The role of ion migration, octahedral tilt, and the A-site cation on the instability of Cs1-xFAxPbI3.

Organic-inorganic hybrid perovskites are promising materials for the next generation photovoltaics and optoelectronics; however, their practical application has been hindered by poor structural stability mainly caused by ion migration and external stimuli. Understanding the mechanism(s) of ion migration and structure decomposition is thus critical. Here we observe the sequence of structural changes at the atomic level that precede structural decomposition in the technologically important Cs1-xFAxPbI3 using ultralow dose transmission electron microscopy. We find that these changes differ, depending upon the A-site composition. Initially, there is a random loss of FA+, complemented by the loss of I-. The remaining FA+ and I- ions then migrate, unit cell by unit cell, into an ordered and more stable phase with a √2 x √2 superstructure. Further ion loss is accompanied by A-site dependent octahedral tilt modes and associated tetragonal phases with different stabilities. These observations of the loss of FA+/I- ion pairs, ion migration, octahedral tilt modes, and the role of the A-cation, provide insights into the atomic-scale structural mechanisms that drive and block ion loss and ion migration, opening pathways to inhibit ion loss, migration and improve structural stability.

Extensively Microtwinned Diamond with Nanolaminates of Lonsdaleite Formed by Flash Laser Heating of Glassy Carbon.

Diamond's unique properties on the nanoscale make it one of the most important materials for use in biosensors and quantum computing and for components that can withstand the harsh environments of space. We synthesize oriented, faceted diamond particles by flash laser heating of glassy carbon at 16 GPa and 2300 K. Detailed transmission electron microscopy shows them to consist of a mosaic of diamond nanocrystals frequently joined at twin boundaries forming microtwins. Striking 3-fold translational periodicity was observed in both imaging and diffraction. This periodicity was shown to originate from nanodimensional wedge-shaped overlapping regions of twinned diamond and not from a possible 9R polytype, which has also been reported in other group IVa elements and water ice. Extended bilayers of hexagonal layer stacking were observed, forming lonsdaleite nanolaminates. The particles exhibited optical fluorescence with a rapid quench time (<1 ns) attributed to their unique twinned microstructure.

Bottom-up, Chip-Scale Engineering of Low Threshold, Multi-Quantum-Well Microring Lasers.

Integrated, on-chip lasers are vital building blocks in future optoelectronic and nanophotonic circuitry. Specifically, III-V materials that are of technological relevance have attracted considerable attention. However, traditional microcavity laser fabrication techniques, including top-down etching and bottom-up catalytic growth, often result in undesirable cavity geometries with poor scalability and reproducibility. Here, we utilize the selective area epitaxy method to deterministically engineer thousands of microring lasers on a single chip. Specifically, we realize a catalyst-free, epitaxial growth of a technologically critical material, InAsP/InP, in a ring-like cavity with embedded multi-quantum-well heterostructures. We elucidate a detailed growth mechanism and leverage the capability to deterministically control the adatom diffusion lengths on selected crystal facets to reproducibly achieve ultrasmooth cavity sidewalls. The engineered devices exhibit a tunable emission wavelength in the telecommunication O-band and show low-threshold lasing with over 80% device efficacy across the chip. Our work marks a significant milestone toward the implementation of a fully integrated III-V materials platform for next-generation high-density integrated photonic and optoelectronic circuits.

Modulation of Cathodoluminescence by Surface Plasmons in Silver Nanowires.

The waveguide modes in chemically-grown silver nanowires on silicon nitride substrates are observed using spectrally- and spatially-resolved cathodoluminescence (CL) excited by high-energy electrons in a scanning electron microscope. The presence of a long-range, travelling surface plasmon mode modulates the coupling efficiency of the incident electron energy into the nanowires, which is observed as oscillations in the measured CL with the point of excitation by the focused electron beam. The experimental data are modeled using the theory of surface plasmon polariton modes in cylindrical metal waveguides, enabling the complex mode wavenumbers and excitation strength of the long-range surface plasmon mode to be extracted. The experiments yield insight into the energy transfer mechanisms between fast electrons and coherent oscillations in surface charge density in metal nanowires and the relative amplitudes of the radiative processes excited in the wire by the electron.

Complementary ADF-STEM: a Flexible Approach to Quantitative 4D-STEM.

Scanning transmission electron microscopy (STEM) has a broad range of applications in materials characterization, including real-space imaging, spectroscopy, and diffraction, at length scales from the micron to sub-Ångström. The recent development and adoption of high-speed, direct electron STEM detectors has enabled diffraction patterns to be collected at each probe position, generating four-dimensional STEM (4D-STEM) datasets and opening new imaging modalities. However, the limited pixel numbers in these detectors enforce a tradeoff between angular resolution and maximum collection angle. In this paper, we describe a straightforward method for quantifying 4D-STEM data by utilizing the full flux of the electron beam, including electrons scattered beyond the limits of the detector. This enables significantly increased experimental flexibility, including the synthesis of quantitative, high-contrast complementary annular dark field (cADF) STEM images from low-angle diffraction patterns whilst maintaining high angular resolution; as well as the optimization of electron dose and the more effective use of low dynamic range detectors.

A symmetry-derived mechanism for atomic resolution imaging.

We introduce an image-contrast mechanism for scanning transmission electron microscopy (STEM) that derives from the local symmetry within the specimen. For a given position of the electron probe on the specimen, the image intensity is determined by the degree of similarity between the exit electron-intensity distribution and a chosen symmetry operation applied to that distribution. The contrast mechanism detects both light and heavy atomic columns and is robust with respect to specimen thickness, electron-probe energy, and defocus. Atomic columns appear as sharp peaks that can be significantly narrower than for STEM images using conventional disk and annular detectors. This fundamentally different contrast mechanism complements conventional imaging modes and can be acquired simultaneously with them, expanding the power of STEM for materials characterization.

Cathodoluminescence visualisation of local thickness variations of GaAs/AlGaAs quantum-well tubes on nanowires.

We present spatially and spectrally resolved emission from nanowires with a thin radial layer of GaAs embedded in AlGaAs barriers, grown radially around taper-free GaAs cores. The GaAs layers are thin enough to show quantization, and are quantum wells. Due to their shape, they are referred to as quantum well tubes (QWTs). We have investigated three different nominal QWT thicknesses: 1.5, 2.0, and 6.0 nm. They all show average emission spectra from the QWT with an energy spread corresponding to a thickness variation of ±30%. We observe no thickness gradient along the length of the nanowires. Individual NWs show a number of peaks, corresponding to different QW thicknesses. Apart from the thinnest QWT, the integrated emission from the QWTs shows homogeneous emission intensity along the NW. The thinnest QWTs show patchy emission patterns due to the incomplete coverage of the QWT. We observe a few NWs with larger diameters. The QWTs in these NWs show spatially resolved variations across the NW. An increase in the local thickness of the QWT at the corners blocks the diffusion of carriers from facet to facet, thereby enabling us to visualise the thickness variations of the radial quantum wells.

Constructing a library of metal and metal-oxide nanoparticle heterodimers through colloidal assembly.

Nanoparticle dimers composed of different metals or metal oxides, as well as different shapes and sizes, are of wide interest for applications ranging from nanoplasmonic sensing to nanooptics to biomedical engineering. Shaped nanoparticles, like triangles and nanorods, can be particularly useful in applications due to the strong localized plasmonic hot-spot that forms at the tips or corners. By placing catalytic, but traditionally weakly- or non-plasmonic nanoparticles, such as metal oxides and metals like palladium, in these hot-spots, an enhanced function for sensing, photocatalysis or optical use is predicted. Here, we present an electrostatic colloidal assembly strategy for nanoparticles, incorporating different sizes, shapes and metal or metal oxide compositions into heterodimers with smaller gaps than are achievable using nanofabrication techniques. This versatile method is demonstrated on 14 combinations, including a variety of shaped gold nanoparticles as well as palladium, iron oxide, and titanium oxide nanoparticles. These colloidal nanoparticles are stabilized with traditional surfactants, such as citrate, CTAB, PVP and oleic acid/oleylamines, indicating the wide applicability of our approach. Heterodimers of gold and palladium are further analyzed using cathodoluminescence to demonstrate the tunability of these "plasmonic molecules". Since systematically altering the absorption and emission of the plasmonic nanoparticles dimers is crucial to extending their functionality, and small gap sizes produce the strongest hot-spots, this method indicates that the electrostatic approach to heterodimer assembly can be useful in creating new nanoparticle dimers for many applications.

Direct experimental evidence of physical origin of electronic phase separation in manganites.

Electronic phase separation in complex oxides is the inhomogeneous spatial distribution of electronic phases, involving length scales much larger than those of structural defects or nonuniform distribution of chemical dopants. While experimental efforts focused on phase separation and established its correlation with nonlinear responses under external stimuli, it remains controversial whether phase separation requires quenched disorder for its realization. Early theory predicted that if perfectly "clean" samples could be grown, both phase separation and nonlinearities would be replaced by a bicritical-like phase diagram. Here, using a layer-by-layer superlattice growth technique we fabricate a fully chemically ordered "tricolor" manganite superlattice, and compare its properties with those of isovalent alloyed manganite films. Remarkably, the fully ordered manganite does not exhibit phase separation, while its presence is pronounced in the alloy. This suggests that chemical-doping-induced disorder is crucial to stabilize the potentially useful nonlinear responses of manganites, as theory predicted.

Size Induced Structural Changes in Molybdenum Oxide Nanoparticles.

Nanosizing of metal oxide particles is a common strategy for improving materials properties; however, small particles often take structures different from the bulk material. MoO2 nanoparticles show a structure that is distinct from the bulk distorted rutile structure and which has not yet been determined. Here, we present a model for nanostructured MoO2 obtained through detailed atomic pair distribution function analysis combined with high-resolution electron microscopy. Defects occur in the arrangement of [MoO6] octahedra, in both large (40-100 nm) nanoparticles, where the overall distorted rutile structure is preserved, and in small nanoparticles (<5 nm), where a new nanostructure is formed. The study provides a piece in the puzzle of understanding the structure/properties relationship of molybdenum oxides and further our understanding of the origin of structural changes taking place upon nanosizing in oxide materials.

Efficient and stable emission of warm-white light from lead-free halide double perovskites.

Lighting accounts for one-fifth of global electricity consumption1. Single materials with efficient and stable white-light emission are ideal for lighting applications, but photon emission covering the entire visible spectrum is difficult to achieve using a single material. Metal halide perovskites have outstanding emission properties2,3; however, the best-performing materials of this type contain lead and have unsatisfactory stability. Here we report a lead-free double perovskite that exhibits efficient and stable white-light emission via self-trapped excitons that originate from the Jahn-Teller distortion of the AgCl6 octahedron in the excited state. By alloying sodium cations into Cs2AgInCl6, we break the dark transition (the inversion-symmetry-induced parity-forbidden transition) by manipulating the parity of the wavefunction of the self-trapped exciton and reduce the electronic dimensionality of the semiconductor4. This leads to an increase in photoluminescence efficiency by three orders of magnitude compared to pure Cs2AgInCl6. The optimally alloyed Cs2(Ag0.60Na0.40)InCl6 with 0.04 per cent bismuth doping emits warm-white light with 86 ± 5 per cent quantum efficiency and works for over 1,000 hours. We anticipate that these results will stimulate research on single-emitter-based white-light-emitting phosphors and diodes for next-generation lighting and display technologies.

Three-beam convergent-beam electron diffraction for measuring crystallographic phases.

Under almost all circumstances, electron diffraction patterns contain information about the phases of structure factors, a consequence of the short wavelength of an electron and its strong Coulombic interaction with matter. However, extracting this information remains a challenge and no generic method exists. In this work, a set of simple analytical expressions is derived for the intensity distribution in convergent-beam electron diffraction (CBED) patterns recorded under three-beam conditions. It is shown that these expressions can be used to identify features in three-beam CBED patterns from which three-phase invariants can be extracted directly, without any iterative refinement processes. The octant, in which the three-phase invariant lies, can be determined simply by inspection of the indexed CBED patterns (i.e. the uncertainty of the phase measurement is ±22.5°). This approach is demonstrated with the experimental measurement of three-phase invariants in two simple test cases: centrosymmetric Si and non-centrosymmetric GaAs. This method may complement existing structure determination methods by providing direct measurements of three-phase invariants to replace 'guessed' invariants in ab initio phasing methods and hence provide more stringent constraints to the structure solution.

Radial Growth Evolution of InGaAs/InP Multi-Quantum-Well Nanowires Grown by Selective-Area Metal Organic Vapor-Phase Epitaxy.

III-V semiconductor multi-quantum-well nanowires (MQW NWs) via selective-area epitaxy (SAE) is of great importance for the development of nanoscale light-emitting devices for applications such as optical communication, silicon photonics, and quantum computing. To achieve highly efficient light-emitting devices, not only the high-quality materials but also a deep understanding of their growth mechanisms and material properties (structural, optical, and electrical) are extremely critical. In particular, the three-dimensional growth mechanism of MQWs embedded in a NW structure by SAE is expected to be different from that of those grown in a planar structure or with a catalyst and has not yet been thoroughly investigated. In this work, we reveal a distinctive radial growth evolution of InGaAs/InP MQW NWs grown by the SAE metal organic vapor-phase epitaxy (MOVPE) technique. We observe the formation of zinc blende (ZB) QW discs induced by the axial InGaAs QW growth on the wurtzite (WZ) base-InP NW and propose it as the key factor driving the overall structure of radial growth. The role of the ZB-to-WZ change in the driving of the overall growth evolution is supported by a growth formalism, taking into account the formation-energy difference between different facets. Despite a polytypic crystal structure with mixed ZB and WZ phases across the MQW region, the NWs exhibit high uniformity and desirable QW spatial layout with bright room-temperature photoluminescence at an optical communication wavelength of ∼1.3 µm, which is promising for the future development of high-efficiency light-emitting devices.

Structural and Chemical Changes to CH3 NH3 PbI3 Induced by Electron and Gallium Ion Beams.

Organic-inorganic hybrid perovskites, such as CH3 NH3 PbI3, have shown highly promising photovoltaic performance. Electron microscopy (EM) is a powerful tool for studying the crystallography, morphology, interfaces, lattice defects, composition, and charge carrier collection and recombination properties at the nanoscale. Here, the sensitivity of CH3 NH3 PbI3 to electron beam irradiation is examined. CH3 NH3 PbI3 undergoes continuous structural and compositional changes with increasing electron dose, with the total dose, rather than dose rate, being the key operative parameter. Importantly, the first structural change is subtle and easily missed and occurs after an electron dose significantly smaller than that typically applied in conventional EM techniques. The electron dose conditions under which these structural changes occur are identified. With appropriate dose-minimization techniques, electron diffraction patterns can be obtained from pristine material consistent with the tetragonal CH3 NH3 PbI3 phases determined by X-ray diffraction. Radiation damage incurred at liquid nitrogen temperatures and using Ga+ irradiation in a focused ion beam instrument are also examined. Finally, some simple guidelines for how to minimize electron-beam-induced artifacts when using EM to study hybrid perovskite materials are provided.

The evolution of size, shape, and surface morphology of gold nanorods.

We investigate the transformation of single crystal gold nanorod surface morphology over extended growth times. After initial rapid anisotropic growth and disappearance of {111} bridging facets, the aspect ratios converge across AgNO3 concentrations. The surface morphology transitions from faceted to curved. These observations imply the final aspect ratio has little dependence on the AgNO3 concentration, consistent with primary control of the AgNO3 over aspect ratio occurring at the symmetry breaking point.

Axicon Lens for Electrons Using a Magnetic Vortex: The Efficient Generation of a Bessel Beam.

We demonstrate experimentally an efficient electron axicon lens using a magnetic vortex. We show that naturally occurring magnetic vortices with circular magnetic moment distributions in a soft-magnetic thin film create conical phase shifts for fast electrons. Such radially symmetric linear phase ramps are equivalent to ideal light optical axicons. We apply this lens to generate efficient nondiffracting electron Bessel beams, which we observe experimentally in through-focus Lorentz images as well as in propagated off-axis electron holograms. This highlights the potential for using magnetic nanostructures as highly efficient and flexible phase plates for crafting desired electron beam shapes.

A Mechanism for Symmetry Breaking and Shape Control in Single-Crystal Gold Nanorods.

The phenomenon of symmetry breaking-in which the order of symmetry of a system is reduced despite manifest higher-order symmetry in the underlying fundamental laws-is pervasive throughout science and nature, playing a critical role in fields ranging from particle physics and quantum theory to cosmology and general relativity. For the growth of crystals, symmetry breaking is the crucial step required to generate a macroscopic shape that has fewer symmetry elements than the unit cell and/or seed crystal from which it grew. Advances in colloid synthesis have enabled a wide variety of nanocrystal morphologies to be achieved, albeit empirically. Of the various nanoparticle morphologies synthesized, gold nanorods have perhaps been the most intensely studied, thanks largely to their unique morphology-dependent optical properties and exciting application potential. However, despite intense research efforts, an understanding of the mechanism by which a single crystal breaks symmetry and grows anisotropically has remained elusive, with many reports presenting seemingly conflicting data and theories. A fundamental understanding of the symmetry breaking process is needed to provide a rational framework upon which future synthetic approaches can be built. Inspired by recent experimental results and drawing upon the wider literature, we present a mechanism for gold nanorod growth from the moments prior to symmetry breaking to the final product. In particular, we describe the steps by which a cuboctahedral seed particle breaks symmetry and undergoes anisotropic growth to form a nanorod. With an emphasis on the evolving crystal structure, we highlight the key geometrical and chemical drivers behind the symmetry breaking process and factors that govern the formation and growth of nanorods, including control over the crystal width, length, and surface faceting. We propose that symmetry breaking is induced by an initial formation of a new surface structure that is stabilized by the deposition of silver, thus preserving this facet in the embryonic nanorod. These new surfaces initially form stochastically as truncations that remove high-energy edge atoms at the intersection of existing {111} facets and represent the beginnings of a {011}-type surface. Crucially, the finely tuned [HAuCl4]:[AgNO3] ratio and reduction potential of the system mean that silver deposition can occur on the more atomically open surface but not on the pre-existing lower-index facets. The stabilized surfaces develop into side facets of the nascent nanorod, while the largely unpassivated {111} facets are the predominant site of Au atom deposition. Growth in the width direction is tightly controlled by a self-sustaining cycle of galvanic replacement and silver deposition. It is the [HAuCl4]:[AgNO3] ratio that directly determines the particle size at which the more open atomic surfaces can be stabilized by silver and the rate of growth in the width direction following symmetry breaking, thus explaining the known aspect ratio control with Ag ion concentration. We describe the evolving surface faceting of the nanorod and the emergence of higher-index facets. Collectively, these observations allow us to identify facet-size and edge-atom effects as a simple fundamental driver of symmetry breaking and the subsequent development of new surfaces in the presence of adsorbates.

Topologically Enclosed Aluminum Voids as Plasmonic Nanostructures.

Recent advances in the ability to synthesize metallic nanoparticles with tailored geometries have led to a revolution in the field of plasmonics. However, studies of the important complementary system, an inverted nanostructure, have so far been limited to two-dimensional sphere-segment voids or holes. Here we reveal the localized surface plasmon resonances (LSPRs) of nanovoids that are topologically enclosed in three-dimensions: an "anti-nanoparticle". We combine this topology with the favorable plasmonic properties of aluminum to observe strongly localized field enhancements with LSPR energies in the extreme UV range, well beyond those accessible with noble metals or yet achieved with aluminum. We demonstrate the resonance tunability by tailoring the shape and size of the nanovoids, which are truncated octahedra in the 10-20 nm range. This system is pristine: the nanovoid cavity is free from any oxide or supporting substrate that would affect the LSPRs. We exploit this to infer LSPRs of pure, sub-20-nm Al nanoparticles, which have yet to be synthesized. Access to this extreme UV range will allow applications in LSPR-enhanced UV photoemission spectroscopy and photoionization.

Bimetallic Ions Codoped Nanocrystals: Doping Mechanism, Defect Formation, and Associated Structural Transition.

Ionic codoping offers a powerful approach for modifying material properties by extending the selection of potential dopant ions. However, it has been a major challenge to introduce certain ions that have hitherto proved difficult to use as dopants (called "difficult-dopants") into crystal structures at high concentrations, especially through wet chemical synthesis. Furthermore, the lack of a fundamental understanding of how codopants are incorporated into host materials, which types of defect structures they form in the equilibrium state, and what roles they play in material performance, has seriously hindered the rational design and development of promising codoped materials. Here we take In3+ (difficult-dopants) and Nb5+ (easy-dopants) codoped anatase TiO2 nanocrystals as an example and investigate the doping mechanism of these two different types of metal ions, the defect formation, and their associated impacts on high-pressure induced structural transition behaviors. It is experimentally demonstrated that the dual mechanisms of nucleation and diffusion doping are responsible for the synergic incorporation of these two dopants and theoretically evidenced that the defect structures created by the introduced In3+, Nb5+ codopants, their resultant Ti3+, and oxygen vacancies are locally composed of both defect clusters and equivalent defect pairs. These formed local defect structures then act as nucleation centers of baddeleyite- and α-PbO2-like metastable polymorphic phases and induce the abnormal trans-regime structural transition of codoped anatase TiO2 nanocrystals under high pressure. This work thus suggests an effective strategy to design and synthesize codoped nanocrystals with highly concentrated difficult-dopants. It also unveils the significance of local defect structures on material properties.