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A combined segregation and desorption process has been observed in situ by ellipsometry in real-time during overgrowth of a CdSe layer by a ZnSe cap layer using migration enhanced epitaxy. This segregation enhanced etching of CdSe during Zn deposition is known to play an important role in the formation process of CdSe quantum dots. The time-resolved ellipsometry data can be fitted assuming a rapid thickness reduction of about 68% of the CdSe layer, consistent with results obtained by high-resolution x-ray diffraction after growth. Furthermore, a significant change in growth rate during deposition of CdSe has been observed.