Ferromagnetism in Co-doped ZnO films grown by molecular beam epitaxy: magnetic, electrical and microstructural studies

We studied structural, optical and magnetic properties of high-quality 5 and 15% Co-doped ZnO films grown by plasma-assisted molecular beam epitaxy (MBE) on (0001)-sapphire substrates. Magnetic force microscopy (MFM) and magnetic measurements with SQUID magnetometer show clear ferromagnetic behavior of the films up to room temperature whereas they are antiferromagnetic below 200 K approximately. Temperature dependence of the carrier mobility was determined using Raman line shape analysis of the longitudinal-optical-phonon-plasmon coupled modes. It shows that the microscopic mechanism for ferromagnetic ordering is coupling mediated by free electrons between spins of Co atoms. These results bring insight into a subtle interplay between charge carriers and magnetism in MBE-grown Zn(1-x)CoxO films.Comment: 10 pages, 9 figures, 2 table

Non stoichiometry effect and disorder in Cu2ZnSnS4 thin films obtained by flash evaporation Raman scattering investigation

The cation disorder in Cu2ZnSnS4 thin films grown by flash evaporation of ZnS, CuS and SnS binary compounds has been studied by Raman spectroscopy. Process parameters such as the substrate temperature during the evaporation and the Ar pressure in the post-thermal treatment determined the samples' composition and Raman spectra. As a measure of cation disorder, the half-width and relative intensity of the Raman band peaking at 331-332 cm-1 is analysed. Comparison of the spectra for different samples of known composition showed that the relative intensity of the 331 cm-1 defect peak correlates with the previously reported theoretical prediction about enhancement of antisite defect formation in Cu2ZnSnS4 under "Cu-poor, Zn-rich" conditions. For "Cu-rich, Zn-poor" films, further experimental confirmation was obtained of the previously detected effect of the enhancement of cation disorder under intense optical excitationThis research is supported by the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Program FP7/2007-2013/ under REA grant greement 269167 (PVICOKEST), the Spanish MINECO project (KEST- PV, ENE2010-21541-C03) and the OPTEC grant. RC acknowledges financial support from Spanish MINECO within the program Ramon y Cajal (RYC-2011-08521

KH2PO4 + Host Matrix (Alumina / SiO2_2) Nanocomposite: Raman Scattering Insight

We report on the synthesis and Raman scattering characterization of composite materials based on the hostnanoporous matrices filled with nanostructured KH2PO4 (KDP) crystal. Silica (SiO2) and anodized aluminium oxide (AAO) were used as host matrices with various pore diameters, inter-pore spacing and morphology. The structure of the nanocomposites was investigated by X-ray diffraction and scanning electron microscopy. Raman scattering reveals the creation of one-dimensional nanostructured KDP inside the SiO2 matrix. We clearly observed the stretching {\nu}1, {\nu}3 and bending {\nu}2 vibrations of PO4 tetrahedral groups in the Raman spectrum of SiO2 + KDP. In Raman scattering spectra of AAO + KDP nanocomposite, the broad fluorescence background of AAO matrix dominates to a great extent, hindering thus the detecting of the KDP compound spectral response.Comment: 4 pages, 2 figures; 21st International Conference on Transparent Optical Networks (ICTON) 201

Paraelectric KH2_2PO4_4 Nanocrystals in Monolithic Mesoporous Silica: Structure and Lattice Dynamics

Combining dielectric crystals with mesoporous solids allows a versatile design of functional nanomaterials, where the porous host provides a mechanical rigid scaffold structure and the molecular filling adds the functionalization. Here, we report a study of the complex lattice dynamics of a SiO$_2$:KH$_2$PO$_4$ nanocomposite consisting of a monolithic, mesoporous silica glass host with KH$_2$PO$_4$ nanocrystals embedded in its tubular channels $\sim$12 nm across. A micro-Raman investigation performed in the spectral range of 70-1600 cm$^{-1}$ reveals the complex lattice dynamics of the confined crystals. Their Raman spectrum resembles the one taken from bulk KH$_2$PO$_4$ crystals and thus, along with X-ray diffraction experiments, corroborates the successful solution-based synthesis of KH$_2$PO$_4$ nanocrystals with a structure analogous to the bulk material. We succeeded in observing not only the high-frequency internal modes ($\sim$900-1200 cm$^{-1}$), typical of internal vibrations of the PO$_4$ tetrahedra, but, more importantly, also the lowest frequency modes typical of bulk KH$_2$PO$_4$ crystals. The experimental Raman spectrum was interpreted with a group theory analysis and first-principle lattice dynamics calculations. The analysis of calculated eigen-vectors indicates the involvement of hydrogen atoms in most phonon modes corroborating the substantial significance of the hydrogen subsystem in the lattice dynamics of paraelectric bulk and of KH$_2$PO$_4$ crystals in extreme spatial confinement. A marginal redistribution of relative Raman intensities of the confined compared to unconfined crystals presumably originates in slightly changed crystal fields and interatomic interactions, in particular for the parts of the nanocrystals in close proximity to the silica pore surfaces.Comment: 10 pages, 4 figures, in pres

SERS of dye film deposited onto gold nano-clusters

Gold nanoclusters were obtained by co-deposition of and polytetrafluoroethylene (PTFE) in vacuum with various gold concentrations. The films deposited were undergone to heating at various temperatures in air. Transformation of ensemble morphology after heating was studied using atomic force microscope (AFM). Raman scattering spectra of an ultra-thin film of Rhodamine 6G deposited onto substrates with gold nano-clusters of different morphology were recorded. The best substrate gave strong amplification of the Raman scattering signal from Rhodamine 6G film. Therefore, produced Au nano-clusters are suitable for surface enhanced Raman scattering spectroscopy of nano-quantities of material

Optical and structural studies of phase transformations and composition fluctuations at annealing of Zn₁₋xCdxO films grown by dc magnetron sputtering

Ternary Zn₁₋xCdxO (x < 0.12) alloy crystalline films with highly preferred orientation (002) have been successfully deposited on sapphire c-Al₂O₃ substrates using the direct current (dc) reactive magnetron sputtering technique and annealed at temperature 600 °C in air. The structural and optical properties of Zn₁₋xCdxO thin films were systematically studied using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), micro-Raman and photoluminescent (PL) spectroscopy. XPS measurements clearly confirmed Cd incorporation into ZnO lattice. XRD data revealed that the growth of wurtzite Zn₁₋xCdxO films occurs preferentially in the (002) direction. Also, when the Cd content is increased, the XRD peaks shift towards smaller angles and the full width at half-maximum of the lines increases. When the Cd content increases, LO A1 ( Zn₁₋CdxO )-like Raman modes show composition dependent frequency decrease and asymmetrical broadening. The near band-edge PL emission at room temperature shifts gradually to lower energies as the Cd content increases and reaches 2.68 eV for the highest Cd content (x = 0.12). The analysis of NBE band emission and Raman LO A1 ( Zn₁₋xCdxO ) mode shows that at a higher Cd content the coexistence of Zn₁₋xCdxO areas with different concentrations of Cd inside the same film occurs. The presence of CdO in annealed Zn₁₋xCdxO films with the higher Cd content was confirmed by Raman spectra of cubic CdO nanoinclusions. The XRD data also revealed phase segregation of cubic CdO in annealed Zn₁₋xCdxO films (Tann = 600 °C) for x ≥ 0.013

The involuntary nature of binge drinking: goal directedness and awareness of intention

Binge drinking represents a public health issue and is a known risk factor in the development of alcohol use disorders. Previous studies have shown behavioural as well as neuroanatomical alterations associated with binge drinking. Here, we address the question of the automaticity or involuntary nature of the behaviour by assessing goal-directed behaviour and intentionality. In this study, we used a computational two-step task, designed to discern between model-based/goal-directed and model-free/habitual behaviours, and the classic Libet clock task, to study intention awareness, in a sample of 31 severe binge drinkers (BD) and 35 matched healthy volunteers. We observed that BD had impaired goal-directed behaviour in the two-step task compared with healthy volunteers. In the Libet clock task, BD showed delayed intention awareness. Further, we demonstrated that alcohol use severity, as reflected by the alcohol use disorders identification test, correlated with decreased conscious awareness of volitional intention in BD, although it was unrelated to performance on the two-step task. However, the time elapsed since the last drinking binge influenced the model-free scores, with BD showing less habitual behaviour after longer abstinence. Our findings suggest that the implementation of goal-directed strategies and the awareness of volitional intention are affected in current heavy alcohol users. However, the modulation of these impairments by alcohol use severity and abstinence suggests a state effect of alcohol use in these measures and that top-down volitional control might be ameliorated with alcohol use cessation.N.D. is a research fellow of the Deutsche Forschungsgemeinschaft (DO1915/1-1). This study was funded by the Wellcome Trust as part of a Wellcome Trust Intermediate Fellowship to V.V. (983705/Z/10/Z). V.V. is funded by a Medical Research Council Senior Fellowship (MR/P008747/1)

Impaired awareness of motor intention in functional neurological disorder: implications for voluntary and functional movement

Functional neurological disorders (FNDs), also known as conversion disorder, are unexplained neurological symptoms unrelated to a neurological cause. The disorder is common, yet poorly understood. The symptoms are experienced as involuntary but have similarities to voluntary processes. Here we studied intention awareness in FND. A total of 26 FND patients and 25 healthy volunteers participated in this functional magnetic resonance study using Libet's clock. FND is characterized by delayed awareness of the intention to move relative to the movement itself. The reporting of intention was more precise, suggesting that these findings are reliable and unrelated to non-specific attentional deficits. That these findings were more prominent with aberrant positive functional movement symptoms rather than negative symptoms may be relevant to impairments in timing for an inhibitory veto process. Attention towards intention relative to movement was associated with lower right inferior parietal cortex activity in FND, a region early in the processing of intention. During rest, aberrant functional connectivity was observed with the right inferior parietal cortex and other motor intention regions. The results converge with observations of low inferior parietal activity comparing involuntary with voluntary movement in FND, emphasizing core deficiencies in intention. Heightened precision of this impaired intention is consistent with Bayesian theories of impaired top-down priors that might influence the sense of involuntariness. A primary impairment in voluntary motor intention at an early processing stage might explain clinical observations of slowed effortful voluntary movement, heightened self-directed attention and underlie functional movements. These findings further suggest novel therapeutic targets.N.D. is a research fellow of the Deutsche Forschungsgemeinschaft (DO1915/1-1). V.V. is a Wellcome Trust Intermediate Fellow (983705/Z/10/Z). The study was funded by the Biomedical Research Council