CN110872376B - 环化靛蓝受体及聚合物及其制备方法与应用 - Google Patents
环化靛蓝受体及聚合物及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种环化靛蓝受体及聚合物及其制备方法与应用。该聚合物的结构如式I所示,其中,R为C1~C40的直链或支链烷基。本发明还提供了式I所示聚合物的制备方法。本发明的原料为商业化产品;合成路线简单;合成方法具有普适性。以本发明的新型环化靛蓝聚合物为有机半导体层制备的有机场效应晶体管的空穴迁移率最高为1.83cm2V‑1s‑1,电子迁移率最高为1.21cm2V‑1s‑1,在双极性有机场效应晶体管器件中有良好的应用前景。
Description
技术领域
本发明属于材料领域,涉及一种环化靛蓝受体及聚合物及其制备方法与应用。
背景技术
有机场效应晶体管(Organic field-effect transistors,简称OFETs)是一类以π共轭的有机半导体材料为传输层,通过垂直电场来控制材料导电能力的有源器件。OFETs是有机光电器件和电路的关键单元器件,具有重量轻可溶液法加工、柔韧性好等优点,在将来的可折叠的显示屏、手机和电脑等电子产品中会有广阔的应用前景。
OFETs半导体层材料既可以是有机小分子材料,也可以是高分子聚合物材料。高分子聚合物材料具有良好的柔性,可溶液法大面积制备加工等优点,引起了研究者的广泛关注。合成新型的有机聚合物材料对于本领域发展的重要动力。在OFETs器件中起关键作用的有机半导体材料按其载流子传输特性可分为p型,n型材料和双极性材料,其载流子分别为空穴,电子,空穴和电子。目前的高性能OFETs材料大部分为p型材料,高性能的n型材料和双极性材料发展滞后。本发明发展了一种通用的方法,合成了几种新型的环化靛蓝(Bay-annulated indigo,简称BAI)受体及聚合物,并研究了其在有机场效应晶体管中的应用。该聚合物的LUMO能级较低,有利于电子的注入,测试结果表明该类聚合物表现出优异的双极性传输特性。环化靛蓝类聚合物扩展了双极性材料的种类,具有良好的应用前景。
发明内容
本发明的目的是提供一种环化靛蓝(BAI)受体及聚合物及其制备方法与应用。
本发明所提供的BAI类聚合物,其结构通式如式I所示:
所述式I中,R为碳原子总数为1-40的直链或支链烷基;
X1和X2选自如下A类基团中的任意一种;
Ar选自如下B类基团中的任意一种;
其中,所述A类基团的结构式如下所示:
所述B类基团的结构式如下所示:
所述式I中,R具体为1-20的直链或支链烷基;更具体可为2-辛基十二烷基;
n为5-100,具体的,n为10-100,具体为10-50或10-20;更具体的,n为14或13。
所述式I所示聚合物具体为聚合物P2FBAI-V和P2ClBAI-V;
其中,所述聚合物P2FBAI-V的结构式如下:
所述聚合物P2ClBAI-V的结构式如下:
本发明提供的式I所示聚合物的方法,包括如下步骤:
将式VI-a或VI-b所示化合物与双锡化合物在催化剂和配体作用下进行聚合反应,得到所述式I所示聚合物;
R的定义与前述式I中R的定义相同。
上述方法中,双锡化合物选自如下化合物中的任意一种:
所述催化剂选自四(三苯基膦)钯、二(三苯基膦)二氯化钯和三(二亚苄基丙酮)二钯中的至少一种;
所述配体选自三苯基膦、三(邻甲苯基)膦和三苯基胂中的至少一种。
所述式VI-a或VI-b所示化合物的投料摩尔份数为1.00份;
所述双锡化合物的投料摩尔份数为0.95~1.05份;具体为1.00份;
所述催化剂的投料摩尔份数为0.01~0.10份;具体为0.028-0.029份;
所述配体的投料摩尔份数为0.04~0.80份;具体为0.236-0.243份;
所述聚合反应步骤中,温度为90~140℃;具体为110℃或120℃;
反应时间为1分钟~24小时;具体为4分钟-24小时;
所述式VI-a或VI-b所示化合物、双锡化合物、催化剂和配体的投料摩尔用量比具体为1.0:1.0:0.03:0.24;
所述聚合反应的溶剂具体选自甲苯、氯苯和二甲苯中的至少一种。
所述方法还可包括如下提纯步骤:
在所述聚合反应完毕后,将所得反应体系冷却后依次加入浓盐酸和甲醇,室温下搅拌过滤,将所得沉淀用索氏提取器依次用甲醇、丙酮、正己烷抽提,抽提至无色后,除去小分子和催化剂,再用三氯甲烷抽提而得;其中,甲醇和盐酸的体积比具体可为20:1,盐酸的浓度具体可为12M。
此外,上述所述的起始原料式VI-a或VI-b所示化合物也属于本发明的保护范围。
R的定义与式I中R的定义相同。
上述式VI-a和VI-b所示化合物可以按照如下步骤制备所得:
1a)5-氟-2-硝基苯甲醛和丙酮在氢氧化钠的丙酮/水溶液中反应,得到式II-a所示的二氟靛蓝(即2F-indigo);
1b)将步骤1a)所得式II-a所示的二氟靛蓝和2-噻吩乙酰氯在邻二甲苯溶液中进行缩合反应,得到式III-a所示二氟环化靛蓝(即2FBAI);
1c)将步骤1b)所得式III-a所示的二氟环化靛蓝与N-溴代丁二酰亚胺(即NBS)在三氯甲烷溶液中反应,得到式IV-a所示二氟环化靛蓝-二溴(即2FBAI-2Br);
1d)将步骤1c)所得式IV-a所示的二氟环化靛蓝-二溴和3-(2-辛基十二烷基)-5-三丁基锡噻吩在三(二亚苄基丙酮)二钯和三(邻甲苯基)膦催化作用下进行偶联反应,得到式V-a所示二氟环化靛蓝-二噻吩(即2FBAI-2T);
R的定义与式I中R的定义相同。
1e)将步骤1d)所得式V-a所示的二氟环化靛蓝-二噻吩与N-溴代丁二酰亚胺(即NBS)在三氯甲烷溶液中反应,得到式VI-a所示二氟环化靛蓝-二噻吩-二溴(即2FBAI-2T-2Br);
R的定义与式I中R的定义相同。
2a)5-氯-2-硝基苯甲醛和丙酮在氢氧化钠的丙酮/水溶液中反应,得到式II-b所示的二氯靛蓝(即2Cl-indigo);
2b)将步骤2a)所得式II-b所示的二氯靛蓝和2-噻吩乙酰氯在邻二甲苯溶液中进行缩合反应,得到式III-b所示二氯环化靛蓝(即2ClBAI);
2c)将步骤2b)所得式III-b所示的二氯环化靛蓝与N-溴代丁二酰亚胺(即NBS)在三氯甲烷溶液中反应,得到式IV-b所示二氯环化靛蓝-二溴(即2ClBAI-2Br);
2d)将步骤2c)所得式IV-b所示的二氯环化靛蓝-二溴和3-(2-辛基十二烷基)-5-三丁基锡噻吩在三(二亚苄基丙酮)二钯和三(邻甲苯基)膦催化作用下进行偶联反应,得到式V-b所示二氯环化靛蓝-二噻吩(即2ClBAI-2T);
R的定义与式I中R的定义相同。
2e)将步骤2d)所得式V-b所示的二氯环化靛蓝-二噻吩与N-溴代丁二酰亚胺(即NBS)在三氯甲烷溶液中反应,得到式VI-b所示二氯环化靛蓝-二噻吩-二溴(即2ClBAI-2T-2Br);
R的定义与式I中R的定义相同。
上述方法步骤1a)或2a)中,所述水和丙酮比为1:0.5~5,优选1:2.3;反应步骤中,温度为-20~40℃,时间为2~60小时;
上述步骤1b)或2b)中,所述二氟靛蓝或二氯靛蓝和2-噻吩乙酰氯的投料摩尔用量比为1:2.0~8.0,优选1:4;反应步骤中,温度为100~150℃,时间为4~48小时;
上述步骤1c)或2c)中,所述二氟环化靛蓝或二氯环化靛蓝与N-溴代丁二酰亚胺的投料摩尔用量比为1:2.0~2.6,优选1:2.2;反应步骤中,温度为-10~35℃,时间为2~24小时;
上述步骤1d)或2d)中,所述二氟环化靛蓝-二溴或二氯环化靛蓝-二溴和3-(2-辛基十二烷基)-5-三丁基锡噻吩投料摩尔用量比为1:2.0~6.0,优选1:2.4;反应步骤中,温度为80~140℃,时间为1~48小时;
上述步骤1e)或2e)中,所述二氟环化靛蓝-二噻吩或二氯环化靛蓝-二噻吩与N-溴代丁二酰亚胺的投料摩尔用量比为1:2.0~2.6,优选1:2.2;反应步骤中,温度为-10~35℃,时间为2~24小时;
所述步骤1d)或2d)中,所述溶剂选自甲苯、氯苯或邻二氯苯中的至少一种。
上述方法的合成路线如图5A和图5B所示。
上述本发明提供的式I所示化合物在制备有机场效应晶体管中的应用及以该化合物为有机半导体层的有机场效应晶体管,也属于本发明的保护范围。
本发明的优点在于:
1、原料为商业化产品,合成路线简单,单体和聚合物都是新分子,同时可以推广到各种直链或支链环化靛蓝类聚合物的合成;
2、环化靛蓝类聚合物的LUMO能级较低,有利于电子的注入和传输,可用于制备高性能的双极性场效应晶体管器件;
3.以本发明环化靛蓝类聚合物为半导体层制备的有机场效应晶体管有较高的迁移率(μ)和开关比(空穴迁移率最高为1.83cm2V-1s-1,电子迁移率最高为1.21cm2V-1s-1),在双极性OFETs中有良好的应用前景。
附图说明
图1为以本发明提供的环化靛蓝聚合物的紫外可见吸收光谱图。
图2为以本发明提供的环化靛蓝聚合物的循环伏安曲线图。
图3为以本发明提供的环化靛蓝聚合物场效应晶体管的结构示意图。
图4为以本发明提供的环化靛蓝聚合物为半导体层的聚合物场效应晶体管的输出特性曲线图和转移特性曲线图(依次为P2FBAI-V和P2ClBAI-V)。
图5为本发明提供的制备式VI-a和VI-b所示化合物的合成路线。
具体实施方式
下面结合具体实施例对本发明作进一步阐述,但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料均能从公开商业途径获得。
实施例1、聚合物P2FBAI-V
1a)二氟靛蓝(即2F-indigo)
30g 5-氟-2-硝基苯甲醛(0.177mol),1000mL丙酮和440mL水依次加入到圆底烧瓶中,混合液超声至澄清。在搅拌下缓慢滴加2mol/L氢氧化钠(8.5g,0.212mol)水溶液。混合液在室温搅拌48小时。得到的悬浮液过滤,依次用水,乙醇,丙酮洗涤,干燥后得到蓝色产物(18.1g,68.4%)。
结构表征数据如下:
产物在常见氘代溶剂中溶解度很差,因此1H NMR和13C NMR暂未得到。质谱:HREI:[M]+calcd for C16H8F2N2O2:298.0554,found:298.0552.
1b)二氟环化靛蓝(即2FBAI)
二氟靛蓝(8.0g,26.8mmol,1.0equiv)溶于350mL邻二甲苯中,加热至140℃。氮气保护下向该悬浮液中滴加2-噻吩乙酰氯(17.2g,107.2mmol,4.0equiv)的邻二甲苯(30mL)溶液。混合溶液在140℃下搅拌24小时。冷却后过滤,依次用乙醇,丙酮和四氢呋喃洗涤,干燥后得到紫红色产物(5.6g,40.9%)。
结构表征数据如下:
1H NMR(300MHz,CDCl3)δ8.56(dd,J=6.9,3.6Hz,2H),7.88(dd,J=6.9,1.8Hz,2H),7.73(m,4H),7.32(m,4H).产物在常见氘代溶剂中溶解度较差,因此13C NMR暂未得到。质谱:HR-MALDI-TOF:[M]calcd for C28H12F2N2O2S2:510.03083,found:510.03162.
1c)二氟环化靛蓝-二溴(即2FBAI-2Br)
二氟环化靛蓝(3.0g,5.88mmol,1.0equiv)溶于300mL氯仿中,混合液冰浴,搅拌,分批加入N-溴代丁二酰亚胺(2.3g,12.94mmol,2.2equiv)。混合液室温搅拌12小时。加水淬灭。过滤,依次用水,乙醇,丙酮洗涤,干燥后得到黑色产物(2.8g,71.4%)。
结构表征数据如下:
产物在常见氘代溶剂中溶解度很差,因此1H NMR和13C NMR暂未得到。质谱:HR-MALDI-TOF:[M]calcd for C28H10Br2F2N2O2S2:667.84980,found:667.85073.
1d)二氟环化靛蓝-二噻吩(即2FBAI-2T)
氮气下,向二口瓶中依次加入二氟环化靛蓝-二溴(1.2g,1.80mmol,1.0equiv),3-(2-辛基十二烷基)-5-三丁基锡噻吩(2.82g,4.31mmol,2.4equiv),三(二亚苄基丙酮)二钯(164.4mg)和三(邻甲苯基)膦(437.2mg)。接着加入50mL除过气体的邻二氯苯。混合液在110℃下搅拌24小时。冷却至室温,旋蒸除去溶剂,过柱。洗脱剂(石油醚:二氯甲烷=2:1)。最后得到蓝色固体(478mg,21.7%)。
结构表征数据如下:
1H NMR(300MHz,CD2Cl2)δ8.32(dd,J=8.7,4.8Hz,2H),7.85(d,J=9.0Hz,2H),7.55(br,2H),7.16(m,6H),6.88(br,2H),2.54(d,J=6.6Hz,4H),1.66(br,2H),1.31–1.22(m,64H),0.87(m,12H).13C NMR(75MHz,CDCl3)δ161.81,159.36,157.64,144.04,143.31,139.32,136.32,133.12,131.26,127.27,127.18,126.59,126.56,126.45,124.62,122.61,121.78,121.29,118.44,118.36,118.28,118.20,111.78,111.52,38.91,35.10,33.37,31.94,30.07,29.73,29.69,29.38,26.67,22.70,14.12.质谱:HR-MALDI-TOF:[M+H]+calcdfor C76H97F2N2O2S4:1235.64021,found:1235.63936.
1e)二氟环化靛蓝-二噻吩-二溴(即2FBAI-2T-2Br)
二氟环化靛蓝-二噻吩(0.4g,0.324mmol,1.0equiv)溶于30mL氯仿中,混合液冰浴,搅拌,分批加入N-溴代丁二酰亚胺(0.127g,0.712mmol,2.2equiv)。混合液室温搅拌12小时。加水淬灭。氯仿萃取,旋干,过柱。洗脱剂(石油醚:氯仿=2:1)。最后得到蓝色固体(0.42g,93.1%)。
结构表征数据如下:
1H NMR(300MHz,CD2Cl2)δ8.46(dd,J=7.5,4.2Hz,2H),7.96(d,J=7.5Hz,2H),7.67(d,J=3.9Hz,2H),7.28(m,4H),7.05(s,2H),2.52(d,J=7.2Hz,4H),1.72(br,2H),1.31–1.21(m,64H),0.86(m,12H).13C NMR(75MHz,CDCl3)δ162.22,158.96,157.50,142.98,142.69,139.21,139.18,136.11,133.43,131.27,127.14,127.01,126.45,126.40,125.81,124.48,122.76,121.68,118.61,118.28,111.86,111.50,110.11,38.62,34.35,33.38,31.96,30.09,29.75,29.71,29.40,26.60,22.72,14.16,14.15.质谱:HR-MALDI-TOF:[M]calcd for C76H94Br2F2N2O2S4:1392.45125,found:1392.45110.
1f)聚合物P2FBAI-V
将二氟环化靛蓝-二噻吩-二溴(200.0mg,0.144mmol)、反式-1,2-双(三丁基锡)乙烯(87.0mg,0.144mmol)、催化剂三(二亚苄基丙酮)二钯(3.9mg,0.004mmol)、配体三(邻甲苯基)膦(10.5mg,0.034mmol)和甲苯(12mL)加入到反应瓶中,在氩气中进行三次冷冻-抽气-解冻循环除氧,然后将反应混合物加热到110℃进行聚合反应4分钟。冷却后,加入10mL12mol/L的浓盐酸,200mL甲醇,室温下搅拌3h,过滤。得到的沉淀物装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色,除去小分子和催化剂,再用三氯甲烷抽提得到最终产物81.2mg,产率45.0%。
结构表征数据如下:
分子量:GPC:Mn=17.5kDa,Mw=23.8kDa,PDI=1.36,n=14。
元素分析:Anal.calcd.for C78H96F2N2O2S4:C 74.36,H 7.68,N 2.22;found:C69.91,H 7.23,N 2.18.
由上可知,该化合物结构正确,为式I所示化合物P2FBAI-V,结构式如下所示:
实施例2、聚合物P2ClBAI-V
2a)二氯靛蓝(即2Cl-indigo)
30g 5-氯-2-硝基苯甲醛(0.162mol),1000mL丙酮和440mL水依次加入到圆底烧瓶中,混合液超声至澄清。在搅拌下缓慢滴加2mol/L氢氧化钠(7.8g,0.194mol)水溶液。混合液在室温搅拌48小时。得到的悬浮液过滤,依次用水,乙醇,丙酮洗涤,干燥后得到蓝色产物(17.7g,66.1%)。
结构表征数据如下:
产物在常见氘代溶剂中溶解度很差,因此1H NMR和13C NMR暂未得到。质谱:HREI:[M]+calcd for C16H8Cl2N2O2:329.9963,found:329.9960.
2b)二氯环化靛蓝(即2ClBAI)
二氯靛蓝(10.0g,30.2mmol,1.0equiv)溶于400mL邻二甲苯中,加热至140℃。氮气保护下向该悬浮液中滴加2-噻吩乙酰氯(19.4g,120.8mmol,4.0equiv)的邻二甲苯(30mL)溶液。混合溶液在140℃下搅拌24小时。冷却后过滤,依次用乙醇,丙酮和四氢呋喃洗涤,干燥后得到紫红色产物(5.3g,32.3%)。
结构表征数据如下:
1H NMR(300MHz,CD2Cl2)δ8.50(d,J=8.7Hz,2H),8.15(d,J=1.8Hz,2H),7.75(m,4H),7.45(dd,J=8.7,1.8Hz,2H),7.32(t,J=4.5Hz,2H).产物在常见氘代溶剂中溶解度较差,因此13C NMR暂未得到。质谱:HR-MALDI-TOF:[M+H]+calcd for C28H13Cl2N2O2S2:542.97966,found:542.97940.
2c)二氯环化靛蓝-二溴(即2ClBAI-2Br)
二氯环化靛蓝(3.0g,5.52mmol,1.0equiv)溶于300mL氯仿中,混合液冰浴,搅拌,分批加入N-溴代丁二酰亚胺(2.2g,12.1mmol,2.2equiv)。混合液室温搅拌12小时。加水淬灭。过滤,依次用水,乙醇,丙酮洗涤,干燥后得到黑色产物(2.9g,74.9%)。
结构表征数据如下:
产物在常见氘代溶剂中溶解度很差,因此1H NMR和13C NMR暂未得到。质谱:HR-MALDI-TOF:[M]calcd for C28H10Br2Cl2N2O2S2:699.79070,found:699.79124.
2d)二氯环化靛蓝-二噻吩(即2ClBAI-2T)
氮气下,向二口瓶中依次加入二氯环化靛蓝-二溴(2.0g,2.85mmol,1.0equiv),3-(2-辛基十二烷基)-5-三丁基锡噻吩(4.47g,6.85mmol,2.4equiv),三(二亚苄基丙酮)二钯(261.3mg)和三(邻甲苯基)膦(694.6mg)。接着加入100mL除过气体的邻二氯苯。混合液在110℃下搅拌24小时。冷却至室温,旋蒸除去溶剂,过柱。洗脱剂(石油醚:二氯甲烷=3:1)。最后得到蓝色固体(1.15g,31.9%)。
结构表征数据如下:
1H NMR(300MHz,CDCl3)δ8.37(d,J=8.7Hz,2H),8.16(d,J=1.8Hz,2H),7.59(d,J=3.9Hz,2H),7.45(dd,J=8.7,1.8Hz,2H),7.24(d,J=3.9Hz,2H),7.13(d,J=1.2Hz,2H),6.86(s,2H),2.53(d,J=6.6Hz,4H),1.63(br,2H),1.35–1.20(m,64H),0.88(m,12H).13CNMR(75MHz,CDCl3)δ157.53,144.18,143.31,141.21,136.31,133.09,132.05,131.32,131.27,127.04,126.46,126.08,124.46,122.60,121.34,121.25,118.11,38.92,35.11,33.37,31.95,30.09,29.74,29.70,29.39,26.68,22.71,14.15,14.13.质谱:HR-MALDI-TOF:[M]calcd forC76H96Cl2N2O2S4:1266.57317,found:1266.57231.
2e)二氯环化靛蓝-二噻吩-二溴(即2ClBAI-2T-2Br)
二氯环化靛蓝-二噻吩(0.7g,0.55mmol,1.0equiv)溶于50mL氯仿中,混合液冰浴,搅拌,分批加入N-溴代丁二酰亚胺(0.22g,1.21mmol,2.2equiv)。混合液室温搅拌12小时。加水淬灭。氯仿萃取,旋干,过柱。洗脱剂(石油醚:氯仿=3:1)。最后得到蓝色固体(0.70g,89.2%)。
结构表征数据如下:
1H NMR(300MHz,CDCl3)δ8.39(d,J=8.7Hz,2H),8.17(d,J=1.8Hz,2H),7.61(d,J=3.9Hz,2H),7.49(dd,J=8.7,1.8Hz,2H),7.20(d,J=3.9Hz,2H),7.00(s,2H),2.49(d,J=6.9Hz,4H),1.69(br,2H),1.33–1.21(m,64H),0.87(m,12H).13C NMR(75MHz,CDCl3)δ157.37,143.14,142.70,141.05,136.11,133.39,132.18,131.38,131.31,126.85,125.90,125.83,124.42,124.31,122.74,121.12,118.09,110.20,38.64,34.37,33.38,31.97,30.11,29.76,29.72,29.41,26.61,22.73,14.18,14.16.质谱:HR-MALDI-TOF:[M]calcdfor C76H94Br2Cl2N2O2S4:1424.39215,found:1424.39079.
2f)聚合物P2ClBAI-V
将二氯环化靛蓝-二噻吩-二溴(100.0mg,0.070mmol)、反式-1,2-双(三丁基锡)乙烯(42.5mg,0.070mmol)、催化剂三(二亚苄基丙酮)二钯(2.0mg,0.002mmol)、配体三(邻甲苯基)膦(5.2mg,0.017mmol)和甲苯(6mL)加入到反应瓶中,在氩气中进行三次冷冻-抽气-解冻循环除氧,然后将反应混合物加热到110℃进行聚合反应24小时。冷却后,加入5mL12mol/L的浓盐酸,100mL甲醇,室温下搅拌3h,过滤。得到的沉淀物装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色,除去小分子和催化剂,再用三氯甲烷抽提得到最终产物79.4mg,产率87.5%。
结构表征数据如下:
分子量:GPC:Mn=17.7kDa,Mw=31.8kDa,PDI=1.80,n=13。
元素分析:Anal.calcd.for C78H96Cl2N2O2S4:C 72.47,H 7.49,N 2.17;found:C71.46,H 7.55,N 2.15.
由上可知,该化合物结构正确,为式I所示化合物P2ClBAI-V,结构式如下所示:
实施例3、聚合物P2FBAI-V和P2ClBAI-V的光谱性能、电化学性能和场效应晶体管性能
1)聚合物P2FBAI-V和P2ClBAI-V的光谱和电化学性能
图1为聚合物P2FBAI-V和P2ClBAI-V在溶液和薄膜中的紫外可见吸收光谱。
由图1可知,聚合物P2FBAI-V和P2ClBAI-V的光学带隙分别为1.15eV和1.09eV(光学带隙根据公式Eg=1240/λ计算,其中Eg为光学带隙,λ为紫外吸收曲线的边界值)。由图1可知,两个聚合物都具有比较强的分子内电荷转移峰,表明该聚合物分子间作用力较强。
图2为聚合物P2FBAI-V和P2ClBAI-V薄膜的循环伏安曲线。测定在CHI660c电化学工作站进行,用传统的三电极结构测试,铂为工作电极,铂丝为对电极,银/氯化银为参比电极,四丁基六氟磷酸铵作为支持电解质。测试在乙腈溶液中进行。循环伏安的条件为:扫描范围为-1.8~1.8伏特(vs.Ag/AgCl),扫描速率为50毫伏每秒。两个聚合物都具有氧化峰和还原峰,可作为有机半导体材料。根据循环伏安曲线,聚合物P2FBAI-V和P2ClBAI-V的HOMO能级分别为–5.58eV和–5.32eV,LUMO能级分别为–3.72eV和–3.70eV。聚合物具有合适的HOMO能级和LUMO能级,因而是双极性材料。
2)聚合物P2FBAI-V和P2ClBAI-V的场效应晶体管性能
图3为有机场效应晶体管的结构示意图,如图所示,采用玻璃作为衬底,在二次水、乙醇、丙酮中超声清洗后与80℃真空干燥。源漏电极为掩膜版热蒸镀的25nm厚的金为源、漏电极。实施例1~实施例2所得的聚合物为半导体层,将其浓度为10mg/ml的邻二氯苯溶液通过匀胶的方法在玻璃基底上形成有源层,并在200℃热台上退火10分钟。
随后在实施例1~实施例2所得的聚合物薄膜表面通过匀胶形成900纳米厚的聚甲基丙烯酸甲酯作为场效应管介电层,90℃除溶剂60分钟;在绝缘层上通过掩膜版热蒸镀80nm厚铝作为栅电极,完成场效应管制备。
在室温下用通过Keithley 4200SCS半导体测试仪测量了所制备的场效应器件的电学性能。决定OFET的性能的两个关键参数是:载流子的迁移率(μ)和器件的开关比(Ion/Ioff)。迁移率是指在单位电场作用下,载流子的平均漂移速度(单位是cm2V-1s-1),它反映了在电场下空穴或电子在半导体中的迁移能力。开关比定义为:晶体管在“开”状态和“关”状态下的电流之比,它反映了器件开关性能的优劣。对于一个高性能的场效应晶体管,其迁移率和开关比应尽可能的高。
图4为基于两个环化靛蓝聚合物所制备的场效应晶体管的转移特性曲线和输出特性曲线。两个聚合物场效应晶体管显示出了明显的双极性传输特性,说明环化靛蓝聚合物是一类双极性材料。
载流子迁移率可由方程计算得出:
IDS=(W/2L)Ciμ(VG–VT)2(饱和区)
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,L为沟道长度,Ci为绝缘体电容。利用(IDS,sat)1/2对VG作图,并作线性回归,可由此回归线的斜率推算出载流子迁移率(μ),由回归线与X轴的截点求得VT。
迁移率可以根据公式从转移曲线的斜率计算得出,上述各例中制备的聚合物场效应晶体管的器件性能如表1所示。开关比可由图4侧源漏电流的最大值与最小值之比得出。
实验结果表明环化靛蓝聚合物是一类优异的新型的双极性材料。本发明并不限于所报道的这两个材料,改变不同的侧链取代基可以得到一系列的聚合物,且本发明给出的合成方法简单、有效,对于合成新的双极性材料有很大的指导意义。
表1、聚合物场效应晶体管的器件性能
Claims (11)
2.根据权利要求1所述的聚合物,其特征在于:所述n为10-100。
3.根据权利要求2所述的聚合物,其特征在于:所述n为10-50。
4.根据权利要求3所述的聚合物,其特征在于:所述n为10-20。
5.根据权利要求4所述的聚合物,其特征在于:所述n为13-14。
8.根据权利要求6或7所述的方法,其特征在于:所述式VI-a或VI-b所示化合物的投料摩尔份数为1.00份;
所述双锡化合物的投料摩尔份数为0.95~1.05份;
所述催化剂的投料摩尔份数为0.01~0.10份;
所述配体的投料摩尔份数为0.04~0.80份;
所述聚合反应步骤中,温度为90~140℃;
反应时间为1分钟~24小时;
所述聚合反应在溶剂中进行。
9.根据权利要求8所述的方法,其特征在于:所述双锡化合物的投料摩尔份数为1.00份;
所述催化剂的投料摩尔份数为0.028-0.029份;
所述配体的投料摩尔份数为0.236-0.243份;
所述聚合反应步骤中,温度为110℃;
反应时间为4分钟-24小时;
所述聚合反应的溶剂选自甲苯、氯苯和二甲苯中的至少一种。
10.权利要求1-5中任一所述聚合物在制备有机效应晶体管中的应用。
11.一种有机场效应晶体管,其特征在于:所述有机场效应晶体管中,构成半导体层的材料为权利要求1-5中任一所述聚合物。
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