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Title: Charge Density Wave in the New Polymorphs of RE 2 Ru 3 Ge 5 ( RE = Pr, Sm, Dy)

Abstract

A new polymorph of the RE 2Ru 3Ge 5 (RE = Pr, Sm, Dy) compounds has been grown as single crystals via an indium flux. These compounds crystallize in tetragonal space group P4/mnc with the Sc 2Fe 3Si 5-type structure, having lattice parameters a = 11.020(2) Å and c = 5.853(1) Å for RE = Pr, a = 10.982(2) Å and c = 5.777(1) Å for RE = Sm, and a = 10.927(2) Å and c = 5.697(1) Å for RE = Dy. These materials exhibit a structural transition at low temperature, which is attributed to an apparent charge density wave (CDW). Both the high-temperature average crystal structure and the low-temperature incommensurately modulated crystal structure (for Sm 2Ru 3Ge 5 as a representative) have been solved. The charge density wave order is manifested by periodic distortions of the onedimensional zigzag Ge chains. From X-ray diffraction, charge transport (electrical resistivity, Hall effect, magnetoresistance), magnetic measurements, and heat capacity, the ordering temperatures (T CDW) observed in the Pr and Sm analogues are ~200 and ~175 K, respectively. The charge transport measurement results indicate an electronic state transition happening simultaneously with the CDW transition. X-ray absorption near-edge spectroscopy (XANES) and electronic band structuremore » results are also reported.« less

Authors:
ORCiD logo; ORCiD logo; ; ; ; ; ; ; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Canadian Light Source, Inc.; Northwestern University - International Institute for Nanotechnology (IIN); National Institutes of Health (NIH) - National Institute of General Medical Sciences; USDOE Office of Science - National Energy Research Scientific Computing Center (NERSC)
OSTI Identifier:
1351311
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 139; Journal Issue: 11
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Bugaris, Daniel E., Malliakas, Christos D., Han, Fei, Calta, Nicholas P., Sturza, Mihai, Krogstad, Matthew J., Osborn, Raymond, Rosenkranz, Stephan, Ruff, Jacob P. C., Trimarchi, Giancarlo, Bud’ko, Sergey L., Balasubramanian, Mahalingam, Chung, Duck Young, and Kanatzidis, Mercouri G. Charge Density Wave in the New Polymorphs of RE 2 Ru 3 Ge 5 ( RE = Pr, Sm, Dy). United States: N. p., 2017. Web. doi:10.1021/jacs.7b00284.
Bugaris, Daniel E., Malliakas, Christos D., Han, Fei, Calta, Nicholas P., Sturza, Mihai, Krogstad, Matthew J., Osborn, Raymond, Rosenkranz, Stephan, Ruff, Jacob P. C., Trimarchi, Giancarlo, Bud’ko, Sergey L., Balasubramanian, Mahalingam, Chung, Duck Young, & Kanatzidis, Mercouri G. Charge Density Wave in the New Polymorphs of RE 2 Ru 3 Ge 5 ( RE = Pr, Sm, Dy). United States. doi:10.1021/jacs.7b00284.
Bugaris, Daniel E., Malliakas, Christos D., Han, Fei, Calta, Nicholas P., Sturza, Mihai, Krogstad, Matthew J., Osborn, Raymond, Rosenkranz, Stephan, Ruff, Jacob P. C., Trimarchi, Giancarlo, Bud’ko, Sergey L., Balasubramanian, Mahalingam, Chung, Duck Young, and Kanatzidis, Mercouri G. Thu . "Charge Density Wave in the New Polymorphs of RE 2 Ru 3 Ge 5 ( RE = Pr, Sm, Dy)". United States. doi:10.1021/jacs.7b00284.
@article{osti_1351311,
title = {Charge Density Wave in the New Polymorphs of RE 2 Ru 3 Ge 5 ( RE = Pr, Sm, Dy)},
author = {Bugaris, Daniel E. and Malliakas, Christos D. and Han, Fei and Calta, Nicholas P. and Sturza, Mihai and Krogstad, Matthew J. and Osborn, Raymond and Rosenkranz, Stephan and Ruff, Jacob P. C. and Trimarchi, Giancarlo and Bud’ko, Sergey L. and Balasubramanian, Mahalingam and Chung, Duck Young and Kanatzidis, Mercouri G.},
abstractNote = {A new polymorph of the RE2Ru3Ge5 (RE = Pr, Sm, Dy) compounds has been grown as single crystals via an indium flux. These compounds crystallize in tetragonal space group P4/mnc with the Sc2Fe3Si5-type structure, having lattice parameters a = 11.020(2) Å and c = 5.853(1) Å for RE = Pr, a = 10.982(2) Å and c = 5.777(1) Å for RE = Sm, and a = 10.927(2) Å and c = 5.697(1) Å for RE = Dy. These materials exhibit a structural transition at low temperature, which is attributed to an apparent charge density wave (CDW). Both the high-temperature average crystal structure and the low-temperature incommensurately modulated crystal structure (for Sm2Ru3Ge5 as a representative) have been solved. The charge density wave order is manifested by periodic distortions of the onedimensional zigzag Ge chains. From X-ray diffraction, charge transport (electrical resistivity, Hall effect, magnetoresistance), magnetic measurements, and heat capacity, the ordering temperatures (TCDW) observed in the Pr and Sm analogues are ~200 and ~175 K, respectively. The charge transport measurement results indicate an electronic state transition happening simultaneously with the CDW transition. X-ray absorption near-edge spectroscopy (XANES) and electronic band structure results are also reported.},
doi = {10.1021/jacs.7b00284},
journal = {Journal of the American Chemical Society},
number = 11,
volume = 139,
place = {United States},
year = {Thu Feb 16 00:00:00 EST 2017},
month = {Thu Feb 16 00:00:00 EST 2017}
}
  • The crystal structures of new rare earth-based germanate compounds (Ca{sub 3}Pr{sub 2}Ge{sub 3}O{sub 12}, Ca{sub 3}Nd{sub 2}Ge{sub 3}O{sub 12}, Ca{sub 3}Sm{sub 2}Ge{sub 3}O{sub 12}, Ca{sub 3}Gd{sub 2}Ge{sub 3}O{sub 12} and Ca{sub 3}Dy{sub 2}Ge{sub 3}O{sub 12}) have been determined by Rietveld refinement calculations on the collected synchrotron X-ray diffraction powder patterns. A different distribution of the rare earth ions in the three available crystal sites was observed, as the main structural feature. The reasons of the instability of the silico-carnotite structure for lanthanide ions out of the range Pr–Dy have been proposed. Finally, the luminescence spectroscopy of the Eu{sup 3+} dopantmore » ion in Ca{sub 3}Gd{sub 2}Ge{sub 3}O{sub 12} was presented and analyzed taking into account the observed structural characteristics. The Eu{sup 3+} luminescence spectroscopy was also compared with the one of Eu{sup 3+} doped Ca{sub 3}Gd{sub 2}Si{sub 3}O{sub 12} and Ca{sub 3}Lu{sub 2}Si{sub 3}O{sub 12} isostructural materials. - Graphical abstract: The structural study on Ca{sub 3}Ln{sub 2}Ge{sub 3}O{sub 12} exploiting synchrotron X-ray diffraction, allows us to determine the detailed geometry of the coordination polyhedra of the metals and their distribution in the crystal sites. These features are, in the case of Ca{sub 3}Gd{sub 2}Ge{sub 3}O{sub 12} host, closely related to the luminescence spectroscopy of the Eu{sup 3+} dopant ion. Display Omitted - Highlights: • The structure of the Ca{sub 3}Ln{sub 2}Ge{sub 3}O{sub 12} (Ln=Pr, Nd, Sm, Gd and Dy) was determined. • Different distribution of Ln{sup 3+} ions on the three available crystal sites was observed. • A detailed structural study focused on the metal coordination polyhedra was performed. • The instability of the silico-carnotite structure out of the range Pr–Dy was discussed. • The luminescence of the dopant Eu{sup 3+} ion in Ca{sub 3}Gd{sub 2}Ge{sub 3}O{sub 12} was presented and analyzed.« less
  • Previously synthesized only as powders, single crystals of the RE 2Ru 3Ge 5 (RE = La, Ce, Nd, Gd, Tb) series of compounds have been now been obtained from molten In. We report that these materials crystallize with the U 2Co 3Si 5-type structure in orthorhombic space group Ibam with lattice parameters a ~ 10.00-9.77 Å (La-Tb), b ~ 12.51-12.35 Å, and c ~ 5.92-5.72 Å. The structure is a three-dimensional framework consisting of RuGe 5 and RuGe 6 units, as well as Ge-Ge zigzag chains. This structure type, along with the other five (Sc 2Fe 3Si 5, Lu 2Comore » 3Si 5, Y 2Rh 3Sn 5, Yb 2Ir 3Ge 5, and Yb 2Pt 3Sn 5) to compose the RE 2T 3X 5 phase space, are discussed in depth. For the three compounds with RE = Nd, Gd, and Tb, multiple magnetic transitions and metamagnetic behavior are observed. Lastly, electronic band structure calculations performed on La 2Ru 3Ge 5 indicate that these materials have a negative band gap and are semimetallic in nature.« less
  • The ..mu..-methylene cluster Ru/sub 3/(CO)/sub 7/(..mu..-CH)/..mu../sub 3/-eta/sup 3/-CH/sub 2/=C=C(i-Pr))/(..mu..-PPh/sub 2/) (2) synthesized from Ru/sub 3/-(CO)/sub 8//..mu..=eta/sup 3/-CH/sub 2/=C=C(i-Pr)/(..mu..-PPh/sub 2/) (1) via reaction with diazomethane, CH/sub 2/N/sub 2/, displays a remarkable reactivity associated with the ..mu..-CH/sub 2/ group under mild conditions. Slow isomerization of 2 to the 2-isopropyl-1,3-butadienediyl cluster (..mu..-H)Ru/sub 3/(CO)/sub 7//..mu../sub 3/-eta/sup 4/-CH=C(i-Pr)C=CH/sub 2//(..mu..-PPh/sub 2/) (3) (crystal data: triclinic, space group P anti 1, a = 9.333 (2) A, b = 10.200 (1) A, c = 16.297 (2) A, ..cap alpha.. = 87.25 (1)/sup 0/, ..beta.. = 83.26 (1)/sup 0/, ..gamma.. = 64.29 (1)/sup 0/, Z = 2, R =more » 0.25, R/sub w/ = 0.029 on 5899 observed reflections) occurs under nitrogen. Cluster 3 contains a triangular Ru/sub 3/ core with ..mu..-PPh/sub 2/ and ..mu..-H groups on one edge and a four-carbon hydrocarbyl ligand derived from a CH fragment of the ..mu..-methylene bride and the allenyl ligand of 2. Under an atmosphere of CO and in the presence of methanol complex 2 yields the open allenyl cluster Ru/sub 3/(CO)/sub 9//..mu../sub 3/-eta/sup 3/-CH/sub 2/=C=C(i-Pr)/(..mu..-PPh/sub 2/) (5) and methyl acetate, both of which were characterized spectroscopically.« less
  • Ba{sub 1-x}RE{sub 2x/3}Nb{sub 2}O{sub 6} nanocrystals with a tetragonal tungsten bronze (TTB) structure are synthesized using a conventional glass crystallization technique in 2.3RE{sub 2}O{sub 3}-27.4BaO-34.3Nb{sub 2}O{sub 5}-36B{sub 2}O{sub 3} (mol%) (RE=Sm, Eu, Gd, Dy, and Er) glasses. One sharp crystallization peak is observed at {approx}670 Degree-Sign C in both powdered and bulk glasses, and the formation of Ba{sub 1-x}RE{sub 2x/3}Nb{sub 2}O{sub 6} nanocrystals with unit cell parameters of a{approx}1.24 nm and c{approx}0.39 nm was confirmed. It is found from high resolution transmission electron microscope observations that the morphology of Ba{sub 1-x}RE{sub 2x/3}Nb{sub 2}O{sub 6} nanocrystals is ellipsoidal. Their average particlemore » size is in the range of 15-60 nm and decreases with decreasing ionic radius of RE{sup 3+} being present in the precursor glasses. The optical transparent crystallized glass (bulk) shows the total photoluminescence (PL) quantum yield of 53% in the visible region of Eu{sup 3+} ions, suggesting a high potential of Ba{sub 1-x}RE{sub 2x/3}Nb{sub 2}O{sub 6} nanocrystals as PL materials. - Graphical abstract: This figure shows a TEM photograph for the heat-treated (667 Degree-Sign C, 3 h) sample of 2.3Dy{sub 2}O{sub 3}-27.4BaO-34.3Nb{sub 2}O{sub 5}-36B{sub 2}O{sub 3}. An ellipsoidal-shaped Ba{sub 1-x}Dy{sub 2x/3}Nb{sub 2}O{sub 6} nanocrystal with diameters of 17 and 28 nm is observed. The ellipsoidal morphology is a common feature in Ba{sub 1-x}RE{sub 2x/3}Nb{sub 2}O{sub 6} nanocrystals synthesized by the crystallization of 2.3RE{sub 2}O{sub 3}-27.4BaO-34.3Nb{sub 2}O{sub 5}-36B{sub 2}O{sub 3} glasses. Highlights: Black-Right-Pointing-Pointer Ba{sub 1-x}RE{sub 2x/3}Nb{sub 2}O{sub 6} nanocrystals with a tetragonal tungsten bronze structure are synthesized. Black-Right-Pointing-Pointer A glass crystallization technique was applied. Black-Right-Pointing-Pointer The morphology of Ba{sub 1-x}RE{sub 2x/3}Nb{sub 2}O{sub 6} nanocrystals is ellipsoidal. Black-Right-Pointing-Pointer The average particle size with 15-60 nm decreases with decreasing ionic radius of RE{sup 3+}. Black-Right-Pointing-Pointer Ba{sub 1-x}RE{sub 2x/3}Nb{sub 2}O{sub 6} nanocrystals have a high potential as photoluminescence materials.« less