Thomas Slater

Annual Review of Materials Research Volume 45, Page 171-193, July 2015

Annual Review of Materials Research Volume 45, Page 85-109, July 2015

Summary

Lay Description

Publication date: June 2015
Source:Micron, Volume 73
Author(s): D.R.G. Mitchell
Modern scanning transmission electron microscopy (STEM) enables imaging and microanalysis at very high magnification. In the case of aberration-corrected STEM, atomic resolution is readily achieved. However, the electron fluxes used may be up to three orders of magnitude greater than those typically employed in conventional STEM. Since specimen contamination often increases with electron flux, specimen cleanliness is a critical factor in obtaining meaningful data when carrying out high magnification STEM. A range of different specimen cleaning methods have been applied to a variety of specimen types. The contamination rate has been measured quantitatively to assess the effectiveness of cleaning. The methods studied include: baking, cooling, plasma cleaning, beam showering and UV/ozone exposure. Of the methods tested, beam showering is rapid, experimentally convenient and very effective on a wide range of specimens. Oxidative plasma cleaning is also very effective and can be applied to specimens on carbon support films, albeit with some care. For electron beam-sensitive materials, cooling may be the method of choice. In most cases, preliminary removal of the bulk of the contamination by methods such as baking or plasma cleaning, followed by beam showering, where necessary, can result in a contamination-free specimen suitable for extended atomic scale imaging and analysis.

Publication date: April 2015
Source:Ultramicroscopy, Volume 151
Author(s): Seiji Takeda , Yasufumi Kuwauchi , Hideto Yoshida
Atomic resolution has been obtained using environmental transmission electron microscopy (ETEM) by installing a spherical aberration corrector (Cs-corrector) on the objective lens. Simultaneously, the technology for controlling the environment around a specimen in ETEM has advanced significantly in the past decade. Quantification methodology has recently been established for deriving relevant experimental data in catalyst materials from substantial and systematic ETEM observation at the atomic scale. With this background, this paper summarizes aspects of the evolutional microscopy technique: necessary conditions for atomic resolution in ETEM; reduction of the scattering of electrons by the medium surrounding a specimen; and an environmental cell for structural imaging of a crystalline specimen. The high spatial resolution of a Cs-corrected ETEM is demonstrated for different observation conditions. After statistical analysis combined with numerical image analysis of ETEM data is briefly described, the recent applications of the Cs-corrected ETEM to catalyst materials are reviewed. For gold nanoparticulate catalysts, the structural information on the reaction sites and adsorption sites are deduced. For Pt nanoparticulate catalysts, ETEM studies elucidate the correlation between the catalytic activity and the morphology of the nanoparticles. These studies also reveal oxidation and reduction on the topmost Pt surface layer at the atomic scale. Finally, current issues and the future perspectives of Cs-corrected ETEM are summarized, including the reproducibility of ETEM observation data, the control of environments, the critical evaluation of electron irradiation effects, the full implementation of transmission electron microscopy technology in ETEM, and the safety issues for an ETEM laboratory.

Publication date: August 2015
Source:Progress in Materials Science, Volume 73
Author(s): Ankur Gupta, Tamilselvan Sakthivel, Sudipta Seal
Discovery of graphene and its astonishing properties have given birth to a new class of materials known as “2D materials”. Motivated by the success of graphene, alternative layered and non-layered 2D materials have become the focus of intense research due to their unique physical and chemical properties. Origin of these properties ascribed to the dimensionality effect and modulation in their band structure. This review highlights the recent progress of the state-of-the-art research on synthesis, characterization and isolation of single and few layer nanosheets and their assembly. Electronic, magnetic, optical and mechanical properties of 2D materials have also been reviewed for their emerging applications in the area of catalysis, electronic, optoelectronic and spintronic devices; sensors, high performance electrodes and nanocomposites. Finally this review concludes with a future prospective to guide this fast evolving class of 2D materials in next generation materials science.

Publication date: January 2015
Source:Micron, Volume 68
Author(s): S. Helveg , C.F. Kisielowski , J.R. Jinschek , P. Specht , G. Yuan , H. Frei
Transmission electron microscopy (TEM) has become an indispensable technique for studying heterogeneous catalysts. In particular, advancements of aberration-corrected electron optics and data acquisition schemes have made TEM capable of delivering images of catalysts with sub-Ångström resolution and single-atom sensitivity. Parallel developments of differentially pumped electron microscopes and of gas cells enable in situ observations of catalysts during the exposure to reactive gas environments at pressures of up to atmospheric levels and temperatures of up to several hundred centigrade. Here, we outline how to take advantage of the emerging state-of-the-art instrumentation and methodologies to study surface structures and dynamics to improve the understanding of structure-sensitive catalytic functionality. The concept of using low electron dose-rates in TEM in conjunction with in-line holography and aberration-correction at low voltage (80kV) is introduced to allow maintaining atomic resolution and sensitivity during in situ observations of catalysts. Benefits are illustrated by exit wave reconstructions of TEM images of a nanocrystalline Co3O4 catalyst material acquired in situ during their exposure to either a reducing or oxidizing gas environment.

Publication date: June 2015
Source:Ultramicroscopy, Volume 153
Author(s): R. Colby , D.H. Alsem , A. Liyu , B. Kabius
Environmental transmission electron microscopy (TEM) has enabled in situ experiments in a gaseous environment with high resolution imaging and spectroscopy. Addressing scientific challenges in areas such as catalysis, corrosion, and geochemistry can require pressures much higher than the ∼20mbar achievable with a differentially pumped environmental TEM. Gas flow stages, in which the environment is contained between two semi-transparent thin membrane windows, have been demonstrated at pressures of several atmospheres. However, the relationship between the pressure at the sample and the pressure drop across the system is not clear for some geometries. We demonstrate a method for measuring the gas pressure at the sample by measuring the ratio of elastic to inelastic scattering and the defocus of the pair of thin windows. This method requires two energy filtered high-resolution TEM images that can be performed during an ongoing experiment, at the region of interest. The approach is demonstrated to measure greater than atmosphere pressures of N2 gas using a commercially available gas-flow stage. This technique provides a means to ensure reproducible sample pressures between different experiments, and even between very differently designed gas-flow stages.

Nature Materials. doi:10.1038/nmat4205

Authors: F. Withers, O. Del Pozo-Zamudio, A. Mishchenko, A. P. Rooney, A. Gholinia, K. Watanabe, T. Taniguchi, S. J. Haigh, A. K. Geim, A. I. Tartakovskii & K. S. Novoselov

The advent of graphene and related 2D materials has recently led to a new technology: heterostructures based on these atomically thin crystals. The paradigm proved itself extremely versatile and led to rapid demonstration of tunnelling diodes with negative differential resistance, tunnelling transistors, photovoltaic devices and so on. Here, we take the complexity and functionality of such van der Waals heterostructures to the next level by introducing quantum wells (QWs) engineered with one atomic plane precision. We describe light-emitting diodes (LEDs) made by stacking metallic graphene, insulating hexagonal boron nitride and various semiconducting monolayers into complex but carefully designed sequences. Our first devices already exhibit an extrinsic quantum efficiency of nearly 10% and the emission can be tuned over a wide range of frequencies by appropriately choosing and combining 2D semiconductors (monolayers of transition metal dichalcogenides). By preparing the heterostructures on elastic and transparent substrates, we show that they can also provide the basis for flexible and semi-transparent electronics. The range of functionalities for the demonstrated heterostructures is expected to grow further on increasing the number of available 2D crystals and improving their electronic quality.

Publication date: April 2015
Source:Ultramicroscopy, Volume 151
Author(s): N.R. Lugg , G. Kothleitner , N. Shibata , Y. Ikuhara
Chemical mapping using energy dispersive X-ray spectroscopy (EDS) in scanning transmission electron microscopy (STEM) has recently shown to be a powerful technique in analyzing the elemental identity and location of atomic columns in materials at atomic resolution. However, most applications of EDS STEM have been used only to qualitatively map whether elements are present at specific sites. Obtaining calibrated EDS STEM maps so that they are on an absolute scale is a difficult task and even if one achieves this, extracting quantitative information about the specimen – such as the number or density of atoms under the probe – adds yet another layer of complexity to the analysis due to the multiple elastic and inelastic scattering of the electron probe. Quantitative information may be obtained by comparing calibrated EDS STEM with theoretical simulations, but in this case a model of the structure must be assumed a priori. Here we first theoretically explore how exactly elastic and thermal scattering of the probe confounds the quantitative information one is able to extract about the specimen from an EDS STEM map. We then show using simulation how tilting the specimen (or incident probe) can reduce the effects of scattering and how it can provide quantitative information about the specimen. We then discuss drawbacks of this method – such as the loss of atomic resolution along the tilt direction – but follow this with a possible remedy: precession averaged EDS STEM mapping.

To visualize water in the catalyst of polymer electrolyte fuel cells (PEFCs), backscattered electron (BSE) imaging by means of scanning electron microscopy was employed. To confine a wet specimen of catalyst, an environmental wet cell was manufactured with a silicon nitride thin film (~100 nm) as the beam window. By supplying humidified gas into the cell, a change in BSE brightness was detected in the catalyst attached to the silicon nitride window. As humidification proceeded, the BSE image became darker and returned brighter by switching to a dry gas. Monte Carlo simulations were performed to evaluate the energy and number of BSE obtained after passing through water with thickness d. Combining the results of the Monte Carlo simulation successfully converted the change in brightness to the change in thickness from d = 100 nm to d = 3 μm. This established method of evaluating water with a thickness resolution of the order of d = 100 nm can be applied to in situ observations of the catalyst in a PEFC during operation.

Summary

Summary

Nature Materials. doi:10.1038/nmat4105

Authors: Jun Sun, Longbing He, Yu-Chieh Lo, Tao Xu, Hengchang Bi, Litao Sun, Ze Zhang, Scott X. Mao & Ju Li

In nanotechnology, small-volume metals with large surface area are used as electrodes, catalysts, interconnects and antennae. Their shape stability at room temperature has, however, been questioned. Using in situ high-resolution transmission electron microscopy, we find that Ag nanoparticles can be deformed like a liquid droplet but remain highly crystalline in the interior, with no sign of dislocation activity during deformation. Surface-diffusion-mediated pseudoelastic deformation is evident at room temperature, which can be driven by either an external force or capillary-energy minimization. Atomistic simulations confirm that such highly unusual Coble pseudoelasticity can indeed happen for sub-10-nm Ag particles at room temperature and at timescales from seconds to months.

Adding only a few atoms or changing the capping ligand can dramatically change the structure of individual metal nanoparticles. Azubel et al. used aberration-corrected transmission – [Read More]

Moiré method in scanning transmission electron microscopy allows observing a magnified two-dimensional atomic column elemental map of a higher pixel resolution with a lower electron dose unlike conventional atomic column mapping. The magnification of the map is determined by the ratio between the pixel size and the lattice spacing. With proper ratios for the x and y directions, we could observe magnified elemental maps, homothetic to the atomic arrangement in the sample of SrTiO₃ [0 0 1]. The map showed peaks at all expected oxygen sites in SrTiO₃ [0 0 1].

Nature advance online publication 30 July 2014. doi:10.1038/nature13661

Authors: Sabine Conrad, Markus Renninger, Jörg Hennenlotter, Tina Wiesner, Lothar Just, Michael Bonin, Wilhelm Aicher, Hans-Jörg Bühring, Ulrich Mattheus, Andreas Mack, Hans-Joachim Wagner, Stephen Minger, Matthias Matzkies, Michael Reppel, Jürgen Hescheler, Karl-Dietrich Sievert, Arnulf Stenzl & Thomas Skutella

Metallic alloy nanoparticles (NPs) are synthesized in situ in an environmental transmission electron microscope. Atomic level characterization of the formed alloy NPs is carried out at synthesis conditions by use of high-resolution transmission electron microscopy, electron diffraction and electron energy-loss spectroscopy.

The prevention of bacterial infections in the health care environment is paramount to providing better treatment. Covering a susceptible environment with an antimicrobial coating is a successful way to avoid bacterial growth. Research on the preparation of durable antimicrobial coatings is promising for both fundamental surface care and clinical care applications. Herein, we report a facile, efficient, and scalable preparation of MoO 3 paint using a cost-effective ball-milling approach. The MoO 3 nanoplates (synthesized by thermal decomposition of ammonium heptamolybdate) are used as a pigment and antibacterial activity moiety in alkyd resin binders and other suitable eco-friendly additives in the preparation of paint. Surface morphology, chemical states, bonding nature, and intermolecular interaction between the MoO 3 and the alkyd resin were studied using Raman and x-ray photoelectron spectroscopic analysis. The antibacterial properties of a prepar...

We demonstrate a new approach to plasmonic enhanced photocatalytic water splitting by developing a novel core-shell Ti@TiO 2 brush nanostructure where an elongated Ti nanorod forms a plasmonic core that concentrates light inside of a nanotubular anodic TiO 2 shell. Following the ubiquitous element approach aimed at providing an enhanced device functionality without the usage of noble or rare earth elements, we utilized only inexpensive Ti to create a complex Ti@TiO 2 nanostructure with an enhanced UV and Vis photocatalytic activity that emerges from the interplay between the surface plasmon resonance in the Ti core, Vis light absorption in the Ti-rich oxide layer at the Ti/TiO 2 interface and UV light absorption in the nanotubular TiO 2 shell.

Investigations on the dynamic behavior of molecules in liquids at high spatial resolution are greatly desired because localized regions, such as solid–liquid interfaces or sites of reacting molecules, have assumed increasing importance with respect to improving material performance. In application to liquids, electron energy loss spectroscopy (EELS) observed with transmission electron microscopy (TEM) is a promising analytical technique with the appropriate resolutions. In this study, we obtained EELS spectra from an ionic liquid, 1-ethyl-3-methylimidazolium bis (trifluoromethyl-sulfonyl) imide (C₂mim-TFSI), chosen as the sampled liquid, using monochromated scanning TEM (STEM). The molecular vibrational spectrum and the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of the liquid were investigated. The HOMO–LUMO gap measurement coincided with that obtained from the ultraviolet–visible spectrum. A shoulder in the spectrum observed ~0.4 eV is believed to originate from the molecular vibration. From a separately performed infrared observation and first-principles calculations, we found that this shoulder coincided with the vibrational peak attributed to the C–H stretching vibration of the [C₂mim⁺] cation. This study demonstrates that a vibrational peak for a liquid can be observed using monochromated STEM–EELS, and leads one to expect observations of chemical reactions or aids in the analysis of the dynamic behavior of molecules in liquid.

Abstract

We investigated the single exciton and multiple exciton generation (MEG) behavior in Ag₇ and single Cu atom-doped Ag₇ quantum clusters using ab initio. MEG is observed for the first time in metal clusters. The results indicate that multiple excitons appear in the visible and near ultraviolet light ranges. Single excitations are main contribution for the optical spectra, while the multiple excitons merely contribute for some peaks at the higher energies. However, occurrence of MEG enhances the optical absorption in Ag₇ cluster. The optical spectrum of pure Ag₇ cluster obtained using the symmetry-adapted cluster theory with configuration interaction, and time-dependent density functional theory is in excellent agreement with experiment spectrum. As observed in both single Cu atom-doped Ag₇ clusters, redshifts and suppressions of the MEG-related absorption peaks are observed compared with pure Ag₇ cluster.

Abstract

To investigate the shell deposited kinetics, CdSe quantum dots (QDs) and nanorods (NRs) with a maximum length of 17 nm were fabricated via organic synthesis routes. CdSe with a hexagonal crystal structure (wurtzite) favors epitaxial growth on the {002} surfaces when well-controlled conditions were used. The morphologies and sizes of CdSe samples depended strongly on chemicals and temperature. In the case of 320 °C, CdSe NRs with adjusted length of 7–17 nm were obtained from trioctylphosphine oxide (TOPO) and tetradecylphosphonic acid (TDPA). In contrast, short CdSe NRs (less than 10 nm) were created from octadecylphosphonic acid (ODPA) and trioctylamine (TOA). Spherical CdSe QDs were further fabricated using stearic acid (SA) and TOPO at 300 °C. CdSe cores were coated with Cd_0.5Zn_0.5S and CdTe shells. Anisotropic growth occurred during shell deposition because CdS shells grown preferentially on the {001} facet of the CdSe core. In the case of CdSe core prepared from TOPO and TDPA, CdSe/Cd_0.5Zn_0.5S core/shell samples prepared from long CdSe NRs (more than 10 nm) revealed a peanut morphology while the core/shell samples created from short ones (less than 10 nm) exhibited a spherical morphology. All of the CdSe/Cd_0.5Zn_0.5S core/shell samples revealed a similar length to that of the CdSe cores. This phenomenon was also observed for the core/shell samples fabricated using CdSe NRs prepared by ODPA and TOA. This is ascribed to the well-developed crystal structure of CdSe NRs fabricated using an organic synthesis at high temperature. In contrast, this anisotropic growth did not occur when spherical CdSe QDs prepared from SA and TOPO and the shell (Cd_0.5Zn_0.5S) coating carried out using SA and TOA. To indicate the shell depositing process, CdSe NRs fabricated using TDPA and TOPO were coated with a CdTe shell. CdTe monomers were deposited on the middle and tip parts of the CdSe NRs to form a tetrapod-like morphology at 220 °C. This is ascribed to the large difference of structure of CdSe (hexagonal) and CdTe (zinc blende).

Summary