Boron and indium incorporation in GaP(0Â 0Â 1) surfaces by vapour deposition: Density-functional supercell calculations of the surface stability

Using surface supercells and the density-functional method, surface formation energies are calculated for probable GaP(0 0 1) reconstructions without and with indium or/and boron substitutions. Obtained surface stability diagrams provide surface compositions and surface structures in dependence on the growth conditions: indium atoms are built into the c(4 × 4) patterns under strongly P-rich conditions and into the β2(2 × 4) reconstruction under less P-rich conditions. Under In-rich and non-P-rich conditions, initial structures of metallic InGa phases are formed in the (2 × 4) mixed-dimer reconstruction. In the c(4 × 4) and (2 × 4) mixed-dimer patterns the full range of In:Ga content is accessible by variation of the In:Ga ratio in the gas phase. Boron can be built into the c(4 × 4) patterns of the GaP(0 0 1) surface in form of isolated atoms or nearest-neighbours under strongly P-rich and moderately to strongly B-rich conditions. The boron incorporation is strongly enhanced at the surface in respect to theoretical predictions for the bulk, what explains the larger content found experimentally. Assuming P-rich conditions, which are suitable for the growth of the ternary alloys, the obtained surface stability diagram for the quaternary (BInGa)P shows that nearly the full range of In:Ga content is accessible. However, the boron content in the alloy is restricted as found analogously for (BGa)P and is independent of the indium content. The expected increase of the boron content in presence of indium cannot be confirmed. Contrary to the analogous GaAs systems, boron atoms do not substitute phosphor atoms (antisite position) in GaP, (InGa)P, (BGa)P, and (BInGa)P.