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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 WSe2 using four-dimensional scanning transmission electron microscopy (4D-STEM). Experimentally, WSe2 from 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 WSe2 was determined to be (3.5 ± 0.9) × 10-6 K-1 and (5.7 ± 2) × 10-5 K-1 for the in- and out-of-plane TEC, respectively, and (3.6 ± 0.2) × 10-5 K-1 for the unit cell volume TEC, in good agreement with historically determined values for bulk crystals.

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.

Using four-dimensional scanning transmission electron microscopy, we demonstrate a method to visualize grains and grain boundaries in WSe2 grown 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.

We report innovative scalable, vertical, ultra-sharp nanowire arrays that are individually addressable to enable long-term, native recordings of intracellular potentials. Stable amplitudes of intracellular potentials from 3D tissue-like networks of neurons and cardiomyocytes are obtained. Individual electrical addressability is necessary for high-fidelity intracellular electrophysiological recordings. This study paves the way toward predictive, high-throughput, and low-cost electrophysiological drug screening platforms.

High‐quality quasi‐2D perovskites in a GaN nano‐wire matrix are grown to build a 3D hetero‐structure for high‐performance X‐ray sensing. In the 3D hetero‐structure, GaN nano‐wire matrix serves as an n‐type charge collector that can rapidly extract carriers through the bulk film of the perovskite layer. Together with a p‐type top electrode, a p–i–n diode with the 3D hetero‐structure is built, that exhibits a rectified current–voltage characteristic. After analyzing the interface energy alignment, it is found that the fermi levels of the perovskite and GaN are aligned in the dark, and a quasi‐fermi level splits upon illumination, introducing a built‐in electrical field at the interface. As a result, strong photo‐induced current is observed from the diode without an external field. Finally, the 3D diode for X‐ray detection demonstration is used, revealing a sensitivity of 308.9 µC Gyair−1 cm−2 at an exceptionally low applied field of 0.125 V µm−1. The X‐ray‐induced signal from the 3D diode is stable after 155 cycles of X‐ray irradiation under a constant electric field. This demonstration informs a new 3D architecture for high‐performance X‐ray sensing, and it shows that GaN is a robust n‐type interface for perovskite optoelectronic devices. [ABSTRACT FROM AUTHOR]

We present a single-step nonthermal plasma method for the synthesis of near-infrared (NIR)-emitting and water-soluble Si quantum dots (QDs) for bioimaging applications. Oxygen gas and water vapor were introduced together with acrylic acid (AA) into the afterglow region of the synthesis plasma leading to the surface functionalization of the upstream synthesized Si QDs. The simultaneous surface oxidation and ligand grafting enabled solubility and colloidal stability of the Si QDs in water, as evidenced by strongly reduced hydrodynamic diameters. Aged Si QDs in water emitted NIR photoluminescence (PL) at around 830 nm. The PL quantum yield of the Si QDs in water increased over time from initially undetectable to ∼30% after 8 days. Cell viability tests showed that >70% of 3T3 cells survived for 24 h at a concentration of 200 μg/mL of oxidized AA grafted Si QDs. The water solubility, NIR emission with a high quantum yield, and cell viability make the Si QDs promising for bioimaging applications. [ABSTRACT FROM AUTHOR]

Safe and efficient operation of lithium ion batteries requires precisely directed flow of lithium ions and electrons to control the first directional volume changes in anode and cathode materials. Understanding and controlling the lithium ion transport in battery electrodes becomes crucial to the design of high performance and durable batteries. Recent work revealed that the chemical potential barriers encountered at the surfaces of heteromaterials play an important role in directing lithium ion transport at nanoscale. Here, we utilize in situ transmission electron microscopy to demonstrate that we can switch lithiation pathways from radial to axial to grain-by-grain lithiation through the systematic creation of heteromaterial combinations in the Si-Ge nanowire system. Our systematic studies show that engineered materials at nanoscale can overcome the intrinsic orientation-dependent lithiation, and open new pathways to aid in the development of compact, safe, and efficient batteries.

Heterogeneous integration of two-dimensional materials and the conventional semiconductor has opened opportunities for next-generation semiconductor devices and their processing. Heterogeneous integration has been studied for economical manufacturing by substrate recycling and novel functionalities by a combination of incommensurate materials. However, utilizing the integration requires controlling locations of the integrated architectures. Here, we show area-selective deposition (ASD) of germanium on the graphene/MoS2 stack. Ge nucleation precisely occurred on the surfaces of the patterned graphene/MoS2 stack via dipole engineering. In this study, the growth temperature of ASD of Ge was significantly lower than that based on precursor desorption on SiO2. The first-principles calculations revealed that Ge deposited by ASD on the graphene/MoS2 stack was not affected by charge transfer. This work provides a viable way to utilize atomically thin materials for next-generation semiconductor devices, which can be applicable for "Beyond Moore" and "More Moore" approaches. [ABSTRACT FROM AUTHOR]

Recent advances in 3D/2D heterostructures have opened up tremendous opportunities in building highly flexible and durable optoelectronic devices. However, the inherit lack of interfacial bonding and low surface energy of van der Waals surfaces limit the nucleation and growth of 3D materials. Enhancing wettability by providing a porous buffer is effective in growing compound semiconductors on graphene while van der Waals epitaxy of Ge remains challenging. Here, the nucleation of Ge has been significantly improved from an islanded mode to granular modes by using a TiN/AlN multilayered buffer prior to Ge/graphene integration. Highly textured Ge growth with dominating (111), (220), and (311) peaks are identified by x-ray diffraction. The microstructure of the buffer TiN/AlN demonstrates a polycrystalline quality with clean interfaces between each interlayer and the substrate. Kelvin probe force microscopy measurements along the lateral TiN/AlN interface identify a potential drop corresponding to the AlN phase. This contact potential difference between TiN and AlN is the key in generating the out-of-plane dipole moment that modifies the surface energy of the monolayer graphene, resulting in enhanced wettability of the Ge adatoms nucleated on top. Surface dipole induced nucleation of 3D semiconductor thin films on 2D materials via the proper design of buffer layer is fundamentally important to enhance the 3D/2D growth toward flexible optoelectronic applications. [ABSTRACT FROM AUTHOR]

The perovskite polycrystalline thin film detector fabricated by solution method is a promising low‐cost, scalable technology for radiation imaging, but its thin volume limits the sensing efficiency for high‐energy X‐ray photons. This work reports 2D perovskite thin film photo‐diodes with a detection gain when sensing visible and X‐ray photons. Detailed power and temperature‐dependent device characterizations reveal a charge multiplication effect to be responsible for the observed high gain. This is caused by a disparity in electron and hole transport, where electron transport is retarded by a trap/de‐trap process via shallow trap states, whereas the hole transport is fast enough to produce a photoconductive gain in satisfying the charge neutrality. The 2D perovskite made with butylamine spacers is also found to exhibit a larger efficiency gain than those made with phenylethylamines because of the higher likelihood of forming shallow traps in the former. The thin film diodes feature a high temporal response over 1 MHz due to the fast charge collection across a thin volume, and the discovery provides device physics mechanisms in connection to material structure‐function relationship for future optoelectronics design that can boost the efficiency of X‐ray sensing and dim light detection. [ABSTRACT FROM AUTHOR]

The discovery of topological Hall effect (THE) has important implications for next‐generation high‐density nonvolatile memories, energy‐efficient nanoelectronics, and spintronic devices. Both real‐space topological spin configurations and two anomalous Hall effects (AHE) with opposite polarity due to two magnetic phases have been proposed for THE‐like feature in SrRuO3 (SRO) films. In this work, SRO thin films with and without THE‐like features are systematically Investigated to decipher the origin of the THE feature. Magnetic measurement reveals the coexistence of two magnetic phases of different coercivity (Hc) in both the films, but the hump feature cannot be explained by the two channel AHE model based on these two magnetic phases. In fact, the AHE is mainly governed by the magnetic phase with higher Hc. A diffusive Berry phase transition model is proposed to explain the THE feature. The coexistence of two Berry phases with opposite signs over a narrow temperature range in the high Hc magnetic phase can explain the THE like feature. Such a coexistence of two Berry phases is due to the strong local structural tilt and microstructure variation in the thinner films. This work provides an insight between structure/micro structure and THE like features in SRO epitaxial thin films. [ABSTRACT FROM AUTHOR]

Transition metal oxides exhibit a plethora of electrical and magnetic properties described by their order parameters. In particular, ferroic orderings offer access to a rich spectrum of fundamental physics phenomena, in addition to a range of technological applications. The heterogeneous integration of ferroelectric and ferromagnetic materials is a fruitful way to design multiferroic oxides. The realization of freestanding heterogeneous membranes of multiferroic oxides is highly desirable. In this study, epitaxial BaTiO3/La0.7Sr0.3MnO3 freestanding bilayer membranes are fabricated using pulsed laser epitaxy. The membrane displays ferroelectricity and ferromagnetism above room temperature accompanying the finite magnetoelectric coupling constant. This study reveals that a freestanding heterostructure can be used to manipulate the structural and emergent properties of the membrane. In the absence of the strain caused by the substrate, the change in orbital occupancy of the magnetic layer leads to the reorientation of the magnetic easy‐axis, that is, perpendicular magnetic anisotropy. These results of designing multiferroic oxide membranes open new avenues to integrate such flexible membranes for electronic applications. [ABSTRACT FROM AUTHOR]

Realizing a tubular conduction channel within a one-dimensional core–shell nanowire (NW) enables better understanding of quantum phenomena and exploration of electronic device applications. Herein, we report the growth of a SiGe(P)/Si core/shell NW heterostructure using a chemical vapor deposition coupled with vapor–liquid–solid growth mechanism. The entire NW heterostructure behaves as a p-type semiconductor, which demonstrates that the high-density carriers are confined within the 4 nm-thick Si shell and form a tubular conduction channel. These findings are confirmed by both calculations and the gate-dependent current–voltage (Id–Vg) characteristics. Atomic resolution microscopic analyses suggest a coherent epitaxial core/shell interface where strain is released by forming dislocations along the axial direction of the NW heterostructure. Additional surface passivation achieved via growing a SiGe(P)/Si/SiGe core/multishell NW heterostructure suggests potential strategies to enhance the tubular carrier density, which could be further modified by improving multishell crystallinity and structural design. [ABSTRACT FROM AUTHOR]

A variety of mechanisms are reported to play critical roles in contributing to the high carrier/electron mobility in oxide/SrTiO3 (STO) heterostructures. By using La0.95Sr0.05TiO3 (LSTO) epitaxially grown on different single crystal substrates (such as STO, GdScO3, LaAlO3, (LaAlO3)0.3(Sr2AlTaO6)0.7, and CeO2 buffered STO) as the model systems, the formation of a conducting substrate surface layer (CSSL) on STO substrate is shown at relatively low growth temperature and high oxygen pressure (725 °C, 5 × 10–4 Torr), which contributes to the enhanced conductivity of the LSTO/STO heterostructures. Different from the conventional oxygen vacancy model, this work reveals that the formation of the CSSL occurs when growing an oxide layer (LSTO in this case) on STO, while neither annealing nor the growth of an Au layer alone at the exact same growth condition generates the CSSL in STO. It demonstrates that the oxide layer actively pulls oxygen from STO substrate at given growth conditions, leading to the formation of the CSSL. The observations emphasize the oxygen transfer across film/substrate interface during the synthesis of oxide heterostructures playing a critical role in functional properties. [ABSTRACT FROM AUTHOR]

In this work, we employ an atomic force microscopy-based technique, Kelvin probe force microscopy, to analyze heterogeneities of four different 2D/3D Ge/MoS2 heterostructures with Ge chemical vapor deposition (CVD) time. High-contrast spatially resolved contact potential difference (CPD) maps reveal the evolution of the samples by Ge deposition. The CPD map in an as-prepared sample does not display any heterogeneity, but CPD contrasts along the grain boundaries are obviously noticed as Ge is deposited on MoS2. With a sufficiently long Ge CVD deposition time, strong grain-to-grain CPD variations over the 2D/3D heterostructures are observed. The results show the variations of the work function from grain to grain that are attributed to the strain induced by the Ge island formation on the cracked MoS2 initiated by sulfur vacancies. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) materials as contacts for semiconductor devices have attracted much attention due to minimizing Fermi level pinning. Schottky–Mott physics has been widely employed to design 2D material-based electrodes and to elucidate their contact behavior. In this study, we revealed that charge transfer across a 2D/semiconductor heterointerface and materials characteristics besides work function should be accounted for in fabrication of electrodes based on 2D materials. Our density functional theory (DFT) calculations predicted that charge transfer between ZnO and NbSe2 lowers the barrier height at the heterojunction and that conductive surface states of ZnO provide an additional conduction channel in the ZnO/NbSe2 heterostructures. Crystalline ZnO/NbSe2 heterostructures were prepared by the hydrothermal method. Electrical characterizations of the ZnO/NbSe2 heterostructures showed Ohmic-like behavior as predicted by the DFT calculations, opposed to the prediction based on the Schottky–Mott model. [ABSTRACT FROM AUTHOR]

The plasma enhanced atomic layer deposition (PEALD) process for MnO2 was demonstrated, exhibiting self-limiting growth as well as stable composition and stable growth rate over a temperature window of 205–265 °C. The PEALD process for MnO2 was combined with the thermal ALD process for LiOH to synthesize Li1+xMn2−xO4 thin film cathodes, where the stoichiometry was effectively controlled to allow for crystallization in the electrochemically active spinel phase. A 3D nanostructure consisting of an Li1+xMn2−xO4 cathode layer, ALD LixAlySizO solid electrolyte, and SiGe nanowire anode was fabricated and characterized via TEM. The Li1+xMn2−xO4 thin films maintained 66% of the areal capacity upon a 100× increase in the rate (4–360 μA cm−2) as well as 97% capacity retention over 100 cycles at ∼5C. The ALD Li1+xMn2−xO4 thin films exhibited a volumetric capacity of 52 μAh cm−2 μm−1 at a C-rate of ∼0.5C and, coupled with the high operating voltage (4.0 V), offer some of best areal energy densities for ALD thin film cathodes, making it a viable material for integration with 3D lithium-ion microbatteries. [ABSTRACT FROM AUTHOR]

Nanowire transistors are typically undoped devices whose characteristics depend strongly on the injection of carriers from the electrical contacts. In this letter, we fabricate and characterize SiGe nanowire transistors with an n-p-n doping profile and with a top gate covering only the p-doped section of the nanowire. For each device, we locate the p-segment with scanning capacitance microscopy, where the p-segment position varies along the channel due to the stochastic nature of our dropcast fabrication technique. The current–voltage characteristics for a series of transistors with different gate positions reveal that the on/off ratios for electrons is the highest when the gated p-type section is closest to the source contact, whereas the on/off ratios for holes is the highest when the gated p-type section is closest to the drain contact. [ABSTRACT FROM AUTHOR]

Semiconductor epitaxy on two-dimensional materials is beneficial for transferrable and flexible device applications. Graphene, due to the absence of permanent electric dipoles, cannot screen the electric field coming from the opposite side surface, allowing remote epitaxy for heteroepitaxy. This study demonstrates remote heteroepitaxy of ZnO microrods (MRs) on the GaN substrate across graphene layers via hydrothermal growth. Even the use of tri-layer graphene yields the remote heteroepitaxial MR arrays. Transmission electron microscopy reveals the remote heteroepitaxial relation between ZnO MRs and the GaN substrate despite the existence of graphene interlayers in between them. Density-functional theory calculations show that charge transfer along the z-direction at graphene/c-GaN possibly attract adatoms leading to remote heteroepitaxy, implying the field permeability of graphene. The ability of graphene to be released from the host substrate is exploited to exfoliate the overlayer MRs and regenerate the substrate. [ABSTRACT FROM AUTHOR]

New discoveries on collective processesin materials fabricationand performance are emerging in the mesoscopic size regime betweenthe nanoscale, where atomistic effects dominate, and the macroscale,where bulk-like behavior rules. For semiconductor electronics andphotonics, dimensional control of the architecture in this regimeis the limiting factor for device performance. Epitaxial crystal growthis the major tool enabling simultaneous control of the dimensionsand properties of such architectures. Although size-dependent effectshave been studied for many small-scale systems, they have not beenreported for the epitaxial growth of Si crystalline surfaces. Here,we show a strong dependence of epitaxial growth rates on size fornano to microscale radial wires and planar stripes. A model for thisunexpected size-dependent vapor phase epitaxy behavior at small dimensionssuggests that these effects are universal and result from an enhancedsurface desorption of the silane (SiH4) growth precursornear facet edges. Introducing phosphorus or boron dopants during thesilicon epitaxy further decreases the growth rates and, for phosphorus,gives rise to a critical layer thickness for single crystalline epitaxialgrowth. This previously unknown mesoscopic size-dependent growth effectat mesoscopic dimensions points to a new mechanism in vapor phasegrowth and promises greater control of advanced device geometries. [ABSTRACT FROM AUTHOR]

Highlyefficient solid-state light-emitting devices require semiconductorarchitectures equipped with high quantum efficiency and integratabilityon conductive substrates. Surface plasmon (SP)-mediated luminescenceenhancement has been considered as one of the most promising solutions,because SP resonance can greatly improve the radiative recombinationrate and be achieved using metal entities compatible with the electrodefabrication process. Nevertheless, metal/semiconductor heterostructureshave had several fabrication-compatible issues due to metal as a potentialcontaminant of the semiconductor. We present here a simple fabricationscheme for a metal-lined semiconductor nanotube heterostructure, inwhich a metal layer is selectively formed on the inner wall of thesemiconductor nanotube. The Ag-lining process in a ZnO nanotube resultedin 7.5-fold enhancement of the photoluminescence intensity at 11 K.This SP fabrication technique looks promising for highly efficientsolid-state lighting based on semiconductor nanostructures withoutdetrimental effects. [ABSTRACT FROM AUTHOR]

In lithium-ion batteries, the electrochemical reaction between the electrodes and lithium is a critical process that controls the capacity, cyclability and reliability of the battery. Despite intensive study, the atomistic mechanism of the electrochemical reactions occurring in these solid-state electrodes remains unclear. Here, we show that in situ transmission electron microscopy can be used to study the dynamic lithiation process of single-crystal silicon with atomic resolution. We observe a sharp interface (?1 nm thick) between the crystalline silicon and an amorphous LixSi alloy. The lithiation kinetics are controlled by the migration of the interface, which occurs through a ledge mechanism involving the lateral movement of ledges on the close-packed {111} atomic planes. Such ledge flow processes produce the amorphous LixSi alloy through layer-by-layer peeling of the {111} atomic facets, resulting in the orientation-dependent mobility of the interfaces. [ABSTRACT FROM AUTHOR]