CN112079996A - 一种高平面n-型聚合物及其制备方法和用途 - Google Patents

一种高平面n-型聚合物及其制备方法和用途 Download PDF

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CN112079996A
CN112079996A CN202010984646.3A CN202010984646A CN112079996A CN 112079996 A CN112079996 A CN 112079996A CN 202010984646 A CN202010984646 A CN 202010984646A CN 112079996 A CN112079996 A CN 112079996A
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王士凡
孙华
堵锡华
董黎明
王晓辉
臧运晓
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Xuzhou University of Technology
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Abstract

本发明公开了一种高平面n‑型聚合物及其制备方法和用途，具有如式(I)所示的结构：
Figure DDA0002688806950000011
本发明通过引入乙烯基，解决两个萘二酰亚胺相连的非共平面的问题，提高n‑型半导体的迁移率。二聚主链骨架的优化实现分子LUMO能级的降低；乙烯基策略提高分子共平面性，结合分子内和分子间弱作用力对分子堆积模式与薄膜形貌的影响。本发明高平面的n‑型聚合物能够作为有机半导体层应用于有机薄膜场效应晶体管器件中，共平面分子结构显著提高器件的稳定性和电子传输性能，为有机场效应晶体管及互补电路的应用奠定基础。

Description

一种高平面n-型聚合物及其制备方法和用途
技术领域
本发明属于高分子光电材料技术领域，特别涉及一种基于主链结构为萘二酰亚胺二聚体的n-型聚合物及其在有机场效应晶体管器件中的应用。
背景技术
有机电子材料及其在信息领域的应用是近年来一个崭新的研究方向，它体现了化学与材料、微电子等多学科的结合，并逐渐形成一个新兴的行业―有机电子产业。有机场效应晶体管(OFET)具有质轻、价廉、可溶液加工和柔韧性好等优点，使其在大面积、低成本的有机电子产品方面有广阔的应用前景，成为有机电子学中的研究热点。
根据晶体管通道中主载流子的极性，半导体聚合物可分为p型(空穴主载)、n型(电子主载)和双极型(空穴与电子)。人们在p-型半导体聚合物的开发上投入了大量的努力，其空穴迁移率超过10cm2 V-1 s-1，优于非晶硅基薄膜晶体管。然而，与成熟的p-型半导体聚合物相比，高性能的n-型半导体聚合物的出现和发展一直比较缓慢，大部分n-型半导体聚合物迁移率低，对空气敏感，很容易与空气中的氧气和水反应，制备的器件稳定性差，限制了它的实际应用。因此，开发高性能n-型有机半导体材料，特别是大气稳定、易加工的n-型半导体聚合物对于构筑大面积、柔性有机逻辑电路具有非常重要的意义。
萘二酰亚胺(NDI)，具有强吸电子特性，LUMO能级低于-3.6eV，其聚合物一般为n-型材料。该受体单元最早于2009年由Facchetti等报道，NDI基聚合物N2200的顶栅有机场效应晶体管的电子迁移率可达到0.85cm2/V s，并且具有良好空气稳定性，受到有机电子领域的广泛关注，成为广泛研究的n-型有机半导体之一。NDI为潜在可构筑高性能纯n-型半导体聚合物的优异单元，以其二聚体构筑多受体型主链结构具有强吸电子特性，并且可有效降低LUMO能级，增强其电子传输能力。然而现阶段NDI二聚体研究较少，特别是用来构筑聚合物骨架。主要是NDI单元具有一定的空间位阻，不利于高分子主链取得高共面性，两个NDI直接相连将出现A-A的“非平面骨架”问题，从而在一定程度上限制了NDI类高分子半导体器件性能的进一步提升。
发明内容
本发明的目的是提供一种高平面n-型聚合物及其制备方法，以解决两个萘二酰亚胺相连的非共平面的问题，提高n-型半导体的迁移率。
本发明另一目的在于提供上述高平面n-型聚合物的用途。
为实现上述目的，本发明采用的技术方案为：
一种高平面n-型聚合物，具有如式(I)所示的结构：
Figure BDA0002688806930000021
其中：
n为小于等于100万的正整数；
R1、R2彼此独立地选自C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30的取代或未取代的环烷基、C1-C30的取代或未取代的烷氧基、C1-C30的取代或未取代的硅烷基、C6-C60的取代或未取代的芳基，或者C3-C30的取代或未取代的杂芳基，所述杂芳基具有至少一个独立地选自氮、硫、氧、磷、硼或硅的杂原子；
R3选自氢、卤素、氰基、C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30的取代或未取代的环烷基、C1-C30的取代或未取代的烷氧基、C1-C30的取代或未取代的硅烷基；
Ar选自苯基、萘基、薁基、芴基、菲基、蒽基、芘基、五苯基、吡喃基、苯并吡喃基、呋喃基、苯并呋喃基、异苯并呋喃基、氧杂蒽基、噁唑啉基、二苯并呋喃基、噻吩基、噻吨基、噻蒽基、萘并噻吩基、二苯并噻吩基、苯并噻吩基、吡咯基、吡唑基、碲唑基、硒唑基、噻唑基、吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基、喹嗪基、咔唑基、芴并咔唑基、吲哚并咔唑基、咪唑基、吩嗪基、咔啉基、吩碲嗪基、三苯二噻嗪基、氮杂二苯并呋喃基、三苯二噁嗪基、苯并噻唑基、苯并咪唑基。
优选的，所述高平面n-型聚合物的结构式如式I-1至I-18任一所示：
Figure BDA0002688806930000031
一种高平面n-型聚合物的制备方法，以式(III)所示化合物和式(II)所示化合物为原料，在催化剂作用下，经偶联反应得到，反应式如下：
Figure BDA0002688806930000041
所述催化剂为Pd(PPh3)4。
本发明的高平面n-型聚合物在有机场效应晶体管器件中的用途。
所述有机场效应晶体管器件由下至上依次包括基底、有机半导体层、介电层、栅极，所述有机半导体层处设置有源电极和漏电极，有机半导体层的材质为所述高平面n-型聚合物。
有益效果：相比于现有技术，本发明的优点在于：
(1)本发明采用萘二酰亚胺二聚的策略合成多受体的聚合物骨架，另外选取不同结构的吸电子或给电子基团Ar改变聚合物分子的主链结构，结合吸电子基团R3，如氟等，从而降低分子的LUMO能级，从而获得n-型半导体材料。
(2)本发明通过在引入乙烯基来解决萘二酰亚胺二聚时存在的非共平面问题，延长主链的共轭长度，结合Ar和R3，形成分子内和分子间的弱作用力，提高π共轭度，获得空气稳定、高迁移率的n-型半导体材料。
附图说明
图1为两个个分子的化学结构式、最优空间构型、电子云分布和HOMO/LUMO能级；
图2为有机场效应晶体管器件结构示意图。
具体实施方式
下面结合实施例，对本发明作进一步描述，以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
本实施例提供一种高平面的n-型聚合物，具有下述式I-1所示的结构：
Figure BDA0002688806930000051
式I-1所示高平面的n-型聚合物的合成路径如下所示：
Figure BDA0002688806930000052
式I-1所示高平面的n-型聚合物的制备方法具体包括以下步骤：将0.12mmol的式III-1所示化合物，0.12mmol的式II-1所示化合物,6.0mg(0.0048mmol)的Pd(PPh3)4加入10mL史莱克管中，氮气保护，加入干燥的甲苯(1.9mL)和DMF(0.5mL)，搅拌于120℃反应过夜，冷却至室温后将溶液倒入100mL的甲醇中沉淀、抽滤，产物依次用甲醇和丙酮进行索氏抽提。最后收集三氯甲烷进行浓缩，在甲醇中重沉淀、过滤。将提纯后的产物经过真空干燥得到深色固体，产率约90％。元素分析：(C118H176N4O8S2)理论值：C,76.91；H,9.63；N,3.04；实测值：C,71.92；H,9.60；N,2.94。
式III-1所示化合物的合成步骤：将0.4mmol的式IV-1所示化合物，0.2mmol的式V-1所示化合物，40mg的Pd(PPh3)4加入50mL史莱克管中，氮气保护，加入40mL干燥的甲苯，搅拌于90℃反应过夜，冷却至室温后萃取，柱层析提纯得式III-1所示化合物。元素分析：(C110H170Br2N4O8)理论值：C,71.95；H,9.33；N,3.05；实测值：C,71.92；H,9.30；N,3.04，HRMS(ESI)m/z(M+)：理论值：9243.46；实测值：9243.72。
选取部分聚合物片段进行理论计算，采用密度泛函理论，以B3LYP/6-31G(d)为计算方法，所得结果如图1。在两个萘二酰亚胺中间引入乙烯基，有效的扩展了π共轭，萘二酰亚胺二聚策略聚合物(P2NDIV-2T，即I-1)与单个萘二酰亚胺聚合物(PNDI-2T)相比，有效降低了LUMO能级。
实施例2
本实施例提供一种高平面的n-型聚合物，具有下述式I-2所示的结构：
Figure BDA0002688806930000061
式I-2所示高平面的n-型聚合物的合成路径如下所示：
Figure BDA0002688806930000062
式I-2所示高平面的n-型聚合物的制备方法与实施例1中的式I-1所示化合物相同，得深色固体，产率约89％。元素分析：(C118H174F2N4O8S2)理论值：C,75.44；H,9.34；N,2.98；实测值：C,75.02；H,9.62；N,2.94。
实施例3
本实施例提供一种高平面的n-型聚合物，具有下述式I-3所示的结构：
Figure BDA0002688806930000063
式I-3所示高平面的n-型聚合物的合成路径如下所示：
Figure BDA0002688806930000071
式I-3所示高平面的n-型聚合物的制备方法与实施例1中的式I-1所示化合物相同，得深色固体，产率约92％。元素分析：(C116H174N6O8S2)理论值：C,75.52；H,9.51；N,4.56；实测值：C,75.32；H,9.42；N,4.94。
实施例4
本实施例提供一种高平面的n-型聚合物，具有下述式I-4所示的结构：
Figure BDA0002688806930000072
式I-4所示高平面的n-型聚合物的合成路径如下所示：
Figure BDA0002688806930000073
式I-4所示高平面的n-型聚合物的制备方法与实施例1中的式I-1所示化合物相同，得深色固体，产率约85％。元素分析：(C124H178N6O8S3)理论值：C,75.33；H,9.08；N,4.25；实测值：C,75.41；H,9.02；N,4.34。
实施例5
本实施例提供一种高平面的n-型聚合物，具有下述式I-5所示的结构：
Figure BDA0002688806930000081
式I-5所示高平面的n-型聚合物的合成路径如下所示：
Figure BDA0002688806930000082
式I-5所示高平面的n-型聚合物的制备方法与实施例1中的式I-1所示化合物相同，得深色固体，产率约80％。元素分析：(C134H195N7O8S3)理论值：C,75.62；H,9.24；N,4.61；实测值：C,75.72；H,9.22；N,4.59。
实施例6
本实施例提供一种有机场效应晶体管器件，如图2所示，在SiO2载体上构建了顶栅底接触结构的器件。十八烷基三氯硅烷(OTS)修饰过的二氧化硅作衬底，铬/金(分别为3nm/12nm)源电极和漏电极通过光刻法制备，通道长度L＝20μm，宽度W＝1mm。将有机半导体层的薄膜以3000rpm的速度从CHCl3溶液(约5mg/mL)中流延，并在手套箱中于120℃退火10分钟。Cytop作为介电层。使用Agilent 4155B半导体参数分析仪测量OFET器件的特性。使用以下公式在饱和状态下确定迁移率：IDS＝(μWCi/2L)(VG-VT)2其中IDS是漏源电流，μ是场效应迁移率，W是沟道宽度，L是沟道长度，Ci是栅极介电层的每单位面积的电容，VT是阈值电压。
有机半导体层分别使用以上实施例中所合成的高平面n-型聚合物I-1,I-2,I-3,I-4和I-5,其有机场效应晶体管器件性能参数如表1：
表1
Figure BDA0002688806930000091
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (6)

1.一种高平面n-型聚合物，其特征在于：具有如式(I)所示的结构：
Figure FDA0002688806920000011
其中：
n为小于等于100万的正整数；
R1、R2彼此独立地选自C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30的取代或未取代的环烷基、C1-C30的取代或未取代的烷氧基、C1-C30的取代或未取代的硅烷基、C6-C60的取代或未取代的芳基，或者C3-C30的取代或未取代的杂芳基，所述杂芳基具有至少一个独立地选自氮、硫、氧、磷、硼或硅的杂原子；
R3选自氢、卤素、氰基、C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30的取代或未取代的环烷基、C1-C30的取代或未取代的烷氧基、C1-C30的取代或未取代的硅烷基；
Ar选自苯基、萘基、薁基、芴基、菲基、蒽基、芘基、五苯基、吡喃基、苯并吡喃基、呋喃基、苯并呋喃基、异苯并呋喃基、氧杂蒽基、噁唑啉基、二苯并呋喃基、噻吩基、噻吨基、噻蒽基、萘并噻吩基、二苯并噻吩基、苯并噻吩基、吡咯基、吡唑基、碲唑基、硒唑基、噻唑基、吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基、喹嗪基、咔唑基、芴并咔唑基、吲哚并咔唑基、咪唑基、吩嗪基、咔啉基、吩碲嗪基、三苯二噻嗪基、氮杂二苯并呋喃基、三苯二噁嗪基、苯并噻唑基、苯并咪唑基。
2.根据权利要求1所述的高平面n-型聚合物，其特征在于：其结构式如式I-1至I-18任一所示：
Figure FDA0002688806920000021
3.一种权利要求1或2所述的高平面n-型聚合物的制备方法，其特征在于：以式(III)所示化合物和式(II)所示化合物为原料，在催化剂作用下，经偶联反应得到，反应式如下：
Figure FDA0002688806920000031
4.根据权利要求3所述的高平面n-型聚合物的制备方法，其特征在于：所述催化剂为Pd(PPh3)4。
5.权利要求1或2所述的高平面n-型聚合物在有机场效应晶体管器件中的用途。
6.根据权利要求5所述的用途，其特征在于：所述有机场效应晶体管器件由下至上依次包括基底、有机半导体层、介电层、栅极，所述有机半导体层处设置有源电极和漏电极，有机半导体层的材质为所述高平面n-型聚合物。
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