Oxidation electronics: bond–band–barrier correlation and its applications

Abstract

This report features the recent progress in understanding the behaviour of atoms and valence electrons involved in the process of oxidation, and some technological development driven by the new knowledge. It is initiated and verified that a chemical bond contracts spontaneously at a surface associated with magnitude rise of the bond energy due to the coordination imperfection and that an oxygen atom hybridizes its sp orbitals upon reacting with a solid surface. The former leads to the bond order–length–strength (BOLS) correlation for the physical aspect of a surface and a nano-solid and the latter to a bond–band–barrier (BBB) correlation for chemical reaction. In the process of oxidation, non-bonding lone pairs, anti-bonding dipoles and hydrogen-like bonds are involved, which add corresponding density-of-states (DOS) features to the valence band of the host. Bond forming also alters the sizes and valencies of the involved atoms and causes a collective dislocation of these atoms, which corrugate the morphology or the potential barrier of the surface. Based on the above premises, the oxidation of the low-index surfaces of transition metals Cu, Co, Ag and V, noble metals Rh, Ru, and Pd and non-metallic diamond has been consistently analyzed. Identities probed with various techniques, such as STM, LEED, XRD, STS, PES, TDS, EELS and Raman, have been systematically defined in terms of atomic valencies, bond geometry, valence DOS, bond strength and bond forming kinetics. It is understood that formation of the basic oxide tetrahedron, and consequently, the four discrete stages of bond forming kinetics and the oxygen-derived DOS features, are intrinsically common for all the analyzed systems though the patterns of observations may vary from situation to situation. What differs one oxide surface from another in observations are: (i) the site selectivity of the oxygen adsorbate, (ii) the order of the ionic bond formation and, (iii) the orientation of the tetrahedron at the host surfaces. The valencies of oxygen, the scale and geometrical orientation of the host lattice and the electronegativity of the host elements determine these specific differences extrinsically. Extending the premise of sp-orbital hybridization to the reactions of (C, N)–Ni(001) surfaces has led to a novel approach neutralizing the diamond–metal interfacial stress and hence strengthening the diamond–metal adhesion substantially. The BOLS correlation has provided consistent insight into the shape-and-size dependence of a number of properties for nano-solids. The BBB correlation has led to new findings in designing and fabricating materials for photoluminescence, electron emission and ultrahigh elasticity, etc.