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Pseudo-MOSFETs (Ψ-MOSFET) are routinely used for silicon-on-insulator (SOI) material characterization, allowing threshold voltage, electron and hole mobility, doping density, oxide charge, interface trap density, etc. to be determined. The HgFET, one version of the Ψ-MOSFET, uses mercury source and drain contacts. It is a very effective SOI test structure, but its current-voltage behavior is critically dependent on the Hg-Si interface. We have investigated this interface through current-voltage measurements of HgFETs and Schottky diodes and through device modeling. We show that modest barrier height changes of 0.2 eV lead to current changes of up to three orders of magnitude. Etching the Si surface in a mild HF :H2O solution can easily change barrier heights and we attribute this behavior to Si surface passivation of dangling bonds. As this surface passivation diminishes with time, the Si surface becomes a more active generation site and the barrier height of the Hg-Si interface changes, taking on the order of 50-100 h at room temperature in air.