An atomic scale study has been performed to understand the influence of the (As,Sb) shutter sequences during interface formation on the optical properties of InGaAs/AlAsSb quantum wells. Our cross-sectional scanning tunneling microscopy results show that the onset of the Sb profile is steep in the Sb-containing layers whereas an appreciable segregation of Sb in the subsequently grown Sb free layers is observed. The steep rise of the Sb profile is due to extra Sb that is supplied to the surface prior to the growth of the Sb-containing layers. No relation is found between the (As,Sb) termination conditions of the Sb-containing layers and the resulting Sb profiles in the capping layers. Correspondingly we see that the optical properties of these quantum wells are also nearly independent on the (As,Sb) shutter sequences at the interface. Digital alloy growth in comparison to conventional molecular beam epitaxy growth was also explored. X-ray results suggest that the structural properties of the quantum well structures grown by conventional molecular beam epitaxy techniques are slightly better than those formed by digital alloy growth. However photoluminescence studies indicate that the digital alloy samples give rise to a more intense and broader photoluminescence emission. Cross-sectional scanning tunneling microscopy measurements reveal that lateral composition modulations present in the digital alloys are responsible for the enhancement of the photoluminescence intensity and inhomogeneous broadening.