Nonlocal dissociative chemistry of adsorbed molecules induced by localized electron injection into metal surfaces

We present a novel approach to surface chemistry studies using scanning tunneling microscopy (STM), where dissociation of molecules adsorbed on metal surfaces is induced nonlocally in a 10-100 nm radius around the STM tip by hot electrons that originate from the STM tip and transport on the surface. Nonlocal molecular excitation eliminates the influence of the STM tip on the outcome of the electron-induced chemical reaction. The spatial attenuation of the nonlocal reaction is used as a direct measure of hot-electron transport on the surface.     

从蘸笔纳米刻印术到力化学打印

蘸笔纳米刻印术(dip-pen nanolithography,DPN)作为一种独特的纳米加工手段,具有在各类基底上书写精细图案的能力.自20世纪末诞生以来,研究者们对DPN中的墨水输运原理有了更深入的理解,同时受惠于材料学的发展并结合复杂生化反应体系,数种基于DPN衍生的纳米加工技术被开发出来.与此同时,依靠机械作用...     

纳米结构电学性质的静电力显微镜研究方法

纳米尺度的材料具有许多不同于宏观体材料的奇特的物理和化学特性.了解纳米结构的物性随材料尺寸及形状的变化关系,对于设计和合成具有特定功能的纳米材料有重要的指导意义.静电力显微镜技术为研究微纳米尺度下材料的电学特性提供了强有力的工具.文章介绍了这种测量技术的基本原理,并列举了几种在静电力显微镜基础上发展起来的纳米材料电学性质的表征方法,包括探针特征电容的标定、表面电荷密度测量、薄膜材料中载流子密度测定等.这些实验方法扩展了静电力显微镜的应用领域,为深入研究纳米材料的性质和纳米器件的功能结构提供了丰富的技术手段.     

扫描探针针尖与试样间的静电力分析与建模

针对主体为圆锥、尖端为球冠的扫描探针针尖物理模型,提出了针尖与试样之间等效电场分布假设,基于该假设导出了二者之间静电力的解析模型,分析了针尖结构参数与静电力间的关系.模拟计算结果和数值计算结果一致,并与相关的实验结果吻合,证实了电场分布假设的合理性.     

Protecting TERS probes from degradation: extending mechanical and chemical stability

The detailed surface chemistry of aluminum oxide protected silver films for use specifically in surface enhanced Raman spectroscopy and tip enhanced Raman spectroscopy (TERS) was investigated. We have demonstrated that increased storage and scanning use lifetimes for silver plasmonic structures are directly connected with the elimination of chemical degradation at the plasmonic structure surface. X‐ray photoelectron spectroscopy of the metal films confirmed that a 2–3 nm thick coating of aluminum oxide prevented chemical attack of the underlying silver film for three months of storage in a desiccator, significantly increasing the storage lifetime of current probes. The scanning lifetime of a TERS probe when used to image a hard patterned silicon substrate was doubled with the addition of this protective coating. These measurements were performed without laser illumination in order to separate laser‐induced heating degradation from pure mechanical degradation of the metallized probe currently encountered during TERS data collection. Copyright © 2013 John Wiley & Sons, Ltd.     

材料化学分析的物理方法(Ⅰ)

材料的化学信息是理解科学、工程与技术领域各种过程、机制和材料行为的最基本要素，材料研究的第一步是要确定材料的化学，包括构成材料的原子的种类、分布以及具体的化学态等内容，任何具有元素特征的物理信息，包括原子量、电子的能级、原子核自旋，甚至局域的电子态密度等都可以用来做材料的化学分析，化学信息由来自材料本身的或用作探针的电子、光子、离子或中性原子携带，相应的分析技术包括X射线光电子能谱、俄歇电子谱、核磁共振、特征X射线分析、二次离子质谱、能量损失谱、溅射中性粒子质谱，各类离子散射谱以及扫描隧道显微学方法等等，文章对上述各种分析方法的物理原理、仪器以及应用等逐一做扼要的介绍。     

扫描近场红外显微镜光纤探针的腐蚀制法

红外光探针是扫描近场红外显微镜(SNIM)中的关键部件,由于探针的种类和材料不同,制作的方法也不同.一般制作光纤探针有两种方法,即热拉伸法和化学腐蚀法.这里叙述了一种化学腐蚀方法,介绍了怎么去除砷硒碲中红外光纤的聚酰胺表层和硫化硒夹层,以及芯层腐蚀成针尖状的具体方法和过程,并对短锥针探针制法进行了探索.最后用此探针在近场范围内探测了氮化镓样品的自由电子激光(FEL)反射谱. 关键词： 扫描探针显微镜(SPM) 近场红外扫描显微镜(SNIM) 光纤探针     

Adsorption of bovine serum albumin on amorphous carbon surfaces studied with dip pen nanolithography

This article reports the use of dip pen nanolithography (DPN) for the study of adsorption of bovine serum albumin (BSA) proteins on amorphous carbon surfaces; tetrahedral amorphous carbon (t-aC) and silicon doped hydrogenated amorphous carbon (a-C:H:Si). Contact angle study shows that the BSA proteins reduce the contact angle on both carbon materials. We also noticed that the drop volume dependence is consistent with a negative line tension, i.e. due to an attractive protein/surface interaction. The DPN technique was used to write short-spaced (100 nm) BSA line patterns on both samples. We found a line merging effect, stronger in the case of the a-C:H:Si material. We discuss possible contributions from tip blunting, scratching, cross-talk between lever torsion and bending and nano-shaving of the patterns. We conclude that the observed effect is caused in large measure by the diffusion of BSA proteins on the amorphous carbon surfaces. This interpretation of the result is consistent with the contact angle data and AFM force curve analysis indicating larger tip/surface adhesion and spreading for the a-C:H:Si material. We conclude by discussing the advantages and limitations of DPN lithography to study biomolecular adsorption in nanoscale wetting environments.     

Image dipole approach and polarization effects in scanning near-field optical microscopy

A coupled-dipole approach is proposed in order to study the coupling between the probe tip and the rough sample in SNOM. In the present model both the optical probe tip and the sample protrusions are represented by polarizable dipole spheres. The induced polarization effects on the sample surface can be replaced by the image dipoles in the circumstance of quasi-static electromagnetic field approximation. Applying the radiation theory of the dipole, we have established a set of self-consistent equations to describe the field distribution at the sites of the probe tip and the sample protrusions. The results are completely the same as those obtained by means of the dyadic electromagnetic propagator formalism and also the derivation procedure is relatively simple. This method permits us to analyze the physical mechanisms of the interaction between the probe tip and the rough surface in SNOM intuitively. Based on this approach, we further discuss the influence of polarization of the incident light on the imaging quality. The calculating result shows that the shape and the contrast of the images of the sample are both sensitive to the field polarization, and the z-polarized mode is proved to give better resolution in SNOM.     

Spin-polarized scanning tunneling microscopy with antiferromagnetic probe tips

We have performed low temperature spin-polarized scanning tunneling microscopy (SP-STM) of two monolayers Fe on W(110) using tungsten tips coated with different magnetic materials. We observe stripe domains with a magnetic period of 50 +/- 5 nm. Employing Cr as a coating material we recorded SP-STM images with an antiferromagnetic probe tip. The advantage of its vanishing dipole field is most apparent in external magnetic fields. This new approach resolves the problem of the disturbing influence of a ferromagnetic tip in the investigation of soft magnetic materials and superparamagnetic particles.     

探针尖带金属微粒的光子扫描隧道显微镜成像数值模拟

引入了色散介质的时域有限差分法散射场方程,并针对光子扫描隧道显微镜的带金属尖光纤扫描成像问题进行三维的数值模拟。在考虑了光纤和样品相互作用的情况下,采用等效入射波法设置入射波,探针扫描模式为等高扫描模式,从成像分辨力和灵敏度的角度,比较了不同入射角、不同的光纤一样品间距,不同金属类型,及不同金属尖大小的成像情况。数值模拟结果显示,带金属颗粒光纤探针尖的光子扫描隧道显微镜在成像分辨力和灵敏度上有显著的改进,而带不同类型金属颗粒情况下对分辨力影响不大,灵敏度是银最好。     

Synchrotron infrared nano-spectroscopy and -imaging

Infrared (IR) spectroscopy has evolved into a powerful analytical technique to probe molecular and lattice vibrations, low-energy electronic excitations and correlations, and related collective surface plasmon, phonon, or other polaritonic resonances. In combination with scanning probe microscopy, near-field infrared nano-spectroscopy and -imaging techniques have recently emerged as a frontier in imaging science, enabling the study of complex heterogeneous materials with simultaneous nanoscale spatial resolution and chemical and quantum state spectroscopic specificity. Here, we describe synchrotron infrared nano-spectroscopy (SINS), which takes advantage of the low-noise, broadband, high spectral irradiance, and coherence of synchrotron infrared radiation for near-field infrared measurements across the mid- to far-infrared with nanometer spatial resolution. This powerful combination provides a qualitatively new form of broadband spatio-spectral analysis of nanoscale, mesoscale, and surface phenomena that were previously difficult to study with IR techniques, or even any form of micro-spectroscopy in general. We review the development of SINS, describe its technical implementations, and highlight selected examples representative of the rapidly growing range of applications in physics, chemistry, biology, materials science, geology, and atmospheric and space sciences.     

Au表面等离子体激元激发的扫描探针电子能谱

结合扫描隧道显微镜（STM）与电子能谱仪是实现表面微区元素分析的途径之一．我们将环形电子能量分析器和三维扫描探针系统相结合,建立了一台扫描探针电子能谱仪(SPEES)．通过测量针尖近场发射束流激发的Au表面能量损失谱,我们用研究了Au原子的等离子体激元激发现象．进一步通过改变针尖－样品距离,我们研究了Au等离子体激元峰与弹性散射峰的强度比随针尖－样品距离变化的关系．研究结果发现该强度比与针尖－样品距离的关系并不是单调变化,而是在一个特定位置存在极大．     

How narrow can a meniscus be?

A water meniscus naturally forms in air between an atomic force microscope (AFM) tip and a substrate. This nanoscale meniscus produces a capillary force on the AFM, and also serves as a molecular transport channel in dip-pen nanolithography (DPN). A stable meniscus is a necessary condition for DPN and for the validity of the Kelvin equation commonly applied to AFM experiments. Lattice gas Monte Carlo simulations show that, due to thermal fluctuation, a stable meniscus has a lower limit in width. We find a minimum width of 5 molecular diameters (1.9 nm) when the tip becomes atomically sharp (terminated by a single atom).     

MANIPULATION OF ATOMS, MOLECULES AND CLUSTERS FOR CONSTRUCTION OF NANOSYSTEMS

Controlled manipulations with the scanning tunneling microscope (STM) down to the scale of small molecules and single atoms allow to built molecular and atomic nanosystems, leading to the fascinating possibility of creating manmade structures on atomic scale. Here we present a short review on atomic scale manipulation investigations. Upon soft lateral manipulation of adsorbed species, in which only tip/particle forces are used, three different manipulation modes (pushing, pulling, sliding) can be discerned. We show that even the manipulation of highly coordinated native substrate atoms is possible and we demonstrate how this can be applied as local analytic and synthetic chemistry tools, with important consequences on surface structure research. Vertical manipulation of Xe and CO is demonstrated, leading to improved imaging with functionalized tips. With CO deliberately transferred to the tip, we have also succeeded to perform vibrational spectroscopy on single molecules. Furthermore, we describe how we have reproduced a full chemical reaction with single molecules, whereby all basic steps, namely preparation of the reactants, diffusion and association, are induced with the STM tip. Finally, we have extended the manipulation techniques to large specially designed molecules by performing lateral manipulation in constant height and realizing the principle of a conformational molecular switch.     

Nanotips: Growth,Model, and Applications

The tip morphology in the nanoscale is discussed as a member of the one-dimensional nanostructure family. Different growth techniques used for the synthesis of the nanotips have been outlined and compared against each other including, etching, pyrolysis, physical, and chemical vapour deposition. Growth models for hollow and solid nanotips are compared and discussed in detail with a thrust on the ‘cone-helix’ model for the hollow tips and the ‘platelet stacking’ model for the solid tips. Application of the nanotips in field emission, scanning probe microscopy, sensing, anti-reflection, and nanoindentation is discussed.     

On the dissipation of mechanical energy in a noncontact dynamic mode of a scanning probe microscope under vacuum

This paper presents a critical review of experiments on the measurement of conservative and dissipative forces in dynamic contacts of nanotips of scanning probe microscopes with surfaces (under high-vacuum conditions). In particular, it is noted that, although the perpendicular and parallel oscillatory motions of tips in the vicinity of the surface of various materials have been investigated experimentally, the question as to the nature of noncontact damping forces at distances ≥0.5 nm remains open. A phenomenological relationship between arbitrary conservative and dissipative forces acting on the tip is proposed. This relationship includes a model parameter characterizing the rate or time of the dissipative process and offers a correct explanation of the observed damping. It is shown that, despite the large differences in the damping coefficients, geometric sizes of tips, and types of conservative interactions in different experiments, the dissipative forces in perpendicular and parallel oscillatory motions of tips are adequately described within the proposed theory.     

The interaction of water with solid surfaces: fundamental aspects revisited

Water is perhaps the most important and most pervasive chemical on our planet. The influence of water permeates virtually all areas of biochemical, chemical and physical importance, and is especially evident in phenomena occurring at the interfaces of solid surfaces. Since 1987, when Thiel and Madey (TM) published their review titled ‘The interaction of water with solid surfaces: fundamental aspects’ in Surface Science Reports, there has been considerable progress made in further understanding the fundamental interactions of water with solid surfaces. In the decade and a half, the increased capability of surface scientists to probe at the molecular-level has resulted in more detailed information of the properties of water on progressively more complicated materials and under more stringent conditions. This progress in understanding the properties of water on solid surfaces is evident both in areas for which surface science methodology has traditionally been strong (catalysis and electronic materials) and also in new areas not traditionally studied by surface scientists such as electrochemistry, photoconversion, mineralogy, adhesion, sensors, atmospheric chemistry and tribology. Researchers in all these fields grapple with very basic questions regarding the interactions of water with solid surfaces such as how is water adsorbed, what are the chemical and electrostatic forces that constitute the adsorbed layer, how is water thermally or non-thermally activated and how do coadsorbates influence these properties of water. The attention paid to these and other fundamental questions in the past decade and a half has been immense. In this review, experimental studies published since the TM review are assimilated with those covered by TM to provide a current picture of the fundamental interactions of water with solid surfaces.     

Measurements of air discharges from insulating,electrostatic dissipative and conductive materials with different ESD probes

In this work, we have compared the performance of three different kinds of passive resistor-transmission line ESD probes: an unshielded ball probe, a shielded ball probe with the ESD current collected on a coaxial wire tip, and a needle-like probe. We have measured discharges from ESD sources having different surface resistivities including charged insulator surfaces, electrostatic dissipative materials and metal plates. In compliance with the results, there is no single probe type that is ideal for all kinds of situations—there are significant differences between the probe responses comprising sensitivity, charge transferred and peak ESD current. As expected, the initiation of air discharges was suppressed in accordance with increasing surface resistivity of the ESD source.     

Nanoscale laser processing and diagnostics

The article summarizes research activities of the Laser Thermal Laboratory on pulsed nanosecond and femtosecond laser-based processing of materials and diagnostics at the nanoscale using optical-near-field processing. Both apertureless and apertured near-field probes can deliver highly confined irradiation at sufficiently high intensities to impart morphological and structural changes in materials at the nanometric level. Processing examples include nanoscale selective subtractive (ablation), additive (chemical vapor deposition), crystallization, and electric, magnetic activation. In the context of nanoscale diagnostics, optical-near-field-ablation-induced plasma emission was utilized for chemical species analysis by laser-induced breakdown spectroscopy. Furthermore, optical-near-field irradiation greatly improved sensitivity and reliability of electrical conductance atomic force microscopy enabling characterization of electron tunneling through the oxide shell on silicon nanowires. Efficient in-situ monitoring greatly benefits optical-near-field processing. Due to close proximity of the probe tip with respect to the sample under processing, frequent degradation of the probe end occurs leading to unstable processing conditions. Optical-fiber-based probes have been coupled to a dual-beam (scanning electron microscopy and focused ion beam) system in order to achieve in-situ monitoring and probe repair.