Probe microscopy

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. 

Scaiming probe microscopies have become the most conspicuous surface analysis tecimiques since their invention in the mid-1980s and the awarding of the 1986 Nobel Prize in Physics [71, 72]- The basic idea behind these tecimiques is to move an extremely fine tip close to a surface and to monitor a signal as a fiinction of the tip s position above the surface. The tip is moved with the use of piezoelectric materials, which can control the position of a tip to a sub-Angstrom accuracy, while a signal is measured that is indicative of the surface topography. These tecimiques are described in detail in section BI.20. 

AFM measures the spatial distribution of the forces between an ultrafme tip and the sample. This distribution of these forces is also highly correlated with the atomic structure. STM is able to image many semiconductor and metal surfaces with atomic resolution. AFM is necessary for insulating materials, however, as electron conduction is required for STM in order to achieve tiumelling. Note that there are many modes of operation for these instruments, and many variations in use. In addition, there are other types of scaiming probe microscopies under development. 

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... 

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... 

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... 

Jarvis S P and Tokumoto FI 1997 Measurement and interpretation of forces in the atomic force microscope Probe Microscopy 1 65... 

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]. 

Surfaces can be characterized using scaiming probe microscopies (see section B1.19). In addition, by attaching a colloidal particle to tire tip of an atomic force microscope, colloidal interactions can be probed as well [27]. Interactions between surfaces can be studied using tire surface force apparatus (see section B1.20). This also helps one to understand tire interactions between colloidal particles. 

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. 

Scanning probe microscopy is a forefront technology that is well established for research in surface physics. STM and SFM are now emerging ftom university laboratories and gaining acceptance in several industrial markets. For topographic analysis and profilometry, the resolution and three-dimensional nature of the data is... 

Atomic Force Microscopy Scanning Probe Microscopy... 

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