Cross-sectional Scanning Transmission Electron Microscopy Research Articles

Giant polarization in tetragonal-like BiFeO3 film via (Ba,Ca)TiO3 doping

BiFeO3 is a multiferroic material, its tetragonality (T) phase usually exhibits large tetragonality (c/a ratio) and strong ferroelectricity. Unlike the commonly used method of strain engineering via substrate, here we present a general and practical approach for obtaining T-like phase BiFeO3 films through (Ba,Ca)TiO3 doping (BF-BCT). The BF-BCT film coherently grows on the La0.7Sr0.3MnO3/(La0.18Sr0.82)(Al0.59Ta0.41)O3 (001) substrate even at 180 nm thick, implying a very large critical thickness, and shows a large tetragonality of 1.12. Impressively, the films exhibit a giant remanent polarization (2Pr) of 320 μC/cm2, which is higher than the corresponding values of any other lead-free ferroelectric films reported to date. Cross-sectional scanning transmission electron microscopy measurements confirm the presence of the T-like phase in BF-BCT films, where the giant polarization might be attributed to the off-center B-site atom. The BF-BCT films are structurally homogeneous without any precipitation of the second phase. The giant polarization observed in the BF-BCT films indicate their great potential for application in next-generation storage and information devices.

Impact of crystallinity on thermal conductivity of RF magnetron sputtered MoS2 thin films

This study investigates the effects of sulfur atomic defects and crystallinity on the thermal conductivity of MoS2 thin films. Utilizing scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), and Raman spectroscopy, we examined MoS2 films, several nanometers thick, deposited on Si/SiO2 substrates. These films were prepared via a combination of RF magnetron sputtering and sulfur vapor annealing (SVA) treatment. Structural analyses, including cross-sectional STEM and in-plane and out-of-plane XRD measurements, revealed an increase in the S/Mo ratio and grain size of the MoS2 films following SVA treatment. Notably, the in-plane thermal conductivity of MoS2 films treated with SVA was found to be at least an order of magnitude higher than that of films without SVA treatment. This research suggests that the in-plane thermal conductivity of MoS2 thin films can be significantly enhanced through crystallinity improvement via SVA treatment.

Lithium Ion Intercalation-Induced Metal-Insulator Transition in Inclined-Standing Grown 2D Non-Layered Cr2S3 Nanosheets.

Gate-controlled ionic intercalation in the van der Waals gap of 2D layered materials can induce novel phases and unlock new properties. However, this strategy is often unsuitable for densely packed 2D non-layered materials. The non-layered rhombohedral Cr2S3 is an intrinsic heterodimensional superlattice with alternating layers of 2D CrS2 and 0D Cr1/3. Here an innovative chemical vapor deposition method is reported, utilizing strategically modified metal precursors to initiate entirely new seed layers, yields ultrathin inclined-standing grown 2D Cr2S3 nanosheets with edge instead of face contact with substrate surfaces, enabling rapid all-dry transfer to other substrates while ensuring high crystal quality. The unconventional ordered vacancy channels within the 0D Cr1/3 layers, as revealed by cross-sectional scanning transmission electron microscope, permitting the insertion of Li+ ions. An unprecedented metal-insulator transition, with a resistance modulation of up to six orders of magnitude at 300 K, is observed in Cr2S3-based ionic field-effect transistors. Theoretical calculations corroborate the metallization induced by Li-ion intercalation. This work sheds light on the understanding of growth mechanism, structure-property correlation and highlights the diverse potential applications of 2D non-layered Cr2S3 superlattice.

Experimental determination of the band offsets at the UWBG p-LiGa5O8/Ga2O3 interface

LiGa5O8, a recently discovered ultrawide bandgap semiconductor exhibiting p-type conductivity at room temperature, is grown on (010) β-Ga2O3 substrate. Utilizing a mist chemical vapor deposition method, LiGa5O8 thin film grown on insulating Ga2O3 substrate exhibits hole concentration ∼2.31 × 1018 cm−3 and hole mobility ∼2.07 cm2/V s. The resulting heterostructure is characterized comprehensively. A smooth, uniform film growth was observed by scanning electron microscopy and atomic force microscopy imaging. Cross-sectional scanning transmission electron microscopy and x-ray diffraction confirm the growth of spinel cubic crystal structure of LiGa5O8 along the [110] direction. Moreover, the valence and conduction band offsets at p-LiGa5O8/β-Ga2O3 heterointerface were determined via x-ray photoelectron spectroscopy. The determined band alignments at LiGa5O8/β-Ga2O3 interface reveal the formation of a type-II (staggered) heterojunction. The experimental measurements provide valuable parameters of the band offsets at the heterointerface, addressing a crucial aspect for future power electronic device design and fabrication based on β-Ga2O3 ultrawide bandgap semiconductors.

Vertically Stacked Amorphous Ir/Ru/Ir Oxide Nanosheets for Boosted Acidic Water Splitting.

Integrating multiple functional components into vertically stacked heterostructures offers a prospective approach to manipulating the physicochemical properties of materials. The synthesis of vertically stacked heterogeneous noble metal oxides remains a challenge. Herein, we report a surface segregation approach to create vertically stacked amorphous Ir/Ru/Ir oxide nanosheets (NSs). Cross-sectional high-angle annular darkfield scanning transmission electron microscopy images demonstrate a three-layer heterostructure in the amorphous Ir/Ru/Ir oxide NSs, with IrOx layers located on the upper and lower surfaces, and a layer of RuOx sandwiched between the two IrOx layers. The vertically stacked heterostructure is a result of the diffusion of Ir atoms from the amorphous IrRuOx solid solution to the surface. The obtained A-Ir/Ru/Ir oxide NSs display an ultralow overpotential of 191 mV at 10 mA cm-2 toward acid oxygen evolution reaction and demonstrate excellent performance in a proton exchange membrane water electrolyzer, which requires only 1.63 V to achieve 1 A cm-2 at 60 °C, with virtually no activity decay observed after a 1300 h test.

Exploring the interfacial structure and crystallinity for direct growth of Mn3Sn(0001) on sapphire (0001) by molecular beam epitaxy

The Kagome antiferromagnet Mn3Sn has garnered a lot of attention due to the presence of interesting properties such as anomalous Hall effects and Nernst effects. Until now, few papers have been reported to grow using molecular beam epitaxy with a buffer layer or on other substrates. In this paper, we discuss the synthesis of crystalline Mn3Sn layers, prepared on Al2O3 (0001) without a buffer layer using molecular beam epitaxy. The growth is monitored in-situ using reflection high energy electron diffraction and measured ex-situ using X-ray diffraction, Rutherford back-scattering, and cross-sectional scanning transmission electron microscopy. The samples were deposited at 524 ± 5 °C, with an Mn: Sn atomic flux ratio of 3.2:1 for 90 min. Orientation relationships between the Mn3Sn films and the sapphire substrates are determined from in-plane and out-of-plane measurements. Our analysis indicates that the resulting film is predominantly c−plane oriented. Lastly, the samples prepared in this way were found to be discontiguous, showing a 3-dimensional morphology. According to first-principles calculations, the Mn3Sn exhibits a displaced Kagome structure in the very first stages of growth, for 2 ML and 4 ML growth on Al2O3 (0001). This result is corroborated by calculating the surface formation energies and explains the observed RHEED patterns.

Observation of comet-shaped defect as killer defect in halide vapor phase epitaxial (001) β-Ga2O3 and its impact on Schottky barrier diodes

We observed killer defects that served as reverse leakage current paths for halide vapor phase epitaxial (001) β-Ga2O3 Schottky barrier diodes, which resulted in a leakage current of −0.46 μA at reverse bias of −100 V. Synchrotron X-ray topography revealed comet-shaped contrasts extending along [010] which are induced from the strain field surrounding the defects. They consisted of perfect (100)-cracks and horizontal-oriented (001) cracks. The cross-sectional scanning transmission electron microscopy observation showed (100)-cracks on the surface and dislocations along [100] beneath the surface. This defect was speculated to be generated from damage during the chemical-mechanical polishing.

Decomposition pathways in nano-lamellar CVD Ti0.2Al0.8N

Recent progress in chemical vapour deposition (CVD) technology has enabled synthesis of metastable cubic Ti1−xAlxN coatings with x as high as 0.8–0.9. These coatings have unique micro- and nano-structures consisting of grains with epitaxially grown nanolamellae with different Al/Ti ratios, and exhibit exceptional hardness and resistance to wear and oxidation. Here, the thermal stability and decomposition of nano-lamellar CVD Ti0.2Al0.8N at temperatures between 800 and 1000 °C have been investigated using a combination of cross-sectional transmission X-ray nano-diffraction and scanning transmission electron microscopy. The decomposition started by formation of hexagonal AlN (h-AlN) in the grain boundaries throughout the coating. Below 900 °C, only limited further decomposition of the grain interiors occurred. At higher temperatures the formation of grain boundary h-AlN was followed by a bulk transformation of the nano-lamellar structure, starting at the top of the coating and subsequently sweeping inwards. The bulk transformation occurred initially through spinodal decomposition, followed by transformation of the Al-rich cubic phase to h-AlN, leading to a coarsened structure with Ti-rich domains in a h-AlN matrix. The behaviour is explained by the higher capability of grain boundaries and free surfaces to accommodate the volumetric expansion from the h-AlN formation. The results increase our understanding of the complicated decomposition processes in these metastable cubic coatings, which are of utmost importance from both technological and scientific perspectives.

Molecular beam epitaxy and crystal structure of majority a-plane-oriented and substrate-strained Mn3Sn thin films grown directly on sapphire (0001)

The Kagome antiferromagnet Mn3Sn has garnered much attention due to the presence of exciting properties such as anomalous Hall and Nernst effects. This paper discusses the synthesis of crystalline Mn3Sn thin films, prepared on Al2O3 (0001) substrates at 453±5°C using molecular beam epitaxy. The growth is monitored in situ using reflection high energy electron diffraction and measured ex situ using x-ray diffraction, Rutherford back-scattering, and cross-sectional scanning transmission electron microscopy. Our analysis shows the in-plane lattice constants of a1,M=4.117±0.027 Å and a2,M=4.943±0.033 Å, which is a very unexpected result when compared to the bulk a-plane Mn3Sn. This indicates a strain in the film and makes it challenging to provide a straightforward explanation. In an effort to explain our results, we discuss two possible orientation relationships between the Mn3Sn films and the sapphire substrates. Samples prepared under these conditions appear to have smooth surfaces locally, but overall the film has a 3D island morphology. First-principles calculations provide atomic models of the Mn3Sn (112¯0) lattice on Al2O3 (0001) high symmetry sites, indicating that the L3-R90° is the most stable configuration. A detailed discussion of the experimental data and theoretical results, as well as strain effects, is provided.

Self-Aligned Nanopatterning and Controlled Lateral Growth by Dual-Material Orthogonal Area-Selective Deposition of Poly(3,4-ethylenedioxythiophene) and Tungsten

Despite recent advances in area-selective deposition (ASD) processes, most studies have focused on single-material ASD. Multi-material ASD processes could provide additional flexibility for fabricating semiconductor devices. In this work, we identify process requirements to sequentially combine two intrinsic ASD processes: (1) poly(3,4-ethylenedioxythiophene) (PEDOT) ASD on SiO2 vs Si–H via oxidative chemical vapor deposition and (2) W ASD on Si–H vs SiO2 via atomic layer deposition. Using ex situ X-ray photoelectron spectroscopy, we show that a preferred orthogonal ASD sequence involves PEDOT ASD on SiO2 vs Si–H, followed by W ASD on Si–H vs PEDOT. We find that the properties of the individual PEDOT and W ASD materials, including resistivity, surface roughness, and growth rate, are affected by the ASD sequence. Furthermore, we successfully demonstrate that orthogonal ASD can be extended to nanoscale starting patterns. The cross-sectional scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy analysis shows that the resulting PEDOT thickness on SiO2 depends on feature geometry and dimension. Finally, we demonstrate the feasibility that the PEDOT layer can control the lateral growth of W onto the non-growth surface.

Multilayer In-Plane Heterostructures Based on Transition Metal Dichalcogenides for Advanced Electronics.

In-plane heterostructures of transition metal dichalcogenides (TMDCs) have attracted much attention for high-performance electronic and optoelectronic devices. To date, mainly monolayer-based in-plane heterostructures have been prepared by chemical vapor deposition (CVD), and their optical and electrical properties have been investigated. However, the low dielectric properties of monolayers prevent the generation of high concentrations of thermally excited carriers from doped impurities. To solve this issue, multilayer TMDCs are a promising component for various electronic devices due to the availability of degenerate semiconductors. Here, we report the fabrication and transport properties of multilayer TMDC-based in-plane heterostructures. The multilayer in-plane heterostructures are formed through CVD growth of multilayer MoS2 from the edges of mechanically exfoliated multilayer flakes of WSe2 or NbxMo1-xS2. In addition to the in-plane heterostructures, we also confirmed the vertical growth of MoS2 on the exfoliated flakes. For the WSe2/MoS2 sample, an abrupt composition change is confirmed by cross-sectional high-angle annular dark-field scanning transmission electron microscopy. Electrical transport measurements reveal that a tunneling current flows at the NbxMo1-xS2/MoS2 in-plane heterointerface, and the band alignment is changed from a staggered gap to a broken gap by electrostatic electron doping of MoS2. The formation of a staggered gap band alignment of NbxMo1-xS2/MoS2 is also supported by first-principles calculations.

Low-Temperature Direct Growth of Nanocrystalline Multilayer Graphene on Silver with Long-Term Surface Passivation.

A wide variety of transition metals, including copper and gold, have been successfully used as substrates for graphene growth. On the other hand, it has been challenging to grow graphene on silver, so realistic applications by combining graphene and silver for improved electrode stability and enhanced surface plasmon resonance in organic light-emitting diodes and biosensing have not been realized to date. Here, we demonstrate the surface passivation of silver through the single-step rapid growth of nanocrystalline multilayer graphene on silver via low-temperature plasma-enhanced chemical vapor deposition (PECVD). The effect of the growth time on the graphene quality and the underlying silver characteristics is investigated by Raman spectroscopy, X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy (XPS), and cross-sectional annular dark-field scanning transmission electron microscopy (ADF-STEM). These results reveal nanocrystalline graphene structures with turbostratic layer stacking. Based on the XPS and ADF-STEM results, a PECVD growth mechanism of graphene on silver is proposed. The multilayer graphene also provides excellent long-term protection of the underlying silver surface from oxidation after 5 months of air exposure. This development thus paves the way toward realizing technological applications based on graphene-protected silver surfaces and electrodes as well as hybrid graphene-silver plasmonics.

Molecular beam epitaxy of KTaO3

Strain-engineering is a powerful means to tune the polar, structural, and electronic instabilities of incipient ferroelectrics. KTaO3 is near a polar instability and shows anisotropic superconductivity in electron-doped samples. Here, we demonstrate growth of high-quality KTaO3 thin films by molecular-beam epitaxy. Tantalum was provided by either a suboxide source emanating a TaO2 flux from Ta2O5 contained in a conventional effusion cell or an electron-beam-heated tantalum source. Excess potassium and a combination of ozone and oxygen (10% O3 + 90% O2) were simultaneously supplied with the TaO2 (or tantalum) molecular beams to grow the KTaO3 films. Laue fringes suggest that the films are smooth with an abrupt film/substrate interface. Cross-sectional scanning transmission electron microscopy does not show any extended defects and confirms that the films have an atomically abrupt interface with the substrate. Atomic force microscopy reveals atomic steps at the surface of the grown films. Reciprocal space mapping demonstrates that the films, when sufficiently thin, are coherently strained to the SrTiO3 (001) and GdScO3 (110) substrates.

Characterization of dislocation of halide vapor phase epitaxial (001) β-Ga2O3 by ultrahigh sensitive emission microscopy and synchrotron X-ray topography and its influence on Schottky barrier diodes

This study elucidates the dislocation responsible for the leakage current in a halide vapor phase epitaxial (001) β-Ga2O3 Schottky barrier diode. A high reverse leakage current of −0.98 μA was observed at −100 V as an emission pattern via ultrahigh-sensitive emission microscopy. This was attributed to the presence of dislocation. Moreover, the Burgers vector of this dislocation was determined to be ⫽ 〈12〉 from the g·b invisibility criteria via synchrotron X-ray topography observation. This dislocation was speculated to be induced by the relaxation of the strain field surrounding the void and subsequently propagated to the surface. Cross-sectional scanning transmission electron microscopy revealed multiple threading dislocations along the (100) plane.

Fabrication and characterization of NbN/(TaN/NbN) N stacked Josephson junctions

In this work, we present a detailed study of the electrical properties of stacked NbN/(TaN/NbN) N Josephson junctions. Cross-sectional scanning transmission electron microscopy analysis of the 5-stacked junction shows that the multilayer interface is very flat, each barrier has the same thickness, and the sidewalls of the junctions are nearly perpendicular to the substrate. Stacked junctions of different sizes and stacking numbers all have only one transition in their current–voltage curves. This indicates that the critical currents of the junctions in the stacked junctions are almost the same, showing the stability and repeatability of the multilayer fabrication and etching process. At 4.2 K, the 4-stacked junction shows excellent Josephson properties with characteristic voltage V c of 3.54 mV, which is about four times the 0.88 mV of the single junction. The temperature dependence of critical current density J c and V c of the stacked junction with N = 1, 2, 4 were measured, all of which can be fitted with dirty-limit theory. Stacked junctions with larger V c or more stacked layers can be achieved by optimizing electrode and barrier thickness, barrier resistivity, and thermal relaxation rate, etc.

Kinetic influences on void formation in epitaxially regrown GaAs-Based PCSELs

We report an investigation into the formation of crystallographic voids during the metalorganic vapour phase epitaxial regrowth of GaAs photonic crystal structures. We employ a combination of cross-sectional scanning electron microscopy and scanning transmission electron microscopy to study structures regrown with AlAs, AlGaAs and GaAs. The change in regrowth material allows the effect of adatom diffusion kinetics on the void structure to be assessed. Whilst complete grating infill is observed for GaAs, void formation is promoted for Al-containing materials, with void size increasing with Al mole fraction, in line with reduced adatom mobility. In the case of both AlAs and AlGaAs-regrown structures, a degree of asymmetry is observed in the shape of the voids within the plane of the photonic crystal. These differences are attributed to variations in group-III adatom surface mobility and the polarities of high-index crystal planes along orthogonal crystal directions. Two growth regimes of stable and dynamic faceting are observed in cross-sections containing crystal planes with A- and B-type polarities, respectively.

Atomistic Insight into the Epitaxial Growth Mechanism of Single-Crystal Two-Dimensional Transition-Metal Dichalcogenides on Au(111) Substrate.

A mechanistic understanding of interactions between atomically thin two-dimensional (2D) transition-metal dichalcogenides (TMDs) and their growth substrates is important for achieving the unidirectional alignment of nuclei and seamless stitching of 2D TMD domains and thus 2D wafers. In this work, we conduct a cross-sectional scanning transmission electron microscopy (STEM) study to investigate the atomic-scale nucleation and early stage growth behaviors of chemical vapor deposited monolayer (ML-) MoS2 and molecular beam epitaxy ML-MoSe2 on a Au(111) substrate. Statistical analysis reveals the majority of as-grown domains, i.e., ∼88% for MoS2 and 90% for MoSe2, nucleate on surface terraces, with the rest (i.e., ∼12% for MoS2 and 10% for MoSe2) on surface steps. Moreover, within the latter case, step-associated nucleation, ∼64% of them are terminated with a Mo-zigzag edge in connection with the Au surface steps, with the rest (∼36%) being S-zigzag edges. In conjunction with ab initio density functional theory calculations, the results confirm that van der Waals epitaxy, rather than the surface step guided epitaxy, plays deterministic roles for the realization of unidirectional ML-MoS2 (MoSe2) domains on a Au(111) substrate. In contrast, surface steps, particularly their step height, are mainly responsible for the integrity and thickness of MoS2/MoSe2 films. In detail, it is found that the lateral growth of monolayer thick MoS2/MoSe2 domains only proceeds across mono-Au-atom high surface steps (∼2.4 Å), but fail for higher ones (bi-Au atom step and higher) during the growth. Our cross-sectional STEM study also confirms the existence of considerable compressive residual strain that reaches ∼3.0% for ML-MoS2/MoSe2 domains on Au(111). The present study aims to understand the growth mechanism of 2D TMD wafers.

Statistical Assessment of High-Performance Scaled Double-Gate Transistors from Monolayer WS2.

Scaling of monolayer transition metal dichalcogenide (TMD) field-effect transistors (FETs) is an important step toward evaluating the application space of TMD materials. Although some work on ultrashort channel monolayer (ML) TMD FETs has been published, there exist no comprehensive studies that assess their performance in a statistically relevant manner, providing critical insights into the impact of the device geometry. Part of the reason for the absence of such a study is the substantial variability of TMD devices when processes are not carefully controlled. In this work, we show a statistical study of ultrashort channel double-gated ML WS2 FETs exhibiting excellent device performance and limited device-to-device variations. From a detailed analysis of cross-sectional scanning transmission electron microscopy (STEM) images and careful technology computer aided design (TCAD) simulations, we evaluated, in particular, an unexpected deterioration of the subthreshold characteristics for our shortest devices. Two potential candidates for the observed behavior were identified, i.e., buckling of the TMD on the substrate and loss of gate control due to the source geometry and the high-k dielectric between the metal gate and the metal source electrode.

Damage threshold of CuCrFeTiV high entropy alloys for nuclear fusion reactors

A CuCrFeTiV high entropy alloy was prepared and irradiated with swift heavy ions in order to check its adequacy for use as a thermal barrier in future nuclear fusion reactors. The alloy was prepared from the elemental powders by ball milling, followed by consolidation by spark plasma sintering at 1178 K and 65 MPa. The samples were then irradiated at room temperature with 300 keV Ar+ ions with fluences in the 3 × 1015 to 3 × 1018 Ar+/cm2 range to mimic neutron-induced damage accumulation during a duty cycle of a fusion reactor. Structural changes were investigated by X-ray diffraction, and scanning electron microscopy and scanning transmission electron microscopy, both coupled with X-ray energy dispersive spectroscopy. Surface irradiation damage was detected for high fluences (3 × 1018 Ar+/cm2) with formation of blisters of up to 1 μm in diameter. Cross-sectional scanning transmission electron microscopy showed the presence of intergranular cavities only in the sample irradiated with 3 × 1018 Ar+/cm2, while all irradiation experiments produced intragranular nanometric-sized bubbles with increased density for higher Ar+ fluence. The Williamson-Hall method revealed a decrease in the average crystallite size and an increase in residual strain with increasing fluence, consistent with the formation of Ar+ bubbles at the irradiated surface.

Realization of p-type conduction in compositionally graded quaternary AlInGaN

Quaternary AlInGaN alloy offers more degree of freedom in independently adjusting the band gap and lattice constant, and it shows the great potential in the fabrication of nitride optoelectronic and electronic devices. In this work, AlInGaN films were grown by metal-organic chemical vapor deposition and the p-type conduction was realized in compositionally graded quaternary AlInGaN. The element compositions in AlInGaN were confirmed by secondary ion mass spectrometry. The structural properties such as layer thickness, lattice polarity and surface morphology of the epilayers were characterized by cross-sectional scanning transmission electron microscopy and atomic force microscopy (AFM). The measured surface AFM images verify that the surface morphology of the quaternary AlInGaN film is smooth and it is free from V-shaped pits. Hall effect measurement results show that the grown graded AlInGaN is p-type with the hole concentration of ∼7.3 × 1016 cm−3 at room temperature. The realization of p-type conduction in AlInGaN can enrich the polarization engineering and the device structures of nitride semiconductors.