Pressure effect on impurity local vibrational mode and phase transitions in n-type iron-doped indium phosphide

The evolution of iron local vibrational mode (Fe LVM) and phase transitions in n-type iron-doped indium phosphide (InP:Fe) were investigated at ambient temperature. In-situ angle-dispersive X-ray diffraction measurements revealed that InP: Fe starts to transform from zinc-blende (ZB) to rock-salt (RS) structure around 8.2(2) GPa and completes around 16.0(2) GPa. The Raman shift of both transverse and longitudinal optical modes increases monotonically with increasing pressure, while their intensities become indiscernible at 11.6(2) GPa, suggesting that the pressure-induced phase transition is accompanied by significant metallization. In contrast, originally absent at ambient pressure, the Raman shift of Fe LVM appears at similar to 420 cm(-1) near 1.2 GPa and exhibits a dome shape behavior with increasing pressure, reaching a maximum value of similar to 440 cm-1 around 5 GPa, with an apparent kink occurring around the ZB-RS transition pressure of similar to 8.5(2) GPa. The Fe K-edge X-ray absorption near edge structure (XANES) confirmed the tetrahedral site occupation of Fe3+ with a crystal field splitting parameter Delta(t)=38k . mole(-1). Our calculations indicate that the energy parameters governing the phase transition are Delta(t)=0.49 and Delta(o) =1.10 kJ . mole(-1),respectively, both are much smaller than Delta(t) = 38 kJ . mole(-1) at ambient.