After having some knowledge on the electrons, we came to know that the outermost shell has the valence electrons which are loosely attached to the nucleus. Such an atom, having valence electrons when brought close to the other atom, the valence electrons of both these atoms combine to form “Electron pairs”. This bonding is not so very strong and hence it is a Covalent bond.
For example, a germanium atom has 32 electrons. 2 electrons in first orbit, 8 in second orbit, 18 in third orbit, while 4 in last orbit. These 4 electrons are valence electrons of germanium atom. These electrons tend to combine with valence electrons of adjoining atoms, to form the electron pairs, as shown in the following figure.
Due to the thermal energy supplied to the crystal, some electrons tend to move out of their place and break the covalent bonds. These broken covalent bonds, result in free electrons which wander randomly. But the moved away electrons creates an empty space or valence behind, which is called as a hole.
This hole which represents a missing electron can be considered as a unit positive charge while the electron is considered as a unit negative charge. The liberated electrons move randomly but when some external electric field is applied, these electrons move in opposite direction to the applied field. But the holes created due to absence of electrons, move in the direction of applied field.
It is already understood that when a covalent bond is broken, a hole is created. Actually, there is a strong tendency of semiconductor crystal to form a covalent bond. So, a hole doesn’t tend to exist in a crystal. This can be better understood by the following figure, showing a semiconductor crystal lattice.
An electron, when gets shifted from a place A, a hole is formed. Due to the tendency for the formation of covalent bond, an electron from B gets shifted to A. Now, again to balance the covalent bond at B, an electron gets shifted from C to B. This continues to build a path. This movement of hole in the absence of an applied field is random. But when electric field is applied, the hole drifts along the applied field, which constitutes the hole current. This is called as hole current but not electron current because, the movement of holes contribute the current flow.
Electrons and holes while in random motion, may encounter with each other, to form pairs. This recombination results in the release of heat, which breaks another covalent bond. When the temperature increases, the rate of generation of electrons and holes increase, thus rate of recombination increases, which results in the increase of densities of electrons and holes. As a result, conductivity of semiconductor increases and resistivity decreases, which means the negative temperature coefficient.