High-pressure Raman investigation of high index facets bounded alpha-Fe2O3 pseudocubic crystals

[EN] High index facet bounded alpha-Fe2O3 pseudocubic crystals has gained the attention of the scientific community due to its promising electrochemical sensing response towards aqueous ammonia. The structural stability of alpha-Fe2O3 pseudocubic crystals is investigated through high-pressure Raman spectroscopy up to 22.2 GPa, and those results are compared with our ab initio theoretical calculations. The symmetry of the experimental Raman-active modes has been assigned by comparison with theoretical data. In addition to the Raman-active modes, two additional Raman features are also detected, whose intensity increases with compression. The origin of these two additional peaks addressed in this study, reveals a strong dependence on the geometry and the low dimensionality as the most plausible explanationNeravathu G Divya acknowledges DST FIST for FESEM analysis, Department of Physics, Cochin University of Science and Technology, Kerala, India. The author also acknowledges the Sophisticated Test and Instrumentation Centre (STIC), Kochi, India, for Rietveld Refinement measurements. This work is partly supported by Spanish MINECO under the projects MAT2016-75586-C4-2/3-P, FIS2017-83295-P, and MALTA Consolider Team project (RED2018-102612-T), and also by Generalitat Valenciana under project PROMETEO/2018/123-EFIMAT. JAS acknowledges the Ramon y Cajal program for funding supports through RYC-2015-17482 and VM to the Juan de la Cierva program through FJCI-2016-27921.Bushiri, MJ.; Gopi, DN.; Monteseguro, V.; Sans-Tresserras, JÁ. (2021). High-pressure Raman investigation of high index facets bounded alpha-Fe2O3 pseudocubic crystals. Journal of Physics Condensed Matter. 33(8):1-10. https://doi.org/10.1088/1361-648X/abcb11S11033

Comment on "mechanisms for Pressure-Induced Isostructural Phase Transitions in EuO"

Authors thank the financial support from Projects PGC2018-101464-B-I00, PGC2018-097520-A-I00, and MALTA-Consolider Team RED2018-102612-T (Ministerio de Ciencia, Innovaci´on y Universidades) is acknowledged. V. Monteseguro acknowledges the “Beatriz Galindo” fellowship (BG20/000777) and the “Juan de la Cierva” fellowship (IJC2019-041586-I)

Crystal-field mediated electronic transitions of EuS up to 35 GPa

An advanced experimental and theoretical model to explain the correlation between the electronic and local structure of Eu2+ in two diferent environments within a same compound, EuS, is presented. EuX monochalcogenides (X: O, S, Se, Te) exhibit anomalies in all their properties around 14 GPa with a semiconductor to metal transition. Although it is known that these changes are related to the 4f 75d0 ?4f 65d1 electronic transition, no consistent model of the pressure-induced modifcations of the electronic structure currently exists. We show, by optical and x-ray absorption spectroscopy, and by ab initio calculations up to 35 GPa, that the pressure evolution of the crystal feld plays a major role in triggering the observed electronic transitions from semiconductor to the half-metal and fnally to the metallic state.Authors thank the financial support from Projects PGC2018-101464-B-I00, PGC2018-097520-A-I00 and MALTA-Consolider Team RED2018-102612-T (Ministerio de Ciencia, Innovación y Universidades) is acknowledged. V. Monteseguro acknowledges the “Beatriz Galindo” fellowship (BG20/000777) and the “Juan de la Cierva” fellowship (IJC2019-041586-I). Authors are grateful to the staff of the BM23 beamline and the high-pressure laboratory at the ESRF for their support during the experiment (proposal number HC-3913), and the SERCAMAT (SCTI) of the University of Cantabria for FTIR facilities

Crystal structure solution of a high-pressure polymorph of scintillating MgMoO4 and its electronic structure

The structure of the potentially scintillating high-pressure phase of [Beta] - MgMoO 4 ( γ - MgMoO 4 ) has been solved by means of high-pressure single-crystal x-ray diffraction. The phase transition occurs above 1.5 GPa and involves an increase of the Mo coordination from fourfold to sixfold accommodated by a rotation of the polyhedra and a concommitant bond stretching resulting in an enlargement of the c axis. A previous high-pressure Raman study had proposed such changes with a symmetry change to space group P 2 / c . Here it has been found that the phase transition is isosymmetrical ( C 2 / m -> C 2 / m ). The bulk moduli and the compressibilities of the crystal axes of both the low- and the high-pressure phase, have been obtained from equation of state fits to the pressure evolution of the unit-cell parameters which were obtained from powder x-ray diffraction up to 12 GPa. The compaction of the crystal structure at the phase transition involves a doubling of the bulk modulus B 0 changing from 60.3(1) to 123.7(8) GPa and a change of the most compressible crystal axis from the (0, b , 0) direction in [Beta] - MgMoO 4 to the ( 0.9 a , 0, 0.5 a ) direction in γ - MgMoO 4 . The lattice dynamical calculations performed here on γ - MgMoO 4 served to explain the Raman spectra observed for the high-pressure phase of [Beta] - MgMoO 4 in a previous work demonstrating that the use of internal modes arguments in which the MoO n polyhedra are considered as separate vibrational units fails at least in this molybdate. The electronic structure of γ - MgMoO 4 was also calculated and compared with the electronic structures of [Beta] - MgMoO 4 and MgWO 4 shedding some light on why MgWO 4 is a much better scintillator than any of the phases of MgMoO 4 . These calculations yielded for γ - MgMoO 4 a Y 2 Γ -> Γ indirect band gap of 3.01 eV in contrast to the direct bandgaps of [Beta] - MgMoO 4 (3.58 eV at Γ ) and MgWO 4 (3.32 eV at Z ).The authors thank I. Collings and M. Handfland from the ID15B beamline at the ESRF for their help during the experiments, and O. Gomis from the Universitat Politècnica de València for the discussions. Most of the work presented in this work benefited from the financial support from the Spanish Ministerio de Ciencia e Innovación (MICINN) under Projects No. PID2019- 106383GB-C41/43 (MCIN/AEI/10.13039/501100011033), MALTA Consolider-Team network RED2018-102612- T (MINECO/AEI/10.13039/501100003329), and from the Generalitat Valenciana under Project PROMETEO/2018/123. V.M. also thanks the MICINN for the Beatriz Galindo distinguished researcher program (BG20/00077)

Pressure-induced charge ordering transition in CaMn7O12

We use high-pressure resistivity and single crystal x-ray diffraction at ambient and low temperature to investigate the charge ordering phase transition of CaMn 7 O 12 . We have found that at ambient temperature the Jahn-Teller distortion of the Mn 3 + O 6 octahedra rapidly decreases above 20 GPa, and vanishes at 28 GPa, when two Mn octahedral sites initially occupied by Mn 3 + and Mn 4 + become regular and equivalent as the result of a charge delocalization. Such a change correlates with a two orders of magnitude drop in the resistivity and a symmetry increase from the low-pressure rhombohedral R ¯ 3 phase to the cubic Im ¯ 3 structure, the same as one found at ambient pressure above 440 K. This yields the slope of the charge ordering phase boundary of d T c / d p ? ? 6 K/GPa. This result is further supported by the lack of a structural phase transition up to the maximum measured pressure of 30 GPa when the experiment is performed at 70 K. The satellite reflections of the structural modulation of the multiferroic phase of CaMn 7 O 12 observed at 70 K were found to hold up to 25 GPa with the structure keeping a constant modulation vector k = ( 0 0 0.925 ) with pressure. The average structure at 70 K does not show other indications of further phase transition.Y. Li and X. Du from Peking University are greatly acknowledged for growing and providing the CaMn7O12 crystals. D. Spahr and J. König from Goethe University are acknowledged for help with the single-crystal diffraction experiments. M.S. would like to acknowledge the financial support under the DFG-ANR Grant No. WI1232/41-1 and DFG GACR Project No. WI3320/3-1. V.M. and J.R.-F. thank the financial support from the Spanish Ministerio de Ciencia e Innovación (MICINN) for the Beatriz Galindo Program (BG20/000777) and for the Project No. PGC2018-097520- A-I00, respectively. DESY Photon Science is gratefully acknowledged. PETRA III at DESY is a member of the Helmholtz Association (HGF)

Synthesis, structure and luminescence of Er3+-doped Y3Ga5O12 nano-garnets

A novel Y3(1-x)Er3xGa5O12 nanocrystalline garnet has been synthesized by a sol-gel technique and a complete structural, morphological, vibrational, and optical characterization has been carried out in order to correlate the local structure of the Er3+ ions with their optical properties. The synthesized nanocrystals are found in a single-phase garnet structure with an average grain size of around 60 nm. The good crystalline quality of the garnet structure is confirmed by FTIR and Raman measurements, since the phonon modes of the nano-garnet are similar to those found in the single crystal garnet. Under blue laser excitation, intense green and red visible and 1.5 mu m infrared luminescences are observed, whose relative intensities are very sensitive to the Er3+ concentration. The dynamics of these emissions under pulsed laser excitations are analyzed in the framework of different energy transfer interactions. Intense visible upconverted luminescence can be clearly observed by the naked eye for all synthesized Er3+-doped Y3Ga5O12 nano-garnets under a cw 790 nm laser excitation. The power dependency and the dynamics of the upconverted luminescence confirm the existence of different two-photon upconversion processes for the green and red emissions that strongly depend on the Er3+ concentration, showing the potential of these nano-garnets as excellent candidates for developing new optical devices.This work has been partially supported by Ministerio de Ciencia e Innovacion of Spain (MICCIN) under The National Program of Materials (MAT2010-21270-C04-02; -03; -04), The Consolider-Ingenio 2010 Program (MALTA CSD2007-0045), and The National Infrastructure Program, by Ministerio de Economia y Competitividad of Spain (MINECO) within 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 (UCAN08-4E-008). S.F. Leon-Luis and V. Monteseguro wish to thank MICINN for the FPI grants (BES-2008-003353 and BES-2011-044596). Dr V. Venkatramu is grateful to DAE-BRNS, Government of India for the award of DAE Research Award for Young Scientists (no. 2010/20/34/5/BRNS/2223).Venkatramu, V.; León-Luis, SF.; Rodriguez-Mendoza, UR.; Monteseguro, V.; Manjón, FJ.; Lozano-Gorrín, AD.; Valiente, R.... (2012). Synthesis, structure and luminescence of Er3+-doped Y3Ga5O12 nano-garnets. Journal of Materials Chemistry. 22:13788-13799. doi:10.1039/c2jm31386cS13788137992

Física II (G417). Julio 2023

Grado en Ingeniería en Tecnologías Industriale

Física II (G417). Junio 2023

Grado en Ingeniería en Tecnologías Industriale

Pressure-induced amorphization of the Y3Ga5O12 garnet studied to 1 Mbar

We use micro-beam synchrotron x-ray diffraction to study the pressure-induced amorphization of nano-sized and single crystals of Y3Ga5O12 up to pressures exceeding 1 Mbar in static compression. The abrupt pressure-induced amorphization found for both 56 nm and bulk micrometric crystals at around 76 GPa independently of the pressure transmitting medium employed demonstrates its intrinsic nature, previously predicted at 79 GPa by ab initio calculations. The single crystal structural solution at 50 GPa shows that the contraction of the unit-cell, mostly accommodated by the compressible YO8 dodecahedra, gives rise to a regularization and tilting increase of the GaO6 polyhedra with the Y?O-Ga angle changing from 104.84° to 102.34° in 50 GPa. We obtain a bulk modulus of 178(3) GPa for the single crystal and 172(3) GPa for the nanocrystals in excellent agreement with previous calculations.V. M. and J.R–F. thank the Spanish Ministry of Science, Innovation and Universities for the Juan de la Cierva program (FJCI-2016-27921) and for project PGC-2018-097520-A-100, respectively

Structural Characterization of Aurophilic Gold(I) Iodide under High Pressure

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.9b00433.[EN] The effects of pressure on the crystal structure of aurophilic tetragonal gold iodide have been studied by means of powder X-ray diffraction up to 13.5 GPa. We found evidence of the onset of a phase transition at 1.5 GPa that is more significant from 3.8 GPa. The low- and high-pressure phases coexist up to 10.7 GPa. Beyond 10.7 GPa, an irreversible process of amorphization takes place. We determined the axial and bulk compressibility of the ambient-pressure tetragonal phase of gold iodide up to 3.3 GPa. This is extremely compressible with a bulk modulus of 18.1(8) GPa, being as soft as a rare gas, molecular solids, or organometallic compounds. Moreover, its response to pressure is anisotropic.The authors are thankful for the financial support of the Spanish Ministerio de Ciencia, Innovacion y Universidades, the Spanish Research Agency (AEI), and the European Fund for Regional Development (FEDER) under Grant MAT2016-75586-C4-1/2-P and of Generalitat Valenciana under Grant Prometeo/2018/123 (EFIMAT). J.A.S. acknowledges the "Ramon y Cajal" fellowship program (RYC-2015-17482) and Spanish Mineco Project FIS2017-83295-P. V.M. acknowledges the "Juan de la Cierva" program (FJCI-2016-27921) for financial support. Experiments were performed at the Materials Science and Powder Diffraction beamline of ALBA Synchrotron. The authors are thankful for the collaboration of ALBA staff and also thank D. Santamaria-Perez for fruitful discussions.Monteseguro, V.; Errandonea, D.; Achary, SN.; Sans-Tresserras, JÁ.; Manjón, F.; Gallego-Parra, S.; Popescu, C. (2019). Structural Characterization of Aurophilic Gold(I) Iodide under High Pressure. Inorganic Chemistry. 58(16):10665-10670. https://doi.org/10.1021/acs.inorgchem.9b004331066510670581