School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo, 454000, China.
College of Physics and Electronic Information & Henan Key Laboratory of Electromagnetic Transformation and Detection, Luoyang Normal University, Luoyang, 471934, China.
Phys Chem Chem Phys. 2023 Feb 22;25(8):6392-6396. doi: 10.1039/d2cp05289j.
Phosphides have been used in a wide range of applications due to their excellent optical, mechanical, and catalytic properties. Using an effective unbiased structure searching method combined with first-principles calculations, the phase diagram and physical and chemical properties of aluminum phosphides have been determined at high pressures. The results reveal that the unconventional stoichiometries of AlP, AlP, and AlP remain stable above 66, 91, and 116 GPa, respectively. Interestingly, the analysis of the phonon spectrum suggests that AlP with 2 symmetry can be dynamically stable at atmospheric pressure. In addition, the band gap of 1.51 eV at the HSE06 level and the estimated Vickers hardness of ∼10.54 GPa make 2-AlP a hard photoelectric material. Moreover, our electronic properties show that AlP with symmetry and AlP with 4/ structure are metallic at high pressures and further electron-phonon coupling calculations indicate -AlP and 4/-AlP are superconductors with estimated values of 3.9 K at 150 GPa and 10.2 K at 100 GPa, respectively. Our work provides significant inputs toward understanding novel chemical bonding in aluminum phosphides and gives a direction for the experimental synthesis of multifunctional materials at high pressures.
由于磷化物具有优异的光学、机械和催化性能，因此被广泛应用。本研究采用有效的无偏结构搜索方法结合第一性原理计算，确定了高压下磷化铝的相图和物理化学性质。结果表明，非传统化学计量比的 AlP、AlP 和 AlP 分别在 66、91 和 116 GPa 以上稳定存在。有趣的是，声子谱分析表明，具有 2 对称性的 AlP 在常压下可以处于动力学稳定状态。此外，在 HSE06 水平下的带隙为 1.51 eV，估计的维氏硬度约为 10.54 GPa，使得 2-AlP 成为一种硬光电材料。此外，我们的电子性质表明，高压下具有 对称性和 4/ 结构的 AlP 是金属的，进一步的电子-声子耦合计算表明，-AlP 和 4/-AlP 是超导材料，在 150 GPa 时的估计 值为 3.9 K，在 100 GPa 时的估计 值为 10.2 K。我们的工作为理解磷化铝中的新型化学键提供了重要的依据，并为在高压下合成多功能材料指明了方向。
