In exsolution, nanoparticles form by emerging from oxide hosts by application of redox driving forces, leading to transformative advances in stability, activity, and efficiency over deposition techniques, and resulting in a wide range of new opportunities for catalytic, energy and net-zero-related technologies. However, the mechanism of exsolved nanoparticle nucleation and perovskite structural evolution, has, to date, remained unclear. Herein, we shed light on this elusive process by following in real time Ir nanoparticle emergence from a SrTiO3 host oxide lattice, using in situ high-resolution electron microscopy in combination with computational simulations and machine learning analytics. We show that nucleation occurs via atom clustering, in tandem with host evolution, revealing the participation of surface defects and host lattice restructuring in trapping Ir atoms to initiate nanoparticle formation and growth. These insights provide a theoretical platform and practical recommendations to further the development of highly functional and broadly applicable exsolvable materials.
Phosphorene nanoribbons (PNRs) have inspired strong research interests to explore their exciting properties that are associated with the unique two-dimensional (2D) structure of phosphorene as well as the additional quantum confinement of the nanoribbon morphology, providing new materials strategy for electronic and optoelectronic applications. Despite several important properties of PNRs, the production of these structures with narrow widths is still a great challenge. Here, a facile and straightforward approach to synthesize PNRs via an electrochemical process that utilize the anisotropic Na+ diffusion barrier in black phosphorus (BP) along the [001] zigzag direction against the [100] armchair direction, is reported. The produced PNRs display widths of good uniformity (10.3 ± 3.8 nm) observed by high-resolution transmission electron microscopy, and the suppressed B2g vibrational mode from Raman spectroscopy results. More interestingly, when used in field-effect transistors, synthesized bundles exhibit the n-type behavior, which is dramatically different from bulk BP flakes which are p-type. This work provides insights into a new synthesis approach of PNRs with confined widths, paving the way toward the development of phosphorene and other highly anisotropic nanoribbon materials for high-quality electronic applications.
A primary mode of failure of thin-film coatings is the mismatch in thermal expansion coefficients of the substrate and the coating, which results in accumulation of interfacial stresses and ultimately in film delamination. While much attention has been devoted to modulation of interfacial bonding to mitigate delamination, current strategies are constrained in their generalizability and have had limited success in imbuing resistance to prolonged thermal cycling. We demonstrate here the incorporation of rigid thermal expansion compensators within polymeric films as a generalizable strategy for minimizing thermal mismatch with the substrate. Nanostructures of the isotropic negative thermal expansion (NTE) material HfV2O7 have been prepared based on the reaction of nanoparticulate precursors. The NTE behavior, derived from transverse oxygen displacement within the cubic structure, has been examined using temperature-variant powder X-ray diffraction, Raman spectroscopy, electron microscopy, and selected-area electron diffraction measurements. HfV2O7 initially crystallizes in a 3 × 3 × 3 superlattice but undergoes phase transformations to stabilize a cubic structure that exhibits strong and isotropic NTE with a coefficient of thermal expansion (CTE) = -6.7 × 10-6 °C-1 across an extended temperature range of 130-700 °C. Incorporation of HfV2O7 in a high-temperature thermoset polybenzimidazole enables the reduction of compressive stress by 67.3% for a relatively small loading of 26.6 vol % HfV2O7. Based on a composite model, we demonstrate that HfV2O7 can reduce the thermal expansion coefficient of polymer nanocomposite films, even at low volume fractions, as a result of its substantially higher elastic modulus compared to the continuous polymer matrix. By changing the volume fraction of HfV2O7, the overall coefficients of thermal expansion of the film can be tuned to match a range of substrates, thereby mitigating thermal stresses and resolving a fundamental challenge for high-temperature composites and nanocomposite coatings.
The search for new functional materials that combine high stability and efficiency with reasonable cost and ease of synthesis is critical for their use in renewable energy applications. Specifically in catalysis, nanoparticles, with their high surface-to-volume ratio, can overcome the cost implications associated with otherwise having to use large amounts of noble metals. However, commercialized materials, that is, catalytic nanoparticles deposited on oxide supports, often suffer from loss of activity because of coarsening and carbon deposition during operation. Exsolution has proven to be an interesting strategy to overcome such issues. Here, the controlled emergence, or exsolution, of faceted iridium nanoparticles from a doped SrTiO3 perovskite is reported and their growth preliminary probed by in situ electron microscopy. Upon reduction of SrIr0.005Ti0.995O3, the generated nanoparticles show embedding into the oxide support, therefore preventing agglomeration and subsequent catalyst degradation. The advantages of this approach are the extremely low noble metal amount employed (â¼0.5% weight) and the catalytic activity reported during CO oxidation tests, where the performance of the exsolved SrIr0.005Ti0.995O3 is compared to the activity of a commercial catalyst with 1% loading (1% Ir/Al2O3). The high activity obtained with such low doping shows the possibility of scaling up this new catalyst, reducing the high cost associated with iridium-based materials.
The hollow core, concentric graphitic shells, and large surface area of the carbon nano-onion (CNO) make these carbon nanostructures promising materials for highly efficient catalytic reactions. Doping CNOs with heteroatoms is an effective method of changing their physical and chemical properties. In these cases, the configurations and locations of the incorporated dopant atoms must be a key factor dictating catalytic activity, yet determining a structural arrangement on the single-atom length scale is challenging. Here we present direct imaging of individual nitrogen and sulfur dopant atoms in CNOs, using an aberration-corrected scanning transmission electron microscopy (STEM) approach, combined with electron energy loss spectroscopy (EELS). Inspection of the statistics of dopant configuration and location in sulfur-, nitrogen-, and co-doped samples reveals dopant atoms to be more closely situated to defects in the graphitic shells for co-doped samples, than in their singly doped counterparts. Correlated with an increased activity for the oxygen reduction reaction in the co-doped samples, this suggests a concerted mechanism involving both the dopant and defect.
Metastable materials that represent excursions from thermodynamic minima are characterized by distinctive structural motifs and electronic structure, which frequently underpins new function. The binary oxides of hafnium present a rich diversity of crystal structures and are of considerable technological importance given their high dielectric constants, refractory characteristics, radiation hardness, and anion conductivity; however, high-symmetry tetragonal and cubic polymorphs of HfO2 are accessible only at substantially elevated temperatures (1720 and 2600 °C, respectively). Here, we demonstrate that the core-shell arrangement of VO2 and amorphous HfO2 promotes outwards oxygen diffusion along an electropositivity gradient and yields an epitaxially matched V2O3/HfO2 interface that allows for the unprecedented stabilization of the metastable cubic polymorph of HfO2 under ambient conditions. Free-standing cubic HfO2, otherwise accessible only above 2600 °C, is stabilized by acid etching of the vanadium oxide core. In contrast, interdiffusion under oxidative conditions yields the negative thermal expansion material HfV2O7. Variable temperature powder X-ray diffraction demonstrate that the prepared HfV2O7 exhibits pronounced negative thermal expansion in the temperature range between 150 and 700 °C. The results demonstrate the potential of using epitaxial crystallographic relationships to facilitate preferential nucleation of otherwise inaccessible metastable compounds.
The creation of nanomaterials requires simultaneous control of not only crystalline structure and composition but also crystal shape and size, or morphology, which can pose a significant synthetic challenge. Approaches to address this challenge include creating nanocrystals whose morphologies echo their underlying crystal structures, such as the growth of platelets of two-dimensional layered crystal structures, or conversely attempting to decouple the morphology from structure by converting a structure or composition after first creating crystals with a desired morphology. A particularly elegant example of this latter approach involves the topotactic conversion of a nanoparticle from one structure and composition to another, since the orientation relationship between the initial and final product allows the crystallinity and orientation to be maintained throughout the process. Here we report a mechanism for creating hollow nanostructures, illustrated via the decomposition of ß-FeOOH nanorods to nanocapsules of α-Fe2O3, γ-Fe2O3, Fe3O4, and FeO, depending on the reaction conditions, while retaining single-crystallinity and the outer nanorod morphology. Using in situ TEM, we demonstrate that the nanostructured morphology of the starting material allows kinetic trapping of metastable phases with a topotactic relationship to the final thermodynamically stable phase.
Layered δ-MnO2 (birnessites) are ubiquitous in nature and have also been reported to work as promising water oxidation catalysts or rechargeable alkali-ion battery cathodes when fabricated under appropriate conditions. Although tremendous effort has been spent on resolving the structure of natural/synthetic layered δ-MnO2 in the last few decades, no conclusive result has been reached. In this Article, we report an environmentally friendly route to synthesizing homogeneous Cu-rich layered δ-MnO2 nanoflowers in large scale. The local and average structure of synthetic Cu-rich layered δ-MnO2 has been successfully resolved from combined Mn/Cu K-edge extended X-ray fine structure spectroscopy and X-ray and neutron total scattering analysis. It is found that appreciable amounts (â¼8%) of Mn vacancies are present in the MnO2 layer and Cu2+ occupies the interlayer sites above/below the vacant Mn sites. Effective hydrogen bonding among the interlayer water molecules and adjacent layer O ions has also been observed for the first time. These hydrogen bonds are found to play the key role in maintaining the intermediate and long-range stacking coherence of MnO2 layers. Quantitative analysis of the turbostratic stacking disorder in this compound was achieved using a supercell approach coupled with anisotropic particle-size-effect modeling. The present method is expected to be generally applicable to the structural study of other technologically important nanomaterials.
High-temperature phases of hafnium dioxide have exceptionally high dielectric constants and large bandgaps, but quenching them to room temperature remains a challenge. Scaling the bulk form to nanocrystals, while successful in stabilizing the tetragonal phase of isomorphous ZrO2, has produced nanorods with a twinned version of the room temperature monoclinic phase in HfO2. Here we use in situ heating in a scanning transmission electron microscope to observe the transformation of an HfO2 nanorod from monoclinic to tetragonal, with a transformation temperature suppressed by over 1000°C from bulk. When the nanorod is annealed, we observe with atomic-scale resolution the transformation from twinned-monoclinic to tetragonal, starting at a twin boundary and propagating via coherent transformation dislocation; the nanorod is reduced to hafnium on cooling. Unlike the bulk displacive transition, nanoscale size-confinement enables us to manipulate the transformation mechanism, and we observe discrete nucleation events and sigmoidal nucleation and growth kinetics.
The well-known vapor-liquid-solid (VLS) mechanism results in high-purity, single-crystalline wires with few defects and controllable diameters, and is the method of choice for the growth of nanowires for a vast array of nanoelectronic devices. It is of utmost importance, therefore, to understand how such wires interact with metallic interconnects-an understanding which relies on comprehensive knowledge of the initial growth process, in which a crystalline wire is ejected from a metallic particle. Though ubiquitous, even in the case of single elemental nanowires the VLS mechanism is complicated by competing processes at multiple heterogeneous interfaces, and despite decades of study, there are still aspects of the mechanism which are not well understood. Recent breakthroughs in studying the mechanism and kinetics of VLS growth have been strongly aided by the use of in situ techniques, and would have been impossible through other means. As well as several systematic studies of nanowire growth, reports which focus on the role and the nature of the catalyst tip reveal that the stability of the droplet is a crucial factor in determining nanowire morphology and crystallinity. Additionally, a reverse of the VLS process dubbed solid-liquid-vapor (SLV) has been found to result in the formation of cavities, or "negative nanowires". Here, we present a series of heating studies conducted in situ in the transmission electron microscope (TEM), in which we observe the complete dissolution of metal oxide nanowires into the metal catalyst particles at their tips. We are able to consistently explain our observations using a solid-liquid-vapor (SLV) type mechanism in which both evaporation at the liquid-vapor interface and adhesion of the catalyst droplet to the substrate surface contribute to the overall rate.
Transitioning energy-intensive and environmentally intensive processes toward sustainable conditions is necessary in light of the current global condition. To this end, photocatalytic processes represent new approaches for H2 generation; however, their application toward tandem catalytic reactivity remains challenging. Here, we demonstrate that metal oxide materials decorated with noble metal nanoparticles advance visible light photocatalytic activity toward new reactions not typically driven by light. For this, Pd nanoparticles were deposited onto Cu2O cubes to generate a composite structure. Once characterized, their hydrodehalogenation activity was studied via the reductive dechlorination of polychlorinated biphenyls. To this end, tandem catalytic reactivity was observed with H2 generation via H2O reduction at the Cu2O surface, followed by dehalogenation at the Pd using the in situ generated H2. Such results present methods to achieve sustainable catalytic technologies by advancing photocatalytic approaches toward new reaction systems.
We illustrate a simple method to synthesize highly ordered ZnO axial p-n homojunction-containing nanowires using a low temperature method, and on a variety of substrates. X-ray diffraction, scanning transmission electron microscopy, scanning electron microscopy, and Raman spectroscopy are used to reveal high quality single-crystalline wires with a [001] growth direction. The study of electrical transport through a single nanowire based device and cathodoluminescence via scanning transmission electron microscopy demonstrates that an axial p-n junction exists within each ZnO nanowire. This represents the first low temperature synthesis of axial p-n homojunction-containing ZnO nanowires with uniform and controllable diameters.
Nanowires/chemistry , Zinc Oxide/chemistry , Microscopy, Electron, Scanning/methods , Nanowires/ultrastructure
Since the observation of single-molecule surface-enhanced Raman scattering (SMSERS) in 1997, questions regarding the nature of the electromagnetic hot spots responsible for such observations still persist. For the first time, we employ electron-energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) to obtain maps of the localized surface plasmon modes of SMSERS-active nanostructures, which are resolved in both space and energy. Single-molecule character is confirmed by the bianalyte approach using two isotopologues of Rhodamine 6G. Surprisingly, the STEM/EELS plasmon maps do not show any direct signature of an electromagnetic hot spot in the gaps between the nanoparticles. The origins of this observation are explored using a fully three-dimensional electrodynamics simulation of both the electron-energy-loss probability and the near-electric field enhancements. The calculations suggest that electron beam excitation of the hot spot is possible, but only when the electron beam is located outside of the junction region.
Plasmonics is a rapidly growing field, yet imaging of the plasmonic modes in complex nanoscale architectures is extremely challenging. Here we obtain spatial maps of the localized surface plasmon modes of high-aspect-ratio silver nanorods using electron energy loss spectroscopy (EELS) and correlate to optical data and classical electrodynamics calculations from the exact same particles. EELS mapping is thus demonstrated to be an invaluable technique for elucidating complex and overlapping plasmon modes.
A structure designed to show functionality on the nanometer length scale ideally would spontaneously form periodic nanometer-scale patterns comprising regions with contrasting properties. Here we report the synthesis of three new oxides that spontaneously form a variety of nanostructures with a periodic arrangement of phases with compositional and functional contrast. This is achieved through the partial substitution of Ti by Al, Cr, and Mn in periodically phase-separated (Nd(2/3-x)Li(3x))TiO(3) nanochessboard structures. The generality of this spontaneous compositional nanopatterning is promising for an array of exotic bulk and nanostructural properties.
We present real-time transmission electron microscopy of nanogap formation by feedback controlled electromigration that reveals a remarkable degree of crystalline order. Crystal facets appear during feedback controlled electromigration indicating a layer-by-layer, highly reproducible electromigration process avoiding thermal runaway and melting. These measurements provide insight into the electromigration induced failure mechanism in sub-20 nm size interconnects, indicating that the current density at failure increases as the width decreases to approximately 1 nm.
The use of bottom-up fabrication of nanostructures for nanotechnology inherently requires two-dimensional control of the nanostructures at a particular surface. This could in theory be achieved crystallographically with a structure whose three-dimensional unit cell has two or more--tuneable--dimensions on the nanometre scale. Here, we present what is to our knowledge the first example of a truly periodic two-dimensional nanometre-scale phase separation in any inorganic material, and demonstrate our ability to tune the unit-cell dimensions. As such, it represents great potential for the use of standard ceramic processing methods for nanotechnology. The phase separation occurs spontaneously in the homologous series of the perovskite-based Li-ion conductor, (Nd(2/3-x)Li(3x))TiO3, to give two phases whose dimensions both extend into the nanometre scale. This unique feature could lead to its application as a template for the assembly of nanostructures or molecular monolayers.
We investigated the effect of substrate-induced strain on the metal-insulator transition (MIT) in single-crystalline VO(2) nanobeams. A simple nanobeam-substrate adhesion leads to uniaxial strain along the nanobeam length because of the nanobeam's unique morphology. The strain changes the relative stability of the metal (M) and insulator (I) phases and leads to spontaneous formation of periodic, alternating M-I domain patterns during the MIT. The spatial periodicity of the M-I domains can be modified by changing the nanobeam thickness and the Young's modulus of the substrate.
Nanostructures/chemistry , Vanadium Compounds/chemistry , Crystallization , Elasticity , Electric Conductivity , Nanostructures/ultrastructure , Oxides/chemistry , Stress, Mechanical , Transducers
