Electron energy-loss spectroscopy (EELS), energy-filtered transmission electron microscopy (EFTEM), and high-resolution transmission electron microscopy (HRTEM) have been applied in mineralogy and materials research to determine the oxidation states of various metals at high spatial resolution. Such information is critical in understanding the kinetics and mechanisms of mineral–microbe interactions. To date, the aforementioned techniques have not been applied widely in the study of such interactions. In the present study, the three techniques above were employed to investigate mineral transformations associated with microbial Fe(III) reduction in magnetite. Shewanella putrefaciens strain CN32, a dissimilatory metal-reducing bacterium, was incubated with magnetite as the sole electron acceptor and lactate as the electron donor for 14 days under anoxic conditions in bicarbonate buffer. The extent of bioreduction was determined by wet chemistry and mineral solids were investigated by HRTEM, EFTEM, and EELS. Magnetite was partially reduced and biogenic siderite formed. The elemental maps of Fe, O, and C and red-green-blue (RGB) composite map for residual magnetite and newly formed siderite were contrasted by the EFTEM technique. The HRTEM revealed nm-sized magnetite crystals coating bacterial cells. The Fe oxidation state in residual magnetite and biogenic siderite was determined using the EELS technique (the integral ratio of L3 to L2). The integral ratio of L3 to L2 for magnetite (6.29) and siderite (2.71) corresponded to 71% of Fe(III) in magnetite, and 24% of Fe(III) in siderite, respectively. A chemical shift (~1.9 eV) in the Fe-L3 edge of magnetite and siderite indicated a difference in the oxidation state of Fe between these two minerals. Furthermore, the EELS images of magnetite (709 eV) and siderite (707 eV) were extracted from the electron energy-loss spectra collected, ranging from 675 to 755 eV, displaying different oxidation states of Fe in the magnetite and siderite phases. The results demonstrate that EELS is a powerful technique for studying the Fe oxidation-state change as a result of microbial interaction with Fe-containing minerals.

Energy-filtering transmission electron microscopy (TEM) and bright-field TEM can be used to extract local sample thickness $t$ and to generate two-dimensional sample thickness maps. Electron tomography can be used to accurately verify the local $t$. The relations of log-ratio of zero-loss filtered energy-filtering TEM beam intensity ($I_{{\rm ZLP}}$) and unfiltered beam intensity ($I_{\rm u}$) versus sample thickness $t$ were measured for five values of collection angle in a microscope equipped with an energy filter. Furthermore, log-ratio of the incident (primary) beam intensity ($I_{\rm p}$) and the transmitted beam $I_{{\rm tr}}$ versus $t$ in bright-field TEM was measured utilizing a camera before the energy filter. The measurements were performed on a multilayer sample containing eight materials and thickness $t$ up to 800 nm. Local thickness $t$ was verified by electron tomography. The following results are reported:

• The maximum thickness $t_{{\rm max}}$ yielding a linear relation of log-ratio, $\ln ( {I_{\rm u}}/{I_{{\rm ZLP}}})$ and $\ln ( {I_{\rm p}}/{I_{{\rm tr}}} )$, versus $t$.

• Inelastic mean free path ($\lambda _{{\rm in}}$) for five values of collection angle.

• Total mean free path ($\lambda _{{\rm total}}$) of electrons excluded by an angle-limiting aperture.

• $\lambda _{{\rm in}}$ and $\lambda _{{\rm total}}$ are evaluated for the eight materials with atomic number from $\approx$10 to 79.

The results can be utilized as a guide for upper limit of $t$ evaluation in energy-filtering TEM and bright-field TEM and for optimizing electron tomography experiments.

In the quest for dynamic multimodal probing of a material’s structure and functionality, it is critical to be able to quantify the chemical state on the atomic-/nanoscale using element-specific electronic and structurally sensitive tools such as electron energy-loss spectroscopy (EELS). Ultrafast EELS, with combined energy, time, and spatial resolution in a transmission electron microscope, has recently enabled transformative studies of photoexcited nanostructure evolution and mapping of evanescent electromagnetic fields. This article aims to describe state-of-the-art experimental techniques in this emerging field and its major uses and future applications.

This article highlights recent advances in analytical electron tomography (AET), the three-dimensional (3D) extension of conventional nanoanalytical techniques, in which electron energy loss, x-ray spectroscopy, and electron diffraction are combined with tomographic acquisition and reconstruction. Examples from the literature illustrate how new 3D information, gleaned from AET, provides insights into not just morphology and composition, but also the electronic, chemical, and optical properties of materials at the nanoscale. We describe how the “multidimensional” nature of AET leads to “big data” sets, how these can be analyzed optimally, and how AET may develop further.

The electron energy-loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) database has been completely rewritten, with an improved design, user interface, and a number of new tools. The database is accessible at https://eelsdb.eu/ and can now be used without registration. The submission process has been streamlined to encourage spectrum submissions and the new design gives greater emphasis on contributors’ original work by highlighting their papers. With numerous new filters and a powerful search function, it is now simple to explore the database of several hundred EELS and XAS spectra. Interactive plots allow spectra to be overlaid, facilitating online comparison. An application-programming interface has been created, allowing external tools and software to easily access the information held within the database. In addition to the database itself, users can post and manage job adverts and read the latest news and events regarding the EELS and XAS communities. In accordance with the ongoing drive toward open access data increasingly demanded by funding bodies, the database will facilitate open access data sharing of EELS and XAS spectra.

A method to remove the effects of elastic and thermal diffuse scattering (TDS) of the incident electron probe from electron energy-loss and energy-dispersive X-ray spectroscopy data for atomically resolved spectrum images of single crystals of known thickness is presented. By calculating the distribution of the probe within a specimen of known structure, it is possible to deconvolve the channeling of the probe and TDS from experimental data by reformulating the inelastic cross-section as an inverse problem. In electron energy-loss spectroscopy this allows valid comparisons with first principles fine-structure calculations to be made. In energy-dispersive X-ray spectroscopy, direct compositional analyses such as ζ-factor and Cliff–Lorimer k-factor analysis can be performed without the complications of channeling and TDS. We explore in detail how this method can be incorporated into existing multislice programs, and demonstrate practical considerations in implementing this method using a simulated test specimen. We show the importance of taking into account the scattering of the probe in k-factor analysis in a zone axis orientation. The applicability and limitations of the method are discussed.

Identifying constituent atoms in materials is the ultimate goal for all analytical techniques. Here, we describe the successful achievement of single atom spectroscopy in nanostructured carbon-based materials using a scanning transmission electron microscope equipped with electron energy-loss spectroscopy. The chemical analyis of individual metallofullerene molecules can be successfully performed without massive beam damage. Atom-by-atom spectroscopy of the edge carbon atoms in single layer graphene is also discussed.

The success of the correction of spherical aberration in the electron microscope has revolutionized our view of oxides. This is a very important class of materials that is promising for future applications of some of the most intriguing phenomena in condensed matter physics: colossal magnetoresistance, colossal ionic conductivity, high Tc superconductivity, and ferroelectricity. Understanding the physics underlying such phenomena, especially in low dimensional systems (thin films, interfaces, nanowires, nanoparticles), relies on the availability of techniques capable of looking at these systems in real space and with atomic resolution and even beyond, with single atom sensitivity; in many cases, the system properties depend on minuscule amounts of point defects that alter the material’s properties dramatically. Atomic resolution spectroscopy in the aberration-corrected electron microscope is one of the most powerful techniques available to materials scientists today. This article will briefly review some state-of-the-art applications to oxide materials: from atomic resolution elemental mapping and single atom imaging to applications to real systems, including oxide interfaces and mapping of physical properties such as the spin state of magnetic atoms.

In the scanning transmission electron microscope, multiple signals can be simultaneously collected, including the transmitted and scattered electron signals (bright field and annular dark field or Z-contrast images), along with spectroscopic signals such as inelastically scattered electrons and emitted photons. In the last few years, the successful development of aberration correctors for the electron microscope has transformed the field of electron microscopy, opening up new possibilities for correlating structure to functionality. Aberration correction not only allows for enhanced structural resolution with incident probes into the sub-Ångstrom range, but can also provide greater probe currents to facilitate mapping of intrinsically weak spectroscopic signals at the nanoscale or even the atomic level. In this issue of MRS Bulletin, we illustrate the power of the new generation of electron microscopes with a combination of imaging and spectroscopy. We show the mapping of elemental distributions at atomic resolution and also the mapping of electronic and optical properties at unprecedented spatial resolution, with applications ranging from graphene to plasmonic nanostructures, and oxide interfaces to biology.

Experimental results from the first monochromated and aberration-corrected scanning transmission electron microscope operated at 200 kV are described. The formation of an electron probe with a diameter of less than 0.2 nm at an energy width significantly under 0.3 eV and its planned application to the chemical analysis of nanometer-scale structures in materials science are described. Both energy and spatial resolution will benefit from this: The monochromator improves the energy resolution for studies of energy loss near edge structures. The Cs corrector allows formation of either a smaller probe for a given beam current or yields, at fixed probe size, an enhanced beam current density using a larger condenser aperture. We also point out another advantage of the combination of both components: Increasing the convergence angle by using larger condenser apertures in an aberration-corrected instrument will enlarge the undesirable chromatic focus spread. This in turn influences spatial resolution. The effect of polychromatic probe tails is proportional to the product of convergence angle, chromatic aberration constant, and energy spread. It can thus be compensated for in our new instrument by decreasing the energy width by the same factor as the beam convergence is increased to form a more intense probe. An alternative in future developments might be hardware correction of the chromatic aberration, which could eliminate the chromatic probe spread completely.

Continued scaling of microelectronic devices is demanding that alternatives to SiO2 as the gate dielectric be developed soon. This in turn has placed enormous pressure on the abilities of physical characterization techniques to address critical issues such as film and interface structure and composition, transport properties, and thermal or chemical stability. This article summarizes the strengths and capabilities of four techniques used for the materials characterization of alternative gate dielectrics: scanning transmission electron microscopy (STEM) in conjunction with electron energy-loss spectroscopy (EELS), medium-energy ion scattering (MEIS), infrared-absorption spectroscopy (IRAS), and x-ray photoelectron spectroscopy (XPS). The complementary nature of these techniques has allowed for a detailed picture of the various properties of alternative gate dielectrics, and in particular of the dielectric/silicon interface. Critical issues and features of several important alternative gate dielectrics, ZrO2, AI2O3, Y2O3, and Gd2O3, are explored in light of the well-studied SiO2/Si system.