Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures

Christopher M. Caskey, Aaron Holder, Sarah Shulda, Steven T. Christensen, David Diercks, Craig P. Schwartz, David Biagioni, Dennis Nordlund, Alon Kukliansky, Amir Natan, David Prendergast, Bernardo Orvananos, Wenhao Sun, Xiuwen Zhang, Gerbrand Ceder, David S. Ginley, William Tumas, John D. Perkins, Vladan Stevanovic, Svitlana Pylypenko & 3 others Stephan Lany, Ryan M. Richards, Andriy Zakutayev

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Recent advances in theoretical structure prediction methods and high-throughput computational techniques are revolutionizing experimental discovery of the thermodynamically stable inorganic materials. Metastable materials represent a new frontier for these studies, since even simple binary non-ground state compounds of common elements may be awaiting discovery. However, there are significant research challenges related to non-equilibrium thin film synthesis and crystal structure predictions, such as small strained crystals in the experimental samples and energy minimization based theoretical algorithms. Here, we report on experimental synthesis and characterization, as well as theoretical first-principles calculations of a previously unreported mixed-valent binary tin nitride. Thin film experiments indicate that this novel material is N-deficient SnN with tin in the mixed ii/iv valence state and a small low-symmetry unit cell. Theoretical calculations suggest that the most likely crystal structure has the space group 2 (SG2) related to the distorted delafossite (SG166), which is nearly 0.1 eV/atom above the ground state SnN polymorph. This observation is rationalized by the structural similarity of the SnN distorted delafossite to the chemically related Sn3N4 spinel compound, which provides a fresh scientific insight into the reasons for growth of polymorphs of metastable materials. In addition to reporting on the discovery of the simple binary SnN compound, this paper illustrates a possible way of combining a wide range of advanced characterization techniques with the first-principle property calculation methods, to elucidate the most likely crystal structure of the previously unreported metastable materials.

Original languageEnglish
Article number144201
JournalJournal of Chemical Physics
Volume144
Issue number14
DOIs
Publication statusPublished - Apr 14 2016

Fingerprint

Tin
Nitrides
nitrides
tin
Crystal structure
crystal structure
synthesis
Polymorphism
inorganic materials
thin films
predictions
spinel
Thin films
valence
optimization
ground state
Ground state
symmetry
cells
crystals

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Caskey, C. M., Holder, A., Shulda, S., Christensen, S. T., Diercks, D., Schwartz, C. P., ... Zakutayev, A. (2016). Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures. Journal of Chemical Physics, 144(14), [144201]. https://doi.org/10.1063/1.4945561

Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures. / Caskey, Christopher M.; Holder, Aaron; Shulda, Sarah; Christensen, Steven T.; Diercks, David; Schwartz, Craig P.; Biagioni, David; Nordlund, Dennis; Kukliansky, Alon; Natan, Amir; Prendergast, David; Orvananos, Bernardo; Sun, Wenhao; Zhang, Xiuwen; Ceder, Gerbrand; Ginley, David S.; Tumas, William; Perkins, John D.; Stevanovic, Vladan; Pylypenko, Svitlana; Lany, Stephan; Richards, Ryan M.; Zakutayev, Andriy.

In: Journal of Chemical Physics, Vol. 144, No. 14, 144201, 14.04.2016.

Research output: Contribution to journalArticle

Caskey, CM, Holder, A, Shulda, S, Christensen, ST, Diercks, D, Schwartz, CP, Biagioni, D, Nordlund, D, Kukliansky, A, Natan, A, Prendergast, D, Orvananos, B, Sun, W, Zhang, X, Ceder, G, Ginley, DS, Tumas, W, Perkins, JD, Stevanovic, V, Pylypenko, S, Lany, S, Richards, RM & Zakutayev, A 2016, 'Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures', Journal of Chemical Physics, vol. 144, no. 14, 144201. https://doi.org/10.1063/1.4945561
Caskey CM, Holder A, Shulda S, Christensen ST, Diercks D, Schwartz CP et al. Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures. Journal of Chemical Physics. 2016 Apr 14;144(14). 144201. https://doi.org/10.1063/1.4945561
Caskey, Christopher M. ; Holder, Aaron ; Shulda, Sarah ; Christensen, Steven T. ; Diercks, David ; Schwartz, Craig P. ; Biagioni, David ; Nordlund, Dennis ; Kukliansky, Alon ; Natan, Amir ; Prendergast, David ; Orvananos, Bernardo ; Sun, Wenhao ; Zhang, Xiuwen ; Ceder, Gerbrand ; Ginley, David S. ; Tumas, William ; Perkins, John D. ; Stevanovic, Vladan ; Pylypenko, Svitlana ; Lany, Stephan ; Richards, Ryan M. ; Zakutayev, Andriy. / Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures. In: Journal of Chemical Physics. 2016 ; Vol. 144, No. 14.
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