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Title: Hydrothermal Crystal Growth of Rare Earth Tin Cubic Pyrochlores, RE2Sn2O7 (RE = La–Lu): Site Ordered, Low Defect Single Crystals

Abstract

A hydrothermal route to single crystals of rare earth stannates RE2Sn2O7 (RE = La–Lu) in the cubic pyrochlore structure is reported. Growth reactions were performed in aqueous fluids at 700 °C and 200 MPa with CsF mineralizers in concentrations ranging from 0 to 30 M, with 20 M CsF providing the most consistent results. Single crystals of the entire range of lanthanides were grown and characterized by single crystal X-ray diffraction and found to be isostructural in the Fd$$\bar{3}$$m space group. The unit cell sizes range from 10.7106(16) Å for La2Sn2O7 to 10.3005(9) Å for Lu2Sn2O7. Both the unit cell size and RE–O distances are found to be essentially linear with respect to the ionic radius of the rare earth ion. The high quality diffraction data strongly indicates that there is very little site disorder or lattice defects in the sample. Of specific interest is the synthesis and single crystal growth of Ce2Sn2O7, which represents one of the few f1 pyrochlore samples. Specific heat measurements were obtained down to 50 mK on both Yb2Sn2O7 and Ce2Sn2O7, with the Yb material displaying a single sharp peak at 138 mK suggesting that the sample does not contain any site disorder or “lattice stuffing”. The Ce analog demonstrates only a broad featureless transition below 100 mK, with this lack of long-range magnetic order consistent with quantum spin liquid behavior

Authors:
 [1];  [1]; ORCiD logo [1];  [2];  [2];  [1]
  1. Clemson Univ., SC (United States)
  2. Colorado State Univ., Fort Collins, CO (United States)
Publication Date:
Research Org.:
Clemson Univ., SC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1596440
Grant/Contract Number:  
SC0014271
Resource Type:
Accepted Manuscript
Journal Name:
Crystal Growth and Design
Additional Journal Information:
Journal Volume: 19; Journal Issue: 9; Journal ID: ISSN 1528-7483
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Hydrothermal; Single Crystals; Spin Liquids; Pyrochlores; stannates

Citation Formats

Powell, Matthew, Sanjeewa, Liurukara D., McMillen, Colin D., Ross, Kate A., Sarkis, Colin L., and Kolis, Joseph W. Hydrothermal Crystal Growth of Rare Earth Tin Cubic Pyrochlores, RE2Sn2O7 (RE = La–Lu): Site Ordered, Low Defect Single Crystals. United States: N. p., 2019. Web. doi:10.1021/acs.cgd.8b01889.
Powell, Matthew, Sanjeewa, Liurukara D., McMillen, Colin D., Ross, Kate A., Sarkis, Colin L., & Kolis, Joseph W. Hydrothermal Crystal Growth of Rare Earth Tin Cubic Pyrochlores, RE2Sn2O7 (RE = La–Lu): Site Ordered, Low Defect Single Crystals. United States. https://doi.org/10.1021/acs.cgd.8b01889
Powell, Matthew, Sanjeewa, Liurukara D., McMillen, Colin D., Ross, Kate A., Sarkis, Colin L., and Kolis, Joseph W. Fri . "Hydrothermal Crystal Growth of Rare Earth Tin Cubic Pyrochlores, RE2Sn2O7 (RE = La–Lu): Site Ordered, Low Defect Single Crystals". United States. https://doi.org/10.1021/acs.cgd.8b01889. https://www.osti.gov/servlets/purl/1596440.
@article{osti_1596440,
title = {Hydrothermal Crystal Growth of Rare Earth Tin Cubic Pyrochlores, RE2Sn2O7 (RE = La–Lu): Site Ordered, Low Defect Single Crystals},
author = {Powell, Matthew and Sanjeewa, Liurukara D. and McMillen, Colin D. and Ross, Kate A. and Sarkis, Colin L. and Kolis, Joseph W.},
abstractNote = {A hydrothermal route to single crystals of rare earth stannates RE2Sn2O7 (RE = La–Lu) in the cubic pyrochlore structure is reported. Growth reactions were performed in aqueous fluids at 700 °C and 200 MPa with CsF mineralizers in concentrations ranging from 0 to 30 M, with 20 M CsF providing the most consistent results. Single crystals of the entire range of lanthanides were grown and characterized by single crystal X-ray diffraction and found to be isostructural in the Fd$\bar{3}$m space group. The unit cell sizes range from 10.7106(16) Å for La2Sn2O7 to 10.3005(9) Å for Lu2Sn2O7. Both the unit cell size and RE–O distances are found to be essentially linear with respect to the ionic radius of the rare earth ion. The high quality diffraction data strongly indicates that there is very little site disorder or lattice defects in the sample. Of specific interest is the synthesis and single crystal growth of Ce2Sn2O7, which represents one of the few f1 pyrochlore samples. Specific heat measurements were obtained down to 50 mK on both Yb2Sn2O7 and Ce2Sn2O7, with the Yb material displaying a single sharp peak at 138 mK suggesting that the sample does not contain any site disorder or “lattice stuffing”. The Ce analog demonstrates only a broad featureless transition below 100 mK, with this lack of long-range magnetic order consistent with quantum spin liquid behavior},
doi = {10.1021/acs.cgd.8b01889},
journal = {Crystal Growth and Design},
number = 9,
volume = 19,
place = {United States},
year = {2019},
month = {7}
}

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Cited by: 5 works
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Figures / Tables:

Figure 1 Figure 1: View of several of the crystals prepared hydrothermally. Left to right: Ce2Sn2O7, Er2Sn2O7, Pr2Sn2O7 and Tm2Sn2O7 respectively.

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Works referencing / citing this record:

Alkali Transition‐Metal Molybdates: A Stepwise Approach to Geometrically Frustrated Systems
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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.