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Spectroscopic Investigation of Ce(3+) Doped Fluoride Crystals

Doping of the trivalent rare-earth cerium ion into fluoride crystals is of interest in producing turnable ultra-violet solid state lasers. These lasers are desirable for many applications in medicine, industry, and scientific research, including remote sensing. High absorption and stimulated emission cross sections of the dipole allowed 4f-5d transitions show promise in cerium as a laser ion in crystals. Several research groups have already reported the observation of stimulated emission of cerium in LiYF4, LiSrAlF6, and LiCaAlF6. However, the color center formation in the crystals due to the excited state absorption of ultra-violet pump light adds difficulty to achieving laser action. We have investigated the spectroscopic properties of cerium such as absorption and emission spectra, and lifetimes in four different fluoride crystals, including LiCaAlF6, LiSrAlF6, KyF4 and LiYF4. We have derived the polarized absorption and stimulated emission cross sections from transmission and fluorescence emission measurements for each of the host crystals. we have measured the lifetime of the lowest 5d level; moreover, investigated the temperature dependence of this lifetime and color center formation. Our results on absorption and stimulated emission cross sections for LiCaAlF6 and LiSrAlF6 are similar to the results already published.

Reinhart, Donald H.↗

Magnetism and superconductivity of some Tl-Cu oxides

Many copper oxide based Thallium compounds have now been discovered. In comparison to the Bi-compounds, the Tl-system shows a richer diversity; viz., High Temperature Superconductors (HTSC) can be obtained with either one or two Tl-0 layers (m = 1,2); also, the triple-digit phases are easier to synthesize. The value of d, oxygen stoichiometry, is critical to achieving superconductivity. The Tl system is robust to oxygen loss; Tl may be lost or incorporated by diffusion. A diffusion coefficient equal to 10 ms at 900 C was determined. Both ortho-rhombic and tetragonal structures are evidenced, but HTSC behavior is indifferent to the crystal symmetry. This system has the highest T(sub c) confirmed. T(sub c) generally increases with p, the number of CuO layers, but tends to saturate at p = 3. Zero resistance as high as 125K has been observed. Most of these HTSC's are hole type, but the Ce-doped specimens may be electronic. The magnetic aspects were studied; because in addition to defining the perfectly diamagnetic ground state as in the conventional superconductors, magnetism of the copper oxides show a surprising variety. This is true of both the normal and the superconducting states. Also, due to the large phonon contribution to the specific heat at the high T(sub c) accurate thermal measurement of important parameters such as the sp. heat jump, electronic density of states, D(Ef) and coherence length are uncertain, and thus, are estimated from the magnetic results. Results from the Tl-system CuO, LaBaCuO, 120 and the Bi-CuO compounds are discussed. The emphasis is on the role of magnetism in the TlCuO HTSC, but technological aspects are also pointed out.

Datta, Timir↗

Magnetism and superconductivity of some Tl-Cu oxides

Many copper oxide based Thallium compounds are now known. In comparison to the Bi-compounds, the Tl-system shows a richer diversity; i.e., High Temperature Superconductors (HTSC) can be obtained with either one or two Tl-0 layers (m = 1,2); also, the triple-digit phases are easier to synthesize. The value of d, oxygen stoichiometry, is critical to achieving superconductivity. The Tl system is robust to oxygen loss; Tl may be lost or incorporated by diffusion. A diffusion coefficient equal to 10 ms at 900 C was determined. Both ortho-rhombic and tetragonal structures are found, but HTSC behavior is indifferent to the crystal symmetry. This system has the highest T(sub c) confirmed. T(sub c) generally increases with p, the number of CuO layers, but tends to saturate at p = 3. Zero resistance was observed at temperatures as great as 125 K. Most of these HTSC's are hole type, but the Ce-doped specimens may be electronic. The magnetic aspects were studied; because in addition to defining the perfectly diamagnetic ground state as in conventional superconductors, magnetism of the copper oxides show a surprising variety. This is true of both the normal and the superconducting states. Also, due to the large phonon contribution to the specific heat at the high T(sub c) jump, electronic density of states, D(Ef), and coherence length are uncertain, and thus, are estimated from the magnetic results. Results from the Tl-system CuO, LaBaCuO,120 and the Bi-CuO compounds are discussed. The emphasis is on the role of magnetism in the Tl-CuO HTSC, but technological aspects are also pointed out.

Datta, Timir↗

New Scintillator Materials (K2CeBr5) and (Cs2CeBr5)

Cesium cerium bromide (Cs2CeBr5) and potassium cerium bromide (K2CeBr5) are new scintillator materials for X-ray and gamma ray detector applications. Recently halide scintillator materials, such as Ce doped lanthanum bromide has been proved to be very important material for the same purpose. These materials are highly hygroscopic; a search for high light yield non-hygroscopic materials was highly desirable to advance the scintillator technology. In this paper, we are reporting the crystal growth of novel scintillator materials, cesium cerium bromide (Cs2CeBr5) and potassium cerium bromide (K2CeBr5). Crystals were successfully grown from the melt using the vertical Bridgman-Stockbarger technique, in a comparison with the high performance LaBr3 or LaCl3 crystals, cerium based alkali halides crystals, (Cs2CeBr5) and (K2CeBr5) have similar scintillation properties, while being much less hygroscopic. Furthermore, cesium based compounds will not suffer from the self-activity present in potassium and lanthanum compounds. However the Cs2CeBr5 crystals did not grow properly probably due to non-congruent melting or to some phase transition during cooling. Keywords." Scintillator materials; Ce3+; Energy resolution; Light yield; K2CeBr5

Hawrami, R.↗

POSS(Registered TradeMark) Coatings for Solar Cells: An Update

Presently, solar cells are covered with Ce-doped microsheet cover glasses that are attached with Dow Corning DC 93-500 silicone adhesive. Various antireflection coatings are often applied to the cover glass to increase cell performance. This general approach has been used from the beginning of space exploration. However, it is expensive and time consuming. Furthermore, as the voltage of solar arrays increases, significant arcing has occurred in solar arrays, leading to loss of satellite power. The cause has been traced to differential voltages between strings and the close spacing between them with no insulation covering the edges of the solar cells. In addition, this problem could be ameliorated if the cover glass extended over the edges of the cell, but this would impact packing density. An alternative idea that might solve all these issues and be less expensive and more protective is to develop a coating that could be applied over the entire array. Such a coating must be resistant to atomic oxygen for low earth orbits below about 700 km, it must be resistant to ultraviolet radiation for all earth and near-sun orbits and, of course, it must withstand the damaging effects of space radiation. Coating flexibility would be an additional advantage. Based on past experience, one material that has many of the desired attributes of a universal protective coating is the Dow Corning DC 93-500. Of all the potential optical plastics, it appears to be the most suitable for use in space. As noted above, DC 93-500 has been extensively used to attach cover glasses to crystalline solar cells and has worked exceptionally well over the years. It is flexible and generally resistant to electrons, protons and ultraviolet (UV and VUV) radiation; although a VUV-rejection coating or VUV-absorbing ceria-doped cover glass may be required for long mission durations. It can also be applied in a thin coating (< 25 m) by conventional liquid coating processes. Unfortunately, when exposed to atomic oxygen (AO) DC 93-500 develops a frosty surface. Such frosting can lead to a loss of light transmitted into the cells and destroy the essential clarity needed for a concentrator lens.

Brandhorst, Henry↗

Preparation and characteristics of superconducting cuprate thin films: Nd(2-x)Ce(x)CuO4 and substituted Bi-system

Characteristics of the electron-doped-type Nd(2-x)Ce(x)CuO4 systems and substituted Bi2(Sr,Ln)3Cu2Oy system were systematically studied using the high quality thin-film samples. The Nd(2-x)Ce(x)CuO4 thin films with various Ce concentrations, x, were prepared by RF magnetron sputtering on SrTiO3 heated at around 500 C. After subsequent annealing at 1100 C in air, the films showed the c-axis orientation normal to the substrates. By means of the reducing treatment (annealing in a vacuum), superconductivity was induced for the films with 0.14 is less than or equal to x is less than or equal to 0.18. The superconductivity and transport properties of the films were strongly affected by the reducing treatment. The x = 0.15 film exhibited a sharp superconducting transition with zero resistivity at 22 K, in consistent with the diamagnetic properties. The resistivity of the films was fairly low with metallic characteristics, and the sight of the Hall coefficient was negative in the normal state. On the other hand, the normal-state optical measurements showed that the undoped Nd2CuO4 is a semiconductor with a charge transfer gap of 1.3 eV, and that, when Ce ions were doped, a plasma reflection due to the free-carriers came to be seen with the plasma frequency of 1.07 eV for 0.14 is less than or equal to x is less than or equal to 0.18. Moreover, x ray photoemission study revealed that the Cu valence of the film decreased for 2(+) for x = 0 to 1(+) for x = 0.15. These physical properties are in contrast with those of hole-doped-type cuprate superconductors. Bi2(Sr,Ln)3Cu2Oy thin films were also prepared on MgO substrates heated at 600 to 700 C by similar methods. It was found that the growth conditions for Bi-systems with two CuO2 planes were different for each composition and species of lanthanoid in the films. Moreover, preparation of Bi-system with three CuO2 planes was very difficult when lanthanoid atoms were doped in the system. Their electric transport properties and x ray photoemission spectroscopy were investigated. Carrier concentration and Cu valence were discussed with regard to the superconductivity.

Adachi, H.↗

Thermal Stability of M x O y Doped Zirconia Aerogels (M = Y, Yb, Gd, Ce, Ca) Studied Through 1200°C

The high porosities and low densities of ceramic aerogels offer outstanding insulative performance in applications where weight is a critical factor. The high surface area-to-volume ratios and specific surface areas provide extremely low thermal conductivity, but also contribute to rapid densification of the pore structure at elevated temperatures. This densification diminishes their favorable properties and inhibits use of aerogels in high temperature applications. This work contributes to a design framework for thermally stable aerogels via the study of dopant chemistry (Y, Yb, Gd, Ca, Ce) in zirconia aerogels. The structural evolution was studied to 1200°C using nitrogen physisorption, scanning electron microscopy, and x-ray diffraction. The role of dopant identity and concentration in thermal stability was elucidated. In context of the design framework, dopant chemistry is an aggregate for many closely related material properties, each of which may contribute to aerogel structural evolution. To develop a truly predictive design framework for ceramic-based aerogels, systematic and comprehensive evaluation of thermodynamic and kinetic properties must be performed in conjunction with studies on structural evolution.

aerogel↗

Unreported Emission Lines of Rb, Ce, La, Sr, Y, Zr, Pb and Se Detected Using Laser-Induced Breakdown Spectroscopy

Information on emission lines for major and minor elements is readily available from the National Institute of Standards and Technology (NIST) as part of the Atomic Spectra Database. However, tabulated emission lines are scarce for some minor elements and the wavelength ranges presented on the NIST database are limited to those included in existing studies. Previous work concerning minor element calibration curves measured using laser-induced break-down spectroscopy found evidence of Zn emission lines that were not documented on the NIST database. In this study, rock powders were doped with Rb, Ce, La, Sr, Y, Zr, Pb and Se in concentrations ranging from 10 percent to 10 parts per million. The difference between normalized spectra collected on samples containing 10 percent dopant and those containing only 10 parts per million were used to identify all emission lines that can be detected using LIBS (Laser-Induced Breakdown Spectroscopy) in a ChemCam-like configuration at the Mount Holyoke College LIBS facility. These emission spectra provide evidence of many previously undocumented emission lines for the elements measured here.

LIBS↗

Preparation and characteristics of superconducting cuprate thin films: Nd(2-x)Ce(x)CuO4 and substrated Bi-system

Characteristics of the electron-doped-type Nd(sub 2-x)Ce(sub x)CuO4 system and substituted Bi-system were studied using the high quality thin film samples grown by rf magnetron sputtering and/or subsequent heat treatment. The Nd(sub 2-x)Ce(sub x)CuO4 samples with excellent superconducting properties were obtained in thin films and their optical and X-ray photoelectron spectroscopy (XPS) studies were performed with regard to the Ce content and reducing treatment. Substituted BiSr-Ln-Cu-O thin films were prepared and growth conditions for Bi-system with 2-2-1-2 and 2-2-2-2 phases were found. Moreover, a new 2-2-1-2 phase in the simple Bi-Sr-Cu-O system was fabricated by thin film processing and 80 K superconductivity was obtained.

Adachi, H.↗

Gadolinia-Doped Ceria Cathodes for Electrolysis of CO2

Gadolinia-doped ceria, or GDC, (Gd(0.4)Ce(0.6)O(2-delta), where the value of delta in this material varies, depending on the temperature and oxygen concentration in the atmosphere in which it is being used) has shown promise as a cathode material for high-temperature electrolysis of carbon dioxide in solid oxide electrolysis cells. The polarization resistance of a GDC electrode is significantly less than that of an otherwise equivalent electrode made of any of several other materials that are now in use or under consideration for use as cathodes for reduction of carbon dioxide. In addition, GDC shows no sign of deterioration under typical temperature and gas-mixture operating conditions of a high-temperature electrolyzer. Electrolysis of CO2 is of interest to NASA as a way of generating O2 from the CO2 in the Martian atmosphere. On Earth, a combination of electrolysis of CO2 and electrolysis of H2O might prove useful as a means of generating synthesis gas (syngas) from the exhaust gas of a coal- or natural-gas-fired power plant, thereby reducing the emission of CO2 into the atmosphere. The syngas a mixture of CO and H2 could be used as a raw material in the manufacture, via the Fisher-Tropsch process, of synthetic fuels, lubrication oils, and other hydrocarbon prod

Adler, Stuart B.↗

Rare Earth Element Partition Coefficients from Enstatite/Melt Synthesis Experiments

Enstatite (En(80)Fs(19)Wo(01)) was synthesized from a hypersthene normative basaltic melt doped at the same time with La, Ce, Nd, Sm, Eu, Dy, Er, Yb and Lu. The rare earth element concentrations were measured in both the basaltic glass and the enstatite. Rare earth element concentrations in the glass were determined by electron microprobe analysis with uncertainties less than two percent relative. Rare earth element concentrations in enstatite were determined by secondary ion mass spectrometry with uncertainties less than five percent relative. The resulting rare earth element partition signature for enstatite is similar to previous calculated and composite low-Ca pigeonite signatures, but is better defined and differs in several details. The partition coefficients are consistent with crystal structural constraints.

Schwandt, Craig S.↗

A Solid State Ultraviolet Lasers Based on Cerium-Doped LiCaAIF(sub 6) Crystal Resonator

We report the first demonstration of a UV laser using a high-Q whispering gallery mode (WGM) resonator of Ce+: LiCaAlF6. We show that WGM resonators from LiCaAlF6 can achieve a Q of 2.6 x 10(sup 7) at UV. We demonstrated a UV laser at 290 nm with a pulsed pump laser at 266 nm. The experiments showed the low pump threshold intensity of 7.5 x 10(sup 9) W/m(sup 2) and slope efficiency of 25%. We have also observed lasing delay dynamics. These results are consistent with our modeling and theoretical estimates, and pave the way for a low threshold cw UV laser using WGM resonator cavity.

Whispering Gallery Mode Resonators↗

Crystal Growth in the SUBSA furnace in MSG: 2002 to 2022

In 2002, the investigation “Solidification Using a Baffle In Sealed Ampoules (SUBSA)” was the first investigation to utilize the Microgravity Science Glovebox (MSG) Facility on the International Space Station (ISS). The SUBSA furnace was designed for growth of indium antimonide. It features a transparent section, which allows a side view of the melt, the solid-liquid (SL) interface and the growing crystal. In 2002, four Te-doped and three Zn-doped InSb crystals were grown in microgravity. Subsequently, the SUBSA furnace was used in several materials science investigations, including growing the radiation detector materials, InI and Cs2LiYCl6:Ce from the melt and vapor phase (2017 to 2019) and “Brazing of Aluminum alloys in Space (BRAINS)”. A review of the SUBSA furnace features and parameters will be presented, including the design of the growth ampoules, charge preparation, and the procedures used to grow InSb (in 2002) and InI (in 2019).

Aleksandar Ostrogorsky↗

Crystal Growth in the SUBSA furnace at the International Space Station (ISS)

In 2002, our investigation Solidification Using a Baffle In Sealed Ampoules (SUBSA) was the first investigation to utilize the Microgravity Science Glovebox (MSG) Facility on the International Space Station (ISS). The SUBSA furnace was designed for growth of indium antimonide. It features a transparent section, which allows a side view of the melt, the solid-liquid (SL) interface and the growing crystal. In 2002, four Te- doped and three Zn-doped InSb crystals were grown in microgravity. Subsequently, the SUBSA furnace was used in several other materials science investigations, including growing the radiation detector materials InI and Cs2LiYCl6:Ce from the melt and vapor phase (2017 to 2019) and Brazing of Aluminum alloys in Space (BRAINS). A review of the SUBSA furnace features and parameters will be presented, including the design of the growth ampoules, charge preparation, and the procedures used to grow InSb (in 2002) and InI (in 2019).

A.G. Ostrogorsk↗

X-ray photoelectron spectroscopy study of chemically-etched Nd-Ce-Cu-O surfaces

Acetic acid, Br2, and HCl solutions are investigated for removing insulating species from Nd(1.85)Ce(0.15)CuO(4-delta) (NCCO) thin film surfaces. X-ray photoelectron spectroscopy (XPS) shows that the HCl etch is most effective, yielding O 1s spectra comparable to those obtained from samples cleaned in vacuum and a clear Fermi edge in the valence band region. Reduction and oxidation reversibly induces and eliminates, respectively, Fermi level states for undoped samples, but has no clearly observable effect on the XPS spectra for doped samples. Reactivity to air is much less for NCCO compared to hole superconductors, which is attributed to the lack of reactive alkaline earth elements in NCCO.

Vasquez, R. P.↗