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Residual stresses influence most physical properties of thin films and are closely related to their microstructure. Among the most widely used methods, X-ray diffraction is the only one allowing the determination of both the mechanical and microstructural state of each diffracting phase. Diffracting planes are used as a strain gauge to measure elastic strains in one or several directions of the diffraction vector. Important information on the thin-film microstructure may also be extracted from the width of the diffraction peaks: in particular, the deconvolution of these peaks allows values of coherently diffracting domain size and microdistortions to be obtained. The genesis of residual stresses in thin films results from multiple mechanisms. Stresses may be divided into three major types: epitaxic stresses, thermal stresses and intrinsic stresses. Diffraction methods require the knowledge of the thin-film elastic constants, which may differ from the bulk-material values as a result of the particular microstructure. Combining an X-ray diffractometer with a tensile tester, it is possible to determine X-ray elastic constants of each diffracting phase in a thin-film/substrate system, in particular the Poisson ratio and the Young modulus. It is important to notice that numerous difficulties relative to the application of diffraction methods may arise in the case of thin films.