National Institute Of Materials Physics - Romania

Cubic boron nitride (c-BN) crystalline superabrasive powder (Borazon** CBN 400), consisting of 200-300 microns sized amber colored crystallites prepared by HP/HT synthesis, has been examined from 2.1 K to 293 K by X-band ESR spectroscopy. The observed spectrum consists of a component line A1, visible in the whole temperature range, and two component lines A2 and A3, visible at high and low temperatures, respectively. The A1 and A3 lines originate from transitions inside S = 1/2 ground states of distinct paramagnetic species and A2 from transitions inside an excited state of another paramagnetic center. The intensity of the A1 and A3 lines changes differently during in situ low temperature illumination in the UV-VIS range. (C) 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The <001> axially symmetric Fe+(II) center observed in SrCl2:Fe2+ crystals has been studied by the electron nuclear double resonance (ENDOR) technique in the microwave X and Q bands. This center is produced only in crystals grown in chlorine atmosphere and x-ray irradiated at low temperature (below 100 K). The analysis of the ENDOR spectra unambiguously confirms the structural model earlier suggested by the electron paramagnetic resonance (EPR) study, as a Fe+ ion strongly displaced off center along an <001> axis, almost in the center of the square determined by the four nearest Cl- ligands. The unpaired spin densities f(3s) and f(3p) in the 3s and 3p chlorine orbitals have been determined from the resulting ENDOR parameters.

Isolated Ge islands, i.e., islands not connected by a wetting layer can be obtained by selective epitaxial growth in voids of ultrathin oxides of thickness 1-2 nm. Voids of 30-600 nm size were created before epitaxy during a high temperature anneal of the ultrathin oxide. The formation of one island per window was investigated at 700 degreesC as a function of Ge thickness and void size. Islands nucleate mainly at the edge of the void and for this reason they have an anisotropic shape. In voids smaller than 300 nm only one island is nucleated. Islands form only in voids greater than a critical size (30-80 nm) which depends on the total amount of Ge deposited. We observe that height, width, and aspect ratio of isolated islands increase with void size for a given Ge thickness. A metastable state of Ge in small windows was observed. Moreover, the Si interdiffusion is strongly reduced with decreasing island size (i.e., with void size) reaching only similar to10% in comparison with similar to50% in islands on large areas. (C) 2004 American Institute of Physics.

Tin-doped indium oxide (ITO) thin films have been deposited by sol-gel process using 'sols' of indium and tin isopropoxides. The thickness of one deposited ITO layer is approximately 50 nm. The desired thickness was obtained by 1-5 successive depositions. The XTEM cross-sectional view of an ITO sample with five depositions showed a clear delimitation of the layers with an alternating structure dense/porous ITO layers. The void fraction in porous regions varies between 20 and 25%. Cubic bixbyite In2O3 nanocrystals with size of 10-20 nm and no phases separation of tin oxide were observed. The optical properties of the films have been investigated by optical transmission and spectroscopic ellipsometry. Reliable optical constants and porosity are obtained only with the model of internal structure based on XTEM results. (C) 2003 Elsevier B.V. All rights reserved.

We report some results of a comparison between thin films of pullulan biopolymer obtained by pulsed laser deposition (PLD) and matrix-assisted pulsed laser evaporation (MAPLE). In experiments we used a KrF* laser source generating pulses of 248 nm and 20 ns pulse duration. We demonstrate by Fourier transformed infrared spectroscopy (FTIR) that MAPLE is more appropriate than conventional PLD for transfer with high structural fidelity of biopolymers from target to substrate. In case of MAPLE, besides FTIR spectra, atomic force microscopy micrographs and scanning electron microscopy images prove that the film composition and structure strongly depend on the solvent used for the targets preparation: distilled water, ethylene glycol, ethanol, tert-butanol and dimethyl sulfoxide. Our best results for pullulan deposition were obtained using dimethyl sulfoxide as a solvent. This is the first report of successful MAPLE deposition of this material as thin films. (C) 2003 Elsevier B.V. All rights reserved.

Electrical conduction mechanisms in Si-SiO2 nanocomposite films were experimentally investigated and theoretically modelled. The films with silicon volume concentration varying from 0% to 100% were deposited on rectangular quartz substrates. They were prepared by co-sputtering CVD from two targets, one of silicon and one of silicon dioxide. Their middle part is formed by Si nanodots embedded in SiO2. 50 parallel aluminium electrodes were deposited, forming 49 coplanar samples, centred around x = 45% Si concentration. The microstructure investigations proved that the silicon nanodots have diameters between 4 nm (x = 23%) and 36 nm (x = 81%). The current-voltage characteristics were measured at room temperature, in the -25 divided by +25 V interval. The obtained curves are symmetric and superlinear. As the current - voltage characteristic is determined by the maximum resistance met by the carriers in their path, the experimental curve is modelled by the field-assisted tunnelling under Coulomb blockade. The used parameters are correlated with previous results obtained on nanocrystalline porous silicon. The correlation coefficient between the theoretical formula and the experimental data is greater than 99.95%.

Thallium related paramagnetic centers of Tl2+ (6s(1)) and Tl-0 (6p(1)) type were produced by low temperature x-ray irradiation in ferroelectric Rb2ZnCl4:Tl single crystals. Extensive EPR investigations have been performed in order to elucidate their intrinsic properties and sensitivity as paramagnetic probes for structural phase transitions studies. Compared to the s-type Tl2+ centers, already used in many such studies, it was found that the p-type Tl-0 centers are much more sensitive to the small variations in the local crystal field associated with these transformations. Their EPR spectra provided information about the unit cell tripling in the P2(1)cn phase, as well as the symmetry lowering and lattice dynamics in the C1c1 phase. The temperature induced, continuous changes observed in the EPR spectra of both Tl-0 and Tl2+ centers were explained by the influence of the soft modes responsible for the 74-K structural phase transition.

The electron paramagnetic resonance (EPR) properties of the Mn2+ ions in PbWO4 single crystals grown by the Czochralski method have been investigated in the X-band microwave frequency, at T = 20 K. The angular dependence of the EPR line positions obtained by rotating the magnetic field in the main crystallographic planes shows that the local symmetry at the Mn2+ impurity ions is tetragonal, strongly suggesting that the Mn2+ ions substitute for the Pb2+ lattice cations, without charge compensation. The resulting spin Hamiltonian parameters compare well with the corresponding values for the Mn2+ ions in other isomorphous tungstates. The observed strong angular variation of the EPR linewidth has been quantitatively described considering a random distribution of lattice strains. (C) 2003 Elsevier Ltd. All rights reserved.

Ceramics in the ternary system (Pb,Sr)TiO3-PbZrO3-Pb(Mg1/3Nb2/3)O-3, in the ratio 85.976/5.817/8.207 mol%, was prepared by mixed oxide route. With about 13.98 at % Sr+2, as isovalent substitution in A-position of the lead titanate, high-density samples were obtained for the sintering temperatures of about 1220 and 1230 degreesC. Tetragonal phases were identified both by XRD method and selected area electron diffraction pattern (SAED). The lattice parameter ratio, c/a, of about 1.017 indicated a decrease of tetragonal distortion. The typical TEM micrographs showed domains of about 50 nm wide. The reflection spectra were recorded to prove the presence of the transition Ti+4 to Ti+3. The principal mechanical, electrical and electromechanical properties were discussed as a function of the sintering temperature. The variation of the relative constant with the temperature and frequency evidenced a relaxation-like behavior of this ternary system. By combining the ferroelectric and relaxor end member we tried to improve the piezoelectric properties of a ceramic with a high content of lead titanate, and to achieve a material with both piezoelectric and relaxor-like properties. (C) 2003 Elsevier Ltd. All rights reserved.

The paper presents the inicrostructure of the Si/SiO2 nanocomposite films prepared by co-sputtering from Si and SiO2 targets. High resolution transmission electron microscopy and electron diffraction were used to reveal and compare the structures with different silicon/oxygen (SiOx, 0 < x < 2) coinposition. Si nanocrystallites have been evidenced clearly in the SiO1.6 areas. Percolation limits between the Si crystallites was observed in the x=1 areas. The morphology of the Si nanocrystallites and the amorphous SiO2 zones were compared in regions with different composition.