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With continued scaling toward higher component densities, integrated circuits (ICs) contain ever greater lengths of nanowire that are vulnerable to failure via electromigration. Previously, plastic electromigration driven by the "electron wind" has been observed, but not the elastic response to the wind force itself. Here we describe mapping, via electron energy-loss spectroscopy, the density of a lithographically defined aluminum nanowire with sufficient precision to determine both its temperature and its internal pressure. An electrical current density of 10 8 A/cm 2 produces Joule heating, tension upwind, and compression downwind. Surprisingly, the pressure returns to its ambient value well inside the wire, where the current density is still high. This spatial discrepancy points to physics that are not captured by a classical "wind force" model and to new opportunities for optimizing electromigration-resistant IC design.

Phyllosilicate clays are layered structures with diverse nanoscale morphology depending on the composition. Size mismatch between the sheets can cause them to form nanoscrolls, a spiral structure with different inner and outer surface charges. The hydroxyls on the exposed surface of the nanoscrolls determine the adsorption properties and hydrophilicity of the surface. Vibrational sum frequency generation (VSFG) spectroscopy was applied to study the surface hydroxyls of nickel phyllosilicate (Ni 3 Si 2 O 5 (OH) 4 ), revealing three distinct in-phase OH-stretch modes: 3642, 3645, and 3653 cm -1 . The relative signs of the peaks allow their assignment as "outward" and "inward" pointing hydroxyls on the opposite sides of the scrolled sheet, consistent with the crystal structure. Orientational analysis of polarization-selected VSFG spectra is consistent with a broad (140-164°) step-function distribution of the OH-stretch tilt angles, which we attribute to the uncompensated portion of the scroll rolled more than a whole number of full turns.

Nanoscale oxide layer protected semiconductor photoelectrodes show enhanced stability and performance for solar fuels generation, although the mechanism for the performance enhancement remains unclear due to a lack of understanding of the microscopic interfacial field and its effects. Here, we directly probe the interfacial fields at p-GaP electrodes protected by n-TiO 2 and its effect on charge carriers by transient reflectance spectroscopy. Increasing the TiO 2 layer thickness from 0 to 35 nm increases the field in the GaP depletion region, enhancing the rate and efficiency of interfacial electron transfer from the GaP to TiO 2 on the ps time scale as well as retarding interfacial recombination on the microsecond time scale. This study demonstrates a general method for providing a microscopic view of the photogenerated charge carrier's pathway and loss mechanisms from the bulk of the electrode to the long-lived separated charge at the interface that ultimately drives the photoelectrochemical reactions.

I 2 -II-IV-VI 4 and I-III-VI 2 semiconductor nanocrystals have found applications in photovoltaics and other optoelectronic technologies because of their low toxicity and efficient light absorption into the near-infrared. Herein, we report the discovery of a metastable wurtzite-like polymorph of Cu 2 FeSnSe 4 , a member of the I 2 -II-IV-VI 4 family of semiconductors containing only earth-abundant metals. Density functional theory calculations on this metastable polymorph of Cu 2 FeSnSe 4 indicate that it may be a superior semiconductor for solar energy and optoelectronics applications compared to the thermodynamically preferred stannite polymorph, since the former displays a sharper dispersion of energy levels near the conduction band minimum that can enhance electron mobility and suppress hot electron cooling. The experimental optical band gap was measured by the inverse logarithmic derivative method to be direct, in agreement with theory, and in the range of 1.48-1.59 eV. Mechanistic studies reveal that this metastable phase derives from intermediate Cu 3 Se 2 nanocrystals that serve as a structural template for the final hexagonal wurtzite-like product. We compare the chemistry of wurtzite-like Cu 2 FeSnSe 4 to the related CuFeSe 2 material system. Our experimental and computational comparisons between Cu 2 FeSnSe 4 and CuFeSe 2 help explain both the crystal chemistry of CuFeSe 2 that prevents it from forming wurtzite-like polymorphs and the essential role of Sn in stabilizing the metastable structure of Cu 2 FeSnSe 4 . This work provides insight into the importance of elemental composition when designing syntheses for metastable materials.

Structural polymorphism is known for many bulk materials; however, on the nanoscale metastable polymorphs tend to form more readily than in the bulk, and with more structural variety. One such metastable polymorph observed for colloidal Ag 2 Se nanocrystals has traditionally been referred to as the "tetragonal" phase. While there are reports on the chemistry and properties of this metastable polymorph, its crystal structure, and therefore electronic structure, has yet to be determined. We report that an anti-PbCl 2 -like structure type (space group P 2 1 / n ) more accurately describes the powder X-ray diffraction and X-ray total scattering patterns of colloidal Ag 2 Se nanocrystals prepared by several different methods. Density functional theory (DFT) calculations indicate that this anti-PbCl 2 -like Ag 2 Se polymorph is a dynamically stable, narrow-band-gap semiconductor. The anti-PbCl 2 -like structure of Ag 2 Se is a low-lying metastable polymorph at 5-25 meV/atom above the ground state, depending on the exchange-correlation functional used.

Crystalline solids exhibiting glass-like thermal conductivity have attracted substantial attention both for fundamental interest and applications such as thermoelectrics. In most crystals, the competition of phonon scattering by anharmonic interactions and crystalline imperfections leads to a non-monotonic trend of thermal conductivity with temperature. Defect-free crystals that exhibit the glassy trend of low thermal conductivity with a monotonic increase with temperature are desirable because they are intrinsically thermally insulating while retaining useful properties of perfect crystals. However, this behavior is rare, and its microscopic origin remains unclear. Here, we report the observation of ultralow and glass-like thermal conductivity in a hexagonal perovskite chalcogenide single crystal, BaTiS 3 , despite its highly symmetric and simple primitive cell. Elastic and inelastic scattering measurements reveal the quantum mechanical origin of this unusual trend. A two-level atomic tunneling system exists in a shallow double-well potential of the Ti atom and is of sufficiently high frequency to scatter heat-carrying phonons up to room temperature. While atomic tunneling has been invoked to explain the low-temperature thermal conductivity of solids for decades, our study establishes the presence of sub-THz frequency tunneling systems even in high-quality, electrically insulating single crystals, leading to anomalous transport properties well above cryogenic temperatures.

More efficient thermoelectric devices would revolutionize refrigeration and energy production, and low-dimensional thermoelectric materials are predicted to be more efficient than their bulk counterparts. But nanoscale thermoelectric devices generate thermal gradients on length scales that are too small to resolve with traditional thermometry methods. Here we fabricate, using single-crystal bismuth telluride (Bi 2 Te 3 ) and antimony/bismuth telluride (Sb 2- x Bi x Te 3 ) flakes exfoliated from commercially available bulk materials, functional thermoelectric coolers (TECs) that are only 100 nm thick. These devices are the smallest TECs ever demonstrated by a factor of 10 4 . After depositing indium nanoparticles to serve as nanothermometers, we measure the heating and cooling produced by the devices with plasmon energy expansion thermometry (PEET), a high-spatial-resolution, transmission electron microscopy (TEM)-based thermometry technique, demonstrating a Δ T = -21 ± 4 K from room temperature. We also establish proof-of-concept for condensation thermometry, a quantitative temperature-change mapping technique with a spatial precision of ≲300 nm.

Heterostructure devices with specific and extraordinary properties can be fabricated by stacking two-dimensional crystals. Cleanliness at the inter-crystal interfaces within a heterostructure is crucial for maximizing device performance. However, because these interfaces are buried, characterizing their impact on device function is challenging. Here, we show that electron-beam induced current (EBIC) mapping can be used to image interfacial contamination and to characterize the quality of buried heterostructure interfaces with nanometer-scale spatial resolution. We applied EBIC and photocurrent imaging to map photo-sensitive graphene-MoS 2 heterostructures. The EBIC maps, together with concurrently acquired scanning transmission electron microscopy images, reveal how a device's photocurrent collection efficiency is adversely affected by nanoscale debris invisible to optical-resolution photocurrent mapping.

Conductive bridge random access memory (CBRAM) is a leading candidate to supersede flash memory, but poor understanding of its switching process impedes widespread implementation. The underlying physics and basic, unresolved issues such as the connecting filament's growth direction can be revealed with direct imaging, but the nanoscale target region is completely encased and thus difficult to access with real-time, high-resolution probes. In Pt/Al2O3/Cu CBRAM devices with a realistic topology, we find that the filament grows backward toward the source metal electrode. This observation, consistent over many cycles in different devices, corroborates the standard electrochemical metallization model of CBRAM operation. Time-resolved scanning transmission electron microscopy (STEM) reveals distinct nucleation-limited and potential-limited no-growth periods occurring before and after a connection is made, respectively. The subfemtoampere ionic currents visualized move some thousands of atoms during a switch and lag the nanoampere electronic currents.

We report a robust method for engineering the optoelectronic properties of many-layer MoS2 using low-energy oxygen plasma treatment. Gas phase treatment of MoS2 with oxygen radicals generated in an upstream N2 -O2 plasma is shown to enhance the photoluminescence (PL) of many-layer, mechanically exfoliated MoS2 flakes by up to 20 times, without reducing the layer thickness of the material. A blueshift in the PL spectra and narrowing of linewidth are consistent with a transition of MoS2 from indirect to direct bandgap material. Atomic force microscopy and Raman spectra reveal that the flake thickness actually increases as a result of the plasma treatment, indicating an increase in the interlayer separation in MoS2 . Ab initio calculations reveal that the increased interlayer separation is sufficient to decouple the electronic states in individual layers, leading to a transition from an indirect to direct gap semiconductor. With optimized plasma treatment parameters, we observed enhanced PL signals for 32 out of 35 many-layer MoS2 flakes (2-15 layers) tested, indicating that this method is robust and scalable. Monolayer MoS2 , while direct bandgap, has a small optical density, which limits its potential use in practical devices. The results presented here provide a material with the direct bandgap of monolayer MoS2 , without reducing sample thickness, and hence optical density., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Modern microelectronic devices have nanoscale features that dissipate power nonuniformly, but fundamental physical limits frustrate efforts to detect the resulting temperature gradients. Contact thermometers disturb the temperature of a small system, while radiation thermometers struggle to beat the diffraction limit. Exploiting the same physics as Fahrenheit's glass-bulb thermometer, we mapped the thermal expansion of Joule-heated, 80-nanometer-thick aluminum wires by precisely measuring changes in density. With a scanning transmission electron microscope and electron energy loss spectroscopy, we quantified the local density via the energy of aluminum's bulk plasmon. Rescaling density to temperature yields maps with a statistical precision of 3 kelvin/hertz(-1/2), an accuracy of 10%, and nanometer-scale resolution. Many common metals and semiconductors have sufficiently sharp plasmon resonances to serve as their own thermometers., (Copyright © 2015, American Association for the Advancement of Science.)

Engineering silicon into nanostructures has been a well-adopted strategy to improve the cyclic performance of silicon as a lithium-ion battery anode. Here, we show that the electrode performance can be further improved by alloying silicon with germanium. We have evaluated the electrode performance of SixGe1-x nanoparticles (NPs) with different compositions. Experimentally, SixGe1-x NPs with compositions approaching Si50Ge50 are found to have better cyclic retention than both Si-rich and Ge-rich NPs. During the charge/discharge process, NP merging and Si-Ge homogenization are observed. In addition, a distinct morphology difference is observed after 100 cycles, which is believed to be responsible for the different capacity retention behavior. The present study on SixGe1-x alloy NPs sheds light on the development of Si-based electrode materials for stable operation in lithium-ion batteries (e.g., through a comprehensive design of material structure and chemical composition). The investigation of composition-dependent morphology evolution in the delithiated Li-SiGe ternary alloy also significantly broadens our understanding of dealloying in complex systems, and it is complementary to the well-established understanding of dealloying behavior in binary systems (e.g., Au-Ag alloys).