Metastable (GaSb)_(1-x)(Sn₂)_x alloys: Crystal growth and phase stability of single crystal and polycrystalline layers

Single-phase metastable (GaSb)_(1-x)(Sn₂)_x alloys with x ≤ 0.23 far exceeding the equilibrium solid solubility limit of x {less-than or approximate} 0.02 for Sn in GaSb, have been grown by rf sputter deposition. The key feature allowing the growth of single phase alloys was the use of low energy ion-bombardment-induced collisional mixing during deposition. Films grown at elevated temperatures T_s on GaAs(100) substrates were found to be single crystals while polycrystalline films with very strong (220) perferred orientation and grain sizes of 20-40 nm were obtained on amorphous glass substrates. The maximum film growth temperatures T_m at which single phase films could be obtained was a function of the negative substrate potential V_s during deposition and the composition x. For V_s = 75 V, T_m ranged from 375 °C at x = 0.06 to 125 °C at x = 0.23. Crystal growth and post-annealing studies both indicated that the transformation from the single-phase metastable state to the equilibrium (GaSb + βSn) state occurs through a continuous set of metastable GaSb-rich phases and that Sn precipitates out first in the α-diamond structure and then transforms to the β-tetragonal structure. In single crystal films, the GaSb-rich phase precipitates out coherently with the alloy matrix. The activation energy for phase separation ranged from ∼ 1.4 eV for alloys with x = 0.06 to 0.9 eV at x = 0.23. A phase map for crystal growth, plotted as a function of T_s and x, and an annealing transformation diagram for (GaSb)_0.86(Sn₂)_0.14 was determined.