Optical reflectivity and the Brillouin zones are closely linked, since the band gap energy in the Brillouin zone determines if a photon is absorbed or reflected. If the band gap energy in the Brillouin zone is smaller than the photon energy, the photon will be absorbed, while the photon will be transmitted/reflected if the band gap energy is larger than the photon energy. For example, the photon energies of visible light lie in a range between 1.8 eV (red light) and 3.1 eV (violet light), So if the band gap energy is larger than 3.2 eV, photons of visible light will not be absorbed, but reflected/transmitted: the material appears transparent. This is the case for diamond, quartz etc. But if the band gap is roughly 2.6 eV (this is the case for cadmium sulfide) only blue and violet light is absorbed, while red and green light are transmitted, resulting in a reddish looking material.
When an electric field is added to a (semi)conductor, the material will try to cancel this field by inducing an electric field at its surface. Because of this electric field, the optical properties of the surface layer will change, due to the change in size of critical band gaps, and hence changing its energy. Since the change in band gap only occurs on the surface of the (semi)conductor, optical properties will not change in the core of bulk materials, but for very thin films, where almost all particles can be found at the surface, the optical properties can change: absorption or transmittance of certain wavelengths depending on the strength of the electric field. This can result in more accurate measurements in case there are multiple compounds in the semiconductor, practically canceling the background noise of data.
Commonly, the band gaps are smallest close to, or at the Brillouin zone boundary. Adding an electric field will alter the whole band structure of the material where the electric field penetrates, but the effect will be especially noticeable at the Brillouin zone boundary. When the smallest band gap changes in size, this alters the optical reflectivity of the material more than the change in an already larger band gap. This can be explained by noticing that the smallest band gap determines a lot of the reflectivity, as lower energy photons cannot be absorbed and re-emitted.