Recent experiments combining lifetime and laser spectroscopy of positronium (Ps) show that these atoms are emitted from p-Si(100) at a rate that depends on the sample temperature, suggesting a thermal activation process, but with an energy that does not, precluding direct thermal activation as the emission mechanism. Moreover, the amount of Ps emitted is substantially increased if the target is irradiated with 532 nm laser light just prior to the implantation of the positrons. Our interpretation of these data was that the Ps was emitted via an exciton-like positron-electron surface state, not dissimilar to an electronic surface exciton observed on Si in two-photon photoemission measurements. The hypothesis that this state may be populated by electrons from one of the occupied electronic surface states, either thermally or by laser excitation, is consistent with our observations and suggests that one should expect a high Ps yield at room temperature from an n-doped Si(100) sample, since in this case the same surface states will already be occupied. Here we present data obtained with an n-Si(100) target that supports our model, and also reveals the unexpected result that the kinetic energy of Ps emitted from this material actually decreases when it is heated, an effect we attribute to shifts in the surface energy levels due to the presence of a high density of thermally generated electrons. We show data obtained with a Ge(100) sample that corroborate the idea that the effects we observe are related to surface electron states, and hence should occur for any indirect band gap semiconductor with dangling bond states. Our model is further confirmed by the observation that the Ps yield from p-Si depends linearly on the surface density of the implanted positrons due to the effects of electron-hole pairs created as the positrons slow down.