CN109137083A - 一种大面积分子晶体及其制备方法 - Google Patents
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Abstract
本发明公开了一种大面积分子晶体及其制备方法。所述大面积分子晶体的制备方法包括如下步骤：将有机半导体溶液置于疏水性基底上，并用亲水性基底覆盖所述疏水性基底，经生长即在所述亲水性基底上得到分子晶体；所述有机半导体溶液采用的溶剂为氯苯、三氯甲烷、二氯苯和二甲苯中至少一种；所述有机半导体溶液的质量体积浓度为0.01mg/mL～15mg/mL；所述有机半导体溶液的溶质为有机半导体分子。本发明提供的大面积分子晶体具有面积大、均匀度高及表面平整的特征，由这些大面积二维分子晶体制备的场效应晶体管具有较高的载流子迁移率与较低的阈值电压，为后续的P‑N异质结的制备打下了坚实的基础。
Description
技术领域
本发明涉及一种大面积分子晶体及其制备方法，属于有机半导体材料技术领域。
背景技术
自石墨烯的出现，二维原子晶体引起了广泛的关注。当今大部分集中于研究无机材料如氮化硼以及过渡金属硫族化合物，然而由于制备困难，关于有机二维半导体的研究相对较少。众所周知大面积二维分子晶体(2DMC)可以构筑高性能的晶体管，有望超过与基底键合的自组装单分子层的迁移率，其一般低于0.05cm2V-1s-1。大面积二维晶体管可以降低体电阻，减少半导体电荷累积层的暴露，这种低缺陷密度为探测和应用他们的电子传输性质提供了很好的实验平台。因此发展制备大面积分子晶体的技术迫在眉睫。
发明内容
本发明的目的是提供一种大面积分子晶体及其制备方法，大面积分子晶体具有面积大、均匀度高及表面平整的特征，由这些大面积二维分子晶体制备的场效应晶体管具有较高的载流子迁移率与较低的阈值电压，为后续的P-N异质结的制备打下了坚实的基础；本发明方法具有普适性好、操作简便、成本低的特点。
本发明所述的分子晶体指的是以分子间作用力(主要是弱的范德华力)构成的晶体。
本发明中的“大面积”指的是所述分子晶体的二维平面面积尺寸较大，最大可以和基底面积一样大。
本发明所提供的大面积分子晶体的制备方法，包括如下步骤：
将有机半导体溶液置于疏水性基底上，并用亲水性基底覆盖所述疏水性基底，经生长即在所述亲水性基底上得到分子晶体。
上述的制备方法中，所述生长的时间可为0.5小时～2天，如12小时或16小时，在常温(15～25℃)下进行生长即可。
上述的制备方法中，所述有机半导体溶液采用的溶剂可为四氢呋喃、氯苯、三氯甲烷、正己烷、异丙醇、石油醚、二甲基甲酰胺、二甲基乙酰胺、二氯苯、苯、甲苯、二甲苯和均三甲苯中至少一种；
采用滴注、打印、印刷等方式将所述有机半导体溶液加注于所述疏水性基底上；
加注的所述有机半导体溶液的体积没有要求，可根据所述疏水性基底的尺寸确定；
所述有机半导体溶液的质量体积浓度可为0.01mg/mL～15mg/mL，具体可为0.01mg/mL或15mg/mL。
上述的制备方法中，所述有机半导体溶液的溶质为有机半导体分子；
所述有机半导体分子可选自下述至少一种：烷基取代联噻吩类化合物(如α,ω-二己基联六噻吩(DH6T)、α,ω-二全氟己基联四噻吩(DFH4T)、2,2’-3,7-二-3-己基十一烷基-2,6-二氰代亚甲基-并四噻吩(CMUT))、烷基取代苯并噻吩类化合物(如2,7-二辛基[1]苯并噻吩[3,2-b][1]苯并噻吩(C8-BTBT))、烷基取代并五苯类稠环化合物(如二己基取代二苯并[d,d]噻吩并[3,2-b；4,5-b]噻吩(C6-DBTDT))、烷基取代并五噻吩类化合物(如2,7-二己基噻吩[2',3':4,5]噻吩[3,2-b]噻吩[2',3':4,5]噻吩[2,3-d]噻吩(C6-PTA))、苝酰亚胺类化合物(如N,N′-1H,1H-全氟丁基二氰基苝酰亚胺(PDIF-CN2)、苯基取代蒽类化合物(如二己基取代-2,6-二苯联蒽(C6-DPA))和其他多种具有平面结构溶解性良好的共轭有机半导体化合物(如苝、2-苯基蒽或1,4-二-5’-己基-2,2’-二噻吩-5-乙炔基苯((HTEB))。
上述的制备方法中，所述疏水性基底可为十八烷基三氯硅烷(OTS)、2-(苄氧羰基)苄基(BCB)、十八烷基三甲氧基硅烷(OTMS)、六甲基二硅烷(HMDS)、聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)或聚苯乙烯磺酸钠(PSS)修饰的氧化掺杂的硅片。
上述的制备方法中，所述亲水性基底可为氧化掺杂的硅片；
所述亲水性基底的面积要稍大于所述疏水性基底的面积。
本发明制备方法中，由于所述有机半导体溶液采用的所述溶剂均为有机溶剂，大部分都具有毒性，所以需要在通风的环境中进行，但是通风会使得所述溶剂挥发过快，不利于所述分子晶体的生长，因此需要在非敞开式体系中进行所述生长步骤，如半封闭体系或全封闭体系，以使溶剂挥发的速度适宜，不至于过快或过慢，如在器皿中进行。
本发明上述方法制备得到的有机半导体大面积分子晶体也属于本发明的保护范围。
在所述亲水性基底上得到的所述大面积分子晶体均匀度高、结晶性好，为单晶，分子结构严格有序排列，有利于载流子传输以及大规模电路与器件的制备。
所述大面积分子晶体可用于制备电子与光电器件。
所述电子与光电器件可为场效应晶体管、有机发光二极管、有机太阳能能电池和光检测器中的至少一种。
本发明提供的大面积分子晶体具有面积大、均匀度高及表面平整的特征，由这些大面积二维分子晶体制备的场效应晶体管具有较高的载流子迁移率与较低的阈值电压，为后续的P-N异质结的制备打下了坚实的基础。
本发明具有以下优点：
1)方法简单易行，无需复杂昂贵的设备，结果重复性好，具有非常好的普适性；
2)所需有机半导体材料原料少，节省原料；
3)实验在室温下即可进行，基于得到的大面积分子晶体的场效应晶体管器件无需高温退火，节能环保；
4)得到的大面积分子晶体表面平整，易于制备不同的电子与光电器件；
5)所得大面积分子晶体面积较大、单晶质量高，制备的场效应晶体管器件具有高迁移率(无栅压依赖)、高开关比及低阈值电压等特点，具有广阔的应用前景。
6)所得二维分子晶体集成的P-N异质结具有栅压以及光调控两种作用，具有高整流比与高光敏值等特点。
附图说明
图1为本发明制备大面积二维分子晶体(2DMC)方法的示意图。
图2(a)为本发明实施例1制备的厘米级别CMUT大面积分子晶态膜的光学照片。
图2(b)为本发明实施例1制备的CMUT大面积分子晶态膜的光学照片。
图3a和图3b分别为本发明实施例1制备的CMUT大面积分子晶体结构的原子力显微镜照片和高分辨原子力显微镜照片。
图4为本发明实施例1制备的CMUT大面积分子晶体结构的掠入射X射线衍射。
图5a和图5b分别为本发明实施例1制备的CMUT大面积分子晶体结构的场效应晶体管的转移特性曲线和输出特性曲线。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1、CMUT单分子层分子晶体的制备及表征
本实施例使用的CMUT按照文献(Wu,Q.et al.Dicyanomethylene-SubstitutedFused Tetrathienoquinoid for High-Performance,Ambient-Stable,Solution-Processable n-Channel Organic Thin-Film Transistors.Chem.Mater.23,3138-3140(2011))的方法合成。
按照图1所示的示意图，室温条件下在器皿中放置一较小尺寸的的OTS疏水性基底修饰过的氧化掺杂的硅片作为疏水性基底，在其上滴注体积浓度为15mg/mL的有机半导体溶液(溶剂为氯苯)，接着在其上覆盖尺寸稍大于疏水性基底的氧化掺杂的硅片作为亲水性基底，盖上器皿盖子。12h后取出，在上方亲水性基底上便得到了大面积有机半导体二维分子晶体。
图2a为本实施例制备的CMUT厘米级别二维分子晶态膜的光学照片，图2b为本实施例制备的CMUT二维分子晶态膜的光学照片，由两个图可以看出，本发明制备的二维分子晶态膜均一光滑。
图3a和图3b分别为本实施例制备的CMUT二维分子晶体结构的原子力显微镜照片和高分辨原子力显微镜照片，由两个图可以看出，本发明制备的二维分子晶体的排列结构严格有序排列。
图4为本实施例制备的CMUT二维分子晶体结构的掠入射X射线衍射，由图可以看出，二维分子晶体晶格结构，长程有序。
实施例2、器件制备
采用机械探针转移金膜的方法，将实施例1制备的CMUT有机半导体二维分子晶体构筑成场效应晶体管。
图5a和图5b分别为CMUT二维分子晶体结构的场效应晶体管的转移特性曲线和输出特性曲线，可以看出器件的迁移率最高可达2.8cm2V-1s-1。
实施例3、HTEB单分子层分子晶体的制备及表征
本实施例使用的HTEB按照文献(Meng,Q.et al.New Type of OrganicSemiconductors for Field-Effect Transistors with Carbon-carbon Triple Bonds,Ambient-Stable,Solution-Processable n-Channel Organic Thin-FilmTransistors.J.Mater.Chem.19,1477-1482(2009))的方法合成。
按照图1所示的示意图，室温条件下在器皿中放置一较小尺寸的的BCB修饰过的氧化掺杂的硅片作为疏水性基底，在其上滴注一定体积浓度为0.01mg/mL的有机半导体溶液(溶剂为氯苯)，接着在其上覆盖尺寸稍大于疏水性基底的氧化掺杂的硅片作为亲水性基底，盖上器皿盖子。16h后取出，在上方亲水性基底上便得到了大面积有机半导体二维分子晶体。
本实施例制备的HTEB二维分子晶态膜的光学照片与图2b无实质性差异，具有均一光滑的特点。
本实施例制备的HTEB二维分子晶体结构的原子力显微镜照片和高分辨原子力显微镜照片分别如图3a和图3b无实质性差异，说明本实施例制备的二维分子晶体具有排列结构严格有序排列的特点。
本实施例制备的HTEB二维分子晶体结构的掠入射X射线衍射与图4无实质性差异，说明本实施例制备的二维分子晶体晶格结构，长程有序。
按照实施例2的方法将本实施例制备的HTEB分子晶体构筑成场效应晶体管，测试其转移特性曲线和输出特性曲线，可以看出器件的迁移率最高可达1cm2V-1s-1。
由上述各实施例可以看出，本发明方法是一种普适性好、操作简便、成本低的有机半导体二维分子晶体的制备方法。
Claims (9)
1.一种大面积分子晶体的制备方法，包括如下步骤：
将有机半导体溶液置于疏水性基底上，并用亲水性基底覆盖所述疏水性基底，经生长即在所述亲水性基底上得到分子晶体。
2.根据权利要求1所述的制备方法，其特征在于：所述生长的时间为0.5小时～2天。
3.根据权利要求1或2所述的制备方法，其特征在于：所述有机半导体溶液采用的溶剂为氯苯、三氯甲烷、二氯苯和二甲苯中至少一种；
所述有机半导体溶液的质量体积浓度为0.01mg/mL～15mg/mL。
4.根据权利要求1-3中任一项所述的制备方法，其特征在于：所述有机半导体溶液的溶质为有机半导体分子。
5.根据权利要求1-4中任一项所述的制备方法，其特征在于：所述疏水性基底为十八烷基三氯硅烷、2-(苄氧羰基)苄基、十八烷基三甲氧基硅烷、六甲基二硅烷、聚甲基丙烯酸甲酯、聚苯乙烯或聚苯乙烯磺酸钠修饰的氧化掺杂的硅片。
6.根据权利要求1-5中任一项所述的制备方法，其特征在于：所述亲水性基底为氧化掺杂的硅片。
7.权利要求1-6中任一项所述制备方法制备得到的大面积分子晶体。
8.权利要求7所述大面积分子晶体在制备电子与光电器件中的应用。
9.根据权利要求8所述的应用，其特征在于：所述电子与光电器件为场效应晶体管、有机发光二极管、有机太阳能能电池和光检测器中的至少一种。
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