Charge transfer studies of semiconductor interfaces

Author: Kumar, Amit

Year: 1992

Degree: Dissertation (Ph.D.)

Advisor: Lewis, Nathan Saul

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/3s37-cw77

Abstract

For all semiconductors (n-Si, p-Si, n-GaAs, n-InP, a-Si:H), the spectral response of liquids junctions, in the short wavelength region (200-600 nm), showed higher quantum yields than metal junctions. This general trend was independent of redox species, solvent, supporting electrolyte, and metal overlayer. This technique was also used to distinguish between Schottky barrier behavior from electrocatalytic behavior of metal overlayers.

Studies of n-Si photoelectrodes in aqueous and non-aqueous electrolytes have been conducted. For all n-Si/CH_3OH-dimethylferrocne^(+/O)(Me_2Fc^(+/O)) cells, the forward bias dark currents,the open circuit voltage (V_(oc)), and temperature dependence of V_(oc) were independent redox species concentrations. All n-Si photoanodes (naked and coated with discontinuous metal overlayers) were found to be unstable in aqueous electrolytes.

Novel metal/insulator/semiconductor devices have been fabricated through the anodic growth of the insulator layer in a methanol based electrolyte. These devices do not suffer from Fermi level pining restrictions, and some exhibit electronic properties limited by minority carrier transport.

A theoretical framework has been formulated to describe the behavior of photoelectrolysis cells, and experiments at n-SrTiO3/5.0 M KOH(aq)/Pt junctions have been conducted. The data exhibits a photocurrent threshold in the short circuit electrolysis current at 0.02-0.03 mW/cm^2 of 325 nm illumination, which is consistent with the theoretical framework.

The behavior of Si/CH_3OH-Me_2Fc^(+/O) junctions has been investigated under high injection conditions. With a structure having n+ diffused back contacts, V_(oc)s of 626+5 mV were obtained at short circuit photocurrent densities of 20 mA/cm^2. The diode quality factor and reverse saturation current were 1.8+0.1 and (2.6+1.5)x 10^(-8) A/cm^2, respectively. These data are consistent with recombination dominated by the base and back contact regions, and not at the Si/CH_3OH interface.

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