In this paper, we present an experimental study on the structural and crystalline properties of electron beam evaporated Mo/Si multilayers. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) experiments were used to characterize the crystalline nature of Mo and Si. TEM and XRD show that Si grows amorphous, while Mo clearly crystallizes. The Mo crystallites show no preferred growth orientations and a columnar growth mode, with crystallite sizes limited by the Mo layer thickness. From samples with low Mo content, we show that crystallization of Mo starts directly at the Mo/Si interfaces, with the formation of a MO3Si compound. The crystallite lattice strains that develop during Mo-on-Si growth due to lattice mismatches, will add to the macroscopic multilayer stress. By comparing Mo lattice strains derived from XRD with changes in substrate curvatures, as determined by interferometry, we show that compressive and tensile substrate deformations are predominantly caused by the internal crystallite strains. (c) 2006 Elsevier B.V All rights reserved.