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     

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.     

自组装双硫醇分子膜阻抗谱的研究

对交流电场下双巯基烷烃硫醇自组装分子膜的阻抗谱进行了研究.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．明确了膜的作用范围为阻抗谱中频部分为了解释该阻抗谱,提出了一种串联的等效电路来进行了拟合,并与其他的模型进行比较.同时,观察到在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并得出双巯基硫醇(C6-C10)在交流电场下的激活能为23～39 meV．     

分子间相互作用对硫醇分子膜电输运性质的影响

利用密度泛函理论和弹性散射格林函数方法,对硫醇分子膜的电学特性进行模拟.计算结果表明,由于分子间的相互作用,导致分子膜的导电能力比单分子提高2~3个数量级.分子结的导电能力随着压力增加而增加,电极距离的变化使分子与电极以及分子间的耦合增强、分子结的链内隧穿和链间隧穿几率增大,导致电流增加.     

压力对硫醇分子膜电输运性质的影响

利用密度泛函理论和弹性散射格林函数方法,对硫醇分子膜的电学特性进行了理论模拟,计算结果表明,分子结的导电能力随着压力增加而增加,对单分子构成的分子结来说,电流的增加主要是由于电极距离的变化导致单个分子与电极的耦合增强,对于由多个分子构成的分子膜来说,由于外加压力的变化,导致分子结的链内隧穿和链间隧穿几率增大,从而导致导...     

分子自组装膜表面滴膜共存冷凝传热的研究

本文以不同处理工艺制备十八烷基硫醇自组装膜,研究制备的表面上蒸气冷凝传热过程.结果表明不同的成膜温度,可以实现膜表面上水蒸气冷凝形态从膜状到滴状的过渡.并研究了该表面上滴膜共存状态下的冷凝传热特性,表明过渡状冷凝传热随固液自由能差渐进变化的实质是冷凝形态的渐进变化,表面上冷凝液运动形态的不同也将导致传热性能的改变,并对自组装膜表面上的冷凝传热系数可能随操作时间的增加而回升的现象进行了分析.     

压力膨化处理对正极性聚丙烯蜂窝膜的驻极体性质的影响

压力膨化处理工艺能够显著改善聚丙烯蜂窝薄膜（cellular polypropylene） 驻极体的压 电活性.通过热脉冲技术、表面电位衰减测量及TSD 电流谱分析等研究了经恒压正电晕充电 的聚丙烯蜂窝膜的陷阱能级分布特征，讨论了压力膨化处理工艺对这类蜂窝膜驻极体电荷稳 定性及电荷输运特性的影响.结果说明，PP 蜂窝膜内存在着位于中能级区的能值各异的三种 分立陷阱，深能值陷阱和浅能值陷阱的大多数位于孔洞膜近表面的体层或体内，而中等能值 陷阱则主要位于自由面附近.压力膨化处理改变了PP 蜂窝膜的能阱状态并在一定程度上降低 了这类孔洞膜驻极体的电荷储存稳定性，但没有明显影响其由慢再俘获效应占主导地位的脱 阱电荷输运特性. 关键词： 压力膨化处理 聚丙烯蜂窝膜 驻极体 电荷储存与陷阱分布 电荷输运     

隧道电子激发的辛硫醇条纹相自组装膜上卟啉单分子荧光

利用扫描隧道显微镜诱导发光技术,对单个卟啉分子的电致荧光现象进行了研究. 为了避免金属衬底对单个卟啉分子的荧光淬灭,利用条纹状辛硫醇自组装膜作为脱耦合层,实现了单个中性卟啉分子的电致荧光,并且发现分子荧光的产生呈现双极性特征. 另外,分子瓣上的荧光强度要强于分子中心的荧光强度.     

不同取向的1,8-辛二硫醇分子的伏安特性研究

以1,8-辛二硫醇分子为研究对象,在第一性原理基础上,利用弹性散射格林函数方法,研究了1,8-辛二硫醇分子在金原子团簇上不同取向对该分子结电输运特性的影响.计算结果表明,分子与金原子团簇表面之间方位角的不同会导致分子结构、电子结构的改变,从而影响分子体系的电输运特性.当1,8-辛二硫醇分子S-S轴线与金(111)面的法线成25°夹角时,所得到的电流-电压曲线与实验值符合较好.     

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。     

ToF-SIMS study on the cleaning methods of Au surface and their effects on the reproducibility of self-assembled monolayers

The production of reproducible self-assembled monolayers (SAMs) is essential to many nano(bio)technology applications. To check the effects of different cleaning methods on a reproducible SAMs formation, the cleaning methods were varied and then used for preparing each SAM. The reproducibility of each SAM was examined by ToF-SIMS analysis along with principal component analysis (PCA). Using what we found to be a superior method of cleaning gold surfaces, alkanethiol SAMs with different terminal groups such as 1-dodecanethiol (DDT), 11-mercaptoundecanoic acid (MUA), 11-mercapto-1-undecanol (MUD) were reproduced. Our statistical results show that reproducible alkanethiol SAMs on a well-cleaned gold surface can be produced within only a few standard deviation percentages obtained from point-to-point and sample-to-sample spectra.     

Patterned self-assembled monolayers of alkanethiols on copper nanomembranes by submerged laser ablation

Self-assembled monolayers (SAMs) of alkanethiols are major building blocks for nanotechnology. SAMs provide a functional interface between electrodes and biomolecules, which makes them attractive for biochip fabrication. Although gold has emerged as a standard, copper has several advantages, such as compatibility with semiconductors. However, as copper is easily oxidized in air, patterning SAMs on copper is a challenging task. In this work we demonstrate that submerged laser ablation (SLAB) is well-suited for this purpose, as thiols are exchanged in-situ, avoiding air exposition. Using different types of ω-substituted alkanethiols we show that alkanethiol SAMs on copper surfaces can be patterned using SLAB. The resulting patterns were analyzed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Both methods indicate that the intense laser beam promotes the exchange of thiols at the copper surface. Furthermore, we present a procedure for the production of free-standing copper nanomembranes, oxidation-protected by alkanethiol SAMs. Incubation of copper-coated mica in alkanethiol solutions leads to SAM formation on both surfaces of the copper film due to intercalation of the organic molecules. Corrosion-protected copper nanomembranes were floated onto water, transferred to electron microscopy grids, and subsequently analyzed by electron energy loss spectroscopy (EELS).     

Molecular dynamics simulation study of the nano-wear characteristics of alkanethiol self-assembled monolayers

A molecular dynamics (MD) simulation study of the probe-based nano-lithography of an alkanethiol self-assembled monolayer (SAM) on a metal surface was performed. The motivation of this work was to understand the nano-tribological phenomena of the nano-metric scribing process of alkanethiol molecules and gain insight into the interaction between the probe tip and the SAM-coated surface during the scribing process. The simulation results revealed that the organothiol molecules were displaced and dragged by the probe tip during scribing due to the strong interchain interactions. It was also found that the scribed pattern width was largely dependent on the tip–surface interaction induced by the probe shape rather than the tip–surface contact size. Also, the minimum load for tip–substrate contact changed with the number of molecules that interact with the probe tip. Furthermore, from the investigation of the effect of the scribing speed on the surface-damage characteristics of the chain molecules, it was found that relatively high-speed scribing could induce excessive removal of the SAM molecules from the surface. PACS 02.70.Ns; 31.15.Qg; 81.16.Nd; 68.35.Af     

Chemistry of metal atoms reacting with alkanethiol self-assembled monolayers

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is utilized to investigate the behavior of vapor-deposited K, Au and Ti atoms on several alkanethiol self-assembled monolayers (SAM). The goals are to acquire information about chemical reactions between metal atoms and surface organic functional groups, penetration of metal atoms through the SAMs, growth modes of metal overlayers on top of the SAMs and damage of organic molecules. It is found that appearance of new characteristic peaks and disappearance of initial peaks may indicate chemical reactions or decomposition of organic molecules. The relationship between metal dose and intensity of surface organic functional group-related peaks provides information about penetration or cluster-formation of metal atoms. In addition, removing the metal overlayers by chemical etching and then characterizing samples again is a complementary approach that can reveal valuable information about the location of the metal atoms.     

An atomic force microscope study of vanadium-benzene sandwich clusters soft-landed on self-assembled monolayers

Multiple-decker vanadium-benzene sandwich clusters V_n(benzene)_n+1 produced by a laser-vaporization synthesis method were soft-landed onto self-assembled monolayers of alkanethiol (C₁₈H-SAM) and fluorinated alkanethiol (C₁₀F-SAM) at 200 K. Noncontact atomic force microscopy has been used to examine the resulting adsorption states of the clusters landed on the SAMs at room temperature. For each SAM substrate, the aggregates of the deposited clusters were observed at the vacancy islands and near the steps of the SAM surface. The result indicates that, at room temperature, the clusters landed on the SAM substrate thermally diffuse on the surface to form columnar-shape islands around the defect sites of the SAM surface.     

Matrix effects on the surface plasmon resonance of dry supported gold nanocrystals

We present a method to characterize surface-chemical properties of gold nanocrystals. Spherical, 60 nm gold nanocrystals were immobilized on quartz substrates by a coupling agent and cleaned in a hydrogen plasma. The nanocrystals were then functionalized with alkanethiol self-assembled monolayers (SAM) of varying chain lengths by adsorption from the gas phase, and localized surface plasmon resonance (LSPR) spectroscopy was performed on the samples. Depending on the alkanethiol chain length, the adsorption of the SAM redshifted the LSPR to different extents, in accordance with Mie theory. SAM thickness differences below 1 nm could be easily resolved. Our results demonstrate that LSPR spectroscopy can be applied to characterize thin organic layers on dry supported gold particles with high sensitivity.     

Organized molecular assemblies for scanning probe microscope lithography

Nanostructures down to a few ten nanometers in size have been fabricated with Langmuir–Blodgett (LB) films and self-assembled monolayers (SAMs) using scanning probe microscope lithography. The SAMs have been prepared with organosilane and bipolar amphiphiles, alkanethiol molecules as ultrathin resists on Si and Au substrates. The LB films on silicon substrates using both the polymer of thiophene derivatives and the mixture of palmitic acid and hexadecylamine were prepared and fabricated. The effect of functional groups of molecules on the atomic force microscope (AFM) anodization has been studied in the optimized process conditions. Applied voltage between the AFM tip and sample, the scanning speed and the relative humidity in the laboratory are also important factors for nanometer-scale lithography of the ultrathin films. The STM lithography with an octadecanethiol SAM on Au film in the air was carried out at the pulse mode of tip bias with respect to the suitability of STM lithography. The high structural orderness and perfect thickness of ultrathin organic molecular assemblies are the major advantages as required for nanoscale lithography.     

Adsorption behavior of binary mixed alkanethiol molecules on Au: Scanning tunneling microscope and linear-scan voltammetry investigation

Adsorption behavior of binary mixed alkanethiol molecules of octanethiol (OT) and dodecanethiol (DDT) on Au substrate has been investigated with a variation of molar fraction in solution at room temperature. Linear-scan voltammograms (LSV) taken from the binary mixed self-assembled monolayer (SAM) on Au/Si showed a single reductive desorption peak, continuously shifting with a variation of mixing ratio in solution. Molecule-resolved scanning tunneling microscope (STM) images obtained from the binary SAM on Au/mica showed the phase separation with a few nanometer sized domains. The difference in the chain length between OT and DDT was not large enough to induce the phase separation with much larger domains, which could be well detected by LSV. There was no preferential adsorption of DDT to OT.     

Photopatterning of gold and copper surfaces by using self-assembled monolayers

A photolithographic technique was successfully employed to generate micropatterns of gold and copper by using self-assembled monolayer (SAMs) as resist materials. Copper patterns were successfully prepared from SAMs of 11-mercaptoundecanoic acid (MUA) and dodecanethiol (DDT) on Cu after UV irradiation followed by etching but gold patterns were prepared only from the SAM of MUA and not from the SAM of DDT, which revealed the difference of photooxidation of the metal–sulfur bond on SAMs. However, the maximum resolution of the pattern was about 1.0 μm on gold and 5.0 μm on copper. This may be due to lower quality packing of SAM on copper than gold. Ellipsometric and cyclovoltammetric observation of SAMs during the UV irradiation indicated the gradual removal of SAMs on copper and gold. Photopatterning of gold and copper by using SAM is more compatible with the current microelectronics process and is complementary to the microcontact printing technique.