Anisotropic thermal expansion of silicon monolayer in biphenylene network

Materials with a negative thermal expansion property are of great importance in the emerging family of two-dimensional materials. For example, mixing two materials with negative and positive coefficients of thermal expansion avoids volume changing with temperature. In this work, based on first-principles calculations and Grüneisen's theory, we investigated the thermal expansion properties of a silicon monolayer in biphenylene networks. Our results show that the thermal expansion is greatly negative and anisotropic, as the linear thermal expansion coefficient along the a-direction is significantly smaller than the one along the b-direction, even at high temperatures. At 300 K, the thermal expansion coefficients along the two lattice directions are −17.010 × 10⁻⁶ K⁻¹ and −2.907 × 10⁻⁶ K⁻¹, respectively. By analyzing the Grüneisen parameters and the elastic compliance, we obtained an understanding of the giant negative thermal expansion of the material. Rigid unit modes are also responsible for the negative thermal expansion behavior. Our work provides fundamental insights into the thermal expansion of silicon monolayer in biphenylene networks and should stimulate the further exploration of the possible thermoelectric and thermal management applications of the material.