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

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 the metastable material. In addition to reporting on the discovery ofmore » the simple binary SnN compound, this study 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] ;  [2] ;  [3] ;  [2] ;  [3] ;  [4] ;  [2] ;  [4] ;  [5] ;  [5] ;  [6] ;  [7] ;  [6] ;  [8] ;  [9] ;  [2] ;  [2] ;  [2] ;  [10] ;  [3] more »;  [2] ;  [3] ;  [2] « less
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States); Larix Chemical Sciences, Golden, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. Colorado School of Mines, Golden, CO (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Tel Aviv Univ., Ramat Aviv (Israel)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  7. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  8. Univ. of Colorado, Boulder, CO (United States)
  9. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  10. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
Publication Date:
OSTI Identifier:
1248078
Report Number(s):
NREL/JA--5K00-66167
Journal ID: ISSN 0021-9606
Grant/Contract Number:
AC36-08GO28308
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 14; Related Information: Journal of Chemical Physics; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
NREL (National Renewable Energy Laboratory (NREL), Golden, CO (United States))
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE crystal structure; x-ray diffraction; tin; polymorphism; x-ray absorption spectroscopy