New, stable stoichiometries in Be-P systems are investigated up to 100 GPa by the CALYPSO structure prediction method. Along with the BeP2-I41/amd structure, we identify two novel compounds of Be3P2-P-421m and Be3P2-C2/m. It should be noted that the Be-P compounds are predicted to be energetically unfavorable above 40 GPa. As can be seen, interesting structures may be experimentally synthesizable at modest pressure. Our results indicate that at 33.2 GPa, the most stable ambient-pressure tetragonal Be3P2-P-421m transitions to the monoclinic Be3P2-C2/m structure. Moreover, the predicted Be3P2-P-421m and Be3P2-C2/m phases are energetically favored compared with the Be3P2-Ia-3 structure synthesized experimentally. Electronic structure calculations reveal that BeP2-I41/amd, Be3P2-P-421m, and Be3P2-C2/m are all semiconductors with a narrow band gap. The present findings offer insight and guidance for exploration toward further fundamental understanding and potential applications in the semiconductor field.
Keywords: first-principles; high pressure; phase transition; structural prediction.