Deliberate modification of the behavior of n-type cadmium telluride/electrolyte interfaces by surface etching. Removal of Fermi level pinning

Single crystal, n-type CdTe (E sub g = 1.4 eV) has been studied with respect to barrier height, E sub B, when contacting a liquid electrolyte solution containing a fast, one-electron, outer-sphere redox reagent. We approximate E sub B as equal to the photovoltage measured by cyclic voltammetry of various redox couples at illuminated n-CdTe vs. a reversible electrode. N-CdTe surfaces pretreated with an oxidizing etch give an E sub B of approximately 0.5 V + or - 0.1 V in H2O/0.1 M NaClO4 or CH3CN/0.1 M (n-Bu4N)ClO4 that is independent of the E sub 1/2 of the added redox couple. A reducing etch pretreatment gives an E sub B in either of the electrolyte solutions that depends on E sub 1/2 of the redox couple in a manner consistent with a nearly ideal semiconductor. The reduced CdTe exhibits an E sub B of up to 0.9 V for a redox couple having E sub 1/2 near 0.0V vs. SCE, whereas couples having E sub 1/2 negative of approx. -1.0 V vs. SCE give zero photovoltage. Auger and X-ray photoelectron spectroscopy of the reduced and oxidized surfaces are qualitatively different. The reduced surface exhibits signals for Cd and Te in relative intensities that are consistent with a close to stoichiometric (1/1) surface. The oxidized surface exhibits little or no detectable Cd signal and the Te signal is consistent with a thick overlayer of elemental Te.