Search

Palladium (Pd) catalysts have been extensively studied for the direct synthesis of H2O through the hydrogen oxidation reaction at ambient conditions. This heterogeneous catalytic reaction not only holds considerable practical significance but also serves as a classical model for investigating fundamental mechanisms, including adsorption and reactions between adsorbates. Nonetheless, the governing mechanisms and kinetics of its intermediate reaction stages under varying gas conditions remains elusive. This is attributed to the intricate interplay between adsorption, atomic diffusion, and concurrent phase transformation of catalyst. Herein, the Pd-catalyzed, water-forming hydrogen oxidation is studied, in situ, to investigate intermediate reaction stages via fluid cell transmission electron microscopy. The dynamic behaviors of water generation, associated with reversible palladium hydride formation, are captured in real time with a nanoscale spatial resolution. Our findings suggest that the hydrogen oxidation rate catalyzed by Pd is significantly affected by the sequence in which gases are introduced. Through direct evidence of electron diffraction and density functional theory calculation, we demonstrate that the hydrogen oxidation rate is limited by adsorption processes of gas precursors. These nanoscale insights help identify the optimal reaction conditions for Pd-catalyzed hydrogen oxidation, which has substantial implications for water production technologies. The developed understanding also advocates a broader exploration of analogous mechanisms in other metal-catalyzed reactions., Comment: 30 pages, 4 figures

Superconducting Nb thin films have recently attracted significant attention due to their utility for quantum information technologies. In the processing of Nb thin films, fluoride-based chemical etchants are commonly used to remove surface oxides that are known to affect superconducting quantum devices adversely. However, these same etchants can also introduce hydrogen to form Nb hydrides, potentially negatively impacting microwave loss performance. Here, we present comprehensive materials characterization of Nb hydrides formed in Nb thin films as a function of fluoride chemical treatments. In particular, secondary-ion mass spectrometry, X-ray scattering, and transmission electron microscopy reveal the spatial distribution and phase transformation of Nb hydrides. The rate of hydride formation is determined by the fluoride solution acidity and the etch rate of Nb2O5, which acts as a diffusion barrier for hydrogen into Nb. The resulting Nb hydrides are detrimental to Nb superconducting properties and lead to increased power-independent microwave loss in coplanar waveguide resonators. However, Nb hydrides do not correlate with two-level system loss or device aging mechanisms. Overall, this work provides insight into the formation of Nb hydrides and their role in microwave loss, thus guiding ongoing efforts to maximize coherence time in superconducting quantum devices.

Leveraging the high energy electrons as probe for the atomic landscape of materials, the importance of understanding radiolysis chemistry in the field of transmission electron microscopy (TEM) is exceptionally important. Reactive chemical species generated from electron-material interactions diffuse throughout the sample and may induce "artifact" reactions with the specimen of interest. However, in other aspects, this radiolysis can be utilized to intentionally trigger chemical reactions related to the nucleation and growth of colloidal nanoparticles, as well as chemical etching under a priori conditions in fluid condition. Therefore, systematic research and new theories are required to help researchers gain a deeper understanding of these electron-materials interactions either to mitigate damage or rationally use radical chemistry especially in the environmental TEM (E-TEM). Radiolysis in open-cell gas phase TEM (GPTEM) under reduced pressures is usually disregarded considering the low density of molecules and high diffusivity. However, for emerging closed-cell GPTEM, which usually involves the usage of higher pressures, less is known. Here, we utilize an ultrathin (UT) silicon nitride gas cell to investigate and quantify the effects of electron dosage on the oxidation behavior of {100}-faceted aluminum (Al) nanocubes under various conditions. In addition, we develop a generalized computational code to elucidate radiolysis chemistry in varying media with consideration of the diffusion dynamics, while rationalizing the experimental observations. Based on these theoretical electron-fluid interaction models, we propose guidelines to control the radical species of the closed-cell in situ nanoreactors, paving the way to the nanoscale control of chemical reactions in E-TEM.

Scanning transmission electron microscopy (STEM) has been extensively used for imaging complex materials down to atomic resolution. The most commonly employed STEM modality, annular dark-field imaging, produces easily-interpretable contrast, but is dose-inefficient and produces little to no discernible contrast for light elements and weakly-scattering samples. An alternative is to use STEM phase retrieval imaging, enabled by high speed detectors able to record full images of a diffracted STEM probe over a grid of scan positions. Phase retrieval imaging in STEM is highly dose-efficient, enabling the measurement of the structure of beam-sensitive materials such as biological samples. Here, we comprehensively describe the theoretical background, algorithmic implementation details, and perform both simulated and experimental tests for three iterative phase retrieval STEM methods: focused-probe differential phase contrast, defocused-probe parallax imaging, and a generalized ptychographic gradient descent method implemented in two and three dimensions. We discuss the strengths and weaknesses of each of these approaches by comparing the transfer of information using analytical expressions and numerical results for a white-noise model. This presentation of STEM phase retrieval methods aims to make these methods more approachable, reproducible, and more readily adoptable for many classes of samples., Comment: 25 pages, 14 figures, 1 table

Calcium carbonate (CaCO3), the most abundant biogenic mineral on earth, plays a crucial role in various fields. Of the four polymorphs, calcite, aragonite, vaterite, and amorphous CaCO3, vaterite is the most enigmatic one due to an ongoing debate regarding its structure that has persisted for nearly a century. In this work, based on systematic transmission electron microscopy characterizations, elaborate crystallographic analysis and machine learning aided molecular dynamics simulations with ab initio accuracy, we reveal that vaterite can be regarded as a polytypic structure. The basic phase is a monoclinic lattice possessing pseudohexagonal symmetry. Direct imaging and atomic-scale simulations provide evidence that a single grain of vaterite can have three orientation variants. Additionally, we find that vaterite undergoes a second-order phase transition. These atomic scale insights provide a comprehensive understanding of the structure of vaterite and offer new perspectives on the biomineralization process of calcium carbonate.

We present a novel transmon qubit fabrication technique that yields systematic improvements in T$_1$ relaxation times. We fabricate devices using an encapsulation strategy that involves passivating the surface of niobium and thereby preventing the formation of its lossy surface oxide. By maintaining the same superconducting metal and only varying the surface structure, this comparative investigation examining different capping materials, such as tantalum, aluminum, titanium nitride, and gold, and film substrates across different qubit foundries definitively demonstrates the detrimental impact that niobium oxides have on the coherence times of superconducting qubits, compared to native oxides of tantalum, aluminum or titanium nitride. Our surface-encapsulated niobium qubit devices exhibit T$_1$ relaxation times 2 to 5 times longer than baseline niobium qubit devices with native niobium oxides. When capping niobium with tantalum, we obtain median qubit lifetimes above 300 microseconds, with maximum values up to 600 microseconds, that represent the highest lifetimes to date for superconducting qubits prepared on both sapphire and silicon. Our comparative structural and chemical analysis suggests why amorphous niobium oxides may induce higher losses compared to other amorphous oxides. These results are in line with high-accuracy measurements of the niobium oxide loss tangent obtained with ultra-high Q superconducting radiofrequency (SRF) cavities. This new surface encapsulation strategy enables even further reduction of dielectric losses via passivation with ambient-stable materials, while preserving fabrication and scalable manufacturability thanks to the compatibility with silicon processes.

In a scanning transmission electron microscope (STEM), producing a high-resolution image generally requires an electron beam focused to the smallest point possible. However, the magnetic lenses used to focus the beam are unavoidably imperfect, introducing aberrations that limit resolution. Modern STEMs overcome this by using hardware aberration correctors comprised of many multipole lenses, but these devices are complex, expensive, and can be difficult to tune. We demonstrate a design for an electrostatic phase plate that can act as an aberration corrector. The corrector is comprised of annular segments, each of which is an independent two-terminal device that can apply a constant or ramped phase shift to a portion of the electron beam. We show the improvement in image resolution using an electrostatic corrector. Engineering criteria impose that much of the beam within the probe-forming aperture be blocked by support bars, leading to large probe tails for the corrected probe that sample the specimen beyond the central lobe. We also show how this device can be used to create other STEM beam profiles such as vortex beams and beams with a high degree of phase diversity, which improve information transfer in ptychographic reconstructions., Comment: 12 pages, 10 figures

Material properties strongly depend on the nature and concentration of defects. Characterizing these features may require nano- to atomic-scale resolution to establish structure-property relationships. 4D-STEM, a technique where diffraction patterns are acquired at a grid of points on the sample, provides a versatile method for highlighting defects. Computational analysis of the diffraction patterns with virtual detectors produces images that can map material properties. Here, using multislice simulations, we explore different virtual detectors that can be applied to the diffraction patterns that go beyond the binary response functions that are possible using ordinary STEM detectors. Using graphene and lead titanate as model systems, we investigate the application of virtual detectors to study local order and in particular defects. We find that using a small convergence angle with a rotationally varying detector most efficiently highlights defect signals. With experimental graphene data, we demonstrate the effectiveness of these detectors in characterizing atomic features, including vacancies, as suggested in simulations. Phase and amplitude modification of the electron beam provides another process handle to change image contrast in a 4D-STEM experiment. We demonstrate how tailored electron beams can enhance signals from short-range order and how a vortex beam can be used to characterize local symmetry., Comment: 16 pages, 14 figures

Superconducting thin films of niobium have been extensively employed in transmon qubit architectures. Although these architectures have demonstrated remarkable improvements in recent years, further improvements in performance through materials engineering will aid in large-scale deployment. Here, we use information retrieved from secondary ion mass spectrometry and electron microscopy to conduct a detailed assessment of the surface oxide that forms in ambient conditions for transmon test qubit devices patterned from a niobium film. We observe that this oxide exhibits a varying stoichiometry with NbO and NbO$_2$ found closer to the niobium film and Nb$_2$O$_5$ found closer to the surface. In terms of structural analysis, we find that the Nb$_2$O$_5$ region is semicrystalline in nature and exhibits randomly oriented grains on the order of 1-2 nm corresponding to monoclinic N-Nb$_2$O$_5$ that are dispersed throughout an amorphous matrix. Using fluctuation electron microscopy, we are able to map the relative crystallinity in the Nb$_2$O$_5$ region with nanometer spatial resolution. Through this correlative method, we observe that amorphous regions are more likely to contain oxygen vacancies and exhibit weaker bonds between the niobium and oxygen atoms. Based on these findings, we expect that oxygen vacancies likely serve as a decoherence mechanism in quantum systems., Comment: 13 pages, 4 figures

To fully leverage the power of image simulation to corroborate and explain patterns and structures in atomic resolution microscopy (e.g., electron and scanning probe), an initial correspondence between the simulation and experimental image must be established at the outset of further high accuracy simulations or calculations. Furthermore, if simulation is to be used in context of highly automated processes or high-throughput optimization, the process of finding this correspondence itself must be automated. In this work, we introduce ingrained, an open-source automation framework which solves for this correspondence and fuses atomic resolution image simulations into the experimental images to which they correspond. We describe herein the overall ingrained workflow, focusing on its application to interface structure approximations, and the development of an experimentally rationalized forward model for scanning tunneling microscopy simulation.

In situ electron microscopy is a key tool for understanding the mechanisms driving novel phenomena in 2D structures. Unfortunately, due to various practical challenges, technologically relevant 2D heterostructures prove challenging to address with electron microscopy. Here, we use the differential phase contrast imaging technique to build a methodology for probing local electrostatic fields during electrical operation with nanoscale precision in such materials. We find that by combining a traditional DPC setup with a high pass filter, we can largely eliminate electric fluctuations emanating from short-range atomic potentials. With this method, a priori electric field expectations can be directly compared with experimentally derived values to readily identify inhomogeneities and potentially problematic regions. We use this platform to analyze the electric field and charge density distribution across layers of hBN and MoS2., Comment: 13 pages, 4 figures

Layered heterostructure materials with two different functional building blocks can teach us about emergent physical properties and phenomena arising from interactions between the layers. We report the intergrowth compounds KLa$M$$_{1-x}$Te$_{4}$ ($M$ = Mn, Zn; $x\approx$ 0.35) featuring two chemically distinct alternating layers [LaTe$_3$] and [K$M$$_{1-x}$Te]. Their crystal structures are incommensurate, determined by single X-ray diffraction for the Mn compound and transmission electron microscope (TEM) study for the Zn compound. KLaMn$_{1-x}$Te$_{4}$ crystallizes in the orthorhombic superspace group $Pmnm$(01/2${\gamma}$)$s$00 with lattice parameters $a$ = 4.4815(3) {\AA}, $b$ = 21.6649(16) {\AA} and $c$ = 4.5220(3) {\AA}. It exhibits charge density wave (CDW) order at room temperature with a modulation wave vector $\mathbf{q}$ = 1/2$\mathbf{b}$* + 0.3478$\mathbf{c}$* originating from electronic instability of Te-square nets in [LaTe$_{3}$] layers. The Mn analog exhibits a cluster spin glass behavior with spin freezing temperature $T_{\mathrm{f}}$ $\approx$ 5 K attributed to disordered Mn vacancies and competing magnetic interactions in the [Mn$_{1-x}$Te] layers. The Zn analog also has charge density wave order at room temperature with a similar $\mathbf{q}$-vector having the $\mathbf{c}$* component ~ 0.346 confirmed by selected-area electron diffraction (SAED). Electron transfer from [K$M_{1-x}$Te] to [LaTe$_{3}$] layers exists in KLa$M_{1-x}$Te$_{4}$, leading to an enhanced electronic specific heat coefficient. The resistivities of KLa$M_{1-x}$Te$_{4}$ ($M$ = Mn, Zn) exhibit metallic behavior at high temperatures and an upturn at low temperatures, suggesting partial localization of carriers in the [LaTe$_{3}$] layers with some degree of disorder associated with the $M$ atom vacancies in the [$M_{1-x}$Te] layers., Comment: 1 table, 10 figures, 35 pages

Exploiting polaritons in natural vdW materials has been successful in achieving extreme light confinement and low-loss optical devices and enabling simplified device integration. Recently, a-MoO3 has been reported as a semiconducting biaxial vdW material capable of sustaining naturally orthogonal in-plane phonon polariton modes in IR. In this study, we investigate the polarization-dependent optical characteristics of cavities formed using a-MoO3 to extend the degrees of freedom in the design of IR photonic components exploiting the in-plane anisotropy of this material. Polarization-dependent absorption over 80% in a multilayer Fabry-Perot structure with a-MoO3 is reported without the need for nanoscale fabrication on the a-MoO3. We observe coupling between the a-MoO3 optical phonons and the Fabry-Perot cavity resonances. Using cross-polarized reflectance spectroscopy we show that the strong birefringence results in 15% of the total power converted into the orthogonal polarization with respect to incident wave. These findings can open new avenues in the quest for polarization filters and low-loss, integrated planar IR photonics and in dictating polarization control.

Physically vitrifying single-element metallic glass requires ultrahigh cooling rates, which are still unachievable for most of the closest-packed metals. Here, we report a facile synthetic strategy for creating mono-atomic palladium metallic glass nanoparticles with a purity of 99.35 +/- 0.23 at% from palladium-silicon liquid droplets using a cooling rate below 1000 K/s. In-situ environmental transmission electron microscopy directly detected the leaching of silicon. Further hydrogen absorption experiment showed that this palladium metallic glass expanded little upon hydrogen uptake, exhibiting a great potential application for hydrogen separation. Our results provide insight into the formation of mono-atomic metallic glass at nanoscale., Comment: Nano Res. (2022)

For years, solution processing has provided a versatile platform to extend the applications of transition metal dichalcogenides (TMDs) beyond those achievable with traditional preparation methods. However, existing solution-based synthesis and exfoliation approaches are not compatible with complex geometries, particularly when interfacial control is desired. As a result, promising TMD structures, including MoS2/WS2 heterostructures, are barred from the rich assembly and modification opportunities possible with solution preparation. Here, we introduce a strategy that combines traditional vapor phase deposition and solution chemistry to build TMD core-shell heterostructures housed in aqueous media. We report the first synthesized TMD core-shell heterostructure, Au@MoS2@WS2, with an Au nanoparticle core and MoS2 and WS2 shells, and provide a means of suspending the structure in solution to allow for higher order patterning and ligand-based functionalization. High-resolution electron microscopy and Raman spectroscopy provide detailed analysis of the structure and interfaces of the core-shell heterostructures. UV-vis, dynamic light scattering, and zeta potential measurements exhibit the outstanding natural stability and monodispersity of Au@MoS2@WS2 in solution. As a proof of concept, the aqueous environment is utilized to both functionalize the core-shell heterostructures with electrostatic ligands and pattern them into desired configurations on a target substrate. This work harnesses the advantages of vapor phase preparation of nanomaterials and the functionality possible with aqueous suspension to expand future engineering and application opportunities of TMD heterostructures., Comment: 7 pages, 4 figures

Layered transition metal dichalcogenides (TMDs) offer many attractive features for next-generation low-dimensional device geometries. Due to the practical and fabrication challenges related to in situ methods, the atomistic dynamics that give rise to realizable macroscopic device properties are often unclear. In this study, in situ transmission electron microscopy techniques are utilized in order to understand the structural dynamics at play, especially at interfaces and defects, in the prototypical film of monolayer MoS2 under electrical bias. Through our sample fabrication process, we clearly identify the presence of mass transport in the presence of a lateral electric field. In particular, we observe that the voids present at grain boundaries combine to induce structural deformation. The electric field mediates a net vacancy flux from the grain boundary interior to the exposed surface edge sites that leaves molybdenum clusters in its wake. Following the initial biasing cycles, however, the mass flow is largely diminished, and the resultant structure remains stable over repeated biasing. We believe insights from this work can help explain observations of non-uniform heating and preferential oxidation at grain boundary sites in these materials., Comment: 4 figures, ACS Nano

Two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs) are new members of the 2D materials family with wide tunability, highly dynamic structural features and excellent physical properties. Ultrathin 2D HOIPs and their heterostructures with other 2D materials have been exploited for study of new physical phenomena and novel device applications. The in-plane mechanical properties of 2D ultrathin HOIPs are critical for understanding the coupling between mechanical and other physical fields and for integrated devices applications. Here we report for the first time the in-plane mechanical properties of ultrathin freestanding 2D lead iodide perovskite membranes and their dependence on the membrane thickness. The in-plane Young's moduli of 2D HOIPs are smaller than that of conventional covalently bonded 2D materials. Both the Young's modulus and breaking strength first decrease and then plateau as the thickness increases from monolayer to 4 layers due to interlayer slippage during deformation. Our results show that ultrathin 2D HOIPs exhibit outstanding breaking strength/Young's Modulus ratio compared to many other widely used engineering materials and polymeric flexible substrates, which renders them suitable for application into flexible electronic devices.

The interactions between nanoparticles and solvents play a critical role in the formation of complex, metastable nanostructures. However, direct observation of such interactions with high spatial and temporal resolution is challenging with conventional liquid-cell transmission electron microscopy (TEM) experiments. Here, a windowless system consisting of polymer nanoreactors deposited via scanning probe block copolymer lithography (SPBCL) on an amorphous carbon film is used to investigate the coarsening of ultrafine (1-3 nm) Au-Pt bimetallic nanoparticles as a function of solvent evaporation. In such reactors, homogeneous Au-Pt nanoparticles are synthesized from metal ion precursors in situ under electron irradiation. The non-uniform evaporation of the thin polymer film not only concentrates the nanoparticles, but also accelerates the coalescence kinetics at the receding polymer edges. Qualitative analysis of the particle forces influencing coalescence suggests that capillary dragging by the polymer edges plays a significant role in accelerating this process. Taken together, this work: 1) provides fundamental insight into the role of solvents in the chemistry and coarsening behavior of nanoparticles during the synthesis of polyelemental nanostructures, 2) provides insight into how particles form via the SPBCL process, and 3) shows how SPBCL-generated domes, instead of liquid cells, can be used to study nanoparticle formation. More generally, it shows why conventional models of particle coarsening, which do not take into account solvent evaporation, cannot be used to describe what is occurring in thin film, liquid-based syntheses of nanostructures., Comment: 27 pages, 6 figures. Accepted for publication in JACS

2D layered hybrid organic-inorganic perovskites (HOIPs) have demonstrated improved stability and promising photovoltaic performance. The mechanical properties of such functional materials are both fundamentally and practically important to achieve both high performance and mechanical stable (flexible) devices. Here we report the mechanical properties of a series of 2D layered lead iodide HOIPs and investigate the role of structural sub-units (e.g., variation of the length of the organic spacer molecules -R and the number of inorganic layer -n) on the mechanical properties. While 2D HOIPs have much lower nominal elastic moduli and hardness than 3D HOIPs, larger n number and shorter R lead to stiffer materials. DFT simulations showed a similar trend to the experimental results. We compared these findings with other 2D layered crystals and shed light on routes to further tune the out-of-plane mechanical properties of 2D layered HOIPs.

Solid-state transformation is often accompanied by mechanical expansion/compression, due to their volume change and structural evolution at interfaces at the atomic scale. However, these two types of dynamics are usually difficult to monitor in the same time. In this work, we use in-situ transmission electron microscopy to directly study the reduction transformation at the AgCl-Ag interface. Three stages of lattice fluctuations were identified and correlated to the structural evolution. During the steady state, a quasi-layered growth mode of Ag in both vertical and lateral directions were observed due to the confinement of AgCl lattices. The development of planar defects and depletion of AgCl are respectively associated with lattice compression and relaxation. Topography and structure of decomposing AgCl was further monitored by in-situ scanning transmission electron microscopy. Silver species are suggested to originate from both the surface and the interior of AgCl, and be transported to the interface. Such mass transport may have enabled the steady state and lattice compression in this volume-shrinking transformation., Comment: 21 pages, 5 figures; accepted for publication in J. Phys. Chem. Lett

Multicomponent nanoparticles can be synthesized with either homogeneous or phase-segregated architectures depending on the synthesis conditions and elements incorporated. To understand the parameters that determine their structural fate, multicomponent metal-oxide nanoparticles consisting of combinations of Co, Ni, and Cu were synthesized via scanning probe block copolymer lithography and characterized using correlated electron microscopy. These studies revealed that the miscibility, ratio of the metallic components, and the synthesis temperature determine the crystal structure and architecture of the nanoparticles. A Co-Ni-O system forms a rock salt structure largely due to the miscibility of CoO and NiO, while Cu-Ni-O, which has large miscibility gaps, forms either homogeneous oxides, heterojunctions, or alloys depending on the annealing temperature and composition. Moreover, a higher ordered structure, Co-Ni-Cu-O, was found to follow the behavior of lower ordered systems., Comment: 7 pages, 3 figures, 1 scheme. Accepted for publication in Angewandte Chemie

Single layers of transition metal dichalcogenides are two-dimensional direct bandgap semiconductors with degenerate, but inequivalent, `valleys' in the electronic structure that can be selectively excited by polarized light. Coherent superpositions of light and matter, exciton-polaritons, have been observed when these materials are strongly coupled to photons, but these hybrid quasiparticles do not harness the valley-sensitive excitations of monolayer transition metal dichalcogenides. Here, we demonstrate evidence for valley polarized exciton-polaritons in monolayers of MoS$_2$ embedded in a dielectric microcavity. Unlike traditional microcavity exciton-polaritons, these light-matter quasiparticles emit polarized light with spectral Rabi splitting. The interplay of cavity-modified exciton dynamics and intervalley relaxation in the high-cooperativity regime causes valley polarized exciton-polaritons to persist to room temperature, distinct from the vanishing polarization in bare monolayers. Achieving polarization-sensitive polaritonic devices operating at room temperature presents a pathway for manipulating novel valley degrees of freedom in coherent states of light and matter., Comment: 8 pages, 4 figures, and Supplementary Information