Phase relations and thermoelasticity of magnesium silicide at high pressure and temperature

Within the exploration of sustainable and functional materials, narrow bandgap magnesium silicide semiconductors have gained growing interest. Intriguingly, squeezing silicides to extreme pressures and exposing them to non-ambient temperatures proves fruitful to study the structural behavior, tune the electronic structure, or discover novel phases. Herein, structural changes and thermoelastic characteristics of magnesium silicides were probed with synchrotron x-ray diffraction techniques using the laser-heated diamond anvil cell and large volume press at high pressure and temperature and temperature-dependent synchrotron powder diffraction. Probing the ambient phase of Mg2Si (anti-CaF2-type Mg2Si, space group: Fm3m) at static pressures of giga-Pascals possibly unveiled the transformation to metastable orthorhombic anti-PbCl2-type Mg2Si (Pnma). Interestingly, heating under pressures introduced the decomposition of Mg2Si to hexagonal Mg9Si5 (P6(3)) and minor Mg. Using equations of state (EoS), which relate pressure to volume, the bulk moduli of anti-CaF2-type Mg2Si, anti-PbCl2-type Mg2Si, and Mg9Si5 were determined to be B-0 = 47(2) GPa, B-0 approximate to 72(5) GPa, and B-0 = 58(3) GPa, respectively. Employing a high-temperature EoS to the P-V-T data of anti-CaF2-type Mg2Si provided its thermoelastic parameters: B-T0 = 46(3) GPa, B ' (T0) = 6.1(8), and (partial derivative B-T0/partial derivative T)(P) = -0.013(4) GPa K-1. At atmospheric pressure, anti-CaF2-type Mg2Si kept stable at T = 133-723 K, whereas Mg9Si5 transformed to anti-CaF2-type Mg2Si and Si above T >= 530 K. This temperature stability may indicate the potential of Mg9Si5 as a mid-temperature thermoelectric material, as suggested from previous first-principles calculations. Within this realm, thermal models were applied, yielding thermal expansion coefficients of both silicides together with estimations of their Gruneisen parameter and Debye temperature.

Automated summary

In the study of narrow bandgap magnesium silicide semiconductors, extreme pressures and non-ambient temperatures were found to be fruitful for studying structural behavior and discovering new phases. Using synchrotron x-ray diffraction techniques at high pressure and temperature, structural changes and thermoelastic characteristics of magnesium silicides were investigated. The results provide valuable insights into the thermal stability and potential applications of these materials.