13～15作为空穴传输材料制备的钙钛矿电池的J/V曲线图；
图7为采用本发明提供的化合物16～18作为空穴传输材料制备的钙钛矿电池的J/V曲线图；
图8为采用本发明提供的化合物19～20作为空穴传输材料制备的钙钛矿电池的J/V曲线图；
图9为采用本发明提供的化合物1～3作为空穴传输材料制备的钙钛矿发光二极管的电流密度和亮度随电压变化图；
图10为采用本发明提供的化合物4～6作为空穴传输材料制备的钙钛矿发光二极管的电流密度和亮度随电压变化图；
图11为采用本发明提供的化合物7～9作为空穴传输材料制备的钙钛矿发光二极管的电流密度和亮度随电压变化图；
图12为采用本发明提供的化合物10～12作为空穴传输材料制备的钙钛矿发光二极管的电流密度和亮度随电压变化图；
图13为采用本发明提供的化合物13～15作为空穴传输材料制备的钙钛矿发光二极管的电流密度和亮度随电压变化图；
图14为采用本发明提供的化合物16～18作为空穴传输材料制备的钙钛矿发光二极管的电流密度和亮度随电压变化图；
图15为采用本发明提供的化合物19～20作为空穴传输材料制备的钙钛矿发光二极管的电流密度和亮度随电压变化图。
具体实施方式
为更进一步阐述本发明为实现预定发明目的所采取的技术手段及功效，以下结合附图及较佳实施例，对依据本发明的具体实施方式、结构、特征及其功效进行详细说明。更加具体地，实施例化合物是选自如下结构：
实施例1
化合物1的合成
(1)中间体1的合成：
称量SM1(48g,1.0eq)加入500mL三口烧瓶中，加入200mL POCl3，接尾气处理装置，用NaOH的水溶液吸收酸性尾气，升温至100℃，回流搅拌约10h，停止反应；旋出剩余的POCl3；将叔丁醇(40mL)，DMAP(10g)，20mL超干DCM，10mL吡啶加入500mL的烧瓶中，搅拌均匀；将上一步的浓缩液用50mL超干DCM稀释，转移至恒压滴液漏斗中缓慢滴入烧瓶中；搅拌约12h后，浓缩反应液，柱色谱分离，共得到白色固体产物42.68g，产率57.6％。1H NMR(400MHz,DMSO-d6)δ7.38(s,2H),0.86(s,18H).HRMS(ESI,m/z):[M+H]+calculated forC15H21ClNO4,314.1159,found 314.1168.
(2)化合物1的合成：
称量SM2(0.30g,1.0eq),中间体1(0.62g,1.1eq),NaH(0.22g,5.0eq),加入50mL三口烧瓶中，加入超干THF(20mL)，升温至50℃；搅拌24h后,开始下一步；向反应液中缓慢加入5mL纯化水，在碱性条件下水解，搅拌约12h；反应液中析出大量固体产物，浓缩反应液，旋出少量THF后，抽滤，烘干，得到黄色固体；将固体用大量乙醇溶解，抽滤，滤去在乙醇中不溶的杂质，浓缩乙醇，抽滤，得到产物，烘干，得到黄色固体130mg，产率22.0％。1H NMR(400MHz,Chloroform-d)δ7.55(s,2H),7.32-7.25(m,4H),7.14-7.08(m,4H),7.04(tt,J＝7.7,1.4Hz,2H).HRMS(ESI,m/z):[M+H]+calculated for C19H13N2O4,333.0875,found333.0816.。
实施例2
化合物2的合成
(1)中间体1的合成：与实施例1中的中间体1的合成相同，产率57.6％。1H NMR(400MHz,DMSO-d6)δ7.38(s,2H),0.86(s,18H).。
(2)中间体2的合成：
称量中间体1(5.0g,1.0eq),联硼酸频那醇酯(4.87g，1.2eq)，醋酸钾(4.69g，3.0eq)，Pd2(dba)3(0.15g),X-phos(0.30g)溶于50mL超干THF中，60℃搅拌，氩气保护；搅拌约10h后，反应完毕；抽滤反应液，除盐，浓缩反应液，至约剩余10mL时，搅拌约30min后，析出大量产物；抽滤，用石油醚洗涤，烘干，得到白色固体产物6.59g，产率65.4％。1H NMR(400MHz,DMSO-d6)δ7.38(s,2H),0.86(s,30H).HRMS(ESI,m/z):[M+H]+calculated forC21H32BNO6,405.2323,found 405.2349.。
(3)中间体3的合成：
称量SM3(0.30g,1eq)，中间体2(0.45g,1.2eq)，NaH(0.60g,3eq)，加入50mL三口烧瓶中，加入THF(20mL)和水(5mL)，升温至50℃；搅拌过夜，旋干后柱色谱分离(PE:EA＝8:1)，得到黄色产物；烘干，得到0.36g，产率75％。1H NMR(400MHz,Chloroform-d)δ8.20(s,2H),7.63-7.57(m,2H),7.31-7.26(m,4H),7.21-7.18(m,2H),7.13-7.08(m,4H),7.04(tt,J＝7.7,1.4Hz,2H),1.56(s,18H).HRMS(ESI,m/z):[M+H]+calculated for C33H34N2O4,522.2519,found 522.2589.。
(4)化合物2的合成：
称量中间体3(0.11g,0.21mmol)，加入20mL THF,10mL水，搅拌12h水解酯，点板，水解完毕；滴入浓盐酸，调节pH至2，无沉淀析出；浓缩反应液至约剩余10mL水时,有沉淀析出；抽滤后，产物用水反复洗涤；烘干，得到产物73mg，产率84.8％。1H NMR(400MHz,Chloroform-d)δ8.28(s,2H),7.64-7.58(m,2H),7.32-7.25(m,4H),7.22-7.16(m,2H),7.11(d,J＝1.3Hz,1H),7.11-7.00(m,5H).HRMS(ESI,m/z):[M+H]+calculated for C25H18N2O4,410.1267,found 410.1217.。
实施例3
化合物3的合成：
化合物3的合成和化合物2的合成步骤相似，得到产物156mg，产率74.6％。1H NMR(400MHz,Chloroform-d)δ8.28(s,2H),7.64-7.58(m,2H),7.22-7.16(m,2H),7.14-7.09(m,4H),6.95-6.89(m,4H),3.79(s,6H).HRMS(ESI,m/z):[M+H]+calculated for C27H23N2O6,471.1556,found 471.1594.。
实施例4
化合物4的合成：
化合物4的合成和化合物2的合成步骤相似，得到产物215mg，产率81.4％。1H NMR(400MHz,Chloroform-d)δ8.29(s,2H),8.16-8.11(m,2H),7.72-7.68(m,2H),7.68-7.59(m,4H),7.35(ddd,J＝7.5,6.1,1.3Hz,1H),7.33-7.27(m,3H).HRMS(ESI,m/z):[M+H]+calculated for C25H17N2O4,409.1188,found 409.1113.。
实施例5
化合物5的合成：
化合物5的合成和化合物1的合成步骤相似，得到产物109mg，产率41.6％。1H NMR(400MHz,Chloroform-d)δ8.99(s,2H),7.89(d,J＝2.7Hz,1H),7.66(d,J＝1.8Hz,1H),7.29(dd,J＝8.1,2.6Hz,2H),6.93(ddd,J＝9.5,8.0,2.4Hz,2H),3.83(s,6H).HRMS(ESI,m/z):[M+H]+calculated for C21H17N2O6,393.1087,found 393.1027.。
实施例6
化合物6的合成：
化合物6的合成和化合物2的合成步骤相似，得到产物315mg，产率86.1％。1H NMR(400MHz,Chloroform-d)δ8.29(s,2H),7.89(d,J＝2.8Hz,1H),7.73-7.59(m,5H),7.36(t,J＝8.0Hz,2H),6.92(ddd,J＝9.5,8.1,2.4Hz,2H),3.83(s,6H).HRMS(ESI,m/z):[M+H]+calculated for C27H21N2O6,469.1400,found 469.1413.。
实施例7
化合物7的合成：
化合物7的合成和化合物1的合成步骤相似，得到产物136mg，产率51.6％。1H NMR(400MHz,Chloroform-d)δ7.86(s,2H),7.19(dd,J＝7.3,1.7Hz,2H),7.09(td,J＝7.3,1.5Hz,2H),7.08(td,J＝7.4,1.5Hz,2H),6.73(dd,J＝7.4,1.6Hz,2H).HRMS(ESI,m/z):[M+H]+calculated for C19H12N2O5,348.0746,found 348.0728.。
实施例8
化合物8的合成：
化合物8的合成和化合物1的合成步骤相似，得到产物105mg，产率46.8％。1H NMR(400MHz,Chloroform-d)δ7.84(s,2H),7.30(dd,J＝7.3,1.4Hz,2H),7.27-7.20(m,4H),7.13(ddd,J＝7.5,6.6,2.4Hz,2H).HRMS(ESI,m/z):[M+H]+calculated for C19H12N2O4S,364.0518,found 364.0573.。
实施例9
化合物9的合成：
化合物9的合成和化合物1的合成步骤相似，得到产物142mg，产率41.2％。1H NMR(400MHz,Chloroform-d)δ8.02(dd,J＝7.6,1.5Hz,2H),7.85(s,2H),7.39(td,J＝7.4,1.5Hz,2H),7.29(dd,J＝7.5,1.6Hz,2H),7.08(td,J＝7.5,1.6Hz,2H).HRMS(ESI,m/z):[M+H]+calculated for C20H12N2O5,360.0746,found 360.0729.。
实施例10
化合物10的合成：
化合物10的合成和化合物1的合成步骤相似，得到产物212mg，产率51.9％。1H NMR(400MHz,Chloroform-d)δ7.88-7.83(m,2H),7.51(td,J＝7.4,1.7Hz,4H),7.41-7.30(m,2H).HRMS(ESI,m/z):[M+H]+calculated for C19H12N2O6S,396.0416,found 396.0490.。
实施例11
化合物11的合成：
化合物11的合成和化合物1的合成步骤相似，得到产物115mg，产率47.9％。1H NMR(400MHz,Chloroform-d)δ7.85(s,2H),7.17(ddd,J＝19.6,7.4,1.5Hz,6H),7.07(td,J＝7.4,1.7Hz,2H),1.54(s,6H).HRMS(ESI,m/z):[M+H]+calculated for C22H18N2O4,374.1267,found 374.1217.。
实施例12
化合物12的合成：
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化合物12的合成和化合物1的合成步骤相似，得到产物141mg，产率43.8％。1H NMR(400MHz,Chloroform-d)δ7.84(s,2H),7.17-7.09(m,4H),7.06(dd,J＝7.8,1.1Hz,2H),6.99-6.91(m,2H),3.41(s,3H).HRMS(ESI,m/z):[M+H]+calculated for C20H15N3O4,361.1063,found 361.1002.。
实施例13
化合物13的合成：
化合物13的合成和化合物1的合成步骤相似，得到产物115mg，产率39.4％。1H NMR(400MHz,Chloroform-d)δ7.86(s,2H),7.48-7.40(m,2H),7.36-7.27(m,4H),7.27-7.19(m,2H),1.44(s,6H).HRMS(ESI,m/z):[M+H]+calculated for C21H18N2O4Si,390.1036,found390.1099.。
实施例14
化合物14的合成：
化合物14的合成和化合物2的合成步骤相似，得到产物215mg，产率66.3％。1H NMR(400MHz,Chloroform-d)δ8.15(s,2H),7.70-7.64(m,2H),7.33-7.27(m,2H),7.22-7.14(m,2H),7.11-7.03(m,4H),6.84-6.77(m,2H).HRMS(ESI,m/z):[M+H]+calculated forC25H16N2O5,424.1059,found 424.1090.。
实施例15
化合物15的合成：
化合物15的合成和化合物2的合成步骤相似，得到产物175mg，产率63.8％。1H NMR(400MHz,Chloroform-d)δ8.15(s,2H),7.71-7.66(m,2H),7.29(dd,J＝7.4,1.3Hz,4H),7.26-7.18(m,4H),7.13(td,J＝7.3,1.9Hz,2H).HRMS(ESI,m/z):[M+H]+calculated forC25H16N2O4S,440.0831,found 440.0892.。
实施例16
化合物16的合成：
化合物16的合成和化合物2的合成步骤相似，得到产物118mg，产率68.1％。1H NMR(400MHz,Chloroform-d)δ8.10(s,2H),8.02(dd,J＝7.6,1.5Hz,2H),7.71–7.66(m,2H),7.41(td,J＝7.4,1.4Hz,2H),7.32(dd,J＝7.5,1.6Hz,2H),7.30–7.26(m,2H),7.09(td,J＝7.4,1.5Hz,2H).HRMS(ESI,m/z):[M+H]+calculated for C26H16N2O5,436.1059,found436.1010.。
实施例17
化合物17的合成：
化合物17的合成和化合物2的合成步骤相似，得到产物331mg，产率79.5％。1H NMR(400MHz,Chloroform-d)δ8.10(s,2H),7.86(dd,J＝7.5,1.3Hz,2H),7.72-7.66(m,2H),7.48(td,J＝7.1,2.0Hz,2H),7.38-7.30(m,4H),7.30-7.25(m,2H).HRMS(ESI,m/z):[M+H]+calculated for C25H16N2O6S,472.0729,found 472.0680.。
实施例18
化合物18的合成：
化合物18的合成和化合物2的合成步骤相似，得到产物266mg，产率62.7％。1H NMR(400MHz,Chloroform-d)δ8.10(s,2H),7.72-7.66(m,2H),7.31-7.25(m,2H),7.21-7.14(m,4H),7.08(ddd,J＝7.0,6.3,1.5Hz,4H),1.54(s,6H).HRMS(ESI,m/z):[M+H]+calculatedfor C28H22N2O4,450.1580,found 450.1521.。
实施例19
化合物19的合成：
化合物19的合成和化合物2的合成步骤相似，得到产物253mg，产率73.8％。1H NMR(400MHz,Chloroform-d)δ8.10(s,2H),7.71-7.66(m,2H),7.33-7.27(m,2H),7.14(ddd,J＝7.5,6.1,2.6Hz,2H),7.09(dd,J＝7.1,1.1Hz,2H),7.01-6.93(m,4H),3.41(s,3H).HRMS(ESI,m/z):[M+H]+calculated for C26H19N3O4,437.1376,found 437.1302.。
实施例20
化合物20的合成：
化合物20的合成和化合物2的合成步骤相似，得到产物310mg，产率78.3％。1H NMR(400MHz,Chloroform-d)δ8.10(s,2H),7.71-7.65(m,2H),7.47-7.40(m,2H),7.35-7.26(m,6H),7.23-7.15(m,2H),0.44(s,6H).HRMS(ESI,m/z):[M+H]+calculated for C27H22N2O4Si,466.1349,found 466.1368.。
以下通过本发明的化合物制备的钙钛矿太阳能电池器件A1至A20和钙钛矿发光二极管器件B1至B20的制备过程及性能检测效果分析，对本发明化合物的用途及效果进行进一步详细说明。
应用例1
器件A1钙钛矿电池的制备，方法步骤如下：
1)IT0导电玻璃基底的清洗；
2)空穴传输层(HTL)的制备：将化合物1溶解于乙醇溶剂中，旋涂于ITO上方后，120℃退火20min除去吸附的水分子备用；
3)钙钛矿薄膜(钙钛矿(perovskite)层)的制备：钙钛矿前驱体溶液的溶度为1.2M，钙钛矿薄膜由反溶剂一步法制备得到。旋涂分为两个阶段，第一阶段速度为1000rpms-1，旋涂10s，加速度为200rpms-2；第二阶段为5000rpm s-1涂30s，加速度为2000rpm s-2，在第二阶段结束前20s，将600微升甲苯作为反溶剂滴加在钙钛矿膜中央，最后100℃加热30min即可得到最终的钙钛矿薄膜；
3)电子传输层(ETL)和空穴阻挡层制备：使用氯苯配制PCBM的溶液，浓度为20mgmL-1，两步程序旋涂(800rmp s-1，10s；4000rmp s-1，30s)，80℃退火10min。
4)空穴阻挡层制备：最后，滴涂120uL BCP的异丙醇溶液制备空穴阻挡层(ITO)；
5)背电极制备：使用真空蒸镀仪(<5×10-4Pa)蒸镀100nm银构成负极。
器件A2制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物2)层。
器件A3制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物3)层。
器件A4制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物4)层。
器件A5制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物5)层。
器件A6制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物6)层。
器件A7制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物7)层。
器件A8制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物8)层。
器件A9制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物9)层。
器件A10制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物10)层。
器件A11制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物11)层。
器件A12制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物12)层。
器件A13制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物13)层。
器件A14制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物14)层。
器件A15制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物15)层。
器件A16制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物16)层。
器件A17制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物17)层。
器件A18制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物18)层。
器件A19制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物19)层。
器件A20制备方法与流程与器件A1相同，除ITO上制备本发明提供的空穴传输材料(化合物20)层。
应用比较例1
制备方法与流程与器件A1相同，除ITO上制备的空穴传输材料为Ref，Ref的结构式如下:
钙钛矿电池性能测试：太阳能电池的伏安特性曲线(I-V)由Keithley 2400数字源表记录，光源为氙灯(0sramXBO 450)模拟AM 1.5太阳光，强度为1000W/m2,经硅电池校正，测试温度25℃。入射光子转化效率(Incidentphoton-to-electron covertionefficiency，IPCE)，也称外量子效率(External quantum efficiency，EQE)测试系统为oriel-74125，光源为300W氙灯(ILC Technology，USA)，调制频率2Hz。测试电池的J-V数据如表1及图1-图8所示。
钙钛矿太阳能电池的稳定性测试：将制备的钙钛矿太阳能电池器件在相对湿度(RH)为85％和温度50℃的条件下放置240h后，其光电转换效率比原始效率的相对值如表1。
表1
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从表1和图2-图8可以看出：(1)本发明的吡啶羧基化合物作为空穴传输材料应用在钙钛矿电池里面，电池的短路密度大于14mA/cm-2，开路电压大于1.10V，填充子大于73％。在模拟太阳光强为1.5AM下的光电转化效率均大于13％，最高达到17.45％。对比参考化合物，显示出较高的光转换效率。这主要是由于传输单元和吡啶羧基的引入，调节材料的前线轨道能级，使其与活性层材料能级更加匹配,提高界面载流子注入与提取效率，提升器件效率。另外能够钝化界面的结构缺陷,延长钙钛矿活性层中的载流子寿命，提升钙钛矿电池的开路电压和填充因子。(2)由于传输单元和吡啶羧基的引入，可以提高空穴传输材料的光稳定性，氧化还原稳定性，从表1可以看出，在高温高湿状态下放置240小时后，利用本发明化合物作为空穴传输材料的钙铁矿电池，仍具有良好的光电转换效率，对比原始值，均高于80％，而参比器件只有45％，显示出本发明的电池良好的稳定性。传输单元除了可以增加材料的稳定性外，还可以增加材料的疏水性，减少钙钛矿电池工作时空气中的水分对钙钛矿层的侵蚀作用，提升电池的使用寿命。
应用例2
器件B1钙钛矿发光二极管器件的制备，方法步骤如下：
1)ITO阳极:将涂层厚度为150nm的ITO(氧化铟锡)玻璃基板用乙醇擦洗，然后用丙酮清洗两次，超声波洗涤20min，洗涤结束后，然后转移至等热台烘干，烘烤结束后降温，转移至UV-O3处理15min；
2)空穴传输层(HTL)的制备：将化合物9溶解于乙醇溶剂中，旋涂于ITO上方后，120℃退火20min除去吸附的水分子备用；
3)将钙钛矿量子点以2000rpm/45s，加速度为1000的旋涂参数旋于传输层上，并使用真空蒸镀仪，蒸镀45nm的TPBi作为电子传输层，在电子注入层上面真空蒸镀100nm的Al作为背电极。
器件B2制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物2)层。
器件B3制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物3)层。
器件B4制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物4)层。
器件B5制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物5)层。
器件B6制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物6)层。
器件B7制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物7)层。
器件B8制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物8)层。
器件B9制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物9)层。
器件B10制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物10)层。
器件B11制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物11)层。
器件B12制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物12)层。
器件B13制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物13)层。
器件B14制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物14)层。
器件B15制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物15)层。
器件B16制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物16)层。
器件B17制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物17)层。
器件B18制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物18)层。
器件B19制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物19)层。
器件B20制备方法与流程与器件B1相同，除ITO上制备本发明提供的空穴传输材料(化合物20)层。
应用比较例2
制备方法与流程与器件B1相同，除ITO上制备的空穴传输材料为Ref，Ref的结构式如下:
采用上述所得的钙钛矿发光器件进行I-V-L测试，得到其相关性能参数如表2。
表2
从表2和图9-图15可以看出：(1)本发明的吡啶羧基化合物作为空穴传输材料应用在钙钛矿发光二极管里面，启亮电压为2.6V，发光亮度均大于10000cd/m2，外量子效率均大于13％，甚至达到15％。由于传输单元和吡啶羧基的引入，调节材料的前线轨道能级，使其与活性层材料能级更加匹配，显示出良好的界面载流子注入与提取效率。
Claims (10)
1.一种含吡啶二羧基的空穴传输材料，其特征在于，具有式(I)所示的化学结构通式：
式中，R1-R2独立地选自为氢、卤素、烷氧基、硫代烷氧基、三氟甲基、Cl-C6烷基中任一种或多种，且Rl-R2为不同的取代位置或不同取代数目；L表示为单键、苯基、噻吩、呋喃、联苯；X表示为空、单键、氧、硫、羰基、磺酰基、碳二甲基、氮甲基、硅二甲基。
2.如权利要求1所述的空穴传输材料，其特征在于，其为如下结构的化合物i到viii中任意一种：
其中，R1、R2取代基独立地是-H、-F、-Cl、-Br、-I、-OCH3、-SCH3、-CH3、-CH2CH3、-CF3中任一种或多种，且Rl和R2为不同的取代位置或不同取代数目；L表示为单键、苯基、噻吩、呋喃、联苯。
3.如权利要求2所述的空穴传输材料，其特征在于，R1、R2取代基为-H或-OCH3，且Rl和R2在相同的对位取代位置；L为单键、苯基。
4.一种如权利要求1-3任一所述的空穴传输材料的合成方法，其特征在于，包括：
S1、将4-羟基吡啶-2,6-二羧酸与三氯氧磷氯化，并与叔丁醇在4-二甲氨基吡啶和二氯甲烷的混合溶液中进行酯化反应，制备中间体1的步骤，
S2、将中间体1与芳胺化合物在四氢呋喃和氢化钠的混合溶液中进行偶联反应，并在盐酸体系中发生水解反应，制备含吡啶二羧基的空穴传输材料，
5.如权利要求4所述的方法，其特征在于，步骤(S1)中，4-羟基吡啶-2,6-二羧酸、三氯氧磷、叔丁醇和4-二甲氨基吡啶的摩尔比为1:2～3:2～3:0.05～0.1；酯化反应温度为80～100℃，酯化反应时间为12～24h；步骤(S2)中，中间体1、芳胺化合物和氢化钠的摩尔比为1:1～1.5:1～1.2；偶联反应温度为40～50℃，偶联反应时间为24～48h。
6.一种如权利要求1-3任一所述的空穴传输材料的合成方法，其特征在于，包括：
(a)将4-羟基吡啶-2,6-二羧酸与三氯氧磷氯化，并与叔丁醇在4-二甲氨基吡啶和二氯甲烷的混合溶液中进行酯化反应，制备中间体1的步骤，
(b)将中间体1和联硼酸频那醇酯在醋酸钾和四氢呋喃的混合溶液中，通过三(二亚苄基丙酮)钯和2-二环己基磷-2′,4′,6′-三异丙基联苯催化偶联反应，制备中间体2的步骤，
(c)将中间体2和溴代芳烃在磷酸钾和四氢呋喃的混合溶液中，通过醋酸钯和X-phos进行催化偶联反应，制备含吡啶二羧基的空穴传输材料的步骤，
7.如权利要求6所述的方法，其特征在于，步骤(a)中，4-羟基吡啶-2,6-二羧酸、三氯氧磷、叔丁醇和4-二甲氨基吡啶的摩尔比为1:2～3:2～3:0.05～0.1；酯化反应温度为80～100℃，酯化反应时间为12～24h；步骤(b)中，中间体1、联硼酸频那醇酯、醋酸钾、三(二亚苄基丙酮)钯和2-二环己基磷-2′,4′,6′-三异丙基联苯的摩尔比为1:1～1.5:1～3:0.02～0.03:0.04～0.06；偶联反应温度为50～60℃，偶联反应时间为8～12h；步骤(c)中，中间体2、溴代芳烃、磷酸钾、醋酸钯和2-二环己基磷-2′,4′,6′-三异丙基联苯的摩尔比为1:1～1.5:1～3:0.02～0.03:0.04～0.06；偶联反应温度为50～60℃，偶联反应时间为12～24h。
8.如权利要求1-3任一所述的空穴传输材料在制备光电器件的空穴传输层中的应用。
9.一种光电器件，所述的光电器件至少包括依次设置的透明导电氧化物衬底、空穴传输层、光吸收层、电子传输层和电极层；或者，至少包括依次设置的透明导电氧化物衬底、空穴传输层、发光层、电子传输层和电极层，其特征在于，所述的空穴传输层含有权利要求1-3任一所述的空穴传输材料。
10.如权利要求9所述的光电器件，其特征在于，所述的有机空穴传输层通过将所述空穴传输材料溶解于醇类溶剂中制成浓度为1～10mg/mL的溶液，再涂覆在透明导电氧化物衬底上得到。
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