We apply the desorption mass spectrometry (DMS) technique and analyze the desorbed Sb species in-situ during MBE growth of mixed As/Sb heterostructures. We demonstrate how DMS is useful in pregrowth calibration of the Vila ratio, the group-Ill ratio, as well as the Sb-content in quaternary or quinary mixed As/Sb alloys. We also apply DMS to the digital alloy growth method. For demonstration purposes, we start with an un-calibrated MBE system, use the DMS technique to calibrate all of the previously undetermined MBE parameters and grow a similar to 3.3 mu m diode laser heterostructure in only one attempt. The results demonstrate that the DMS technique will allow the MBE to quickly converge toward a set of acceptable growth parameters without the need for ex-situ calibration of alloy composition. Published by Elsevier B.V.