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.

Though ZnO is known as a diamagnetic material, recent studies have revealed that its nanostructures can be ferromagnetic (FM). The FM origin has been ascribed to intrinsic defects. This work shines light on an alternate method based on mechanical milling to induce defect-related ferromagnetism in ZnO nanoparticles (NPs) from initial diamagnetic ZnO powders. Our idea is motivated by the fact that mechanical milling introduces more defects to a ground material. We point out that the FM order increases with increasing the density of defects in ZnO NPs. The experimental results obtained from analyzing X-ray absorption, electron spin resonance, and Raman scattering spectra demonstrate that the ferromagnetism in ZnO NPs is due to intrinsic defects mainly related to oxygen and zinc vacancies. Among these, zinc vacancies play a decisive role in introducing a high FM order in ZnO NPs.

Polycrystalline samples of BaTiO3 doped with 2.0 at. % Mn were prepared by solid-state reaction at various temperatures (Tan) ranging from 500 to 1350 °C, used high-pure powders of BaCO3, TiO2, and MnCO3 as precursors. Experimental results obtained from x-ray diffraction patterns and Raman scattering spectra reveal that tetragonal Mn-doped BaTiO3 starts constituting as Tan ≈ 500 °C. The Tan increase leads to the development of this phase. Interestingly, there is the tetragonal-hexagonal transformation in the crystal structure of BaTiO3 as Tan ≈ 1100 °C. Such the variations influence directly magnetic properties of the samples. Besides paramagnetic contributions of Mn2+ centers traced to electron spin resonance, the room-temperature ferromagnetism found in the samples is assigned to exchange interactions taking place between Mn3+ and Mn4+ ions located in tetragonal BaTiO3 crystals.

Having based on x-ray absorption spectroscopy, we point out structural phase separation in polycrystalline Zn1-xMnxO ceramics prepared by solid-state reaction. The samples are single phase in the wurtzite structure as x < 0.04. A Mn-concentration increase with x ≥ 0.04 results in the formation of a secondary phase of tetragonal ZnMn2O4 spinel. The feature of x-ray absorption spectra for the Mn K edge reveals an existence of Mn2+ and Mn3+ ions in Zn1-xMnxO, which are responsible for room-temperature paramagnetism. Particularly, when Mn content is increased, there is a chemical shift of the absorption edge toward higher energies, indicating an increase in concentration of Mn3+ ions. Fourier analyses for the spectra of extended x-ray absorption fine structure (EXAFS) shows up the substitution of Mn for Zn sites in the ZnO host lattice. The parameters related to the local structure have been determined and discussed in detail.