Nanoscale LiZnN - Luminescent Half-Heusler Quantum Dots.

Colloidal semiconductor quantum dots are a well-established technology, with numerous materials available either commercially or through the vast body of literature. The prevalent materials are cadmium-based and are unlikely to find general acceptance in most applications. While the III-V family of materials is a likely substitute, issues remain about its long-term suitability, and other earth-abundant materials are being explored. In this report, we highlight a nanoscale half-Heusler semiconductor, LiZnN, composed of readily available elements as a potential alternative system to luminescent II-VI and III-V nanoparticle quantum dots.

Quantifying oxygen distortions in lithium-rich transition-metal-oxide cathodes using ABF STEM.

Lithium-rich cathodes can store excess charge beyond the transition metal redox capacity by participation of oxygen in reversible anionic redox reactions. Although these processes are crucial for achieving high energy densities, their structural origins are not yet fully understood. Here, we explore the use of annular bright-field (ABF) imaging in scanning transmission electron microscopy (STEM) to measure oxygen distortions in charged Li1.2Ni0.2Mn0.6O2. We show that ABF STEM data can provide positional accuracies below 20 pm but this is restricted to cases where no specimen mistilt is present, and only for a range of thicknesses above 3.5 nm. The reliability of these measurements is compromised even when the experimental and post-processing designs are optimised for accuracy and precision, indicating that extreme care must be taken when attempting to quantify distortions in these materials.

Imaging the atomic structure and local chemistry of platelets in natural type Ia diamond.

In the past decades, many efforts have been devoted to characterizing {001} platelet defects in type Ia diamond. It is known that N is concentrated at the defect core. However, an accurate description of the atomic structure of the defect and the role that N plays in it is still unknown. Here, by using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy we have determined the atomic arrangement within platelet defects in a natural type Ia diamond and matched it to a prevalent theoretical model. The platelet has an anisotropic atomic structure with a zigzag ordering of defect pairs along the defect line. The electron energy-loss near-edge fine structure of both carbon K- and nitrogen K-edges obtained from the platelet core is consistent with a trigonal bonding arrangement at interstitial sites. The experimental observations support an interstitial aggregate mode of formation for platelet defects in natural diamond.

Characterisation of the Medipix3 detector for 60 and 80keV electrons.

In this paper we report quantitative measurements of the imaging performance for the current generation of hybrid pixel detector, Medipix3, used as a direct electron detector. We have measured the modulation transfer function and detective quantum efficiency at beam energies of 60 and 80keV. In single pixel mode, energy threshold values can be chosen to maximize either the modulation transfer function or the detective quantum efficiency, obtaining values near to, or exceeding those for a theoretical detector with square pixels. The Medipix3 charge summing mode delivers simultaneous, high values of both modulation transfer function and detective quantum efficiency. We have also characterized the detector response to single electron events and describe an empirical model that predicts the detector modulation transfer function and detective quantum efficiency based on energy threshold. Exemplifying our findings we demonstrate the Medipix3 imaging performance recording a fully exposed electron diffraction pattern at 24-bit depth together with images in single pixel and charge summing modes. Our findings highlight that for transmission electron microscopy performed at low energies (energies <100keV) thick hybrid pixel detectors provide an advantageous architecture for direct electron imaging.

Wax: A benign hydrogen-storage material that rapidly releases H2-rich gases through microwave-assisted catalytic decomposition.

Hydrogen is often described as the fuel of the future, especially for application in hydrogen powered fuel-cell vehicles (HFCV's). However, its widespread implementation in this role has been thwarted by the lack of a lightweight, safe, on-board hydrogen storage material. Here we show that benign, readily-available hydrocarbon wax is capable of rapidly releasing large amounts of hydrogen through microwave-assisted catalytic decomposition. This discovery offers a new material and system for safe and efficient hydrogen storage and could facilitate its application in a HFCV. Importantly, hydrogen storage materials made of wax can be manufactured through completely sustainable processes utilizing biomass or other renewable feedstocks.

Assessing the precision of strain measurements using electron backscatter diffraction--part 1: detector assessment.

We analyse the link between precision of pattern shift measurements and the resolution of the measurement of elastic strain and lattice rotation using high resolution electron backscatter diffraction (HR-EBSD). This study combines analysis of high quality experimentally obtained diffraction patterns from single crystal silicon; high quality dynamical simulations using Bloch wave theory; quantitative measurements of the detector Modulation Transfer Function (MTF) and a numerical model. We have found that increases in exposure time, when 1×1 binning is selected, are the primary reason for the observed increase in sensitivity at greater than 2×2 binning and therefore use of software integration and high bit depth images enables a significant increase in strain resolution. This has been confirmed using simulated diffraction patterns which provide evidence that the ultimate theoretical resolution of the cross correlation based EBSD strain measurement technique with a 1000×1000 pixel image could be as low as 4.2×10(-7) in strain based on a shift precision of 0.001 pixels.

Assessing the precision of strain measurements using electron backscatter diffraction--part 2: experimental demonstration.

The residual impression after performing a microhardness indent in silicon has been mapped with high resolution EBSD to reveal residual elastic strain and lattice rotation fields. Mapping of the same area has been performed with variable pattern binning and exposure times to reveal the qualitative and quantitative differences resulting from reducing the pattern size and exposure time. Two dimension 'image' plots of these fields indicate that qualitative assessment of the shape and size of the fields can be performed with as much as 4×4 binning. However, quantitative assessment using line scans reveals that the smoothest profile can be obtained using minimal pattern binning and long exposure times. To compare and contrast with these experimental maps, finite element analysis has been performed using a continuum damage-plasticity material law which has been independently calibrated to Si [9]. The constitutive law incorporates isotropic hardening in compression, and isotropic hardening and damage in tension. To accurately capture the localised damage which develops during indentation via the nucleation and propagation of cracks around the indentation site cohesive elements were assigned along the interfaces between the planes which experience the maximum traction. The residual strain state around the indenter and the size of the cracks agree very well with the experimentally measured value.

Recording low and high spatial frequencies in exit wave reconstructions.

Aberration corrected Transmission Electron Microscope (TEM) images can currently resolve information at significantly better than 0.1 nm. Aberration corrected imaging conditions seek to optimize the transfer of high-resolution information but in doing so they prevent the transfer of low spatial frequency information. To recover low spatial frequency information, aberration corrected images must be acquired at a large defocus which compromises high spatial frequency information transfer. In this paper we present two a posteriori solutions to this problem in which the information bandwidth in an exit wave reconstruction is increased. In the first we reconstruct the electron exit wavefunction from two focal series datasets, with different, uniform focal steps, experimentally demonstrating that the width of the transfer interval can be extended from 0.2 nm⁻¹ (∼5 nm) to better than 10 nm⁻¹ (0.1 nm). In the second we outline the use of a focal series recorded with a non-uniform focal step to recover a wider range of spatial frequencies without the need for a large number of images. Using simulated data we show that using this non-uniform focal step the spatial frequency interval for a five image data set may be increased to between 0.25 nm⁻¹ (4 nm) and 8.3 nm⁻¹ (0.12 nm) compared to between 0.74 nm⁻¹ (1.4 nm) and 8.3 nm⁻¹ (0.12 nm) for the standard focal series geometry.

Optimized conditions for imaging the effects of bonding charge density in electron microscopy.

We report on the observability of valence bonding effects in aberration-corrected high resolution electron microscopy (HREM) images along the [010] projection of the mineral Forsterite (Mg2SiO4). We have also performed exit wave restorations using simulated noisy images and have determined that both the intensities of individual images and the modulus of the restored complex exit wave are most sensitive to bonding effects at a level of 25% for moderately thick samples of 20-25 nm. This relatively large thickness is due to dynamical amplification of bonding contrast arising from partial de-channeling of 1s states. Simulations also suggest that bonding contrast is similarly high for an un-corrected conventional electron microscope, implying an experimental limitation of signal to noise ratio rather than spatial resolution.

Aberration measurement using the Ronchigram contrast transfer function.

The bright field contrast transfer function is one of the most useful concepts in conventional transmission electron microscopy. However, the electron Ronchigram contrast transfer function, as derived by Cowley, is inherently more complicated since it is not isoplanatic. Here, we derive a local contrast transfer function for small patches in a Ronchigram and demonstrate its utility for the direct measurement of aberrations from single Ronchigrams of an amorphous film. We describe the measurement of aberrations from both simulated and experimental images and elucidate the effects due to higher-order aberrations, separating those arising from the pre- and post-sample optics, and partial coherence.

Transformations of gold nanoparticles investigated using variable temperature high-resolution transmission electron microscopy.

Recently designed advanced in-situ specimen holders for transmission electron microscopy (TEM) have been used in studies of gold nanoparticles. We report results of variable temperature TEM experiments in which structural transformations have been correlated with specimen temperature, allowing general trends to be identified. Transformation to a decahedral morphology for particles in the size range 5-12nm was observed for the majority of particles regardless of their initial structure. Following in-situ annealing, decahedra were found to be stable at room temperature, confirming this as the equilibrium morphology, in agreement with recently calculated phase diagrams. Other transitions at low temperature in addition to surface roughening have also been observed and correlated with the same nanoscale phase diagram. Investigations of gold particles at high temperature have revealed evidence for co-existing solid and liquid phases. Overall, these results are important in a more precise understanding of the structure and action of catalytic gold nanoparticles and in the experimental verification of theoretical calculations.

Effect of amorphous layers on the interpretation of restored exit waves.

The effects of amorphous layers on the quality of exit wave restorations have been investigated. Two independently developed software implementations for exit wave restoration have been used to simulated focal series of images of <001> SrTiO3 with amorphous carbon layers incorporated. The restored exit waves have been compared both qualitatively and quantitatively. We have shown that amorphous layers have a strong impact on the quantitative measurements of atomic column positions, however, the error in the position measurements is still in the picometer range.

Three-dimensional imaging in double aberration-corrected scanning confocal electron microscopy, part II: inelastic scattering.

The implementation of spherical aberration-corrected pre- and post-specimen lenses in the same instrument has facilitated the creation of sub-Angstrom electron probes and has made aberration-corrected scanning confocal electron microscopy (SCEM) possible. Further to the discussion of elastic SCEM imaging in our previous paper, we show that by performing a 3D raster scan through a crystalline sample using inelastic SCEM imaging it will be possible to determine the location of isolated impurity atoms embedded within a bulk matrix. In particular, the use of electron energy loss spectroscopy based on inner-shell ionization to uniquely identify these atoms is explored. Comparisons with scanning transmission electron microscopy (STEM) are made showing that SCEM will improve both the lateral and depth resolution relative to STEM. In particular, the expected poor resolution of STEM depth sectioning for extended objects is overcome in the SCEM geometry.

Three-dimensional imaging in double aberration-corrected scanning confocal electron microscopy, part I: elastic scattering.

A transmission electron microscope fitted with both pre-specimen and post-specimen spherical aberration correctors enables the possibility of aberration-corrected scanning confocal electron microscopy. Imaging modes available in this configuration can make use of either elastically or inelastically scattered electrons. In this paper we consider image contrast for elastically scattered electrons. It is shown that there is no linear phase contrast in the confocal condition, leading to very low contrast for a single atom. Multislice simulations of a thicker crystalline sample show that sample vertical location and thickness can be accurately determined. However, buried impurity layers do not give strong, nor readily interpretable contrast. The accompanying paper examines the detection of inelastically scattered electrons in the confocal geometry.

Imaging modes for scanning confocal electron microscopy in a double aberration-corrected transmission electron microscope.

Aberration correction leads to reduced focal depth of field in the electron microscope. This reduced depth of field can be exploited to probe specific depths within a sample, a process known as optical sectioning. An electron microscope fitted with aberration correctors for both the pre- and postspecimen optics can be used in a confocal mode that provides improved depth resolution and selectivity over optical sectioning in the scanning transmission electron microscope (STEM). In this article we survey the coherent and incoherent imaging modes that are likely to be used in scanning confocal electron microscopy (SCEM) and provide simple expressions to describe the images that result. Calculations compare the depth response of SCEM to optical sectioning in the STEM. The depth resolution in a crystalline matrix is also explored by performing a Bloch wave calculation for the SCEM geometry in which the pre- and postspecimen optics are defocused away from their confocal conditions.

Ultrahigh resolution imaging of local structural distortions in intergrowth tungsten bronzes.

Details of the local structure of a complex tungsten bronze, K(x)WO(3) have been determined using focal series exit wave reconstruction. Octahedral rotations in different structural regions of the same crystal have been directly measured from the exit wave phase and correlated with variations in cation occupancy determined from the exit wave modulus.

HREM of the [111] surfaces of iron oxide nanoparticles.

Mixed phase Fe3O4-gamma-Fe2O3 (magnetite-maghemite) iron oxide nanoparticles have been fabricated by colloidal routes. HRTEM/HRSTEM images of the nanoparticles show the presence of [111] facets that terminate with enhanced contrast, which is shown to be caused by the presence of additional cations at the edges of the nanoparticles. HRTEM images were taken on a FEI CM200 FEGTEM, a JEOL 3100 with a LaB6 source, and a double aberration corrected JEOL-JEM 2200FS FEGTEM. The enhanced contrast effect was observed on the [111] surface atomic layers resolved using each machine. HRSTEM images, taken on an aberration corrected STEM, resolved enhanced contrast at specific surface sites. Exit wave reconstruction was also carried out on focal series taken on a double aberration corrected JEOL-JEM 2200FS and showed similar highly resolved enhanced contrast at specific surface cation sites. It is apparent that additional cations are occupying the [111] terminating layers of these nanoparticle surfaces. The use of different microscopes and techniques in this paper provides strong evidence that the enhanced contrast is a real effect and not an effect caused by microscope aberrations.

On the importance of fifth-order spherical aberration for a fully corrected electron microscope.

Next generation aberration correctors will not only eliminate the third-order spherical aberration, but also improve the information limit by correction of chromatic aberration. As a result of these improvements, higher order aberrations, which have largely been neglected in image analysis, will become important. In this paper, we concern ourselves with situations where sub-A resolution can be achieved, and where the third-order spherical aberration is corrected and the fifth-order spherical aberration is measurable. We derive formulae to explore the maximum value of the fifth-order spherical aberration for directly interpretable imaging and discuss the optimum imaging conditions and their applicable range.

Hot STM of nanostructure dynamics on SrTiO(3)(001).

The dynamics of nanostructured surface phases on SrTiO(3)(001) have been analysed using in situ scanning tunnelling microscopy (STM) above 800 degrees C. During high-temperature annealing, the formation, growth and ordering of the nanostructures has been observed. Dilines, with a width of approximately 1 nm, are formed from a TiO(2)-rich intermediary at 800 degrees C. STM during annealing at 825 degrees C has enabled us to follow both the growth and dissolution of dilines. Following extended annealing, trilines with a width of approximately 2 nm and ordered two-dimensional (2D) nano-arrays form from the diline domains. Our observations of diline dissolution implies random nucleation and growth, followed by rearrangement at elevated temperature to form domains.