A pressure-induced superhard SiCN4 compound uncovered by first-principles calculations

• Published in: Physical chemistry chemical physics : PCCP Vol. 26; no. 11; pp. 8938 - 8944
• Main Authors: Wang, Chengyu, Yu, Guoliang, Zhang, Shoutao, Zhao, Yu, Chen, Hui, Cheng, Taimin, Zhang, Xinxin
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 13.03.2024
• Subjects: Algorithms; Diamond pyramid hardness; Enthalpy; First principles; Mathematical analysis; Modulus of elasticity; Particle swarm optimization; Phase transitions; Physical properties; Pressure; Silicon
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d3cp06272d

Silicon–carbon–nitride (Si–C–N) compounds are a family of potential superhard materials with many excellent chemical and physical properties; however, only SiCN, Si2CN4 and SiC2N4 were synthesized. Here, we theoretically report a new SiCN4 compound with P41212, Fdd2 and R3 structures by first-principles structural predictions based on the particle swarm optimization algorithm. Pressure-induced structural phase transitions from P41212 to Fdd2, and then to the R3 phase were determined at 2 GPa and 249 GPa. By comparing enthalpy differences with 1/3Si3N4 + C + 4/3N2, it was found that these structures tend to decompose at ambient pressure. However, with the increase of pressure, the enthalpy differences of Fdd2 and R3 structures turn to be negative and they can be stabilized at a pressure of more than 41 GPa. They are also dynamically stable as no imaginary frequencies were found in their stabilized pressure ranges. The calculated band gap is 4.37 eV for P41212, 3.72 eV for Fdd2 and 3.81 eV for the R3 phase by using the Heyd–Scuseria–Ernzerhof (HSE06) method and the estimated Vickers hardness values are higher than 40 GPa by adopting the elastic modulus based hardness formula, which confirmed their superhard characteristics. These results provide significant insights into Si–C–N systems and will inevitably promote the future experimental works.