自组装双硫醇分子膜在交流电场下的介电特性

研究了交流电场下双巯基烷烃硫醇自组装分子膜的阻抗谱.利用汞金属作为衬底,制备出双巯基烷烃硫醇自组装分子膜,并通过交流频谱仪对其进行频谱的扫描.通过实验明确了膜的作用范围为阻抗谱中频部分,并给出相应的等效电路对阻抗谱进行了拟合.同时,根据损耗谱中损耗峰随硫醇碳链原子数的增加而向低频方向移动的现象得出双巯基硫醇Cn(n=3～10)在交流电场下的动能为14～48 meV.     

自组装硫醇分子膜电输运特性的导电原子力显微镜研究

在Au(111)表面自组装制备了不同链长的烷烃硫醇分子膜，并利用导电原子力显微镜研究了 自组装分子膜的输运特性随外加压力的变化.结果发现分子膜的电流随压力的增加而增大， 其变化特征可以较好地用Hertz模型描述.在相同压力和电压下，通过分子膜的电流随分子链 长的增加呈指数衰减，其衰减因子先随压力的增加而减小，后逐渐趋于稳定.此外，长链分 子自组装膜的电流随压力的变化比短链分子膜更为明显.分析表明，自组装硫醇分子膜输运 特征的压力依赖性主要源于电荷在分子膜中的链间隧穿过程. 关键词： 分子自组装 输运特性 原子力显微镜     

介质pH对银基上4-甲基-4H-3-巯基-1,2,4-三氮唑成膜结构和缓蚀性能影响的SERS和电化学研究

在不同pH介质中,缓蚀试剂4-甲基-4H-3-巯基-1,2,4-三氮唑(4-MTTL)都能在银基底上形成自组装膜。SERS光谱表明:当pH=3时,4-MTTL分子是以硫醇式,通过两个氮原子为吸附位点,以较平躺方式在银表面构筑自组装膜;当介质为pH=7和pH=11时,4-MTTL以硫醇式,通过氮和硫原子为吸附位点倾斜或垂直方式作用于银表面。由于后者的吸附方式比前者更为垂直于表面,所以形成的膜中分子排列更为致密。电化学极化实验也表明,在pH=3的条件下,形成的4-MTTL单层有更正的腐蚀电位;在pH=11时,构筑的膜缓蚀能力强于pH=7的。并由电化学交流阻抗数据解析了相应的缓蚀机理。     

表面增强拉曼光谱研究正己硫醇分子在银基底表面自组装过程的时间和浓度因素影响

表面增强拉曼光谱(SERS)是一种具有超灵敏检测能力的谱学技术,可以在单分子水平上检测分子结构的动态变化过程。烷基硫醇的自组装膜是一类典型的类晶态有序结构薄膜,在仿生、材料、电子和化学等领域有着重要的应用,越来越受到人们的关注。本文利用SERS对正己硫醇(hexanethiol,HT)分子在银基底上的吸附和组装过程进行研究,对HT的拉曼和自组装膜SERS光谱进行了指认。根据C-S,C-C和CH₃键结构的反式和旁式的特征光谱信息,研究HT吸附在银纳米粒子表面的构象,以及自组装膜结构的有序性。研究了吸附时间和浓度两个因素对成膜规律产生的影响。实验结果表明,当HT溶液浓度较高时,HT单层膜成膜速率较快,且有序性较好;当HT溶液浓度较低时,HT单层膜成膜速率较慢,且有序性较差。这一研究结果对成膜动力学以及烷基硫醇的有序单层膜的制备具有重要的指导意义,为基于烷基硫醇的自组装单层膜在防腐、器件和生物方面的应用奠定了基础。     

硫醇自组装分子膜末端基团对其电荷输运特性的影响

在金(111)表面组装了具有不同末端基团的硫醇单层分子膜，并利用导电原子力显微镜研究了分子膜的电输运性质，发现不同末端基团的分子自组装膜的导电能力有明显差别.结合X射线光电子能谱，研究了末端基团中碳原子的结合能与相应硫醇分子电导的关系.结果表明不同末端基团分子膜导电能力的差别可归结为末端基团碳原子电子结合能的差异.结合能越高，末端基团电子的局域化程度越强，导致电子有效注入分子主链的势垒越高，从而减弱了分子膜对电子的输运能力.此外，实验还发现不同末端基团的硫醇单层分子膜有不同的表面电势，导致分子膜电流电压特性曲线的零点产生偏离. 关键词： 分子自组装膜 输运特性 末端基团 导电原子力显微镜     

ω-巯基己酸自组装修饰金电极及其对叶绿素的催化氧化还原作用

用自组装技术以ω－巯基己酸（６－ＭＨＡ）对金电极进行修饰。通过表面增强拉曼散射（ＳＥＲＳ）光谱和电化学方法研究了６－ＭＨＡ自组装单分子膜（ＳＡＭ）在金电极表面的形成及由此引起的电极双电层电容的变化,并研究了该自组装单分子膜的结构模型及修饰电极对叶绿素的催化性能。结果表明,６－ＭＨＡ在金电极表面能够形成一层自组装膜,并对叶绿素的氧化还原过程具有明显的催化作用。     

溶液酸碱性对金纳米粒子在端基功能化单分子膜表面组装影响的SERS光谱研究

在4,4’-二硫联吡啶在Au表面形成自组装单分子层膜的基础上,采用表面增强拉曼散射光谱(SERS)研究了在不同pH值条件下金纳米粒子在4,4’-二硫联吡啶自组装单分子膜/Au体系表面的组装。研究结果表明,由于处于单分子膜表面的吡啶环中氮原子的质子化程度随溶液环境中pH值的变化而变化,使得金纳米粒子与单分子膜表面间的结合作用程度不同,由此会引起金纳米粒子在单分子膜表面的覆盖度存在差异,并最终导致所观测到的4-巯基吡啶自组装单分子膜的SERS光谱强度存在明显的差异。而且,令人感兴趣的是,所观测到的SERS谱峰强度随金纳米粒子组装时pH值的变化呈现出明显的规律性。结合分子结构特征的分析,初步阐明了SERS谱峰强度随pH值这一组装条件的改变而发生规律性变化的内在原因。     

烷基硫醇/金自组装单分子膜表面上金属沉积特性研究进展

本文介绍了金属原子在烷基硫醇自组装单分子膜表面的再沉积行为,从理论上分析了其作用机理,归纳出了金属在自组装单层膜表面的再沉积规律。     

烷基硫醇/金自组装单分子膜表面上金属沉积特性研究进展

本文介绍了金属原子在烷基硫醇自组装单分子膜表面的再沉积行为,从理论上分析了其作用机理,归纳出了金属在自组装单层膜表面的再沉积规律。     

金属电极对有机分子非弹性电子隧穿谱的影响

利用第一性原理计算金属电极下1,6-己二硫醇和1,4-二巯基苯分子结的非弹性电子隧穿谱,发现非弹性电子隧穿谱对金属电极的变化十分灵敏,并且非弹性电子隧穿谱的振动峰位置和强度与硫原子和金属电极表面的距离密切相关.结果表明电极材料和分子与金属成键的情况是影响分子结的非弹性电子输运的重要因素.理论分析进一步表明不同金属电极和有机分子的耦合能不同导致了谱峰强弱的调整.     

ac field-induced Fano resonances in a parallel-coupled double quantum dot system

The effects of an ac electric field on the Fano resonance in a parallel-coupled double quantum dot system are investigated theoretically. The field can induce the photon-assisted Fano resonances for both symmetrical and asymmetrical parallel configurations. The magnitude and position of the photon-assisted Fano peak can be tuned by the ac field strength and frequency, respectively. Furthermore, the Fano resonance can appear with increasing the field frequency for both the symmetrical and asymmetrical configurations. This provides an efficient mechanism to control the Fano resonance. The photon-electron pumping effects for the symmetrical and asymmetrical cases are also studied in the weak- and strong-coupling regime.     

Electrochemical STM investigation of 1,8-octanedithiol monolayers on Au(1 1 1).: Experimental and theoretical study

The surface structure of Au(1 1 1) electrodes covered by 1,8-octanedithiol self-assembled monolayers (SAMs) was studied with in situ scanning tunnelling microscopy (STM) as a function of the electrode potential in acidic and alkaline electrolytes. We investigated the correlation between the dynamics of the SAM and the underlying gold atoms during the reductive desorption and oxidative readsorption processes. The reductive desorption of 1,8-octanedithiol is characterized by a transition from a compact monolayer with an upright molecular configuration to a striped phase with flat lying dithiol molecules, whereas during the oxidative readsorption process the surface first becomes increasingly covered by the striped phase until the transition to the compact phase occurs. We also considered under equivalent conditions 1-octanethiol/Au(1 1 1) SAMs which were used as a reference to evaluate the influence of the -SH terminal group on the structure and stability of dithiol SAMs. The desorption and readsorption of both the dithiol and the monothiol have a considerable influence on the substrate morphology which is manifested in the dynamics of vacancy islands, gold islands and indentation of step edges. Quantum mechanical calculations in the framework of density functional theory (DFT) show that adsorbed thiols greatly facilitate the detachment of gold atoms from step edges. The high mobility of gold atoms observed experimentally is compatible with the presence of a defected layer of gold atoms. The DFT results suggest that the formation of a monolayer may involve the diffusion and self assembly of thiolate-Au moieties rather than the diffusion of the bare thiolates across the surface. This mechanism explains the formation of a defected layer of gold atoms.     

Intraband Dynamics and Terahertz Emission in Biased GaAs/In0.53Ga0.47As Semiconductor Superlattices

Using an excitonic basis, we investigate the intraband polarization, opticalabsorption spectra, and terahertz emission of semiconductor superlattice withthe density matrix theory. The excitonic Bloch oscillation is driven by the dcand ac electric fields. The slow variation in the intraband polarizationdepends on the ac electric field frequency. The intraband polarizationincreases when the ac electric field frequency is below the Bloch frequency.When the ac electric field frequency is above the Bloch frequency, theintraband polarization downwards and its intensity decreases. The satellitestructures in the optical absorption spectra are presented. Due to excitonicdynamic localization, the emission lines of terahertz shift in different acelectric field and dc electric field.     

二次发射微波电子枪的模拟计算及其特性分析

 采用URMEL-T程序进行了二次发射微波电子枪的腔内电磁计算和特性分析。同时利用URMEL-T得出的腔内轴向电场及自编程序,模拟电子在该高频场作用下的运动。计算表明二次发射微波电子枪确实具有相位选择性,进而探讨了腔形尺寸、射频电场强度对相位选择性和产生二次倍增的有关条件的影响,以及输出电子的能量稳定性。模拟结果表明,这类电子枪（MPG）可得到高电流密度（5303A/cm²）及短脉冲（3.15~10ps）的电子束。     

Dynamical behaviors of an exciton in an asymmetric double coupled quantum dot

Dynamical behaviors of an exciton in an asymmetric double coupled quantum dot and an alternatingcurrent (ac) electric field have been analyzed based on the two-level approximation theory, and the conditions under which dynamical localization occurs are obtained. It shows that when the amplitude of the ac electric field is small, the Coulomb interaction plays an important role. The dynamical behaviors of the exciton are mainly confined in the low-level subspace. When the ratio of the field intensity to frequency is the root of Bessel function, electron and hole are localized in one dot, and they can be divided with the increasing amplitude of the ac electric field. __________ Translated from Chinese Journal of Semiconductors, 2005, 26(6) (in Chinese)     

具有部分本征GaN帽层新型AlGaN/GaN高电子迁移率晶体管特性分析

为了优化传统Al GaN/GaN高电子迁移率晶体管(high electron mobility transistors,HEMTs)器件的表面电场,提高击穿电压,本文提出了一种具有部分本征GaN帽层的新型Al GaN/GaN HEMTs器件结构.新型结构通过在Al GaN势垒层顶部、栅电极到漏电极的漂移区之间引入部分本征GaN帽层,由于本征GaN帽层和Al GaN势垒层界面处的极化效应,降低了沟道二维电子气(two dimensional electron gas,2DEG)的浓度,形成了栅边缘低浓度2DEG区域,使得沟道2DEG浓度分区,由均匀分布变为阶梯分布.通过调制沟道2DEG的浓度分布,从而调制了Al GaN/GaN HEMTs器件的表面电场.利用电场调制效应,产生了新的电场峰,且有效降低了栅边缘的高峰电场,Al GaN/GaN HEMTs器件的表面电场分布更加均匀.利用ISE-TCAD软件仿真分析得出:通过设计一定厚度和长度的本征GaN帽层,Al GaN/GaN HEMTs器件的击穿电压从传统结构的427 V提高到新型结构的960 V.由于沟道2DEG浓度减小,沟道电阻增加,使得新型Al GaN/GaN HEMTs器件的最大输出电流减小了9.2%,截止频率几乎保持不变,而最大振荡频率提高了12%.     

超晶格电流振荡的分岔图和Poincaré映射

基于超晶格输运的分立漂移模型,数值模拟了掺杂弱耦合GaAs AlAs超晶格在外加交流偏压下电场畴的输运行为.以黄金分割比固定交流驱动频率,模拟并分析不同交流幅度下电流的准周期、锁频及混沌现象.     

Molecular simulation studies of self-assembled monolayers of alkanethiols on Au(111)

A review is presented of this group's recent molecular simulation studies of self-assembled monolayers (SAMs) of alkanethiols on Au(111) surfaces. SAMs are very useful for the systematic alteration of the chemical and structural properties of a surface by varying chain length, tail group and composition. The scientific and technological importance of SAMs cannot be overestimated. The present work has been centred on studies of atomic scale surface properties of SAMs. First, configurational-bias Monte Carlo simulations were performed in both semigrand canonical and canonical ensembles to investigate the preferential adsorption and phase behaviour of mixed SAMs on Au(111) surfaces. Second, a novel hybrid molecular simulation technique was developed to simulate atomic force microscopy (AFM) over experimental timescales. The method combines a dynamic element model for the tip-cantilever system in AFM and a molecular dynamics relaxation approach for the sample. The hybrid simulation technique was applied to investigate atomic scale friction and adhesion properties of SAMs as a function of chain length. Third, dual-control-volume grand canonical molecular dynamics (DCV-GCMD) simulations were performed of transport diffusion of liquid water and methanol through a slit pore with both inner walls consisting of Au(111) surfaces covered by SAMs under a chemical potential gradient. Surface hydrophobicity was adjusted by varying the terminal group of CH₃ (hydrophobic) or OH (hydrophilic) of the SAMs. Finally, ab initio quantum chemical calculations were performed on both clusters and periodic systems of methylthiols on Au(111) surfaces. Based on the ab initio results, an accurate force field capable of predicting c(4×2) superlattice structures over a wide range of temepratures for alkanethiols on Au(111) was developed. The extension of current work is discussed briefly.     

Study of ac hopping conductivity on one—dimensional nanometre systems

In this paper, we establish a one-dimensional random nanocrystalline chain model, we derive a new formula of ac electron－phonon－field conductance for electron tunnelling transfer in one-dimensional nanometre systems. By calculating the ac conductivity, the relationship between the electric field, temperature and conductivity is analysed, and the effect of crystalline grain size and distortion of interfacial atoms on the ac conductance is discussed. A characteristic of negative differential dependence of resistance and temperature in the low-temperature region for a nanometre system is found. The ac conductivity increases linearly with rising frequency of the electric field, and it tends to increase as the crystalline grain size increases and to decrease as the distorted degree of interfacial atoms increases.     

Some dielectric properties of novel nano‐s‐triazine derivatives

The evaluation of the dielectric properties of s‐triazine and its mono‐, di‐, tri‐(trityloxy)triazine derivates as a function of temperature from room temperature to 200°C, and frequency varying from 50 Hz to 5 MHz was performed. The dielectric constant increases with the increase of both temperature and frequency. Moreover, from the measured dielectric loss ε″ we found that there are different types of electric energy losses in the presence of an alternating electric field from which we calculate the entropy ΔS and the enthalpy change ΔH of the dielectric relaxation for each sample. The dielectric relaxation was attributed to the phase transition of the s‐triazine derivatives. Additionally, ac‐electrical conductivity as a function of frequency at different temperatures were studied. Analysis of ac conductivity data indicates that the correlated barrier hopping model is the most suitable mechanism for the ac‐conductance behavior. X‐ray diffraction and scanning electron microscopy were performed on the compounds under consideration to determine the grain size of each sample, which was found in the range of 3 to 100 nm.