Calibration of polarization-state generators (PSG's), polarimeters, and Mueller-matrix ellipsometers (MME's) is an important factor in the practical use of these instruments. A new general procedure, the eigenvalue calibration method (ECM), is presented. It can calibrate any complete MME consisting of a PSG and a polarimeter that generate and measure, respectively, all the states of polarization of light. In the ECM, the PSG and the polarimeter are described by two 4 x 4 matrices W and A, and their 32 coefficients are determined from three or four measurements performed on reference samples. Those references are smooth isotropic samples and perfect linear polarizers. Their optical characteristics are unambiguously determined during the calibration from the eigenvalues of the measured matrices. The ECM does not require accurate alignment of the various optical elements and does not involve any first-order approximation. The ECM also displays an efficient error control capability that can be used to improve the MME behavior. The ECM is illustrated by an experimental calibration, at two wavelengths (458 and 633 nm), of a MME consisting of a coupled phase modulator associated with a prism division-of-amplitude polarimeter.

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