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Vacancy-Mediated NiAs–Ni2In-Type Intermetallic Phases : Ni1+δ(In/Sb)

Kuila, Sandip Kumar LU ; Lidin, Sven LU and Jana, Partha Pratim LU (2026) In Inorganic Chemistry 65(10). p.5408-5418
Abstract

Ni1+δSn (δ = 0.2, 0.4) and Ni1+δ(In/Sb) (δ = 0.1–0.5) (NiAs/Ni2In type) were synthesized, and their crystal structures were studied in this report. In Ni1+δ(In/Sb), the excess nickel atoms (δ = 0.1–0.5) occupy the vacant trigonal bipyramidal interstitial sites in the NiAs-type structural arrangement, leading to the evolution of a fully disordered to ordered superstructure through a series of incommensurately ordered structures within the B8 phase field. In the phase field, Ni1+δ(In/Sb) (δ = 0.15) that crystallize in the space group P63/mmc adopt structure having an intermediate atomic arrangement between NiAs- and Ni2In-type structures. Phases with δ = 0.2–0.4,... (More)

Ni1+δSn (δ = 0.2, 0.4) and Ni1+δ(In/Sb) (δ = 0.1–0.5) (NiAs/Ni2In type) were synthesized, and their crystal structures were studied in this report. In Ni1+δ(In/Sb), the excess nickel atoms (δ = 0.1–0.5) occupy the vacant trigonal bipyramidal interstitial sites in the NiAs-type structural arrangement, leading to the evolution of a fully disordered to ordered superstructure through a series of incommensurately ordered structures within the B8 phase field. In the phase field, Ni1+δ(In/Sb) (δ = 0.15) that crystallize in the space group P63/mmc adopt structure having an intermediate atomic arrangement between NiAs- and Ni2In-type structures. Phases with δ = 0.2–0.4, adopt incommensurate modulation, and the structure was modeled using (3 + 1)D superspace formalism. The structures of Ni1+δSn (δ = 0.2, 0.4) and Ni1+δ(In/Sb) (δ = 0.2–0.4) crystallize in the orthorhombic superspace group Cmcm(α00)0s0 (a ≈ 4.05 Å, b ≈ 7 Å, and c ≈ 5.15 Å) with a modulation vector q ≈ αa* (where α = 0.42–0.48). Ni1+δ(In/Sb) (δ = 0.45, 0.5) that adopts the ternary variant of Ni3Sn2 type (Pnma with a = 7.111(3) Å, b = 5.193(3) Å, and c = 8.2113(2) Å) can alternatively be represented as a commensurately modulated structure (lock-in phase, Cmcm(α00)0s0, α = 0.5). The structural outcome in the phase field is primarily governed by the partial Ni occupancy, and the vacancy disorder in the Ni1+δ(In/Sb) (δ = 0.15) was rationalized by density functional theory (DFT) calculations.

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Contribution to journal
publication status
published
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Inorganic Chemistry
volume
65
issue
10
pages
11 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:105032849952
  • pmid:41782506
ISSN
0020-1669
DOI
10.1021/acs.inorgchem.5c05376
language
English
LU publication?
yes
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Publisher Copyright: © 2026 American Chemical Society
id
123ec699-bcd1-46aa-8b7e-0b8bb6a1cf51
date added to LUP
2026-05-11 14:30:20
date last changed
2026-06-08 16:24:07
@article{123ec699-bcd1-46aa-8b7e-0b8bb6a1cf51,
  abstract     = {{<p>Ni<sub>1+δ</sub>Sn (δ = 0.2, 0.4) and Ni<sub>1+δ</sub>(In/Sb) (δ = 0.1–0.5) (NiAs/Ni<sub>2</sub>In type) were synthesized, and their crystal structures were studied in this report. In Ni<sub>1+δ</sub>(In/Sb), the excess nickel atoms (δ = 0.1–0.5) occupy the vacant trigonal bipyramidal interstitial sites in the NiAs-type structural arrangement, leading to the evolution of a fully disordered to ordered superstructure through a series of incommensurately ordered structures within the B8 phase field. In the phase field, Ni<sub>1+δ</sub>(In/Sb) (δ = 0.15) that crystallize in the space group P6<sub>3</sub>/mmc adopt structure having an intermediate atomic arrangement between NiAs- and Ni<sub>2</sub>In-type structures. Phases with δ = 0.2–0.4, adopt incommensurate modulation, and the structure was modeled using (3 + 1)D superspace formalism. The structures of Ni<sub>1+δ</sub>Sn (δ = 0.2, 0.4) and Ni<sub>1+δ</sub>(In/Sb) (δ = 0.2–0.4) crystallize in the orthorhombic superspace group Cmcm(α00)0s0 (a ≈ 4.05 Å, b ≈ 7 Å, and c ≈ 5.15 Å) with a modulation vector q ≈ αa* (where α = 0.42–0.48). Ni<sub>1+δ</sub>(In/Sb) (δ = 0.45, 0.5) that adopts the ternary variant of Ni<sub>3</sub>Sn<sub>2</sub> type (Pnma with a = 7.111(3) Å, b = 5.193(3) Å, and c = 8.2113(2) Å) can alternatively be represented as a commensurately modulated structure (lock-in phase, Cmcm(α00)0s0, α = 0.5). The structural outcome in the phase field is primarily governed by the partial Ni occupancy, and the vacancy disorder in the Ni<sub>1+δ</sub>(In/Sb) (δ = 0.15) was rationalized by density functional theory (DFT) calculations.</p>}},
  author       = {{Kuila, Sandip Kumar and Lidin, Sven and Jana, Partha Pratim}},
  issn         = {{0020-1669}},
  language     = {{eng}},
  month        = {{03}},
  number       = {{10}},
  pages        = {{5408--5418}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Inorganic Chemistry}},
  title        = {{Vacancy-Mediated NiAs–Ni<sub>2</sub>In-Type Intermetallic Phases : Ni<sub>1+δ</sub>(In/Sb)}},
  url          = {{http://dx.doi.org/10.1021/acs.inorgchem.5c05376}},
  doi          = {{10.1021/acs.inorgchem.5c05376}},
  volume       = {{65}},
  year         = {{2026}},
}