Thermally activated cation ordering in ZnGa2Se4 single crystals studied by Raman scattering, optical absorption, and ab initio calculations.

Order-disorder phase transitions induced by thermal annealing have been studied in the ordered-vacancy compound ZnGa2Se4 by means of Raman scattering and optical absorption measurements. The partially disordered as-grown sample with tetragonal defect stannite (DS) structure and I4¯2m space group has been subjected to controlled heating and cooling cycles. In situ Raman scattering measurements carried out during the whole annealing cycle show that annealing the sample to 400 °C results in a cation ordering in the sample, leading to the crystallization of the ordered tetragonal defect chalcopyrite (DC) structure with I4¯ space group. On decreasing temperature the ordered cation scheme of the DC phase can be retained at ambient conditions. The symmetry of the Raman-active modes in both DS and DC phases is discussed and the similarities and differences between the Raman spectra of the two phases emphasized. The ordered structure of annealed samples is confirmed by optical absorption measurements and ab initio calculations, that show that the direct bandgap of DC-ZnGa2Se4 is larger than that of DS-ZnGa2Se4.

Raman scattering in Me-doped ZnO nanorods (Me = Mn, Co, Cu and Ni) prepared by thermal diffusion.

We have investigated normal and resonant Raman scattering in Me-doped ZnO nanorods (Me = Mn, Co, Cu and Ni) prepared by thermal diffusion. Experimental results show that the normal Raman spectra consist of the conventional modes associated with wurtzite ZnO and impurity-related additional modes. Under resonant conditions, only longitudinal optical (LO) phonon scattering and its overtones are observed. The number of LO phonon lines and their relative intensity depend on the doping element and level. For the nanorods doped with Cu and Ni, we have observed LO phonon overtones up to eleventh order. This situation does not happen for the Mn-doped nanorods, which show only five LO phonon modes. By co-doping Mn and Co into the ZnO host lattice, however, the LO phonon overtones up to eleventh order are observed again. The nature of this phenomenon is explained by means of the study of XRD, TEM and photoluminescence.

The impact of morphology upon the radiation hardness of ZnO layers.

It is shown that ZnO nanorods and nanodots grown by MOCVD exhibit enhanced radiation hardness against high energy heavy ion irradiation as compared to bulk layers. The decrease of the luminescence intensity induced by 130 MeV Xe(23+) irradiation at a dose of 1.5 × 10(14) cm(-2) in ZnO nanorods is nearly identical to that induced by a dose of 6 × 10(12) cm(-2) in bulk layers. The damage introduced by irradiation is shown to change the nature of electronic transitions responsible for luminescence. The change of excitonic luminescence to the luminescence related to the tailing of the density of states caused by potential fluctuations occurs at an irradiation dose around 1 × 10(14) cm(-2) and 5 × 10(12) cm(-2) in nanorods and bulk layers, respectively. More than one order of magnitude enhancement of radiation hardness of ZnO nanorods grown by MOCVD as compared to bulk layers is also confirmed by the analysis of the near-bandgap photoluminescence band broadening and the behavior of resonant Raman scattering lines. The resonant Raman scattering analysis demonstrates that ZnO nanostructures are more radiation-hard as compared to nanostructured GaN layers. High energy heavy ion irradiation followed by thermal annealing is shown to be a way for the improvement of the quality of ZnO nanorods grown by electrodeposition and chemical bath deposition.