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X-rays with a relatively high energy. These photons are capable of exciting (ejecting) the electrons in the core levels of the material under investigation. The induced excited state relaxes under emission of a X-ray photon with a smaller energy. This emitted light is analysed in a spectrometer. Because the core levels have very different energies for different elements the XRF spectrum contains information on the elemental composition of the sample under investigation.
The lightest element that can be analysed is boron (Z = 5), but usually, it is difficult to quantify elements lighter than sodium (Z = 11).
There are two types of spectrometer:
It is also possible to create a characteristic secondary X-ray emission with other incident radiation to excite the sample:
The de-excitation also gives ejection of Auger electrons, but the Auger electron spectroscopy (AES) uses an electron beam as primary beam.