Both n-type and p-type doping of silicon is at odds with the charge transfer predicted by Pauling electronegativities and can only be reconciled if we no longer regarding dopant species as isolated atoms but rather consider them as clusters consisting of the dopant and its four nearest neighbor silicon atoms. The process that gives rise to n-type and p-type effects is the charge redistribution that occurs between the dopant and its neighbors, as we illustrate here using electronic structure calculations. This view point is able to explain why conventional substitutional n-type doping of carbon has been so difficult.
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