Matthew F. Chisholm

Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy

Direct imaging and chemical identification of all the atoms in a material with unknown three-dimensional structure would constitute a very powerful general analysis tool. Transmission electron microscopy should in principle be able to fulfil this role, as many scientists including Feynman realized early on. It images matter with electrons that scatter strongly from individual atoms and whose wavelengths are about 50 times smaller than an atom. Recently the technique has advanced greatly owing to the introduction of aberration-corrected optics. However, neither electron microscopy nor any other experimental technique has yet been able to resolve and identify all the atoms in a non-periodic material consisting of several atomic species. Here we show that annular dark-field imaging in an aberration-corrected scanning transmission electron microscope optimized for low voltage operation can resolve and identify the chemical type of every atom in monolayer hexagonal boron nitride that contains substitutional defects. Three types of atomic substitutions were found and identified: carbon substituting for boron, carbon substituting for nitrogen, and oxygen substituting for nitrogen. The substitutions caused in-plane distortions in the boron nitride monolayer of about 0.1 Å magnitude, which were directly resolved, and verified by density functional theory calculations. The results demonstrate that atom-by-atom structural and chemical analysis of all radiation-damage-resistant atoms present in, and on top of, ultra-thin sheets has now become possible.

Deformation of electrodeposited nanocrystalline nickel

The mechanisms of deformation and damage evolution in electrodeposited, fully dense, nanocrystalline Ni with an average grain size of ~30 nm and a narrow grain size distribution were investigated by recourse to (i) tensile tests performed in situ in the transmission electron microscope and (ii) microscopic observations made at high resolution following ex situ deformation induced by compression, rolling and nanoindentation. Particular attention was also devoted to the characterization of the structure in grain interiors and in the vicinity of grain boundaries at Angstromlevel resolution in the as-deposited material and following compression, and to the real-time video-imaging of the evolution of dislocation activity and damage during deformation; these images are presented in this paper and in the web sites provided as supplementary material to this paper. These observations clearly reveal that dislocation-mediated plasticity plays a dominant role in the deformation of nanocrystalline Ni examined in this study. Fracture surface examination confirms dimpled rupture with the scale of the dimples being several times larger than the grain size. Dislocation emission at grain boundaries together with intragranular slip and unaccommodated grain boundary sliding facilitate the nucleation of voids at boundaries and triple junctions. Individual monocrystal ligaments, formed by the growth/linking of these voids, undergo extensive local plasticity to the extent that many of them neck down to a chisel point. These voids as well as those that may have existed prior to deformation can act as nucleation sites for dimples leading to fracture that does not occur preferentially along grain boundaries. The transmission electron microscopy observations of in situ and ex situ deformed specimens are synthesized to formulate a mechanistic framework that provides new insights into the mechanisms of flow and fracture in nanostructured metals.  2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Strong polarization enhancement in asymmetric three-component ferroelectric superlattices

Theoretical predictions—motivated by recent advances in epitaxial engineering—indicate a wealth of complex behaviour arising in superlattices of perovskite-type metal oxides. These include the enhancement of polarization by strain and the possibility of asymmetric properties in three-component superlattices. Here we fabricate superlattices consisting of barium titanate (BaTiO3), strontium titanate (SrTiO3) and calcium titanate (CaTiO3) with atomic-scale control by high-pressure pulsed laser deposition on conducting, atomically flat strontium ruthenate (SrRuO3) layers. The strain in BaTiO3 layers is fully maintained as long as the BaTiO3 thickness does not exceed the combined thicknesses of the CaTiO3 and SrTiO3 layers. By preserving full strain and combining heterointerfacial couplings, we find an overall 50% enhancement of the superlattice global polarization with respect to similarly grown pure BaTiO3, despite the fact that half the layers in the superlattice are nominally non-ferroelectric. We further show that even superlattices containing only single-unit-cell layers of BaTiO3 in a paraelectric matrix remain ferroelectric. Our data reveal that the specific interface structure and local asymmetries play an unexpected role in the polarization enhancement.

ZnO: growth, doping & processing

Abstract A review is given here of recent results in developing improved control of growth, doping, and fabrication processes for ZnO devices with possible applications to ultraviolet (UV) light emitters, spin functional devices, gas sensors, transparent electronics, and surface acoustic wave devices. ZnO can be grown on cheap substrates such as glass at relatively low temperatures and may have advantages over the GaN system in some of these applications.

Atomic-resolution chemical analysis using a scanning transmission electron microscope

This corrects the article DOI: 10.1038/366143a0

Ferromagnetism in cobalt-implanted ZnO

The magnetic and structural properties of cobalt-implanted ZnO single crystals are reported. High-quality, (110)-oriented single-crystal Sn-doped ZnO substrates were implanted at ∼350 °C with Co to yield transition metal concentrations of 3–5 at. % in the near-surface (∼2000 A) region. After implantation, the samples were subject to a 5 min rapid thermal annealing at 700 °C. Magnetization measurements indicate ferromagnetic behavior, with hysteresis observed in the M vs H behavior at T=5 K. Coercive fields were ⩽100 Oe at this measurement temperature. Temperature-dependent magnetization measurements showed evidence for ordering temperatures of >300 K, although hysteresis in the M vs H behavior was not observed at room temperature. Four-circle x-ray diffraction results indicate the presence of (110)-oriented hexagonal phase Co in the ZnO matrix. From the 2θ full width at half maximum (FWHM) of the Co (110) peak, the nanocrystal size is estimated to be ∼3.5 nm, which is below the superparamagnetic limit at ...

Optical functions of chemical vapor deposited thin‐film silicon determined by spectroscopic ellipsometry

The optical functions of several forms of thin‐film silicon (amorphous Si, fine‐grain polycrystalline Si, and large‐grain polycrystalline Si) grown on oxidized Si have been determined using 2‐channel spectroscopic polarization modulation ellipsometry from 240 to 840 nm (∼1.5–5.2 eV). It is shown that the standard technique for simulating the optical functions of polycrystalline silicon (an effective medium consisting of crystalline Si, amorphous Si, and voids) does not fit the ellipsometry data.

Direct determination of grain boundary atomic structure in SrTiO3

An atomic structure model for a 25� [001] symmetric tilt grain boundary in SrTiO3 has been determined directly from experimental data with the use of high-resolution Z-contrast imaging coupled with electron energy loss spectroscopy. The derived model of the grain boundary was refined by bond-valence sum calculations and reveals candidate sites for dopant atoms in the boundary plane. These results show how the combined techniques can be used to deduce the atomic structure of defects and interfaces without recourse to preconceived structural models or image simulations.

Growth and relaxation mechanisms of YBa2Cu3O7−x films

Abstract Using a combination of Z-contrast scanning transmission electron microscopy, scanning tunneling microscopy, and plan view diffraction contrast imaging, we have studied the growth and relaxation mechanisms of YBa2Cu3O7−x deposited on MgO and SrTiO3 substrates. Two-dimensional island growth occurs on SrTiO3 substrates, with relaxation through the nucleation of dislocation half-loops. The threading dislocation segments then have a screw component and can lead to kinetic roughening through the development of growth pyramids. In contrast, growth on MgO occurs by true three-dimensional island growth (with no wetting layer), most of the interface being incommensurate with the substrate (although crystallographically aligned). Dislocations with both edge and screw components are generated on island coalescence. A highly anisotropic surface energy is shown to be responsible for cell-by-cell c⊥ growth being thermodynamically preferred, although at high supersaturations a transition to a⊥ growth occurs.

Reversible redox reactions in an epitaxially stabilized SrCoO x oxygen sponge

Fast, reversible redox reactions in solids at low temperatures without thermomechanical degradation are a promising strategy for enhancing the overall performance and lifetime of many energy materials and devices. However, the robust nature of the cations oxidation state and the high thermodynamic barrier have hindered the realization of fast catalysis and bulk diffusion at low temperatures. Here, we report a significant lowering of the redox temperature by epitaxial stabilization of strontium cobaltites (SrCoO(x)) grown directly as one of two distinct crystalline phases, either the perovskite SrCoO(3-δ) or the brownmillerite SrCoO(2.5). Importantly, these two phases can be reversibly switched at a remarkably reduced temperature (200-300 °C) in a considerably short time (< 1 min) without destroying the parent framework. The fast, low-temperature redox activity in SrCoO(3-δ) is attributed to a small Gibbs free-energy difference between two topotatic phases. Our findings thus provide useful information for developing highly sensitive electrochemical sensors and low-temperature cathode materials.