X-ray spectroscopy

X-ray spectroscopy is a general term for several spectroscopic techniques for characterization of materials by using x-ray excitation.Fig. 1Fig. 2 X-ray spectroscopy is a general term for several spectroscopic techniques for characterization of materials by using x-ray excitation. When an electron from the inner shell of an atom is excited by the energy of a photon, it moves to a higher energy level. When it returns to the low energy level, the energy which it previously gained by the excitation is emitted as a photon which has a wavelength that is characteristic for the element (there could be several characteristic wavelengths per element). Analysis of the X-ray emission spectrum produces qualitative results about the elemental composition of the specimen. Comparison of the specimen's spectrum with the spectra of samples of known composition produces quantitative results (after some mathematical corrections for absorption, fluorescence and atomic number). Atoms can be excited by a high-energy beam of charged particles such as electrons (in an electron microscope for example), protons (see PIXE) or a beam of X-rays (see X-ray fluorescence, or XRF or also recently in transmission XRT). These methods enable elements from the entire periodic table to be analysed, with the exception of H, He and Li.In electron microscopy an electron beam excites X-rays; there are two main techniques for analysis of spectra of characteristic X-ray radiation: energy-dispersive X-ray spectroscopy (EDS) and wavelength dispersive X-ray spectroscopy (WDS). In X-Ray Transmission (XRT), the equivalent atomic composition (Zeff) is captured based on photo electric and Compton effects. In an energy-dispersive X-ray spectrometer, a semiconductor detector measures energy of incoming photons. To maintain detector integrity and resolution it should be cooled with liquid nitrogen or by Peltier cooling. EDS is widely employed in electron microscopes (where not spectroscopy but imaging is a main task) and in cheaper and/or portable XRF units. In a wavelength-dispersive X-ray spectrometer, a single crystal diffracts the photons according to Bragg's law, which are then collected by a detector. By moving the diffraction crystal and detector relative to each other, a wide region of the spectrum can be observed. To observe a large spectral range, three of four different single crystals may be needed. In contrast to EDS, WDS is a method of sequential spectrum acquisition. While WDS is slower than EDS and more sensitive to positioning specimen in the spectrometer, it has superior spectral resolution and sensitivity. WDS is widely used in microprobes (where X-ray microanalysis is the main task) and in XRF; it is widely used in the field of x ray diffraction to calculate various data such as interplanar spacing and wavelength of the incident x ray using Bragg's law. The father-and-son scientific team of William Lawrence Bragg and William Henry Bragg, who were 1915 Nobel Prize Winners, were the original pioneers in developing X-ray emission spectroscopy. Jointly they measured the X-ray wavelengths of many elements to high precision, using high-energy electrons as excitation source. The cathode ray tube or an x-ray tube was the method used to pass electrons through a crystal of numerous elements. They also painstakingly produced numerous diamond-ruled glass diffraction gratings for their spectrometers. The law of diffraction of a crystal is called Bragg's law in their honor. Intense and wavelength-tunable X-rays are now typically generated with synchrotrons. In a material, the X-rays may suffer an energy loss compared to the incoming beam. This energy loss of the re-emerging beam reflects an internal excitation of the atomic system, an X-ray analogue to the well-known Raman spectroscopy that is widely used in the optical region. In the X-ray region there is sufficient energy to probe changes in the electronic state (transitions between orbitals; this is in contrast with the optical region, where the energy loss is often due to changes in the state of the rotational or vibrational degrees of freedom). For instance, in the ultra soft X-ray region (below about 1 keV), crystal field excitations give rise to the energy loss. The photon-in-photon-out process may be thought of as a scattering event. When the x-ray energy corresponds to the binding energy of a core-level electron, this scattering process is resonantly enhanced by many orders of magnitude. This type of X-ray emission spectroscopy is often referred to as resonant inelastic X-ray scattering (RIXS). Due to the wide separation of orbital energies of the core levels, it is possible to select a certain atom of interest. The small spatial extent of core level orbitals forces the RIXS process to reflect the electronic structure in close vicinity of the chosen atom. Thus, RIXS experiments give valuable information about the local electronic structure of complex systems, and theoretical calculations are relatively simple to perform.