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

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 Sn{sub 3}N{sub 4} 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 ofmore » 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.« less

Authors:
 [1]; ; ; ; ; ; ; ;  [1]; ; ; ;  [2]; ;  [3]; ;  [4]; ;  [5];  [6] more »; « less
  1. National Renewable Energy Laboratory, Golden, Colorado 80401 (United States)
  2. Colorado School of Mines, Golden, Colorado 80401 (United States)
  3. SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States)
  4. Tel Aviv University, Tel Aviv-Yafo (Israel)
  5. Lawrence Berkeley National Laboratory, Berkley, California 94720 (United States)
  6. Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)
Publication Date:
OSTI Identifier:
22657903
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 14; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CALCULATION METHODS; CRYSTAL GROWTH; CRYSTAL LATTICES; EXPERIMENTAL DATA; GROUND STATES; SEALING MATERIALS; SPACE GROUPS; SYNTHESIS; THIN FILMS; TIN NITRIDES

Citation Formats

Caskey, Christopher M., Colorado School of Mines, Golden, Colorado 80401, Larix Chemical Science, Golden, Colorado 80401, Holder, Aaron, Christensen, Steven T., Biagioni, David, Ginley, David S., Tumas, William, Perkins, John D., Lany, Stephan, Zakutayev, Andriy, Shulda, Sarah, Diercks, David, Pylypenko, Svitlana, Richards, Ryan M., Schwartz, Craig P., Nordlund, Dennis, Kukliansky, Alon, Natan, Amir, Prendergast, David, Sun, Wenhao, Orvananos, Bernardo, and others, and. Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures. United States: N. p., 2016. Web. doi:10.1063/1.4945561.
Caskey, Christopher M., Colorado School of Mines, Golden, Colorado 80401, Larix Chemical Science, Golden, Colorado 80401, Holder, Aaron, Christensen, Steven T., Biagioni, David, Ginley, David S., Tumas, William, Perkins, John D., Lany, Stephan, Zakutayev, Andriy, Shulda, Sarah, Diercks, David, Pylypenko, Svitlana, Richards, Ryan M., Schwartz, Craig P., Nordlund, Dennis, Kukliansky, Alon, Natan, Amir, Prendergast, David, Sun, Wenhao, Orvananos, Bernardo, & others, and. Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures. United States. doi:10.1063/1.4945561.
Caskey, Christopher M., Colorado School of Mines, Golden, Colorado 80401, Larix Chemical Science, Golden, Colorado 80401, Holder, Aaron, Christensen, Steven T., Biagioni, David, Ginley, David S., Tumas, William, Perkins, John D., Lany, Stephan, Zakutayev, Andriy, Shulda, Sarah, Diercks, David, Pylypenko, Svitlana, Richards, Ryan M., Schwartz, Craig P., Nordlund, Dennis, Kukliansky, Alon, Natan, Amir, Prendergast, David, Sun, Wenhao, Orvananos, Bernardo, and others, and. Thu . "Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures". United States. doi:10.1063/1.4945561.
@article{osti_22657903,
title = {Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures},
author = {Caskey, Christopher M. and Colorado School of Mines, Golden, Colorado 80401 and Larix Chemical Science, Golden, Colorado 80401 and Holder, Aaron and Christensen, Steven T. and Biagioni, David and Ginley, David S. and Tumas, William and Perkins, John D. and Lany, Stephan and Zakutayev, Andriy and Shulda, Sarah and Diercks, David and Pylypenko, Svitlana and Richards, Ryan M. and Schwartz, Craig P. and Nordlund, Dennis and Kukliansky, Alon and Natan, Amir and Prendergast, David and Sun, Wenhao and Orvananos, Bernardo and others, and},
abstractNote = {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 Sn{sub 3}N{sub 4} 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.},
doi = {10.1063/1.4945561},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 14,
volume = 144,
place = {United States},
year = {2016},
month = {4}
}