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X-ray spectroscopy is a general term for several spectroscopic techniques for characterization of materials by using x-ray radiation. [1]
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 photoelectric 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 imaging rather than spectroscopy is a main task) and in cheaper and/or portable XRF units.[ citation needed ]
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 the positioning of the sample 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. [2] An example of a spectrometer developed by William Henry Bragg, which was used by both father and son to investigate the structure of crystals, can be seen at the Science Museum, London. [3] 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 [4] 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.
There exist several efficient designs for analyzing an X-ray emission spectrum in the ultra soft X-ray region. The figure of merit for such instruments is the spectral throughput, i.e. the product of detected intensity and spectral resolving power. Usually, it is possible to change these parameters within a certain range while keeping their product constant.
Usually X-ray diffraction in spectrometers is achieved on crystals, but in Grating spectrometers, the X-rays emerging from a sample must pass a source-defining slit, then optical elements (mirrors and/or gratings) disperse them by diffraction according to their wavelength and, finally, a detector is placed at their focal points.
Henry Augustus Rowland (1848–1901) devised an instrument that allowed the use of a single optical element that combines diffraction and focusing: a spherical grating. Reflectivity of X-rays is low, regardless of the used material and therefore, grazing incidence upon the grating is necessary. X-ray beams impinging on a smooth surface at a few degrees glancing angle of incidence undergo external total reflection which is taken advantage of to enhance the instrumental efficiency substantially.
Denoted by R the radius of a spherical grating. Imagine a circle with half the radius R tangent to the center of the grating surface. This small circle is called the Rowland circle. If the entrance slit is anywhere on this circle, then a beam passing the slit and striking the grating will be split into a specularly reflected beam, and beams of all diffraction orders, that come into focus at certain points on the same circle.
Similar to optical spectrometers, a plane grating spectrometer first needs optics that turns the divergent rays emitted by the x-ray source into a parallel beam. This may be achieved by using a parabolic mirror. The parallel rays emerging from this mirror strike a plane grating (with constant groove distance) at the same angle and are diffracted according to their wavelength. A second parabolic mirror then collects the diffracted rays at a certain angle and creates an image on a detector. A spectrum within a certain wavelength range can be recorded simultaneously by using a two-dimensional position-sensitive detector such as a microchannel photomultiplier plate or an X-ray sensitive CCD chip (film plates are also possible to use).
Instead of using the concept of multiple beam interference that gratings produce, the two rays may simply interfere. By recording the intensity of two such co-linearly at some fixed point and changing their relative phase one obtains an intensity spectrum as a function of path length difference. One can show that this is equivalent to a Fourier transformed spectrum as a function of frequency. The highest recordable frequency of such a spectrum is dependent on the minimum step size chosen in the scan and the frequency resolution (i.e. how well a certain wave can be defined in terms of its frequency) depends on the maximum path length difference achieved. The latter feature allows a much more compact design for achieving high resolution than for a grating spectrometer because x-ray wavelengths are small compared to attainable path length differences.
Philips Gloeilampen Fabrieken, headquartered in Eindhoven in the Netherlands, got its start as a manufacturer of light bulbs, but quickly evolved until it is now one of the leading manufacturers of electrical apparatus, electronics, and related products including X-ray equipment. It also has had one of the world's largest R&D labs. In 1940, the Netherlands was overrun by Hitler’s Germany. The company was able to transfer a substantial sum of money to a company that it set up as an R&D laboratory in an estate in Irvington on the Hudson in NY. As an extension to their work on light bulbs, the Dutch company had developed a line of X-ray tubes for medical applications that were powered by transformers. These X-ray tubes could also be used in scientific X-ray instrumentations, but there was very little commercial demand for the latter. As a result, management decided to try to develop this market and they set up development groups in their research labs in both Holland and the United States.
They hired Dr. Ira Duffendack, a professor at University of Michigan and a world expert on infrared research to head the lab and to hire a staff. In 1951 he hired Dr. David Miller as Assistant Director of Research. Dr. Miller had done research on X-ray instrumentation at Washington University in St. Louis. Dr. Duffendack also hired Dr. Bill Parish, a well known researcher in X-ray diffraction, to head up the section of the lab on X-ray instrumental development. X-ray diffraction units were widely used in academic research departments to do crystal analysis. An essential component of a diffraction unit was a very accurate angle measuring device known as a goniometer. Such units were not commercially available, so each investigator had do try to make their own. Dr Parrish decided this would be a good device to use to generate an instrumental market, so his group designed and learned how to manufacture a goniometer. This market developed quickly and, with the readily available tubes and power supplies, a complete diffraction unit was made available and was successfully marketed.
The U.S. management did not want the laboratory to be converted to a manufacturing unit so it decided to set up a commercial unit to further develop the X-ray instrumentation market. In 1953 Norelco Electronics was established in Mount Vernon, NY, dedicated to the sale and support of X-ray instrumentation. It included a sales staff, a manufacturing group, an engineering department and an applications lab. Dr. Miller was transferred from the lab to head up the engineering department. The sales staff sponsored three schools a year, one in Mount Vernon, one in Denver, and one in San Francisco. The week-long school curricula reviewed the basics of X-ray instrumentation and the specific application of Norelco products. The faculty were members of the engineering department and academic consultants. The schools were well attended by academic and industrial R&D scientists. The engineering department was also a new product development group. It added an X-ray spectrograph to the product line very quickly and contributed other related products for the next 8 years.
The applications lab was an essential sales tool. When the spectrograph was introduced as a quick and accurate analytical chemistry device, it was met with widespread skepticism. All research facilities had a chemistry department and analytical analysis was done by “wet chemistry” methods. The idea of doing this analysis by physics instrumentation was considered suspect. To overcome this bias, the salesman would ask a prospective customer for a task the customer was doing by “wet methods”. The task would be given to the applications lab and they would demonstrate how accurately and quickly it could be done using the X-ray units. This proved to be a very strong sales tool, particularly when the results were published in the Norelco Reporter, a technical journal issued monthly by the company with wide distribution to commercial and academic institutions.
An X-ray spectrograph consists of a high voltage power supply (50 kV or 100 kV), a broad band X-ray tube, usually with a tungsten anode and a beryllium window, a specimen holder, an analyzing crystal, a goniometer, and an X-ray detector device. These are arranged as shown in Fig. 1.
The continuous X-spectrum emitted from the tube irradiates the specimen and excites the characteristic spectral X-ray lines in the specimen. Each of the 92 elements emits a characteristic spectrum. Unlike the optical spectrum, the X-ray spectrum is quite simple. The strongest line, usually the Kalpha line, but sometimes the Lalpha line, suffices to identify the element. The existence of a particular line betrays the existence of an element, and the intensity is proportional to the amount of the particular element in the specimen. The characteristic lines are reflected from a crystal, the analyzer, under an angle that is given by the Bragg condition. The crystal samples all the diffraction angles theta by rotation, while the detector rotates over the corresponding angle 2-theta. With a sensitive detector, the X-ray photons are counted individually. By stepping the detectors along the angle, and leaving it in position for a known time, the number of counts at each angular position gives the line intensity. These counts may be plotted on a curve by an appropriate display unit. The characteristic X-rays come out at specific angles, and since the angular position for every X-ray spectral line is known and recorded, it is easy to find the sample's composition.
A chart for a scan of a Molybdenum specimen is shown in Fig. 2. The tall peak on the left side is the characteristic alpha line at a two theta of 12 degrees. Second and third order lines also appear.
Since the alpha line is often the only line of interest in many industrial applications, the final device in the Norelco X- ray spectrographic instrument line was the Autrometer. This device could be programmed to automatically read at any desired two theta angle for any desired time interval.
Soon after the Autrometer was introduced, Philips decided to stop marketing X-ray instruments developed in both the U.S. and Europe and settled on offering only the Eindhoven line of instruments.
In 1961, during the development of the Autrometer, Norelco was given a sub-contract from the Jet Propulsion Lab. The Lab was working on the instrument package for the Surveyor spaceship. The composition of the Moon’s surface was of major interest and the use of an X-ray detection instrument was viewed as a possible solution. Working with a power limit of 30 watts was very challenging, and a device was delivered but it wasn’t used. Later NASA developments did lead to an X-ray spectrographic unit that did make the desired moon soil analysis.
The Norelco efforts faded but the use of X-ray spectroscopy in units known as XRF instruments continued to grow. With a boost from NASA, units were finally reduced to handheld size and are seeing widespread use. Units are available from Bruker, Thermo Scientific, Elvatech Ltd. and SPECTRA.
Spectroscopy is the field of study that measures and interprets electromagnetic spectra. In narrower contexts, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum.
An optical spectrometer is an instrument used to measure properties of light over a specific portion of the electromagnetic spectrum, typically used in spectroscopic analysis to identify materials. The variable measured is most often the irradiance of the light but could also, for instance, be the polarization state. The independent variable is usually the wavelength of the light or a closely derived physical quantity, such as the corresponding wavenumber or the photon energy, in units of measurement such as centimeters, reciprocal centimeters, or electron volts, respectively.
X-ray fluorescence (XRF) is the emission of characteristic "secondary" X-rays from a material that has been excited by being bombarded with high-energy X-rays or gamma rays. The phenomenon is widely used for elemental analysis and chemical analysis, particularly in the investigation of metals, glass, ceramics and building materials, and for research in geochemistry, forensic science, archaeology and art objects such as paintings.
The emission spectrum of a chemical element or chemical compound is the spectrum of frequencies of electromagnetic radiation emitted due to electrons making a transition from a high energy state to a lower energy state. The photon energy of the emitted photons is equal to the energy difference between the two states. There are many possible electron transitions for each atom, and each transition has a specific energy difference. This collection of different transitions, leading to different radiated wavelengths, make up an emission spectrum. Each element's emission spectrum is unique. Therefore, spectroscopy can be used to identify elements in matter of unknown composition. Similarly, the emission spectra of molecules can be used in chemical analysis of substances.
Absorption spectroscopy is spectroscopy that involves techniques that measure the absorption of electromagnetic radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is performed across the electromagnetic spectrum.
A synchrotron light source is a source of electromagnetic radiation (EM) usually produced by a storage ring, for scientific and technical purposes. First observed in synchrotrons, synchrotron light is now produced by storage rings and other specialized particle accelerators, typically accelerating electrons. Once the high-energy electron beam has been generated, it is directed into auxiliary components such as bending magnets and insertion devices in storage rings and free electron lasers. These supply the strong magnetic fields perpendicular to the beam that are needed to stimulate the high energy electrons to emit photons.
In many areas of science, Bragg's law, Wulff–Bragg's condition, or Laue–Bragg interference are a special case of Laue diffraction, giving the angles for coherent scattering of waves from a large crystal lattice. It describes how the superposition of wave fronts scattered by lattice planes leads to a strict relation between the wavelength and scattering angle. This law was initially formulated for X-rays, but it also applies to all types of matter waves including neutron and electron waves if there are a large number of atoms, as well as visible light with artificial periodic microscale lattices.
Fluorescence spectroscopy is a type of electromagnetic spectroscopy that analyzes fluorescence from a sample. It involves using a beam of light, usually ultraviolet light, that excites the electrons in molecules of certain compounds and causes them to emit light; typically, but not necessarily, visible light. A complementary technique is absorption spectroscopy. In the special case of single molecule fluorescence spectroscopy, intensity fluctuations from the emitted light are measured from either single fluorophores, or pairs of fluorophores.
A monochromator is an optical device that transmits a mechanically selectable narrow band of wavelengths of light or other radiation chosen from a wider range of wavelengths available at the input. The name is from the Greek roots mono-, "single", and chroma, "colour", and the Latin suffix -ator, denoting an agent.
Wavelength-dispersive X-ray spectroscopy is a non-destructive analysis technique used to obtain elemental information about a range of materials by measuring characteristic x-rays within a small wavelength range. The technique generates a spectrum in which the peaks correspond to specific x-ray lines and elements can be easily identified. WDS is primarily used in chemical analysis, wavelength dispersive X-ray fluorescence (WDXRF) spectrometry, electron microprobes, scanning electron microscopes, and high precision experiments for testing atomic and plasma physics.
Energy-dispersive X-ray spectroscopy, sometimes called energy dispersive X-ray analysis or energy dispersive X-ray microanalysis (EDXMA), is an analytical technique used for the elemental analysis or chemical characterization of a sample. It relies on an interaction of some source of X-ray excitation and a sample. Its characterization capabilities are due in large part to the fundamental principle that each element has a unique atomic structure allowing a unique set of peaks on its electromagnetic emission spectrum. The peak positions are predicted by the Moseley's law with accuracy much better than experimental resolution of a typical EDX instrument.
An electron microprobe (EMP), also known as an electron probe microanalyzer (EPMA) or electron micro probe analyzer (EMPA), is an analytical tool used to non-destructively determine the chemical composition of small volumes of solid materials. It works similarly to a scanning electron microscope: the sample is bombarded with an electron beam, emitting x-rays at wavelengths characteristic to the elements being analyzed. This enables the abundances of elements present within small sample volumes to be determined, when a conventional accelerating voltage of 15-20 kV is used. The concentrations of elements from lithium to plutonium may be measured at levels as low as 100 parts per million (ppm), material dependent, although with care, levels below 10 ppm are possible. The ability to quantify lithium by EPMA became a reality in 2008.
Gamma-ray spectroscopy is the qualitative study of the energy spectra of gamma-ray sources, such as in the nuclear industry, geochemical investigation, and astrophysics. Gamma-ray spectrometry, on the other hand, is the method used to acquire a quantitative spectrum measurement.
Ultrafast laser spectroscopy is a category of spectroscopic techniques using ultrashort pulse lasers for the study of dynamics on extremely short time scales. Different methods are used to examine the dynamics of charge carriers, atoms, and molecules. Many different procedures have been developed spanning different time scales and photon energy ranges; some common methods are listed below.
X-ray optics is the branch of optics that manipulates X-rays instead of visible light. It deals with focusing and other ways of manipulating the X-ray beams for research techniques such as X-ray crystallography, X-ray fluorescence, small-angle X-ray scattering, X-ray microscopy, X-ray phase-contrast imaging, and X-ray astronomy.
The Extreme Ultraviolet Explorer was a NASA space telescope for ultraviolet astronomy. EUVE was a part of NASA's Explorer spacecraft series. Launched on 7 June 1992. With instruments for ultraviolet (UV) radiation between wavelengths of 7 and 76 nm, the EUVE was the first satellite mission especially for the short-wave ultraviolet range. The satellite compiled an all-sky survey of 801 astronomical targets before being decommissioned on 31 January 2001.
Rigaku Corporation is an international manufacturer and distributor of scientific, analytical and industrial instrumentation specializing in X-ray related technologies, including X-ray crystallography, X-ray diffraction (XRD), X-ray reflectivity, X-ray fluorescence (XRF), automation, cryogenics and X-ray optics.
Resonant inelastic X-ray scattering (RIXS) is an advanced X-ray spectroscopy technique.
A spectrometer is a scientific instrument used to separate and measure spectral components of a physical phenomenon. Spectrometer is a broad term often used to describe instruments that measure a continuous variable of a phenomenon where the spectral components are somehow mixed. In visible light a spectrometer can separate white light and measure individual narrow bands of color, called a spectrum. A mass spectrometer measures the spectrum of the masses of the atoms or molecules present in a gas. The first spectrometers were used to split light into an array of separate colors. Spectrometers were developed in early studies of physics, astronomy, and chemistry. The capability of spectroscopy to determine chemical composition drove its advancement and continues to be one of its primary uses. Spectrometers are used in astronomy to analyze the chemical composition of stars and planets, and spectrometers gather data on the origin of the universe.
X-ray emission spectroscopy (XES) is a form of X-ray spectroscopy in which a core electron is excited by an incident x-ray photon and then this excited state decays by emitting an x-ray photon to fill the core hole. The energy of the emitted photon is the energy difference between the involved electronic levels. The analysis of the energy dependence of the emitted photons is the aim of the X-ray emission spectroscopy.
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