photoelectric device can be either intrinsic or extrinsic. An intrinsic semiconductor has its own charge carriers and is not an efficient semiconductor, e.g. silicon. In intrinsic devices the only available electrons are in the valence band, and hence the photon must have enough energy to excite the electron across the entire bandgap.
Extrinsic devices have impurities, also called dopants, added whose ground state energy is closer to the conduction band; since the electrons do not have as far to jump, lower energy photons (i.e., longer wavelengths and lower frequencies) are sufficient to trigger the device. If a sample of silicon has some of its atoms replaced by phosphorus atoms (impurities), there will be extra electrons available for conduction. This is an example of an extrinsic semiconductor.