Silicon surface nano-oxidation using scanning probe microscopy

This paper focuses on the nano-oxidation of a silicon surface using scanning probe microscopes in air ambient and in UHV. Special emphasis is put in air ambient on the preparation of the surfaces and on the oxidation mechanism. The characteristics of the patterned nanostructures are reviewed versus the parameters which govern the process (tip–surface voltage, tip speed, humidity) as well as the kinetics models of the oxidation process. The oxide patterns can act as robust masks for dry or wet etching. Fabrication of nanostructures is presented and allows to realize electronic nanodevices. In UHV, there is no direct nano-oxidation of the surface by the microscope tip. First the surface is hydrogenated, second a local hydrogen desorption is performed with the STM tip and finally the bare desorbed area is exposed to oxygen. The desorption process is analyzed versus tip–surface voltage and tunneling current. The oxidation of a desorbed area using molecular or atomic oxygen is actually difficult to achieve.     

Observation of single dinuclear metal-complex molecules using scanning tunneling microscopy

We report a scanning tunneling microscopy (STM) investigation of a dinuclear organometallic molecule, trans-[Cl(dppe)2Ru(C[triple bond]C)6Ru(dppe)2Cl] (Ru2), absorbed on a Au(111) surface; this molecule is a potential candidate for use in molecular quantum-dot cellular automata (QCA) devices. Isolated Ru2 molecules were observed under ultra-high-vacuum conditions. Submolecular structure was clearly discernible in the STM images, with a bright feature corresponding to each of the two Ru-ligand complexes within the Ru2 molecule. Rotation and translation of the Ru2 molecules were observed to be induced by the STM tip under some tunneling conditions.     

Single-nanoparticle-terminated tips for scanning probe microscopy

We have developed a wet-chemistry procedure to attach a 10-40 nm colloidal gold nanoparticle to the top of a scanning probe microscopy (SPM) probe tip, making experiments of single nanoparticle interaction possible. This procedure of particle attachment is flexible and can be modified to attach nanoparticles of different kinds and sizes. The single-nanoparticle-terminated tips also have potential in various other applications, such as probes of enhanced sensitivity for optical and magnetic modes SPM.     

Enhanced feature analysis using wavelets for scanning probe microscopy images of surfaces

In this work we develop wavelet theory for the analysis of surface topography images obtained by scanning probe microscopy (SPM) such as atomic force microscopy (AFM). Wavelet transformation is localized in space and frequency, which can offer an advantage for analyzing information on surface morphology and topography. Wavelet transformation is an ideal tool to detect trends, discontinuities, and short periodicities on a surface. Additionally, wavelets can be used to remove artifacts and noise from scanning microscopy images. In terms of 3-D image analysis, discrete wavelet transform can capture patterns at all relevant frequency scales, thus providing a level of image analysis that is not possible otherwise. It is also possible to use the methodology for analyzing surface structures at the molecular level. The results demonstrate superior capabilities of wavelet approach to scanning probe microscopy image analysis compared to traditional analysis techniques.     

In situ surface reduction of a NiO-YSZ-alumina composite using scanning probe microscopy

In situ surface reductions of NiO-YSZ-Al₂O₃ composites into Ni-YSZ-Al₂O₃ cermets were carried out at 312–525 °C in a controlled atmosphere high-temperature scanning probe microscope (CAHT-SPM) in dry and humidified 9 % H₂ in N₂. The reduction of NiO was followed by contact mode scanning of topography and conductance. A reproducible sequence of events was observed which included a conductance decrease upon hydrogen introduction and a reappearance of conductance after some time. It was found that this incubation time from introduction of hydrogen and until conducting Ni appeared was temperature dependent and followed the Arrhenius equation. For samples reduced in dry hydrogen, the Arrhenius plot showed two regions with different activation energies. Scanning electron microscopy confirmed a difference in microstructure between these temperature regimes. A strong retarding effect of steam (H₂O) on the nucleation time of Ni particles was observed.     

The scanning probe microscopy of metalloproteins and metalloenzymes

In recent years, the concept of microscopy and the ability to study processes at a truly molecular level have been revolutionised by the development of a family of instruments based on acquiring data through the scanning of a proximal probe across a surface. Scanning Probe Microscopes (SPMs) enable surface-confined structures to be resolved at ?ngstrom-resolution, in real time, and under a variety of controllable conditions. Despite initial difficulties, much progress has been in the application of this technology to the high-resolution analysis of biological systems; these have varied from complex cellular systems to molecular biopolymers. Studying the interactions of protein with surfaces has been intrinsic to the development of our understanding of blood coagulation, fibrinolysis, thrombus formation and the synthesis of biocompatible materials. The specific interactions of metalloproteins and enzymes with electrode surfaces remains central to the understanding of the bioelectrochemical processes and to the development of biosensing devices. Though ellipsometry, Raman, microcalorimetry, surface plasmon resonance, and other spectroscopic methods, can provide much information on these interfaces, the acquired data are averaged over a large number of molecular species with a low spatial resolution. Proximal probe methods have much to offer in this regard and have revolutionized our ability to monitor such interactions.     

Nanoscale surface modification via scanning electrochemical probe microscopy

Micro- and nanoscale surface modification using scanning probe microscopy techniques in combination with electrochemically induced surface structuring provides a maskless in situ fabrication strategy enabling deposition or etching of three-dimensional nanostructures. This current opinion article focuses on scanning electrochemical probe microscopy techniques highlighting recent progress in nanoscale 3D surface modification along with a spotlight on approaches of practical relevance.     

A study of the surface morphology of poly(p-phenylene terephthalamide) chars using scanning probe microscopy

The objective of this work was to investigate the changes in surface morphology associated with thermal degradation of poly(p-phenylene terephthalamide) (PPTA) into chars. To this end, PPTA samples decomposed at several temperatures up to 800 °C were studied on a local scale using atomic force microscopy (AFM) and scanning tunnelling microscopy (STM). Domains with a diameter of 40-50 nm started appearing among PPTA nanofibrils at about 500 °C. At this temperature and above, a film coating the fibre developed. This layer was much less rigid than PPTA, and remained deposited on the fibres, even at high temperatures. At 800 °C, the STM images showed a surface distribution typical of a carbonaceous material, isotropic although somewhat heterogeneous. When an intermediate isothermal step (500 °C, 200 min) was introduced along with heat treatment of PPTA under a constant rate, the material obtained at the end of this step was conductive enough to be studied by STM. Although the coating over the fibres also remained after the isothermal step, it was less homogeneous than in the absence of isothermal treatment. On further heating, the residue exhibited a surface morphology typical of a carbonaceous material, but much more homogeneous and isotropic than in the absence of the isothermal step.     

Determining charge transport pathways through single porphyrin molecules using scanning tunneling microscopy break junctions

Charge transport in a porphyrin with four identical pyridyl substituents, 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP), was investigated using the scanning tunneling microscopy break junction method. To determine the dominant pathway, we studied two structurally similar porphyrins, o-DPyP and p-DPyP. Our experiments reveal that charge transport through TPyP in a break junction configuration does not follow the traditional assumption, i.e., the shortest path between the neighboring side groups. Instead, the charge transport pathway was dominated by the farthest anchoring groups. Furthermore, these single molecule experiments can distinguish between the two structural isomers, which is important in molecular discrimination, porphyrin chemistry, and molecular electronics.     

A temperature-deformation unit for scanning electron probe microscopy of polymers

An attachment to a scanning probe microscope was designed and constructed. The attachment allows analysis of polymer specimens subjected to tensile drawing at different temperatures directly in the microscope. High-quality images can be obtained for the same microscopic reference region with a size of 2.5 × 2.5 μm at different temperatures (ranging from 25 to 175°C) and an absolute elongation of the specimen more than three orders of magnitude above the size of the reference region.     

Implementation of recycling routes for scanning probe microscopy tips.

In this work, effective, yet simple, recycling mechanisms for used scanning probe microscopy (SPM) tips were implemented. Comprising a tip profile characterization methodology and specific cleaning procedures, which decontaminate SPM tips whether the contamination nature is known or not, such routes were optimized during numerous tests with brand new, previously used, and already discarded categories of SPM tips. The results show that if the used tip suffered contamination only, but no physical damages, during its scanning lifetime, it becomes readily available for reutilization after the cleansing process, characterizing a recycling route. On the other hand, if the tip went through wear and breakages during its utilization, it still can be decontaminated, but may not be directly reutilized due to its inadequate physical profile. Nevertheless, the methodology developed in this work may yet be applied as part of a more complex recycling route.     

Applications of scanning probe microscopy in intrinsically conducting polymer research

The applications of scanning probe microscopy (SPM) in intrinsically conducting polymer research is briefly reviewed, including morphology observation, nanofabrication, microcosmic electrical property measurements, electrochemistry researches, in-situ measurements of film thickness change, and so on. At the same time, some important variations of SPM and the related techniques are briefly introduced. Finally, the future development of SPM in the study of intrinsically conducting polymers is prospected. Translated from Chinese Journal of Applied Chemistry, 2006, 23 (2) (in Chinese)     

Organic monolayers chemisorbed on gold observed by scanning probe microscopy

Scanning force (SFM) and scanning tunneling (STM) microscopies are suitable techniques for the investigation of the structure of organic monolayers. Results are presented on thioalkane monolayers and thiolipid monolayers on gold. Both molecules attach covalently to the gold surface. STM images of the self assembled dodecanethiol layer display the molecular order of the film and reveal the presence of defects at the molecular scale. Moreover, domains and domain boundaries can be distinguished. Thiolipid layers on gold have been observed by SFM. The monolayer separates in solid-analogous star shaped domains and fluid-analogous domains. Imaging under water demonstrates the stability of the layer.     

Single-molecule chemistry and physics explored by low-temperature scanning probe microscopy

It is well known that scanning probe techniques such as scanning tunnelling microscopy (STM) and atomic force microscopy (AFM) routinely offer atomic scale information on the geometric and the electronic structure of solids. Recent developments in STM and especially in non-contact AFM have allowed imaging and spectroscopy of individual molecules on surfaces with unprecedented spatial resolution, which makes it possible to study chemistry and physics at the single molecule level. In this feature article, we first review the physical concepts underlying image contrast in STM and AFM. We then focus on the key experimental considerations and use selected examples to demonstrate the capabilities of modern day low-temperature scanning probe microscopy in providing chemical insight at the single molecule level.     

Single-molecule conductance of redox molecules in electrochemical scanning tunneling microscopy

Experimental data and theoretical notions are presented for 6-[1'-(6-mercapto-hexyl)-[4,4']bipyridinium]-hexane-1-thiol iodide (6V6) "wired" between a gold electrode surface and tip in an in situ scanning tunneling microscopy configuration. The viologen group can be used to "gate" charge transport across the molecular bridge through control of the electrochemical potential and consequently the redox state of the viologen moiety. This gating is theoretically considered within the framework of superexchange and coherent two-step notions for charge transport. It is shown here that the absence of a maximum in the Itunneling versus electrode potential relationship can be fitted by a "soft" gating concept. This arises from large configurational fluctuations of the molecular bridge linked to the gold contacts by flexible chains. This view is incorporated in a formalism that is well-suited for data analysis and reproduces in all important respects the 6V6 data for physically sound values of the appropriate parameters. This study demonstrates that fluctuations of isolated configurationally "soft" molecules can dominate charge transport patterns and that theoretical frameworks for compact monolayers may not be directly applied under such circumstances.     

Catalysis resolved using scanning tunnelling microscopy

The technique of scanning tunnelling microscopy has revolutionised our understanding of surface chemistry, due to its ability to image at the atomic and molecular scale, the very realm at which chemistry operates. This critical review focuses on its contribution to the resolution of various problems in heterogeneous catalysis, including surface structure, surface intermediates, active sites and spillover. In the article a number of images of surfaces are shown, many at atomic resolution, and the insights which these give into surface reactivity are invaluable. The article should be of interest to catalytic chemists, surface and materials scientists and those involved with nanotechnology/nanoscience. (129 references.)The graphical abstract shows the reaction between gas phase methanol and oxygen islands on Cu(110), courtesy of Philip Davies of Cardiff University. The added-row island is shown as silver-coloured spheres (copper) and red (oxygen) on the copper surface. Methanol preferentially reacts with the terminal oxygen atoms in the island forming adsorbed methoxy and OH groups. Only the terminal oxygen atoms in the island are active sites for the reaction.     

Determination of relative binding affinities of labeling molecules with amino acids by using scanning tunneling microscopy

The binding behaviour of labeling molecule copper phthalocyanine tetrasulfonate sodium (PcCu(SO(3)Na)(4)) on the assemblies of representative polyamino acids has been studied by using scanning tunneling microscopy (STM). By directly visualizing the adsorption and distribution of the labeling species on the peptide assemblies in STM images, one could obtain relative binding affinities of the labeling molecule with different amino acid residues.     

Mapping peroxidase in plant tissues by scanning electrochemical microscopy.

Scanning electrochemical microscopy has been firstly used to map the enzymatic activity in natural plant tissues. The peroxidase (POD) was maintained in its original state in the celery (Apium graveolens L.) tissues and electrochemically visualized under its native environment. Ferrocenemethanol (FMA) was selected as a mediator to probe the POD in celery tissues based on the fact that POD catalyzed the oxidation of FMA by H(2)O(2) to increase FMA(+) concentration. Two-dimensional reduction current profiles for FMA(+) produced images indicating the distribution and activity of the POD at the surface of the celery tissues. These images showed that the POD was widely distributed in the celery tissues, and larger amounts were found in some special regions such as the center of celery stem and around some vascular bundles.     

In situ scanning probe microscopy and new perspectives in analytical chemistry

The resolution of scanning tunnelling microscopy (STM) and other scanning probe microscopies is unprecedented but the techniques are fraught with limitations as analytical tools. These limitations and their relationship to the physical mechanisms of image contrast are first discussed. Some new options based on in situ STM, which hold prospects for molecular- and mesoscopic-scale analytical chemistry, are then reviewed. They are illustrated by metallic electro-crystallisation and -dissolution, and in situ STM spectroscopy of large redox molecules. The biophysically oriented analytical options of in situ atomic force microscopy, and analytical chemical perspectives for the new microcantilever sensor techniques are also discussed.