Wavelength-dispersive X-ray spectroscopy is based on known principles of how the characteristic x-rays are generated by a sample and how the x-rays are measured.
X-ray measurement
According to Bragg's law, when an X-ray beam of wavelength "λ" strikes the surface of a crystal at an angle "Θ" and the crystal has atomic lattice planes a distance "d" apart, then constructive interference will result in a beam of diffracted x-rays that will be emitted from the crystal at angle "Θ" if
- nλ = 2d sin Θ, where n is an integer.[1]
This means that a crystal with a known lattice size will deflect a beam of x-rays from a specific type of sample at a pre-determined angle. The x-ray beam can be measured by placing a detector (usually a scintillation counter or a proportional counter) in the path of the deflected beam and, since each element has a distinctive x-ray wavelength, multiple elements can be determined by having multiple crystals and multiple detectors.[1]
To improve accuracy the x-ray beams are usually collimated by parallel copper blades called a Söller collimator. The single crystal, the specimen, and the detector are mounted precisely on a goniometer with the distance between the specimen and the crystal equal to the distance between the crystal and the detector. It is usually operated under vacuum to reduce the absorption of soft radiation (low-energy photons) by the air and thus increase the sensitivity for the detection and quantification of light elements (between boron and oxygen). The technique generates a spectrum with peaks corresponding to x-ray lines. This is compared with reference spectra to determine the elemental composition of the sample.[2]
As the atomic number of the element increases so there are more possible electrons at different energy levels that can be ejected resulting in x-rays with different wavelengths. This creates spectra with multiple lines, one for each energy level. The largest peak in the spectrum is labelled Kα, the next Kβ, and so on.