An extrinsic semiconductor is one that has been doped; during manufacture of the semiconductor crystal a trace element or chemical called a doping agent has been incorporated chemically into the crystal, for the purpose of giving it different electrical properties than the pure semiconductor crystal, which is called an intrinsic semiconductor. In an extrinsic semiconductor it is these foreign dopant atoms in the crystal lattice that mainly provide the charge carriers which carry electric current through the crystal. The doping agents used are of two types, resulting in two types of extrinsic semiconductor. An electron donor dopant is an atom which, when incorporated in the crystal, releases a mobile conduction electron into the crystal lattice. An extrinsic semiconductor which has been doped with electron donor atoms is called an n-type semiconductor, because the majority of charge carriers in the crystal are negative electrons. An electron acceptor dopant is an atom which accepts an electron from the lattice, creating a vacancy where an electron should be called a hole which can move through the crystal like a positively charged particle. An extrinsic semiconductor which has been doped with electron acceptor atoms is called a p-type semiconductor, because the majority of charge carriers in the crystal are positive holes.

Doping is the key to the extraordinarily wide range of electrical behavior that semiconductors can exhibit, and extrinsic semiconductors are used to make semiconductor electronic devices such as diodes, transistors, integrated circuits, semiconductor lasers, LEDs, and photovoltaic cells. Sophisticated semiconductor fabrication processes like photolithography can implant different dopant elements in different regions of the same semiconductor crystal wafer, creating semiconductor devices on the wafer's surface. For example a common type of transistor, the n-p-n bipolar transistor, consists of an extrinsic semiconductor crystal with two regions of n-type semiconductor, separated by a region of p-type semiconductor, with metal contacts attached to each part.