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The depletion region in PN junctions is created by charges from the N part diffusing into the P part, thus completing an octet of covalent bonds in the P part. This shift however leaves positive ions in the N region and negative ions in the P region, which in turn resist this shift of charges.

What physical principle makes the "octet rule" dominate the electrostatic repulsive force, allowing the depletion region to form in the first place?

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The electron in the $n$ semiconductor and the hole in the $p$ type semiconductor are delocalised and not bound to any particular atom, so arguments based on completing octets aren't useful.

This diagram shows roughly how the depletion layer forms:

Depletion layer

In the $n$ type semiconductor the doping creates donor states in the band gap, and electrons from these states are thermally promoted to the conduction band where they are delocalised. In the $p$ type semiconductor the doping creates acceptor states and electrons are thermally promoted into these states to leave holes in the valence band, and again these holes are delocalised. An electron in the conduction band on the $n$ side can lower its energy by recombining with a hole on the $p$ side.

The electron lowers its energy by about the band gap, but its energy increases because it has to do work crossing the depletion layer against the potential across the depletion layer. The charge separation and depletion layer thickness increases until these two energies are equal.

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  • $\begingroup$ electrons from N diffuse towards P and complete an octet, until an equilibrium is reached. these octets are stable, despite the electrostatic repulsion. the fact that the charges are delocalized does not change the electrostatic forces they should feel due to the created ions. the question is what move the electrons towards completing an octet rather than staying put in their currently neutral atom. $\endgroup$
    – Sparkler
    Commented Oct 13, 2014 at 6:16
  • $\begingroup$ @Sparkler: You say electrons from N diffuse towards P and complete an octet but this is not true. The electrons in the $p$ type semiconductor valence band are delocalised so any particular electron is not associated with any particular atom. The electrons are not grouped into octets around a particular silcon atom. Similarly any charges created by movement of electrons are spread out over the whole system. $\endgroup$ Commented Oct 13, 2014 at 7:02

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