亚酞菁n型半导体材料的合成及其场效应性能研究

Since high mobility and stable n-type organic semiconductormaterials are seriously lack，the development of organic semiconductor devices is restricted. The aim of this project is to develop efficient and stable n-type organic semiconductor materials and reveal the relationship between the molecular structure and the performance of the semiconductor materials. Trifluoro-, hexafluoro- and perfluoro- substituted subphthalocyanine n-type semiconductor materials will be synthesized by introducing different number of fluorine substituent in the axial substituted subphthalocyanine ring and changing the electronegativity of the axial ligand group in this research. Synthesis and purification methods of these target materials will be deeply studied to prepare semiconductor purity subphthalocyanine compounds. Photoelectrochemical properties of synthetic semiconductor materials and their application in organic field-effect transistors will be also investigated. The effect of fluorine number and electronegativity of axial substituted group on the material performance will be discussed. The relationship between the molecular structure and properties of subphthalocyanine semiconductors will be established and their charge transfer mechanism will be also revealed by quantum chemistry calculation. Organic field-effect transistors with good electron mobility, higher on-off current ratio and smaller threshold voltage will be fabricated. Three or four postgraduates will be trained, and three SCI Papers as well as one or two patents will be published.

高迁移率且稳定的n型有机半导体材料严重缺乏，难以满足有机半导体器件的发展。本课题拟开发高效稳定的n型有机半导体材料，揭示亚酞菁类半导体材料的分子结构与性能关系，拟以轴向配位的硼亚酞菁环结构为基础，通过在其环上引入不同数目的氟取代基及改变轴向配位基团的电负性，以期合成出三氟、六氟及全氟取代的亚酞菁类n型半导体材料。深入研究这类材料的合成与提纯方法以制备半导体纯度的氟代亚酞菁化合物；研究合成半导体材料的光电化学性质及在场效应器件中的应用；研究氟取代基数目及轴向配位基团的电负性对合成材料性能的影响。同时，通过量子化学计算建立分子结构与有机半导体材料性能间的关系并揭示材料的电荷传输机制。预期制备的有机场效应晶体管具有良好的电子迁移率、较高的开关电流比和较小的阈值电压；培养硕士研究生3-4名；发表SCI 收录论文3篇，申请发明专利1-2篇。

有机半导体材料是有机场效应器件的重要组成部分，在有机薄膜晶体管中直接影响器件的迁移率等性质。酞菁以及亚酞菁类化合物拥有多π电子共轭体系、良好的热稳定性能以及真空蒸镀成膜等特点，是制造OFETs器件的良好有机半导体材料。本项目通过将氟原子取代基引入到化合物分子中，将p型材料转变成n型材料，并将它们应用到OFETs中。以四氟邻苯二甲腈及邻苯二甲腈为原料合成酞菁及亚酞菁类半导体化合物并研究它们的光热及电化学性质。溶液UV-Vis光谱测试表明合成化合物在Q带具有较强吸收峰。全氟金属酞菁化合物MPcF16（M = Cu, Zn, VO）的LUMO能级值介于-4.57 ~ -4.50 eV之间；硼亚酞菁及全氟硼亚酞菁化合物的LUMO能级值介于-4.08 ~ -4.00 eV之间。氟代金属酞菁化合物MPcF16（M = Cu, Zn, VO）其热分解温度（Td）均在380 ℃以上；亚酞菁及全氟硼亚酞菁化合物的热分解温度在280 ℃以上，它们具有良好的热稳定性。制备的基于合成化合物的场效应器件显示n-沟道特性，具有较高的电子迁移率，在有机光电子器件中具有潜在的应用前景。