National Institute Of Materials Physics - Romania

The synthesis by pulsed laser deposition of ZnO thin films with a Nd:YAG laser system delivering pulses of 40 ps @ 532 nm is reported. The laser beam irradiated the target placed inside a vacuum chamber evacuated down to 1.33x10(-1) Pa. The incident laser fluence was of 28 J/cm(2) in a spot of 0.1 mm(2). The ablated material was collected onto double face polished (111) Si or quartz wafers placed parallel at a separation distance of 7 mm. The AFM, SEM, UV-Vis, FT-IR and absorption ellipsometry results indicated that we obtained pure ZnO films with a rather uniform surface, having an average roughness of 37 nm. We observed by SEM that particulates are present on ZnO film surface or embedded into bulk. Their density and dimension were intermediary between particulates observed on similar structures deposited with fs or ns laser pulses. We noticed that the density of the particulates is increasing while their average size is decreasing when passing from ns to ps and fs laser pulses. The average transmission in the UV-Vis spectral region was found to be higher than 85%.

Glass-ceramics containing RE3+-doped BaF2 nanocrystals (RE = Eu, Sm, Dy, Ho and Pr) with the size below 10 nm size have been made by using the controlled crystallization at higher temperatures of the RE3+-doped SiO2-BaF2 xerogels. Photoluminescence measurements have indicated the incorporation of the RE3+ ions in both silica network and in the BaF2 nanocrystals. Thermoluminescence measurements have shown a peak whose position depends on the nature of RE3+-dopant as it follows: 140 degrees C (for Ho3+, Dy3+), 340 degrees C (for Sm3+) and 370 degrees C (for Eu3+); in Eu3+-doped SiO2 glass the TL peak is shifted to 383 degrees C. The peaks in glass-ceramics were assigned to the recombination of the electrons thermal released from the RE3+-electron traps located in both glass-matrix and BaF2 nanocrystals. Within the series the trivalent lanthanide ions act as increasingly deeper electron trapping centres. (C) 2011 Elsevier B.V. All rights reserved.

Rare-earth doped xerogels (Eu3+, Sm3+, Ho3+, Pr3+) were prepared by using the sal-gel method and their magneto-optical and optical properties have been studied. The Magnetic Circular Dichroism (MCD) spectra are quite similar to those recorded in the RE-doped fluorozirconate glasses; the fine structures shown by the MCD spectra are better resolved compared to the optical absorption spectra. The MCD technique has been correlated with optical measurements in order to investigate the site symmetry in the particular case of Eu3+-doped xerogel and oxyfluoride glasses. In the xerogel, coordination symmetry around the Eu3+ ions is close to (D) under bar (3h) and is lower in the oxyfluoride glass. (C) 2011 Elsevier B.V. All rights reserved.

Nanocrystalline Ho-doped BaTiO3, with average nanocrystals size of 20 nm, have been prepared using a sol-gel combustion technique. The structural and morphological properties of the powders have been investigated by X-ray powder diffraction and high resolution transmission electron microscopy. Chemical states of the holmium on the Ba0.97Ho0.03TiO3 ceramic surface were analyzed using X-ray photoelectron spectroscopy. Furthermore, their photoluminescence properties were analyzed.

A large model of amorphous silicon (2052 atoms) with 0.5% dangling bonds has been built and investigated. The refinement of the coordinates evidenced the presence of small domains with advanced ordering. These domains preclude the formation of crystallization nuclei and play an essential role in the redistribution of the defects in the material with homogenization of the free energy and stabilization against aging. An effect of amorphization of the ordered nuclei due to free energy redistribution is assessed. The glass relaxation of a-Si (a-Ge) occurring during heating below T(g) receives a natural explanation as a structural change from local quasi-ordering to homogeneous disordering. (C) 2011 Elsevier B.V. All rights reserved.

The switching mechanism in phase change memories was described on the basis of minimum switching unit: the commuton. A commuton is a minimum cluster of atoms that supports a reversible phase change from high to low electrical conduction state and back under the influence of an external signal. The switching process in a phase change chalcogenide film was modeled using two dimensional cellular automata approach. A system of 50 x 50 cells, each cell containing a commuton, was simulated. In the particular case of Ge(2)Sb(2)Te(5) (investigated here) this system corresponds to a 30 x 30 nm area. The formation of the percolation path as a function of phase change induced in commutons explains the switching phenomenon. The influence of the percent of defects in the material on the percolation threshold has been studied. (C) 2011 Elsevier B.V. All rights reserved.

Oxyfluoride glass-ceramic in the system SiO2-Al2O3-CaF2-SmF3 containing Sm3+-doped CaF2 nanocrystals in the range from 15 to 150 nm size were produced by using the controlled ceramization of the precursor glass. The incorporation of the Sm3+-dopant ion in the glass ceramic creates new electron-trapping centers and thermoluminescence (TL) method has been used in order to trace their evolution during glass ceramization. The 370 A degrees C TL peak observed in precursor glass has been assigned to the recombination of the electrons released from the Sm2+-traps in the amorphous glass network. In the glass-ceramic sample containing nanocrystals with about 15 nm size the new weak TL peaks at 270, 290, and 310 A degrees C were attributed to the recombination of the electrons released from the Sm2+-traps located mainly at the surface of the CaF2 nanocrystals. In the glass-ceramic sample containing nanocrystals with about 150 nm size, the new TL peaks at 232, 270, and 302 A degrees C size have been assigned to the recombination of the electrons released from the Sm2+-traps located inside the CaF2 nanocrystals.

In this paper, we report on Raman scattering and Surface Enhanced Raman Scattering (SERS) studies of single walled carbon nanotubes (SWNTs) and carbon nanotube/conjugated polymers composites. We demonstrate that under SERS conditions we induce an abnormal anti-Stokes Raman emission, that can be interpreted as being due to a "single-beam pumped" Coherent Anti-Stokes Raman Scattering (CARS) effect. We also investigate in detail the anti-Stokes/Stokes (aS/S) intensity ratios of the radial breathing modes (RBMs) of SWNTs as a function of several parameters. From calculations, we show that resonance phenomena mostly explain the aS/S intensity ratio anomalies, but only at low frequencies. In addition, we describe results obtained with polymers like poly(bithiophene) (PBTh) polymerized on carbon nanotube thin films which exhibit also an amplification of its high frequency Raman modes in the anti-Stokes branch, generated by the plasmon excitation of metallic tubes. This phenomenon occurs in several other materials such as composites based on SWNTs and conjugated polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT) and polyparaphenylene-vinylene (PPV) for modes located around 1500 cm(-1). (C) 2011 Elsevier B.V. All rights reserved.

Photoluminescence (PL) and Raman spectroscopy were used to characterize the tin dioxide (SnO(2)) powder and the SnO(2)/single-walled carbon-nanotube (SWCNT) composites. The SnO(2) powder shows a strong PL broad band centered at 1.95 eV (635 nm) under excitation at 280 nm (4.43 eV) and four PL bands peaking at: 1.95 eV (635 nm), 2.67 eV (464 nm), 2.82 eV (439 nm), and 2.98 eV (416 nm) under excitation at 350 nm (3.54 eV). PL decay-time measurements of the SnO(2) powder indicates a PL lifetime of about 1.53 ns. In the SnO(2)/SWCNT composites, prepared mechanicochemically, a quenching of PL is observed as the concentration of SWCNT increases. The Raman spectra were recorded at two excitation wavelengths: 514.5 and 676.4 nm. At the excitation wavelength of 676.4 nm (1.83 eV), the Raman spectrum shows a narrowed asymmetric profile of the G band (similar to 1585 cm similar to 1), which indicates that in the SnO(2)/SWCNT composite there is an interaction between SnO(2) and metallic SWCNTs. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

In this paper, we demonstrate that, by continuous single beam excitation, one can generate an abnormal anti-Stokes Raman emission (AASRE) whose properties are similar to a coherent anti-Stokes Raman scattering (CARS). The effect has been observed in materials which possess intrinsically nonlinear properties (LiNbO(3) and CdS), which have the electric susceptibility of third order different from zero, chi((3)) not equal 0, as well as in materials that become nonlinear under resonant optical excitation. In the latter case, we used poly-3,4-ethylendioxythiophene (PEDOT) in its undoped state deposited electrochemically on Au support. Raman studies corroborated with images of optical microscopy demonstrate that the production of AASRE is conditioned by the existence of a particular morphology of the sample able to ensure efficient transport of the light inside the sample through a multiple light scattering mechanism. In this context, it was found that LiNbO3 and CdS in powder form as well as the PEDOT films layered on a rough Au substrate are suitable morphological forms. We explain AASRE as resulting from a wave-mixing mechanism of the incident laser light omega(l) with a Stokes-shifted Raman light omega(S) produced by a spontaneous Raman light scattering process, both strongly scattered inside the sample. As a CARS process, AASRE is conditioned by the achievement of phase-matching requirements, which makes the difference between the wave vectors of mixing light close to zero, Delta k = /2k(l) - k(S) - k(CARS) /approximate to 0. In condensed media, the small dispersion of the refractive index makes Delta k approximate to 0 so that the formation of a favourable phase-matching geometry may be accomplished even at a crossing angle. of travelling scattered light omega(l) and omega(S). For tightly focused beams, the requirement of phase matching relaxes; it is no longer sensitive to the Raman shift, so that a wide intense anti-Stokes Raman spectrum is observed at an angle larger than the Stokes Raman spectrum.