Photogeneration of charge carriers

When a photon hits a piece of silicon, one of three things can happen:

1. the photon can pass straight through the silicon — this (generally) happens for lower energy photons,
2. the photon can reflect off the surface,
3. the photon can be absorbed by the silicon, if the photon energy is higher than the silicon band gap value. This generates an electron-hole pair and sometimes heat, depending on the band structure.

When a photon is absorbed, its energy is given to
an electron in the crystal lattice. Usually this electron is in the valence band, and is tightly bound in covalent bonds between neighboring atoms, and hence unable to move far. The energy given to it by the photon "excites" it into the conduction band, where it is free to move around within the semiconductor.

The covalent bond that the electron was previously a part of now has one fewer electron — this is known as a hole. The presence of a missing covalent bond allows the bonded electrons of neighboring atoms to move into the "hole," leaving another hole behind, and in this way a hole can move through the lattice. Thus, it can be said that photons absorbed in the semiconductor create mobile electron-hole pairs.

A photon need only have greater energy than that of the band gap in order to excite an electron from the valence band into the conduction band. However, the solar frequency spectrum approximates a black body spectrum at ~6000 K, and as such, much of the solar radiation reaching the Earth is composed of photons with energies greater than the band gap of silicon. These higher energy photons will be absorbed by the solar cell, but the difference in energy between these photons and the silicon band gap is converted into heat (via lattice vibrations — called phonons) rather than into usable electrical energy.