Joanne Etheridge

A Fast Deposition‐Crystallization Procedure for Highly Efficient Lead Iodide Perovskite Thin‐Film Solar Cells

Thin-film photovoltaics based on alkylammonium lead iodide perovskite light absorbers have recently emerged as a promising low-cost solar energy harvesting technology. To date, the perovskite layer in these efficient solar cells has generally been fabricated by either vapor deposition or a two-step sequential deposition process. We report that flat, uniform thin films of this material can be deposited by a one-step, solvent-induced, fast crystallization method involving spin-coating of a DMF solution of CH3NH3PbI3 followed immediately by exposure to chlorobenzene to induce crystallization. Analysis of the devices and films revealed that the perovskite films consist of large crystalline grains with sizes up to microns. Planar heterojunction solar cells constructed with these solution-processed thin films yielded an average power conversion efficiency of 13.9±0.7% and a steady state efficiency of 13% under standard AM 1.5 conditions.

Scattering of Å-scale electron probes in silicon

We use frozen phonon multislice calculations to examine the scattering behaviour of A-scale electron probes in <001> and <110> silicon. For each crystal orientation, we consider the distribution of scattered intensity in real space as a function of crystal thickness, probe size and probe position. The scattered intensity distribution is found to vary drastically for different probe sizes. For a given probe size, the scattered intensity distribution is also significantly influenced by the crystal orientation. We discuss the implications for the simultaneous acquisition of an annular dark-field image and electron energy loss spectra in the scanning transmission electron microscope, with specific reference to the spatial resolution with which electron energy loss spectra can be related to local atomic structure.

Optical, Structural, and Numerical Investigations of GaAs/AlGaAs Core–Multishell Nanowire Quantum Well Tubes

The electronic properties of thin, nanometer scale GaAs quantum well tubes embedded inside the AlGaAs shell of a GaAs core-multishell nanowire are investigated using optical spectroscopies. Using numerical simulations to model cylindrically and hexagonally symmetric systems, we correlate these electronic properties with structural characterization by aberration-corrected scanning transmission electron microscopy of nanowire cross sections. These tubular quantum wells exhibit extremely high quantum efficiency and intense emission for extremely low submicrowatt excitation powers in both photoluminescence and photoluminescence excitation measurements. Numerical calculations of the confined eigenstates suggest that the electrons and holes in their ground states are confined to extremely localized one-dimensional filaments at the corners of the hexagonal structure which extend along the length of the nanowire.

Enhanced minority carrier lifetimes in GaAs/AlGaAs core-shell Nanowires through shell growth optimization

The effects of AlGaAs shell thickness and growth time on the minority carrier lifetime in the GaAs core of GaAs/AlGaAs core-shell nanowires grown by metal-organic chemical vapor deposition are investigated. The carrier lifetime increases with increasing AlGaAs shell thickness up to a certain value as a result of reducing tunneling probability of carriers through the AlGaAs shell, beyond which the carrier lifetime reduces due to the diffusion of Ga-Al and/or impurities across the GaAs/AlGaAs heterointerface. Interdiffusion at the heterointerface is observed directly using high-angle annular dark field scanning transmission electron microscopy. We achieve room temperature minority carrier lifetimes of 1.9 ns by optimizing the shell growth with the intention of reducing the effect of interdiffusion.

The bonding electron density in aluminum

A combination of microscopy and first-principle calculations is used to study the bonding charge density in aluminum. Aluminum is considered to approach an “ideal” metal or free electron gas. The valence electrons move freely, as if unaffected by the presence of the metal ions. Therefore, the electron redistribution due to chemical bonding is subtle and has proven extremely difficult to determine. Experimental measurements and ab initio calculations have yielded substantially different results. We applied quantitative convergent-beam electron diffraction to aluminum to provide an experimental determination of the bonding electron distribution. Calculation of the electron distribution based on density functional theory is shown to be in close agreement. Our results yield an accurate quantitative correlation between the anisotropic elastic properties of aluminum and the bonding electron and electrostatic potential distributions.

Polarity-driven 3-fold symmetry of GaAs/AlGaAs core multishell nanowires

AlGaAs/GaAs quantum well heterostructures based on core-multishell nanowires exhibit excellent optical properties which are acutely sensitive to structure and morphology. We characterize these heterostructures and observe them to have 3-fold symmetry about the nanowire axis. Using aberration-corrected annular dark field scanning transmission electron microscopy (ADF-STEM), we measure directly the polarity of the crystal structure and correlate this with the shape and facet orientation of the GaAs core, quantum wells and cap, and the width of radial Al-rich bands. We discuss how the underlying polarity of the crystal structure drives the growth of these heterostructures with a 3-fold symmetry resulting in a nonuniform GaAs quantum well tube and AlGaAs shell. These observations suggest that the AlGaAs growth rate is faster along the [112] B compared to the [112] A directions and/or that there is a polarity driven surface reconstruction generating AlGaAs growth fronts inclined to the {110} planes. In contrast, the observations suggest that the opposite is true for the GaAs growth, with the preferred surface reconstruction plane being parallel to {110} and an apparent faster growth rate along the [112] A. This two-dimensional layer growth of the nanowire multishells strongly depends on the surface energies and surface reconstruction of the facets which are related to the crystal polarity and lead to the 3-fold symmetry observed here.

Sub-0.1 nm-resolution quantitative scanning transmission electron microscopy without adjustable parameters

Atomic-resolution imaging in the scanning transmission electron microscope (STEM) constitutes a powerful tool for nanostructure characterization. Here, we demonstrate the quantitative interpretation of atomic-resolution high-angle annular dark-field (ADF) STEM images using an approach that does not rely on adjustable parameters. We measure independently the instrumental parameters that affect sub-0.1 nm-resolution ADF images, quantify their individual and collective contributions to the image intensity, and show that knowledge of these parameters enables a quantitative interpretation of the absolute intensity and contrast across all accessible spatial frequencies. The analysis also provides a method for the in-situ measurement of the STEM’s effective source distribution.

Symmetry Breaking and Silver in Gold Nanorod Growth

Formation of anisotropic nanocrystals from isotropic single-crystal precursors requires an essential symmetry breaking event. Single-crystal gold nanorods have become the model system for investigating the synthesis of anisotropic nanoparticles, and their growth mechanism continues to be the subject of intense investigation. Despite this, very little is known about the symmetry breaking event that precedes shape anisotropy. In particular, there remains limited understanding of how an isotropic seed particle becomes asymmetric and of the growth parameters that trigger and drive this process. Here, we present direct atomic-scale observations of the nanocrystal structure at the embryonic stages of gold nanorod growth. The onset of asymmetry of the nascent crystals is observed to occur only for single-crystal particles that have reached diameters of 4-6 nm and only in the presence of silver ions. In this size range, small, asymmetric truncating surfaces with an open atomic structure become apparent. Furthermore, {111} twin planes are observed in some immature nanorods within 1-3 monolayers of the surface. These results provide direct observation of the structural changes that break the symmetry of isotropic nascent nanocrystals and ultimately enable the growth of asymmetric nanocrystals.

Method to measure spatial coherence of subangstrom electron beams

A method is described for measuring the intensity distribution of the electron source in a scanning transmission electron microscope (STEM) fitted with an objective lens aberration corrector. The method is applied to a Cs-corrected 300kV field emission gun TEM/STEM, which is found to have an effective source size of 0.56A full width at half maximum (FWHM) under optical conditions suitable for high resolution STEM imaging. This corresponds to a probe intensity distribution at the specimen plane of 0.72A FWHM using a probe-forming aperture of 25mrad and including the measured residual lens aberrations.

Stability of Crystal Facets in Gold Nanorods

Metal nanocrystals can be grown in a variety of shapes through the modification of surface facet energies via surfactants. However, the surface facets are only a few atoms wide, making it extremely challenging to measure their geometries and energies. Here, we locate and count atoms in Au nanorods at successive time intervals using quantitative scanning transmission electron microscopy. This enables us to determine the atomic-level geometry and the relative stability of the facets and to expound their relationship to the overall three-dimensional nanocrystal shape and size. We reveal coexisting high- and low-index facets with comparable stability and dimensions and find the geometry of the nanorods is remarkably stable, despite significant atom movements. This information provides unique insights into the mechanisms that govern growth kinetics and nanocrystal morphology.