单分子器件的拉伸与断裂过程第一性原理研究:末端基团效应

基于密度泛函理论,研究了含S以及含N末端基团的分子结的拉伸与断裂过程.计算结果显示,对于尖端为锥形的金电极,当末端基团为—S时,拉断分子结的作用力大小为0.,59 nN,大于H原子未解离的—SH从金电极上断裂所需的0.25 nN作用力,但明显小于—S末端从平面金电极上断裂下来的约1.5 nN的作用力.当末端基团是—NH_2或—NO_2时,分子结断裂所需拉力分别为0.45和0.33 nN.体系轨道分布表明,分子与电极通过前线占据轨道耦合后形成的扩展体系分子轨道离域性越好,拉断分子结所需的作用力越大.自然键轨道(natural bond orbital,NBO)分析显示,若分子末端与电极间未形成成键轨道,末端原子上更多的NBO净电荷可以提高分子与电极间结合的稳定性.结合我们以前的研究,可以发现,—S末端和—NH_2末端对金电极界面的微观构型具有明显的识别功能,这为精确操控并理解分子与金电极间的相互作用及界面结构提供了有用信息.     

Gas-sensor property of single-molecule device:F_2 adsorbing effect

The single thiolated arylethynylene molecule with 9,10-dihydroanthracene core(denoted as TADHA) possesses pronounced negative differential conductance(NDC) behavior at lower bias regime. The adsorption effects of F_2 molecule on the current and NDC behavior of TADHA molecular junctions are studied by applying non-equilibrium Green's formalism combined with density functional theory. The numerical results show that the F_2 molecule adsorbed on the benzene ring of TADHA molecule near the electrode can dramatically suppresses the current of TADHA molecular junction. When the F_2 molecule adsorbed on the conjugated segment of 9,10-dihydroanthracene core of TADHA molecule, an obviously asymmetric effect on the current curves induces the molecular system showing apparent rectifier behavior. However, the current especially the NDC behavior have been significantly enlarged when F_2 addition reacted with triple bond of TADHA molecule.     

Electric Field Induced Permanent Superconductivity in Layered Metal Nitride Chlorides HfNCl and ZrNCl

Devices of electric double-layer transistors(EDLTs) with ionic liquid have been employed as an effective way to dope carriers over a wide range. However, the induced electronic states can hardly survive in the materials after releasing the gate voltage V_G at temperatures higher than the melting point of the selected ionic liquid. Here we show that a permanent superconductivity with transition temperature T_c of 24 and 15 K is realized in single crystals and polycrystalline samples of HfNCl and ZrNCl upon applying proper V_G's at different temperatures.Reversible change between insulating and superconducting states can be obtained by applying positive and negative V_G at low temperature such as 220 K, whereas V_G's applied at 250 K induce the irreversible superconducting transition. The upper critical field H_(c2) of the superconducting states obtained at different gating temperatures shows similar temperature dependence. We propose a reasonable scenario that partial vacancy of Cl ions could be caused by applying proper V_G's at slightly higher processing temperatures, which consequently results in a permanent electron doping in the system. Such a technique shows great potential to systematically tune the bulk electronic state in the similar two-dimensional systems.