Ab Initio study of magnetic interactions in the KCuF3 and K2CuF4 low-dimensional Systems

The ab initio cluster model approach has been used to study the electronic structure and magnetic coupling of KCuF3 and K2CuF4 in their various ordered polytype crystal forms. Due to a cooperative Jahn-Teller distortion these systems exhibit strong anisotropies. In particular, the magnetic properties strongly differ from those of isomorphic compounds. Hence, KCuF3 is a quasi-one-dimensional (1D) nearest neighbor Heisenberg antiferromagnet whereas K2CuF4 is the only ferromagnet among the K2MF4 series of compounds (M=Mn, Fe, Co, Ni, and Cu) behaving all as quasi-2D nearest neighbor Heisenberg systems. Different ab initio techniques are used to explore the magnetic coupling in these systems. All methods, including unrestricted Hartree-Fock, are able to explain the magnetic ordering. However, quantitative agreement with experiment is reached only when using a state-of-the-art configuration interaction approach. Finally, an analysis of the dependence of the magnetic coupling constant with respect to distortion parameters is presented.

Radiometric age constraints on mineral growth, metamorphism, and tectonism of the Gummfluh klippe, Brianconnais domain of the Prealpes, Switzerland

A combined Ar-40/Ar-39, K/Ar, Rb/Sr and stable isotope study has been made of white micas from the Gummfluh klippe (Brianconnais domain of the Prealpes), Switzerland. The klippe consists mainly of Mesozoic to early Tertiary carbonate rocks metamorphosed from anchizonal to epizonal conditions. At the base of the klippe is a 10-50 m thick, ductilely deformed marble mylonite containing deformed authigenic quartz segregations. Stable isotope measurements of the coexisting calcite (deltaO-18SMOW=24.5) and quartz (deltaO-18SMOW=28.4) from the mylonite indicate relatively low temperatures (< 300-degreesC) during mylonitization. Analyses of white mica separates of varying size fractions from the mylonitic rocks by K/Ar and Rb/Sr techniques yield ages between 57 and 103 Ma. This variation is correlated with two parameters, the size of the mineral fraction, and the proportion of 2M1 (more phengitic) to 1M (more muscovitic) polytype in the sample. The K/Ar and Rb/Sr ages are generally younger in the smaller size fractions, which also containless 2M1 phengite. High precision Ar-40/Ar-39 age spectra from different size fractions of these micas record three distinct components, a small Hercynian component (ca. 200-300 Ma), a significant Eoalpine component (64-80 Ma) forming Ar-40/Ar-39 age plateaus, and a very minor Tertiary component (ca. 20-40 Ma). Characterization of the samples by SEM indicates the presence of two white mica populations, a coarser grained, deformed, detrital mica that probably corresponds to the 2M1 phengite and a finer grained neoformed 1M mica. Collectively these observations suggest that the Gummfluh samples contain a mixture of detrital phengites of Hercynian age together with neocrystallized muscovites grown during the late Eoalpine metamorphic event followed by minor argon loss during the Tertiary. The main geologic episode recorded in the Ar-40/Ar-39 age spectra of white micas in the mylonite is of Late Cretaceous/Early Tertiary age (64-80 Ma), representing the first reliable Eoalpine ages ever to be reported from the Prealpes. Contrary to tectonic models, the marble mylonite at the base of the Gummfluh klippe appears to be a Cretaceous thrust plane and not the thrust surface formed during transport of the klippe into its present position from the Penninic Alps during the Tertiary. The late Cretaceous thrust developed during marine sedimentation at a depth of 800 m below the seafloor at temperatures of approximately 280-degrees-C, facilitated by warm fluids along the tectonic discontinuity.

Piikarbidipuolijohdekomponentit tehoelektroniikassa

Piikarbidi (SiC) on tunnettu korkealuokkaisena hioma-aineena ja hiekkapaperin pin-noitteena yli 100 vuoden ajan. Nykyisin ainetta käytetään pääasiassa puolijohteiden raaka-aineena. Piikarbidi on puolijohteena ylivoimainen tavanomaiseen piihin (Si) verrattuna lähes joka suhteessa johtuen sen kiderakenteesta, mutta sen valmistus on osoittautunut erittäin monimutkaiseksi johtuen pääasiassa vaikeudesta kasvattaa riittävän suuria ja laadukkaita SiC-kiteitä. Siksi tehoelektroniikan SiC-puolijohdekomponenttien laajamittaista käyttöä joudutaan yhä odottamaan. Tässä diplomityössä tehdään perusteellinen selvitys, miten piikarbidin valmistuspro-sessit eroavat normaaleista piin valmistusprosesseista, mitä etuja piikarbidin käytöllä saavutetaan ja vastaavasti mitä varjopuolia sillä on. Työssä selvitetään tällä hetkellä markkinoilla olevien SiC-tehopuolijohdekomponenttien ominaisuuksia, ketkä ovat teh-neet tutkimusta alalla, sekä esitetään arvioita SiC-tekniikan tulevaisuuden näkymistä.

Polytypism and Silicon carbide : a solid state nuclear magnetic resonance study

A survey of predominantly industrial silicon carbide has been carried out using Magic Angle Spinning nuclear magnetic resonance (MAS nmr); a solid state technique. Three silicon carbide polytypes were studied; 3C, 6H, and 15R. The 13C and 29 Si MAS nmr spectra of the bulk SiC sample was identified on the basis of silicon (carbon) site type in the d iff ere n t pol Y t Y pes • Out to 5.00 A fro mac en t r a lsi 1 i con (0 r carbon) atom four types of sites were characterized using symmetry based calculations. This method of polytype analysis was also considered, in the prelminary stages, for applications with other polytypic material; CdBr 2 , CdI 2 , and PbI 2 " In an attempt to understand the minor components of silicon carbide, such as its surface, some samples were hydrofluoric acid washed and heated to extreme temperatures. Basically, an HF removable species which absorbs at -110 ppm (Si0 2 ) in the 29 Si MAS nmr spectrum is found in silicon carbide after heating. Other unidentified peaks observed at short recycle delays in some 29 Si MAS nmr spectra are considered to be impurities that may be within the lattice. These components comprise less than 5% of the observable silicon. A Tl study was carried out for 29 Si nuclei in a 3C ii polytype sample, using the Driven Equilibrium Single-Pulse Observation of T1 (DESPOT) technique. It appears as though there are a number of nuclei that have the same chemical shift but different T1 relaxation times. The T1 values range from 30 seconds to 11 minutes. Caution has to be kept when interpreting these results because this is the first time that DESPOT has been used for solid samples and it is not likely in full working order. MAS nmr indicates that the 13C and 29 Si ~sotropic chemical shifts of silicon carbide appear to have a reciprocal type of relationship_ Single crystal nmr analysis of a 6H sample is accordance with this finding when only the resultant isotropic shift is considered. However, single crystal nmr also shows that the actual response of the silicon and carbon nuclear environment to the applied magnetic field at various angles is not at all reciprocal. Such results show that much more single crystal nmr work is required to determine the actual behavior of the local magnetic environment of the SiC nuclei.

Solid state NMR chemical shifts as an alternative to diffraction data in the determination of SIC polytypic structures

Silicon carbide, which has many polytypic modifications of a very simple and very symmetric structure, is an excellent model system for exploring, the relationship between chemical shift, long-range dipolar shielding, and crystal structure in network solids. A simple McConnell equation treatment of bond anisotropy effects in a poly type predicts chemical shifts for silicon and carbon sites which agree well with the experiment, provided that contributions from bonds up to 100 A are included in the calculation. The calculated chemical shifts depend on three factors: the layer stacking sequence, electrical centre of gravity, and the spacings between silicon and carbon layers. The assignment of peaks to lattice sites is proved possible for three polytypes (6H, 15R, and 3C). The fact that the calculated chemical shifts are very sensitive to layer spacings provides us a potential way to detennine and refine a crystal structure. In this work, the layer spacings of 6H SiC have been calculated and are within X-ray standard deviations. Under this premise, the layer spacings of 15R have been detennined. 29Si and 13C single crystal nmr studies of 6H SiC polytype indicate that all silicons and carbons are magnetically anisotropic. The relationship between a magnetic shielding tensor component and layer spacings has been derived. The comparisons between experimental and semi-empirical chemical shielding tensor components indicate that the paramagnetic shielding of silicon should be included in the single crystal chemical shift calculation.

Ab Initio study of magnetic interactions in the KCuF3 and K2CuF4 low-dimensional Systems

The ab initio cluster model approach has been used to study the electronic structure and magnetic coupling of KCuF3 and K2CuF4 in their various ordered polytype crystal forms. Due to a cooperative Jahn-Teller distortion these systems exhibit strong anisotropies. In particular, the magnetic properties strongly differ from those of isomorphic compounds. Hence, KCuF3 is a quasi-one-dimensional (1D) nearest neighbor Heisenberg antiferromagnet whereas K2CuF4 is the only ferromagnet among the K2MF4 series of compounds (M=Mn, Fe, Co, Ni, and Cu) behaving all as quasi-2D nearest neighbor Heisenberg systems. Different ab initio techniques are used to explore the magnetic coupling in these systems. All methods, including unrestricted Hartree-Fock, are able to explain the magnetic ordering. However, quantitative agreement with experiment is reached only when using a state-of-the-art configuration interaction approach. Finally, an analysis of the dependence of the magnetic coupling constant with respect to distortion parameters is presented.

Growth and Characterization of Silicon Carbide Thin Films Using a Nontraditional Hollow Cathode Sputtering Technique

Silicon carbide (SiC) is considered a suitable candidate for high-power, high-frequency devices due to its wide bandgap, high breakdown field, and high electron mobility. It also has the unique ability to synthesize graphene on its surface by subliming Si during an annealing stage. The deposition of SiC is most often carried out using chemical vapor deposition (CVD) techniques, but little research has been explored with respect to the sputtering of SiC. Investigations of the thin film depositions of SiC from pulse sputtering a hollow cathode SiC target are presented. Although there are many different polytypes of SiC, techniques are discussed that were used to identify the film polytype on both 4H-SiC substrates and Si substrates. Results are presented about the ability to incorporate Ge into the growing SiC films for the purpose of creating a possible heterojunction device with pure SiC. Efforts to synthesize graphene on these films are introduced and reasons for the inability to create it are discussed. Analysis mainly includes crystallographic and morphological studies about the deposited films and their quality using x-ray diffraction (XRD), reflection high energy electron diffraction (RHEED), transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), Auger electron spectroscopy (AES) and Raman spectroscopy. Optical and electrical properties are also discussed via ellipsometric modeling and resistivity measurements. The general interpretation of these analytical experiments indicates that the films are not single crystal. However, the majority of the films, which proved to be the 3C-SiC polytype, were grown in a highly ordered and highly textured manner on both (111) and (110) Si substrates.

Superspace description of wagnerite-group minerals (Mg,Fe,Mn) 2 (PO 4 )(F,OH)

Reinvestigation of more than 40 samples of minerals belonging to the wagnerite group (Mg, Fe, Mn)2(PO4)(F,OH) from diverse geological environments worldwide, using single-crystal X-ray diffraction analysis, showed that most crystals have incommensurate structures and, as such, are not adequately described with known polytype models (2b), (3b), (5b), (7b) and (9b). Therefore, we present here a unified superspace model for the structural description of periodically and aperiodically modulated wagnerite with the (3+1)-dimensional superspace group C2/c(0[beta]0)s0 based on the average triplite structure with cell parameters a [asymptotically equal to] 12.8, b [asymptotically equal to] 6.4, c [asymptotically equal to] 9.6 Å, [beta] [asymptotically equal to] 117° and the modulation vectors q = [beta]b*. The superspace approach provides a way of simple modelling of the positional and occupational modulation of Mg/Fe and F/OH in wagnerite. This allows direct comparison of crystal properties.

Geochemistry of the oceanic crust from ocean drilling samples

This book presents new data on chemical and mineral compositions and on density of altered and fresh igneous rocks from key DSDP and ODP holes drilled on the following main tectonomagmatic structures of the ocean floor: 1. Mid-ocean ridges and abyssal plains and basins (DSDP Legs 37, 61, 63, 64, 65, 69, 70, 83, and 91 and ODP Legs 106, 111, 123, 129, 137, 139, 140, 148, and 169); 2. Seamounts and guyots (DSDP Legs 19, 55, and 62 and ODP Legs 143 and 144); 3. Intraplate rises (DSDP Legs 26, 33, 51, 52, 53, 72, and 74 and ODP Legs 104, 115, 120, 121, and 183); and 4. Marginal seas (DSDP Legs 19, 59, and 60 and ODP Legs 124, 125, 126, 127, 128, and 135). Study results of altered gabbro from the Southwest Indian Ridge (ODP Leg 118) and serpentinized ultramafic rocks from the Galicia margin (ODP Leg 103) are also presented. Samples were collected by the authors from the DSDP/ODP repositories, as well as during some Glomar Challenger and JOIDES Resolution legs. The book also includes descriptions of thin sections, geochemical diagrams, data on secondary mineral assemblages, and recalculated results of chemical analyses with corrections for rock density. Atomic content of each element can be quantified in grams per standard volume (g/1000 cm**3). The suite of results can be used to estimate mass balance, but parts of the data need additional work, which depends on locating fresh analogs of altered rocks studied here. Results of quantitative estimation of element mobility in recovered sections of the upper oceanic crust as a whole are shown for certain cases: Hole 504B (Costa Rica Rift) and Holes 856H, 857C, and 857D (Middle Valley, Juan de Fuca Ridge).

Mineralogy and inorganic geochemistry of sediments at DSDP Leg 65 Holes

During Leg 65, 15 holes were drilled at four sites located on young crust in the mouth of the Gulf of California. Quaternary to upper Pliocene hemipelagic sediments above and interlayered within the young basaltic basement were cored. The influence of hot lava, high temperature gradients, and hydrothermal activity on the mineralogy and geochemistry of the terrigenous sediments near contacts with basalts might therefore be expected. The purpose of the present study was to determine the mineralogy and inorganic geochemistry of these sediments and to analyze the nature and extent of low temperature alteration. To this end we studied the mineralogy and inorganic geochemistry of 75 sediment samples, including those immediately overlying uppermost basalts and those from layers alternating with basalts within the basement. We separated three size fractions - <2 µm (clay), 2-20 µm (intermediate), and >20 µm (coarse) - and applied the following mineralogical determinations: x-ray diffraction (XRD), infrared spectroscopy, transmission and scanning electron microscopy, and optical microscopy (for coarse fractions, using thin sections and smear slides). We calculated the percentages of clay minerals using Biscaye's (1964) method, and used routine wet chemical analyses to determine bulk composition and quantitative spectral analyses for trace elements.

Mineral and chemical compositions of clay sediments from the Pacific Ocean, DSDP data

Mineral and chemical compositions, as well as conditions of formation of clay sediments in major structural elements of the Pacific Ocean floor with different ages are under consideration in the monograph. Depending on evolution of the region two ways of clay sediment formation are identified: terrigenous and authigenic. It is shown that terrigenous clay sediments predominate in marginal parts of the Pacific Ocean. Authigenic mineral formation occurring in the basal part of the sedimentary cover primarily results from removal of material from underlying basalts. This material is released during secondary alteration of the basalts due to their interaction with sea water, as well as with deep solutions.