  We analyze the valley composition of one electron bound to a shallow donor
close to a Si/barrier interface as a function of an applied electric field. A
full six-valley effective mass model Hamiltonian is adopted. For low fields,
the electron ground state is essentially confined at the donor. At high fields
the ground state is such that the electron is drawn to the interface, leaving
the donor practically ionized. Valley splitting at the interface occurs due to
the valley-orbit coupling, V_vo^I = |V_vo^I| e^{i theta}. At intermediate
electric fields, close to a characteristic shuttling field, the electron states
may constitute hybridized states with valley compositions different from the
donor and the interface ground states. The full spectrum of energy levels shows
crossings and anti-crossings as the field varies. The degree of level
repulsion, thus the width of the anti-crossing gap, depends on the relative
valley compositions, which vary with |V_vo^I|, theta and the interface-donor
distance. We focus on the valley configurations of the states involved in the
donor-interface tunneling process, given by the anti-crossing of the three
lowest eigenstates. A sequence of two anti-crossings takes place and the
complex phase theta affects the symmetries of the eigenstates and level
anti-crossing gaps. We discuss the implications of our results on the practical
manipulation of donor electrons in Si nanostructures.
