Local nanoscale phase impurities are degradation sites in halide perovskites.

Understanding the nanoscopic chemical and structural changes that drive instabilities in emerging energy materials is essential for mitigating device degradation. The power conversion efficiency of halide perovskite photovoltaic devices has reached 25.7 per cent in single-junction and 29.8 per cent in tandem perovskite/silicon cells1,2, yet retaining such performance under continuous operation has remained elusive3. Here we develop a multimodal microscopy toolkit to reveal that in leading formamidinium-rich perovskite absorbers, nanoscale phase impurities, including hexagonal polytype and lead iodide inclusions, are not only traps for photoexcited carriers, which themselves reduce performance4,5, but also, through the same trapping process, are sites at which photochemical degradation of the absorber layer is seeded. We visualize illumination-induced structural changes at phase impurities associated with trap clusters, revealing that even trace amounts of these phases, otherwise undetected with bulk measurements, compromise device longevity. The type and distribution of these unwanted phase inclusions depends on the film composition and processing, with the presence of polytypes being most detrimental for film photo-stability. Importantly, we reveal that both performance losses and intrinsic degradation processes can be mitigated by modulating these defective phase impurities, and demonstrate that this requires careful tuning of local structural and chemical properties. This multimodal workflow to correlate the nanoscopic landscape of beam-sensitive energy materials will be applicable to a wide range of semiconductors for which a local picture of performance and operational stability has yet to be established.

Performance-limiting nanoscale trap clusters at grain junctions in halide perovskites.

Halide perovskite materials have promising performance characteristics for low-cost optoelectronic applications. Photovoltaic devices fabricated from perovskite absorbers have reached power conversion efficiencies above 25 per cent in single-junction devices and 28 per cent in tandem devices1,2. This strong performance (albeit below the practical limits of about 30 per cent and 35 per cent, respectively3) is surprising in thin films processed from solution at low-temperature, a method that generally produces abundant crystalline defects4. Although point defects often induce only shallow electronic states in the perovskite bandgap that do not affect performance5, perovskite devices still have many states deep within the bandgap that trap charge carriers and cause them to recombine non-radiatively. These deep trap states thus induce local variations in photoluminescence and limit the device performance6. The origin and distribution of these trap states are unknown, but they have been associated with light-induced halide segregation in mixed-halide perovskite compositions7 and with local strain8, both of which make devices less stable9. Here we use photoemission electron microscopy to image the trap distribution in state-of-the-art halide perovskite films. Instead of a relatively uniform distribution within regions of poor photoluminescence efficiency, we observe discrete, nanoscale trap clusters. By correlating microscopy measurements with scanning electron analytical techniques, we find that these trap clusters appear at the interfaces between crystallographically and compositionally distinct entities. Finally, by generating time-resolved photoemission sequences of the photo-excited carrier trapping process10,11, we reveal a hole-trapping character with the kinetics limited by diffusion of holes to the local trap clusters. Our approach shows that managing structure and composition on the nanoscale will be essential for optimal performance of halide perovskite devices.

Hole-limited electrochemical doping in conjugated polymers.

Simultaneous transport and coupling of ionic and electronic charges is fundamental to electrochemical devices used in energy storage and conversion, neuromorphic computing and bioelectronics. While the mixed conductors enabling these technologies are widely used, the dynamic relationship between ionic and electronic transport is generally poorly understood, hindering the rational design of new materials. In semiconducting electrodes, electrochemical doping is assumed to be limited by motion of ions due to their large mass compared to electrons and/or holes. Here, we show that this basic assumption does not hold for conjugated polymer electrodes. Using operando optical microscopy, we reveal that electrochemical doping speeds in a state-of-the-art polythiophene can be limited by poor hole transport at low doping levels, leading to substantially slower switching speeds than expected. We show that the timescale of hole-limited doping can be controlled by the degree of microstructural heterogeneity, enabling the design of conjugated polymers with improved electrochemical performance.

Revisiting metal fluorides as lithium-ion battery cathodes.

Metal fluorides, promising lithium-ion battery cathode materials, have been classified as conversion materials due to the reconstructive phase transitions widely presumed to occur upon lithiation. We challenge this view by studying FeF3 using X-ray total scattering and electron diffraction techniques that measure structure over multiple length scales coupled with density functional theory calculations, and by revisiting prior experimental studies of FeF2 and CuF2. Metal fluoride lithiation is instead dominated by diffusion-controlled displacement mechanisms, and a clear topological relationship between the metal fluoride F- sublattices and that of LiF is established. Initial lithiation of FeF3 forms FeF2 on the particle's surface, along with a cation-ordered and stacking-disordered phase, A-LixFeyF3, which is structurally related to α-/ß-LiMn2+Fe3+F6 and which topotactically transforms to B- and then C-LixFeyF3, before forming LiF and Fe. Lithiation of FeF2 and CuF2 results in a buffer phase between FeF2/CuF2 and LiF. The resulting principles will aid future developments of a wider range of isomorphic metal fluorides.

Secondary magnetite in ancient zircon precludes analysis of a Hadean geodynamo.

Zircon crystals from the Jack Hills, Western Australia, are one of the few surviving mineralogical records of Earth's first 500 million years and have been proposed to contain a paleomagnetic record of the Hadean geodynamo. A prerequisite for the preservation of Hadean magnetization is the presence of primary magnetic inclusions within pristine igneous zircon. To date no images of the magnetic recorders within ancient zircon have been presented. Here we use high-resolution transmission electron microscopy to demonstrate that all observed inclusions are secondary features formed via two distinct mechanisms. Magnetite is produced via a pipe-diffusion mechanism whereby iron diffuses into radiation-damaged zircon along the cores of dislocations and is precipitated inside nanopores and also during low-temperature recrystallization of radiation-damaged zircon in the presence of an aqueous fluid. Although these magnetites can be recognized as secondary using transmission electron microscopy, they otherwise occur in regions that are indistinguishable from pristine igneous zircon and carry remanent magnetization that postdates the crystallization age by at least several hundred million years. Without microscopic evidence ruling out secondary magnetite, the paleomagnetic case for a Hadean-Eoarchean geodynamo cannot yet been made.

Nanomagnetic properties of the meteorite cloudy zone.

Meteorites contain a record of their thermal and magnetic history, written in the intergrowths of iron-rich and nickel-rich phases that formed during slow cooling. Of intense interest from a magnetic perspective is the "cloudy zone," a nanoscale intergrowth containing tetrataenite-a naturally occurring hard ferromagnetic mineral that has potential applications as a sustainable alternative to rare-earth permanent magnets. Here we use a combination of high-resolution electron diffraction, electron tomography, atom probe tomography (APT), and micromagnetic simulations to reveal the 3D architecture of the cloudy zone with subnanometer spatial resolution and model the mechanism of remanence acquisition during slow cooling on the meteorite parent body. Isolated islands of tetrataenite are embedded in a matrix of an ordered superstructure. The islands are arranged in clusters of three crystallographic variants, which control how magnetic information is encoded into the nanostructure. The cloudy zone acquires paleomagnetic remanence via a sequence of magnetic domain state transformations (vortex to two domain to single domain), driven by Fe-Ni ordering at 320 °C. Rather than remanence being recorded at different times at different positions throughout the cloudy zone, each subregion of the cloudy zone records a coherent snapshot of the magnetic field that was present at 320 °C. Only the coarse and intermediate regions of the cloudy zone are found to be suitable for paleomagnetic applications. The fine regions, on the other hand, have properties similar to those of rare-earth permanent magnets, providing potential routes to synthetic tetrataenite-based magnetic materials.

Magnetic Vortex States in Toroidal Iron Oxide Nanoparticles: Combining Micromagnetics with Tomography.

Iron oxide nanorings have great promise for biomedical applications because of their magnetic vortex state, which endows them with a low remanent magnetization while retaining a large saturation magnetization. Here we use micromagnetic simulations to predict the exact shapes that can sustain magnetic vortices, using a toroidal model geometry with variable diameter, ring thickness, and ring eccentricity. Our model phase diagram is then compared with simulations of experimental geometries obtained by electron tomography. High axial eccentricity and low ring thickness are found to be key factors for forming vortex states and avoiding net-magnetized metastable states. We also find that while defects from a perfect toroidal geometry increase the stray field associated with the vortex state, they can also make the vortex state more energetically accessible. These results constitute an important step toward optimizing the magnetic behavior of toroidal iron oxide nanoparticles.

Functional Group Mapping by Electron Beam Vibrational Spectroscopy from Nanoscale Volumes.

Vibrational spectroscopies directly record details of bonding in materials, but spatially resolved methods have been limited to surface techniques for mapping functional groups at the nanoscale. Electron energy loss spectroscopy (EELS) in the scanning transmission electron microscope presents a route to functional group analysis from nanoscale volumes using transmitted subnanometer electron probes. Here, we now use vibrational EELS to map distinct carboxylate and imidazolate linkers in a metal-organic framework (MOF) crystal-glass composite material. Domains <100 nm in size are observed using vibrational EELS, with recorded spatial resolution <15 nm at interfaces in the composite. This nanoscale functional group mapping is confirmed by correlated EELS at core ionization edges as well as X-ray energy dispersive spectroscopy for elemental mapping of the metal centers of the two constituent MOFs. These results present a complete nanoscale analysis of the building blocks of the MOF composite and establish spatially resolved functional group analysis using electron beam spectroscopy for crystalline and amorphous organic and metal-organic solids.

Direct Imaging of Correlated Defect Nanodomains in a Metal-Organic Framework.

Defect engineering can enhance key properties of metal-organic frameworks (MOFs). Tailoring the distribution of defects, for example in correlated nanodomains, requires characterization across length scales. However, a critical nanoscale characterization gap has emerged between the bulk diffraction techniques used to detect defect nanodomains and the subnanometer imaging used to observe individual defects. Here, we demonstrate that the emerging technique of scanning electron diffraction (SED) can bridge this gap uniquely enabling both nanoscale crystallographic analysis and the low-dose formation of multiple diffraction contrast images for defect analysis in MOFs. We directly image defect nanodomains in the MOF UiO-66(Hf) over an area of ca. 1000 nm and with a spatial resolution ca. 5 nm to reveal domain morphology and distribution. Based on these observations, we suggest possible crystal growth processes underpinning synthetic control of defect nanodomains. We also identify likely dislocations and small angle grain boundaries, illustrating that SED could be a key technique in developing the potential for engineering the distribution of defects, or "microstructure", in functional MOF design.

Mechanical Properties and Processing Techniques of Bulk Metal-Organic Framework Glasses.

Melt quenched metal-organic framework (MOF) glasses define a new category of glass, distinct from metallic, organic, and inorganic glasses, owing to the dominant role of metal-ligand coordination bonding. The mechanical properties of glasses in general are important given their application in protective coatings and display technologies, though little is known about MOF glasses in this respect. The experimental elucidation of key properties such as their scratch resistance has been limited by the lack of processing methodologies capable of producing bulk glass samples. Here, nanoindentation was used to investigate the Young's modulus and hardness of four melt-quenched glasses formed from zeolitic imidazolate frameworks (ZIF): agZIF-4, agZIF-62, agZIF-76, and agZIF-76-mbIm. The creep resistance of the melt-quenched glasses was studied via strain-rate jump (SRJ) tests and through constant load and hold (CLH) indentation creep experiments. Values for the strain-rate sensitivity were found to be close to those for other glassy polymers and Se-rich GeSe chalcogenide glasses. Vacuum hot-pressing of agZIF-62 resulted in an inhomogeneous bulk sample containing the glass and amorphous non-melt-quenched aZIF-62. Remelting and annealing, however, resulted in the fabrication of a transparent, bubble-free bulk specimen, which allowed the first scratch testing experiments to be performed on an MOF glass.

Synthesis and Properties of a Compositional Series of MIL-53(Al) Metal-Organic Framework Crystal-Glass Composites.

Metal-organic framework crystal-glass composites (MOF-CGCs) are materials in which a crystalline MOF is dispersed within a MOF glass. In this work, we explore the room-temperature stabilization of the open-pore form of MIL-53(Al), usually observed at high temperature, which occurs upon encapsulation within a ZIF-62(Zn) MOF glass matrix. A series of MOF-CGCs containing different loadings of MIL-53(Al) were synthesized and characterized using X-ray diffraction and nuclear magnetic resonance spectroscopy. An upper limit of MIL-53(Al) that can be stabilized in the composite was determined for the first time. The nanostructure of the composites was probed using pair distribution function analysis and scanning transmission electron microscopy. Notably, the distribution and integrity of the crystalline component in a sample series were determined, and these findings were related to the MOF-CGC gas adsorption capacity in order to identify the optimal loading necessary for maximum CO2 sorption capacity.

A sol-gel monolithic metal-organic framework with enhanced methane uptake.

A critical bottleneck for the use of natural gas as a transportation fuel has been the development of materials capable of storing it in a sufficiently compact form at ambient temperature. Here we report the synthesis of a porous monolithic metal-organic framework (MOF), which after successful packing and densification reaches 259 cm3 (STP) cm-3 capacity. This is the highest value reported to date for conformed shape porous solids, and represents a greater than 50% improvement over any previously reported experimental value. Nanoindentation tests on the monolithic MOF showed robust mechanical properties, with hardness at least 130% greater than that previously measured in its conventional MOF counterparts. Our findings represent a substantial step in the application of mechanically robust conformed and densified MOFs for high volumetric energy storage and other industrial applications.

Three-dimensional imaging of localized surface plasmon resonances of metal nanoparticles.

The remarkable optical properties of metal nanoparticles are governed by the excitation of localized surface plasmon resonances (LSPRs). The sensitivity of each LSPR mode, whose spatial distribution and resonant energy depend on the nanoparticle structure, composition and environment, has given rise to many potential photonic, optoelectronic, catalytic, photovoltaic, and gas- and bio-sensing applications. However, the precise interplay between the three-dimensional (3D) nanoparticle structure and the LSPRs is not always fully understood and a spectrally sensitive 3D imaging technique is needed to visualize the excitation on the nanometre scale. Here we show that 3D images related to LSPRs of an individual silver nanocube can be reconstructed through the application of electron energy-loss spectrum imaging, mapping the excitation across a range of orientations, with a novel combination of non-negative matrix factorization, compressed sensing and electron tomography. Our results extend the idea of substrate-mediated hybridization of dipolar and quadrupolar modes predicted by theory, simulations, and electron and optical spectroscopy, and provide experimental evidence of higher-energy mode hybridization. This work represents an advance both in the understanding of the optical response of noble-metal nanoparticles and in the probing, analysis and visualization of LSPRs.

Atom-by-Atom Resolution of Structure-Function Relations over Low-Nuclearity Metal Catalysts.

Controlling the structure sensitivity of catalyzed reactions over metals is central to developing atom-efficient chemical processes. Approaching the minimum ensemble size, the properties enter a non-scalable regime in which each atom counts. Almost all trends in this ultra-small frontier derive from surface science approaches using model systems, because of both synthetic and analytical challenges. Exploiting the unique coordination chemistry of carbon nitride, we discriminate through experiments and simulations the interplay between the geometry, electronic structure, and reactivity of palladium atoms, dimers, and trimers. Catalytic tests evidence application-dependent requirements of the active ensemble. In the semi-hydrogenation of alkynes, the nuclearity primarily impacts activity, whereas the selectivity and stability are affected in Suzuki coupling. This powerful approach will provide practical insights into the design of heterogeneous catalysts comprising well-defined numbers of atoms.

Subwavelength Spatially Resolved Coordination Chemistry of Metal-Organic Framework Glass Blends.

Microstructured metal-organic framework (MOF) glasses have been produced by combining two amorphous MOFs. However, the electronic structure of these materials has not been interrogated at the length scales of the chemical domains formed in these glasses. Here, we report a subwavelength spatially resolved physicochemical analysis of the electronic states at visible and UV energies in a blend of two zeolitic imidazolate frameworks (ZIFs), ZIF-4-Co and ZIF-62-Zn. By combining spectroscopy at visible and UV energies as well as at core ionization energies in electron energy loss spectroscopy in the scanning transmission electron microscope with density functional theory calculations, we show that domains less than 200 nm in size retain the electronic structure of the precursor crystalline ZIF phases. Prototypical signatures of coordination chemistry including d- d transitions in ZIF-4-Co are assigned and mapped with nanoscale precision.

Synthetic mimetics of the endogenous gastrointestinal nanomineral: Silent constructs that trap macromolecules for intracellular delivery.

Amorphous magnesium-substituted calcium phosphate (AMCP) nanoparticles (75-150nm) form constitutively in large numbers in the mammalian gut. Collective evidence indicates that they trap and deliver luminal macromolecules to mucosal antigen presenting cells (APCs) and facilitate gut immune homeostasis. Here, we report on a synthetic mimetic of the endogenous AMCP and show that it has marked capacity to trap macromolecules during formation. Macromolecular capture into AMCP involved incorporation as shown by STEM tomography of the synthetic AMCP particle with 5nm ultra-fine iron (III) oxohydroxide. In vitro, organic cargo-loaded synthetic AMCP was taken up by APCs and tracked to lysosomal compartments. The AMCP itself did not regulate any gene, or modify any gene regulation by its cargo, based upon whole genome transcriptomic analyses. We conclude that synthetic AMCP can efficiently trap macromolecules and deliver them to APCs in a silent fashion, and may thus represent a new platform for antigen delivery.

3D Visualization of the Iron Oxidation State in FeO/Fe3O4 Core-Shell Nanocubes from Electron Energy Loss Tomography.

The physicochemical properties used in numerous advanced nanostructured devices are directly controlled by the oxidation states of their constituents. In this work we combine electron energy-loss spectroscopy, blind source separation, and computed tomography to reconstruct in three dimensions the distribution of Fe(2+) and Fe(3+) ions in a FeO/Fe3O4 core/shell cube-shaped nanoparticle with nanometric resolution. The results highlight the sharpness of the interface between both oxides and provide an average shell thickness, core volume, and average cube edge length measurements in agreement with the magnetic characterization of the sample.

Multicomponent signal unmixing from nanoheterostructures: overcoming the traditional challenges of nanoscale X-ray analysis via machine learning.

The chemical composition of core-shell nanoparticle clusters have been determined through principal component analysis (PCA) and independent component analysis (ICA) of an energy-dispersive X-ray (EDX) spectrum image (SI) acquired in a scanning transmission electron microscope (STEM). The method blindly decomposes the SI into three components, which are found to accurately represent the isolated and unmixed X-ray signals originating from the supporting carbon film, the shell, and the bimetallic core. The composition of the latter is verified by and is in excellent agreement with the separate quantification of bare bimetallic seed nanoparticles.

The Dark Side of EDX Tomography: Modeling Detector Shadowing to Aid 3D Elemental Signal Analysis.

A simple model is proposed to account for the loss of collected X-ray signal by the shadowing of X-ray detectors in the scanning transmission electron microscope. The model is intended to aid the analysis of three-dimensional elemental data sets acquired using energy-dispersive X-ray tomography methods where shadow-free specimen holders are unsuitable or unavailable. The model also provides a useful measure of the detection system geometry.

Measurement of molecular motion in organic semiconductors by thermal diffuse electron scattering.

Many of the remarkable electrical and optical properties of organic semiconductors are governed by the interaction of electronic excitations with intra- and intermolecular vibrational modes. However, in specific systems this interaction is not understood in detail at a molecular level and this has been due, at least in part, to the lack of easy-to-use and widely available experimental probes of the structural dynamics. Here we demonstrate that thermal diffuse scattering in electron diffraction patterns from organic semiconductors, such as 6,13-bistriisopropyl-silylethynyl pentacene, allows the dominant lattice vibrational modes to be probed directly. The amplitude and direction of the dominant molecular motions were determined by comparison of the diffuse scattering with simulations and molecular dynamics calculations. Our widely applicable approach enables a much deeper understanding of the structural dynamics in a broad range of organic semiconductors.