Computer simulations of atomic force microscopy: crystalline polymers and the effects of surface contaminants

The atomistic dynamics of the interaction of an atomic force microscopic (AFM) probe with a crystalline polyethylene surface was examined by using the molecular dynamics method. The results show that the internal dynamics of the polymer crystal is such that rapid relaxation occurs, providing for a large amount of structural reversibility and making it possible to perform nondestructive AFM experiments. However, surface and/or AFM tip defects or contaminants (such as those which can be induced by polar molecules adsorbed on the surface), can result in significant perturbations in the AFM images produced, causing large and sharp structures to appear on the surface topology. A rationale of the mechanisms responsible for the image distortions is presented, and a relationship to defects observed in AFM and STM experiments is given.     

AFM and STM investigations of hydrogenated amorphous silicon: topography and barrier heights

As-grown films of hydrogenated amorphous silicon (a-Si?:?H, highly phosphorous-doped) were investigated by atomic force microscopy (AFM) and scanning tunneling microscopy (STM). Hills up to 10 nm in height and 10 to 20 nm in diameter have been observed by AFM. By using STM in a new high-sensitivity mode, (1) atomically smooth areas (roughness about 0.3 Å rms) which occur at the top of the hills, (2) subnanometer structures several Å in height which cover large parts of the surface have been identified. Simultaneous measurements of the local apparent barrier heights (LABH) show a clear correlation to the topography. Areas showing subnanometer structures have always low LABHs while the highest values of the LABH occur on the smooth areas.     

XPS谱最大熵退卷积

阐述了ＸＰＳ谱线退卷积的必要性，传统傅里叶变换退卷积的弊病，ＭＥＭ最大退卷积的原理、方法和优越性；重点说明了ＭＥＭ退卷积中如何选择最佳抽样点数的原理和方法，介绍了所研制的ＭＥＭ最大熵退卷积计算机软件系统在 ＸＰＳ谱线退卷积中的应用情况，显示了这一方法在ＸＰＳ谱退卷积中所带来的突破性进展。     

多层碳纳米球的研究

用弧光放电法制备了碳的巴基葱.用原子力显微镜（AFM）、扫描隧道显微镜（STM）和透射电镜（TEM）研究了在高定向石墨(HOPG)和金(Au)基底上的巴基葱的行为和电学特性.扫描隧道谱表明,巴基葱的电学特性具有与单壁碳纳米管相似的非线性特性.较小尺寸的巴基葱呈半导体特性,尺寸增大倾向金属线性.AFM/STM图像显示,在HOPG和Au基底上的巴基葱能够聚集成二聚体.利用较小尺寸巴基葱的电学非线性特性,有希望构造纳米电子学的单电子器件.     

Maximum entropy deconvolution of secondary ion mass spectra with a measured response

The Maximum Entropy Method (MEM) has, for the first time, been successfully applied for the deconvolution of Secondary Ion Mass Spectra. Phosphorus-doped silicon was used as an analytical system. The commonly used technique to eliminate the interferences between phosphorus and the silicon hydride peaks (measurement at high mass resolution) strongly reduces the signal intensities. With MEM the mass resolution could be increased by a factor of ten without intensity loss. The response was determined by the lineshape of a non-overlapped mass peak of silicon. The validity of this approach was proved by comparison of the MEM solution with high resolution mass spectra.     

Investigation of the Effect of Thermal Annealing on Poly(3‐hexylthiophene) Nanofibers by Scanning Probe Microscopy: From Single‐Chain Conformation and Assembly Behavior to the Interfacial Interactions with Graphene Oxide

Poly(3‐hexylthiophene) (P3HT) has been widely used in devices owing to its excellent properties and structural features. However, devices based on pure P3HT have not exhibited high performance. Strategies, such as thermal annealing and surface doping, have been used to improve the electrical properties of P3HT. In this work, different from previous studies, the effect of thermal annealing on P3HT nanofibers are examined, ranging from the single polymer chain conformation to chain packing, and the interfacial interactions with graphene oxide (GO) at nanoscale dimensions, by using scanning tunneling microscopy (STM), atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). High‐resolution STM images directly show the conformational changes of single polymer chains after thermal annealing. The morphology of P3HT nanofibers and the surface potential changes of the P3HT nanofibers and GO is further investigated by AFM and KPFM at the nanoscale, which demonstrate that the surface potentials of P3HT decrease, whereas that of GO increases after thermal annealing. All of the results demonstrate the stronger interfacial interactions between P3HT and GO occur after thermal treatments due to the changes in P3HT chain conformation and packing order.     

Microfaceting explains complicated structures on rutile TiO2 surfaces

Surface structures on rutile TiO2 (001) have been studied by using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional calculations. Prior investigations have observed many kinds of complicated surface structures; however, detailed atomic structures and the mechanism of the reconstructions are still unknown. We evaluate the energetical stability of the surface structures. The calculational results suggest that a [111] microfaceting model is energetically stable compared with the unreconstructed (1 x 1) model. We propose microfaceting structural models that are in good agreement with atomically resolved STM images. This structural concept can be extended to other rutile TiO2 surfaces in general.     

Design of Aromatic Helical Polymers for STM Visualization: Imaging of Single and Double Helices with a Pattern of π–π Stacking

From scanning tunneling microscopy (STM) images of rationally designed helical polymers with a pattern of π–π stacking, we successfully identified the single‐ and double‐helical superstructures. The STM images of the helical structures revealed the smallest helical architecture (diameter ca. 1.3 nm) that has been seen so far. Furthermore, the interconversion of single and double helices was further underpinned by experimental analyses. Significantly, the formation of double helices induced different supramolecular chirality to that observed for the single helices.     

Adsorption of atomic hydrogen on ZnO(1010): STM study

The adsorption of atomic hydrogen on a single crystal ZnO(1010) surface has been studied by scanning tunneling microscopy (STM) under ultrahigh vacuum conditions at room temperature and at elevated temperatures. High resolution STM images indicate that a well-ordered (1x1) H adlayer is formed on the ZnO(1010) surface. The STM data strongly indicate that the hydrogen adsorbs on top of the oxygen atoms forming hydroxyl species. Scanning tunneling spectroscopy (STS) studies reveal a H atom induced metallization at room temperature. In contrast to the clean surface for the hydrogen-covered surface distinct defects structures consisting of missing O and Zn atoms could be identified.     

A multisource image processing environment in surface analysis

To use data from a number of different surface analytical instruments (such as SAM, SIMS, STM, EPMA, AFM)¹ in a synergistic manner, the problem of interchangeability of surface analytical data as well as that of multi-method analysis has to be solved. Starting from the measured images being stored in a standardized format, a preliminary set of low-level data processing routines based on the software packages Khoros [1] and HDF² [2] has been implemented. The aim is to standardize the storage as well as the processing of the images or spectra. A first version is presented.     

STM study of morphology and electron transport features in cytochrome c and nanocluster molecule monolayers.

The morphology and electron tunneling through single cytochrome c and nanocluster Pt(5)(CO)(7)[P(C(6)H(5))](4) molecules organized as monolayer Langmuir-Blodgett (LB) films on graphite substrate have been studied experimentally using scanning tunneling microscopy (STM) and spectroscopy techniques with sub-nanometer spatial resolution in a double barrier tunnel junction configuration STM tip-monomolecular film-conducting substrate at ambient conditions. STM images of the films revealed globular structures with characteristic diameters (approximately 3.5 nm for the protein molecule and approximately 1.2 nm for the nanocluster). The spectroscopic study by recording the tunneling current-bias voltage (I-V) curves revealed tunneling I-V characteristics with features as steps of different width and heights that are dependent on the STM tip position over the molecule in the monolayer, giving evidence for sequential discrete electron-tunneling effects with the combination of the single electron Coulomb-charging energy and the electronic energy level separation (molecular spectrum) in such immobilized metalloprotein and nanocluster structures that can be of interest for the development of bioelectronic and hybrid functional nanosystems.     

The initial growth behavior of perylene on Cu(100)

Using scanning tunneling microscopy (STM) together with density functional theory (DFT) the growth behavior of perylene on the Cu(100) substrate has been investigated. As revealed by STM images, perylene molecules prefer to adopt lying configuration with their molecular plane parallel to the substrate, and two symmetrically equivalent ordered domains were observed. DFT calculations show that perylene molecule prefers to adsorb on the top site of substrate Cu atoms with its long molecular axis aligning along the [011] or [01-1] azimuth of the substrate which is the most stable adsorption geometry according to its highest binding energy. Consequently, two adsorption structures of c(8×4) and c(8×6), each containing two perylene molecules per unit cell, are proposed based on our STM images. The growth mechanism for ordered perylene domains on Cu(100) can be attributed to the balance between weak adsorbate-adsorbate interaction and comparable adsorbate-substrate interaction.     

液晶CPBOB吸附的STM研究

利用STM对吸附在导电基底上的液晶进行研究，能提供近原子分辨的液晶分子图象，这一创新不仅拓宽了STM的研究领域，也使STM成为研究液晶吸附的重要手段之一．根据液晶相变特征不同，样品的制备方法大致分四种情况：直接法，加热法，气相沉积法和溶剂法．无论采用以上哪种方法，     

Near-edge electronic structure in NbS2

The near-edge electronic and structural properties of 2H-NbS(2) were investigated using scanning tunneling microscopy (STM) and density-functional calculations. Geometry optimization of the near-edge structure using density-functional calculations was performed on [1010]- and [1010]-terminated layer edges. Ribbon model systems also included variation of the number of bound sulfur atoms at the edges. Atomic resolution STM data exhibit a pronounced electronic density of states at the outermost edge atomic sites but are otherwise bulk-like in the near-edge region. Optimized NbS2 ribbon structures confirm the STM results indicating that minimal reconstruction occurs and that the edge electronic structure exhibits a significant increase in local density of states compared to bulk. Simulated STM images using extended Hückel tight-binding calculations based on optimized ribbon structures successfully modeled the experimental STM results. The results indicate that the [1010] "Nb" edges are preferentially observed compared to the [1010] "S" edge possibly due to differences in stability.     

Electronic structures of one-dimensional metal-molecule hybrid chains studied using scanning tunneling microscopy and density functional theory

The electronic structures of self-assembled hybrid chains comprising Ag atoms and organic molecules were studied using scanning tunneling microscopy (STM) and spectroscopy (STS) in parallel with density functional theory (DFT). Hybrid chains were prepared by catalytic breaking of Br-C bonds in 4,4″-dibromo-p-terphenyl molecules, followed by spontaneous formation of Ag-C bonds on Ag(111). An atomic model was proposed for the observed hybrid chain structures. Four electronic states were resolved using STS measurements, and strong energy dependence was observed in STM images. These results were explained using first-principles calculations based on DFT.     

Organic bonding to silicon via a carbonyl group: new insights from atomic-scale images

The ability to covalently attach organic molecules to semiconductor surfaces in a controllable and selective manner is currently receiving much attention due to the potential for creating hybrid silicon-organic molecular-electronic devices. Here we use scanning tunneling microscopy (STM) and density functional theory calculations to study the adsorption of a simple ketone [acetone; (CH(3))(2)CO] to the silicon (001) surface. We show both bias and time-dependent STM images and their agreement with total energy DFT calculations, simulated STM images, and published spectroscopic data. We investigate the stability of the resulting adsorbate structures with respect to temperature and applied STM tip bias and current. We demonstrate the ability to convert from the kinetically favored single-dimer alpha-H cleavage adsorbate structure to thermodynamically favored bridge-bonded adsorbate structures. This can be performed for the entire surface using a thermal anneal or, for individual molecules, using the highly confined electron beam of the STM tip. We propose the use of the carbonyl functional group to tether organic molecules to silicon may lead to increased stability of the adsorbates with respect to current-voltage characterization. This has important implications for the creation of robust single-molecule devices.     

Atomic force microscopy and magnetic force microscopy study of model colloids

Atomic force microscopy (AFM) is used to study the size, shape, and polydispersity of a variety of magnetic and nonmagnetic model colloids, previously imaged by transmission electron microscopy (TEM) only. Both height and phase images are analyzed and special attention is given to 3D morphology and softness of particles, as well as structures and presence of secondary components in the colloid, difficult to investigate with TEM. Several methods of tip characterization followed by deconvolution were applied in order to improve the accuracy of lateral diameter determination. In the case of magnetite particles dispersed in conventional ferrofluids, we explore both experimentally and theoretically the possibility of using magnetic force microscopy (MFM). We propose and discuss several models which allow to estimate the magnetic moment of a single domain superparamagnetic sphere using MFM, which cannot be done with other techniques; alternatively the tip magnetization can be determined.     

Nanoscale investigation of the structural and chemical changes induced by oxidation on carbon black surfaces: a scanning probe microscopy approach

Scanning tunneling microscopy (STM) and noncontact tapping mode atomic force microscopy (AFM) have been employed to study on a local scale the structural and, for the first time, the chemical changes of carbon black (CB) particles following plasma oxidation. STM imaging of the pristine, untreated particles revealed a relatively ordered structure of tiny crystallites with a few amorphous regions. After plasma treatment, the crystallites were no longer observed and the CB particle surface exhibited a noticeable and ubiquitous increase in atomic-scale disorder. Phase contrast images obtained with noncontact tapping mode AFM indicated that the untreated CB particles were essentially hydrophobic as a pristine basal surface of graphite, but with occasional hydrophilic patches. By contrast, their plasma-treated counterparts displayed enhanced hydrophilicity as a result of the introduction of oxygen onto the CB surface, the presence of which was evidenced by X-ray photoelectron spectroscopy, but most significantly, such enhancement was observed to be quite uniform at a local scale of individual particles. The possibility of investigating on a very local scale the chemical behavior of oxidized CB particles should be useful for the control and optimization of their dispersion properties in different systems.     

Surface physics at the nano-scale via scanning probe microscopy and molecular dynamics simulations

Probe-based scanning microscopes, such as the STM and the AFM, are used to obtain the topographical and electronic structure maps of material surfaces, and to modify their morphologies on nanoscopic scales. They have generated new areas of research in condensed matter physics and materials science. We will review some examples from the fields of experimental nano-mechanics, nano-electronics and nano-magnetism. These now form the basis of the emerging field of Nano-technology. A parallel development has been brought about in the field of Computational Nano-science, using quantum-mechanical techniques and computer-based numerical modelling, such as the Molecular Dynamics (MD) simulation method. We will report on the simulation of nucleation and growth of nano-phase films on supporting substrates. Furthermore, a theoretical modelling of the formation of STM images of metallic clusters on metallic substrates will also be discussed within the non-equilibrium Keldysh Green function method to study the effects of coherent tunnelling through different atomic orbitals in a tip-sample geometry.     

Rastertunnelmikroskopie an chiralen Molekülen: Nanochemie

The imaging and manipulation capabilities of the scanning tunnelling microscope (STM) render possible a novel nanoscale chemistry based on experiments with single molecules. Herein, we address several aspects of a nanoscale stereochemistry using the STM. As an example, we investigate 1‐nitronaphthalene on Au(111). 1‐Nitronaphthalene becomes chiral upon planar adsorption on the metal surface. High‐resolution STM images reflect the asymmetric electronic structure of the molecules and allow for the determination of the absolute configuration of any individual molecule within complex molecular structures. At medium coverage, spontaneous breaking of the chiral symmetry results in the formation of homochiral conglomerates, while at high coverage racemic structures prevail. Finally, the tip of the STM is used to separate “supramolecule‐by‐supramolecule” a racemic mixture of chiral 1‐nitronaphthalene aggregates into the enantiopure compounds.