Photo-excitation and subsequent thermionic currents are essential components of photo-excited carrier transport in multi-quantum-well photovoltaic (hetero-PV) structures. p-i-n multi-quantum structures are useful probes for a better understanding of PV device properties. Illumination of the intrinsic region of p-i-n multi-structures causes carrier trapping in any of the quantum wells, and subsequent carrier recombination or thermal escape is possible. At the vicinity of a quantum well, we find that the (quasi) Fermi levels undergo an upward split by a small, but non-negligible, energy amount Delta E-f in the order of 12 meV We conclude this fact by comparing the photo-excited carriers trapped in a quantum well, under illumination, to the carrier concentrations under dark. Based on such a prediction, we subsequently relate thermionic current density dependence on Fermi level splitting, concluding that excess thermal currents may increase by a factor of the order of 2. We conclude that illumination causes (a) Fermi level separation and (b) an apparent increase in thermionic currents. (c) 2005 Elsevier B.V All rights reserved.