(111) Silicon quantum wells have been studied extensively, yet no convincing explanation exists for the experimentally observed breaking of 6 fold valley degeneracy into 2 and 4 fold degeneracies. Here, systematic sp3d5s* tight-binding and effective
mass calculations are presented to show that a typical miscut modulates the energy levels which leads to breaking of 6 fold valley degeneracy into 2 lower and 4 raised valleys. An effective mass based valley-projection model is used to determine the directions of valley-minima in tight-binding calculations of large supercells. Tight-binding calculations are in better agreement with experiments compared to effective mass calculations.
