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

Powell, Matthew; Sanjeewa, Liurukara D.; McMillen, Colin D.; Ross, Kate A.; Sarkis, Colin L.; Kolis, Joseph W.

doi:10.1021/acs.cgd.8b01889

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:

Powell, Matthew ^[1]; Sanjeewa, Liurukara D. ^[1];

^[1]; Ross, Kate A. ^[2]; Sarkis, Colin L. ^[2]; Kolis, Joseph W. ^[1]

Clemson Univ., SC (United States)
Colorado State Univ., Fort Collins, CO (United States)

Publication Date:: Fri Jul 26 00:00:00 EDT 2019

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.

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                    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

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                    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.

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@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         = {Fri Jul 26 00:00:00 EDT 2019},

  month        = {Fri Jul 26 00:00:00 EDT 2019}

}

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Journal Article:

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https://doi.org/10.1021/acs.cgd.8b01889

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Cited by: 17 works

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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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Chemistry – A European Journal, Vol. 26, Issue 3
DOI: 10.1002/chem.201904193

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This dataset is a supplement to the current record

CSD 1885539: Experimental Crystal Structure Determination
dataset, January 2019

Matthew, Powell,; D., Sanjeewa, Liurukara; D., McMillen, Colin
FIZ Karlsruhe - Leibniz Institute for Information Infrastructure
DOI: 10.25505/fiz.icsd.cc2191v8
This dataset is a supplement to the current record

CSD 1885540: Experimental Crystal Structure Determination
dataset, January 2019

Matthew, Powell,; D., Sanjeewa, Liurukara; D., McMillen, Colin
FIZ Karlsruhe - Leibniz Institute for Information Infrastructure
DOI: 10.25505/fiz.icsd.cc2191w9
This dataset is a supplement to the current record

CSD 1885531: Experimental Crystal Structure Determination
dataset, January 2019

Matthew, Powell,; D., Sanjeewa, Liurukara; D., McMillen, Colin
FIZ Karlsruhe - Leibniz Institute for Information Infrastructure
DOI: 10.25505/fiz.icsd.cc2191l0
This dataset is a supplement to the current record

CSD 1885532: Experimental Crystal Structure Determination
dataset, January 2019

Matthew, Powell,; D., Sanjeewa, Liurukara; D., McMillen, Colin
FIZ Karlsruhe - Leibniz Institute for Information Infrastructure
DOI: 10.25505/fiz.icsd.cc2191m1
This dataset is a supplement to the current record

CSD 1885533: Experimental Crystal Structure Determination
dataset, January 2019

Matthew, Powell,; D., Sanjeewa, Liurukara; D., McMillen, Colin
FIZ Karlsruhe - Leibniz Institute for Information Infrastructure
DOI: 10.25505/fiz.icsd.cc2191n2
This dataset is a supplement to the current record

CSD 1885528: Experimental Crystal Structure Determination
dataset, January 2019

Matthew, Powell,; D., Sanjeewa, Liurukara; D., McMillen, Colin
FIZ Karlsruhe - Leibniz Institute for Information Infrastructure
DOI: 10.25505/fiz.icsd.cc2191hx
This dataset is a supplement to the current record

CSD 1885541: Experimental Crystal Structure Determination
dataset, January 2019

Matthew, Powell,; D., Sanjeewa, Liurukara; D., McMillen, Colin
FIZ Karlsruhe - Leibniz Institute for Information Infrastructure
DOI: 10.25505/fiz.icsd.cc2191xb
This dataset is a supplement to the current record

CSD 1885529: Experimental Crystal Structure Determination
dataset, January 2019

Matthew, Powell,; D., Sanjeewa, Liurukara; D., McMillen, Colin
FIZ Karlsruhe - Leibniz Institute for Information Infrastructure
DOI: 10.25505/fiz.icsd.cc2191jy
This dataset is a supplement to the current record

CSD 1885530: Experimental Crystal Structure Determination
dataset, January 2019

Matthew, Powell,; D., Sanjeewa, Liurukara; D., McMillen, Colin
FIZ Karlsruhe - Leibniz Institute for Information Infrastructure
DOI: 10.25505/fiz.icsd.cc2191kz
This dataset is a supplement to the current record

Similar Records
Related Works
dataset (14)

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

Abstract

Citation Formats

Figures / Tables:

Oxide pyrochlores — A review journal, January 1983

Magnetic pyrochlore oxides journal, January 2010

Frustrated rare earth magnetism: Spin glasses, spin liquids and spin ices in pyrochlore oxides journal, February 2006

Geometrically frustrated magnetic materials journal, January 2001

Frustration in Ising-type spin models on the pyrochlore lattice journal, April 1998

Spin Correlations in Ho 2 Ti 2 O 7 : A Dipolar Spin Ice System journal, July 2001

The Structure and Entropy of Ice and of Other Crystals with Some Randomness of Atomic Arrangement journal, December 1935

Zero-point entropy in ‘spin ice’ journal, May 1999

Spin liquids in frustrated magnets journal, March 2010

Quantum spin liquids: a review journal, November 2016

Quantum Excitations in Quantum Spin Ice journal, October 2011

Experimental Insights into Ground-State Selection of Quantum XY Pyrochlores journal, March 2018

Tolerance factor for pyrochlores and related structures journal, September 2013

The tolerance factors of the pyrochlore crystal structure journal, January 2011

Structural and crystal chemical properties of rare-earth titanate pyrochlores journal, August 2014

Effective ionic radii in oxides and fluorides journal, May 1969

Zur Kristallstruktur von Nd2Ti2O7 journal, November 1975

Anisotropic paramagnetism of monoclinic Nd 2 Ti 2 O 7 single crystals journal, May 2011

Phases and structural relations of the rare earth germanates RE2Ge2O7, RE ≡ La-Lu journal, February 1987

Frustration under pressure: Exotic magnetism in new pyrochlore oxides journal, April 2015

High pressure route to generate magnetic monopole dimers in spin ice journal, September 2011

Chemical pressure effects on magnetism in the quantum spin liquid candidates Yb 2 X 2 O 7 ( X = Sn , Ti, Ge) journal, February 2014

Universal dynamic magnetism in Yb pyrochlores with disparate ground states journal, March 2016

Single Crystals of Cubic Rare-Earth Pyrochlore Germanates: RE 2 Ge 2 O 7 (RE = Yb and Lu) Grown by a High-Temperature Hydrothermal Technique journal, September 2018

Zirconate Pyrochlore Frustrated Magnets: Crystal Growth by the Floating Zone Technique journal, July 2016

Synthesis, floating zone crystal growth and characterization of the quantum spin ice Pr2Zr2O7 pyrochlore journal, September 2014

Predicted structure and stability of A 4 B 3 O 12 δ -phase compositions journal, November 2009

Low-Temperature Magnetic Properties of Pyrochlore Stannates journal, June 2002

Dynamic Spin Ice: Pr 2 Sn 2 O 7 journal, November 2008

Crystal growth of pyrochlore rare-earth stannates journal, June 2017

Growth, characterization, and properties of bulk SnO 2 single crystals : Growth, characterization, and properties of bulk SnO journal, October 2013

Crystal growth of spin-ice pyrochlores by the floating-zone method journal, March 2011

Growth and Faraday rotation characteristics of Tb2Sn2O7 crystal journal, July 2014

Pyrochlores. III. X-Ray, neutron, infrared, and dielectric studies of A 2 Sn 2 O 7 stannates journal, March 1968

The structural parameters, structural stability and bulk modulus in RE 2 Sn 2 O 7 by first-principles calculations journal, October 2017

Structural and Bonding Trends in Tin Pyrochlore Oxides journal, April 1997

Bulk single crystal growth from hydrothermal solutions journal, July 2012

Crystal growth and phase stability of Ln:Lu2O3 (Ln=Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb) in a higher-temperature hydrothermal regime journal, October 2016

Hydrothermal crystal growth of yttrium and rare earth stabilized hafnia journal, January 2010

Crystal Chemistry of Alkali Thorium Silicates Under Hydrothermal Conditions journal, May 2015

The optical floating zone technique: A review of experimental procedures with special reference to oxides journal, September 2008

Lightly stuffed pyrochlore structure of single-crystalline Yb 2 Ti 2 O 7 grown by the optical floating zone technique journal, November 2012

Defect formation energies in A 2 B 2 O 7 pyrochlores journal, October 2015

Impact of stoichiometry of Yb 2 Ti 2 O 7 on its physical properties journal, March 2017

Candidate Quantum Spin Liquid in the Ce 3 + Pyrochlore Stannate Ce 2 Sn 2 O 7 journal, August 2015

Symmetry enriched U(1) topological orders for dipole-octupole doublets on a pyrochlore lattice journal, January 2017

Crystal structure refinement with SHELXL journal, January 2015

Reentrant Phase Diagram of Yb 2 Ti 2 O 7 in a ⟨ 111 ⟩ Magnetic Field journal, September 2017

Stuffed rare earth pyrochlore solid solutions journal, October 2006

Glassy dynamics in the low-temperature inhomogeneous ferromagnetic phase of the quantum spin ice Yb 2 Sn 2 O 7 journal, January 2014

Alkali Transition‐Metal Molybdates: A Stepwise Approach to Geometrically Frustrated Systems journal, November 2019

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

Oxide pyrochlores — A review
journal, January 1983

Magnetic pyrochlore oxides
journal, January 2010

Frustrated rare earth magnetism: Spin glasses, spin liquids and spin ices in pyrochlore oxides
journal, February 2006

Geometrically frustrated magnetic materials
journal, January 2001

Frustration in Ising-type spin models on the pyrochlore lattice
journal, April 1998

Spin Correlations in ${Ho}_{2} {Ti}_{2} O_{7}$ : A Dipolar Spin Ice System
journal, July 2001

The Structure and Entropy of Ice and of Other Crystals with Some Randomness of Atomic Arrangement
journal, December 1935

Zero-point entropy in ‘spin ice’
journal, May 1999

Spin liquids in frustrated magnets
journal, March 2010

Quantum spin liquids: a review
journal, November 2016

Quantum Excitations in Quantum Spin Ice
journal, October 2011

Experimental Insights into Ground-State Selection of Quantum XY Pyrochlores
journal, March 2018

Tolerance factor for pyrochlores and related structures
journal, September 2013

The tolerance factors of the pyrochlore crystal structure
journal, January 2011

Structural and crystal chemical properties of rare-earth titanate pyrochlores
journal, August 2014

Effective ionic radii in oxides and fluorides
journal, May 1969

Zur Kristallstruktur von Nd2Ti2O7
journal, November 1975

Anisotropic paramagnetism of monoclinic Nd ₂ Ti ₂ O ₇ single crystals
journal, May 2011

Phases and structural relations of the rare earth germanates RE2Ge2O7, RE ≡ La-Lu
journal, February 1987

Frustration under pressure: Exotic magnetism in new pyrochlore oxides
journal, April 2015

High pressure route to generate magnetic monopole dimers in spin ice
journal, September 2011

Chemical pressure effects on magnetism in the quantum spin liquid candidates Yb $_{2} X_{2}$ O $_{7}$ ( $X = Sn$ , Ti, Ge)
journal, February 2014

Universal dynamic magnetism in Yb pyrochlores with disparate ground states
journal, March 2016

Single Crystals of Cubic Rare-Earth Pyrochlore Germanates: RE ₂ Ge ₂ O ₇ (RE = Yb and Lu) Grown by a High-Temperature Hydrothermal Technique
journal, September 2018

Zirconate Pyrochlore Frustrated Magnets: Crystal Growth by the Floating Zone Technique
journal, July 2016

Synthesis, floating zone crystal growth and characterization of the quantum spin ice Pr2Zr2O7 pyrochlore
journal, September 2014

Predicted structure and stability of $A_{4} B_{3} O_{12}$ $δ$ -phase compositions
journal, November 2009

Low-Temperature Magnetic Properties of Pyrochlore Stannates
journal, June 2002

Dynamic Spin Ice: $\Pr_{2} {Sn}_{2} O_{7}$
journal, November 2008

Crystal growth of pyrochlore rare-earth stannates
journal, June 2017

Growth, characterization, and properties of bulk SnO ₂ single crystals : Growth, characterization, and properties of bulk SnO
journal, October 2013

Crystal growth of spin-ice pyrochlores by the floating-zone method
journal, March 2011

Growth and Faraday rotation characteristics of Tb2Sn2O7 crystal
journal, July 2014

Pyrochlores. III. X-Ray, neutron, infrared, and dielectric studies of A ₂ Sn ₂ O ₇ stannates
journal, March 1968

The structural parameters, structural stability and bulk modulus in RE ₂ Sn ₂ O ₇ by first-principles calculations
journal, October 2017

Structural and Bonding Trends in Tin Pyrochlore Oxides
journal, April 1997

Bulk single crystal growth from hydrothermal solutions
journal, July 2012

Crystal growth and phase stability of Ln:Lu2O3 (Ln=Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb) in a higher-temperature hydrothermal regime
journal, October 2016

Hydrothermal crystal growth of yttrium and rare earth stabilized hafnia
journal, January 2010

Crystal Chemistry of Alkali Thorium Silicates Under Hydrothermal Conditions
journal, May 2015

The optical floating zone technique: A review of experimental procedures with special reference to oxides
journal, September 2008

Lightly stuffed pyrochlore structure of single-crystalline Yb $_{2}$ Ti $_{2}$ O $_{7}$ grown by the optical floating zone technique
journal, November 2012

Defect formation energies in A 2 B 2 O 7 pyrochlores
journal, October 2015

Impact of stoichiometry of ${Yb}_{2} {Ti}_{2} O_{7}$ on its physical properties
journal, March 2017

Candidate Quantum Spin Liquid in the ${Ce}^{3 +}$ Pyrochlore Stannate ${Ce}_{2} {Sn}_{2} O_{7}$
journal, August 2015

Symmetry enriched U(1) topological orders for dipole-octupole doublets on a pyrochlore lattice
journal, January 2017

Crystal structure refinement with SHELXL
journal, January 2015

Reentrant Phase Diagram of ${Yb}_{2} {Ti}_{2} O_{7}$ in a $⟨ 111 ⟩$ Magnetic Field
journal, September 2017

Stuffed rare earth pyrochlore solid solutions
journal, October 2006

Glassy dynamics in the low-temperature inhomogeneous ferromagnetic phase of the quantum spin ice Yb $_{2}$ Sn $_{2}$ O $_{7}$
journal, January 2014

Alkali Transition‐Metal Molybdates: A Stepwise Approach to Geometrically Frustrated Systems
journal, November 2019