CN102604048B - 含氧化胺基团的共轭聚合物光电材料及其应用 - Google Patents
含氧化胺基团的共轭聚合物光电材料及其应用 Download PDFInfo
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Abstract
本发明涉及一类含氧化胺基团的共轭聚合物光电材料及其应用。所述的含氧化胺基团的共轭聚合物光电材料由共轭的主链及含有氧化胺单元的侧链组成,应用在有机光电器件中。本发明的材料具有良好的醇/水溶性以及光电性能,适合做多层溶液加工器件,同时可避免常见聚电解质中可自由移动的反离子对器件的不利影响,可以作为阴极界面修饰层应用在发光、光伏等有机光电器件中,改善器件性能。
Description
技术领域
本发明涉及高分子光电材料领域,具体涉及一类含氧化胺基团的共轭聚合物光电材料及其应用。
背景技术
自从1990年第一个聚合物电致发光二极管发明以来,聚合物电光电材料得到了学术界和工业界的广泛关注。
为了实现高效的聚合物电致发光器件,电子和空穴分别从阴极和阳极高效的注入是其中的关键。因此,很多高效的聚合物电致发光器件都是采用多层器件结构,即除了发光层外,还含有一层或多层空穴传输/注入层或电子传输/注入层。因此,除了开发优异的发光材料,开发优异的电子传输/注入材料和空穴传输/注入材料也是实现高效聚合物电致发光器件的关键。
此前的研究发现共轭聚电解质及其中性前驱体是一类非常优异的电子注入/传输材料,这类材料在极性溶剂中有很好的溶解性,同时具有优异的电子传输性能,从而使得制备高效多层结构的聚合物电致发光器件成为可能。此外,这类材料还能有效的增加从高功函数的金属(如铝,银,金)向聚合物半导体的电子注入,更有利于以印刷的方式实现高分子多层器件(Adv.Mater.2007,19,810.)。后续的研究表明,这类共轭聚电解质材料不但可用于发光器件,还可作为界面修饰层大幅提高有机太阳能电池、场效应晶体管的性能。
然而,绝大多数的共轭聚电解质都有可自由移动的对离子,对离子有可能能够扩散到发光层从而影响器件的长期稳定性。此外,器件的响应速度与共轭聚电解质的电荷迁移率都受到对离子很大影响。
发明内容
为了克服现有技术中存在的缺点与不足,本发明提供了一类含氧化胺基团的共轭聚合物光电材料及其应用;
本发明提供了一类具有优异的醇/水溶性和高效的电子传输/注入性能的含氧化胺基团的共轭聚合物光电材料,这类聚合物不仅具有非常优异的醇/水溶性,并且没有可自由移动的离子;可以作为电子传输/注入材料或界面修饰材料应用于有机光电器件中(例如有机发光二极管,有机太阳能电池,有机场效应晶体管)。
本发明采用如下技术方案:
本发明所述含氧化胺基团的共轭聚合物,具有如下结构:
其中A、B为共轭的主链单元;n1、n2表示A、B两种单元的相对含量,且n1+n2=100%,R1-R4为C1~C20的直链烷基、支链烷基、环状烷基链或烷氧基链;其中一个以上的碳原子可被氧原子、羟基、氨基、砜基、烯基、炔基、芳基、酯基、羰基取代,氢原子可被氟原子、羟基、氨基、砜基、烯基、炔基、芳基、酯基或羰基取代。
上述A、B为共轭的主链单元,具有如下结构的一种以上:
所述的含氧化胺基团的共轭聚合物光电材料在有机光器件中应用。
本发明与现有技术相比具有以下优点:
(1)本发明所合成的共聚物具有优异的电子注入/传输性能,且不受金属阴极功函数的影响,可使用金、银、铝等高功函数金属作为阴极;
(2)本发明所合成的共聚物含有氧化胺强极性基团,电子注入性能要优于一般的含极性基团的中性聚合物;其与共轭聚电解质相比,由于该共聚物不含移动离子,在使用时不会发生离子迁移而降低器件性能;
(3)本发明所合成的含氧化胺基团的共轭聚合物能溶于极性溶剂如甲醇、乙醇中,而活性层材料一般不溶于这类溶剂,因而在构筑多层器件时活性层与阴极界面修饰层之间不会发生互混现象。
附图说明
图1为本发明中所使用的有机共轭聚合物发光二极管以及有机/聚合物太阳能电池结构示意图;
图2为实施例1、2、3、4所合成的聚合物PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py作为阴极界面修饰层的基于绿光材料P-PPV的有机电致发光器件的电流密度/发光亮度-电压曲线图;
图3为实施例1、2、3、4所合成的聚合物PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py的前驱体PF6N、PF6N25Py、PF6N26Py、PF6N35Py作为阴极界面修饰层的基于绿光材料P-PPV的有机电致发光器件的电流密度/发光亮度-电压曲线图;
图4为实施例1、2、3、4所合成的聚合物PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py以及作为对比的CsF、Ba作为阴极界面修饰层的基于绿光材料P-PPV的有机电致发光器件的电流效率-电流密度曲线图;
图5为实施例1、2、3、4所合成的聚合物PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py的前驱体PF6N、PF6N25Py、PF6N26Py、PF6N35Py以及作为对比的CsF、Ba作为阴极界面修饰层的基于绿光材料P-PPV的有机电致发光器件的电流效率-电流密度曲线图;
图6为实施例1、2、3、4所合成的聚合物PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py及其前驱体PF6N、PF6N25Py、PF6N26Py、PF6N35Py作为阴极界面修饰层的有机电致发光器件的归一化电致发光光谱图;
图7为以实施例2所合成的聚合物PF6NO25Py及其前驱体PF6N25Py作为阴极界面修饰层的基于PCDTBT:PC71BM的太阳能电池器件在100毫瓦/平方厘米,AM 1.5G光照下的电流密度与电压关系;
图8为以实施例2所合成的聚合物PF6NO25Py及其前驱体PF6N25Py作为阴极界面修饰层的基于PCDTBT:PC71BM的太阳能电池器件在暗处的电流密度与电压关系。
具体实施方式
下面通过具体实施例对本发明作进一步的说明,其目的在于帮助更好的理解本发明的内容,具体包括合成、表征与器件制备,但这些具体实施方案不以任何方式限制本发明的保护范围。
本发明中使用的有机/聚合物电致发光二极管以及有机/聚合物太阳能电池结构如附图1所示,都是由阴极1、阴极界面修饰层2、活性层3、空穴传输层4、阳极5、玻璃衬底6依次层叠构成,所述有机/聚合物电致发光二极管以及有机/聚合物太阳能电池的阴极界面修饰层2均由本发明合成的含氧化胺基团的共轭聚合物材料组成。
用核磁共振、凝胶渗透色谱、元素分析等分析手段对含有氧化胺基团的共轭聚合物进行表征,对用上述共轭聚合物制备的聚合物电致发光以及太阳能电池器件进行性能表征。
实施例1:聚{2,7-[9,9’-二(N,N-二乙基己基-6-氧化胺)芴]}(PF6NO)的合成合成路线如下:
(1)单体1、2是按文献[Adv.Mater.,2011,23,1665]公开的方法制备;
(2)聚{2,7-[9,9’-二(N,N-二乙基己基-6-胺基)芴]}(PF6N)的制备
将单体2,7-二(三亚甲基硼酸酯)-9,9’-二(N,N-二乙基己基-6-胺基)芴(728mg,1mmol)、单体2,7-二溴-9,9’-二(N,N-二乙基己基-6-胺基)芴(634mg,1mmol)和10mg四合三苯基磷钯催化剂溶于10ml甲苯和5ml四氢呋喃的混合溶剂中,加入4ml 2mol/L的碳酸钠水溶液,在氩气的保护下,回流反应48小时,然后冷却到室温,将反应液在甲醇中沉淀得到粗品,将粗品溶于四氢呋喃中,过0.45μm的有机滤膜,浓缩,将此溶液在甲醇中沉淀得到聚合物颗粒,用丙酮索氏提取器除去小分子物质,最后在真空烘箱中45℃下干燥24小时,得到产物。1H NMR(300MHz,CDCl3,δ):7.82-7.93(m,6H),3.02-3.05(m,12H),2.90-2.93(m,4H),1.98-2.21(m,4H),0.88-1.23(m,24H)。Mn=13500,PDI=1.403;
(3)聚{2,7-[9,9’-二(N,N-二乙基己基-6-氧化胺)芴]}(PF6NO)的制备取PF6N 100mg,加入10ml的甲醇后再加入过量的30%过氧化氢溶液,反应体系在室温下反应2天,减压蒸馏浓缩后,加入80ml的乙酸乙酯沉淀产物,离心分离并用氯仿洗涤后在真空烘箱中45℃下干燥24小时,得到产物。1H NMR(300MHz,CD3OD,δ):7.82-7.93(m,6H),3.22-3.24(m,12H),3.07-3.18(m,4H),1.56-1.57(m,4H),1.18-1.23(m,24H)。
实施例2:聚{2,7-[9,9’-二(N,N-二乙基己基-6-氧化胺)芴]共-2,5-吡啶}(PF6NO25Py)的合成
合成路线如下:
(1)单体2,5-二溴吡啶直接从百灵威公司购买,用甲醇重结晶后使用;
(2)聚{2,7-[9,9’-二(N,N-二乙基己基-6-胺基)芴]共-2,5-吡啶}(PF6N25Py)的制备;
将实施例1中制备的单体2,7-二(三亚甲基硼酸酯)-9,9’-二(N,N-二乙基己基-6-胺基)芴(728mg,1mmol)、单体2,5-二溴吡啶(237mg,1mmol)和10mg四合三苯基磷钯催化剂溶于10ml甲苯和5ml四氢呋喃的混合溶剂中,加入4ml 2mol/L的碳酸钠水溶液,在氩气的保护下,回流反应48小时,然后冷却到室温,将反应液在甲醇中沉淀得到粗品,将粗品溶于四氢呋喃中,过0.45μm的有机滤膜,浓缩,将此溶液在甲醇中沉淀得到聚合物颗粒,用丙酮索氏提取器除去小分子物质,最后在真空烘箱中45℃下干燥24小时,得到产物。1HNMR(300MHz,CDCl3,δ):9.08(s,1H),7.62-8.15(m,8H),2.40-2.45(m,12H),2.27-2.29(m,4H),1.21-1.24(m,4H),1.08-1.10(m,8H),0.90-0.96(m,12H),0.84(m,4H)。Mn=22401,PDI=1.607;
(3)聚{2,7-[9,9’-二(N,N-二乙基己基-6-氧化胺)芴]共-2,5-吡啶}(PF6NO25Py)的制备
取PF6N25Py 100mg,加入10ml的甲醇后再加入过量的30%过氧化氢溶液,反应体系在室温下反应2天,减压蒸馏浓缩后,加入80ml的乙酸乙酯沉淀产物,离心分离并用氯仿洗涤后在真空烘箱中45℃下干燥24小时,得到产物。1H NMR(300MHz,CD3OD,δ):9.06(s,1H),7.88-8.54(m,8H),3.09-3.12(m,12H),2.87-2.89(m,4H),1.50-1.52(m,4H),0.98-1.18(m,24H)。
实施例3:聚{2,7-[9,9’-二(N,N-二乙基己基-6-氧化胺)芴]共-3,5-吡啶}(PF6NO35Py)的合成
合成路线如下:
(1)单体3,5-二溴吡啶直接从百灵威公司购买,用甲醇重结晶后使用;
(2)聚{2,7-[9,9’-二(N,N-二乙基己基-6-胺基)芴]共-3,5-吡啶}(PF6N35Py)的制备
将实施例1中制备的单体2,7-二(三亚甲基硼酸酯)-9,9’-二(N,N-二乙基己基-6-胺基)芴(728mg,1mmol)、单体3,5-二溴吡啶(237mg,1mmol)和10mg四合三苯基磷钯催化剂溶于10ml甲苯和5ml四氢呋喃的混合溶剂中,加入4ml 2mol/L的碳酸钠水溶液,在氩气的保护下,回流反应48小时,然后冷却到室温,将反应液在甲醇中沉淀得到粗品,将粗品溶于四氢呋喃中,过0.45μm的有机滤膜,浓缩,将此溶液在甲醇中沉淀得到聚合物颗粒,用丙酮索氏提取器除去小分子物质,最后在真空烘箱中45℃下干燥24小时,得到产物。1HNMR(300MHz,CDCl3,δ):8.90(s,2H),8.23(s,1H),7.91-7.92(m,2H),7.66-7.73(m,4H),2.66-2.73(m,8H),2.50-2.56(m,4H),2.11(m,4H),1.40-1.41(m,4H),1.09-1.11(m,8H),1.02-1.07(m,12H),0.74(m,4H),Mn=10300,PDI=1.553;
(3)聚{2,7-[9,9’-二(N,N-二乙基己基-6-氧化胺)芴]共-3,5-吡啶}(PF6NO35Py)的制备
取PF6N35Py 100mg,加入10ml的甲醇后再加入过量的30%过氧化氢溶液,反应体系在室温下反应2天,减压蒸馏浓缩后,加入80ml的乙酸乙酯沉淀产物,离心分离并用氯仿洗涤后在真空烘箱中45℃下干燥24小时,得到产物。1HNMR(300MHz,CD3OD,δ):8.92(s,2H),8.50(s,1H),8.03-8.05(m,2H),7.88-7.94(m,4H),3.09-3.16(m,8H),2.97-3.01(m,4H),2.30(m,4H),1.53-1.54(m,4H),1.14-1.28(m,20H),0.94(m,4H)。
实施例4:聚{2,7-[9,9’-二(N,N-二乙基己基-6-氧化胺)芴]共-2,6-吡啶}(PF6NO26Py)的合成
合成路线如下:
(1)单体2,6-二溴吡啶直接从百灵威公司购买,用甲醇重结晶后使用;
(2)聚{2,7-[9,9’-二(N,N-二乙基己基-6-胺基)芴]共-2,6-吡啶}(PF6N26Py)的制备;
将实施例1中制备的单体2,7-二(三亚甲基硼酸酯)-9,9’-二(N,N-二乙基己基-6-胺基)芴(728mg,1mmol)、单体2,6-二溴吡啶(237mg,1mmol)和10mg四合三苯基磷钯催化剂溶于10ml甲苯和5ml四氢呋喃的混合溶剂中,加入4ml 2mol/L的碳酸钠水溶液,在氩气的保护下,回流反应48小时,然后冷却到室温,将反应液在甲醇中沉淀得到粗品,将粗品溶于四氢呋喃中,过0.45μm的有机滤膜,浓缩,将此溶液在甲醇中沉淀得到聚合物颗粒,用丙酮索氏提取器除去小分子物质,最后在真空烘箱中45℃下干燥24小时,得到产物。1HNMR(300MHz,CDCl3,δ):8.29-8.31(m,2H),8.16(s,2H),7.81-7.94(m,5H),2.38-2.45(m,8H),2.25-2.30(m,4H),2.18(m,4H),1.25-1.28(m,4H),1.10-1.12(m,8H),0.91-0.97(m,12H),0.81(m,4H)。Mn=12100,PDI=1.587。
(3)聚{2,7-[9,9’-二(N,N-二乙基己基-6-氧化胺)芴]共-2,6-吡啶}(PF6NO26Py)的制备;
取PF6N26Py 100mg,加入10ml的甲醇后再加入过量的30%过氧化氢溶液,反应体系在室温下反应2天,减压蒸馏浓缩后,加入80ml的乙酸乙酯沉淀产物,离心分离并用氯仿洗涤后在真空烘箱中45℃下干燥24小时,得到产物。1H NMR(300MHz,CD3OD,δ):8.36-8.53(m,4H),7.98-8.04(m,5H),3.01-3.03(m,8H),2.90-2.91(m,4H),2.31(m,4H),1.46-1.47(m,4H),1.27-1.29(m,8H),1.04-1.09(m,12H),0.86(m,4H)。
实施例5:聚{2,7-[9,9’-二(N,N-二羟乙基己基-6-氧化胺)芴]}(PF6OHNO)的合成
合成路线如下:
(1)单体1、2及聚合物前驱体PF6Br、PF6OHN是按文献[Adv.Mater.2007,19,2010]公开的方法制备;
(2)聚{2,7-[9,9’-二(N,N-二羟乙基己基-6-氧化胺)芴]}(PF6OHNO)的制备;
取PF6OHN100mg,加入10ml的甲醇后再加入过量的30%过氧化氢溶液,反应体系在室温下反应2天,减压蒸馏浓缩后,加入80ml的乙酸乙酯沉淀产物,离心分离并用氯仿洗涤后在真空烘箱中45℃下干燥24小时,得到产物。1H NMR(300MHz,CD3OD,δ):8.05-7.79(m,6H),4.94(m,8H),2.81-2.70(m,16H),1.42-0.94(m,16H)。
实施例6:以实施例1、例2、例3、例4所合成的聚合物PF6NO、PF6NO25Py、PF6NO35Py、PF6NO26Py为例说明此类聚合物作为阴极界面修饰材料在有机/聚合物电致发光器件(ITO阳极/空穴传输层/发光层/阴极界面修饰层/铝阴极)中应用
将ITO导电玻璃,方块电阻~20欧/平方厘米,预切成15毫米×15毫米方片。依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清洗,氮气吹哨后置于恒温烘箱备用。使用前,ITO玻璃片在氧等离子体刻蚀仪中以等离子体轰击10分钟。PEDOT:PSS水分散液(约1%)购自Bayer公司,缓冲层以匀胶机(KW-4A)高速旋涂,厚度由溶液浓度和转速决定,用表面轮廓仪(Tritek公司Alpha-Tencor-500型)实测监控。成膜后,于恒温真空烘箱中驱除溶剂残余、竖膜。在ITO基片上甩PEDOT:PSS的膜厚40纳米左右为佳。
将荧光共轭聚合物P-PPV(P-PPV为发绿光材料)于干净瓶中称量后,转入氮气保护成膜专用手套箱(VAC公司),在甲苯中溶解,以0.45微米滤膜过滤。在PEDOT:PSS膜上甩荧光聚合物,聚合物发光层最佳厚度为70~90纳米。膜厚用Alpha-Tencor-500表面轮廓仪测定。将含氧化胺基团的共轭聚合物PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py,以及胺基取代前驱聚合物PF6N、PF6N25Py、PF6N26Py、PF6N35Py置于洁净小瓶中,转入氮气保护成膜专用手套箱中,用极性溶剂甲醇配成浓度为0.5%的溶液,置于搅拌台上搅拌均匀,用0.45微米滤膜过滤得澄清溶液。将上述溶液在聚合物发光层上旋涂为阴极界面修饰层。在阴极界面修饰层上真空蒸镀铝(80纳米)作阴极。镀腔真空度在3×10-4Pa以下,镀膜速率与各层金属电极薄膜厚度由石英振子膜厚监测仪(STM-100型,Sycon公司制造)实时监控。器件的发光光谱由经校准的ORIEL公司的Instaspec IV电荷耦合光探测仪CCD测得。利用由Keithley236电流电压源及一个经校准的硅光二极管组成的半导体测量系统测出器件的发光强度和外量子效率。外量子效率与发光强度分别用Labsphere公司IS080积分球及PR705光度光谱仪(Photoresearch)校准。为显示本发明所采用的阴极界面修饰层的效果,采用在发光层上真空蒸镀Ba/Al、CsF/Al作为阴极,或者在发光层上真空蒸镀Al作为阴极。
附图2、附图3为基于绿光材料聚苯基取代苯乙烯撑P-PPV作为发光层,四种含氧化胺基团的共轭聚合物(PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py)及其前驱体聚合物(PF6N、PF6N25Py、PF6N26Py、PF6N35Py)分别作为阴极界面修饰层所制得的高分子发光二极管的电流密度/发光亮度-电压曲线图;可以明显看出,四种含氧化胺基团的共轭聚合物(PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py)的加入可以大幅提高器件的亮度。
附图4、附图5为基于绿光材料聚苯基取代苯乙烯撑P-PPV作为发光层,四种含氧化胺基团的共轭聚合物(PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py)及其前驱体聚合物(PF6N、PF6N25Py、PF6N26Py、PF6N35Py)分别作为阴极界面修饰层所制得的高分子发光二极管的电流效率-电流密度曲线图。可以看出,四种含氧化胺基团的共轭聚合物(PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py)的加入大幅提高了器件的电流效率。
附图6为基于绿光材料聚苯基取代苯乙烯撑P-PPV作为发光层,四种含氧化胺基团的共轭聚合物(PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py)及其前驱体聚合物(PF6N、PF6N25Py、PF6N26Py、PF6N35Py)分别作为阴极界面修饰层所制得的高分子发光二极管的有机电致发光器件的归一化电致发光光谱图。可以看出,所有器件的载流子复合区域都在P-PPV层,引入阴极界面层并没有改变器件的载流子复合区域,相关器件的具体性能如表1。
表1:PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py作为阴极界面修饰层器件的电致发光性能
器件结构ITO/PEDOT 4083/Active Layer(P-PPV,80nm)/ETL/Al(~80nm)
其中LEmax:最大电流效率,LE:电流效率,V电压,Von:亮度为1坎德拉/平方米时的电压,Lmax:最大亮度,J:电流密度
以上结果表明采用本发明制备的含氧化胺基团的共轭聚合物(PF6NO、PF6NO25Py、PF6NO26Py、PF6NO35Py)作为阴极界面修饰层,可以大幅提高传统发光材料在高功函金属铝电极器件中的性能,其效果甚至超过了胺基取代前驱聚合物(PF6N、PF6N25Py、PF6N26Py、PF6N35Py)。其器件性能已经接近或超过相应低功函数金属钡作阴极的器件。
上述极性溶剂除甲醇外,还可以为乙醇、水、N,N-二甲基甲酰胺、异丙醇、乙二醇、乙二醇单甲醚等的一种以上。
实施例7:以实施例2所合成的聚合物PF6NO25Py为例说明此类聚合物能作为阴极界面修饰材料在有机/聚合物太阳能电池器件(ITO阳极/空穴传输层/活性层/阴极界面修饰层/铝阴极)中应用
以下实例将对本发明所提出的含氧化胺基团的共轭聚合物光电材料在高分子太阳能器件中的应用工艺过程进行说明,但本发明不限于所列之例。
将ITO导电玻璃,方块电阻~20欧/平方厘米,预切成15毫米×15毫米方片。依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清洗,氮气吹哨后置于恒温烘箱备用。使用前,ITO玻璃片在氧等离子体刻蚀仪中以等离子体轰击10分钟。PEDOT:PSS水分散液(约1%)购自Bayer公司,缓冲层以匀胶机(KW-4A)高速旋涂,厚度由溶液浓度和转速决定,用表面轮廓仪(Tritek公司Alpha-Tencor-500型)实测监控。成膜后,于恒温真空烘箱中驱除溶剂残余、竖膜。在ITO基片上甩PEDOT:PSS的膜厚40纳米左右为佳。
将活性层给体材料共轭聚合物PCDTBT及受体材料PC71BM于干净瓶中称量后(质量比1∶4),转入氮气保护成膜专用手套箱(VAC公司),在邻二氯苯/氯苯混合溶剂(体积比3∶1)中溶解,以0.45微米滤膜过滤。在PEDOT:PSS膜上甩PCDTBT/PC71BM膜,最佳厚度为70~90纳米。膜厚用Alpha-Tencor-500表面轮廓仪测定。将含氧化胺基团的共轭聚合物PF6NO25Py以及胺基取代前驱聚合物PF6N25Py置于洁净小瓶中,转入氮气保护成膜专用手套箱中,用极性溶剂甲醇配成浓度为0.5%的溶液,置于搅拌台上搅拌均匀,用0.45微米滤膜过滤得澄清溶液。将上述溶液在活性层上旋涂为阴极界面修饰层。在阴极界面修饰层上真空蒸镀铝(80纳米)作阴极。镀腔真空度在3×10-4Pa以下,镀膜速率与各层金属电极薄膜厚度由石英振子膜厚监测仪(STM-100型,Sycon公司制造)实时监控。所有制备过程均在提供氮气氛围的手套箱内进行。器件的电流-电压特性,由Keithley236电流电压-测量系统及一个经校正的硅光二极管测得。器件的能量转换效率在标准太阳光谱AM1.5G模拟器(Oriel model 91192)下测得。模拟阳光的能量在测试前用标准硅太阳能电池校正为100毫瓦/平方厘米。为显示本发明所采用的阴极界面修饰层的效果,在活性层上真空蒸镀Al作为阴极。器件在光照下的电流密度与电压关系如图7所示,在暗处的电流密度与电压关系如图8所示。
附图7为基于聚咔唑二噻吩苯并噻二唑(PCDTBT)/富勒烯衍生物(PC71BM)作为活性层,含氧化胺基团的共轭聚合物PF6NO25Py及其前驱体聚合物PF6N25Py分别作为阴极界面修饰层所制得的高分子太阳能电池在100毫瓦/平方厘米,AM 1.5G光照下的电流密度-电压曲线图,可以看出,含氧化胺基团的共轭聚合物PF6NO25Py的加入大幅提高了器件的开路电压与短路电流,相关器件的具体性能如表2所示。
附图8为基于聚咔唑二噻吩苯并噻二唑(PCDTBT)/富勒烯衍生物(PC71BM)作为活性层,含氧化胺基团的共轭聚合物PF6NO25Py及其前驱体聚合物PF6N25Py分别作为阴极界面修饰层所制得的高分子太阳能电池在暗处的电流密度与电压关系。可以看出,引入阴极界面层后,器件的启动电压比纯铝阴极器件提高了0.5~0.6V,表明引入阴极界面层能提高器件的内建电势,从而提高器件的开路电压。
表2:PF6NO25Py作为阴极界面修饰层的太阳能电池器件性能
器件结构ITO/PEDOT 4083/Active Layer(PCDTBT/PC71BM,80nm)/ETL/Al(~80nm)
其中Jsc:短路电流,Voc:开路电压,FF:填充因子,PCE:能量转换效率
以上结果表明采用本发明制备的含氧化胺基团的共轭聚合物PF6NO25Py作为阴极界面修饰层,可以大幅提高传统电池材料在高功函金属铝电极器件中的性能,其效果甚至超过了胺基取代前驱聚合物PF6N25Py。
上述极性溶剂除甲醇外,还可以为乙醇、水、N,N-二甲基甲酰胺、异丙醇、乙二醇、乙二醇单甲醚等的一种以上。
Claims (3)
2.根据权利要求1所述含氧化胺基团的共轭聚合物光电材料,其特征在于所述结构R1-R4中一个以上的碳原子被氧原子、羟基、氨基、砜基、烯基、炔基、芳基、酯基或羰基取代,氢原子被氟原子、羟基、氨基、砜基、烯基、炔基、芳基、酯基或羰基取代。
3.权利要求1至2任一项所述的含氧化胺基团的共轭聚合物光电材料在有机光器件中的应用。
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