Force spectroscopy in noncontact mode

We have analyzed the possibility of using noncontact scanning force microscopy (NCAFM) to detect variations in surface composition, i.e., to detect a ‘spectroscopic image' of the sample. This ability stems from the fact that the long-range forces, acting between the AFM tip and sample, depend on the composition of the AFM tip and sample. The long-range force can be magnetic, electrostatic, or van der Waals forces. Detection of the first two forces is presently used in scanning force microscopy technique, but van der Waals forces have not been used. We demonstrate that the recovery of spectroscopic image has a unique solution. Furthermore, the spectroscopic resolution can be as good as lateral one.     

基于扫描电子显微镜的碳纳米管拾取操作方法研究

碳纳米管场效应管是未来纳米器件的发展方向,而制造纳米器件的前提是拾取碳纳米管,基于扫描电子显微镜(SEM)的微纳机器人操作系统能够实现碳纳米管拾取操作.本文建立拾取操作中碳纳米管与原子力显微镜(AFM)探针间范德瓦耳斯力力学模型,不同接触状态下范德瓦耳斯力越大越有利于拾取碳纳米管.在SEM视觉反馈图像中建立相对坐标系,首先提出倾角变值方法检测碳纳米管与AFM探针的接触状态,然后运用动态差值方法识别碳纳米管与AFM探针空间位姿并校正碳纳米管位姿,最后自下而上拾取碳纳米管.实验结果表明:拟合直线倾角变值较大时碳纳米管与AFM探针发生接触,动态差值变化为零时碳纳米管与AFM探针为空间线接触,在完全线接触模型下选择合适的接触角度、接触长度和拾取速度能够成功拾取碳纳米管.     

Adsorption and manipulation of carbon onions on highly oriented pyrolytic graphite studied with atomic force microscopy

Carbon onions produced by DC arc discharge method were deposited on highly oriented pyrolytic graphite (HOPG) surface and their adsorption and manipulation was studied using an atomic force microscopy (AFM). Well-dispersed adsorption of carbon onions on HOPG surface was obtained and aggregations of onions were not observed. The van der Waals interaction between the onion and HOPG surface and that between two onions, were calculated and discussed using Hamaker's theory. The manipulation of adsorbed onions on HOPG surface was realized using the AFM in both the raster mode and the vector mode. The controllability and precision of two manipulation modes were compared and the vector mode manipulation was found superior, and is a useful technique for the construction of nano-scale devices based on carbon onions.     

Atomic-resolution dynamic force microscopy and spectroscopy of a single-walled carbon nanotube: characterization of interatomic van der Waals forces

We report atomic-resolution imaging and site-specific quantitative force measurements on a single-walled carbon nanotube by dynamic force microscopy and three-dimensional force field spectroscopy at low temperatures. The topography imaged in the attractive force regime reflects the trigonal arrangement of the hollow sites as maxima. Individual force curves were unambiguously assigned to carbon atoms and hollow sites, respectively. Site-specific quantitative evaluation revealed that the short-range interatomic van der Waals forces are responsible for the atomic-scale contrast.     

Theory of higher harmonics imaging in tapping-mode atomic force microscopy

The periodic impact force induced by tip-sample contact in tapping mode atomic force microscope (AFM) gives rise to non-harmonic response of a micro-cantilever. These non-harmonic signals contain the full characteristics of tip-sample interaction. A complete theoretical model describing the dynamical behaviour of tip--sample system was developed in this paper. An analytic formula was introduced to describe the relationship between time-varying tip--sample impact force and tip motion. The theoretical analysis and numerical results both show that the time-varying tip--sample impact force can be reconstructed by recording tip motion. This allows for the reconstruction of the characteristics of the tip--sample force, like contact time and maximum contact force. It can also explain the ability of AFM higher harmonics imaging in mapping stiffness and surface energy variations.     

Guidelines for the achievement of true atomic resolution with noncontact atomic force microscopy

We investigated the conditions to achieve true atomic resolution with an atomic force microscope under noncontact mode (NC-AFM). At first, we derived the equation of vertical resolution as a function of the signal-to-noise ratio and the decay length of frequency shift by assuming an exponential tip-to-sample distance dependence of frequency shift. Next, by assuming a single atom probe, we derived the equation of lateral resolution as a function of the vertical resolution and the tip-to-sample distance, from which we clarified the guidelines to achieve true atomic resolution with NC-AFM. At last, we made clear the attainable decay length of frequency shift both for the van der Waals potential and the electrostatic (Coulomb) potential.     

Lateral force microscopy in low normal force limit

We have studied frictional force between SiN tip and Si surface by using lateral force microscopy. The cantilever we have used has very low stiffness of 0.006 N/m, and the normal force acting on the surface was much lower than the attractive force such as van der Waals force. In this low normal force limit, it was found that the frictional force did not depend on the normal force. We suggest a calibration method to estimate the attractive force from the lateral force data in this limit. The estimated attractive force between Si sample and SiN tip with radius of 10 nm was 0.4 nN in flat region and 0.65 nN at the corner of a rectangular hole.     

True atomic resolution imaging of surface structure and surface charge on the GaAs(110)

We demonstrated a novel method to detect the van der Waals and the electrostatic force interactions simultaneously on an atomic scale, which is based on frequency modulation detection method. For the first time, the surface structure and the surface charge at atomic-scale point defects on the GaAs(110) surface have been simultaneously resolved with true atomic resolution under ultra-high vacuum condition. From the bias voltage dependence of the image contrast, we can verify that the sign of the atomically resolved surface charge at the point defect was positive.     

原子力显微镜扫描成像DNA分子

采用Mg2+处理DNA、APTES或戊二醛修饰云母表面、DNA拉直方法制备了λ-DNA及DNA-组蛋白复合物样品.室温下原子力显微镜以轻敲模式在空气中扫描样品成像.实验结果表明:AFM扫描成像的效果与样品的制备方法有关,同时也受操作因素影响.     

原子力显微镜探针耦合变形下的微观扫描力研究

原子力显微镜(AFM)的微探针系统是典型的微机械构件，它在接触扫描过程处于耦合变形状态.采用数值模拟方法探究恒力模式下探针耦合变形对微观扫描力信号、微观形貌信号的影响.研究表明，AFM的恒力模式扫描中，法向扫描力并不是恒定大小，与轴向扫描力存在耦合作用，在粗糙峰峰值增加阶段，二力均增加；在粗糙峰峰值减小阶段，二力均减小；该耦合作用随形貌坡度、针尖长度等增加而加强.微观形貌的测试信号和横向扫描侧向力信号受探针耦合变形影响较小，但侧向力与形貌斜率密切相关，且其极值点与形貌极值点存在位置偏差，这些结果均与原子力 关键词： 原子力显微镜 探针悬臂梁 耦合变形 扫描力     

表/界面水的扫描探针技术研究进展

表面和界面水在自然界、人们的日常生活以及现代科技中无处不在.它在物理、化学、环境学、材料学、生物学、地质学等诸多基础学科和应用领域起到至关重要的作用.因此,表面和界面水的功能与特性的研究,是水基础科学的一项核心任务.然而,由于水分子之间氢键相互作用的复杂性,及其与水-固界面相互作用的竞争,使得表(界)面水对于局域环境的影响非常敏感,往往需要深入到分子层次研究其微观结构和动力学过程.近年来,新型扫描探针技术的发展使得人们可以在单分子甚至亚分子尺度上对表(界)面水展开细致的实空间研究.本文着重介绍几种代表性的扫描探针技术及其在表(界)面水体系中的应用,包括:超高真空扫描隧道显微术、单分子振动谱技术、电化学扫描隧道显微术和非接触式原子力显微术.此外,本文还将对表(界)面水扫描探针技术研究面临的挑战和未来发展方向进行了展望.     

Distance dependence of noncontact-AFM image contrast on Si(111) × –Ag structure

Atomic resolution imaging of the Si(111) × R30°–Ag surface was investigated using a noncontact atomic force microscopy (NC-AFM) in ultrahigh vacuum. NC-AFM images showed three types of contrasts depending on the distance between an AFM tip and a sample surface. When the tip–sample distance was about 1–3 Å, the images showed the honeycomb arrangement with weak contrast. When the tip–sample distance was about 0–0.5 Å, the images showed the periodic structure composed of three bright spots with relatively strong contrast. On the other hand, the contrasts of images measured at the distance of 0.5–1 Å seemed to be composed of the above-mentioned two types of contrasts. By comparing the site of bright spots in the AFM images with honeycomb-chained trimer (HCT) model, we suggested the following models: when the tip is far from the sample surface, tip–sample interaction force contributing to imaging is dominated by physical bonding interaction such as Coulomb force and/or van der Waals (vdW) force between the tip apex Si atoms and Ag trimer on the sample surface. On the other hand, just before the contact, tip–sample interaction force contributing to imaging is dominated by chemical bonding such as the force due to hybridization between the dangling bond out of the tip apex Si atom and the orbit of Si–Ag covalent bond on the sample surface.     

Effect of chain length on the adhesion behaviour of n-alkanethiol self-assembled monolayers on Au(111): An atomic force microscopy study

The effect of chain length on the adhesion behaviour of n-alkanethiols CH₃(CH₂)_nSH, wheren = 5, 6, 7, 9, 10, 11, 14 and 15 has been followed by carrying out pull-off force measurement using atomic force microscopy (AFM). The self-assembled monolayers on Au(111) surface has been characterized by reflection absorption infra-red spectroscopy (RAIRS) and contact mode AFM. It is observed that the work of adhesion is independent of thiol chain length though the standard deviation is high for short chain length thiol-based monolayers. This may be attributed to the relatively more deformable nature of the short chain thiol films due to their heterogeneity in the monolayer structure than the long chain ones. This, in turn, increases the contact area/volume between the AFM tip and the monolayer, and hence the force of adhesion. However, in the presence of water, the force of adhesion is lower than that observed in air reflecting the effects of capillary forces/polar components associated with the surface energy.     

A new approach to the evaluation of Casimir and van der Waals forces in the transition region

This paper studies the incorporation of Casimir and van der Waals forces applied to a nanostructure with parallel configuration. The focus of this study is in a transition region in which Casimir force gradually transforms into van der Waals force. It is proposed that in the transition region, a proportion of both Casimir and van der Waals forces, as the interacting nanoscale forces, can be considered based on the separation distance between upper structure and substrate during deflection. Moreover, as the separation distance descends during deflection, the nanoscale forces could transform from Casimir to a proportion of both Casimir and van der Waals forces and so as to van der Waals. This is also extended to the entire surface of the nanostructure in such a way that any point of the structure may be subjected to Casimir, van der Waals or a proportion of both of them about its separation distance from the substrate. Therefore, a mathematical model is presented which calculate the incorporation of Casimir and van der Waals forces considering transition region and their own domination area. The mechanical behavior of a circular nano-plate has been investigated as a case study to illustrate how different approaches to nanoscale forces lead to different results. For this purpose, the pull-in phenomena and frequency response in terms of magnitude have been studied based on Eringen nonlocal elasticity theory. The results are presented using different values of the nonlocal parameter and indicated in comparison with those of the classical theory. These results also amplify the idea of studying the mechanical behavior of nanostructures using the nonlocal elasticity theory.     

Imitation of non-contact mode while scanning in the presence of an electric double layer?

Non-contact atomic force microscopy (NCAFM) minimizes the physical interaction between the AFM tip and the surface of interest. Several recent studies have reported observation of single atom defects using this technique. The repulsive force is presumably the primary interatomic force (cf. our paper on pseudo-non-contact mode in this issue) responsible for the reported atomic resolution in these studies. The combination of these factors, minimal tip–sample deformation and repulsive force interaction, are responsible for the observation of the single atom defects. In the present study, we show that similar resolution can be achieved utilizing the same two factors but which employs scanning in a surfactant. The method decreases the tip–sample interaction by eliminating the attractive forces between the tip and sample. The surfactant solution induces an electrical double-layer (EDL) on the surface of the tip and sample. This EDL creates additional repulsion that is distributed over a large area, and hence does not contribute noticeably to the image contrast during scanning. However, it does compensate for the high pressures normally experienced by the tip in the absence of surfactant. In addition, the presence of the EDL enhances tip stability during the image scan. This method has been tested on surfaces of such minerals as mica, chlorite, and anhydrite.     

Characterization of English ivy (<Emphasis Type="Italic">Hedera helix</Emphasis>) adhesion force and imaging using atomic force microscopy

English ivy (Hedera helix) is well known for its ability to climb onto and strongly adhere to a variety of solid substrates. It has been discovered that the ivy aerial rootlet secretes an adhesive composed of polysaccharide and spherical nanoparticles. This study aims to characterize the mechanical properties of the nanocomposite adhesive using atomic force microscopy (AFM). The adhesive was first imaged by AFM to visualize the nanocomposite. Mechanical properties were then determined at various time points, from secretion to hardening. The experimental results indicate that the ivy adhesive exhibited strong adhesion strength and high elasticity. There was a decrease in adhesive force over time, from 298 to 202 nN during the 24-h study. Accompanying with it were the limited changes in extension length and Young’s modulus. The limited curing process of the ivy adhesive helps fill gaps in the attaching surface, leading to more intimate contact and increased van der Waals interactions with the surface. However, study based on a mechanical model indicated that van der Waals force alone is not significant enough to account for all of the measured force. Other chemical interactions and cross linking likely contribute to the strong adhesion strength of ivy.     

Measurements of metal-polymer adhesion properties with dynamic force spectroscopy

We investigate nanoscale interface properties using dynamic mode atomic force microscopy (AFM) operated in the frequency modulation mode in ultrahigh vacuum. The AFM tip was was functionalised by a thin layer of aluminium and the polymer was treated by plasma-etching. In the spectroscopy mode we could measure the adhesion properties between the metal and the polymer surfaces. We found that plasma-etching of the polymer resulted in strongly enhanced force interactions, indicating a chemical activation of the polymer surface. Values for the adhesion force and work of adhesion were measured on the nanometer scale and are compared to conventional macroscopic adhesion failure tests.     

Electrostatic and van der Waals forces in the air contact between the atomic force microscope probe and a conducting surface

Electrostatic and van der Waals forces of interaction between commercial probes of atomic force microscopes (AFMs) and conducting surfaces under atmospheric conditions are measured using contact atomic force microscopy. An algorithm of statistical processing of the initial photocurrent-displacement dependences is developed, which makes it possible to transform these dependences into the force-distance dependences. The Hamaker constant at the platinum (probe)-graphite (sample) contact is determined. It is shown that the measurement of electrostatic forces makes it possible to determine geometrical parameters of the AFM probe and to independently calibrate the stiffness of the cantilever.     

Morphology of nanostructures formed on the van der Waals surface of GaSe layered crystals annealed in sulfur vapor

The morphology of nanostructures, which were grown on the (0001) van der Waals surface of layered GaSe crystals and annealed under thermodynamically equilibrium conditions at high pressures of sulfur vapor, has been investigated using atomic force microscopy. The morphology and phase composition of the nanostructures are determined by the deformation and chemical interactions between the vapor phase and the crystal surface and by the thermodynamic conditions of annealing. Elements of nanostructures are formed as small Ga₂S₃ nanocrystallites, pyramidal quantum dots, and quantum rings on the defective (0001) van der Waals surface that contains nanosized indentations (nanocavities) and liquid gallium.     

Hexagonal boron nitride film substrate for fabrication of nanostructures

The fabrication of material with an atomic scale manipulation requires the suitable advanced substrate for epitaxial growth without the effect by the substrate lattice structure. Hexagonal boron nitride (h-BN) can be the advanced substrate for atomic manipulation due to van der Waals’ gap with little attractive force along to c axis. We have successfully synthesized h-BN layer on the co-deposited Cu/BN film by surface segregation phenomena using helicon wave plasma enhanced radio frequency (rf) magnetron sputtering system. Auger electron spectroscopy (AES) and X-ray photon spectroscopy (XPS) analysis showed that the h-BN composite segregated on the surface of Cu/BN film covered over 95% of the film annealed at 900 K for 30 min. Atomic forces microscopy (AFM) and scanning tunneling microscopy (STM) analysis showed that attractive force on the film surface is uniformly distributed to an extent of 2nN and that the h-BN surface can be a good electric insulator like sintered h-BN plate.