Nitrogen and tellurium co-doped ZnO (ZnO:[N+Te]) films have been grown on (0001) ZnO substrate by plasma-assisted molecular beam epitaxy. The electron concentration of tellurium doped ZnO (ZnO:Te) gradually increases, compared that of undoped ZnO (u-ZnO). On the other hand, conductivity of ZnO:[N+Te] changes from n-type to p-type characteristic with a hole concentration of 4×1016 cm-3. However, nitrogen doped ZnO film (ZnO:N) still remain as n-type conductivity with a electron concentration of 2.5×1017 cm-3. Secondary ion mass spectroscopy reveals that nitrogen concentration ([N]) of ZnO:[N+Te] film (2×1021 cm-3) is relatively higher than that of ZnO:N film (3×1020 cm-3). 10 K photoluminescence spectra shows that considerable improvement of emission properties of ZnO:[N+Te] with an emergence of narrow acceptor bound exciton (A°X, 3.359 eV) and donor-acceptor pair (DAP, 3.217 eV), compared with those of u-ZnO. Consequently, high quality p-type ZnO with high N concentration is realized by using Te and N co-doping technique due to reduction of Madelung energy.

We report that the nonlinear optical response of polarity controlled ZnO films grown by selective growth technique of Zn-polar and O-polar ZnO layers on sapphire substrate using Cr-compound buffer layers. ZnO layers grown on CrN/sapphire show Zn polar, while those grown on Cr2O3/sapphire result in O-polar ZnO films. In order to verify the origin of nonlinear optical response of ZnO, the polarity-controlled ZnO thin films grown on different buffer layers were investigated as nonlinear optical materials for second harmonic generation (SHG). The effective nonlinear optical coefficient (deff) of ZnO grown on Cr-compound buffer layers showed a higher value than that of ZnO grown on MgO buffer layers. Finally, by combining suggested in-situ polarity control technique with photolithography technique, we have fabricated 1D and 2D periodically-polarity-inverted (PPI) hetro-structures with periodicity ranging from 60 μm to 2 μm. The lateral polarity inversion is confirmed by piezo response microscopy. Such PPI ZnO heterostructures show the enhancement of SHG intensity comparing with the ZnO films.

Epitaxial ZnO films are successfully grown on Al2O3 substrates with phase controlled CrN buffer layer using Zn and O-plasma pre-exposures on CrN layers by plasma assisted molecular beam epitaxy (P-MBE). The Zn exposures on CrN layers prior to ZnO film growth result in the formation of rocksalt CrN without surface oxidation. On the other hand, the surface of the initially deposited CrN layers with rocksalt structure changes into hexagonal structured Cr2O3 after O-plasma exposure as confirmed by reflection high-energy electron diffraction (RHEED) and high resolution transmission electron microscopy (HR TEM). Etching studies show that the ZnO films grown on CrN have +C polarity, while the polarity of ZnO on Cr2O3/CrN double buffer is -C polarity. The interdiffusion of Zn and Cr occurs at the ZnO/CrN interface, while the interdiffusion is negligible at the ZnO/ Cr2O3 interface. The interdiffusion of Cr and Zn can be suppressed by inserting a low-temperature ZnO buffer layer in between ZnO and CrN layers, which helps improve the crystal quality of ZnO layers grown with CrN buffer.