Publications

Although impurity doping of nanocrystals is essential in controlling their physical properties for various applications, the doping mechanism of ultrasmall, colloidal II-VI semiconductor nanocrystals, corresponding to the initial stages of growth, is not yet understood. In this study the concentrations of Mn2+ ions in the core, on the surface, and as an agglomerated separate phase in 2.9 nm cubic ZnS nanocrystals, prepared by a surfactant-assisted liquid liquid synthesis within 20 to 20 000 ppm nominal impurity concentration range, have been determined by quantitative multifrequency electron paramagnetic resonance. The unexpected strong decrease in the core doping efficiency with the nominal concentration increase, in contrast to the small variation of the doping efficiency for the surface-bound Mn2+ ions, and the sizable core doping efficiency observed for 1.8 nm nanocrystals were explained with the extended lattice defect assisted mechanism of incorporation. According to this mechanism, which is not size or shape limited, being active from the initial growth stages, the incorporation of Mn2+ ions takes place at surface sites with high binding energy on dislocation steps formed by the emerging stacking defects. High resolution transmission electron microscopy confirms the presence of such stacking defects in a large proportion of the investigated cubic ZnS nanocrystals, ensuring the operation of the proposed doping mechanism.

Up-conversion properties of Yb3+/Er3+ co-doped LiYF4 nanocrystals embedded in a sol-gel derived oxyfluoride glass-ceramic have been studied by comparison to the corresponding polycrystalline sample. Under 980 rim laser light pumping, both Yb3+/Er3+ co-doped LiYF4 samples show green ((H-2(11/2,) S-4(3/2)) I-4(15/2)) and red (F-4(9/2) I-4(15/2)) up-conversion luminescences explained by a two-photon processes. The tendency for the saturation of the red up-conversion luminescence band observed in the glass ceramic was ascribed to a back energy transfer process Er3+-Yb3+ and cross-relaxation processes caused by the high Yb3+ and Er3+ ions Concentrations in the nanocrystals. (C) 2015 Elsevier B.V. All rights reserved.

The ability of photoelectron spectro-microscopy with sub-micrometer lateral resolution to identify ferroelectric domains by analysis of surface band bendings is demonstrated on lead zirco-titanate PZT(1 1 1) thin films grown by pulsed laser deposition. Conventional synchrotron radiation X-ray photoelectron spectroscopy allowed one to derive the surface composition of the sample and evidenced shifts toward higher binding energy when the sample is subject to intense soft X-ray beam. A basic model is developed which supposes that photogenerated carriers reduce the depolarization field, yielding a lower torque applied to the ferroelectric polarization. As a consequence, the out-of-plane component of the polarization increases. Domain migration during irradiation with soft X-ray is inferred from the relative amplitude of the components with different binding energy. When the flux density of soft X-ray is on the order of 1011 photons/(s mu m(2)), metal Pb clusters are formed at the surface on areas with the out-of-plane component of the polarization pointing outwards only. (C) 2015 Elsevier B.V. All rights reserved.

The compensation of the depolarization field in ferroelectric layers requires the presence of a suitable amount of charges able to follow any variation of the ferroelectric polarization. These can be free carriers or charged defects located in the ferroelectric material or free carriers coming from the electrodes. Here we show that a self-doping phenomenon occurs in epitaxial, tetragonal ferroelectric films of Pb(Zr0.2Ti0.8)O-3, consisting in generation of point defects (vacancies) acting as donors/acceptors. These are introducing free carriers that partly compensate the depolarization field occurring in the film. It is found that the concentration of the free carriers introduced by selfdoping increases with decreasing the thickness of the ferroelectric layer, reaching values of the order of 10(26) m(-3) for 10 nm thick films. One the other hand, microscopic investigations show that, for thicknesses higher than 50 nm, the 2O/(Ti+Zr+Pb) atomic ratio increases with the thickness of the layers. These results suggest that the ratio between the oxygen and cation vacancies varies with the thickness of the layer in such a way that the net free carrier density is sufficient to efficiently compensate the depolarization field and to preserve the outward direction of the polarization.

GeTe and GaSb thin films obtained by pulsed laser deposition were investigated by spectroscopic ellipsometry at controlled temperatures. The GeTe films were fully amorphous, while the GaSb films were partially crystalized in the as-deposited state. The Tauc-Lorentz model was employed to fit the experimental data. From the temperature study of the optical constants, it was observed the crystallization in the 150-160 degrees C range of GeTe amorphous films and between 230 and 240 degrees C of GaSb amorphous phase. A second transition in the resonance energy and the broadening parameter of the Lorentz oscillator was observed due to the crystallization of Sb after 250 degrees C. The temperatures of 85 degrees C and 130 degrees C are noticed as the start of the relaxation of the amorphous GeTe phase and as-deposited GaSb. The peaks of the imaginary part of the dielectric function red shifted after the phase change, while the variation with temperature of the crystalline phase follows the Varshni law. The electron-phonon coupling constants are 2.88 and 1.64 for c-GeTe and c-GaSb, respectively. An optical contrast up to 60% was obtained for GeTe films and a maximum value of 7.5% is revealed in the case GaSb, which is altered by the partial crystallinity of the as-deposited films. (C) 2015 AIP Publishing LLC.

The current-voltage (C-V) characteristic of epitaxial ferroelectric films is simulated assuming the presence of Schottky-type contacts at the two electrode interfaces. The model assumes that the overall capacitance of the metal-ferroelectric-metal (MFM) structure is composed of two parts: (i) one associated with the Schottky contacts, in which the ferroelectric polarization is saturated, the dielectric constant is independent on the voltage and only the linear response to the applied electric field is taken into account; (ii) one related to the ferroelectric volume, where the dielectric constant is voltage dependent through the hysteresis response of the ferroelectric polarization. Themost important result of the model is that it can simulate the experimentally observed thickness dependence of the dielectric constant without considering a so-called "dead layer" at the electrode interface. The model renders C-V characteristics in good qualitative agreement with the experimental ones in the case of an MFM structure based on epitaxial PZT films. The quantitative fit suggests that the behaviour of the ferroelectric polarization during the C-V measurement may be very different from its behaviour during the hysteresis measurement. This is explained by the fact that the two measurements have very different principles. It is also found that the dielectric constant of the ferroelectric volume has a different voltage dependence compared to the one derived from the hysteresis loop or from the experimental C-V characteristic. This is also related to the different measurement principles and to the fact that the measured capacitance of the MFM structure includes, besides the ferroelectric volume, the voltage dependent capacitance of the Schottky contacts. (C) 2015 Elsevier B.V. All rights reserved.

The sites of incorporation of Cu2+ impurity ions in Bi12GeO20 single crystals co-doped with copper and vanadium have been investigated by electron paramagnetic resonance (EPR). While the X-band EPR spectra consist of a simple broad (Delta B similar to 50 mT) line with anisotropic lineshape, the W-band EPR spectra exhibit well resolved, strongly anisotropic lines, due to transitions within the 3d(9)-D-2 ground manifold of the Cu2+ ions. The most intense group of lines, attributed to the dominant Cu2+(I) center, displays a characteristic four components hyperfine structure for magnetic field orientations close to a direction. The g and A tensor main axes are very close to one of the 12 possible sets of orthogonal , and crystal directions. Several less intense lines, with unresolved hyperfine structure and similar symmetry properties, mostly overlapped by the Cu2+(I) spectrum, were attributed to Cu-2 (+)(II) centers. The two paramagnetic centers are identified as substitutional Cu2+ ions at Bi3+ sites with low C-1 symmetry, very likely resulting from different configurations of neighboring charge compensating defects. (C) 2015 Elsevier Inc. All rights reserved.