Forward and reverse high-pressure transitions in bulklike AlAs and GaAs epilayers

We report Raman studies of the transformations between the zinc-blende (±) and high-pressure () phases of bulk GaAs and AlAs epitaxial films under increasing and decreasing hydrostatic pressure using a 300-K diamond-anvil press. The forward - thresholds, as measured by the simultaneous onset of opacity and loss of Raman signal, are Pat=12.4±0.4 GPa for AlAs and Pgt=17.3±0.4 GPa for GaAs. On decompression from 20 GPa or less, reversal to the zinc-blende state occurs in both materials with a hysteresis of 68 GPa; otherwise, GaAs enters a metastable phase. After reversal, the returning optical-phonon peaks exhibit asymmetric broadening and negative frequency shifts. Analogy to ion-bombarded GaAs shows that postreversal material is comprised of zinc-blende microcrystallites with diameters 65 and 175 in GaAs and AlAs, respectively. Thermodynamic considerations based on the hysteresis and microcrystallite size suggest that the surface energy per unit area for a nucleus in a pure matrix is 0.040.15 eV/A2, in rough agreement with previous microscopic calculations for a rocksalt zinc-blende AlAs/GaAs heterointerface. We propose that the kinetic homointerface in the bulk nucleation transitions is similar to the static sixfold-fourfold heterointerface involved in the superlattice phase changes discussed in the second paper.