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Current reports of thermal expansion coefficients (TEC) of two-dimensional (2D) materials show large discrepancies that span orders of magnitude. Determining the TEC of any 2D material remains difficult due to approaches involving indirect measurement of samples that are atomically thin and optically transparent. We demonstrate a methodology to address this discrepancy and directly measure TEC of nominally monolayer epitaxial WSe2using four-dimensional scanning transmission electron microscopy (4D-STEM). Experimentally, WSe2from metal–organic chemical vapor deposition (MOCVD) was heated through a temperature range of 18–564 °C using a barrel-style heating sample holder to observe temperature-induced structural changes without additional alterations or destruction of the sample. By combining 4D-STEM measurements with quantitative structural analysis, the thermal expansion coefficient of nominally monolayer polycrystalline epitaxial 2D WSe2was determined to be (3.5 ± 0.9) × 10–6K–1and (5.7 ± 2) × 10–5K–1for the in- and out-of-plane TEC, respectively, and (3.6 ± 0.2) × 10–5K–1for the unit cell volume TEC, in good agreement with historically determined values for bulk crystals. more...

Defect engineering of van der Waals semiconductors has been demonstrated as an effective approach to manipulate the structural and functional characteristics toward dynamic device controls, yet correlations between physical properties with defect evolution remain underexplored. Using proton irradiation, we observe an enhanced exciton-to-trion conversion of the atomically thin WS2. The altered excitonic states are closely correlated with nanopore induced atomic displacement, W nanoclusters, and zigzag edge terminations, verified by scanning transmission electron microscopy, photoluminescence, and Raman spectroscopy. Density functional theory calculation suggests that nanopores facilitate formation of in-gap states that act as sinks for free electrons to couple with excitons. The ion energy loss simulation predicts a dominating electron ionization effect upon proton irradiation, providing further evidence on band perturbations and nanopore formation without destroying the overall crystallinity. This study provides a route in tuning the excitonic properties of van der Waals semiconductors using an irradiation-based defect engineering approach. more...

During the lithation of silicon anodes, the solid-state diffusion of lithium into LixSi follows the Arrhenius law, the resulting morphology and fracture behavior are determined by the silicon anode operation temperature. Here, we reveal the temperature dependence of the lithiation mechanics of crystalline silicon nanopillars (SiNPs) via microscopic observations of the anisotropic growth and fracture behavior. We fabricated 1D SiNP structures with various orientations (⟨100⟩, ⟨110⟩, and ⟨111⟩) as working electrodes and operated them at temperatures ranging from −20 to 40 °C. The lithiation of crystalline silicon at low temperatures exhibited preferential volume expansion along ⟨110⟩ and decreased fracture resistance. Furthermore, low temperatures caused the catastrophic fracture of amorphous silicon after the second lithiation. Our findings demonstrate the importance of silicon anode temperature control to prevent mechanical fracture during the cycle of lithium-ion batteries in harsh environments (e.g., electric vehicles in winter). more...

The solid–electrolyte interphase (SEI), a layer formed on the electrode surface, is essential for electrochemical reactions in batteries and critically governs the battery stability. Active materials, especially those with extremely high energy density, such as silicon (Si), often inevitably undergo a large volume swing upon ion insertion and extraction, raising a critical question as to how the SEI interactively responds to and evolves with the material and consequently controls the cycling stability of the battery. Here, by integrating sensitive elemental tomography, an advanced algorithm and cryogenic scanning transmission electron microscopy, we unveil, in three dimensions, a correlated structural and chemical evolution of Si and SEI. Corroborated with a chemomechanical model, we demonstrate progressive electrolyte permeation and SEI growth along the percolation channel of the nanovoids due to vacancy injection and condensation during the delithiation process. Consequently, the Si–SEI spatial configuration evolves from the classic ‘core–shell’ structure in the first few cycles to a ‘plum-pudding’ structure following extended cycling, featuring the engulfing of Si domains by the SEI, which leads to the disruption of electron conduction pathways and formation of dead Si, contributing to capacity loss. The spatially coupled interactive evolution model of SEI and active materials, in principle, applies to a broad class of high-capacity electrode materials, leading to a critical insight for remedying the fading of high-capacity electrodes. more...

Organic–inorganic hybrid perovskites have electronic and optoelectronic properties that make them appealing in many device applications1–4. Although many approaches focus on polycrystalline materials5–7, single-crystal hybrid perovskites show improved carrier transport and enhanced stability over their polycrystalline counterparts, due to their orientation-dependent transport behaviour8–10and lower defect concentrations11,12. However, the fabrication of single-crystal hybrid perovskites, and controlling their morphology and composition, are challenging12. Here we report a solution-based lithography-assisted epitaxial-growth-and-transfer method for fabricating single-crystal hybrid perovskites on arbitrary substrates, with precise control of their thickness (from about 600 nanometres to about 100 micrometres), area (continuous thin films up to about 5.5 centimetres by 5.5 centimetres), and composition gradient in the thickness direction (for example, from methylammonium lead iodide, MAPbI3, to MAPb0.5Sn0.5I3). The transferred single-crystal hybrid perovskites are of comparable quality to those directly grown on epitaxial substrates, and are mechanically flexible depending on the thickness. Lead–tin gradient alloying allows the formation of a graded electronic bandgap, which increases the carrier mobility and impedes carrier recombination. Devices based on these single-crystal hybrid perovskites show not only high stability against various degradation factors but also good performance (for example, solar cells based on lead–tin-gradient structures with an average efficiency of 18.77 per cent). more...

The ever-increasing demand for faster, smaller, and energy-efficient devices has pushed the frontiers of research toward silicon photonics to meet the challenges for fabricating the next generation of computing systems. In order to design new devices at the nanoscale, it is important to understand and be able to control material properties, which may differ significantly from their bulk counterparts. Here, we demonstrate very large tunability of phonon–photon interactions in Si nanowire cavities by engineering the cavity mode at the emission wavelength. Raman scattering measurements performed to quantify these interactions reveal that the anti-Stokes to Stokes scattering ratio can vary from 0.035 to 0.405 in Si nanowires compared to a value of 0.1 for bulk Si, demonstrating tunability by over an order of magnitude. Moreover, a ratio of 0.85 was attained at a temperature of 580 K, which is the highest value ever reported for Si. Cavity modes that can be easily changed by changing the nanowire diameter, cavity geometry, or excitation wavelength provide efficient ways of tuning these interactions. Nanocavity engineering offers a new approach for tuning phonon–photon interactions in silicon and opens up new avenues of research and applications in the fields of silicon photonics, Raman lasers, telecommunication, and optical cooling. more...

The growth of the information era economy is driving the pursuit of advanced materials for microelectronics, spurred by exploration into “Beyond CMOS” and “More than Moore” paradigms. Atomically thin 2D materials, such as transition metal dichalcogenides (TMDCs), show great potential for next-generation microelectronics due to their properties and defect engineering capabilities. This perspective delves into atomic precision processing (APP) techniques like atomic layer deposition (ALD), epitaxy, atomic layer etching (ALE), and atomic precision advanced manufacturing (APAM) for the fabrication and modification of 2D materials, essential for future semiconductor devices. Additive APP methods like ALD and epitaxy provide precise control over composition, crystallinity, and thickness at the atomic scale, facilitating high-performance device integration. Subtractive APP techniques, such as ALE, focus on atomic-scale etching control for 2D material functionality and manufacturing. In APAM, modification techniques aim at atomic-scale defect control, offering tailored device functions and improved performance. Achieving optimal performance and energy efficiency in 2D material-based microelectronics requires a comprehensive approach encompassing fundamental understanding, process modeling, and high-throughput metrology. The outlook for APP in 2D materials is promising, with ongoing developments poised to impact manufacturing and fundamental materials science. Integration with advanced metrology and codesign frameworks will accelerate the realization of next-generation microelectronics enabled by 2D materials. more...

Silicon photonics has been a very active area of research especially in the past two decades in order to meet the ever-increasing demand for more computational power and faster device speeds and their natural compatibility with complementary metal-oxide semiconductor. In order to develop Si as a useful photonics material, essential photonic components such as light sources, waveguides, wavelength convertors, modulators, and detectors need to be developed and integrated. However, due to the indirect electronic bandgap of Si, conventional light emission devices such as light-emitting diodes and lasers cannot be built. Therefore, there has been considerable interest in developing Si-based Raman lasers, which are nonlinear devices and require large stimulated Raman scattering (SRS) in an optical cavity. However, due to the low quantum yield of SRS in Si, Raman lasers have very large device footprints and high lasing threshold, making them unsuitable for faster, smaller, and energy-efficient devices. Here, we report strong SRS and extremely high Raman gain in Si nanowire optical cavities in the visible region with measured SRS threshold as low as 30 kW/cm2. At cavity mode resonance, light is confined into a low mode volume and high intensity electromagnetic mode inside the Si nanowire due to its high refractive index, which leads to strong SRS at low pump intensities. Electromagnetic calculations reveal greater than 6 orders of magnitude increase in Raman gain coefficient at 532 nm pump wavelength, compared to the gain value at 1.55 μm wavelength reported in literature, despite the 108higher losses at 532 nm. Because of the high gain in such small structures, we believe that this is a significant first step in realizing a monolithically integrable nanoscale low-powered Si Raman laser. more...

In this study, we investigate the thermochemical stability of graphene on the GaN substrate for metal–organic chemical vapor deposition (MOCVD)-based remote epitaxy. Despite excellent physical properties of GaN, making it a compelling choice for high-performance electronic and light-emitting device applications, the challenge of thermochemical decomposition of graphene on a GaN substrate at high temperatures has obstructed the achievement of remote homoepitaxy via MOCVD. Our research uncovers an unexpected stability of graphene on N-polar GaN, thereby enabling the MOCVD-based remote homoepitaxy of N-polar GaN. Our comparative analysis of N- and Ga-polar GaN substrates reveals markedly different outcomes: while a graphene/N-polar GaN substrate produces releasable microcrystals (μCs), a graphene/Ga-polar GaN substrate yields nonreleasable thin films. We attribute this discrepancy to the polarity-dependent thermochemical stability of graphene on the GaN substrate and its subsequent reaction with hydrogen. Evidence obtained from Raman spectroscopy, electron microscopic analyses, and overlayer delamination points to a pronounced thermochemical stability of graphene on N-polar GaN during MOCVD-based remote homoepitaxy. Molecular dynamics simulations, corroborated by experimental data, further substantiate that the thermochemical stability of graphene is reliant on the polarity of GaN, due to different reactions with hydrogen at high temperatures. Based on the N-polar remote homoepitaxy of μCs, the practical application of our findings was demonstrated in fabrication of flexible light-emitting diodes composed of p–n junction μCs with InGaN heterostructures. more...

High-performance photovoltaic (PV) devices require strong light absorption, low reflection and efficient photogenerated carrier collection for high quantum efficiency. Previous optical studies of vertical wires arrays have revealed that extremely efficient light absorption in the visible wavelengths is achievable. Photovoltaic studies have further advanced the wire approach by employing radial p-njunction architectures to achieve more efficient carrier collection. While radial p-njunction formation and optimized light absorption have independently been considered, PV efficiencies have further opportunities for enhancement by exploiting the radial p-njunction fabrication procedures to form arrays that simultaneously enhance bothlight absorption and carrier collection efficiency. Here we report a concept of morphology control to improve PV performance, light absorption and quantum efficiency of silicon radial p-i-njunction arrays. Surface energy minimization during vapor phase epitaxy is exploited to form match-head structures at the tips of the wires. The match-head structure acts as a built-in light concentrator and enhances optical absorptance and external quantum efficiencies by 30 to 40%, and PV efficiency under AM 1.5G illumination by 20% compared to cylindrical structures without match-heads. The design rules for these improvements with match-head arrays are systematically studied. This approach of process-enhanced control of three-dimensional Si morphologies provides a fab-compatible way to enhance the PV performance of Si radial p-njunction wire arrays. more...

The mechanisms and kinetics of axial Ge–Si nanowire heteroepitaxial growth based on the tailoring of the Au catalyst composition viaGa alloying are studied by environmental transmission electron microscopy combined with systematic ex situCVD calibrations. The morphology of the Ge–Si heterojunction, in particular, the extent of a local, asymmetric increase in nanowire diameter, is found to depend on the Ga composition of the catalyst, on the TMGa precursor exposure temperature, and on the presence of dopants. To rationalize the findings, a general nucleation-based model for nanowire heteroepitaxy is established which is anticipated to be relevant to a wide range of material systems and device-enabling heterostructures. more...

This proceeding summarizes the materials preparation of position-controlled ZnO-based nanorod heterostructures and fabrication of vertically-aligned wide band gap semiconductor nanorod light-emitting devices. Especially the fabrication of GaN/InxGa1-xN/GaN/ZnO nanorod heterostructured visible-light-emitter arrays on sapphire and Si substrates, representing important progress in the field of nanoheteroepitaxy and photonic devices in nanoscale, are reported. Particularly, position-controlled vertical nanostructure arrays make those possible to prepare high-quality material systems without stress or strain accumulation and to fabricate high-performance light-emitting devices (LEDs) with a three-dimensional device configuration. Our method based on nanoheteroepitaxy and position-controlled nanodevice integration for fabricating GaN-based micro-LED arrays constitutes a promising strategy for resolving the issues of conventional GaN LEDs and fabricating high-performance LEDs on various substrates for potential optoelectronic integrated circuits and solid-state lighting applications. more...

The position‐controlled growth and structural and optical characteristics of ZnO nanotubes and their coaxial heterostructures are reported. To control both the shape and position of ZnO nanotubes, hole‐patterned SiO2growth‐mask layers on Si(111) substrates with GaN/AlN intermediate layers using conventional lithography are prepared. ZnO nanotubes are grown only on the hole patterns at 600 °C by catalyst‐free metal–organic vapor‐phase epitaxy. Furthermore, the position‐controlled nanotube growth method allows the fabrication of artificial arrays of ZnO‐based coaxial nanotube single‐quantum‐well structures (SQWs) on Si substrates. In situ heteroepitaxial growth of ZnO and Zn0.8Mg0.2O layers along the circumference of the ZnO nanotube enable an artificial formation of quantum‐well arrays in a designed fashion. The structural and optical characteristics of the ZnO nanotubes and SQW arrays are also investigated using synchrotron radiation X‐ray diffractometry and photoluminescence and cathodoluminescence spectroscopy. more...

Using four-dimensional scanning transmission electron microscopy, we demonstrate a method to visualize grains and grain boundaries in WSe2grown by metal organic chemical vapor deposition (MOCVD) directly onto silicon dioxide. Despite the chemical purity and uniform thickness and texture of the MOCVD-grown WSe2, we observe a high density of small grains that corresponds with the overall selenium deficiency we measure through ion beam analysis. Moreover, reconstruction of grain information permits the creation of orientation maps that demonstrate the nucleation mechanism for new layers–triangular domains with the same orientation as the layer underneath induces a tensile strain increasing the lattice parameter at these sites. more...

Advances in epitaxy have enabled the preparation of high-quality material architectures consisting of incommensurate components. Remote epitaxy based on lattice transparency of atomically thin graphene has been intensively studied for cost-effective advanced device manufacturing and heterostructure formation. However, remote epitaxy on nongraphene two-dimensional (2D) materials has rarely been studied even though it has a broad and immediate impact on various disciplines, such as many-body physics and the design of advanced devices. Herein, we report remote epitaxy of ZnO on monolayer MoS2and the realization of a whispering-gallery-mode (WGM) cavity composed of a single crystalline ZnO nanorod and monolayer MoS2. Cross-sectional transmission electron microscopy and first-principles calculations revealed that the nongraphene 2D material interacted with overgrown and substrate layers and also exhibited lattice transparency. The WGM cavity embedding monolayer MoS2showed enhanced luminescence of MoS2and multimodal emission. more...