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A general methodology is developed to experimentally characterize the spatial distribution of occupied traps in dielectric films on a semiconductor. The effects of parasitics such as leakage, charge transport through more than one interface, and interface trap charge are quantitatively addressed. Charge transport with contributions from multiple charge species is rigorously treated. The methodology is independent of the charge transport mechanism(s), and is directly applicable to multilayer dielectric structures. The centroid capacitance, rather than the centroid itself, is introduced as the fundamental quantity that permits the generic analysis of multilayer structures. In particular, the form of many equations describing stacked dielectric structures becomes independent of the number of layers comprising the stack if they are expressed in terms of the centroid capacitance and/or the flatband voltage. The experimental methodology is illustrated with an application using thermally stimulated current (TSC) measurements. The centroid of changes (via thermal emission) in the amount of trapped charge was determined for two different samples of a triple‐layer dielectric structure. A direct consequence of the TSC analyses is the rigorous proof that changes in interface trap charge can contribute, though typically not significantly, to thermally stimulated current.