Library Materials

Most of the basic information about surface chemistry and the analytical instrumentation can be obtained from the books on reserve in the Chemistry Library. Many of the topics covered in the lectures are treated more completely in these books.

Additional notes and interesting figures, references and journal articles are placed in a file kept in the Chemistry Library. Please check it frequently.

Introduction to Solids

• Part of chapter 1 from "Solid State Physics" by J.S. Blakemore discussing crystallinity in some detail.

• Part of chapter 1 from "The Solid State" by H.M. Rosenberg giving a general, but not very detailed, introduction to solids.

  Defects and Disorder

• Part of chapter 3 from "The Solid State" by H.M. Rosenberg discussing defects and disorder in solids at about the same level as we need to know.

• Section 1.6 from "Solid State Physics" by J.S. Blakemore with information on defects in solids. Brief but worth reading.

  Simple Electronic Structure

• Part of chapter 3, section 3.3 from "The Electronic Structure and Chemistry of Solids" by P.A. Cox describing the free-electron model. The same derivations that we used in lectures.

• Section 3.1 from "Solid State Physics" by J.S. Blakemore discussing the classical and quantized free electron models from a physics viewpoint. These start from and use different notation than we did but the principles are similar. Useful background material.

  Surface Structure

• "Local structural and vibrational properties of stepped surfaces: Cu(211), Cu(511) and Cu(331)" (Phys. Rev. B 55 (1997) 13894-13904) by Durukanoglu, Kara and Rahman. Theoretical study which calculates the vibrational DOS for various stepped surfaces. Don't worry about the calculations but read about the structure of the steps and how they relax.

• "Scanning tunneling microscopy investigation of the oxygen-induced faceting and "nano-faceting" of a vicinal copper surface" (Surf. Sci. 376 (1997) 374-388) by Knight, Driver and Woodruff. Experimental investigation of the gross reconstruction of vicinal copper surfaces to form small facets (small areas of low index planes). Also discusses adsorbate induced reconstruction - in this case O.

• "Interlayer interactions in epitaxial oxide growth: FeO on Pt(111)" (Phys. Rev. B 55 (1997) 13448-13451) by Kim, Westphal, Ynzunza, Galloway, Salmeron, Van Hove and Fadley. Epitaxy is the process by which a material is deposited onto a surface in a layer-by-layer manner. this paper is an example of an incommensurate system (adsorbates sit at different binding sites) where the sizes of the adsorbate and substrate lattice are different and a simple commensurate layer cannot form. Don't worry about the techniques used but look at the complicated patterns formed and the very large adsorbate unit mesh (superlattice). Note that it is rotated with respect to the underlying Pt(111) lattice.

  Adsorption

• Part of chapter 6 from "Surface Physics" by M. Prutton describing the adsorption of molecules and atoms on solids surfaces.

• Part of chapter 3 from "Vacuum Physics and Techniques" by T.A. Delchar describing chemisorption and physisorption.

• Part of section 2.6 from "An Introduction to Surface Chemistry and Catalysis" by G.A. Somorjai describing the structure of adsorbed monolayers and the reasons for ordering.

• "Spatial self-organization of surface structure during an oscillating catalytic reaction" (Phys. Rev. Lett. 54 (1985) 1725) by Cox, Ertl and Imbihl. Also see other papers by Gerhard Ertl from about this period. Discusses the oscillating surface reaction of the oxidation of CO on Pt(100) and its connection with adsorbate-induced reconstruction.

• "An ultrahigh vacuum single crystal adsorption microcalorimeter" (Rev. Sci. Instrum. 62 (1991) 2177) by Borroni-Bird, King. David King at Cambridge pioneered much of the microcalorimeter instrumentation being developed and used worldwide. Although only a few such machines have been built to date this is a very active area of surface science research at present. This paper describes the instrumental details.

• "Single-crystal adsorption microcalorimetry" (Chem. Phys. Lett. 183 (1991) 516) by Borroni-Bird, Al-Sarraf, Andersson and King. Describes the technique of microcalorimetry for direct measurement of the differential heat of adsorption, sticking coefficient and coverages on a single crystal surface.

  Introduction to Instumentation and Techniques

• "Analytical chemistry of surfaces" (Anal. Chem. 58 (1986) 1177A) by David M. Hercules. Gives some of the historical background of various analytical techniques (the "Big Four": XPS, SIMS, AES and ISS), some applications to catalysis and his future outlook for surface analysis.

• "The quest for universal curves to describe the surface sensitivity of electron spectroscopies" (J. Electron Spec. and Rel. Phenom. 47 (1988) 197) by C.J. Powell. A comparison of measurements and calculations for determining the inelastic mean free path (IMFP) for low energy electrons in solids. These numbers lead to the "universal curve" of electron escape depth with electron kinetic energy allowing us to extract the effective sampling depth and surface sensitivity.

  Electron Spectroscopy: X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES)

• "Advances in the application of x-ray photoelectron spectroscopy (ESCA). Parts I and II" (Crit. Rev. Anal. Chem. 115 (1991) 115) by Tery Barr. Very detailed description of the principles of photoemission and some of the exciting recent developments. Includes discussion of the theory of XPS and it's present status. Also mentions (1) charging and Fermi level references (2) valance band analysis (3) loss structure (4) surface chemical shifts (5) clusters (6) photoemission electron microscopy (PEEM) (7) inverse photoemission (IPES) (8) resonance effects (9) adsorbed Xe (10) photoelectron diffraction and (11) liquid XPS.

• "Quantification of Auger and x-ray photoelectron spectroscopies" (Anal. Chem. 61 (1989) 469A) by Nebesny, Maschloff and Armstrong. A consideration of various factors involved in making XPS and AES quantitative. These factors include determination of peak shape and background (plasmons and excitation processes), use of standards, measurement of peak heights and areas and conversion to an atomic %.

• "Inelastic interactions of electrons with surfaces: application to Auger electron spectroscopy and x-ray photoelectron spectroscopy." (Surf. Sci. 299/300 (1994) 34) by C.J. Powell (Powell has produced many papers discussing the quantification of particularly XPS. This is another example.) Overview of the processes leading to energy loss in solids (inelastic scattering) and a discussion of intensity measurement in XPS and AES.

• "Studies of the CO-H, H₂-Ni(100) system using photoelectron spectroscopy" (Surf. Sci. 273 (1992) 47) by Tillborg, Nilsson and Martensson from Uppsala, Sweden. An example of the strength of XPS and UPS for determining molecular environments by chemical shifts and the presence of satellite structure. This is a very high resolution study performed on a special instrument. Kai Seigbahn, the pioneer of XPS, built his first spectrometers at Uppsala.

• "Growth, structure and energetics of ultrathin ferromagnetic single crystal films on Mo(110)" (Surf. Sci. 232 (1990) 73) by Tikhov and Bauer. An example of how AES is used to determine the growth mode for various adsorbates deposited on this surface. This technique is especially powerful when supported by other methods, in this case, electron diffraction and work-function measurements to circumvent some of the difficulties associated with obtaining absolute coverages from AES data. In particular look at the Auger signal changes during the annealing studies.

  Incident Ion Techniques

• "Interaction of water, oxygen and hydrogen with TiO2(110) surfaces having different defect densities" (J. Vac. Sci. Technol. A 10 (1992) 2470) by Pan, Maschhoff, Diebold and Madey. Low energy ion scattering (LEIS) has been used in this paper to "titrate" the defects (missing O atoms) on the rutile surface. Uptake of isotopically labelled O and water was observed. Adsorbed and bulk O atoms could be distinguished using LEIS.

• "Surface MS: probing real-world samples" (Anal. Chem. 65 (1993) 630A) by Benninghoven, Hagenhoff and Niehuis (much of Benninghoven's previous work has been important in the development of modern SIMS). Review article of some of the basics of SIMS and SNMS. Also discusses imaging. If you can find the original article you will be able to better appreciate some of the beautiful SIMS maps contained in this work.

• "Ion beams and laser postionization for molecule specific imaging" (Anal. Chem. 65 (1993) 622A) by Nick Winograd. Discussion of imaging spectrometers based on TOF-SNMS and TOF-SIMS (using a reflectron arrangement).

  Diffraction Techniques:

• "Reconstruction of TiO2(110) surface: STM study with atomic-scale resolution" (Surf. Sci. 313 (1994) L783) by Onishi and Iwasawa. Despite the title, this paper contains LEED images as well as STM images allowing a direct comparison of "real space" and "reciprocal space". Rutile is a very important oxide surface because of its electrochemical, optical and catalytic properties.

  Scanning Probe Techniques: Scanning Tunneling Microscopy (STM) and Atomic Force Microscopy (AFM)

• Part of section 7.10 from "The Solid State" by H.M. Rosenberg giving a general, but not very detailed, introduction to workfunction and field emission.

• "Surface studies by scanning tunneling microscopy" (Phys. Rev. Lett. 49 (1982) 57) by Binnig, Rohrer, Gerber and Weibel. One of the earliest (and seminal) papers on STM. Short and very readable although the beautiful images realized by the technique didn't come until a few years later.

• "Scanning tunneling microscopy: a surface structural tool" (Anal. Chem. 59 (1987) 1267A) by Chiang and Wilson. In just a few years, STM had exploded in popularity. Here is another early paper showing some good images.

• "Atomic level structure of TiO2(110) as a function of surface oxygen coverage" (Surf. Sci. 302 (1994) L263) by Sander and Engel. Perfect rutile is a wide band-gap semiconductor and so cannot be imaged by STM. However, by introducing a small quantity of Ti III defect sites, some electrical conductivity is conferred. The presence of defects vastly complicates the surface chemistry of this important oxide.

  Other Techniques:

• "Characterization of Organic Surfaces" (Anal. Chem. 66 (1994) 403A) by Perry and Somorjai. Introductory paper which briefly discusses some of the other techniques applied to determination of surface chemistry. For more details and more techniques, consult the references given on pages 19-35 in Somorjai's book.