Probe-scanning

The development of scanning probe microscopies and x-ray reflectivity (see Chapter VIII) has allowed molecular-level characterization of the structure of the electrode surface after electrochemical reactions [145]. In particular, the important role of adsorbates in determining the state of an electrode surface is illustrated by scanning tunneling microscopic (STM) images of gold (III) surfaces in the presence and absence of chloride ions [153]. Electrodeposition of one metal on another can also be measured via x-ray diffraction [154]. 

A number of methods that provide information about the structure of a solid surface, its composition, and the oxidation states present have come into use. The recent explosion of activity in scanning probe microscopy has resulted in investigation of a wide variety of surface structures under a range of conditions. In addition, spectroscopic interrogation of the solid-high-vacuum interface elucidates structure and other atomic processes. 

The ability to control the position of a fine tip in order to scan surfaces with subatomic resolution has brought scanning probe microscopies to the forefront in surface imaging techniques. We discuss the two primary techniques, scanning tunneling microscopy (STM) and atomic force microscopy (AFM) the interested reader is referred to comprehensive reviews [9, 17, 18]. 

We confine ourselves here to scanning probe microscopies (see Section VIII-2B) scanning tunneling microscopy (STM) and atomic force microscopy (AFM), in which successive profiles of a surface (see Fig. VIII-1) are combined to provide a contour map of a surface. It is conventional to display a map in terms of dark to light areas, in order of increasing height above the surface ordinary contour maps would be confusing to the eye. 

With the exception of the scanning probe microscopies, most surface analysis teclmiques involve scattering of one type or another, as illustrated in figure A1.7.11. A particle is incident onto a surface, and its interaction with the surface either causes a change to the particles energy and/or trajectory, or the interaction induces the emission of a secondary particle(s). The particles that interact with the surface can be electrons, ions, photons or even heat. An analysis of the mass, energy and/or trajectory of the emitted particles, or the dependence of the emitted particle yield on a property of the incident particles, is used to infer infomiation about the surface. Although these probes are indirect, they do provide reliable infomiation about the surface composition and structure. 

The most popular of the scanning probe tecimiques are STM and atomic force microscopy (AFM). STM and AFM provide images of the outemiost layer of a surface with atomic resolution. STM measures the spatial distribution of the surface electronic density by monitoring the tiumelling of electrons either from the sample to the tip or from the tip to the sample. This provides a map of the density of filled or empty electronic states, respectively. The variations in surface electron density are generally correlated with the atomic positions. 

There are many other experiments in which surface atoms have been purposely moved, removed or chemically modified with a scanning probe tip. For example, atoms on a surface have been induced to move via interaction with the large electric field associated with an STM tip [78]. A scaiming force microscope has been used to create three-dimensional nanostructures by pushing adsorbed particles with the tip [79]. In addition, the electrons that are tunnelling from an STM tip to the sample can be used as sources of electrons for stimulated desorption [80]. The tuimelling electrons have also been used to promote dissociation of adsorbed O2 molecules on metal or semiconductor surfaces [81, 82]. 

Wiesendanger R 1994 Scanning Probe Microscopy and Spectroscopy Methods and Appiications (New York Cambridge University Press)... 

Vansteenkiste S O, Davies M C, Roberts C J, Tendler S J B and Williams P M 1998 Scanning probe microscopy of biomedical interfaces Prog. Surf. Sc/. 57 95... 

Light microscope Scanning electron microscope Transmission electron microscope Scanning probe microscope... 

Colton R J ef a/ (eds) 1998 Procedures in Scanning Probe Microscopies (New York Wiley)... 

Durig U, Zuger O and Staider A 1992 interaction force detection in scanning probe microscopy methods and appiications J. Appl. Phys. 72 1778... 

Salmeron M, Liu G-Y and Ogletree D F 1995 Molecular arrangement and mechanical stability of self-assembled monolayers on Au(111) under applied load Force in Scanning Probe Methods ed H-J Guntherodt et al (Amsterdam Kluwer)... 

Wagner P 1998 Immobilization strategies for biological scanning probe microscopy FEBS Lett. 430 112... 

Bottomley L A, Coury J E and First P N 1996 Scanning probe microscopy Ana/. Chem. 68 185R... 

Gewirth A A and Niece B K 1997 Electrochemical applications of in situ scanning probe microscopy Chem. Rev. 971129... 

A wide variety of measurements can now be made on single molecules, including electrical (e.g. scanning tunnelling microscopy), magnetic (e.g. spin resonance), force (e.g. atomic force microscopy), optical (e.g. near-field and far-field fluorescence microscopies) and hybrid teclmiques. This contribution addresses only Arose teclmiques tliat are at least partially optical. Single-particle electrical and force measurements are discussed in tire sections on scanning probe microscopies (B1.19) and surface forces apparatus (B1.20). 

Monolayers of alkanetliiols adsorbed on gold, prepared by immersing tire substrate into solution, have been characterized by a large number of different surface analytical teclmiques. The lateral order in such layers has been investigated using electron [1431, helium [144, 1451 and x-ray [146, 1471 diffraction, as well as witli scanning probe microscopies [122, 1481. Infonnation about tire orientation of tire alkyl chains has been obtained by ellipsometry [149], infrared (IR) spectroscopy [150, 151] and NEXAFS [152]. 

The lubricant properties of alkanethiols and fluorinated alkanes have been studied extensively by scanning probe techniques [163]. In agreement with experiments on LB monolayers it was found that the fluorocarbon monolayers show considerably higher friction than the corresponding hydrocarbon monolayers [164, 165 and 166] even though the fluorocarbons are known to have the lowest surface free energy of all organic materials. 

Gewirth A A and Siegentlialer H (eds) 1995 Nano. icale Probes of the SoUd/Liquid Interface (NATO ASI Series 288) (London Kluwer) A survey of applications of scanning probes to electrochemical problems. 

Schleef D ef a/1997 Radial-histogram transform of scanning probe microscopy images Phys. Rev. B 55 2535... 

Nobel-laureate Richard Feynman once said that the principles of physics do not preclude the possibility of maneuvering things atom by atom (260). Recent developments in the fields of physics, chemistry, and biology (briefly described in the previous sections) bear those words out. The invention and development of scanning probe microscopy has enabled the isolation and manipulation of individual atoms and molecules. Research in protein and nucleic acid stmcture have given rise to powerful tools in the estabUshment of rational synthetic protocols for the production of new medicinal dmgs, sensing elements, catalysts, and electronic materials. 

New types of scanning probe microscopies are continually being developed. These tools will continue to be important for imaging of surfaces at atomic-scale resolution. 

R. Howland and L. Benatar, A Practical Guide to Scanning Probe Microscopy, Park Scientific Instmments, 1996. 

STM and SFM belong to an expanding family of instruments commonly termed Scanning Probe Microscopes (SPMs). Other common members include the magnetic force microscope, the scanning capacitance microscope, and the scanning acoustic microscope. ... 

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