A method and device that analyzes a sample with a diffractometer that includes a collimated source, a spectrometric detector, and a detection collimator. The sample is irradiated with an incident beam and the detector has a detection plane with multiple physical or virtual pixels. An measured energy spectrum is established for each pixel and each measured energy spectrum is readjusted. The spectrum is expressed as a function of a variable that accounts for the energy of the scattered radiation and an angle of diffraction. The fulfillment of at least one multiple material criterion is verified. Groups of pixels are formed using the results of the verification step, each group corresponding to a layer of material and different groups corresponding to different layers of material, and the spectra are combined by group, during which, for each group, the readjusted spectra for the pixels of the group are combined.