Shallow acceptor state in ZnO realized by simple irradiation and   annealing route
  Activation of shallow acceptor state has been observed in ion irradiated and subsequently air annealed polycrystalline ZnO material. Low temperature photoluminescence (PL) spectrum of the sample exhibits clear signature of acceptor bound exciton (ABX) emission at 3.360 eV. The other two samples, pristine and ion irradiated (without annealing), however, do not show acceptor related PL emission in the nearby energy region. Electron transition from shallow donor (most probable site is interstitial zinc for undoped ZnO) to such newly formed shallow acceptor state creates new donor-acceptor pair (DAP) luminescence peak ~ 3.229 eV. ABX and DAP peak energy positions confirm that the acceptor is N related. The acceptor exciton binding energy has been estimated to be 180 +/- 15 meV which is in conformity with earlier reports. The activation of shallow acceptors without any source of atomic nitrogen can only be possible through diffusion of molecular nitrogen inside the sample during annealing. The N2 molecules get trapped at bulk defect sites incorporated by ion irradiation and subsequent annealing. X-ray diffraction (XRD) and Raman spectroscopic (RS) investigation have been employed to probe the changing defective nature of the ZnO samples. Irradiation induced increased disorder has been detected (both by XRD and RS) which is partially removed/modified by annealing at 300 oC. Simultaneous activation of molecular nitrogen acceptor in purposefully defective ZnO is the key finding of this work. Results presented here provide a simple but controlled way of producing shallow acceptor state in ZnO. If optimized through suitable choice of ion, its energy and fluence as well as the annealing temperature, this methodology can trigger further scope to fabricate devices using ZnO epitaxial thin films or nanowires. 
S. Pal and D. Jana, T. Rakshit, S. S. Singha, K. Asokan, S. Dutta and   A. Sarkar
cond-mat.mtrl-sci