Search

Surface strain plays a key role in enhancing the activity of Pt-alloy nanoparticle oxygen reduction catalysts. However, the details of strain effects in real fuel cell catalysts are not well-understood, in part due to a lack of strain characterization techniques that are suitable for complex supported nanoparticle catalysts. This work investigates these effects using strain mapping with nanobeam electron diffraction and a continuum elastic model of strain in simple core-shell particles. We find that surface strain is relaxed both by lattice defects at the core-shell interface and by relaxation across particle shells caused by Poisson expansion in the spherical geometry. The continuum elastic model finds that in the absence of lattice dislocations, geometric relaxation results in a surface strain that scales with the average composition of the particle, regardless of the shell thickness. We investigate the impact of these strain effects on catalytic activity for a series of Pt-Co catalysts treated to vary their shell thickness and core-shell lattice mismatch. For catalysts with the thinnest shells, the activity is consistent with an Arrhenius dependence on the surface strain expected for coherent strain in dislocation-free particles, while catalysts with thicker shells showed greater activity losses indicating strain relaxation caused by dislocations as well., Comment: 23 pages,7 figures, includes appendix

MX monopnictide compounds (M=Nb,Ta, X = As,P) are prototypical three-dimensional Weyl semimetals (WSMs) that have been shown in bulk single crystal form to have potential for a wide variety of novel devices due to topologically protected band structures and high mobilities. However, very little is known about thin film synthesis, which is essential to enable device applications. We synthesize TaAs(001) epilayers by molecular beam epitaxy on GaAs(001) and provide an experimental phase diagram illustrating conditions for single phase, single-crystal-like growth. We investigate the relationship between nanoscale defects and electronic structure, using angle-resolved photoemission spectroscopy, Kelvin probe microscopy and transmission electron microscopy. Our results provide a roadmap and platform for developing 3D WSMs for device applications., Comment: 12 pages, 5 figures

Hexagonal $AB$O$_3$ oxides ($A$, $B$ = cation) are a rich materials class for realizing novel quantum phenomena. Their hexagonal symmetry, oxygen trigonal bipyramid coordination and quasi-two dimensional layering give rise to properties distinct from those of the cubic $AB$O$_3$ perovskites. As bulk materials, most of the focus in this materials class has been on the rare earth manganites, $R$MnO$_3$ ($R$ = rare earth); these materials display coupled ferroelectricity and antiferromagnetic order. In this review, we focus on the thin film manifestations of the hexagonal $AB$O$_3$ oxides. We cover the stability of the hexagonal oxides and substrates which can be used to template the hexagonal structure. We show how the thin film geometry not only allows for further tuning of the bulk-stable manganites but also the realization of metastable hexagonal oxides such as the $R$FeO$_3$ that combine ferroelectricity with weak ferromagnetic order. The thin film geometry is a promising platform to stabilize additional metastable hexagonal oxides to search for predicted high-temperature superconductivity and topological phases in this materials class., Comment: The following article has been accepted by Applied Physics Reviews

The quantum anomalous Hall (QAH) effect is characterized by a dissipationless chiral edge state with a quantized Hall resistance at zero magnetic field. Manipulating the QAH state is of great importance in both the understanding of topological quantum physics and the implementation of dissipationless electronics. Here, we realized the QAH effect in the magnetic topological insulator Cr-doped (Bi,Sb)2Te3 (CBST) grown on an uncompensated antiferromagnetic insulator Al-doped Cr2O3. Through polarized neutron reflectometry (PNR), we find a strong exchange coupling between CBST and Al-Cr2O3 surface spins fixing interfacial magnetic moments perpendicular to the film plane. The interfacial coupling results in an exchange-biased QAH effect. We further demonstrate that the magnitude and sign of the exchange bias can be effectively controlled using a field training process to set the magnetization of the Al-Cr2O3 layer. Our work demonstrates the use of the exchange bias effect to effectively manipulate the QAH state, opening new possibilities in QAH-based spintronics.

Transmission electron microscopes use electrons with wavelengths of a few picometers, potentially capable of imaging individual atoms in solids at a resolution ultimately set by the intrinsic size of an atom. Unfortunately, due to imperfections in the imaging lenses and multiple scattering of electrons in the sample, the image resolution reached is 3 to 10 times worse. Here, by inversely solving the multiple scattering problem and overcoming the aberrations of the electron probe using electron ptychography to recover a linear phase response in thick samples, we demonstrate an instrumental blurring of under 20 picometers. The widths of atomic columns in the measured electrostatic potential are now no longer limited by the imaging system, but instead by the thermal fluctuations of the atoms. We also demonstrate that electron ptychography can potentially reach a sub-nanometer depth resolution and locate embedded atomic dopants in all three dimensions with only a single projection measurement., Comment: 13 pages and 4 figures in the main text. Supplementary materials included

Transition metal oxides such as vanadium dioxide (VO$_2$), niobium dioxide (NbO$_2$), and titanium sesquioxide (Ti$_2$O$_3$) are known to undergo a temperature-dependent metal-insulator transition (MIT) in conjunction with a structural transition within their bulk. However, it is not typically discussed how breaking crystal symmetry via surface termination affects the complicated MIT physics. Using synchrotron-based x-ray spectroscopy, low energy electron diffraction (LEED), low energy electron microscopy (LEEM), transmission electron microscopy (TEM), and several other experimental techniques, we show that suppression of the bulk structural transition is a common feature at VO$_2$ surfaces. Our density functional theory (DFT) calculations further suggest that this is due to inherent reconstructions necessary to stabilize the surface, which deviate the electronic structure away from the bulk d$^1$ configuration. Our findings have broader ramifications not only for the characterization of other "Mott-like" MITs, but also for any potential device applications of such materials.

We construct ferroelectric (LuFeO3)m/(LuFe2O4) superlattices with varying index m to study the effect of confinement on topological defects. We observe a thickness-dependent transition from neutral to charged domain walls and the emergence of fractional vortices. In thin LuFeO3 layers, the volume fraction of domain walls grows, lowering the symmetry from P63cm to P3c1 before reaching the non-polar P63/mmc state, analogous to the high-temperature ferroelectric to paraelectric transition. Our study shows how dimensional confinement stabilizes textures beyond those in bulk ferroelectric systems.

Friedel's law guarantees an inversion-symmetric diffraction pattern for thin, light materials where a kinematic approximation or a single-scattering model holds. Typically, breaking Friedel symmetry is ascribed to multiple scattering events within thick, non-centrosymmetric crystals. However, two-dimensional (2D) materials such as a single monolayer of MoS$_2$ can also violate Friedel's law, with unexpected contrast between conjugate Bragg peaks. We show analytically that retaining higher order terms in the power series expansion of the scattered wavefunction can describe the anomalous contrast between $hkl$ and $\overline{hkl}$ peaks that occurs in 2D crystals with broken in-plane inversion symmetry. These higher-order terms describe multiple scattering paths starting from the same atom in an atomically thin material. Furthermore, 2D materials containing heavy elements, such as WS$_2$, always act as strong phase objects, violating Friedel's law no matter how high the energy of the incident electron beam. Experimentally, this understanding can enhance diffraction-based techniques to provide rapid imaging of polarity, twin domains, in-plane rotations, or other polar textures in 2D materials., Comment: 26 pages, 5 main figures, 3 supplemental figures, submitted to Ultramicroscopy

Scanning nanobeam electron diffraction (NBED) with fast pixelated detectors is a valuable technique for rapid, spatially resolved mapping of lattice structure over a wide range of length scales. However, intensity variations caused by dynamical diffraction and sample mistilts can hinder the measurement of diffracted disk centers as necessary for quantification. Robust data processing techniques are needed to provide accurate and precise measurements for complex samples and non-ideal conditions. Here we present an approach to address these challenges using a transform, called the exit wave power cepstrum (EWPC), inspired by cepstral analysis in audio signal processing. The EWPC transforms NBED patterns into real-space patterns with sharp peaks corresponding to inter-atomic spacings. We describe a simple analytical model for interpretation of these patterns that cleanly decouples lattice information from the intensity variations in NBED patterns caused by tilt and thickness. By tracking the inter-atomic spacing peaks in EWPC patterns, strain mapping is demonstrated for two practical applications: mapping of ferroelectric domains in epitaxially strained PbTiO3 films and mapping of strain profiles in arbitrarily oriented core-shell Pt-Co nanoparticle fuel-cell catalysts. The EWPC transform enables lattice structure measurement at sub-pm precision and sub-nm resolution that is robust to small sample mistilts and random orientations., Comment: 31 pages, 11 figures

A major motivation for the scientific study of artworks is to understand their states of preservation and ongoing degradation mechanisms. This enables preservation strategies to be developed for irreplaceable works. Intensely-hued cadmium sulphide (CdS) yellow pigments are of particular interest because these are key to the palettes of many important late 19th and early 20th century masters, including Vincent Van Gogh, Pablo Picasso, Henri Matisse, and Edvard Munch. As these paintings age, their cadmium yellow paints are undergoing severe fading, flaking, and discolouration. These effects are associated with photodegradation, the light-facilitated reactions of CdS with oxygen, moisture, and even the paint binding medium. The use of common optical and X-ray methods to characterize the physical state of the pigment is challenging due to the mixing of the various components of the paint at length scales smaller than their resolution. Here, we present an atomic-scale structural and chemical analysis of the CdS pigment in Edvard Munch's The Scream (c. 1910, Munch Museet), enabled by new electron microscope detector technologies. We show that the CdS pigment consists of clusters of defective nanoparticles ~5-10 nm in diameter. It is known from the modern use of such particles in photocatalysis that they are inherently vulnerable to photodegradation. Chlorine doping and a polytype crystal structure further enhance the sensitivity of the CdS pigment to photodegradation. In addition to The Scream, we have also observed this inherently unstable pigment structure in Henri Matisse's Flower Piece (1906, Barnes Foundation). The fundamental understanding of the pigments' nanoscale structures and impurities described here can now be used to predict which paintings are most at risk of photooxidation, and guide the most effective preservation strategies for iconic masterpieces., Comment: Version 2 has updated the Acknowledgement section to report a new grant number. This is the only change from Version 1

Intricate biomineralization processes in molluscs engineer hierarchical structures with meso-, nano-, and atomic architectures that give the final composite material exceptional mechanical strength and optical iridescence on the macroscale. This multiscale biological assembly inspires new synthetic routes to complex materials. Our investigation of the prism-nacre interface reveals nanoscale details governing the onset of nacre formation using high-resolution scanning transmission electron microscopy. A wedge polishing technique provides unprecedented, large-area specimens required to span the entire interface. Within this region, we find a transition from nanofibrillar aggregation to irregular early-nacre layers, to well-ordered mature nacre suggesting the assembly process is driven by aggregation of nanoparticles (~50-80 nm) within an organic matrix that arrange in fiber-like polycrystalline configurations. The particle number increases successively and, when critical packing is reached, they merge into early-nacre platelets. These results give new insights into nacre formation and particle-accretion mechanisms that may be common to many calcareous biominerals., Comment: 5 Figures

Certain pyrochlore oxides are among the best oxygen catalysts in alkaline media. Hence, exploring epitaxial films of these materials is of great fundamental and technological interest. Unfortunately, direct film growth of one of the most promising pyrochlores, Bi$_2$Pt$_2$O$_7$, has not yet been achieved, owing to the difficulty of oxidizing platinum metal in the precursor material to Pt$^{4+}$. In this work, in order to induce oxidation of the platinum, we annealed pulsed laser deposited films consisting of epitaxial $\delta$-Bi$_2$O$_3$ and co-deposited, comparatively disordered platinum. We present synchrotron x-ray diffraction results that show the annealed films are the first epitaxial crystals of Bi$_2$Pt$_2$O$_7$. We also visualized the pyrochlore structure by scanning transmission electron microscopy, and observed ordered cation vacancies in a bismuth-rich film but not in a platinum-rich film. The similarity between the $\delta$-Bi$_2$O$_3$ and Bi$_2$Pt$_2$O$_7$ structures appears to facilitate the pyrochlore formation. These results constitute a new approach for synthesis of novel pyrochlore thin film oxygen catalysts., Comment: 7 pages, 4 figures

A major challenge in the development of new battery materials is understanding their fundamental mechanisms of operation and degradation. Their microscopically inhomogeneous nature calls for characterization tools that provide operando and localized information from individual grains and particles. Here we describe an approach that images the nanoscale distribution of ions during electrochemical charging of a battery in a transmission electron microscope liquid flow cell. We use valence energy-loss spectroscopy to track both solvated and intercalated ions, with electronic structure fingerprints of the solvated ions identified using an ab initio non-linear response theory. Equipped with the new electrochemical cell holder, nanoscale spectroscopy and theory, we have been able to determine the lithiation state of a LiFePO4 electrode and surrounding aqueous electrolyte in real time with nanoscale resolution during electrochemical charge and discharge. We follow lithium transfer between electrode and electrolyte and observe charging dynamics in the cathode that differ among individual particles. This technique represents a general approach for the operando nanoscale imaging of electrochemically active ions in a wide range of electrical energy storage systems.

In situ scanning transmission electron microscopy (STEM) through liquids is a promising approach for exploring biological and materials processes. However, options for in situ chemical identification are limited: X-ray analysis is precluded because the liquid cell holder shadows the detector, and electron energy-loss spectroscopy (EELS) is degraded by multiple scattering events in thick layers. Here, we explore the limits of EELS for studying chemical reactions in their native environments in real time and on the nanometer scale. The determination of the local electron density, optical gap and thickness of the liquid layer by valence EELS is demonstrated. By comparing theoretical and experimental plasmon energies, we find that liquids appear to follow the free-electron model that has been previously established for solids. Signals at energies below the optical gap and plasmon energy of the liquid provide a high signal-to-background ratio regime as demonstrated for LiFePO4 in aqueous solution. The potential for using valence EELS to understand in situ STEM reactions is demonstrated for beam-induced deposition of metallic copper: as copper clusters grow, EELS develops low-loss peaks corresponding to metallic copper. From these techniques, in situ imaging and valence EELS offer insight into the local electronic structure of nanoparticles and chemical reactions., Comment: 15 pages, 5 figures, submitted to Microscopy and Microanalysis