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中国物理学会期刊

偶氮类分子结整流与开关特性理论研究:立体异构效应

Theoretical Study on Rectification and Switching Properties of Azo Molecular Junctions: Stereoisomerism Effects

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  • 含偶氮中心的分子由于具有顺反两种立体异构体,在单分子功能器件设计中受到广泛关注。我们在密度泛函理论基础上利用非平衡格林函数方法研究了偶氮苯和偶氮萘分子结体系的电输运性质。计算表明采用不对称连接的硫酚末端锚接基不仅可以使偶氮苯和偶氮萘分子结体系产生很好的整流特性,而且能够明显提高低偏压下分子结在顺反立体异构变化中的开关比。分子体系的电输运特性由最低未占据分子轨道(LUMO)贡献的透射峰主导,负偏压下LUMO贡献的透射峰远离费米能级,抑制了电子在分子结中的透射概率,从而使偶氮苯和偶氮萘分子体系产生了较高的整流比。计算结果显示,处于“关”态的分子结体系,分子末端与漏极的连接点一般位于电子透射本征态的节面附近,这导致了电子进入漏电极时产生了明显量子干涉相消效应。因此控制电子透射波的量子干涉可以有效提高分子结的开关与整流性能。侧基调控不仅可以有效提高反式偶氮萘分子体系在低偏压下的整流性能,而且使偶氮萘分子的立体异构开关特性在正负偏压下发生翻转,这一特性可以用于设计单分子逻辑电路。

    Azobenzene derivatives, which can change their conformation between cis and trans stereoisomers upon ultraviolet or visible light irradiation, have attracted considerable attention in the designs of single-molecule functional device. The electronic transport properties of azobenzene and azonaphthalene molecular junctions are investigated by using the density functional theory and non-equilibrium Green's function method . The calculations demonstrate that the azobenzene and azonaphthalene molecular junctions with asymmetric thiol anchoring groups show excellent rectification properties. In addition, the low-bias switching ratio of the molecular junctions during the cis-trans stereoisomerization transformations is significantly enhanced. The electronic transport properties of the molecular systems are dominated by the lowest unoccupied molecular orbitals (LUMOs). In the negative bias regime, the LUMO-contributed transmission peaks move away from the Fermi level, thereby suppressing the transmission probability of the azo molecular junctions. This mechanism is responsible for the high rectification ratio of the azobenzene and azonaphthalene molecular junctions. The numerical results show that, for the molecular junctions with "off" states, the contacts between the molecules and the drain electrodes are located near the nodes of transmission eigenstates, which lead to significant destructive quantum interference effect when electrons enter the drain electrode. Therefore, controlling the quantum interference of the electron wave can effectively enhance the switching and rectification performance of the molecular junction. Side-substituent not only enhances the low-bias rectification performance of the trans- azonaphthalene molecular junctions, but also results in the reverse of stereoisomeric switch of the azonaphthalene molecular junction under positive and negative biases. This property can be used to design single-molecule logic circuits. Compared with the caluculations of the HSE06 hybrid functional, the HOMO-LUMO energy gaps caluculated with the PBE functional are relatively smaller, which results in higher current values. Consequently, the rectification characteristics obtained using the HSE06 hybrid functional shift towards the higher bias region compared to those obtained using the PBE functional.

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