Single-crystal semiconductors have a particularly important place in optoelectronics, since they are the starting material for high-quality sources, receivers and amplifiers. Other materials, however, can be relevant to some device classes: polycrystalline or amorphous semiconductors can be exploited in light-emitting diodes (LEDs) and solar cells; dielectrics (also amorphous) are the basis for passive devices (e.g., waveguides and optical fibers); and piezoelectric (ferroelectric) crystals such as lithium niobate are the enabling material for a class of electrooptic (EO) modulators. Moreover, polymers have been recently exploited in the development of active and passive optoelectronic devices, such as emitters, detectors, and waveguides (e.g., fibers). Nevertheless, the peculiar role of single-crystal semiconductors justifies the greater attention paid here to this material class with respect to other optoelectronic materials.
From the standpoint of electron properties, semiconductors are an intermediate step between insulators and conductors. The electronic structure of crystals generally includes a set of allowed energy bands, that electrons populate according to the rules of quantum mechanics. The two topmost energy bands are the valence and conduction band, respectively, see Fig. 1.1. At some energy above the conduction band, we find the vacuum level, i.e., the energy of an electron free to leave the crystal. In insulators, the valence band (which hosts the electrons participating to the chemical bonds) is separated from the conduction band by a large energy gap Eg, of the order of a few electronvolts (eV). Due to the large gap, an extremely small number of electrons have enough energy to be promoted to the conduction band, where they could take part into electrical conduction. In insulators, therefore, the conductivity is extremely small.