Combined vibrational, structural, elemental and Mössbauer spectroscopic analysis of natural phillipsite (zeolite) from historical eruptions in Tenerife, Canary Islands: Implication for Mars

The outcrop of “Las Arenas” volcano in Tenerife, Canary Islands (Spain) has been presented as Terrestrial volcanic analog for ancient Mars, showing a great variety of alteration processes and interesting mineralogy. The current analysis has been done by means of measurement techniques used or proposed on Martian studies. The new analysis of the zeolite has been carried out using Raman spectroscopy, Mössbauer spectroscopy, X-ray diffraction (XRD), Infrared spectroscopy, Laser induced breakdown spectroscopy and Scanning electron microscopy (SEM-EDX). The zeolite has been carefully analyzed using vibrational spectroscopy and it has been identified as Ca-phillipsite. The other techniques support and confirm the results. The measurements and results using the Raman Laser Spectrometer (RLS) simulator system show the capabilities RLS system in the ESA Exo- Mars mission. The chemometrical methods for the vibrational mineral detection show the advantages of Raman spectroscopy to understand the possible geological context. Furthermore, the proposed diagenesis and formation of the zeolites in southern part of Tenerife island have been confirmed by the twin space prototypes used. A new hypothesis about the origin for the special case of “Las Arenas” volcano Ca-phillipsite has been proposed. Finally, a multi-complementary comparison among the different techniques used on the current studie has been done and, also an analogy with the next space mission has been established. These analyses emphasize the strength of the different techniques and the working synergy of the different techniques together for planetary space missions

Analysis of the upconversion emission of yttrium orthoaluminate nanoperovskite co-doped with Er3+/Yb3+ ions for thermal sensing applications

[EN] The upconversion emissions of yttrium orthoaluminate nano-perovskite co-doped with Er3+/Yb3+ have been studied. Strong green and red upconversion emissions, which can be observed by naked eyes, were observed when exciting the sample at 980 nm. In particular, the green band was monitored as a function of temperature and the obtained results suggest that this nano-perovskite can be used as an optical temperature sensor by exciting in the infrared range. The viability of YAP: Er3+/Yb3+ nano-perovskite in laser heating applications has been tested and discussed.This research was partially supported MINECO (MAT2013-46649-C4-2/4-P, MAT2015-71070-REDC, and MAT2016-75586-C4-2/4-P), and by the EU-FEDER. M.A. Hernández-Rodríguez thanks to MINECO for FPI grant (BES-2014-068666).Hernández-Rodríguez, M.; Lozano-Gorrín, A.; Lavin, V.; Rodriguez-Mendoza, U.; Martin, I.; Manjón, F. (2018). Analysis of the upconversion emission of yttrium orthoaluminate nanoperovskite co-doped with Er3+/Yb3+ ions for thermal sensing applications. Journal of Luminescence. 202:316-321. https://doi.org/10.1016/j.jlumin.2018.05.078S31632120

Nd3+-doped TeO2–PbF2–AlF3 glasses for laser applications

A study of the optical properties of Nd3+ ion in TeO2–PbF2–AlF3 glasses has been carried out for different Nd3+ concentrations. Based on the Judd–Ofelt theory, intensity parameters and radiative properties were determined from the absorption spectra. Focusing on the suitability of this host for laser applications, the spectroscopic quality factor v was obtained with a value of 1.07, a value of the order of other compositions proposed as laser hosts. For the most intense emission corresponding with the 4F3/2?4I11/2 transition (1.06 lm), the absorption and emission and have been calculated with values of 1.20 10 20 cm2, 2.08 10 20 cm2. A positive value for the gain cross-sections has been found for a population inversion factor c of 0.4 in the spectral range from 1060 to 1110 nm. All these results suggest the potentially use of this system as a laser host

X-ray nanoimaging of Nd3+ optically active ions embedded in Sr0.5Ba0.5Nb2O6 nanocrystals

[EN] The spatial distribution of Sr0.5Ba0.5Nb2O6 nanocrystals is analyzed in a borate-based glass-ceramic by a synchrotron hard X-ray nanoimaging tool. Based on X-ray excited optical luminescence, we examined 2D projections of the Nd3+ optically active ions in the Sr0.5Ba0.5Nb2O6 nanocrystals, as well as in the glassy phase where they are embedded. Our findings reveal areas of agglomerations and/or clusters of nanocrystals ascribed to the diffusion coefficients of their constituent elements. They are characterized by high Nd3+ concentrations that may act as heterogeneous agents for the nucleation and growth of these nanocrystals. (C) 2017 Optical Society of AmericaMINECO, EU-FEDER and CSIC through the projects MAT2013-46649-C4-4-P, MAT201571070-REDC, MAT2016-75586-C4-2-P, MAT2016-75586-C4-4-P, 201550I021 and 201660I001, respectively. JAS acknowledges the Spanish Program Ramón y Cajal for his fellowship. We also thank the ESRF for the beam time allocated and experimental facilities.Martínez-Criado, G.; Alén, B.; Sans-Tresserras, JÁ.; Lozano-Gorrín, A.; Haro-González, P.; Martin, I.; Lavin, V. (2017). X-ray nanoimaging of Nd3+ optically active ions embedded in Sr0.5Ba0.5Nb2O6 nanocrystals. Optical Materials Express. 7(7):2424-2431. https://doi.org/10.1364/OME.7.002424S2424243177Nagata, K., Yamamoto, Y., Igarashi, H., & Okazaki, K. (1981). Properties of the hot-pressed strontium barium niobate ceramics. Ferroelectrics, 38(1), 853-856. doi:10.1080/00150198108209556Imai, T., Yagi, S., Yamazaki, H., & Ono, M. (1999). Effects of Heat Treatment on Photorefractive Sensitivity of Ce- and Eu-Doped Strontium Barium Niobate. Japanese Journal of Applied Physics, 38(Part 1, No. 4A), 1984-1988. doi:10.1143/jjap.38.1984Volk, T., Isakov, D., Salobutin, V., Ivleva, L., Lykov, P., Ramzaev, V., & Wöhlecke, M. (2004). Effects of Ni doping on properties of strontium–barium–niobate crystals. Solid State Communications, 130(3-4), 223-226. doi:10.1016/j.ssc.2004.01.039Romero, J. J., Andreeta, M. R. B., Andreeta, E. R. M., Bausá, L. E., Hernandes, A. C., & García Solé, J. (2004). Growth and characterization of Nd-doped SBN single crystal fibers. Applied Physics A, 78(7), 1037-1042. doi:10.1007/s00339-003-2151-3Chayapiwut, N., Honma, T., Benino, Y., Fujiwara, T., & Komatsu, T. (2005). Synthesis of Sm3+-doped strontium barium niobate crystals in glass by samarium atom heat processing. Journal of Solid State Chemistry, 178(11), 3507-3513. doi:10.1016/j.jssc.2005.09.002Haro-González, P., Martín, I. R., Martín, L. L., León-Luis, S. F., Pérez-Rodríguez, C., & Lavín, V. (2011). Characterization of Er3+ and Nd3+ doped Strontium Barium Niobate glass ceramic as temperature sensors. Optical Materials, 33(5), 742-745. doi:10.1016/j.optmat.2010.11.026Ivleva, L. I., Volk, T. R., Isakov, D. V., Gladkii, V. V., Polozkov, N. M., & Lykov, P. A. (2002). Growth and ferroelectric properties of Nd-doped strontium–barium niobate crystals. Journal of Crystal Growth, 237-239, 700-702. doi:10.1016/s0022-0248(01)01997-2Marcinkevičius, A., Juodkazis, S., Watanabe, M., Miwa, M., Matsuo, S., Misawa, H., & Nishii, J. (2001). Femtosecond laser-assisted three-dimensional microfabrication in silica. Optics Letters, 26(5), 277. doi:10.1364/ol.26.000277Sato, R., Benino, Y., Fujiwara, T., & Komatsu, T. (2001). YAG laser-induced crystalline dot patterning in samarium tellurite glasses. Journal of Non-Crystalline Solids, 289(1-3), 228-232. doi:10.1016/s0022-3093(01)00736-0Haro-González, P., Martín, L. L., González-Pérez, S., & Martín, I. R. (2010). Formation of Nd3+ doped Strontium Barium Niobate nanocrystals by two different methods. Optical Materials, 32(10), 1389-1392. doi:10.1016/j.optmat.2010.03.011Haro-González, P., Martín, I. R., & Creus, A. H. (2010). Nanocrystals distribution inside the writing lines in a glass matrix using Argon laser irradiation. Optics Express, 18(2), 582. doi:10.1364/oe.18.000582Haro-González, P., Martín, I. R., Arbelo-Jorge, E., González-Pérez, S., Cáceres, J. M., & Núñez, P. (2008). Laser irradiation in Nd3+ doped strontium barium niobate glass. Journal of Applied Physics, 104(1), 013112. doi:10.1063/1.2952011Kowalska, D., Haro-González, P., Martín, I. R., & Cáceres, J. M. (2010). Analysis of the optical properties of Er3+-doped strontium barium niobate nanocrystals using time-resolved laser spectroscopy. Applied Physics A, 99(4), 771-776. doi:10.1007/s00339-010-5716-yPellicer-Porres, J., Segura, A., Martínez-Criado, G., Rodríguez-Mendoza, U. R., & Lavín, V. (2012). Formation of nanostructures in Eu3+doped glass–ceramics: an XAS study. Journal of Physics: Condensed Matter, 25(2), 025303. doi:10.1088/0953-8984/25/2/025303Martínez-Criado, G., Alén, B., Sans, J. A., Homs, A., Kieffer, I., Tucoulou, R., … Yi, G. (2012). Spatially resolved X-ray excited optical luminescence. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 284, 36-39. doi:10.1016/j.nimb.2011.08.013Martínez-Criado, G., Sans, J. A., Segura-Ruiz, J., Tucoulou, R., Solé, A. V., Homs, A., … Alén, B. (2011). X-ray excited optical luminescence imaging of InGaN nano-LEDs. physica status solidi (c), 9(3-4), 628-630. doi:10.1002/pssc.201100430Villanova, J., Segura-Ruiz, J., Lafford, T., & Martinez-Criado, G. (2012). Synchrotron microanalysis techniques applied to potential photovoltaic materials. Journal of Synchrotron Radiation, 19(4), 521-524. doi:10.1107/s0909049512021383Smith, J., Akbari-Sharbaf, A., Ward, M. J., Murphy, M. W., Fanchini, G., & Kong Sham, T. (2013). Luminescence properties of defects in nanocrystalline ZnO. Journal of Applied Physics, 113(9), 093104. doi:10.1063/1.4794001Armelao, L., Heigl, F., Jürgensen, A., Blyth, R. I. R., Regier, T., Zhou, X.-T., & Sham, T. K. (2007). X-ray Excited Optical Luminescence Studies of ZnO and Eu-Doped ZnO Nanostructures. The Journal of Physical Chemistry C, 111(28), 10194-10200. doi:10.1021/jp071379fMartínez-Criado, G., Villanova, J., Tucoulou, R., Salomon, D., Suuronen, J.-P., Labouré, S., … Morse, J. (2016). ID16B: a hard X-ray nanoprobe beamline at the ESRF for nano-analysis. Journal of Synchrotron Radiation, 23(1), 344-352. doi:10.1107/s1600577515019839Jamieson, P. B., Abrahams, S. C., & Bernstein, J. L. (1968). Ferroelectric Tungsten Bronze‐Type Crystal Structures. I. Barium Strontium Niobate Ba0.27Sr0.75Nb2O5.78. The Journal of Chemical Physics, 48(11), 5048-5057. doi:10.1063/1.1668176Haro-González, P., Martín, I. R., & Hernández Creus, A. (2011). Nanocrystals formation on Ho3+ doped strontium barium niobate glass. Journal of Luminescence, 131(4), 657-661. doi:10.1016/j.jlumin.2010.11.011Lavı́n, V., Rodrı́guez-Mendoza, U. R., Martı́n, I. R., & Rodrı́guez, V. D. (2003). Optical spectroscopy analysis of the Eu3+ ions local structure in calcium diborate glasses. Journal of Non-Crystalline Solids, 319(1-2), 200-216. doi:10.1016/s0022-3093(02)01914-2Chernaya, T. S., Volk, T. R., Verin, I. A., Ivleva, L. I., & Simonov, V. I. (2002). Atomic structure of (Sr0.50Ba0.50)Nb2O6 single crystals in the series of (SrxBa1 − x )Nb2O6 compounds. Crystallography Reports, 47(2), 213-216. doi:10.1134/1.1466494Erbil, A., Cargill III, G. S., Frahm, R., & Boehme, R. F. (1988). Total-electron-yield current measurements for near-surface extended x-ray-absorption fine structure. Physical Review B, 37(5), 2450-2464. doi:10.1103/physrevb.37.2450Solé, V. A., Papillon, E., Cotte, M., Walter, P., & Susini, J. (2007). A multiplatform code for the analysis of energy-dispersive X-ray fluorescence spectra. Spectrochimica Acta Part B: Atomic Spectroscopy, 62(1), 63-68. doi:10.1016/j.sab.2006.12.002Martínez-Criado, G., Homs, A., Alén, B., Sans, J. A., Segura-Ruiz, J., Molina-Sánchez, A., … Yi, G.-C. (2012). Probing Quantum Confinement within Single Core–Multishell Nanowires. Nano Letters, 12(11), 5829-5834. doi:10.1021/nl303178uMartínez-Criado, G., Segura-Ruiz, J., Alén, B., Eymery, J., Rogalev, A., Tucoulou, R., & Homs, A. (2014). Exploring Single Semiconductor Nanowires with a Multimodal Hard X-ray Nanoprobe. Advanced Materials, 26(46), 7873-7879. doi:10.1002/adma.201304345Shyu, J.-J., & Wang, J.-R. (2000). Crystallization and Dielectric Properties of SrO-BaO-Nb2O5-SiO2Tungsten-Bronze Glass-Ceramics. Journal of the American Ceramic Society, 83(12), 3135-3140. doi:10.1111/j.1151-2916.2000.tb01694.

Optical nanothermometer based on the calibration of the Stokes and upconverted green emissions of Er3+ ions in Y3Ga5O12 nano-garnets

The temperature-dependent green luminescence of Y3Ga5O12 nano-garnets doped with different concentrations of Er3+ ions has been measured from 300 to 850 K and, in more detail, in the biological range from 292 to 335 K. The green emissions were obtained by excitation under 488 nm blue or 800 nm near-infrared laser radiations. Both excitations give rise to bright green luminescence that can be seen by the naked eye, and which can be associated either with Stokes processes, i.e. multiphonon relaxations followed by green spontaneous emission, in the former case or with infrared-to-visible upconversion processes in the latter. The temperature-induced changes in the Er3+ green emissions have been calibrated for both excitations and results point to a strong dependence on the concentration of optically active Er3+ ions. The maximum value of the thermal sensitivity, 64 × 10−4 K−1 at 547 K, has been obtained for the nano-garnets doped with the lowest concentration of Er3+ ions, which is one of the highest values found in the literature. These results allow to conclude that a relatively low concentration of optically active ions is advisable and the changes induced by temperature on the green emissions are independent of the laser excitation radiation used, which is necessary to calibrate the temperature of the immediate environment of the Er3+-doped Y3Ga5O12 nano-garnets.This work have been partially supported by Ministerio de Economía y Competitividad de España (MINECO) under The National Program of Materials (MAT2010-21270-C04-02/-03, and MAT2013-46649-C4-3-P/-4-P), The Consolider-Ingenio 2010 Program (MALTA CSD2007-00045), and the Indo- Spanish Joint Programme of Cooperation in Science and Technology (PRI-PIBIN-2011-1153/DST-INT-Spain-P-38-11), and by the EU-FEDER funds. V. Venkatramu is also grateful to Council of Scientific and Industrial Research (CSIR), New Delhi for the sanction of major research project (No. 03(1229)/12/EMR-II, dated: 16th April, 2012). V. Monteseguro wishes to thank MICINN for the FPI grant (BES-2011- 044596)

Structural, Vibrational, and Elastic Properties of Yttrium Orthoaluminate Nanoperovskite at High Pressures

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/page/policy/articlesonrequest/index.html."[EN] The structural and vibrational properties of nanocrystalline yttrium orthoaluminate perovskite (YAlO3) under compression have been experimentally studied. Experimental results have been compared to ab initio simulations of. bulk YAlO3, in the framework of the density functional theory. Furthermore, they have been complemented with an ab initio study of its elastic properties at different pressures. Calculated total and partial phonon density of states have allowed us to understand the contribution of the different atoms and structural units, YO12 dodecahedra and AlO6 octahedra, to the vibrational modes. The calculated infrared-active modes and their pressure dependence are also reported. Finally, the pressure dependences of the, elastic constants and the mechanical stability of the perovskite structure have been analyzed in detail, showing that this phase is mechanically stable until 92 GPa. In fact, experimental results up to 30 GPa show no evidence of any phase transition. A previously proposed possible phase transition in YAlO3 above 80 GPa is also discussed.This research was partially supported by MINECO (MAT2013-46649-C4-2/3/4-P, MAT2015-71070-REDC, and MAT2016-75586-C4-2/3/4-P) and by EU-FEDER funds. M.A.H.-R. thanks MINECO for an FPI grant (BES-2014-068666).Hernández-Rodríguez, M.; Monteseguro, V.; Lozano-Gorrín, A.; Manjón, F.; González-Platas, J.; Rodríguez-Hernández, P.; Muñoz, A.... (2017). Structural, Vibrational, and Elastic Properties of Yttrium Orthoaluminate Nanoperovskite at High Pressures. The Journal of Physical Chemistry C. 121(28):15353-15367. https://doi.org/10.1021/acs.jpcc.7b04245S15353153671212