Search NASA⌕ Search

SEARCH · Search NASA

Results for “crystal fields”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2

Spectral characteristics of the iron oxides with application to the Martian bright region mineralogy

Reflectance spectra of eight polymorphs of FeOOH and Fe2O3 are determined in order to clarify the nature and significance of the iron oxide mineralogy on Mars. The effect of other components that might interfere with iron oxide absorption features is qualitatively constrained through the use of the Kebulka-Munk theory. It is found that the effect of temperature complicates the identification of a given Fe(3+) phase based on the position of the 6A1-4T1 absorption feature. While the Fe(3+) crystal field transitions are spin forbidden, most of the iron oxide polymorphs exhibit anomalously intense crystal field absorption features due to magnetic coupling between adjacent FeO6 octahedra. It is suggested that the resulting deviations from observed remotely sensed reflectance spectra of Mars may provide a basis for the exclusion of many iron oxide phases as significant components of the Martian Fe(3+) mineralogy. A comparison of these results with the visible region spectra of Martian bright regions indicates that the predominant Fe(3+)-bearing phase may be a magnetically disordered material, such as amorphous gels, some ferric sulphates, and other minerals in which Fe(3+) ions in the crystal structure are not magnetically coupled.

Sherman, D. M.↗

Theoretical temperature-dependent branching ratios and laser thresholds of the 3F4 to 3H6 levels of Tm(3+) in ten garnets

The calculated energy levels, the branching ratios, and the estimated thresholds for thulium operating on the 3F4 to 3H6 transitions are reported. Garnet materials with the general formula A3B2C3O12 are evaluated. Calculations are performed for the A side under the assumption of D2 symmetry. X-ray data available in the literature are used to evaluate the crystal-field components, A sub nm. Even-n components are employed to calculate the crystal-field splittings within the manifold. Thermal occupation factors are determined in a straightforward manner using a Boltzmann distribution for the respective manifolds. Odd-n components are applied to calculate the transition probabilities for electric field transitions. It is determined that the magnetic dipole contributions to the transition probability are comparable to the electric dipole contributions in some cases. Thresholds as a function of the density of thulium atoms are calculated.

Filer, Elizabeth D.↗

Static Magnetic Fields in Semiconductor Floating-Zone Growth

Heat and mass transfer in semiconductor float-zone processing are strongly influenced by convective flows in the zone, originating from sources such as buoyancy convection, thermocapillary (Marangoni) convection, differential rotation, or radio frequency heating. Because semiconductor melts are conducting, flows can be damped by the use of static magnetic fields to influence the interface shape and the segregation of dopants and impurities. An important objective is often the suppression of time-dependent flows and the ensuing dopant striations. In RF-heated Si-FZ - crystals, fields up to O.STesla show some flattening of the interface curvature and a reduction of striation amplitudes. In radiation-heated (small-scale) SI-FZ crystals, fields of 0.2 - 0.5 Tesla already suppress the majority of the dopant striations. The uniformity of the radial segregation is often compromised by using a magnetic field, due to the directional nature of the damping. Transverse fields lead to an asymmetric interface shape and thus require crystal rotation (resulting in rotational dopant striations) to achieve a radially symmetric interface, whereas axial fields introduce a coring effect. A complete suppression of dopant striations and a reduction of the coring to insignificant values, combined with a shift of the axial segregation profile towards a more diffusion-limited case, are possible with axial static fields in excess of 1 Tesla. Strong static magnetic fields, however, can also lead to the appearance of thermoelectromagnetic convection, caused by the interaction of thermoelectric currents with the magnetic field.

Croll, Arne↗

Theoretical branching ratios for the 5I7 to 5I7 levels of Ho(3+) in the garnets A3B2C3O12 (A = Y,La,Lu,Gd; B = Al,Lu,Sc,Ga; C = Al,Ga)

Results are reported from an experimental study investigating triply ionized holmium in 10 garnets using the point-change model to predict theoretical energy levels and temperature-dependent branching ratios for the 5I7 to 5I8 manifolds for temperatures between 50 and 400 K. Plots were made for the largest lines at 300 K. YScAG was plotted twice, once for each set of X-ray data available. Energy levels are predicted based on theoretical crystal-field parameters, and good agreement to experiment is found. It is suggested that the present set of theoretical crystal-field parameters provides good estimates of the energy levels for the other hosts on which there are no experimental optical data. X-ray and index-of-refraction data are used to evaluate the performance of 10 lasers via a quantum mechanical model to predict the position of the energy levels and the temperature-dependent branching rations of the 5I7 to 5I8 levels of holmium. The fractional population inversion required for threshold is also evaluated.

Filer, Elizabeth D.↗

Recent advances in efficient long-life, eye-safe solid state and CO2 lasers for laser radar applications

The key problems in the development of eye-safe solid-state lasers are discussed, taking into account the energy transfer mechanisms between the complicated energy level manifolds of the Tm, Ho, Er ion dopants in hosts with decreasing crystal fields such as YAG or YLF. Optimization of energy transfer for efficient lasing through choice of dopant concentration, power density, crystal field and temperature is addressed. The tailoring of energy transfer times to provide efficient energy extraction for short pulses used in DIAL and Doppler lidar is considered. Recent advances in Pt/SnO2 oxide catalysts and other noble metal/metal oxide combinations for CO2 lasers are discussed. Emphasis is given to the dramatic effects of small quantities of H2O vapor for increasing the activity and lifetime of Pt/SnO2 catalysts and to increased lifetime operation with rare isotope (C-12)(O-18)2 lasing mixtures.

Hess, R. V.↗

Coordination chemistry of iron in glasses contributing to remote-sensed spectra of the moon

Ferric iron and tetrahedrally coordinated Fe(2+) ions are identified using Moessbauer and electronic absorption spectroscopic measurements of synthetic glasses equilibrated at P(O2) less than 10 to the -11 atm, simulating the Luna 24 brown glass and Apollo 15 green glass compositions. The presence of 10-20% ferric iron in these low Ti glasses is a result of the absence of Ti(3+) ions. In the brown glass absorption spectra, tetrahedral Fe(3+) and Fe(2+) ions induce an extension of the oxygen-metal charge transfer band into the visible region further than in the green glass containing predominantly octahedral Fe(2+) and Fe(3+) ions. Whereas the glass one-micron band originates from crystal field transitions in octahedral Fe(2+), the glass two-micron band is now positively correlated with tetrahedral Fe(2+) rather than with Fe(2+) ions in pyroxene M2-like sites in the glass structure. The tetrahedral Fe(2+) do not, however, substitute for Si(4+) in glass network-forming sites, instead occurring as network modifiers in larger tetrahedral interstices. The effect of temperature is to induce a pronounced red-shift of the oxygen-iron charge transfer absorption edge, especially for the brown glass, and to intensify significantly the tetrahedral Fe(2+) crystal field two micron band.

Dyar, M. D.↗

Optical Characterization and 2,525 micron Lasing of Cr(2+):Cd(0.85)Mn(0.15)Te

Transition metal doped solids are of significant current interest for the development of tunable solid-state lasers for the near and mid-infrared (1-4 pm) spectral region. Applications of these lasers include basic research in atomic, molecular, and solid-state physics, optical communication, medicine, and environmental studies of the atmosphere. In transition metal based laser materials, absorption and emission of light arises from electronic transitions between crystal field split energy levels of 3d transition metal ions. The optical spectra generally exhibit broad bands due to the strong interaction between dopant and host (electron-phonon coupling). Broad emission bands offer the prospect of tunable laser activity over a wide wavelength range, e.g. the tuning range of Ti:Sapphire extends from 700-1100 run. The only current transition metal laser operating in the mid-infrared wavelength region (1.8-2.4 micro-m) is CO(2+):MgF2, but its performance is severely limited due to strong nonradiative decay at room temperature. Based on lifetime data, the quantum efficiency is estimated to be less than 3 deg/0 11,21. In general, the probability for non-radiative decay via multi-phonon relaxation increases with decreasing energy gap between ground and excited state. Therefore, efficient transition metal lasers beyond -1.6 micro-m are rare. Recently, tunable laser activity around 2.3 micro-m was observed from Cr doped ZnS and ZnSe. The new lasing center in these materials was identified as Cr(2+) occupying the tetrahedral Zn site. Tetrahedrally coordinated optical centers are rather unusual among transition metal lasers. Their potential usefulness, however, has been demonstrated by the recent development of near infrared laser materials such as Cr:forsterite and Cr:YAG, which are based on tetrahedrally coordinated Cr(4+) ions. According to the Laporte selection rule, electric-dipole transition within the optically active 3d-electron shells are parity forbidden. However, a static acentric electric crystal field or the coupling of asymmetric phonons can force electric-dipole transitions by the admixture of wave functions with opposite parity. Tetrahedral sites lack inversion symmetry which provides the odd-parity field necessary to relax the parity selection rule. Therefore, high absorption and emission cross sections are observed. An enhanced radiative emission rate is also expected to reduce the detrimental effect of non-radiative decay. Motivated by the initial results on Cr doped ZnS and ZnSe, we have started a comprehensive effort to study Cr(2+) doped II-VI semiconductors for solid-state laser applications. In this paper we present the optical properties and the demonstration of mid-infrared lasing from Cr doped Cd(0.85)Mn(0.15)Te.

Davis, V. R.↗

The Effects of a Magnetic Field on the Crystallization of a Fluorozirconate Glass

An axial magnetic field of 0.1T was applied to ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) fibers during heating to the glass crystallization temperature. Scanning electron microscopy and x-ray diffraction were used to identify crystal phases. It was shown that fibers exposed to the magnetic field did not crystallize while fibers not exposed to the field did crystallize. A hypothesis based on magnetic work was proposed to explain the results and tested by measuring the magnetic susceptibilities of the glass and crystal.

Tucker, Dennis S.↗

Optical and chemical analysis of iron in Luna 20 plagioclase.

Review of analytical data on the iron content of Luna 20 anorthitic plagioclase, obtained by a highly sensitive technique for measuring polarized absorption related to crystal-field splittings and by automated electron microprobe analysis of oriented single crystals. The iron content is found to range from a few hundredths to a few tenths of a weight per cent from crystal to crystal. The optical and chemical properties of the iron appear to be caused by postcrystallization migration and exsolution. Postcrystallization effects may obscure evidence of the original oxidation state and iron concentration of these crystals.

Bell, P. M.↗

The infrared spectrum of solid chlorotrifluoromethane

The infrared spectrum of solid chlorotrifluoromethane (CF3Cl) has been studied and compared with that of matrix-isolated CF3Cl. Crystal field splitting patterns of the strongest modes nu1 and nu4 suggest the crystal structure to be orthorhombic with a C(2v) factor group and two molecules per unit cell located on C(s) sites.

Frazier, D. O.↗

Reflectance and Mossbauer spectroscopy of ferrihydrite-montmorillonite assemblages as Mars soil analog materials

Spectroscopic analyses show that Fe(3+)-doped smectites prepared in the laboratory exhibit important similarities to the soils on Mars. Ferrihydrite has been identified as the interlayer ferric component in Fe(3+)-doped smectites by a low quadrupole splitting and magnetic field strength of approximately 48 tesla in Mossbauer spectra measured at 4.2 K, as well as a crystal field transition at 0.92 micrometer. Ferrihydrite in these smectites explains features in the visible-near infrared region that resemble the energies and band strengths of features in reflectance spectra observed for several bright regions on Mars. Clay silicates have met resistance in the past as Mars soil analogs because terrestrial clay silicates exhibit prominent hydrous spectral features at 1.4, 1.9, and 2.2 micrometers; and these are observed weakly, if at all, in reflectance spectra of Mars. However, several mechanisms can weaken or compress these features, including desiccation under low-humidity conditions. The hydration properties of the interlayer cations also effect band strengths, such that a ferrihydrite-bearing smectite in the Martian environment would exhibit a 1.9 micrometers H2O absorption that is even weaker than the 2.2 micrometers structural OH absorption. Mixing experiments demonstrate that infrared spectral features of clays can be significantly suppressed and that the reflectance can be significantly darkened by mixing with only a few percent of a strongly absorbing opaque material. Therefore, the absolute reflectance of a soil on Mars may be disproportionately sensitive to a minor component. For this reason, the shape and position of spectral features and the chemical composition of potential analogs are of utmost importance in assessing the composition of the soil on Mars. Given the remarkable similarity between visible-infrared reflectance spectra of soils in bright regions on Mars and Fe(3+)-doped montmorillonites, coupled with recent observations of smectites in SNC meteorites and a weak 2.2 micrometers absorption in some Mars soils, ferrihydrite-bearing smectites warrant serious consideration as a Mars soil analog.

NASA Discipline Exobiology↗

Thermal-capillary model for Czochralski growth of semiconductor materials

The success of efficiently calculating the temperature field, crystal radius, melt mensicus, and melt/solid interface in the Czochralski crystal growth system by full finite-element solution of the government thermal-capillary model is demonstrated. The model predicts realistic response to changes in pull rate, melt volume, and the thermal field. The experimentally observed phenomena of interface flipping, bumping, and the difficulty maintaining steady-state growth as the melt depth decreases are explained by model results. These calculations will form the basis for the first quantitative picture of Cz crystal growth. The accurate depiction of the melt meniscus is important in calculating the crystal radius and solidification interface. The sensitivity of the results to the equilibrium growth angle place doubt on less sophisticated attempts to model the process without inclusion of the meniscus. Quantitative comparison with experiments should be possible once more representation of the radiation and view factors in the thermal system and the crucible are included. Extensions of the model in these directions are underway.

Derby, J. J.↗

Bridgman Growth of Germanium

The high-magnetic-field crystal growth facility at the Marshall Space Flight Center will be briefly described. This facility has been used to grow bulk germanium by the Bridgman technique in magnetic fields up to 5 Tesla. The results of investigations of ampoule material on the interface shape and thermal field applied to the melt on stability against convection will be discussed.

Szofran, F. R.↗

An EPR investigation of the dynamic Jahn-Teller effect in SrCl2:y(2 plus) and SrCl2:Sc(2 plus)

EPR spectra have been observed for SrCl2:Y(2+) and SrCl2:Sc(2+) at liquid helium temperatures. At 1.2 K the spectra were dominated by anisotropic hyperfine patterns whose lineshapes and angular dependences were explained using second order solutions of the effective Hamiltonian for an isolated 2Eg state split by large random internal strains. Pronounced asymmetries in some of the strin produced lineshapes for Srcl2:Sc(2+) are shown to result from second order terms in the solution of the effective Hamiltonian. Coexisting with the anisotropic hyperfine patterns are weak nearly isotropic hyperfine patterns with typical lineshapes. Variations in the apparent intensity of lines in these weak hyperfine patterns as functions of the applied magnetic field direction and temperature imply that these lines result from averaging by vibronic relaxation of a portion of the anisotropic pattern. The effective Hamiltonian parameters for SrCl2:La(2+), SrCl2:y(2+), and SrCl2:SC(2+) are analyzed in terms of crystal field theory modified to include a dynamic Jahn-Teller effect.

Herrington, J. R.↗