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Phase relations and structural properties of the ternary narrow gap semiconductors Zn5Sb4In2-δ (δ=0.15) and Zn9Sb6In2

Wu, Yang ; Tengå, Andreas ; Lidin, Sven LU and Häussermann, Ulrich (2010) In Journal of Solid State Chemistry 183(7). p.1574-1581
Abstract

A systematic study of the Zn-rich corner of the ternary system Zn-Sb-In revealed the presence of two ternary compounds: stable Zn5Sb4In2-δ (δ=0.15) and metastable Zn9Sb6In2 with closely related crystal structures. Their common motif is a tetragonal basic structure of 32434 nets formed by the Sb atoms. The nets are stacked in antiposition to yield layers of square antiprisms sharing edges plus intervening tetracapped tetrahedra (tetreadersterns). The majority of Zn atoms occupy peripheral tetrahedra of such tetraedersterns, which produces frameworks with a composition "ZnSb". These frameworks represent orthorhombic superstructures: (2×1×1) for... (More)

A systematic study of the Zn-rich corner of the ternary system Zn-Sb-In revealed the presence of two ternary compounds: stable Zn5Sb4In2-δ (δ=0.15) and metastable Zn9Sb6In2 with closely related crystal structures. Their common motif is a tetragonal basic structure of 32434 nets formed by the Sb atoms. The nets are stacked in antiposition to yield layers of square antiprisms sharing edges plus intervening tetracapped tetrahedra (tetreadersterns). The majority of Zn atoms occupy peripheral tetrahedra of such tetraedersterns, which produces frameworks with a composition "ZnSb". These frameworks represent orthorhombic superstructures: (2×1×1) for Zn5Sb4In2-δ (Z=4) and (2×3×1) for Zn9Sb6In2 (Z=8) with respect to the tetragonal arrangement of Sb atoms. The In and remaining Zn atoms are distributed in the channels formed by the square antiprisms. Phase relations in the Zn-Sb-In system are complex. Crystals of metastable Zn9Sb6In2 are regularly intergrown with various amounts of Zn5Sb4In2-δ. Additionally, a monoclinic variant to orthorhombic Zn9Sb6In2 could be identified. Zn9Sb6In2 decomposes exothermically into a mixture of Zn5Sb4In2-δ, Zn4Sb3 and elemental Zn at around 480 K. Both Zn5Sb4In2-δ and Zn9Sb6In2 are poor metals with resistivity values that are characteristic of heavily doped or degenerate semiconductors (0.2-3 m Ω cm at room temperature).

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author
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publishing date
type
Contribution to journal
publication status
published
keywords
Narrow gap semiconductors, Superstructures, Zinc antimonides
in
Journal of Solid State Chemistry
volume
183
issue
7
pages
8 pages
publisher
Elsevier
external identifiers
  • scopus:77953913327
ISSN
0022-4596
DOI
10.1016/j.jssc.2010.05.001
language
English
LU publication?
no
id
555838ed-9e0b-41b3-9541-dba83834c836
date added to LUP
2019-04-08 15:00:13
date last changed
2022-01-31 18:46:44
@article{555838ed-9e0b-41b3-9541-dba83834c836,
  abstract     = {{<p>A systematic study of the Zn-rich corner of the ternary system Zn-Sb-In revealed the presence of two ternary compounds: stable Zn<sub>5</sub>Sb<sub>4</sub>In<sub>2-δ</sub> (δ=0.15) and metastable Zn<sub>9</sub>Sb<sub>6</sub>In<sub>2</sub> with closely related crystal structures. Their common motif is a tetragonal basic structure of 3<sup>2</sup>434 nets formed by the Sb atoms. The nets are stacked in antiposition to yield layers of square antiprisms sharing edges plus intervening tetracapped tetrahedra (tetreadersterns). The majority of Zn atoms occupy peripheral tetrahedra of such tetraedersterns, which produces frameworks with a composition "ZnSb". These frameworks represent orthorhombic superstructures: (2×1×1) for Zn<sub>5</sub>Sb<sub>4</sub>In<sub>2-δ</sub> (Z=4) and (2×3×1) for Zn<sub>9</sub>Sb<sub>6</sub>In<sub>2</sub> (Z=8) with respect to the tetragonal arrangement of Sb atoms. The In and remaining Zn atoms are distributed in the channels formed by the square antiprisms. Phase relations in the Zn-Sb-In system are complex. Crystals of metastable Zn<sub>9</sub>Sb<sub>6</sub>In<sub>2</sub> are regularly intergrown with various amounts of Zn<sub>5</sub>Sb<sub>4</sub>In<sub>2-δ</sub>. Additionally, a monoclinic variant to orthorhombic Zn<sub>9</sub>Sb<sub>6</sub>In<sub>2</sub> could be identified. Zn<sub>9</sub>Sb<sub>6</sub>In<sub>2</sub> decomposes exothermically into a mixture of Zn<sub>5</sub>Sb<sub>4</sub>In<sub>2-δ</sub>, Zn<sub>4</sub>Sb<sub>3</sub> and elemental Zn at around 480 K. Both Zn<sub>5</sub>Sb<sub>4</sub>In<sub>2-δ</sub> and Zn<sub>9</sub>Sb<sub>6</sub>In<sub>2</sub> are poor metals with resistivity values that are characteristic of heavily doped or degenerate semiconductors (0.2-3 m Ω cm at room temperature).</p>}},
  author       = {{Wu, Yang and Tengå, Andreas and Lidin, Sven and Häussermann, Ulrich}},
  issn         = {{0022-4596}},
  keywords     = {{Narrow gap semiconductors; Superstructures; Zinc antimonides}},
  language     = {{eng}},
  month        = {{07}},
  number       = {{7}},
  pages        = {{1574--1581}},
  publisher    = {{Elsevier}},
  series       = {{Journal of Solid State Chemistry}},
  title        = {{Phase relations and structural properties of the ternary narrow gap semiconductors Zn<sub>5</sub>Sb<sub>4</sub>In<sub>2-δ</sub> (δ=0.15) and Zn<sub>9</sub>Sb<sub>6</sub>In<sub>2</sub>}},
  url          = {{http://dx.doi.org/10.1016/j.jssc.2010.05.001}},
  doi          = {{10.1016/j.jssc.2010.05.001}},
  volume       = {{183}},
  year         = {{2010}},
}