  We compare the charge transport characteristics of heavy doped p- and
n-Si-alkyl chain/Hg junctions. Photoelectron spectroscopy (UPS, IPES and XPS)
results for the molecule-Si band alignment at equilibrium show the Fermi level
to LUMO energy difference to be much smaller than the corresponding Fermi level
to HOMO one. This result supports the conclusion we reach, based on negative
differential resistance in an analogous semiconductor-inorganic insulator/metal
junction, that for both p- and n-type junctions the energy difference between
the Fermi level and LUMO, i.e., electron tunneling, controls charge transport.
The Fermi level-LUMO energy difference, experimentally determined by IPES,
agrees with the non-resonant tunneling barrier height deduced from the
exponential length-attenuation of the current.
