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Activation of shallow acceptor state has been observed in ion irradiated andsubsequently air annealed polycrystalline ZnO material. Low temperaturephotoluminescence (PL) spectrum of the sample exhibits clear signature ofacceptor bound exciton (ABX) emission at 3.360 eV. The other two samples,pristine and ion irradiated (without annealing), however, do not show acceptorrelated PL emission in the nearby energy region. Electron transition fromshallow donor (most probable site is interstitial zinc for undoped ZnO) to suchnewly formed shallow acceptor state creates new donor-acceptor pair (DAP)luminescence peak ~ 3.229 eV. ABX and DAP peak energy positions confirm thatthe acceptor is N related. The acceptor exciton binding energy has beenestimated to be 180 +/- 15 meV which is in conformity with earlier reports. Theactivation of shallow acceptors without any source of atomic nitrogen can onlybe possible through diffusion of molecular nitrogen inside the sample duringannealing. The N2 molecules get trapped at bulk defect sites incorporated byion irradiation and subsequent annealing. X-ray diffraction (XRD) and Ramanspectroscopic (RS) investigation have been employed to probe the changingdefective nature of the ZnO samples. Irradiation induced increased disorder hasbeen detected (both by XRD and RS) which is partially removed/modified byannealing at 300 oC. Simultaneous activation of molecular nitrogen acceptor inpurposefully defective ZnO is the key finding of this work. Results presentedhere provide a simple but controlled way of producing shallow acceptor state inZnO. If optimized through suitable choice of ion, its energy and fluence aswell as the annealing temperature, this methodology can trigger further scopeto fabricate devices using ZnO epitaxial thin films or nanowires.

Shallow acceptor state in ZnO realized by simple irradiation and annealing route