Annular Dark-field Scanning Transmission Electron Research Articles

Ferroelectric behavior arising from polar topologies in epitaxially strained SrTiO3-δ ultrathin films

In this work, we show that epitaxially strained SrTiO3-δ thin films, grown by ion-beam sputtering onto (001)Nb:SrTiO3 substrates, exhibit a ferroelectric behavior. At the atomic-scale, through high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images, it was possible to identify the presence of polar nanoregions with a non-trivial polar topological structures in the SrTiO3-δ film, which are induced through oxygen vacancies. To further confirm the presence of strained regions with a polar structure, Raman spectroscopy and high-resolution X-ray diffraction were employed and it was possible to confirm the presence of a tetragonal structure in the SrTiO3-δ film, with a tetragonality ratio (c/a) of 1.005. Scanning probe microscopy and macroscopic polarization-electric field hysteresis loops show ferroelectric behavior with maximum polarization of ∼1.5 μC/cm2, remnant polarization of ∼0.4 μC/cm2 and coercive field of ∼0.3 MV/cm. This work opens a window for exploring novel polar topological effects in sub-10 nm thin film materials for non-volatile memory application.

Hidden Impurities Generate False Positives in Single Atom Catalyst Imaging.

Single-atom catalysts (SACs) are an emerging class of materials, leveraging maximum atom utilization and distinctive structural and electronic properties to bridge heterogeneous and homogeneous catalysis. Direct imaging methods, such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, are commonly applied to confirm the atomic dispersion of active sites. However, interpretations of data from these techniques can be challenging due to simultaneous contributions to intensity from impurities introduced during synthesis processes, as well as any variation in position relative to the focal plane of the electron beam. To address this matter, this paper presents a comprehensive study on two representative SACs containing isolated nickel or copper atoms. Spectroscopic techniques, including X-ray absorption spectroscopy, were employed to prove the high metal dispersion of the catalytic atoms. Employing scanning transmission electron microscopy imaging combined with single-atom-sensitive electron energy loss spectroscopy, we scrutinized thin specimens of the catalysts to provide an unambiguous chemical identification of the observed single-atom species and thereby distinguish impurities from active sites at the single-atom level. Overall, the study underscores the complexity of SACs characterization and establishes the importance of the use of spectroscopy in tandem with imaging at atomic resolution to fully and reliably characterize single-atom catalysts.

Homogeneous distribution of highly dispersed Pt species over O and P co-doped g-C3N4 and its superior photocatalytic H2 evolution activity

In this study, we synthesized O and P co-doped graphitic C3N4 (OPCN) materials by a one-step calcination method and prepared Pt/OPCN photocatalysts for the photocatalytic H2 evolution reaction. Among the Pt/OPCN catalysts with various O and P contents, Pt/OPCN2 exhibited the highest H2 evolution rate of 2198 μmol·g−1 (AQE = 7.33%), which was 1.65 times higher than that of Pt/CN (1330 μmol·g−1). Moreover, Pt/OPCN2 demonstrated excellent photocatalytic properties, such as suitable band gap (2.50eV) for visible light and efficient charge separation of photoexcited electron–hole pairs, which was confirmed by ultraviolet-visible spectroscopy, electrochemical impedance spectroscopy, photoluminescence spectroscopy, and time-resolved photoluminescence measurements. Fundamentally, the Pt species effectively interacted with neighboring P=O and C=O functional groups that optimally located defective OPCN2, resulting in a homogeneous formation of highly dispersed PtO evenly distributed over Pt/OPCN2, as confirmed by X-ray photoelectron spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, and density functional theory calculations. However, excessive O and P contents of OPCN3 damaged the morphological structure of g-C3N4, inducing a poor interaction between the Pt species and OPCN3 and forming isolated Pt nanoparticles, resulting in the low photocatalytic activity of Pt/OPCN3.

Atomic-level investigation of structure and formation process of Y3Al5O12 with super-high content of Ce emitting anomalous orange-red emissions

Ce-doped yttrium aluminum garnet (YAG:Ce, Y3Al5O12:Ce) is the most commonly used yellow phosphor in white light-emitting diodes. Recently, we found that (Y1–xCex)3Al5O12:Ce with a super-high content of Ce (x = 0.11–0.21) can be prepared by a polymerized complex method and exhibits anomalous orange–red emission. To understand the nature of this anomalous behavior from the atomic level, we applied high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and scanning transmission electron microscopy–energy dispersive X-ray spectroscopy (STEM-EDS), a state-of-the-art technique that enables analysis of the atomic-level elemental distributions of Al, Y, and Ce. STEM-EDS images on the atomic level were successfully obtained for YAG:Ce. It was found that Ce in Y site has spatially uneven for few nanometers. Ce–K edge extended X-ray absorption fine structure (EXAFS) analysis was also conducted, which revealed a high level of asymmetry around Ce. By combining the STEM-EDS and EXAFS results, a dynamic model for the red emission was proposed. STEM-EDS also revealed that CeO2 nanocrystals were firstly formed with low-temperature annealing and that the reaction of Y with the CeO2 nanocrystals subsequently yielded YAG:Ce, unlike in the conventional one-step high-temperature synthesis.

Aminosilane assisted deposition of gold nanoparticles on Zn(OH)2 nanosheets and their application in electrochemical sensor

A facile and efficient method for systematical deposition of gold nanoparticles (AuNPs) on Zn(OH)2 nanosheets (NS) with different Zn and Au ratios was established in the presence of N-[3-(trimethoxysilyl)propyl]diethylenetriamine (TPDT silane), without adding any external reducing agents, at room temperature. Here, TPDT silane behaves as both a stabilizing and reducing agent. UV–vis absorption spectroscopy, transmission electron microscopy, high-angle annular dark-field scanning transmission electron microscopy-energy dispersive X-ray spectroscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy were used to confirm the formation of AuNPs on Zn(OH)2 NS. As the concentration of AuNPs increased, a proportional increase in both the number and size of deposited AuNPs on Zn(OH)2 NS was observed. To understand how the variation in the number and size of AuNPs affects their catalytic activity, the electrocatalytic activity of different composition ratios of Zn(OH)2-Au NS toward nitrite ions was studied using cyclic voltammetry and amperometric technique. The TPDT-stabilized Zn(OH)2-Au NS showed high electrocatalytic activity, attributed to the effective electron transfer from Zn(OH)2 NS to AuNPs, creating a synergistic effect that enhances the overall activity. The optimal Zn(OH)2-Au NS modified electrode showed an amperometric sensitivity of 5.72 nA/µM and a limit of detection of 1.2 µM for nitrite ions in water sample well below the guideline value of WHO. This demonstrates the practical applicability of this method for real-world water analysis.

Electrodeposition of Cu with Amino Acids toward Electrocatalytic Enhancement of CO2 Reduction Reaction

This study investigates the effect of five amino acids on the electrodeposition of Cu to enhance its electrocatalytic performance in CO2 reduction reactions (CO2RR). The amino acids significantly influenced the deposition potential, crystallite size, and surface morphology of the electrodeposited Cu. Electrodeposited Cu with amino acids exhibit significantly smaller crystallites and higher particle density on carbon paper relative to amino acid-free samples. The integration of amino acids into the electrodeposited Cu was confirmed via high-angle annular dark-field scanning transmission electron microscopy, energy dispersive X-ray spectroscopy and hard X-ray photoelectron spectroscopy. All electrodeposited Cu exhibits a higher faradaic efficiency (FE) in the electrochemical reduction of CO2 to CH4 relative to Cu foil (24.2%), regardless of the presence or absence (55.0%) of amino acids when the electrolysis was conducted at −1.27 V vs RHE. Electrodeposited Cu with L-histidine, containing an imidazole group, demonstrates a higher FE of CH4 (67.6%) and effectively suppressed the hydrogen evolution reaction, highlighting the crucial role of amino acid functional groups, particularly imidazole, in augmenting the electrochemical conversion of CO2 to CH4. The study demonstrates the critical influence of specific functional groups in amino acids on the catalytic efficiency of electrodeposited Cu in CO2RR electrocatalysis applications.

Complementary nanodomain structures in topologically close-packed precipitates of Al-Zn-Mg-Cu alloy

High-strength aluminium alloys attract continuous research interest, owing to their wide use in aerospace and terrestrial transportation industries. The performance of the alloys is essentially determined by nanoscale precipitates, thus understanding the structure and formation mechanism of the precipitates during thermal processing is of great importance. Here, we reveal complementary domain structures in precipitates in a high-strength Al-Zn-Mg-Cu alloy using a combination of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. Through the transfer of fivefold symmetry polyhedra at domain boundaries, the intermediate precipitates develop two sets of highly ordered and structurally complementary nanoscale domains in their nucleation and growth. This new type of atom packing maintains the topologically close-packed structure inside the precipitates while reducing the lattice misfit with the Al matrix and the barrier of structural transformations on two interfaces, demonstrating good thermal stability. Our discoveries lead to insight into the precipitate evolution in the Al-Zn-Mg-Cu alloy system and can help understand other precipitation processes of complex structured phases. Furthermore, the evolution process demonstrates an advanced mode of building metastable architectures with nanoscale interlocking pieces in alloy matrixes, which may inspire strategies to obtain high-strength, lightweight and thermostable alloys.

Microstructural Evolution and Tensile Properties of Al-Si Piston Alloys during Long-Term Thermal Exposure

The present study investigated microstructural evolution and changes in tensile properties of an Al-Si piston alloy subjected to thermal exposures at 250 and 350 °C for 150, 300, and 500 h. Microstructural and nanoscale precipitates were characterized using a combination of high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) images and scanning electron microscopy (SEM). The tensile testing was performed. The results demonstrated that the thermal exposure induced granulation of the δ-Al3CuNi particles, alongside precipitation of the θ-Al2Cu phase particles and AlCu clusters within the matrix. Specifically, an increase in the size and number density of the θ-Al2Cu phase particles was observed with exposure time at 250 °C. Conversely, at 350 °C, the θ-Al2Cu particles exhibited a gradual increase in size with prolonged thermal exposure, coupled with a decrease in their number density. AlCu clusters precipitated solely at a thermal exposure temperature of 350 °C, with precipitation intensifying over time. Moreover, a decrease in the alloy’s tensile strength and an increase in elongation were noted after thermal exposure. Finally, the present study discussed the precipitation mechanisms of θ-Al2Cu particles and AlCu clusters within the grains, suggesting that the AlCu clusters exerted a more effective strengthening effect compared to the θ-Al2Cu particles.

Universal Synthesis of Single-Atom Catalysts by Direct Thermal Decomposition of Molten Salts for Boosting Acidic Water Splitting.

Single-atom catalysts (SACs) are considered prominent materials in the field of catalysis due to their high metal atom utilization and selectivity. However, the wide-ranging applications of SACs remain a significant challenge due to their complex preparation processes. Here, a universal strategy is reported to prepare a series of noble metal single atoms on different non-noble metal oxides through a facile one-step thermal decomposition of molten salts. By using a mixture of non-noble metal nitrate and a small-amount noble metal chloride as the precursor, noble metal single atoms can be easily introduced into the non-noble metal oxide lattice owing to the cation exchange in the in situ formed molten salt, followed by the thermal decomposition of nitrate anions during the heating process. Analyses using aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure spectroscopy confirm the formation of the finely dispersed single atoms. Specially, the as-synthesized Ir single atoms (10.97 wt%) and Pt single atoms (4.60 wt%) on the Co3O4 support demonstrate outstanding electrocatalytic activities for oxygen evolution reaction and hydrogen evolution reaction, respectively.

Scaling-Up Microwave-Assisted Synthesis of Highly Defective Pd@UiO-66-NH2 Catalysts for Selective Olefin Hydrogenation under Ambient Conditions.

The need to develop green and cost-effective industrial catalytic processes has led to growing interest in preparing more robust, efficient, and selective heterogeneous catalysts at a large scale. In this regard, microwave-assisted synthesis is a fast method for fabricating heterogeneous catalysts (including metal oxides, zeolites, metal-organic frameworks, and supported metal nanoparticles) with enhanced catalytic properties, enabling synthesis scale-up. Herein, the synthesis of nanosized UiO-66-NH2 was optimized via a microwave-assisted hydrothermal method to obtain defective matrices essential for the stabilization of metal nanoparticles, promoting catalytically active sites for hydrogenation reactions (760 kg·m-3·day-1 space time yield, STY). Then, this protocol was scaled up in a multimodal microwave reactor, reaching 86% yield (ca. 1 g, 1450 kg·m-3·day-1 STY) in only 30 min. Afterward, Pd nanoparticles were formed in situ decorating the nanoMOF by an effective and fast microwave-assisted hydrothermal method, resulting in the formation of Pd@UiO-66-NH2 composites. Both the localization and oxidation states of Pd nanoparticles (NPs) in the MOF were achieved using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray photoelectron spectroscopy (XPS), respectively. The optimal composite, loaded with 1.7 wt % Pd, exhibited an extraordinary catalytic activity (>95% yield, 100% selectivity) under mild conditions (1 bar H2, 25 °C, 1 h reaction time), not only in the selective hydrogenation of a variety of single alkenes (1-hexene, 1-octene, 1-tridecene, cyclohexene, and tetraphenyl ethylene) but also in the conversion of a complex mixture of alkenes (i.e., 1-hexene, 1-tridecene, and anethole). The results showed a powerful interaction and synergy between the active phase (Pd NPs) and the catalytic porous scaffold (UiO-66-NH2), which are essential for the selectivity and recyclability.

Sampling Real-Time Atomic Dynamics in Metal Nanoparticles by Combining Experiments, Simulations, and Machine Learning.

Even at low temperatures, metal nanoparticles (NPs) possess atomic dynamics that are key for their properties but challenging to elucidate. Recent experimental advances allow obtaining atomic-resolution snapshots of the NPs in realistic regimes, but data acquisition limitations hinder the experimental reconstruction of the atomic dynamics present within them. Molecular simulations have the advantage that these allow directly tracking the motion of atoms over time. However, these typically start from ideal/perfect NP structures and, suffering from sampling limits, provide results that are often dependent on the initial/putative structure and remain purely indicative. Here, by combining state-of-the-art experimental and computational approaches, how it is possible to tackle the limitations of both approaches and resolve the atomistic dynamics present in metal NPs in realistic conditions is demonstrated. Annular dark-field scanning transmission electron microscopy enables the acquisition of ten high-resolution images of an Au NP at intervals of 0.6 s. These are used to reconstruct atomistic 3D models of the real NP used to run ten independent molecular dynamics simulations. Machine learning analyses of the simulation trajectories allow resolving the real-time atomic dynamics present within the NP. This provides a robust combined experimental/computational approach to characterize the structural dynamics of metal NPs in realistic conditions.

Characteristics of Oxide Films on Zr702 and Their Corrosion Performance in Boiling Fluorinated Nitric Acid

Fluoride ions, which interfere with the oxide formation on zirconium have been over-looked until recently. The effect of fluoride ions on oxide formation and dissolution behaviors in zirconium was investigated in this study. A detailed quantitative characterization of the oxide films formed on Zr702 immersed in a fluorinated nitric acid solution was performed using X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and representative high-angle annular dark-field scanning Transmission Electron Microscope, (TEM). The corrosion performance in a fluorinated nitric acid solution was discussed. The results reveal that the thickness of the oxide films immersed in the fluorinated nitric acid solution was between 42–48 nm, which is much thinner than that of the oxide layer (~98.85 nm thickness) in the F− free HNO3 solution. The oxide film was identified to be a nanocrystalline cluster, comprised of outermost HfO2 and HfF4 layers, sub-outer ZrO2 and ZrF4 layers, and an innermost Zr (F, O)3.6 layer. This fluoride species penetration through the oxide films indicated that the fluoride ions are responsible for the dissolution of the oxide film of Zr702.

Insights into the Construction of Robust Pt Clusters with Satisfactory Stability on CeO2 for the Catalytic Oxidation of CO.

Improving the efficiency of platinum group metals (Pt, Pd, Rh, etc.) in catalytic oxidation reactions remains an urgent topic. The conflict between the low-temperature activity and high-temperature stability of noble metals can hardly reach a consensus. For instance, Pt cluster catalysts supported on CeO2 with high low-temperature activity will suffer from deactivation due to the redispersion under high-temperature lean-burn reaction conditions. Herein, two Pt1/CeO2 prepared by the incipient wetness impregnation method using different Pt precursors possessed varied Pt-O and Pt-O-Ce coordination numbers (CNs). They showed various priorities in CO oxidation versus NH3 selective catalytic oxidation, materials with higher CNPt-O-Ce selectively catalyzing NH3 oxidation to N2 more superior, conversely materials with lower CNPt-O-Ce performing better in CO oxidation. After activation by H2 reduction, both formed massive Pt clusters on the CeO2 surface but showed drastically distinct stability in lean-burn CO oxidation reactions. By summarizing the experimental results of high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, Raman spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy, etc., it is beyond doubt that the difference in the initial states of Pt1 due to distinct precursors indeed determine the redispersion behavior of the reduced Pt clusters on CeO2. Materials with lower CNPt-O-Ce and higher CNPt-O are more likely to form robust Pt clusters, as they are not conducive to Pt anchoring, thus restricting the reversible structural evolution occurring under lean-burn CO oxidation and reductive conditions. This approach serves as a guide for the convenient and efficient construction and exploration of robust Pt cluster catalysts.

Observation of broad triangular Frank-type stacking faults and characterization of stacking faults with emission wavelengths below 430 nm in 4H–SiC epitaxial layers

Frank-type stacking faults in 4H–SiC epitaxial layers were investigated using room-temperature photoluminescence mapping and high-angle annular dark-field high-resolution scanning transmission electron microscopy. Remarkably, the intrinsic Frank-type stacking fault (5,2) and intrinsic multilayer Frank-type stacking fault (4,2), which have been reported to have elongated triangular shapes to date, were found to have broader triangular shape, which was typical shape of Shockley-type stacking faults. The shaping of stacking faults could be explained based on the directions of the partial dislocations bounding the stacking faults. Formation models for the intrinsic (5,2) and (4,2) stacking faults were proposed. In addition, we observed Frank-type stacking faults (3,2,2,3) and (3,3) and Shockley-type stacking faults (3,3,3,2,3,2) and (3,2,3,3,3,2), which were not reported before. All of these stacking faults were composed with the stacking numbers 2 and 3 in the Zhdanov notation and showed very close characteristic photoluminescence emission wavelengths of 427–428 nm. Formation models for the stacking faults of (3,2,2,3), (3,3), (3,3,3,2,3,2), and (3,2,3,3,3,2) were proposed, also. Based on the proposed formation models of (4,2) and (3,3) stacking faults, formation models for the Frank-type stacking faults (4,1) and (3,2) were discussed. Finally, we pointed out that the (4,1) Frank-type stacking fault should be the intrinsic not the extrinsic fault, and the (3,2) Frank-type stacking fault is the extrinsic fault.

The Development of the Regenerable Catalytic System in Selective Catalytic Oxidation of Ammonia with High N2 Selectivity.

Supported particulate noble-metal catalysts are widely used in industrial catalytic reactions. However, these metal species, whether in the form of nanoparticles or highly dispersed entities, tend to aggregate during reactions, leading to a reduced activity or selectivity. Addressing the frequent necessity for the replacement of industrial catalysts remains a significant challenge. Herein, we demonstrate the feasibility of the 'regenerable catalytic system' exemplified by selective catalytic oxidation of ammonia (NH3-SCO) employing Ag/Al2O3 catalysts. Results demonstrate that our highly dispersed Ag catalyst (Ag HD) maintains >90% N2 selectivity at 80% NH3 conversion and >80% N2 selectivity at 100% NH3 conversion after enduring 5 cycles of reducible aggregation and oxidative dispersion. Moreover, it consistently upholds over 98% N2 selectivity at 100% NH3 conversion after 10 cycles of Ar treatment. During the aggregation-dispersion process, the Ag HD catalyst intentionally aggregated into Ag nanoparticles (Ag NP) after H2 reduction and exhibited remarkable regenerable capabilities, returning to the Ag HD state after calcination in the air. This structural evolution was characterized through in situ transmission electron microscopy, atomically resolved high-angle annular dark-field scanning transmission electron microscopy, and X-ray absorption spectroscopy, revealing the on-site oxidative dispersion of Ag NP. Additionally, in situ diffuse reflectance infrared Fourier transform spectroscopy provided insights into the exceptional N2 selectivity on Ag HD catalysts, elucidating the critical role of NO+ intermediates. Our findings suggest a sustainable and cost-effective solution for various industry applications.

Experimental High-Resolution Observation of the Truncated Double-Icosahedron Structure: A Stable Twinned Shell in Alloyed Au-Ag Core@Shell Nanoparticles.

Given the binary nature of nanoalloy systems, their properties are dependent on their size, shape, structure, composition, and chemical ordering. When energy and entropic factors for shapes and structure variations are considered in nanoparticle growth, the spectra of shapes become so vast that even metastable arrangements have been reported under ambient conditions. Experimental and theoretical variations of multiply twinned particles have been observed, from the Ino and Marks decahedra to polyicosahedra and polydecahedra with comparable energetic stability among them. Herein, we report the experimental production of a stable doubly truncated double-icosahedron structure (TdIh) in Au-Ag nanoparticles, in which a twinned Ag-rich alloyed shell is reconstructed on a Au-Ag alloyed Ino-decahedral core. The structure, chemical composition, and growth pathway are proposed on the basis of high-angle annular dark-field scanning transmission electron microscopy analysis and excess energy calculations, while its structural stability is estimated by large-scale atomic molecular dynamics simulations. This novel nanostructure differs from other structures previously reported.

Experimental and theoretical studies on a Mg2InRE-type prismatic precipitate plate in a series of Mg-In-RE ternary alloys

In precipitation-hardening Mg-In-Sm alloy, a category of novel Mg2InSm prismatic plates have been built successfully and its crystal structure and atomic coordination were studied by atomic scale high-angle annular dark-field scanning transmission electron microscopy. The Mg2InSm plate has an orthorhombic structure, whose stability can be verified by first-principles calculations. Similarly, with the substitution of other rare earth (RE) for Sm, a series of Mg2InRE orthorhombic structures are also predicted to be stable. The findings are expected to guide the future design of effective precipitation strengthening phases in Mg–based alloys.

Vacancy-Enhanced Sb-N4 Sites for the Oxygen Reduction Reaction and Zn-Air Battery.

With the advantages of a Fenton-inactive characteristic and unique p electrons that can hybridize with O2 molecules, p-block metal-based single-atom catalysts (SACs) for the oxygen reduction reaction (ORR) have tremendous potential. Nevertheless, their undesirable intrinsic activity caused by the closed d10 electronic configuration remains a major challenge. Herein, an Sb-based SAC featuring carbon vacancy-enhanced Sb-N4 active centers, corroborated by the results of high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure, has been developed for an incredibly effective ORR. The obtained SbSA-N-C demonstrates a positive half-wave potential of 0.905 V and excellent structural stability in alkaline environments. Density functional theory calculations reveal that the carbon vacancies weaken the adsorption between Sb atoms and the OH* intermediate, thus promoting the ORR performance. Practically, the SbSA-N-C-based Zn-air batteries achieve impressive outcomes, such as a high power density of 181 mW cm-2, showing great potential in real-world applications.

Reconstructing the 3D Coordinates of Guest:Host OLED Blends with Single Atom Resolution.

The performance of electronic and semiconductor devices is critically dependent on the distribution of guest molecules or atoms in a host matrix. One prominent example is that of organic light-emitting diode (OLED) displays containing phosphorescent emitters, now ubiquitous in handheld devices and high-end televisions. In such OLEDs the phosphorescent guest [normally an iridium(III)-based complex] is typically blended into a host matrix, and charge injection and transport, exciton formation and decay, and hence overall device performance are governed by the distribution of the emissive guest in the host. Here high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) is used with depth sectioning to reconstruct the 3D distribution of emissive iridium(III) complexes, fac-tris(2-phenylpyridine)iridium(III) [Ir(ppy)3], blended into the amorphous host material, tris(4-carbazoyl-9-ylphenyl)amine (TCTA), by resolving the position of each single iridium(III) ion. It is found that most Ir(ppy)3 complexes are clustered with at least one other, even at low concentrations, and that for films of 20wt.% Ir(ppy)3 essentially all the complexes are interconnected. The results validate the morphology of blend films created using molecular dynamics simulations which mimic the evaporation film-forming process and are also consistent with the experimentally measured charge transport and photophysical properties.

“Invisible” radioactive cesium atoms revealed: Pollucite inclusion in cesium-rich microparticles (CsMPs) from the Fukushima Daiichi Nuclear Power Plant

Understanding radioactive Cs contamination has been a central issue at Fukushima Daiichi and other nuclear legacy sites; however, atomic-scale characterization of radioactive Cs in environmental samples has never been achieved. Here we report, for the first time, the direct imaging of radioactive Cs atoms using high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). In Cs-rich microparticles collected from Japan, we document inclusions that contain 27 – 36 wt% of Cs (reported as Cs2O) in a zeolite: pollucite. The compositions of three pollucite inclusions are (Cs1.86K0.11Rb0.19Ba0.22)2.4(Fe0.85Zn0.84X0.31)2.0Si4.1O12, (Cs1.19K0.05Rb0.19Ba0.22)1.7(Fe0.66Zn0.32X0.41)1.4Si4.6O12, and (Cs1.27K0.21Rb0.29Ba0.15)1.9(Fe0.60Zn0.32X0.69)1.6Si4.4O12 (X includes other cations). HAADF-STEM imaging of pollucite, viewed along the [111] zone axis, revealed an array of Cs atoms, which is consistent with a simulated image using the multi-slice method. The occurrence of pollucite indicates that locally enriched Cs reacted with siliceous substances during the Fukushima meltdowns, presumably through volatilization and condensation. Beta radiation doses from the incorporated Cs are estimated to reach 106 – 107 Gy, which is more than three orders of magnitude less than typical amorphization dose of zeolite. The atomic-resolution imaging of radioactive Cs is an important advance for better understanding the fate of radioactive Cs inside and outside of nuclear reactors damaged by meltdown events.