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For n- and p-doped III–V compounds, Fermi-level pinning and accompanying phenomena of the (110) cleavage surface have been studied carefully using photoemission at hν≲300 eV (so that core as well as valence band levels could be studied). Both the clean surfaces and the changes produced, as metals or oxygen are added to those surfaces in submonolayer quantities, have been examined. It is found that, in general, the Fermi level stabilizes after a small fraction of a monolayer of either metal or oxygen atoms have been placed on the surface. Most strikingly, Fermi-level pinning produced on a given semiconductor by metals and oxygen are similar. However, there is a strong difference in these pinning positions depending on the semiconductor: The pinning position is near (1) the conduction band maximum (CBM) for InP, (2) midgap for GaAs, and (3) the valence band maximum (VBM) for GaSb. The similarity in the pinning position on a given semiconductor produced by both metals and oxygen suggests that the states responsible for the pinning resulted from interaction between the adatoms and the semiconductor. Support for formation of defect levels in the semiconductor at or near the surface is found in the appearance of semiconductor atoms in the metal and in disorder in the valence band with a few percent of oxygen. Based on the available information on Fermi energy pinning, a model is developed for each semiconductor with two different electronic levels which are produced by removal of anions or cations from their normal positions in the surface region of the semiconductors. The pinning levels have the following locations, with respect to the VBM: GaAs, 0.75 and 0.5 eV; InP, 0.9 and 1.2 eV (all levels + 0.1 eV). The first energy given is assocaited with a missing anion and the second with a missing cation. For GaSb, only an acceptor due to a missing Sb has been located at 0.1 eV. Our work is found to correlate well with that on practical Schottky barriers. A detailed comparison is made with interface state positions and densities found by others on practical MIS structures, and it is suggested that the large density of these states on III–V’s as compared to Si is due to extrinsic interface states created by stoichiometric deficits of the III–V semiconductor. For GaAs, the dominant state is found at 0.7 eV and is associated with an As deficit. For InP, the major interface level is about 0.1 eV below the CBM. These positions are in good agreement with the existing data obtained from a wide variety of samples.

The early stages of the formation of the Au-Si interface have been studied with photoelectron spectroscopy of the valence-band and core levels. In this study, the Si sample was prepared by cleavage in ultrahigh vacuum and Au was deposited in a controlled manner at room temperature, By slowly increasing the Au coverage on the surface, the silicon surface states were depleted rapidly (by a factor of 2 at an Au coverage of 0.2 monolayers) without any observable change ()0.1 eV) in the Fermi-level pinning position. Furthermore, at low coverages, the binding energies of the Au core levels and the Sd peaks in the valence band were similar to those of atomic Au; however, the width of the structure indicated that the Au is strongly interacting with Si. Measurement of the strength of the Au core levels gives evidence for penetration of a fraction of Au into Si. Thus, at low coverages, the Au is probably dispersed in and on the Si, causing the removal of the surface states and production of new states in the band gap. As the Au coverage is increased, the Au 4f and Si 2p core levels shift in such a way as to suggest the formation of an alloy with variable composition at the Au-Si interface. At the highest Au coverages {above 15 monolayers), a small amount (less than 1 monolayer) of Si was observed on the surface of the deposited Au overlayer. Thermal annealing of a thin Au (50 monolayers of Au) on Si at 500'C resulted in an increased Si concentration at the surface with the photoelectron spectra resembling those at low coverages (about 1.5 monolayers), thus indicating a high diffusion coefficient of Si through the Au layer. When less than 1 monolayer of 02 was adsorbed onto the cleaved Si surface prior to the deposition of Au, the intermixing of Au and Si was significantly reduced,

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Research during the last year has led to a better understanding of the electronic and atomic structure of the (110) surfaces of III–V semiconductors. In this paper we will briefly review these new developments as well as point out areas where agreement has been found between various experimental results presented in the literature. It is now generally agreed that there are no intrinsic surface states in the band gap on GaAs and the smaller band-gap materials (e.g., GaSb, InAs, and GaSb) and that Schottky barrier pinning must be due to states produced when the metal adlayer is applied. Particular attention is focused in this paper on the large surface rearrangement which takes place on the (110) GaAs surface and effects of the strain which may be produced in joining this rearranged surface layer to the rest of GaAs crystal. It is pointed out that this may lead to variations in the surface rearrangement which can produce variations in the valence electronic structure at the surface. Such variations are shown in experimental energy distribution curves obtained by the photoemission technique which samples principally the last two molecular layers. It is further shown that surprisingly small amounts of chemisorbed oxygen can produce first-order effects in the valence-band electronic structure. On all GaAs (110) surfaces studied, a phaselike transformation was observed with a few hundredths of a monolayer coverage of chemisorbed oxygen. Near this coverage, the Ga 3d exciton structure disappears and the oxygen uptake increases significantly. On certain samples, first-order changes in the valence-band electronic structure were observed at a coverage of a hundredth of a monolayer or lower. These transformations are discussed in terms of the electronic and atomic configurations at the surface. Experimental data showing As and Ga 3d chemical shifts for oxidation as well as chemisorption are also presented and used to point out difficulties to be expected in passivating practical surfaces. In particular, the effect of mixed As and Ga oxides, the desirability of bonding passivating layers to the GaAs through As bonds, and the effect of strain-induced interface states are discussed.