D. L. Sales

Aberration-corrected scanning transmission electron microscopy: from atomic imaging and analysis to solving energy problems.

The new possibilities of aberration-corrected scanning transmission electron microscopy (STEM) extend far beyond the factor of 2 or more in lateral resolution that was the original motivation. The smaller probe also gives enhanced single atom sensitivity, both for imaging and for spectroscopy, enabling light elements to be detected in a Z-contrast image and giving much improved phase contrast imaging using the bright field detector with pixel-by-pixel correlation with the Z-contrast image. Furthermore, the increased probe-forming aperture brings significant depth sensitivity and the possibility of optical sectioning to extract information in three dimensions. This paper reviews these recent advances with reference to several applications of relevance to energy, the origin of the low-temperature catalytic activity of nanophase Au, the nucleation and growth of semiconducting nanowires, and the origin of the eight orders of magnitude increased ionic conductivity in oxide superlattices. Possible future directions of aberration-corrected STEM for solving energy problems are outlined.

Column-by-column compositional mapping by Z-contrast imaging.

A phenomenological method is developed to determine the composition of materials, with atomic column resolution, by analysis of integrated intensities of aberration-corrected Z-contrast scanning transmission electron microscopy images. The method is exemplified for InAs(x)P(1-x) alloys using epitaxial thin films with calibrated compositions as standards. Using this approach we have determined the composition of the two-dimensional wetting layer formed between self-assembled InAs quantum wires on InP(001) substrates.

Molecular beam epitaxy of GaBiAs on (311)B GaAs substrates

We report the growth by molecular beam epitaxy of GaBixAs1−x epilayers on (311)B GaAs substrates. We use high-resolution x-ray diffraction (HRXRD), transmission electron microscopy, and Z-contrast imaging to characterize the structural properties of the as-grown material. We find that the incorporation of Bi into the GaBiAs alloy, as determined by HRXRD, is sizably larger in the (311)B epilayers than in (001) epilayers, giving rise to reduced band-gap energies as obtained by optical transmission spectroscopy.

Simulation of high angle annular dark field scanning transmission electron microscopy images of large nanostructures

High angle annular dark field scanning transmission electron microscopy (HAADF-STEM) is a powerful tool to quantify size, shape, position, and composition of nano-objects with the assessment of image simulation. Due to the high computational requirements needed, nowadays it can only be applied to a few unit cells in standard computers. To overpass this limitation, a parallel software (SICSTEM) has been developed. This software can afford HAADF-STEM image simulations of nanostructures composed of several hundred thousand atoms in manageable time. The usefulness of this tool is exemplified by simulating a HAADF-STEM image of an InAs nanowire.

Bismuth incorporation and the role of ordering in GaAsBi/GaAs structures

The structure and composition of single GaAsBi/GaAs epilayers grown by molecular beam epitaxy were investigated by optical and transmission electron microscopy techniques. Firstly, the GaAsBi layers exhibit two distinct regions and a varying Bi composition profile in the growth direction. In the lower (25 nm) region, the Bi content decays exponentially from an initial maximum value, while the upper region comprises an almost constant Bi content until the end of the layer. Secondly, despite the relatively low Bi content, CuPtB-type ordering was observed both in electron diffraction patterns and in fast Fourier transform reconstructions from high-resolution transmission electron microscopy images. The estimation of the long-range ordering parameter and the development of ordering maps by using geometrical phase algorithms indicate a direct connection between the solubility of Bi and the amount of ordering. The occurrence of both phase separation and atomic ordering has a significant effect on the optical properties of these layers.PACS78.55.Cr III-V semiconductors; 68.55.Nq composition and phase identification; 68.55.Ln defects and impurities: doping, implantation, distribution, concentration, etc; 64.75.St phase separation and segregation in

Distribution of bismuth atoms in epitaxial GaAsBi

The distribution of Bi atoms in epitaxial GaAs(1−x)Bix is analyzed through aberration-corrected Z-contrast images. The relation between the atomic number and the intensity of the images allows quantifying the distribution of Bi atoms in this material. A bidimensional map of Bi atoms is extracted showing areas where nanoclustering is possible and evidencing the location of Bi at As-substitutional positions in the lattice. The distribution of Bi atoms differs from a random spatial pattern of Bi atoms in the material.

Incorporation of Sb in InAs∕GaAs quantum dots

The formation of a quaternary InGaAsSb alloy is shown to occur in the core of epitaxial GaSb capped InAs∕GaAs quantum dots emitting at 1.3μm. The existence of the four constituent elements is demonstrated by using spatially resolved low-loss electron energy loss spectroscopy and aberration-corrected high angle annular dark field scanning transmission electron microscopy. The intermixing process giving rise to the formation of this quaternary alloy takes place despite the large miscibility gap between InAs and GaSb binary compounds, and is probably driven by the existence of strain in the quantum dots.

Independent tuning of electron and hole confinement in InAs/GaAs quantum dots through a thin GaAsSbN capping layer

The possibility of an independent tuning of the electron and hole confinement in InAs/GaAs quantum dots (QDs) by using a thin GaAsSbN capping layer (CL) is studied. By controlling the Sb and N contents in the quaternary alloy, the band structure of the QDs can be broadly tuned and converted from type-II in the valence band (high Sb contents) to type-I and to type-II in the conduction band (high N contents). Nevertheless, the simultaneous presence of Sb and N is found to induce strain and composition inhomogeneities in the CL and to degrade the photoluminescence of the structure.

High efficient luminescence in type-II GaAsSb-capped InAs quantum dots upon annealing

The photoluminescence efficiency of GaAsSb-capped InAs/GaAs type II quantum dots (QDs) can be greatly enhanced by rapid thermal annealing while preserving long radiative lifetimes which are ∼20 times larger than in standard GaAs-capped InAs/GaAs QDs. Despite the reduced electron-hole wavefunction overlap, the type-II samples are more efficient than the type-I counterparts in terms of luminescence, showing a great potential for device applications. Strain-driven In-Ga intermixing during annealing is found to modify the QD shape and composition, while As-Sb exchange is inhibited, allowing to keep the type-II structure. Sb is only redistributed within the capping layer giving rise to a more homogeneous composition.

Calculation of integrated intensities in aberration-corrected Z-contrast images

Inclusion of spatial incoherence has been shown to give quantitative agreement between non-aberration-corrected high-angle annular dark-field scanning transmission electron microscopy images and theoretical simulations. Here we show that, using the same approach, a significant improvement in the correlation between calculated and experimental normalized integrated intensities is obtained in the InAsP ternary semiconductor alloy, but residual discrepancies remain. We have demonstrated, in good agreement with experimental intensities obtained in calibrated samples, that normalized integrated intensities show a low dependence on the sample thickness over a wide range of thickness values. This behaviour does not occur in conventional (non-aberration-corrected) images and constitutes a powerful tool for straightforward interpretation of high-resolution images in terms of atomic column-resolved compositional maps.