CN109593184A - 一种含醌式结构的聚合物半导体及其制备和应用 - Google Patents
一种含醌式结构的聚合物半导体及其制备和应用 Download PDFInfo
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- CN109593184A CN109593184A CN201811417710.9A CN201811417710A CN109593184A CN 109593184 A CN109593184 A CN 109593184A CN 201811417710 A CN201811417710 A CN 201811417710A CN 109593184 A CN109593184 A CN 109593184A
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- AFVLVVWMAFSXCK-UHFFFAOYSA-N α-cyano-4-hydroxycinnamic acid Chemical compound OC(=O)C(C#N)=CC1=CC=C(O)C=C1 AFVLVVWMAFSXCK-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种含醌式结构的聚合物半导体及其制备和应用,结构通式如式(I)所示,制备方法为:将含醌式结构的单体与芳香单元进行共聚制得。本发明所制备的基于此类新型醌式结构的聚合物半导体材料对太阳光谱有较好的匹配,因此可以用作聚合物太阳电池的活性层。本发明所制备的基于此类新型醌式结构的聚合物半导体材料具有较高的载流子迁移能力,因此也可以用于制作聚合物场效应晶体管的活性层。
Description
技术领域
本发明属于聚合物半导体材料及其制备和应用领域,特别涉及一种含醌式结构的聚合物半导体及其制备和应用。
背景技术
2000年诺贝尔化学奖被授予美国加利福尼亚大学的艾伦-J-黑格、美国宾夕法尼亚大学的艾伦-G-马克迪尔米德和日本筑波大学的白川英树,以表彰他们在发现导电聚合物的卓越贡献。与传统的金属相比,导电聚合物具有低成本、质量轻和容易加工等一系列优点引起了人们的广泛关注。随后,大量科研工作者致力于实现具有实际应用功能的导电聚合物(即聚合物金属)。但是,随着研究的深入与人们对共轭聚合物认识的逐步提高,制备聚合物金属成为了合成化学家不可触及的圣杯。共轭聚合物由于具有离域的π电子,因此容易获得荧光性。同时,共轭聚合物能够从太阳光中吸收光子,还能通过共轭分子主链的交叠进行跳跃式传输载流子。这些特性使得共轭聚合物在有机发光二极管(OLED)、聚合物太阳电池(PSCs)和有机场效应晶体管(OFET)等三方面展现出广阔的应用前景。纵观近几十年来共轭聚合物的发展,材料本身的载流子迁移能力对于实现高性能的OLED、PSCs和OFET这三类半导体器件至关重要。具有高度平面的共轭聚合物可以促进分子主链的堆砌,增大芳香单元的交叠程度,利于载流子在聚合物主链之间的跳跃式传输。通过文献调研发现,提高聚合物主链平面性有多种方法,比如引入具有大平面结构的芳香构筑单元(Cheng,Y.-J.;Yang,S.-H.;Hsu,C.-S.,Chem.Rev.2009,109,5868),巧妙利用分子内弱的相互作用(Huang,H.;Yang,L.;Faccetti,A.;Marks,T.J.,Chem.Rev.,2017,117,10291)等等。相对于传统提高分子平面性的策略,在聚合物主链中引入醌式结构却很少被人重视。醌式结构通过双键与芳香单元链接,这可以显著抑制成键单元之间的自由旋转。但是,醌式结构与芳香结构之间的共振,极易形成高度活泼的自由基,这给化学设计并合成具有醌式结构的单体及其相应聚合物带来了极大的挑战。
近些年来,一些包含醌式结构单元的聚合物半导体,但是这些醌式结构具有合成路线长,(Liu,X.;He,B.;Anderson,C.L.;Kang,J.;Chen,T.;Chen,J.;Feng,S.;Zhang,L.;Kolaczkowski,M.A.;Teat,S.J.;Brady,M.A.;Zhu,C.;Wang,L.-W.;Chen,J.;Liu,Y.;J.Am.Chem.Soc.,2017,139,8355;Deng,Y.;Sun,B.;He,Y.;Quinn,J.;Guo,C.;Li,Y.,Angew.Chem.Int.Ed.,2016,55,3459;Kim,Y.;Hwang,H.;Kim,N.-K.;Hwang,K.;Park,J.-J.;Shin,G.-I.,Kim,D.-Y.,Adv.Mater.,2018,30,1706557;Ren,L.;Fan,H.;Huang,D.;Yuang,D.;Di,C.-a.;Zhu,X.,Chem.Eur.J.,2016,22,17136.)已经被成功制备出来,这些半导体材料在聚合物太阳电池和有机场效应晶体管中均取得了不俗的器件性能。但是,通过引入氮原子和原子稳定的相应醌式结构的合成路线较长,成本较高。Kim,D.-Y.等通过在异靛蓝中插入具有醌式结构的噻吩,但是相应的结构还存在不够稳定、提纯较为繁复等缺点。Li,Y.等通过氧化连噻吩的醌式结构可以得到稳定的聚合单体,但是,氧原子的引入会在一定程度上破坏分子主链的平面性。
发明内容
本发明所要解决的技术问题是提供一种含醌式结构的聚合物半导体及其制备和应用,克服现有技术合成路线长,成本高,所得结构稳定性差,平面性不太好等一系列缺陷,该含醌式结构的聚合物半导体能够吸收太阳光且能够高效传输载流子,在聚合物太阳电池和有机场效应晶体管器件时可以作为活性层材料使用。
本发明的一种如式I含醌式结构的聚合物半导体,
其中R为C1~C36的烷基链或具有C1~C36的醚链;X1-X3为氢原子或部分被卤原子取代;
π为芳香π结构共聚单元;n=2~1000。
所述烷基链为直链烷烃、支链烷烃、全氟烷烃、硅氧烷、脂肪醚。
所述烷基链为:
中的一种。所述卤原子为氟、氯原子中的一种或两种,其中,虚线表示基团的连接位置。
所述芳香π的结构共聚单元为:
中的一种或几种,其中,上述式中R为C1~C36的烷基链,波浪线表示基团连接位置。
本发明的一种所述聚合物半导体的制备方法,包括:
提供如下结构式表示的化合物A:
与芳香π结构单元(也可称为芳香结构π单元)、催化剂、溶剂混合进行共聚,制得聚合物半导体;其中R为C1~C36的烷基链或具有C1~
C36的醚链;X1-X3为氢原子或部分被卤原子取代。
上述制备具体为:化合物A与芳香π结构单元、催化剂加入溶剂中,加热回流12-24h,然后加入溴吩、催化剂和邻二甲苯进行封端,加热回流3-5h,冷却至室温,得到固体后进行索氏提纯,溶剂如甲醇、丙酮、正己烷、二氯甲烷、三氯甲烷等。
所述化合物A与芳香π结构单元的摩尔比为1:1-1.2,优选1:1。
所述催化剂为零价钯试剂,优选四三苯基膦钯。
所述催化剂与化合物A的摩尔比为(0.01-0.05):1,优选0.03:1。
所述化合物A由下列方法制备:
提供如下表示的化合物同噻吩并[3,2-b]噻吩的锂盐溶液,在保护气体条件下,室温反应过夜,然后加入氯化亚锡还原反应制备得到化合物A。
所述噻吩并[3,2-b]噻吩的锂盐通过噻吩并[3,2-b]噻吩或者2,5-二溴噻吩并[3,2-b]噻吩与丁基锂作用,在保护气体低温下制得。
化合物B与噻吩并[3,2-b]噻吩的锂盐的摩尔比为(2-2.3):1,优选2.1:1。
所述氯化亚锡还原化合物B与噻吩并[3,2-b]噻吩的锂盐反应得到的产物,氯化亚锡与这个产物的摩尔例为(5-10):1,优选5:1。
优选,所述化合物A的制备具体为:将2,5-二溴并[3,2-b]噻吩加入溶剂(如无水四氢呋喃),冷却至-50~-78℃,在保护气体条件下,滴加锂盐(如正丁基锂),保温5-10min,得到并噻吩的锂盐溶液;将混合物B溶于溶剂(如四氢呋喃)后滴加入上述并噻吩的锂盐溶液中,室温反应过夜,提纯(萃取、干燥、硅胶柱色谱分离),再加入溶剂(如三氯甲烷),保护气体条件下,一次性加入氯化亚锡,室温搅拌过夜,提纯。
所述化合物
所述化合物B由下列方法制备:溴代靛红或者苯环上部分被卤原子取代的溴代靛红、Br-R或I-R、碱,在保护气体的条件制得,其中R为C1~C36的烷基链或具有C1~C36的醚链。所述溴代靛红或者苯环上部分被卤原子取代的溴代靛红与卤代烷基链的摩尔比为1:(1-2),优选1:1.2。
所述溴代靛红或者苯环上部分被卤原子取代的溴代靛红与碱的摩尔比为1:(2-5),优选1:2。
优选,制备具体为:通过溴代靛红或者苯环上部分被卤原子取代的溴代靛红、溶剂(如无水四氢呋喃和无水N,N-二甲基甲酰胺)、碳酸钾作为碱,保护气体条件下,加入溴(碘)代烷烃、支链烷烃、全氟烷烃或硅氧烷,加热至65-70℃反应过夜,提纯。
所述提纯为二氯甲烷分三次萃取,合并有机相并采用无水硫酸镁干燥,将二氯甲烷蒸干后利用硅胶柱色谱分离。
本发明还提供一种光活性层,包括所述聚合物半导体与电子受体材料组成,其中聚合物半导体和电子受体材料的质量比为1:1-3。
所述电子受体材料为富勒烯及其衍生物、小分子有机电子受体材料中的一种或几种。
所述小分子有机电子受体如ITIC系列。
本发明一种所述含醌式结构的聚合物半导体或所述光活性层在聚合物太阳能电池、聚合物场效应晶体管中的应用。
本发明的聚合物可以按照以下过程实现,(R、x1、x2、x3、π、n的定义同前述):
有益效果
(1)本发明的含醌式结构的聚合物半导体具有高度平面结构的优势,且结构新颖,具有独创性;
(2)本发明的含醌式结构的聚合物半导体具有良好的稳定性,相对于5%质量损失,温度为382℃~397℃,在实验室可以以高效经济的合成路线制备,制备的醌式结构的聚合物半导体对太阳光有较好的响应,聚合物的光学带隙为1.2-1.3eV,使聚合物的吸收与太阳光谱更加匹配,实现对太阳光光谱更宽的覆盖,可以作为聚合物太阳电池的活性层组分,所得电池器件的开路电压为0.3伏特,短路电流为0.37毫安每平方厘米,填充因子为33.82%,能量转换效率0.04%;
(3)制备的醌式结构的聚合物半导体具有较高的载流子迁移率0.1cm2/Vs,可以作为有机场效应晶体管中的活性层。
附图说明
图1为本发明实施例1中目标化合物的核磁共振氢谱图;
图2为本发明实施例1中目标化合物的核磁共振碳谱图;
图3为本发明实施例3中目标化合物的核磁共振氢谱图;
图4为本发明实施例3中目标化合物的核磁共振碳谱图;
图5为本发明实施例3中目标化合物的MALDI-TOF图;
图6为本发明实施例4中聚合物P1的(a)热重和(b)差示扫描热量曲线;
图7为本发明实施例4中聚合物P1的(a)薄膜吸收光谱和(b)循环伏安曲线;
图8为本发明实施例4中聚合物P1的聚合物太阳电池电流-电压曲线;
图9为本发明实施例5中聚合物P2的(a)热重和(b)差示扫描热量曲线;
图10为本发明实施例5中聚合物P2的(a)吸收光谱和(b)循环伏安曲线;
图11为本发明实施例5中聚合物P2的场效应晶体管的输出与转移曲线;
图12为本发明实施例6中目标化合物的核磁共振氢谱;
图13为本发明实施例6中目标化合物的核磁共振碳谱;
图14为本发明实施例8中目标化合物的核磁共振氢谱。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
本发明中,所有的基本化学试剂均通过商业化公司购买(如百灵威、阿拉丁、韶远、国药试剂等),如无特殊说明,使用前都未经进一步纯化处理。
无水四氢呋喃通过金属钠和二苯甲酮蒸馏处理制得。所有反应都在保护性气体下进行。
核磁共振氢谱和碳谱通过瑞士布鲁克600MHz核磁共振仪测试得到。
聚合物的分子量测试由高温GPC(Agilent PL-GPC220),使用1,2,4-三氯苯作为流动相,聚苯乙烯作为参比测试完成。
聚合物的紫外光谱由PerkiElmer LAMBDA 950光谱仪测试。
循环伏安曲线由上海辰华CHI730e电化学工作站测试得到。
热分析由赛默飞热重和差示热量扫描系统测试完成。
基质辅助激光解吸电离飞行时间质谱(MALDI-TOF)测试采用布鲁克-道尔顿公司生产的autoflexTEM speed MALDI-TOF质谱,基质为α-氰基-4-羟基肉桂酸。
实施例1
6-溴-1-(5-十烷基取代十七烷基)吲哚啉-2,3-二酮的制备,反应式如下:
在500毫升的两口烧瓶中加入6-溴吲哚啉-2,3-二酮(10.17克,45毫摩尔),碳酸钾(14.9克,108毫摩尔)、100毫升无水四氢呋喃和100毫升无水N,N-二甲基甲酰胺。在氩气保护的条件下,慢慢加入烷基溴(24.82克,54毫摩尔),随后将该反应液加热至70摄氏度反应过夜。反应结束后,冷却至室温,蒸干溶剂后用450毫升二氯甲烷分三次萃取,合并有机相并采用无水硫酸镁干燥,将二氯甲烷蒸干后利用硅胶柱色谱分离得黄色固体(25.9克,产率95.2%)。
1H NMR测试(600MHz,CDCl3,δ,ppm):7.46(d,1H),7.28(dd,1H),7.06(d,1H),3.69(t,2H),1.67(m,2H),1.37-1.10(m,45H),0.87(t,6H)。13C NMR测试((151MHz,CDCl3,δ,ppm):182.49,158.07,152.00,133.66,126.93,126.52,116.41,113.90,77.37,77.16,76.95,40.68,37.48,33.69,33.44,32.07,30.26,29.85,29.81,29.51,27.76,26.83,24.27,22.84,14.27。结合文献(Yang,J.;Zhao,Z.;Geng,H.;Cheng,C.;Chen,J.;Sun,Y.;Shi,L.;Yi,Y.;Shuai,Z.;Guo,Y.;Wang,S.;Liu,Y.,Adv.Mater.2017,29,1702115)表明目标产物为6-溴-1-(5-十烷基取代十七烷基)吲哚啉-2,3-二酮。
实施例中的烷基溴中的烷基还包括:己基,辛基,2-乙基己基,1-辛基壬基等,但不仅限于此。
实施例2
3,3'-(噻吩[3,2-b]噻吩-2,5-双基)双(6-溴-1-(5-十烷基取代十七烷基)3-羟基吲哚啉-2-酮)
在50毫升反应烧瓶中加入2,5-二溴并噻吩(1克,3.35毫摩尔),加入10毫升无水四氢呋喃,冷却至-78摄氏度。在氩气的保护条件下,滴加正丁基锂(4.4毫升,7.04毫摩尔),滴完后保温10分钟。将实施例1制得的烷基取代靛红(4.26克,7.04毫摩尔)溶于15毫升四氢呋喃后,慢慢滴加到上述并噻吩的锂盐溶液中,回到室温反应过夜。滴加水淬灭反应后,使用200毫升二氯甲烷分三次萃取,收集有机相并干燥,蒸干二氯甲烷后利用硅胶柱色谱分离得淡黄色蜂蜜状粘性液体(4克,产率88%)。
1H NMR测试(600MHz,CDCl3,δ,ppm):7.33(t,2H),7.23(t,2H),7.05(s,1H),7.03(d,2H),6.99(s,2H),3.74(m,2H),3.59(m,2H),1.63(m,2H),1.33-1.18(m,90H),0.87(t,12H)。13C NMR测试((151MHz,CDCl3,δ,ppm):176.16,176.13,146.22,145.93,143.74,143.64,138.93,138.86,129.78,129.77,126.54,126.49,126.44,126.39,124.01,123.91,118.23,118.10,112.82,75.97,75.86,40.86,40.76,37.48,33.71,33.66,33.41,32.08,30.28,29.87,29.82,29.52,27.73,26.83,26.80,24.21,22.85,14.28。1H NMR测试和13CNMR测试表明目标产物为3,3'-(噻吩[3,2-b]噻吩-2,5-双基)双(6-溴-1-(5-十烷基取代十七烷基)3-羟基吲哚啉-2-酮)。
实施例化合物中与N相连的烷基还包括:己基,辛基,2-乙基己基,1-辛基壬基等,但不仅限于此。
实施例3
(3Z,3'Z)-3,3'-(噻吩[3,2-b]噻吩-2,5-二亚基双(6-溴1-(5-十烷基取代十七烷基)3-羟基吲哚啉-2-酮)。
在150毫升反应瓶中,加入实施例2所得的化合物(4.0克,2.9毫摩尔)和50毫升三氯甲烷,在氩气的保护条件下,一次性加入氯化亚锡(2.8克,14.5毫摩尔)。将反应温在室温下搅拌过夜,淬灭反应后,使用100毫升二氯甲烷萃取三次,收集有机相并干燥,蒸干二氯甲烷后利用硅胶柱色谱分离得紫黑色固体(0.7克,产率18%)。
1H NMR测试(600MHz,CDCl3,δ,ppm):8.48(s,2H),7.25(d,2H),7.12(d,2H),6.83(s,2H),3.60(t,4H),1.57(m,4H),1.35-0.99(m,90H),0.87(t,12H)。13C NMR测试(151MHz,CDCl3)δ165.68,154.26,152.88,143.73,125.02,124.28,123.39,122.25,121.69,117.74,111.97,40.37,37.69,33.96,33.69,32.29,30.51,30.09,30.04,29.74,28.42,27.05,24.50,23.06,14.48.1H NMR测试和13C NMR测试表明目标产物为(3Z,3'Z)-3,3'-(噻吩[3,2-b]噻吩-2,5-双二烯双(6-溴1-(5-十烷基取代十七烷基)3-羟基吲哚啉-2-酮。
通过基质辅助激光解析串联飞行时间质谱仪(MALDI-TOF,EI[M+H]+)测得分子量为1315.696,与理论分子量1315.706符合,如图5所示。
该化合物具有较高的稳定性,放置于大气条件下一周测试核磁谱图未发现变化,说明该发明的醌式结构这一单元的稳定相对于文献中(Kim,Y.;Hwang,H.;Kim,N.-K.;Hwang,K.;Park,J.-J.;Shin,G.-I.,Kim,D.-Y.,Adv.Mater.,2018,30,1706557)的报道有大幅度提高。
烷基还包括:己基,辛基,2-乙基己基,1-辛基壬基等,但不仅限于此。
实施例4
聚合物P1的制备,反应式如下:
在手套箱中,向5毫升的反应管中加入3,4-二氟-2,5-双三甲基锡噻吩(77毫克,0.172毫摩尔)、(3Z,3'Z)-3,3'-(噻吩[3,2-b]噻吩-2,5-二亚基双(6-溴1-(5-十烷基取代十七烷基)3-羟基吲哚啉-2-酮)(226毫克,0.172毫摩尔)和四三苯基膦钯(3毫克,0.015当量),使用注射器加入2毫升邻二甲苯和0.3毫升无水N,N-二甲基甲酰胺,加热回流24小时,冷却后加入0.1毫升2-溴吩、5毫克四三苯基膦钯和1毫升邻二甲苯封端,加热回流5小时。冷却至室温后,将目标聚合物在无水甲醇中沉淀出来,过滤后使用甲醇、丙酮和石油醚分别索氏提取,将石油醚组分浓缩后再次在无水甲醇中沉降,真空干燥后得黑色聚合物P1共176毫克,产率为80.2%。所得聚合物的数均分子量为10212,得均分子量为52100。
将聚合物P1进行热学性能测试分析,其热重和差示热量扫描曲线如图6所示。在氮气保护条件下,以10摄氏度每分钟升温速率从30至600摄氏度的范围内,聚合物P1相对于5%质量损失,温度为382℃,说明该聚合物有良好的热稳定性,足够应对各种各样的有机光电器件热处理。聚合物P1以2摄氏度每分钟的升降温速率测试差示热量扫描曲线表明,聚合物在30至250度的范围内并没有明显的吸热或者放热峰。
聚合物P1的薄膜吸收光谱如图7a所示,其薄膜吸收覆盖300纳米到900纳米。最大吸收波长位于640纳米处,且其聚合物的薄膜吸收边为964纳米。计算得聚合物的光学带隙为1.3eV,说明醌式结构的引入可以降低聚合物的带隙,使聚合物的吸收与太阳光谱更加匹配。
将聚合物P1进行电化学性能测试,使用仪器为上海辰华的CHI730e电化学工作站测。工作电极为玻碳电极,对电极为铂丝,参比电极为银/氯化银,电解液为0.1M四丁基六氟膦酸胺的乙腈溶液。聚合物P1的循环伏安曲线如图7b所示,使用二茂铁标定。循环伏安曲线表明,聚合物P1的最高占据轨道(HOMO)能级为-5.43eV,最低未占轨道(LUMO)为-3.63eV,证明这一聚合物可以制备具有高稳定性有机场效应晶体管的潜力,可以用于制备聚合物太阳电池。
将聚合物P1与PC61BM共混制备聚合物太阳电池,研究聚合物P1的光伏性能。以ITO为阳极的聚合物太阳电池器件结构为:ITO/PEDOT:PSS/P1:PC61BM/PFN-Br/Al。
器件制作过程为:以预先清洗的ITO玻璃为阳极,在ITO玻璃上旋涂水醇溶聚合物PEDOT:PSS的水溶液,控制其厚度约为30纳米,干燥后继续旋涂聚合物太阳电池活性层,之后旋涂水醇溶聚合物PFN-Br的甲醇溶液,控制该水醇溶性界面约为5纳米,最后真空蒸镀100纳米的金属银作为阴极。在ITO和Ag金属电极间施加负偏压,在100毫瓦每平方厘米的AM1.5模拟太阳光的照射下测量其电池特性。其中,所制备的聚合物P1与PC61BM采用氯苯作为溶剂,按聚合物与PC61BM重量比为1:2混合旋涂作为聚合物太阳电池的活性层,所得电池器件的开路电压为0.3伏特,短路电流为0.37毫安每平方厘米,填充因子为33.82%,能量转换效率0.04%,如图8所示。
实施例5
聚合物P2的制备,反应式如下:
在手套箱中,向5毫升的反应管中加入2,5-双三甲基锡噻吩[3,2-b]噻吩(126毫克,0.27毫摩尔)、(3Z,3'Z)-3,3'-(噻吩[3,2-b]噻吩-2,5-二亚基双(6-溴1-(5-十烷基取代十七烷基)3-羟基吲哚啉-2-酮)(350.5毫克,0.27毫摩尔)和四三苯基膦钯(15毫克,0.05当量),使用注射器加入2毫升邻二甲苯和0.3毫升无水N,N-二甲基甲酰胺,加热回流24小时,冷却后加入0.1毫升2-溴吩、5毫克四三苯基膦钯和1毫升邻二甲苯封端,加热回流5小时。冷却至室温后,将目标聚合物在无水甲醇中沉淀出来,过滤后使用甲醇、丙酮、石油醚和三氯甲烷分别索氏提取,将三氯甲烷组分浓缩后再次在无水甲醇中沉降,真空干燥后得黑色聚合物P2共310毫克,产率约为90%。所得聚合物的数均分子量为13597,重均分子量为47865。
将聚合物P2进行热学性能测试分析,其热重和差示热量扫描曲线如图9所示。在氮气保护条件下,以10摄氏度每分钟升温速率从30至600摄氏度的范围内,聚合物P2相对于5%质量损失温度为396.8℃,说明该聚合物有良好的热稳定性,足够应对各种各样的有机光电器件热处理过程。聚合物P2以2摄氏度每分钟的升降温速率测试差示热量扫描曲线表明,聚合物在30至250度的范围内并没有明显的吸热或者放热峰。
将聚合物P2进行光谱学性能测试,图a分别为聚合物P2在无水氯苯中的溶液吸收及聚合物使用氯苯溶液制备的固态薄膜吸收光谱。从图10a可以看出,聚合物的溶液和薄膜吸收主要集中在600至1000纳米处,最大吸收峰分别位于为800纳米和850纳米处。从溶液至固态时,聚合物P2的吸收光谱变化不大,说明具有醌式结构的聚合物半层体具有高度平面的结构,醌式结构的引入利于分子链之间的堆砌,可以促进载流子在分子链的传输,进而可以得到性能优异的有机场效应晶体管。聚合物的薄膜吸收边位于1026纳米,对应的光学带隙为1.2eV。
将聚合物P2进行电化学性能测试,使用仪器为上海辰华的CHI730e电化学工作站。工作电极为玻碳电极,对电极为铂丝,参比电极为饱和银/氯化银,电解液为0.1M四丁基六氟膦酸胺的乙腈溶液。聚合物P2的循环伏安曲线如图10b所示,使用二茂铁标定。循环伏安曲线表明,聚合物P2的最高占据轨道(HOMO)能级为-5.2eV,最低未占轨道(LUMO)为-3.62eV。循环伏安曲线表明,聚合物P1的最高占据轨道(HOMO)能级为-5.43eV,最低未占轨道(LUMO)为-3.63eV,证明这一聚合物可以制备具有高稳定性聚合物有场效应晶体管的潜力,也可以用于制备聚合物太阳电池。
利用该聚合物P2作为活性层制备了有机场效应管:采用光刻技术在硼硅玻璃上制备源漏电极(3nm Cr and 30nm Au)。玻璃基底使用丙酮和异丙醇超声10分钟,然后用UV处理30分钟。将基底转移至手套箱中,趁热将聚合物的氯苯溶液(5mg mL-1),然后将聚合物薄膜置于手套箱中200摄氏度退火10分钟。随后,甩上一层约400nm的CYTOP介电层。最后,在相应的介电层上蒸镀一层厚度为50nm的铝作为栅极。在空气中,使用Keithley 4200SCS半导体测试仪测试器件的场效应晶体管性能。
聚合物P2作为活性层在290摄氏度退火条件下制备的场效应晶体管的转移曲线,如图11所示,通过计算饱和区的载流子迁移率得到该聚合物的空穴迁移率约为0.1cm2/Vs,说明这一类具有醌式结构的聚合物半导体相对于文献中的醌式结构可以取得具有较高的载流子迁移率。
其中,IDS为漏极电流,μ为载流子迁移率,VG为栅极电压,VT为阈值电压,W为沟道宽度5mm,L为沟道长度20μm,Ci为绝缘体电容7.5×10-2法每平方厘米,载流子的迁移率通过计算公式ID=(w/2L)Ciμ(VG-VT)2获得。
实施例6
在500毫升的两口烧瓶中加入6-溴-5-氟吲哚啉-2,3-二酮(5克,20.49毫摩尔),碳酸钾(6.8克,49.2毫摩尔)、60毫升无水四氢呋喃和60毫升无水N,N-二甲基甲酰胺。在氩气保护的条件下,慢慢加入烷基溴(11.3克,24.6毫摩尔),随后将该反应液加热至70摄氏度反应过夜。反应结束后,冷却至室温,蒸干溶剂后用300毫升二氯甲烷分三次萃取,合并有机相并采用无水硫酸镁干燥,将二氯甲烷蒸干后利用硅胶柱色谱分离得黄色固体(12克,产率94%)。
1H NMR测试(600MHz,CDCl3,δ,ppm):7.36(d,1H),7.10(dd,1H),3.69(t,2H),1.66(m,2H),1.37-1.21(m,45H),0.87(t,6H)。13C NMR测试((151MHz,CDCl3,δ,ppm):13C NMR(151MHz,CDCl3)δ182.19,182.18,157.77,157.76,156.86,155.22,147.40,147.38,120.38,120.22,117.30,117.25,115.23,113.10,112.93,40.74,37.46,33.73,33.66,33.63,33.41,32.07,30.29,30.26,30.22,29.85,29.80,29.51,27.67,26.81,24.24,22.84,14.27.结合文献(Lei,T.;Xia,X.;Wang,J.-Y.;Liu,C.-J.;Pei,J.,J.Am.Chem.Soc.2014,136,2135)表明目标产物为6-溴-5-氟-1-(5-十烷基取代十七烷基)吲哚啉-2,3-二酮。
烷基还包括:己基,辛基,2-乙基己基,1-辛基壬基等,但不仅限于此。
实施例7
在50毫升反应烧瓶中加入2,5-二溴并噻吩(485毫克,1.63毫摩尔),加入10毫升无水四氢呋喃,冷却至-78摄氏度。在氩气的保护条件下,滴加正丁基锂(2.14毫升,3.42毫摩尔),滴完后保温10分钟。将实施例6制得的烷基取代靛红(2.13克,3.42毫摩尔)溶于15毫升四氢呋喃后,慢慢滴加到上述并噻吩的锂盐溶液中,回到室温反应过夜。滴加水淬灭反应后,使用200毫升二氯甲烷分三次萃取,收集有机相并干燥,蒸干二氯甲烷后得淡黄色蜂蜜状粘性液体,直接用于下一步反应。
烷基还包括:己基,辛基,2-乙基己基,1-辛基壬基等,但不仅限于此。
实施例8
在150毫升反应瓶中,加入实施例7所得的化合物(2.3克,1.44毫摩尔)和50毫升三氯甲烷,在氩气的保护条件下,一次性加入氯化亚锡(1.4克,7.2毫摩尔)。将反应温在室温下搅拌过夜,淬灭反应后,使用100毫升二氯甲烷萃取三次,收集有机相并干燥,蒸干二氯甲烷后利用硅胶柱色谱分离得紫黑色固体(0.3克,产率15%)。
1H NMR测试(600MHz,CDCl3,δ,ppm):8.56(s,1H),7.22(d,1H),6.88(d,1H),3.69(t,2H),1.65(m,2H),1.38-1.22(m,45H),0.86(t,6H)。
基于这一氟代的醌式结构,可以与本发明中π的结构单元共聚得一系列聚合物,这些聚合物可以应用于聚合物太阳电池或者场效应晶体管。
Claims (10)
1.一种如式I含醌式结构的聚合物半导体,
其中R为C1~C36的烷基链或具有C1~C36的醚链;X1-X3为氢原子或部分被卤原子取代;
π为芳香π结构共聚单元;n=2~1000。
2.根据权利要求1所述聚合物半导体,其特征在于,所述烷基链为直链烷烃、支链烷烃、全氟烷烃、硅氧烷、脂肪醚。
3.根据权利要求2所述聚合物半导体,其特征在于,所述烷基链为:
中的一种。
4.根据权利要求1所述聚合物半导体,其特征在于,所述卤原子为氟、氯原子中的一种或两种。
5.根据权利要求1所述聚合物半导体,其特征在于,所述芳香π的结构共聚单元为:
中的一种或几种,上述式中R为C1~C36的烷基链。
6.一种权利要求1-5任一所述聚合物半导体的制备方法,包括:
提供如下结构式表示的化合物A
与芳香π结构单元、催化剂、溶剂混合进行共聚,制得聚合物半导体;其中R为C1~C36的烷基链或具有C1~C36的醚链;X1-X3为氢原子或部分被卤原子取代。
7.根据权利要求6所述制备方法,其特征在于,所述化合物A由下列方法制备:
提供如下表示的化合物B同噻吩并[3,2-b]噻吩的锂盐溶液,在保护气体条件下,室温反应过夜,然后加入氯化亚锡进行还原反应,得到化合物A。
8.根据权利要求7所述的制备方法,其特征在于,所述化合物B由下列方法制备:溴代靛红或者苯环上部分被卤原子取代的溴代靛红、Br-R或I-R、碱,在保护气体的条件制得,其中R为C1~C36的烷基链或具有C1~C36的醚链。
9.一种光活性层,其特征在于,包括权利要求1所述聚合物半导体与电子受体材料组成,其中聚合物半导体和电子受体材料的质量比为1:1-3。
10.一种权利要求1所述含醌式结构的聚合物半导体在聚合物太阳能电池、聚合物场效应晶体管中的应用。
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CN110526932A (zh) * | 2019-08-05 | 2019-12-03 | 东华大学 | 一种含平面醌式结构的小分子有机半导体材料及其制备和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107325266A (zh) * | 2017-07-14 | 2017-11-07 | 华南理工大学 | 含醌式结构的n型共轭聚合物及其在有机光电器件中的应用 |
KR20180001026A (ko) * | 2016-06-24 | 2018-01-04 | 엘지전자 주식회사 | 퀴노이드 구조를 포함하는 화합물 |
-
2018
- 2018-11-26 CN CN201811417710.9A patent/CN109593184A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180001026A (ko) * | 2016-06-24 | 2018-01-04 | 엘지전자 주식회사 | 퀴노이드 구조를 포함하는 화합물 |
CN107325266A (zh) * | 2017-07-14 | 2017-11-07 | 华南理工大学 | 含醌式结构的n型共轭聚合物及其在有机光电器件中的应用 |
Non-Patent Citations (3)
Title |
---|
LONGBIN REN ET AL: ""Dithienoindophenines: p-Type Semiconductors Designed by Quinoid Stabilization for Solar-Cell Applications"", 《CHEMISTRY-A EUROPEAN JOURNAL》 * |
YUNFENGDENG ET AL.: ""Thiophene-S,S-dioxidized Indophenine:A Quinoid-Type Building Block with High Electron Affinity for Constructing n-Type Polymer Semiconductors with Narrow Band Gaps"", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
YUNSEUL KIM ET AL.: ""π-Conjugated Polymers Incorporating a Novel Planar Quinoid Building Block with Extended Delocalization and High Charge Carrier Mobility"", 《ADVANCED MATERIALS》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110526932A (zh) * | 2019-08-05 | 2019-12-03 | 东华大学 | 一种含平面醌式结构的小分子有机半导体材料及其制备和应用 |
CN110526932B (zh) * | 2019-08-05 | 2021-08-10 | 东华大学 | 一种含平面醌式结构的小分子有机半导体材料及其制备和应用 |
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