Synthesis of TiO(2) nanocrystals controlled by means of the size of magnetic elements and the level of doping with them.

TiO(2) nanocrystals were synthesized by a hydrolysis method combined with a thermal treatment. TiO(2) nanocrystals with rutile and anatase structure were selectively synthesized by controlling the pH level in the precursor solution, and the crystallite size was controlled by changing the reaction temperature. Moreover, Co-doped TiO(2) nanocrystals with rutile structure were also synthesized by means of the addition of Co to the precursor solution. Secondary phases such as Co precipitates and Co oxide were not present in the sample tested, with [Co]<10 mol%. With an increase in the Co doping level, the E(g)-phonon signal at 447 cm(-1) was broadened and shifted to a lower frequency, indicating the incorporation of Co into the rutile TiO(2) host lattice and lattice expansion. Optical absorption spectra showed that the absorption edge at ∼3.0 eV corresponded to the band gap of rutile TiO(2) and shifted to the lower energy side upon Co doping. These results indicated the possibility of band gap engineering of rutile TiO(2) via Co doping. On the other hand, the charge transfer gap between O 2p and Co 3d orbitals was also observed for samples with Co, suggesting the possibility of photo-induced magnetism in rutile TiO(2) nanocrystals, obtained by visible light irradiation.

Structural and electronic properties of ZnO polycrystals doped with Co.

Zn(1-x)Co(x)O samples were prepared by a standard solid-state reaction method. Zn(1-x)Co(x)O crystals in the wurtzite structure were obtained with a Co composition of up to 22.1%. The a- and c-axis lengths increased and decreased, respectively, with an increase in Co composition. Raman spectra showed systematic broadening of the E(2) (high) phonon mode associated with the increase in Co composition, and electronic transitions of Co in the oxygen tetrahedron were observed in optical absorption measurement. These results indicated systematic substitution of Co into the Zn sites. Furthermore, an additional broad absorption band at 2.4-3.3 eV corresponding to the charge transfer (CT) process [Formula: see text] was also observed. The Raman spectra showed strong enhancement of the LO phonon due to a resonant Raman process induced with the coupling of the LO phonon and a photo-excited carriers mediated CT gap. These results suggest the possibility of carrier-induced ferromagnetism based on double exchange interaction in Zn(1-x)Co(x)O by visible light irradiation.

Spin-phonon coupling in multiferroic YbMnO(3) studied by Raman scattering.

Hexagonal YbMnO(3) bulk polycrystals were prepared and studied by Raman scattering in the temperature range of 15-300 K. A total of 15 phonon modes of A(1), E(1) and E(2) type were identified. Some E(2) phonon modes showed anomalous temperature variations in frequency at T(N)∼80 K, suggesting a coupling between the spin and phonon systems below T(N). As another evidence of spin-phonon coupling, softening of an A(1)-phonon mode for the O-Mn vibration was observed at ∼T(N). Substitution of Mn by Al suggests this view.

Raman scattering study of multiferroic Ho(3)Fe(5)O(12) thin films.

Ho(3)Fe(5)O(12) crystallizes in a body-centered cubic lattice and shows no ferroelectricity because of its highly symmetric (centrosymmetric) crystal structure. However, in heteroepitaxially grown thin films, Ho(3)Fe(5)O(12) may exhibit ferroelectricity because of lattice strains induced by the substrate. In this work, heteroepitaxial films of Ho(3)Fe(5)O(12) were grown with different thicknesses of 50-160 nm and studied by x-ray diffraction and Raman scattering. The results were compared with those of bulk polycrystals to characterize residual strains. At room temperature, Raman spectra of films revealed a phonon frequency shift from those of bulk samples, showing lattice distortion. There was a difference in the lattice distortion scheme between the thinner and thicker films. Results of x-ray diffraction were well correlated with the Raman data. Raman measurements at 300-800 K showed the existence of lattice strain up to ∼650 K. This suggests a remanent-polarization character of Ho(3)Fe(5)O(12) films up to this temperature. Closeness between the magnetic ordering temperature T(N) = 567 K and T(C)∼650 K may bring us the ideal multiferroic material with an enhanced magnetoelectric effect at room temperature.

Structural properties of nanometre-sized ZnO crystals doped with Co.

Nanometre-sized ZnO crystals doped with Co were synthesized by a co-precipitation method combined with a thermal treatment. By changing the reaction temperature, we can control the crystallite size from roughly 10 nm particles to 20 nm × 200 nm nm rods grown along the hexagonal c-direction. X-ray diffraction and Raman scattering showed growth of high-quality wurtzite ZnO crystals incorporating Co systematically in the ZnO host lattice in the tested range of [Co]<3.0 mol%. Electronic transitions of Co in the oxygen tetrahedron were also observed in optical absorption, giving supporting evidence for systematic substitution of Co into the Zn site.

Observation of phonons in multiferroic BiFeO(3) single crystals by Raman scattering.

We have grown BiFeO(3) bulk single crystals by a flux method and characterized the phonon spectra in detail by Raman scattering in the temperature range 4-1100 K. All the 13 Raman-active phonon modes predicted by group theory, 4A(1)+9E, were observed at low temperature and successfully assigned by a polarized Raman measurement. Moreover, drastic spectral changes in the Raman spectra were observed at temperatures 600-700 K and 1000-1100 K. These features are discussed from the viewpoint of phonon coupling with the magnetic ordering and the structural phase transition, respectively.

Raman scattering studies on multiferroic YMnO(3).

YMnO(3) is a multiferroic material in which ferroelectric and antiferromagnetic ordering can coexist. We have studied a YMnO(3) bulk crystal in detail by Raman scattering in a wide temperature range of 15-1200 K, with comparison to a previous experiment at room temperature and a theoretical prediction for Raman-active phonon modes. In the low-temperature ferroelectric phase, the observed phonon spectra showed anomalous temperature variation at the Néel temperature, T(N)∼80 K, suggesting a coupling between the spin and phonon systems below T(N). Furthermore, spectra for the high-temperature paraelectric phase, reported here for the first time, showed a sudden change at the Curie temperature T(C)>900 K, suggesting an abrupt structural phase change from the ferroelectric to the paraelectric phase.