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This is copied from a similar question to yours fyi.

Using boron, phosphorus, and silicon as examples.

P-type doping is a process where a silicon atom in the lattice is replaced by a boron atom. A Boron atom has 3 electrons in the outer shell, compared with an electron occupancy of 4 for a silicon atom. So a Boron atom provides a vacancy for any free electrons to occupy with a little effort, when an electron chances to be nearby (the four boron-silicon covalent bonds needs 8 electrons to be stable, but only 7 are provided). The net charge of the material is still zero. More about from where the free electron is coming.

N-type doping is using a phosphorus atom to replace a silicon atom. A phosphorus atom has 5 electrons in the outer shell. So a phosphorus atom provides an electron that can be freed with a little effort (the four phosphorus-silicon covalent bonds only need 8 electrons to be stable, each atom needing only to contribute four electrons; the 9th electron will be loosely bound). The net charge of the material is still zero. Where can the electron go?

Magic happens when p-type silicon is brought in contact with n-type silicon to form a pn junction. The excess electron vacancies (holes) in p-Si now can exchange with the excess electrons in n-Si, but the net charge of the p-n silicon entity is still zero. However, microscopically, a depletion region is formed at the pn junction, where excess carriers can cross over to the other side. In the p-Si, excess electrons from the n-Si start filling up the holes (the lack of the 8th outer-shell electron to form the four stable boron-silicon covalent bonds) and negatively-charged boron atoms are formed. In the n-Si, excess holes from the p-Si start swallowing up the loosely-bound electrons (the 9th electron in the outer shell) of phosphorus atoms and positively-charged phosphorus atoms are formed. Once formed, and in the absence of an electric field, the depletion region now presents an energy barrier to any further carrier movement and a steady state results -- no net current in the pn junction.

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