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Title: Synthesis of Bulk BC8 Silicon Allotrope by Direct Transformation and Reduced-Pressure Chemical Pathways

Journal Article · · Inorganic Chemistry
 [1];  [1];  [2];  [2];  [3];  [3];  [3];  [1];  [1];  [1];  [4];  [1]
  1. Sorbonne Univ., Paris (France)
  2. European Synchrotron Radiation Facility (ESRF), Grenoble (France)
  3. Carnegie Inst. of Washington, Washington, DC (United States)
  4. Pennsylvania State Univ., University Park, PA (United States)
+ Show Author Affiliations

The knowledge of stoichiometries of alkalineearth metal nitrides, where nitrogen can exist in polynitrogen forms, is of significant interest for understanding nitrogen bonding and its applications in energy storage. For calcium nitrides, there were three known crystalline forms, CaN2, Ca2N, and Ca3N2, at ambient conditions. In the present study, we demonstrated that there are more stable forms of calcium nitrides than what is already known to exist at ambient and high pressures. Using a global structure searching method, we theoretically explored the phase diagram of CaNx and discovered a series of new compounds in this family. In particular, we found a new CaN phase that is thermodynamically stable at ambient conditions, which may be synthesized using CaN2 and Ca2N. Four other stoichiometries, namely, Ca2N3, CaN3, CaN4, and CaN5, were shown to be stable under high pressure. The predicted CaNx compounds contain a rich variety of polynitrogen forms ranging from small molecules (N2, N4, N5, and N6) to extended chains (N∞). Because of the large energy difference between the single and triple nitrogen bonds, dissociation of the CaNx crystals with polynitrogens is expected to be highly exothermic, making them as potential high-energy-density materials.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research in Extreme Environments (EFree)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001057
OSTI ID:
1388105
Journal Information:
Inorganic Chemistry, Vol. 55, Issue 17; Related Information: EFree partners with Carnegie Institution of Washington (lead); California Institute of Technology; Colorado School of Mines; Cornell University; Lehigh University; Pennsylvania State University; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science

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Cited By (3)

Physical properties of group 14 semiconductor alloys in orthorhombic phase journal July 2019
Infinite family of b c 8 -like metastable phases in silicon journal June 2020
High-Pressure Design of Advanced BN-Based Materials text January 2016

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
36 MATERIALS SCIENCE
catalysis (heterogeneous)
solar (photovoltaic)
phonons
thermoelectric
energy storage (including batteries and capacitors)
hydrogen and fuel cells
superconductivity
charge transport
mesostructured materials
materials and chemistry by design
synthesis (novel materials)