Quaternary selenostannates Na2-xGa2-xSn 1+xSe6 and AGaSnSe4 (A=K, Rb, and Cs) through rapid cooling of melts. Kinetics versus thermodynamics in the polymorphism of AGaSnSe4

Seong Ju Hwang; Ratnasabapathy G. Iyer; Mercouri G. Kanatzidis

doi:10.1016/j.jssc.2004.06.019

Quaternary selenostannates Na_2-xGa_2-xSn _1+xSe₆ and AGaSnSe₄ (A=K, Rb, and Cs) through rapid cooling of melts. Kinetics versus thermodynamics in the polymorphism of AGaSnSe₄

Seong Ju Hwang, Ratnasabapathy G. Iyer, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

24 Scopus citations

Abstract

The quaternary alkali-metal gallium selenostannates, Na _2-xGa_2-xSn_1+xSe₆ and AGaSnSe ₄ (A=K, Rb, and Cs), were synthesized by reacting alkali-metal selenide, Ga, Sn, and Se with a flame melting-rapid cooling method. Na _2-xGa_2-xSn_1+xSe₆ crystallizes in the non-centrosymmetric space group C2 with cell constants a=13.308(3)Å, b=7.594(2)Å, c=13.842(3)Å, β=118.730(4)°, V=1226.7(5)Å³. α-KGaSnSe₄ crystallizes in the tetragonal space group I4/mcm with a=8.186(5)Å and c=6.403(5)Å, V=429.1(5)Å³. β-KGaSnSe₄ crystallizes in the space group P2₁/c with cell constants a=7.490(2)Å, b=12.578(3)Å, c=18.306(5)Å, β=98.653(5)°, V=1705.0(8)Å³. The unit cell of isostructural RbGaSnSe ₄ is a=7.567(2)Å, b=12.656(3)Å, c=18.277(4)Å, β=95.924(4)°, V=1741.1(7)Å³. CsGaSnSe₄ crystallizes in the orthorhombic space group Pmcn with a=7.679(2)Å, b=12.655(3)Å, c=18.278(5)Å, V=1776.1(8)Å³. The structure of Na_2-xGa_2-xSn_1+xSe₆ consists of a polar three-dimensional network of trimeric (Sn,Ga) ₃Se₉ units with Na atoms located in tunnels. The AGaSnSe₄ possess layered structures. The compounds show nearly the same Raman spectral features, except for Na_2-xGa_2-xSn _1+xSe₆. Optical band gaps, determined from UV-Vis spectroscopy, range from 1.50eV in Na_2-xGa_2-xSn _1+xSe₆ to 1.97eV in CsGaSnSe₄. Cooling of the melts of KGaSnSe₄ and RbGaSnSe₄ produces only kinetically stable products. The thermodynamically stable product is accessible under extended annealing, which leads to the so-called γ-form (BaGa ₂S₄-type) of these compounds.

Original language	English (US)
Pages (from-to)	3640-3649
Number of pages	10
Journal	Journal of Solid State Chemistry
Volume	177
Issue number	10
DOIs	https://doi.org/10.1016/j.jssc.2004.06.019
State	Published - Oct 2004

Funding

Financial support from the National Science Foundation (DMR-0127644) is gratefully acknowledged. This work was supported in part by Korea Research Foundation Grant (KRF-2003-042-C00065).

Keywords

Chalcogenicles
Frame melting
Low-dimensional
Phase-transitions
Polymorphism
Selenostannates

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Condensed Matter Physics
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.jssc.2004.06.019

Cite this

@article{c9ed34ba7d6d41ebb1591daea635a92e,

title = "Quaternary selenostannates Na2-xGa2-xSn 1+xSe6 and AGaSnSe4 (A=K, Rb, and Cs) through rapid cooling of melts. Kinetics versus thermodynamics in the polymorphism of AGaSnSe4",

abstract = "The quaternary alkali-metal gallium selenostannates, Na 2-xGa2-xSn1+xSe6 and AGaSnSe 4 (A=K, Rb, and Cs), were synthesized by reacting alkali-metal selenide, Ga, Sn, and Se with a flame melting-rapid cooling method. Na 2-xGa2-xSn1+xSe6 crystallizes in the non-centrosymmetric space group C2 with cell constants a=13.308(3){\AA}, b=7.594(2){\AA}, c=13.842(3){\AA}, β=118.730(4)°, V=1226.7(5){\AA}3. α-KGaSnSe4 crystallizes in the tetragonal space group I4/mcm with a=8.186(5){\AA} and c=6.403(5){\AA}, V=429.1(5){\AA}3. β-KGaSnSe4 crystallizes in the space group P21/c with cell constants a=7.490(2){\AA}, b=12.578(3){\AA}, c=18.306(5){\AA}, β=98.653(5)°, V=1705.0(8){\AA}3. The unit cell of isostructural RbGaSnSe 4 is a=7.567(2){\AA}, b=12.656(3){\AA}, c=18.277(4){\AA}, β=95.924(4)°, V=1741.1(7){\AA}3. CsGaSnSe4 crystallizes in the orthorhombic space group Pmcn with a=7.679(2){\AA}, b=12.655(3){\AA}, c=18.278(5){\AA}, V=1776.1(8){\AA}3. The structure of Na2-xGa2-xSn1+xSe6 consists of a polar three-dimensional network of trimeric (Sn,Ga) 3Se9 units with Na atoms located in tunnels. The AGaSnSe4 possess layered structures. The compounds show nearly the same Raman spectral features, except for Na2-xGa2-xSn 1+xSe6. Optical band gaps, determined from UV-Vis spectroscopy, range from 1.50eV in Na2-xGa2-xSn 1+xSe6 to 1.97eV in CsGaSnSe4. Cooling of the melts of KGaSnSe4 and RbGaSnSe4 produces only kinetically stable products. The thermodynamically stable product is accessible under extended annealing, which leads to the so-called γ-form (BaGa 2S4-type) of these compounds.",

keywords = "Chalcogenicles, Frame melting, Low-dimensional, Phase-transitions, Polymorphism, Selenostannates",

author = "Hwang, {Seong Ju} and Iyer, {Ratnasabapathy G.} and Kanatzidis, {Mercouri G.}",

note = "Funding Information: Financial support from the National Science Foundation (DMR-0127644) is gratefully acknowledged. This work was supported in part by Korea Research Foundation Grant (KRF-2003-042-C00065). ",

year = "2004",

month = oct,

doi = "10.1016/j.jssc.2004.06.019",

language = "English (US)",

volume = "177",

pages = "3640--3649",

journal = "Journal of Solid State Chemistry",

issn = "0022-4596",

publisher = "Academic Press Inc.",

number = "10",

}

Quaternary selenostannates Na_2-xGa_2-xSn _1+xSe₆ and AGaSnSe₄ (A=K, Rb, and Cs) through rapid cooling of melts. Kinetics versus thermodynamics in the polymorphism of AGaSnSe₄. / Hwang, Seong Ju; Iyer, Ratnasabapathy G.; Kanatzidis, Mercouri G.
In: Journal of Solid State Chemistry, Vol. 177, No. 10, 10.2004, p. 3640-3649.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Quaternary selenostannates Na2-xGa2-xSn 1+xSe6 and AGaSnSe4 (A=K, Rb, and Cs) through rapid cooling of melts. Kinetics versus thermodynamics in the polymorphism of AGaSnSe4

AU - Hwang, Seong Ju

AU - Iyer, Ratnasabapathy G.

AU - Kanatzidis, Mercouri G.

N1 - Funding Information: Financial support from the National Science Foundation (DMR-0127644) is gratefully acknowledged. This work was supported in part by Korea Research Foundation Grant (KRF-2003-042-C00065).

PY - 2004/10

Y1 - 2004/10

N2 - The quaternary alkali-metal gallium selenostannates, Na 2-xGa2-xSn1+xSe6 and AGaSnSe 4 (A=K, Rb, and Cs), were synthesized by reacting alkali-metal selenide, Ga, Sn, and Se with a flame melting-rapid cooling method. Na 2-xGa2-xSn1+xSe6 crystallizes in the non-centrosymmetric space group C2 with cell constants a=13.308(3)Å, b=7.594(2)Å, c=13.842(3)Å, β=118.730(4)°, V=1226.7(5)Å3. α-KGaSnSe4 crystallizes in the tetragonal space group I4/mcm with a=8.186(5)Å and c=6.403(5)Å, V=429.1(5)Å3. β-KGaSnSe4 crystallizes in the space group P21/c with cell constants a=7.490(2)Å, b=12.578(3)Å, c=18.306(5)Å, β=98.653(5)°, V=1705.0(8)Å3. The unit cell of isostructural RbGaSnSe 4 is a=7.567(2)Å, b=12.656(3)Å, c=18.277(4)Å, β=95.924(4)°, V=1741.1(7)Å3. CsGaSnSe4 crystallizes in the orthorhombic space group Pmcn with a=7.679(2)Å, b=12.655(3)Å, c=18.278(5)Å, V=1776.1(8)Å3. The structure of Na2-xGa2-xSn1+xSe6 consists of a polar three-dimensional network of trimeric (Sn,Ga) 3Se9 units with Na atoms located in tunnels. The AGaSnSe4 possess layered structures. The compounds show nearly the same Raman spectral features, except for Na2-xGa2-xSn 1+xSe6. Optical band gaps, determined from UV-Vis spectroscopy, range from 1.50eV in Na2-xGa2-xSn 1+xSe6 to 1.97eV in CsGaSnSe4. Cooling of the melts of KGaSnSe4 and RbGaSnSe4 produces only kinetically stable products. The thermodynamically stable product is accessible under extended annealing, which leads to the so-called γ-form (BaGa 2S4-type) of these compounds.

AB - The quaternary alkali-metal gallium selenostannates, Na 2-xGa2-xSn1+xSe6 and AGaSnSe 4 (A=K, Rb, and Cs), were synthesized by reacting alkali-metal selenide, Ga, Sn, and Se with a flame melting-rapid cooling method. Na 2-xGa2-xSn1+xSe6 crystallizes in the non-centrosymmetric space group C2 with cell constants a=13.308(3)Å, b=7.594(2)Å, c=13.842(3)Å, β=118.730(4)°, V=1226.7(5)Å3. α-KGaSnSe4 crystallizes in the tetragonal space group I4/mcm with a=8.186(5)Å and c=6.403(5)Å, V=429.1(5)Å3. β-KGaSnSe4 crystallizes in the space group P21/c with cell constants a=7.490(2)Å, b=12.578(3)Å, c=18.306(5)Å, β=98.653(5)°, V=1705.0(8)Å3. The unit cell of isostructural RbGaSnSe 4 is a=7.567(2)Å, b=12.656(3)Å, c=18.277(4)Å, β=95.924(4)°, V=1741.1(7)Å3. CsGaSnSe4 crystallizes in the orthorhombic space group Pmcn with a=7.679(2)Å, b=12.655(3)Å, c=18.278(5)Å, V=1776.1(8)Å3. The structure of Na2-xGa2-xSn1+xSe6 consists of a polar three-dimensional network of trimeric (Sn,Ga) 3Se9 units with Na atoms located in tunnels. The AGaSnSe4 possess layered structures. The compounds show nearly the same Raman spectral features, except for Na2-xGa2-xSn 1+xSe6. Optical band gaps, determined from UV-Vis spectroscopy, range from 1.50eV in Na2-xGa2-xSn 1+xSe6 to 1.97eV in CsGaSnSe4. Cooling of the melts of KGaSnSe4 and RbGaSnSe4 produces only kinetically stable products. The thermodynamically stable product is accessible under extended annealing, which leads to the so-called γ-form (BaGa 2S4-type) of these compounds.

KW - Chalcogenicles

KW - Frame melting

KW - Low-dimensional

KW - Phase-transitions

KW - Polymorphism

KW - Selenostannates

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DO - 10.1016/j.jssc.2004.06.019

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JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

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