SiGe quantum wells where the well material has a lowest conduction band energy minimum at k=0 (the .GAMMA. point of the first Brillouin zone) are provided. Quantum well structures that satisfy this condition have "Kane-like" bands at and near k=0 which can provide physical effects useful for various device applications, especially optical modulators. In the Si.sub.1-xGe.sub.x material system, this condition on the band structure is satisfied for x greater than about 0.7. The quantum well barrier composition may or may not have Kane-like bands. Embodiments of the invention having a surface parallel configuration are especially suitable for use in fiber coupled devices. Such surface parallel devices have light propagating in the plane of the quantum wells, in a device geometry that is preferably not single-mode waveguided.