Scanning transmission X-ray microscopy

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STXM image of pod-like carbon nanotube decorated with Fe nanoparticles (red). Fe-decorated carbon nanotube.jpg
STXM image of pod-like carbon nanotube decorated with Fe nanoparticles (red).

Scanning transmission X-ray microscopy (STXM) is a type of X-ray microscopy in which a zone plate focuses an X-ray beam onto a small spot, a sample is scanned in the focal plane of the zone plate and the transmitted X-ray intensity is recorded as a function of the sample position. A stroboscopic scheme is used where the excitation is the pump and the synchrotron X-ray flashes are the probe. X-ray microscopes work by exposing a film or charged coupled device detector to detect X-rays that pass through the specimen. The image formed is of a thin section of specimen. Newer X-ray microscopes use X-ray absorption spectroscopy to heterogeneous materials at high spatial resolution. The essence of the technique is a combination of spectromicroscopy, imaging with spectral sensitivity, and microspectroscopy, recording spectra from very small spots. [2]

Contents

Benefits of STXM

Radiation damage

Electron energy loss spectroscopy (EELS) in combination with transmission electron microscopy has modest spectral resolution and is rather damaging to the sample material. STXM with variable X-ray energy gives high spectral resolution. Radiation damage effects are typically two orders of magnitude lower than for EELS. Radiation concerns are also relevant with organic materials. [3]

Samples with water

Unlike other methods such as electron microscopy, the spectra samples with water and carbon can be obtained. STXM run at atmospheric pressure allows for convenient sample installation and fewer restrictions on sample preparation. Cells have even been built which can examine hydrated precipitates and solutions. [3]

Operation

In order to obtain spectromicroscopy data the following operating procedure is followed. The desired monochromator grating is selected along with photon energy in the middle of NEXAFS range. Refocus mirrors are adjusted to put the beam into the microscope and steered to maximize the flux passing through the zone plate. A pinhole is placed in the photon beam upstream in a transverse position to maximize transmission. Pinhole size is determined by demagnification to the size of the diffraction limit of the zone plate lens. An undersized pinhole is often used to reduce intensity which controls radiation damage. The order sorting aperture is positioned to eliminate transmission of unfocused zero order light, which would blur the image. Then an x/y line scan is defined across an intensity variation in the image. The x/y line scans are repeated with varying focus conditions. Adsorption spectra can also be obtained with a stationary photon spot. [3]

Applications

Quantitative polymer analysis

STXM has been used to study reinforce filler particles used in molded compressed polyurethane foams in the automotive and fishing industries to achieve higher load bearing capability. Two types of polymers, copolymer styrene and acrylonitrile (SAN) and aromatic-carbamate rich poly-isocyanate poly-addition (PIPA), are chemically indistinguishable by transmission electron spectroscopy. With NEXAFS, spectra of SAN and PIPA absorb strongly at 285.0 eV associated with the phenyl groups of the aromatic filler particles and thus show the same electron spectroscopy image. Only SAN has a strong absorption at 286.7 eV due to the acrylonitrile component. NEXAFS can be a quick and reliable means to differentiate chemical species at a sub-micron spatial scale. [3]

Distribution of macromolecular subcomponents of biofilm cells and matrix

STXM which uses near-edge X-ray absorption spectroscopy is able to be applied to fully hydrated biological molecules due to the ability of X-rays to penetrate water. Soft X-rays also provide spatial resolution better than 50 nm which is suitable for bacterial and bacterial microfilms. With this, quantitative chemical mapping at a spatial scale below 50 nm may be achieved. Soft X-rays also interact with almost all elements and allow mapping of chemical species based on bonding structure. STXM allows for study of a variety of questions regarding the nature, distribution, and role of protein, carbohydrate, lipid, and nucleic acid in biofilms, especially in the extracellular matrix. The study of these biofilms is useful for environmental remediation applications. [4]

Related Research Articles

Microscopy The viewing of objects which are too small to be seen with the naked eye

Microscopy is the technical field of using microscopes to view objects and areas of objects that cannot be seen with the naked eye. There are three well-known branches of microscopy: optical, electron, and scanning probe microscopy, along with the emerging field of X-ray microscopy.

Microscope Scientific instrument

A microscope is a laboratory instrument used to examine objects that are too small to be seen by the naked eye. Microscopy is the science of investigating small objects and structures using a microscope. Microscopic means being invisible to the eye unless aided by a microscope.

Spectroscopy Study involving matter and electromagnetic radiation

Spectroscopy is the study of the interaction between matter and electromagnetic radiation as a function of the wavelength or frequency of the radiation. In simpler terms, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum; indeed, historically, spectroscopy originated as the study of the wavelength dependence of the absorption by gas phase matter of visible light dispersed by a prism. Matter waves and acoustic waves can also be considered forms of radiative energy, and recently gravitational waves have been associated with a spectral signature in the context of the Laser Interferometer Gravitational-Wave Observatory (LIGO).

Cathodoluminescence

Cathodoluminescence is an optical and electromagnetic phenomenon in which electrons impacting on a luminescent material such as a phosphor, cause the emission of photons which may have wavelengths in the visible spectrum. A familiar example is the generation of light by an electron beam scanning the phosphor-coated inner surface of the screen of a television that uses a cathode ray tube. Cathodoluminescence is the inverse of the photoelectric effect, in which electron emission is induced by irradiation with photons.

Raman spectroscopy

Raman spectroscopy ; is a spectroscopic technique typically used to determine vibrational modes of molecules, although rotational and other low-frequency modes of systems may also be observed. Raman spectroscopy is commonly used in chemistry to provide a structural fingerprint by which molecules can be identified.

Electron energy loss spectroscopy

In electron energy loss spectroscopy (EELS) a material is exposed to a beam of electrons with a known, narrow range of kinetic energies. Some of the electrons will undergo inelastic scattering, which means that they lose energy and have their paths slightly and randomly deflected. The amount of energy loss can be measured via an electron spectrometer and interpreted in terms of what caused the energy loss. Inelastic interactions include phonon excitations, inter- and intra-band transitions, plasmon excitations, inner shell ionizations, and Cherenkov radiation. The inner-shell ionizations are particularly useful for detecting the elemental components of a material. For example, one might find that a larger-than-expected number of electrons comes through the material with 285 eV less energy than they had when they entered the material. This is approximately the amount of energy needed to remove an inner-shell electron from a carbon atom, which can be taken as evidence that there is a significant amount of carbon present in the sample. With some care, and looking at a wide range of energy losses, one can determine the types of atoms, and the numbers of atoms of each type, being struck by the beam. The scattering angle can also be measured, giving information about the dispersion relation of whatever material excitation caused the inelastic scattering.

Energy-dispersive X-ray spectroscopy analytical technique used for the elemental analysis or chemical characterization of a sample

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.

Photoemission electron microscopy is a type of electron microscopy that utilizes local variations in electron emission to generate image contrast. The excitation is usually produced by ultraviolet light, synchrotron radiation or X-ray sources. PEEM measures the coefficient indirectly by collecting the emitted secondary electrons generated in the electron cascade that follows the creation of the primary core hole in the absorption process. PEEM is a surface sensitive technique because the emitted electrons originate from a shallow layer. In physics, this technique is referred to as PEEM, which goes together naturally with low-energy electron diffraction (LEED), and low-energy electron microscopy (LEEM). In biology, it is called photoelectron microscopy (PEM), which fits with photoelectron spectroscopy (PES), transmission electron microscopy (TEM), and scanning electron microscopy (SEM).

X-ray microscope

An X-ray microscope uses electromagnetic radiation in the soft X-ray band to produce magnified images of objects. Since X-rays penetrate most objects, there is no need to specially prepare them for X-ray microscopy observations.

X-ray spectroscopy

X-ray spectroscopy is a general term for several spectroscopic techniques for characterization of materials by using x-ray excitation.

Confocal microscopy

Confocal microscopy, most frequently confocal laser scanning microscopy (CLSM) or laser confocal scanning microscopy (LCSM), is an optical imaging technique for increasing optical resolution and contrast of a micrograph by means of using a spatial pinhole to block out-of-focus light in image formation. Capturing multiple two-dimensional images at different depths in a sample enables the reconstruction of three-dimensional structures within an object. This technique is used extensively in the scientific and industrial communities and typical applications are in life sciences, semiconductor inspection and materials science.

Electron microprobe Instrument for the micro-chemical analysis of solids

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.

X-ray nanoprobe

The hard X-ray nanoprobe at the Center for Nanoscale Materials (CNM), Argonne National Lab advanced the state of the art by providing a hard X-ray microscopy beamline with the highest spatial resolution in the world. It provides for fluorescence, diffraction, and transmission imaging with hard X-rays at a spatial resolution of 30 nm or better. A dedicated source, beamline, and optics form the basis for these capabilities. This unique instrument is not only key to the specific research areas of the CNM; it will also be a general utility, available to the broader nanoscience community in studying nanomaterials and nanostructures, particularly for embedded structures.

Soft x-ray microscopy

An X-ray microscope uses electromagnetic radiation in the soft X-ray band to produce images of very small objects.

X-ray absorption near edge structure (XANES), also known as near edge X-ray absorption fine structure (NEXAFS), is a type of absorption spectroscopy that indicates the features in the X-ray absorption spectra (XAS) of condensed matter due to the photoabsorption cross section for electronic transitions from an atomic core level to final states in the energy region of 50–100 eV above the selected atomic core level ionization energy, where the wavelength of the photoelectron is larger than the interatomic distance between the absorbing atom and its first neighbour atoms.

Characterization (materials science)

Characterization, when used in materials science, refers to the broad and general process by which a material's structure and properties are probed and measured. It is a fundamental process in the field of materials science, without which no scientific understanding of engineering materials could be ascertained. The scope of the term often differs; some definitions limit the term's use to techniques which study the microscopic structure and properties of materials, while others use the term to refer to any materials analysis process including macroscopic techniques such as mechanical testing, thermal analysis and density calculation. The scale of the structures observed in materials characterization ranges from angstroms, such as in the imaging of individual atoms and chemical bonds, up to centimeters, such as in the imaging of coarse grain structures in metals.

Chemical imaging is the analytical capability to create a visual image of components distribution from simultaneous measurement of spectra and spatial, time information. Hyperspectral imaging measures contiguous spectral bands, as opposed to multispectral imaging which measures spaced spectral bands.

Raman microscope

The Raman microscope is a laser-based microscopic device used to perform Raman spectroscopy. The term MOLE is used to refer to the Raman-based microprobe. The technique used is named after C. V. Raman who discovered the scattering properties in liquids.

Solaris (synchrotron)

Solaris is the first synchrotron built in Poland, under the auspices of the Jagiellonian University. It is located on the Campus of the 600th Anniversary of the Jagiellonian University Revival, in the southern part of Krakow. It is the central facility of the National Center of Synchrotron Radiation SOLARIS.

References

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  2. Koprinarov, Ivaylo, and Hitchcock, Adam P.. "X-ray Spectromicroscopy of Polymers: An introduction for the non-specialist".
  3. 1 2 3 4 Warwick, T.; Franck, K.; Kortright, J. B.; Meigs, G.; Moronne, M.; Myneni, S.; Rotenberg, E.; Seal, S.; Steele, W. F.; Ade, H.; Garcia, A.; Cerasari, S.; Denlinger, J.; Hayakawa, S.; Hitchcock, A. P.; Tyliszczak, T.; Kikuma, J.; Rightor, E. G.; Shin, H.-J.; Tonner, B. P. (1998). "A scanning transmission x-ray microscope for materials science spectromicroscopy at the advanced light source" (PDF). Review of Scientific Instruments. 69 (8): 2964. Bibcode:1998RScI...69.2964W. doi:10.1063/1.1149041. hdl: 2027.42/71051 .
  4. Lawrence, J. R.; Swerhone, G. D. W.; Leppard, G. G.; Araki, T.; Zhang, X.; West, M. M.; Hitchcock, A. P. (2003). "Scanning Transmission X-Ray, Laser Scanning, and Transmission Electron Microscopy Mapping of the Exopolymeric Matrix of Microbial Biofilms". Applied and Environmental Microbiology. 69 (9): 5543–54. doi:10.1128/AEM.69.9.5543-5554.2003. PMC   194976 . PMID   12957944.