High resolution synchrotron radiation core level photoemission studies were performed on atomically clean 0.5 mu m thick In0.53Ga0.47As (100) epilayers lattice matched to InP substrates following the removal of a 100 nm protective arsenic cap at 410 degrees C. Both n-type (Si doped 5 x 10(17) cm(-3)) and p-type (Be doped 5 x 10(17) cm(-3)) InGaAs samples were subsequently exposed in situ to molecular sulphur at room temperature, and the resulting changes in the surface chemical composition were recorded. The photoemission spectra indicate evidence of As-S, Ga-S, and In-S bond formation and the substitution of As in the near surface region by sulphur. Annealing to 400 degrees C results in the complete removal of the As-S bonding component with both Ga-S and In-S bonding configurations remaining. After the anneal, the Fermi level position for both n-type and p-type samples resides at the top of the bandgap indicating a near flat band condition for n-type and significant band bending on the p-type sample. The results of angle resolved photoemission measurements suggest that the sulphur has substituted arsenic in the near surface region resulting in both samples displaying n-type surface behaviour. Annealing to higher temperatures results in the loss of In from the surface without any significant change in the Ga, As, or S signals. Work function measurements on both doping types after sulphur deposition and anneal show similar behaviour displaying a value close to 6 eV which is indicative of the formation of a surface dipole layer related to the presence of sulphur on the surface. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4728213]