  We present ab initio density functional calculations that show P (Al) dopant
atoms in small hydrogen-terminated Si crystals to be negatively (positively)
charged. These signs of the dopant charges are reversed relative to the same
dopants in bulk Si. We predict this novel reversal of the dopant charge (and
electronic character of the doping) to occur at crystal sizes of order 100 Si
atoms. We explain it as a result of competition between fundamental principles
governing charge transfer in bulk semiconductors and molecules and predict it
to occur in nanocrystals of most semiconductors.
