Raman spectroscopy analysis of structural photoinduced changes in GeS(2) + Ga(2)O(3) thin films

Photoexpansion and photobleaching effects have been observed in amorphous GeS(2) + Ga(2)O(3) (GGSO) thin films, when their surfaces were exposed to UV light. The photoinduced changes on the surface of the samples are indications that the structure has been changed as a result of photoexcitation. In this paper, micro-Raman, energy dispersive X-ray analysis (EDX) and backscattering electrons (BSE) microscopy were the techniques used to identify the origin of these effects. Raman spectra revealed that these phenomena are a consequence of the Ge-S bonds` breakdown and the formation of new Ge-O bonds, with an increase of the modes associated with Ge-O-Ge bonds and mixed oxysulphide tetrahedral units (S-Ge-O). The chemical composition measured by EDX and BSE microscopy images indicated that the irradiated area is oxygen rich. So, the present paper provides fundamental insights into the influence of the oxygen within the glass matrix on the considered photoinduced effects. (C) 2010 Elsevier B.V. All rights reserved.

Raman spectroscopy analysis of structural photoinduced changes in GeS2 + Ga2O3 thin films

Photoexpansion and photobleaching effects have been observed in amorphous GeS2 + Ga2O3 (GGSO) thin films, when their surfaces were exposed to UV light. The photoinduced changes on the surface of the samples are indications that the structure has been changed as a result of photoexcitation. In this paper, micro-Raman, energy dispersive X-ray analysis (EDX) and backscattering electrons (BSE) microscopy were the techniques used to identify the origin of these effects. Raman spectra revealed that these phenomena are a consequence of the Ge-S bonds' breakdown and the formation of new Ge-O bonds, with an increase of the modes associated with Ge-O-Ge bonds and mixed oxysulphide tetrahedral units (S-Ge-O). The chemical composition measured by EDX and BSE microscopy images indicated that the irradiated area is oxygen rich. So, the present paper provides fundamental insights into the influence of the oxygen within the glass matrix on the considered photoinduced effects. (C) 2010 Elsevier B.V. All rights reserved.

Effects of cation substitutions on the physical properties of M2M1T2O6 pyroxenes

In this PhD study, the effects of the cation substitutions on the physical properties of pyroxenes have been discussed. The results of this work extend the knowledge on pyroxenes with different chemical compositions. These properties might be used in the development of ceramic pigments, advanced materials and for the mineralogical phase identification. First of all, the crystallographic differences between Ge and Si pyroxenes have been examined. The structure of C2/c Ca rich Ge clinopyroxenes is very close to the low pressure C2/c structural configuration found in Ca-rich Si-pyroxenes. The shear of the unit cell is very similar, and the difference between a Ge end member and the corresponding Si-rich one is less than 1°. Instead, a remarkable difference exists between Ca-poor Si and Ge clinopyroxenes. First, Ca-poor Ge pyroxenes do not display a P21/c symmetry, but retain the C2/c symmetry; second, the observed C2/c structure shows, at room pressure, the configuration with highly kinked tetrahedral chains characteristic of the high pressure C2/c symmetry of Si Ca-poor pyroxenes. In orthopyroxenes, with Pbca symmetry, Ge-pyroxenes have volume larger than Si-pyroxenes. Samples along the system CaCoGe2O6 - CoCoGe2O6 have been synthesized at three different temperatures: 1050 °C, 1200 °C and 1250 °C. The aim of these solid state syntheses was to obtain a solid solution at ambient pressure, since the analogues Si-system needs high pressure. Unfortunately, very limited solution occurs because the structure forms of the two end member (high temperature for CaCoGe2O6 and high pressure CoCoGe2O6) are incompatible. The phase diagram of this system has been sketched and compared to that of Si. The cobalt end member (CoCoGe2O6) is stable at ambient pressure in two symmetries: at 1050 °C C2/c and 1200 °C Pbca. The impurity phase formed during these experiments is cobalt spinel. Raman spectroscopy has been used to investigate the vibrational properties of Ca-pyroxenes CaCoGe2O6, CaMgGe2O6, CaMgSi2O6 and CaCoSi2O6. A comparison between silicate and germanate pyroxenes shows significant changes in peak positions of the corresponding modes caused mainly by the difference of the Ge-Si atomic weight along with the distortion and compression of the coordination polyhedra. Red shift in Raman spectra of germanates has been calculated by a rough scale factor calculated by a simple harmonic oscillator model, considering the different bond lengths for 4-coordinated Si ~ 1.60- 1.65 Å vs Ge–O distance ~1.70 - 1.80 Å. The Raman spectra of CaMgGe2O6 and CaCoGe2O6 have been classified, in analogy with silicate (Wang et al., 2001) counterparts, in different ranges: - R1 (880-640 cm-1): strong T-O stretching modes of Ge and non-bridging O1 and O2 atoms within the GeO4 tetrahedron; - R2 (640-480 cm-1): stretching/bending modes of Ge-Obr-Ge bonds (chain stretching and chain bending); - R4 (480-360 cm-1): O-Ge-O vibrations; - R3 (360-240 cm-1): motions of the cations in M2 and M1 sites correlated with tetrahedral chain motion and tilting tetrahedra; - R5 (below 240 cm-1): lattice modes. The largest shift with respect to CaMgSi2O6 - CaCoSi2O6 is shown by the T-O stretching and chain modes. High-pressure Raman spectroscopy (up to about 8 GPa) on the same samples of Ca-pyroxenes using an ETH-type diamond anvil cell shows no phase transition within the P-ranges investigated, as all the peak positions vary linearly as a function of pressure. Our data confirm previous experimental findings on Si-diopside (Chopelas and Serghiou, 2000). In the investigated samples, all the Raman peaks shift upon compression, but the major changes in wavenumber with pressure are attributed to the chain bending (Ge-Obr-Ge bonds) and tetrahedra stretching modes (Ge-Onbr). Upon compression, the kinking angle, the bond lengths and T-T distances between tetrahedra decrease and consequently the wavenumber of the bending chain mode and tetrahedra stretching mode increases. Ge-pyroxenes show the higher P-induced peak-position shifts, being more compressible than corresponding silicates. The vibrational properties of CaM2+Ge2O6 (M2+ =Mg, Mn, Fe, Co, Ni, Zn) are reported for the first time. The wavenumber of Ge-Obr-Ge bending modes decreases linearly with increasing ionic radius of the M1 cation. No simple correlation has been found with M1 atomic mass or size or crystallographic parameters for the peak at ~850 cm-1 and in the low wavenumber regions. The magnetic properties of the system CaCoSi2O6 - CoCoSi2O6 have been investigated by magnetometry. The join is always characterized by 1 a.p.f.u. of cobalt in M1 site and this causes a pure collinear antiferromagnetic behaviour of the intra-chain superexchange interaction involving Co ions detected in all the measurements, while the magnetic order developed by the cobalt ions in M2 site (intra-chain) is affected by weak ferromagnetism, due to the non-collinearity of their antiferromagnetic interaction. In magnetically ordered systems, this non-collinearity effect promotes a spin canting of anti-parallel aligned magnetic moments and thus is a source of weak ferromagnetic behaviour in an antiferromagnetic. The weak ferromagnetism can be observed only for the samples with Co content higher than 0.5 a.p.f.u. in M2, when the concentration is sufficiently high to create a long range order along the M2 chain which is magnetically independent of M1 chain. The ferromagnetism was detected both in the M(T) at 10 Oe and M(H).

Si(100) versus Ge(100): Watching the interface formation for the growth of III-V-based solar cells on abundant substrates

We investigated the atomic surface properties of differently prepared silicon and germanium (100) surfaces during metal-organic vapour phase epitaxy/chemical vapour deposition (MOVPE/MOCVD), in particular the impact of the MOVPE ambient, and applied reflectance anisotropy/difference spectroscopy (RAS/RDS) in our MOVPE reactor to in-situ watch and control the preparation on the atomic length scale for subsequent III-V-nucleation. The technological interest in the predominant opto-electronic properties of III-V-compounds drives the research for their heteroepitaxial integration on more abundant and cheaper standard substrates such as Si(100) or Ge(100). In these cases, a general task must be accomplished successfully, i.e. the growth of polar materials on non-polar substrates and, beyond that, very specific variations such as the individual interface formation and the atomic step structure, have to be controlled. Above all, the method of choice to grow industrial relevant high-performance device structures is MOVPE, not normally compatible with surface and interface sensitive characterization tools, which are commonly based on ultrahigh vacuum (UHV) ambients. A dedicated sample transfer system from MOVPE environment to UHV enabled us to benchmark the optical in-situ spectra with results from various surfaces science instruments without considering disruptive contaminants. X-ray photoelectron spectroscopy (XPS) provided direct observation of different terminations such as arsenic and phosphorous and verified oxide removal under various specific process parameters. Absorption lines in Fourier-transform infrared (FTIR) spectra were used to identify specific stretch modes of coupled hydrides and the polarization dependence of the anti-symmetric stretch modes distinguished different dimer orientations. Scanning tunnelling microscopy (STM) studied the atomic arrangement of dimers and steps and tip-induced H-desorption proved the saturation of dangling bonds after preparati- n. In-situ RAS was employed to display details transiently such as the presence of H on the surface at lower temperatures (T <; 800°C) and the absence of Si-H bonds at elevated annealing temperature and also surface terminations. Ge buffer growth by the use of GeH4 enables the preparation of smooth surfaces and leads to a more pronounced amplitude of the features in the spectra which indicates improvements of the surface quality.

Effect of Mn concentration and atomic structure on the magnetic properties of Ge thin films

This work reports on the magnetic properties of Ge(100-x)Mn(x) (x=0-24 at. %) films prepared by cosputtering a Ge+Mn target and submitted to cumulative thermal annealing treatments up to 500 degrees C. Both as-deposited and annealed films were investigated by means of compositional analysis, Raman scattering spectroscopy, magnetic force microscopy, superconducting quantum interference device magnetometry, and electrical resistivity measurements. All as-deposited films (either pure or containing Mn) exhibit an amorphous structure, which changes to crystalline as the annealing treatments are performed at increasing temperatures. In fact, the magnetic properties of the present Ge(100-x)Mn(x) films are very sensitive to the Mn content and whether their atomic structure is amorphous or crystalline. More specifically: whereas the amorphous Ge(100-x)Mn(x) films (with high x) present a characteristic spin glass behavior at low temperature; after crystallization, the films (with moderate Mn contents) are ferromagnetic at room temperature. Moreover, the magnetic behavior of the films scales with their Mn concentration and tends to be more pronounced after crystallization. Finally, the semiconducting behavior of the films, experienced by previous optical studies, was confirmed through electrical measurements, which also indicate the dependence of the resistivity with the atomic composition of the films. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3520661]

Atomistic origins of the phase transition mechanism in Ge(2)Sb(2)Te(5)

The fast and reversible phase transition mechanism between crystalline and amorphous phases of Ge(2)Sb(2)Te(5) has been in debate for several years. Through employing first-principles density functional theory calculations, we identify a direct structural link between the metastable crystalline and amorphous phases. The phase transition is driven by the displacement of Ge atoms along the rocksalt [111] direction from stable octahedron to high energy unstable tetrahedron sites close to the intrinsic vacancy regions, which generates a high energy intermediate phase between metastable and amorphous phases. Due to the instability of Ge at the tetrahedron sites, the Ge atoms naturally shift away from those sites, giving rise to the formation of local-ordered fourfold motifs and the long-range structural disorder. Intrinsic vacancies, which originate from Sb(2)Te(3), lower the energy barrier for Ge displacements, and hence, their distribution plays an important role in the phase transition. The high energy intermediate configuration can be obtained experimentally by applying an intense laser beam, which overcomes the thermodynamic barrier from the octahedron to tetrahedron sites. The high figure of merit of Ge(2)Sb(2)Te(5) is achieved from the optimal combination of intrinsic vacancies provided by Sb(2)Te(3) and the instability of the tetrahedron sites provided by GeTe.

Magnetostriction of polycrystalline Fe-Ge alloys

The longitudinal and transverse magnetostriction and microstructure of polycrystalline Fe(100-x)Ge(x) (x= 8, 12, 15, 20) alloys were investigated in order to correlate the magnetostriction with microstructure. In order to obtain different microstructures in the Fe(100-x)Ge(x) alloys, the samples were annealed at 600 degrees C during 2 h and at 1150 degrees C for half hour and then quenched in cold water. For Ge concentrations lower than 14 at.%, the longitudinal magnetostriction is positive and increases positively up to 22 ppm at 12 at.% Ge then decreases and vanishes at about 14 at.% Ge. For further Ge concentration increase the longitudinal magnetostriction is negative and reaches -30 ppm for Fe(80)Ge(20). This behavior, that is very similar to that reported for Fe-Si alloys, is explained by the structural changes caused by different thermal histories of the alloys. (C) 2008 Published by Elsevier B. V.

Monte Carlo simulation of the basic features of the GE Millennium MG single photon emission computed tomography gamma camera

Objective - To describe and validate the simulation of the basic features of GE Millennium MG gamma camera using the GATE Monte Carlo platform. Material and methods - Crystal size and thickness, parallel-hole collimation and a realistic energy acquisition window were simulated in the GATE platform. GATE results were compared to experimental data in the following imaging conditions: a point source of 99mTc at different positions during static imaging and tomographic acquisitions using two different energy windows. The accuracy between the events expected and detected by simulation was obtained with the Mann–Whitney–Wilcoxon test. Comparisons were made regarding the measurement of sensitivity and spatial resolution, static and tomographic. Simulated and experimental spatial resolutions for tomographic data were compared with the Kruskal–Wallis test to assess simulation accuracy for this parameter. Results - There was good agreement between simulated and experimental data. The number of decays expected when compared with the number of decays registered, showed small deviation (≤0.007%). The sensitivity comparisons between static acquisitions for different distances from source to collimator (1, 5, 10, 20, 30cm) with energy windows of 126–154 keV and 130–158 keV showed differences of 4.4%, 5.5%, 4.2%, 5.5%, 4.5% and 5.4%, 6.3%, 6.3%, 5.8%, 5.3%, respectively. For the tomographic acquisitions, the mean differences were 7.5% and 9.8% for the energy window 126–154 keV and 130–158 keV. Comparison of simulated and experimental spatial resolutions for tomographic data showed no statistically significant differences with 95% confidence interval. Conclusions - Adequate simulation of the system basic features using GATE Monte Carlo simulation platform was achieved and validated.

Interdiffusion at Sb/Ge interfaces induced in thin multilayer films by nanosecond laser irradiation

Thin films consisting of 3 or 4 Sb and Ge alternating layers are irradiated with single nanosecond laser pulses (12 ns, 193 nm). Real time reflectivity (RTR) measurements are performed during irradiation, and Rutherford backscattering spectrometry (RBS) is used to obtain the concentration depth profiles before and after irradiation. Interdiffusion of the elements takes place at the layer interfaces within the liquid phase. The reflectivity transients allow to determine the laser energy thresholds both to induce and to saturate the process being both thresholds dependent on the multilayer configuration. It is found that the energy threshold to initiate the process is lower when Sb is at the surface while the saturation is reached at lower energy densities in those configurations with thinner layers.

Faunes ichthyologiques du Néogène Supérieur d’Angola, leur âge, remarques sur le Pliocène marin en Afrique Australe

This note is concerned with fish remains from Upper Neogene beds at Farol das Lagostas (and nearby quarry of SECIL) and Baía Farta, mainly recovered by the author in 1960, 1961, 1963 and 1967. For further data see ANTUNES, 1964, pp. 213-215. All the forms identified until now (many of them for the first time) are show in «tableau I». Smaller ones are poorly represented. I. benedeni is provisorily accepted as a distinct species, though it may correspond to a dental morphotype that does exist equally in the extant I. oxyrhinchus (see text): therefore I. benedeni from Farol das Lagostas may after all represent only some dental variations that really belong in the form described as I. cf. oxyrhinchus. The presence of Aprionodon and Hypoprion could not be ascertained: Procarcharodon megalodon, Carcharodon carcharias, Isurus benedeni. Galeocerdo cuvieri, and Carcharhinus sp. I and sp. II are specially discussed. The whole fauna does not correspond either to a very shallow and coastal environment, or to deep waters far away from the coast. It clearly points out to warm waters: an acceptable model would be the fauna from the tropical Atlantic between Northern Angola and Senegal-Cape Verde. The age of this fauna was long regarded as Burdigalian. The data formerly presented (ANTUNES, 1963) that allowed us to ascribe a pliocene age to the uppermost Neogene beds of Farol das Lagostas (Neogene III, ANTUNES, 1964) are reviewed and developed in this paper. This view is corroborated by planctonic foraminifera and stratigraphical data which provide further evidence to prove the presence of miocene beds much younger than Burdigalian, and that some deposits previously correlated to this stage have instead a Plio-Pleistocene age. Fish fauna from Farol das Lagostas is very characteristic, with giant P. megalodon in association with C. carcharias (which predominates, and whose stratigraphical distribution is particularly discussed), and with other very advanced forms like the extant tiger shark, G. cuvieri, enormous I. Benedeni, Hemipristis, and Carcharhinus (whose size largely exceeds the maximum observed with miocene material). With the exception of P. megalodon (extinct) all the other forms show very close affinities, or even identity with modern species. Comparisons with very similar faunas from some South African localities that may also have a Pliocene age are also presented.

Faunes ichthyologiques du Néogène Supérieur d’Angola, leur âge, remarques sur le Pliocène marin en Afrique Australe

This note is concerned with fish remains from upper Neogene beds at Farol das Lagostas (and nearby quarry of SECIL) and Baía Farta, mainly recovered by the author in 1960, 1961, 1963 and 1967. For further data see ANTUNES, 1964, pp. 213-215. All the forms identified until now (many of them for the first time) are show in «tableau I». Smaller ones are poorly represented. I. benedeni is provisorily accepted as a distinct species, though it may correspond to a dental morphotype that does exist equally in the extant I. oxyrhinchus (see text): therefore I. benedeni from Farol das Lagostas may after all represent only some dental variations that really belong in the form described as I. cf. oxyrhinchus. The presence of Aprionodon and Hypoprion could not be ascertained: Procarcharodon megalodon, Carcharodon carcharias, Isurus benedeni. Galeocerdo cuvieri, and Carcharhinus sp. I and sp. II are specially discussed. The whole fauna does not correspond either to a very shallow and coastal environment, or to deep waters far away from the coast. It clearly points out to warm waters: an acceptable model would be the fauna from the tropical Atlantic between Northern Angola and Senegal-Cape Verde. The age of this fauna was long regarded as Burdigalian. The data formerly presented (ANTUNES, 1963) that allowed us to ascribe a pliocene age to the uppermost Neogene beds of Farol das Lagostas (Neogene III, ANTUNES, 1964) are reviewed and developed in this paper. This view is corroborated by planctonic foraminifera and stratigraphical data which provide further evidence to proove the presence of miocene beds much younger than Burdigalian, and that some deposits previously correlated to this stage have instead a Plio-Pleistocene age. Fish fauna from Farol das Lagostas is very characteristic, with giant P. megalodon in association with C. carcharias (which predominates, and whose stratigraphical distribution is particularly discussed), and with other very advanced forms like the extant tiger shark, G. cuvieri, enormous I. Benedeni, Hemipristis, and Carcharhinus (whose size largely exceeds the maximum observed with miocene material). With the exception of P. megalodon (extinct) all the other forms show very close affinities, or even identity with modern species. Comparisons with very similar faunas from some South African localities that may also have a Pliocene age are also presented.

Caracterização de um mamógrafo Senographe 600T Senix da GE com ânodo de Mo. dosimetria das qualidades de radiação

Dissertação para obtenção do Grau de Mestre em Engenharia Biomédica

Héraldique des sceaux du clergé séculier portugais au Moyen Âge

Ce n’est que dans les dernières années que l’héraldique au Portugal a entamé le processus de rénovation qui, en France, a commencé il y a déjà quelques décennies. Dans ce processus, l’étude de l’héraldique médiévale a été peu contemplé, restant pratiquement à faire, en bonne partir dû à l’absence d’armoriaux antérieurs au XVe siècle qui permettent de connaître les armes utilisées par les familles et les diverses entités portugaises. Pour cette raison, les sceaux portant des représentations héraldiques ont une importance extrême, car ils constituent très fréquemment la seule source pour l’étude des armoiries, ayant en plus l’avantage d’être datés avec précision et liées à des personnages ou entités qui sont connues. Cependant, la sigillographie portugaise se trouve aussi dans une phase de son évolution qui, n’étant plus embryonnaire, est encore une phase de formation. Il nous manque des catalogues, des dépouillages systématiques, des études approfondies qui permettent aux héraldistes de faire leurs recherches. C’est dans ce contexte qui est née ce partenariat entre deux médiévalistes très intéressés à la sigillographie et un spécialiste d’héraldique, qui ensemble ont décidé d’entamer l’étude des origines des représentations héraldiques dans les sceaux portugais, en commençant par les sceaux du clergé séculier, qui constitue le sujet par excellence de la recherche des deux historiens. Dans ce vaste univers sigillaire, qui concerne des personnes d’une grande variété d’origines sociales, y compris la noblesse et la riche bourgeoisie urbaine, les éléments héraldiques semblent avoir émergé seulement à partir de la fin du XIIIe siècle, et d’une façon timide. Le XIVe siècle assiste à sa diffusion dans les sceaux d’évêques, dignités et chanoines, mais ce n’est qu’au XVe siècle que l’héraldique s’impose, gagnant même une place primordiale dans quelques représentations sigillographiques. Le but de cette communication sera donc l’analyse du processus d’héraldisation des sceaux du clergé séculier portugais, entre les dernières décennies du XIIIe et le XVe siècle, pour évaluer comme s’est procédé, dans le cas portugais, le phénomène d’«acculturation héraldique» de l’emblématique épiscopale et cléricale.