Aberration-corrected Transmission Electron Microscopy Research Articles

Effect of film thickness on phase structure of epitaxial non-doped hafnium oxide films

HfO2 has been widely used in the electronics industry as a dielectric material with excellent properties. It has attracted much attention since HfO2 was first reported to be ferroelectric in 2011. With the continuous advancement of research, various methods such as oxygen vacancy control and interface control have been proven to be able to stabilize the metastable polar o-phase structure in doped hafnium oxide thin films. However, there are still some shortcomings in the relevant issues concerning non-doped hafnium oxide thin film materials. Here, polycrystalline non-doped HfO2 thin films were grown on SrTiO3 substrates by pulsed laser deposition (PLD). Atomic force microscopy investigation suggests that the surface roughness of HfO2 thin films increases as the film thickness increases. X-ray photoelectron spectroscopy analyses indicate that the HfO2 thin film has a high purity and contain only Hf4+ ions. The band gap of HfO2 was measured by valence EELS and UV–visible spectra. Atomic structures of the HfO2/SrTiO3 heterointerface have been studied by the aberration-corrected transmission electron microscopy and energy-dispersive X-ray spectroscopy. The HfO2/SrTiO3 heterointerface is atomically abrupt and incoherent. Our findings suggest that non-doped HfO2 films with o-phase structure through PLD technology.

An Angstrom-Scale Protective Skin Grown In Situ on Perovskite Oxide to Enhance Stability in Water.

The utilization of perovskite oxide as a catalyst for aqueous reactions is promising but challenging in stability. Here, we propose an in situ growth strategy that constructs an ultrathin protective skin on the Sr0.9Fe0.81Ta0.09Ni0.1O3-δ perovskite surface and thus effectively solves the stability issue. Using a spherical aberration-corrected transmission electron microscope, we observe the coexistence of an angstrom-scale (~7 Å) Fe2O3 protective skin and FeNi alloy nanoparticles. A number of alloy nanoparticles grow along with the skin and uniformly take root on the skin surface. Such a hierarchical structure can reconstruct the surface electronic structure and suppress the ion leaching of perovskite oxide in water. Benefiting from this unique structure, the catalyst has experienced a substantial increase (800 h, more than three orders of magnitude) in its stable operation time in water (for example, in a hydrogen evolution reaction). These results provide valuable insight into solid-solid phase transitions and have substantial implications for using structural defects at surfaces to modulate mass transport and transformation kinetics. Our strategy is sufficiently simple and can be used to subtly manipulate the catalyst structures to improve the performance of perovskite-based catalysts and potentially other oxide catalysts for a wide range of reactions.

Comparative Study of PtM (M=Cu, Zn, Ga, Mn, Fe, In, Ce) Bimetals on Zincosilicate for Propane Dehydrogenation Reaction.

Silicoaluminate zeolites have relatively strong Brönsted (B) acid properties that can easily lead to deep cracking reactions, making them less favourable as carriers for propane dehydrogenation. Here, we utilise zincosilicate zeolite with less B-acid produced by the introduction of the heteroatom Zn into the framework as a carrier, followed by simultaneous ion exchange (IE) of M monometallic or PtM bimetallic (M=Cu, Zn and Ga, etc.). The optimized PtZn/Zn-4 exhibits a superior propane dehydrogenation performance over PtCu/Zn-4 and PtGa/Zn-4, which can achieve a propane conversion of about 30 % in a pure propane atmosphere at 550 °C and can be operated for at least 168 h without significant deactivation. Characterization techniques such as spherical aberration corrected transmission electron microscopy, in situ X-ray photoelectron spectroscopy, and in situ diffuse reflectance infrared fourier transform spectroscopy with different gas adsorptions are used to investigate these PtM@zeolite catalysts in order to deepen the understanding of acid site identification, promoter effect and catalysis.

A Broad-High Temperature Ceramic Capacitor with Local Polymorphic Heterogeneous Structures.

Crafting high-performance dielectrics tailored for pulsed power capacitors, in response to the escalating demands of practical applications, presents a formidable challenge. Herein, this work introduces a novel lineup of lead-free ceramics with local polymorphic heterogeneous structures, defined by the formula (1-x)[0.92BaTiO3-0.08Sr(Mg1/2Ti3/4)O3]-x(Na0.5Bi0.5)TiO3 (BT-SMT-xNBT). This innovative multi-scale synergistic strategy, spanning from the atomic to grain scale, yields materials with a giant recoverable energy density (Wrec) of 10.1 J·cm-3 and an impressive energy efficiency (η) of 95.0%. The integration of linear end elements SMT can significantly mitigate the polarization hysteresis while concurrently boosting the breakdown strength, thus enhancing overall energy efficiency. Furthermore, the inclusion of NBT with high polarization serves to amplify domain size, thereby reinforcing the electric field-induced polarization. This addition also stimulates the creation of polymorphic heterostructures, where tetragonal and rhombohedral nanodomains coexist, as validated by aberration-corrected transmission electron microscopy. Notably, the BT-SMT-0.2NBT ceramics have demonstrated outstanding high-temperature energy storage capabilities, with a Wrec of 7.2 J·cm-3 and an η of 92.2% at 150 °C, along with remarkable broad-temperature stability (ΔWrec, Δη ≤ 4.0%, ≈20-150 °C). These achievements in this work propel the field toward more practical and durable solutions of energy storage dielectrics.

Sublimation Transformation Synthesis of Dual-Atom Fe Catalysts for Efficient Oxygen Reduction Reaction.

Dual-atom catalysts (DACs) have garnered significant interest due to their remarkable catalytic reactivity. However, achieving atomically precise control in the fabrication of DACs remains a major challenge. Herein, we developed a straightforward and direct sublimation transformation synthesis strategy for dual-atom Fe catalysts (Fe2/NC) by utilizing in situ generated Fe2Cl6(g) dimers from FeCl3(s). The structure of Fe2/NC was investigated by aberration-corrected transmission electron microscopy and X-ray absorption fine structure (XAFS) spectroscopy. As-obtained Fe2/NC, with a Fe-Fe distance of 0.3 nm inherited from Fe2Cl6, displayed superior oxygen reduction performance with a half-wave potential of 0.90 V (vs. RHE), surpassing commercial Pt/C catalysts, Fe single-atom catalyst (Fe1/NC), and its counterpart with a common and shorter Fe-Fe distance of ~0.25 nm (Fe2/NC-S). Density functional theory (DFT) calculations and microkinetic analysis revealed the extended Fe-Fe distance in Fe2/NC is crucial for the O2 adsorption on catalytic sites and facilitating the subsequent protonation process, thereby boosting catalytic performance. This work not only introduces a new approach for fabricating atomically precise DACs, but also offers a deeper understanding of the intermetallic distance effect on dual-site catalysis.

Atomic-scale probing of ion migration dynamics in Na3Ni2SbO6 cathode for sodium ion batteries

Honeycomb-layered phases like Na3Ni2SbO6 have been extensively researched as high-voltage and high-rate capability cathode materials for sodium-ion batteries. However, our understanding of the structural stability and dynamic reaction mechanisms of Na3Ni2SbO6 cathode during cycling, especially at atomic-scale, remains limited. Here, we track the microstructure evolution during extraction of Na+ ions in Na3Ni2SbO6 cathode at atomic scale in an aberration-corrected transmission electron microscope. The electron beam irradiation that can provide a driving force for the Na+ ion migration, allows us to mimic the battery charge process. By controlling the electron beam dose, we study the structure evolution behavior to obtain insights into understanding the work principle and failure mechanism of Na3Ni2SbO6 cathode under different charge rate conditions. We find that the real-time structural evolution and ion migration pathways of Na3Ni2SbO6 cathode are distinct under different electron beam doses. High-dose irradiation reveals Na ion depletion, surface cracks, and phase transformations, mimicking rapid capacity decay. In contrast, low-dose irradiation shows slower ion migration, ordered Na vacancy formation, and maintaining structural integrity, which more closely resembles the electrochemical process of actual battery. This study provides an atomistic understanding of the structural stability and Na ions deintercalation mechanism in Na3Ni2SbO6 cathodes, offering new insights into optimizing electrode materials.

Control of Grain Boundary Formation in Atomically Resolved Nanocrystalline Carbon Monolayers: Dependence on Electron Energy

Abstract In this study, we explore the dynamics of grain boundaries in nanocrystalline carbon monolayers, focusing on their variation with electron beam energy and electron dose rate in a spherical and chromatic aberration-corrected transmission electron microscope. We demonstrate that a clean surface, a high-dose rate, and a 60 keV electron beam are essential for precise local control over the dynamics of grain boundaries. The structure of these linear defects has been evaluated using neural network-generated polygon mapping.

Improving Catalytic Performance via the Synergy of Tensile Lattice Strain and Plasmonic Enhancement in Defective AuPd@Pd Short Nanowires.

The synthesis of bimetallic nanocatalysts with strained crystal lattices has attracted considerable interest. This is because, beyond the electronic structure modifications realized through elemental doping, the strain effect offers an extra mechanism to fine-tune the electronic structures, thereby possibly improving the catalytic performances. We present a method for constructing defective AuPd@Pd short nanowires, achieved through a controlled galvanic replacement reaction between short AuCu nanowires and Pd precursors. Advanced structural analyses using spherical aberration-corrected transmission electron microscopy (AC-TEM) validated the expanded crystal lattice on the nanowire surface and also demonstrated pronounced plasmonic absorption in the UV-vis region. Leveraging both plasmonic absorption and strain effects, the AuPd@Pd short nanowires displayed a higher apparent rate constant compared to Pd nanoparticles. Integrating molecular dynamic simulations with density functional theory calculations revealed that the tensile strain on AuPd@Pd short nanowires benefited the catalytic activity by elevating the d-band center, thereby intensifying the adsorption of p-nitrophenol. The current research introduces a unique method for synthesizing noble metal nanocrystals with specific dimensions and elucidates the rational development of high-performance plasmonic nanocatalysts through synergistic exploitation of the beneficial strain effect.

Transient Phase-Mediated Li+ Transportation in the Lithium Lanthanum Titanate Solid-State Electrolyte.

The lithium lanthanum titanium oxide (LLTO) perovskite is one type of superior lithium (Li)-ion conductor that is of great interest as a solid-state electrolyte for all-solid-state lithium batteries. Structural defects and impurity phases formed during the synthesis of LLTO largely affect its Li-ion conductivity, yet the underlying Li+ diffusion mechanism at the atomic scale is still under scrutiny. Herein, we use aberration-corrected transmission electron microscopy to perform a thorough structural characterization of the LLTO ceramic pellet. We reveal a prevalent transient phase transition of (La, Ti)2O3 existing at the antiphase boundaries between single-crystalline LLTO domains. This transient phase exhibits a specific crystal orientation with the LLTO phase and shows a gradual structural transition to a tetragonal LLTO structure, which enables detailed crystallographic analysis to correlate their formation to the sintering process of LLTO powders into ceramic pellets. We also find that Li diffusion is retarded by this phase and correlated with the excess amount of La, which is corroborated by the theoretical evaluation of the atomistic mechanisms of Li diffusion across this phase.

Unraveling the atomic structure evolution of titanium nitride upon oxidation

In this study, state-of-the-art aberration-corrected environmental transmission electron microscopy is utilized to investigate the atomic-scale structural evolution of titanium nitride during dynamic oxidation. Titanium nitride oxidation originates from the migration of Ti atoms along {200} that results in two distinct reaction pathways, characterized by the formation of chains of titanium vacancies and staggered titanium vacancies. We demonstrate that titanium atoms exhibit varied oxidation activity on different crystal facets, with the selection of oxidation pathways significantly influenced by the curvature of the crystal surface, which is also supported by the First Principles Calculations.

High-quality Ge/SiGe heterostructure with atomically sharp interface grown by molecular beam epitaxy

Germanium is a versatile material for realization of spin and topological quantum computing. Here, we report on the epitaxial growth of an undoped Ge/SiGe heterostructure in which a hole quantum well is formed in the sandwiched Ge layer. The heterostructure is grown on Si (001) via molecular beam epitaxy (MBE). Atomic force microscopy characterizations display a flat surface with a root mean square roughness of 0.956 nm, and spherical aberration corrected transmission electron microscopy data show a sharp interface with a characteristic length of 0.49 nm. A mobility of up to 1.2 × 105 cm2 V−1 s−1 was achieved in the SiGe/Ge/SiGe two-dimensional hole gas (2DHG). The low percolation density of 3.70 × 1010 cm−2, light effective mass of 0.079 m0 (where m0 is the free electron mass), and large effective g-factor of 9.5 were obtained. These results show the potential of MBE-grown Ge 2DHG for semiconductor quantum computing.

Comparison of AlN/GaN heterojunctions grown by molecular beam epitaxy with Al and Ga assistance

Although conventional III-nitride molecular-beam-epitaxy growth theories indicate that high-quality AlN should be prepared in Al-assisted regimes, AlN/GaN heterojunctions grown in Ga-assisted regimes actually demonstrate superior performances. In this letter, we compared Al-assisted and Ga-assisted grown AlN/GaN heterojunctions and explored the underlying mechanisms. Aberration-corrected transmission electron microscope, energy dispersive spectrometer, and atomic force microscopy measurements indicate that the Al-assisted growth results in partly-relaxed AlN of high-density defects, deteriorating AlN/GaN interfaces, and surface morphology consisting of irregular and truncated atomic steps. The Ga-assisted growth produces high-quality pseudomorphic AlN with excellent AlN/GaN interfaces, surface morphology, and electrical properties. It is suggested that the better crystalline quality and higher performances of the Ga-assisted grown samples are attributed to a lower N subsurface diffusion barrier resulting from a higher energy of the fcc adsorption positions in the adlayer-enhanced-lateral-diffusion model and intense thermal motions of Ga adatoms. It helps to understand the kinetics of metal-adlayer-enhanced growth of AlN and AlN/GaN heterojunctions at atomic scale and optimize the growth processes. Meanwhile, it is demonstrated that amorphization and Al diffusion near the AlN surfaces occur due to Pt bombardment on highly tensile-strained AlN during focused-ion-beam fabrications. It implies that large strain in AlN/GaN heterojunctions might be an important issue to be considered for device reliability.

Repair Engineering of Crystal Structure in van der Waals Materials by Probe Electron Beam.

The advancement of electronic technology has led to increasing research on performance and stability. Continuous electrical pulse stimulation can cause crystal structure changes, affecting performance and accelerating aging. Controlled repair of these defects is crucial. In this study, we investigated crystal structure changes in van der Waals (vdW) InSe crystals under continuous electric pulses by using electron beam lithography (EBL) and spherical aberration corrected transmission electron microscopy (Cs-TEM). Results show that electrical pulses induce amorphous regions in the InSe lattice, increasing the device resistance. We used Cs-STEM probe scanning for precise repair, abbreviated SPRT, to optimize device performance. SPRT is related to electric fields induced by the electron beam and can be applied to other 2D materials like α-In2Se3 and CrSe2, offering a potential approach to extend device lifespan.

Effect of zirconium addition on microstructural characteristics and nano-mechanical properties of P9 steel

Micro-alloying in steels has significant effects on microstructure and its properties. The main objective of the work is to understand the influence of zirconium (Zr) addition to P9 ferritic/martensitic (F/M) steel on phase stability, microstructure, and nanomechanical properties. The alloy compositions in this study were designed using thermodynamic calculations, based on which steels with Zr concentration in the range of 0.05–2 wt.% were synthesized using vacuum arc melting. The cast alloy was subjected to thermo-mechanical treatments followed by austenitization and tempering treatments. Zr concentration of the steel was found to influence the nature of secondary phases formed, which were quantified through detailed synchrotron X-ray diffraction (XRD) analysis and also characterised extensively using electron microscopy techniques. Detailed structural analysis of the Fe23Zr6 phase using aberration corrected transmission electron microscopy is reported for the first time. The nano-mechanical properties of the heat-treated steels were evaluated using instrumented indentation tests at room temperature with a sphero-conical indenter. A systematic variation in hardness and yield strength with Zr content of P9 steel was observed, which is correlated to the microstructural changes. The P9 F/M steel with optimum concentration of Zr, with better mechanical properties is proposed through this structure-property correlation study.

Obtaining in-situ reacted Fe–W–Ni–Cr–Cu high-entropy alloy within the interlayer of dissimilar Cf/SiC-GH3536 joint by designing non-high-entropy Cu–Ti–W composite filler

In aerospace applications, the development of high-entropy alloys (HEAs) filler is an effective strategy to obtain reliable Cf/SiC nozzles and GH3536 thrust chambers components. Considering the high costs and extended preparation times with HEA fillers, utilizing non-HEA fillers to generate HEAs within brazing seam offers significant advantages. This study successfully joined Cf/SiC with GH3536 using a non-HEA Cu–Ti–W composite filler that facilitated the in-situ formation of Fe–W–Ni–Cr–Cu HEA during the brazing process. Furthermore, the formation and accompanying martensite phase transformation were revealed. The microstructure characteristic of W reinforcements/HEA/Cu(s,s) was ultimately formed in the brazing seam. The atomic structure of the HEA, confirmed to be hexagonal close-packed, was elucidated using spherical aberration-corrected transmission electron microscopy. Additionally, a martensite phase transformation was observed in the HEA, involving two adjacent layers of (0 0 0 1) atomic planes that sheared and move a3 distance alon g [10–10] in opposite directions, resulting in the formation of M-HEA. The inclusion of HEA and M-HEA in the Cf/SiC-GH3536 joint, brazed with Cu–Ti–W composite filler, increased its shear strength to 84.8 MPa, which was 2.15 times higher than that of joints without the W reinforcements. This study offers new insights into the design of composite fillers and the application of HEAs.

In Situ Formation of SnSe2/SnSe Vertical Heterostructures toward Polarization Selectable Band Alignments.

2D van der Waals (vdW) layered semiconductor vertical heterostructures with controllable band alignment are highly desired for nanodevice applications including photodetection and photovoltaics. However, current 2D vdW heterostructures are mainly obtained via mechanical exfoliation and stacking process, intrinsically limiting the yield and reproducibility, hardly achieving large-area with specific orientation. Here, large-area vdW-epitaxial SnSe2/SnSe heterostructures are obtained by annealing layered SnSe. These in situ Raman analyses reveal the optimized annealing conditions for the phase transition of SnSe to SnSe2. The spherical aberration-corrected transmission electron microscopy investigations demonstrate that layered SnSe2 epitaxially forms on SnSe surface with atomically sharp interface and specific orientation. Optical characterizations and theoretical calculations reveal valley polarization of the heterostructures that originate from SnSe, suggesting a naturally adjustable band alignment between type-II and type-III, only relying on the polarization angle of incident lights. This work not only offers a unique and accessible approach to obtaining large-area SnSe2/SnSe heterostructures with new insight into the formation mechanism of vdW heterostructures, but also opens the intriguing optical applications based on valleytronic nanoheterostructures.

Quantitative analysis of atomic migration in lithium-ion conducting oxide solid electrolytes

Direct observation of intrinsic atom migration inside bulk materials is crucial for understanding the ion-conducting property; however, microscopy experiments remain challenging. Here, intrinsic atom migration in bulk lithium-ion conductor La2/3–xLi3xTiO3 was investigated by using aberration-corrected transmission electron microscopy. The atomic migration was triggered by high-energy electron beam irradiation. Through quantitative analysis of high-angle annular dark-field image sequences and estimation of random errors using the 3σ criterion, the subtle contrast variation caused by single atom migration was extracted, in which the validity was further confirmed by image simulations. It provides a simple and feasible methodology for investigating the mechanism of atomic migration in bulk materials.

Unveiling superior chemical mechanical polishing properties of a novel shell-core structure: Insights from an atomic-scale perspective

The precision polishing process plays a crucial role in the modern advanced semiconductor manufacturing field, making it imperative to develop excellent polishing abrasives through new techniques. In this study, we obtained well-defined spherical nano-composite polishing particles CeO2@SiO2 via posterior grafting synthesis, which have a clear core–shell structure and exhibit a high Ce3+ concentration. Atomic force microscopy revealed significant improvement in surface roughness of the abrasives on Si substrates, achieving the material removal rate (MRR) of 300 nm/min. MRR is closely correlated with the Ce3+ concentration. Combining aberration-corrected transmission electron microscopy with first-principles calculations demonstrated that surface oxygen vacancies and interfacial charge transfer were the primary origins of high Ce3+ concentration, and revealed the material removal mechanism. This work not only provides new insights into the process but also offers new routes for the development of novel polishing abrasives in the future.

Determination of MAX phase structure and surface reconstruction behavior of a novel V–Sn–C system

The crystal structure of a novel MAX phase is determined using X-ray powder diffraction, spherical aberration corrected transmission electron microscopy, and first-principles calculations. In the new V–Sn–C system, the R 3‾ m space group aligns more closely with the experimental data than the P63/mmc space group. The lattice parameters of the new trigonal V2SnC phase are a = 0.291 nm and c = 2.08 nm. Moreover, the surface of the new phase has a tin-doped carbide face-centered cubic (FCC) structure reconstruction layer. First-principles calculations indicate that the new trigonal V2SnC phase is metastable compared with the hexagonal V2SnC phase. However, the thermal stability of the metastable trigonal V2SnC in air is significantly enhanced owing to the presence of the reconstruction layer.

Structure and Formation Mechanisms in Tantalum and Niobium Oxides in Superconducting Quantum Circuits.

Improving the qubit's lifetime (T1) is crucial for fault-tolerant quantum computing. Recent advancements have shown that replacing niobium (Nb) with tantalum (Ta) as the base metal significantly increases T1, likely due to a less lossy native surface oxide. However, understanding the formation mechanism and nature of both surface oxides is still limited. Using aberration-corrected transmission electron microscopy and electron energy loss spectroscopy, we found that Ta surface oxide has fewer suboxides than Nb oxide. We observed an abrupt oxidation state transition from Ta2O5 to Ta, as opposed to the gradual shift from Nb2O5, NbO2, and NbO to Nb, consistent with thermodynamic modeling. Additionally, amorphous Ta2O5 exhibits a closer-to-crystalline bonding nature than Nb2O5, potentially hindering H atomic diffusion toward the oxide/metal interface. Finally, we propose a loss mechanism arising from the transition between two states within the distorted octahedron in an amorphous structure, potentially causing two-level system loss. Our findings offer a deeper understanding of the differences between native amorphous Ta and Nb oxides, providing valuable insights for advancing superconducting qubits through surface oxide engineering.