In this investigation, surfactant-mediated growth of SiGe/Si single quantum-well structures is studied by photoluminescence and secondary ion mass spectrometry. The samples were grown by molecular-beam epitaxy and Sb was used as a surfactant. The photon energy of the SiGe-related near-band-edge photoluminescence was used to probe the action of Sb as a surfactant to promote two-dimensional growth and to reduce segregation of Ge during growth. First, the "growth-temperature window" at which Sb acts preferentially as a surfactant was determined. Then, at this optimized temperature of 700°C, the influence of different Sb coverages was investigated and it was found that 0.5 monolayer was a sufficient coverage to obtain full surfactant action. Ge concentration depth profiles obtained by secondary ion mass spectrometry confirmed the effect of surfactant-mediated growth and, in addition, the unintentional incorporation of the Sb surfactant during growth was determined quantitatively. In a final experiment the effect of deposition of Sb on either the lower or the upper heterointerface is addressed.