  Experimental studies of Zn1-xCoxO as thin films or nanocrystals have found
ferromagnetism and Curie temperatures above room temperature and that p- or
n-type doping of Zn1-xCoxO can change its magnetic state. Bulk Zn1-xCoxO with a
low defect density and x in the range used in experimental thin film studies
exhibits ferromagnetism only at very low temperatures. Therefore defects in
thin film samples or nanocrystals may play an important role in promoting
magnetic interactions between Co ions in Zn1-xCoxO. The electronic structures
of Co substituted for Zn in ZnO, Zn and O vacancies, substituted N and
interstitial Zn in ZnO were calculated using the B3LYP hybrid density
functional in a supercell. The B3LYP functional predicts a band gap of 3.34 eV
for bulk ZnO, close to the experimental value of 3.47 eV. Occupied minority
spin Co 3d levels are at the top of the valence band and unoccupied levels lie
above the conduction band minimum. Majority spin Co 3d levels hybridize
strongly with bulk ZnO states. The neutral O vacancy and interstitial Zn are
deep and shallow donors, respectively. The Zn vacancy is a deep acceptor and
the acceptor level for substituted N is at mid gap. The possibility that p- or
n-type dopants promote exchange coupling of Co ions was investigated by
computing total energies of magnetic states of ZnO supercells containing two Co
ions and an oxygen vacancy, substituted N or interstitial Zn in various charge
states. The neutral N defect and the singly-positively charged O vacancy are
the only defects which strongly promote ferromagnetic exchange coupling of Co
ions at intermediate range.
