Prediction of novel hard phases of Si{sub 3}N{sub 4}: First-principles calculations
Abstract
Exploration of novel hard metastable phases of silicon nitride was performed using a recently developed particle-swarm optimization method within the CALYPSO software package. Three potential hard metastable phases of t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4}, and o-Si{sub 3}N{sub 4} were predicted. These phases are mechanically and dynamically stable at ambient pressure based on their elastic constants and phonon dispersions. t-Si{sub 3}N{sub 4} and m-Si{sub 3}N{sub 4} exhibit lower energies than γ-Si{sub 3}N{sub 4} at pressures below 2.5 GPa and 2.9 GPa, respectively, which promise that the formers could be obtained by quenching from γ-Si{sub 3}N{sub 4}. o-Si{sub 3}N{sub 4} is a better high-pressure metastable phase than CaTi{sub 2}O{sub 4}-type Si{sub 3}N{sub 4} proposed by Tatsumi et al. and it can come from the transition of γ-Si{sub 3}N{sub 4} under 198 GPa. The theoretical band gaps of t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4}, and o-Si{sub 3}N{sub 4} at ambient pressure were 3.15 eV, 3.90 eV, and 3.36 eV, respectively. At ambient pressure, the Vickers hardness values of t-Si{sub 3}N{sub 4} (32.6 GPa), m-Si{sub 3}N{sub 4} (31.5 GPa), and o-Si{sub 3}N{sub 4} (36.1 GPa) are comparable to β-Si{sub 3}N{sub 4} and γ-Si{sub 3}N{sub 4}. With the pressure increasing, t-Si{sub 3}N{sub 4}, m-Si{submore »
- Authors:
- Publication Date:
- OSTI Identifier:
- 22486716
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Solid State Chemistry
- Additional Journal Information:
- Journal Volume: 228; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BRITTLE-DUCTILE TRANSITIONS; COMPARATIVE EVALUATIONS; COMPUTERIZED SIMULATION; CRYSTAL STRUCTURE; ENERGY GAP; ENTHALPY; PARTICLES; PHASE STABILITY; PHASE STUDIES; PHASE TRANSFORMATIONS; PHONONS; PRESSURE DEPENDENCE; QUENCHING; SILICON NITRIDES; VICKERS HARDNESS
Citation Formats
Cui, Lin, Hu, Meng, Wang, Qianqian, Xu, Bo, Yu, Dongli, Liu, Zhongyuan, and He, Julong. Prediction of novel hard phases of Si{sub 3}N{sub 4}: First-principles calculations. United States: N. p., 2015.
Web. doi:10.1016/J.JSSC.2015.04.002.
Cui, Lin, Hu, Meng, Wang, Qianqian, Xu, Bo, Yu, Dongli, Liu, Zhongyuan, & He, Julong. Prediction of novel hard phases of Si{sub 3}N{sub 4}: First-principles calculations. United States. https://doi.org/10.1016/J.JSSC.2015.04.002
Cui, Lin, Hu, Meng, Wang, Qianqian, Xu, Bo, Yu, Dongli, Liu, Zhongyuan, and He, Julong. 2015.
"Prediction of novel hard phases of Si{sub 3}N{sub 4}: First-principles calculations". United States. https://doi.org/10.1016/J.JSSC.2015.04.002.
@article{osti_22486716,
title = {Prediction of novel hard phases of Si{sub 3}N{sub 4}: First-principles calculations},
author = {Cui, Lin and Hu, Meng and Wang, Qianqian and Xu, Bo and Yu, Dongli and Liu, Zhongyuan and He, Julong},
abstractNote = {Exploration of novel hard metastable phases of silicon nitride was performed using a recently developed particle-swarm optimization method within the CALYPSO software package. Three potential hard metastable phases of t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4}, and o-Si{sub 3}N{sub 4} were predicted. These phases are mechanically and dynamically stable at ambient pressure based on their elastic constants and phonon dispersions. t-Si{sub 3}N{sub 4} and m-Si{sub 3}N{sub 4} exhibit lower energies than γ-Si{sub 3}N{sub 4} at pressures below 2.5 GPa and 2.9 GPa, respectively, which promise that the formers could be obtained by quenching from γ-Si{sub 3}N{sub 4}. o-Si{sub 3}N{sub 4} is a better high-pressure metastable phase than CaTi{sub 2}O{sub 4}-type Si{sub 3}N{sub 4} proposed by Tatsumi et al. and it can come from the transition of γ-Si{sub 3}N{sub 4} under 198 GPa. The theoretical band gaps of t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4}, and o-Si{sub 3}N{sub 4} at ambient pressure were 3.15 eV, 3.90 eV, and 3.36 eV, respectively. At ambient pressure, the Vickers hardness values of t-Si{sub 3}N{sub 4} (32.6 GPa), m-Si{sub 3}N{sub 4} (31.5 GPa), and o-Si{sub 3}N{sub 4} (36.1 GPa) are comparable to β-Si{sub 3}N{sub 4} and γ-Si{sub 3}N{sub 4}. With the pressure increasing, t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4}, and o-Si{sub 3}N{sub 4} will change from the brittle to ductile state at about 15.7 GPa, 7.3 GPa and 28.9 GPa, respectively. - Graphical abstract: This figure shows the crystal structures of three Si{sub 3}N{sub 4} predicted in this manuscript, and left to right: t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4} and o-Si{sub 3}N{sub 4}. - Highlights: • We explored three metastable phases of Si{sub 3}N{sub 4} — t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4}, and o-Si{sub 3}N{sub 4}. • The enthalpies of t and m- are much lower than that of γ at ambient pressure. • ois one further high pressure phase than γ. • o-Si{sub 3}N{sub 4} is the most hardest phase in Si{sub 3}N4 system. • Increasing pressure will change them from brittle to ductile state.},
doi = {10.1016/J.JSSC.2015.04.002},
url = {https://www.osti.gov/biblio/22486716},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 228,
place = {United States},
year = {Sat Aug 15 00:00:00 EDT 2015},
month = {Sat Aug 15 00:00:00 EDT 2015}
}