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Title: Semiconducting cubic titanium nitride in the Th 3 P 4 structure

Abstract

We report the discovery of a long-sought-after phase of titanium nitride with stoichiometry Ti 3 N 4 using diamond anvil cell experiments combined with in situ high-resolution x-ray diffraction and Raman spectroscopy techniques, supported by ab initio calculations. Ti 3 N 4 crystallizes in the cubic Th 3 P 4 structure [space group I ¯ 4 3 d (220)] from a mixture of TiN and N 2 above ≈ 75 GPa and ≈ 2400 K. The density ( ≈ 5.22 g/cc) and bulk modulus ( K 0 = 290 GPa) of cubic- Ti 3 N 4 ( c - Ti 3 N 4 ) at 1 atm, estimated from the pressure-volume equation of state, are comparable to rocksalt TiN. Ab initio calculations based on the GW approximation and using hybrid functionals indicate that c - Ti 3 N 4 is a semiconductor with a direct band gap between 0.8 and 0.9 eV, which is larger than the previously predicted values. The c - Ti 3 N 4 phase is not recoverable to ambient pressure due to dynamic instabilities, but recovery of Ti 3 N 4 in the defect rocksalt (or related) structure may be feasible.

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research in Extreme Environments (EFree)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCESNSFDOE-NNSAAHA
OSTI Identifier:
1418047
Resource Type:
Journal Article
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 1; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Bhadram, Venkata S., Liu, Hanyu, Xu, Enshi, Li, Tianshu, Prakapenka, Vitali B., Hrubiak, Rostislav, Lany, Stephan, and Strobel, Timothy A. Semiconducting cubic titanium nitride in the Th3P4 structure. United States: N. p., 2018. Web. doi:10.1103/PhysRevMaterials.2.011602.
Bhadram, Venkata S., Liu, Hanyu, Xu, Enshi, Li, Tianshu, Prakapenka, Vitali B., Hrubiak, Rostislav, Lany, Stephan, & Strobel, Timothy A. Semiconducting cubic titanium nitride in the Th3P4 structure. United States. doi:10.1103/PhysRevMaterials.2.011602.
Bhadram, Venkata S., Liu, Hanyu, Xu, Enshi, Li, Tianshu, Prakapenka, Vitali B., Hrubiak, Rostislav, Lany, Stephan, and Strobel, Timothy A. Mon . "Semiconducting cubic titanium nitride in the Th3P4 structure". United States. doi:10.1103/PhysRevMaterials.2.011602.
@article{osti_1418047,
title = {Semiconducting cubic titanium nitride in the Th3P4 structure},
author = {Bhadram, Venkata S. and Liu, Hanyu and Xu, Enshi and Li, Tianshu and Prakapenka, Vitali B. and Hrubiak, Rostislav and Lany, Stephan and Strobel, Timothy A.},
abstractNote = {We report the discovery of a long-sought-after phase of titanium nitride with stoichiometry Ti 3 N 4 using diamond anvil cell experiments combined with in situ high-resolution x-ray diffraction and Raman spectroscopy techniques, supported by ab initio calculations. Ti 3 N 4 crystallizes in the cubic Th 3 P 4 structure [space group I ¯ 4 3 d (220)] from a mixture of TiN and N 2 above ≈ 75 GPa and ≈ 2400 K. The density ( ≈ 5.22 g/cc) and bulk modulus ( K 0 = 290 GPa) of cubic- Ti 3 N 4 ( c - Ti 3 N 4 ) at 1 atm, estimated from the pressure-volume equation of state, are comparable to rocksalt TiN. Ab initio calculations based on the GW approximation and using hybrid functionals indicate that c - Ti 3 N 4 is a semiconductor with a direct band gap between 0.8 and 0.9 eV, which is larger than the previously predicted values. The c - Ti 3 N 4 phase is not recoverable to ambient pressure due to dynamic instabilities, but recovery of Ti 3 N 4 in the defect rocksalt (or related) structure may be feasible.},
doi = {10.1103/PhysRevMaterials.2.011602},
journal = {Physical Review Materials},
issn = {2475-9953},
number = 1,
volume = 2,
place = {United States},
year = {2018},
month = {1}
}

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