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The electron beam (e-beam) in the scanning electron microscopy (SEM) provides an appealing mobile heating source for thermal metrology with spatial resolution of ∼1 nm, but the lack of systematic quantification of the e-beam heating power limits such application development. Here, we systemically study e-beam heating in LPCVD silicon nitride (SiNx) thin-films with thickness ranging from 200 to 500 nm from both experiments and complementary Monte Carlo simulations using the CASINO software package. There is good agreement about the thickness-dependent e-beam energy absorption of thin-film between modeling predictions and experiments. Using the absorption results, we then demonstrate adapting the e-beam as a quantitative heating source by measuring the thickness-dependent thermal conductivity of SiNx thin-films, with the results validated to within 7% by a separate Joule heating experiment. The results described here will open a new avenue for using SEM e-beams as a mobile heating source for advanced nanoscale thermal metrology development.

Membranes made of layer-stacked two-dimensional molybdenum disulfide (MoS2) nanosheets have recently shown great promise for water filtration. At present, the reported water fluxes vary significantly, while the accountable structure and properties of MoS2 nanochannels are largely unknown. This paper aims to mechanistically relate the performance of MoS2 membranes to the size of their nanochannels in different hydration states. We discovered that fully hydrated MoS2 membranes retained a 1.2 nm interlayer spacing (or 0.9 nm free spacing), leading to high water permeability and moderate-to-high ionic and molecular rejection. In comparison, completely dry MoS2 membranes had a 0.62 nm interlayer spacing (or 0.3 nm free spacing) due to irreversible nanosheet restacking and were almost impermeable to water. Furthermore, we revealed that the interlayer spacing of MoS2 membranes in aqueous solution is maintained by comparable van der Waals and hydration forces, thereby ensuring the aqueous stability of MoS2 membra...

A novel core/shell porous crystalline structure was prepared using a large pore metal organic framework (MOF, UiO-66-NH2, pore size, ∼ 0.6 nm) as core surrounded by a small pore zeolitic imidazolate framework (ZIF, ZIF-8, pore size, ∼ 0.4 nm) through a layer-by-layer deposition method and subsequently used as an engineered filler to construct hybrid polysulfone (PSF) membranes for CO2 capture. Compared to traditional fillers utilizing only one type of porous material with rigid channels (either large or small), our custom designed core/shell fillers possess clear advantages via pore engineering: the large internal channels of the UiO-66-NH2 MOFs create molecular highways to accelerate molecular transport through the membrane, while the thin shells with small pores (ZIF-8) or even smaller pores generated at the interface by the imperfect registry between the overlapping pores of ZIF and MOF enhance molecular sieving thus serving to distinguish slightly larger N2 molecules (kinetic diameter, 0.364 nm) from ...

Despite the exceptional optoelectronic characteristics of the emergent perovskite nanocrystals, the ionic nature greatly limits their stability, and thus restricts their potential applications. Here we have adapted a self-assembly strategy to access a rarely reported nanorod suprastructure that provide excellent encapsulation of perovskite nanocrystals by polymer-grafted graphene oxide layers. Polyacrylic acid-grafted graphene oxide (GO-g-PAA) was used as a surface ligand during the synthesis of the CsPbX3 perovskite nanocrystals (NCs), yielding particles (5–12 nm) with tunable halide compositions that were homogeneously embedded in the GO-g-PAA matrix. The resulting NC-GO-g-PAA exhibits a higher photoluminescence quantum yield than previously reported encapsulated NCs while maintaining an easily tunable bandgap, allowing for emission spanning the visible spectrum. The NC-GO-g-PAA hybrid further self-assembles into well-defined nanorods upon solvent treatment. The resulting nanorod morphology imparts extr...

Thermal transport in silicon nanowires has captured the attention of scientists for understanding phonon transport at the nanoscale, and the thermoelectric figure-of-merit (ZT) reported in rough nanowires has inspired engineers to develop cost-effective waste heat recovery systems. Thermoelectric generators composed of silicon target high-temperature applications due to improved efficiency beyond 550 K. However, there have been no studies of thermal transport in silicon nanowires beyond room temperature. High-temperature measurements also enable studies of unanswered questions regarding the impact of surface boundaries and varying mode contributions as the highest vibrational modes are activated (Debye temperature of silicon is 645 K). Here, we develop a technique to investigate thermal transport in nanowires up to 700 K. Our thermal conductivity measurements on smooth silicon nanowires show the classical diameter dependence from 40 to 120 nm. In conjunction with Boltzmann transport equation, we also probe an increasing contribution of high-frequency phonons (optical phonons) in smooth silicon nanowires as the diameter decreases and the temperature increases. Thermal conductivity of rough silicon nanowires is significantly reduced throughout the temperature range, demonstrating a potential for efficient thermoelectric generation (e.g., ZT = 1 at 700 K).

This work demonstrates the first method for controlled growth of heterostructures within hybrid organic/inorganic nanocomposite thermoelectrics. Using a facile, aqueous technique, semimetal–alloy nanointerfaces are patterned within a hybrid thermoelectric system consisting of tellurium (Te) nanowires and the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS). Specifically, this method is used to grow nanoscale islands of Cu1.75Te alloy subphases within hybrid PEDOT:PSS-Te nanowires. This technique is shown to provide tunability of thermoelectric and electronic properties, providing up to 22% enhancement of the system’s power factor in the low-doping regime, consistent with preferential scattering of low energy carriers. This work provides an exciting platform for rational design of multiphase nanocomposites and highlights the potential for engineering of carrier filtering within hybrid thermoelectrics via introduction of interfaces with controlled structural and energe...

Membranes made of layer-stacked two-dimensional molybdenum disulfide (MoS

A novel core/shell porous crystalline structure was prepared using a large pore metal organic framework (MOF, UiO-66-NH

As a model system for hydrogen storage, magnesium hydride exhibits high hydrogen storage density, yet its practical usage is hindered by necessarily high temperatures and slow kinetics for hydrogenation-dehydrogenation cycling. Decreasing particle size has been proposed to simultaneously improve the kinetics and decrease the sorption enthalpies. However, the associated increase in surface reactivity due to increased active surface area makes the material more susceptible to surface oxidation or other side reactions, which would hinder the overall hydrogenation-dehydrogenation process and diminish the capacity. Previous work has shown that the chemical stability of Mg nanoparticles can be greatly enhanced by using reduced graphene oxide as a protecting agent. Although no bulklike crystalline MgO layer has been clearly identified in this graphene-encapsulated/Mg nanocomposite, we propose that an atomically thin layer of honeycomb suboxide exists, based on first-principles interpretation of Mg K-edge X-ray absorption spectra. Density functional theory calculations reveal that in contrast to conventional expectations for thick oxides this interfacial oxidation layer permits H

Polycrystallinity leads to increased phonon scattering at grain boundaries and is known to be an effective method to reduce thermal conductivity in thermoelectric materials. However, the fundamental limits of this approach are not fully understood, as it is difficult to form uniform sub-20 nm grain structures. We use colloidal nanocrystals treated with functional inorganic ligands to obtain nanograined films of CdSe with controlled characteristic grain size between 3 and 6 nm. Experimental measurements demonstrate that thermal conductivity in these composites can fall beneath the prediction of the so-called minimum thermal conductivity for disordered crystals. The measurements are consistent, however, with diffuse boundary scattering of acoustic phonons. This apparent paradox can be explained by an overattribution of transport to high-energy phonons in the minimum thermal conductivity model where, in compound semiconductors, optical and zone edge phonons have low group velocity and high scattering rates.

A simple approach is described to fabricate reversible, thermally- and optically responsive actuators utilizing composites of poly(N-isopropylacrylamide) (pNIPAM) loaded with single-walled carbon nanotubes. With nanotube loading at concentrations of 0.75 mg/mL, we demonstrate up to 5 times enhancement to the thermal response time of the nanotube-pNIPAM hydrogel actuators caused by the enhanced mass transport of water molecules. Additionally, we demonstrate the ability to obtain ultrafast near-infrared optical response in nanotube-pNIPAM hydrogels under laser excitation enabled by the strong absorption properties of nanotubes. The work opens the framework to design complex and programmable self-folding materials, such as cubes and flowers, with advanced built-in features, including tunable response time as determined by the nanotube loading.

We have demonstrated hyperspectral tip-enhanced Raman imaging on dielectric substrates using linearly polarized light and nanofabricated coaxial antenna tips. A full Raman spectrum was acquired at each pixel of a 256 by 256 pixel contact-mode atomic force microscope image of carbon nanotubes grown on a fused silica microscope coverslip, allowing D and G mode intensity and D-mode peak shifts to be measured with ∼20 nm spatial resolution. Tip enhancement was sufficient to acquire useful Raman spectra in 50-100 ms. Coaxial scan probes combine the efficiency and enhanced, ultralocalized optical fields of plasmonically coupled antennae with the superior topographical imaging properties of sharp metal tips. The yield of the coaxial tip fabrication process is close to 100%, and the tips are sufficiently durable to support hours of contact-mode force microscope imaging. Our coaxial probes avoid the limitations associated with the "gap-mode" imaging geometry used in most tip-enhanced Raman studies to date, where a sharp metal tip is held ∼1 nm above a metallic substrate with the sample located in the gap.

We report the synthesis and thermoelectric characterization of composite nanocrystals composed of a tellurium core functionalized with the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). Solution processed nanocrystal films electronically out perform both PEDOT:PSS and unfunctionalized Te nanorods while retaining a polymeric thermal conductivity, resulting in a room temperature ZT ∼ 0.1. This combination of electronic and thermal transport indicates the potential for tailored transport in nanoscale organic/inorganic heterostructures.

We report scanned probe characterizations of the ferroelectric phase transition in individual barium titanate (BaTiO3) nanowires. Variable-temperature electrostatic force microscopy is used to manipulate, image, and evaluate the diameter-dependent stability of ferroelectric polarizations. These measurements show that the ferroelectric phase transition temperature (TC) is depressed as the nanowire diameter (dnw) decreases, following a 1/dnw scaling. The diameter at which TC falls below room temperature is determined to be approximately 3 nm, and extrapolation of the data indicates that nanowires with dnw as small as 0.8 nm can support ferroelectricity at lower temperatures. We also present density functional theory (DFT) calculations of bare and molecule-covered BaTiO3 surfaces. These calculations indicate that ferroelectricity in nanowires is stabilized by molecular adsorbates such as OH and carboxylates. These adsorbates are found to passivate polarization charge more effectively than metallic electrodes, explaining the observed stability of ferroelectricity in small-diameter BaTiO3 nanowires.

We report a hydrothermal synthesis of single-crystalline nanocubes composed of lanthanum barium manganite (La1-xBaxMnO3) with three different doping levels (x = 0.3, 0.5, and 0.6). The synthesis yields clearly faceted nanocubes with a pseudo-cubic perovskite structure. Typical nanocubes have sizes ranging between 50 and 100 nm irrespective of doping level. Magnetic measurements performed on nanocube ensembles show that the magnetic properties depend on the doping level. The ability to synthesize nanoscale manganites of a desired doping level should enable detailed investigations of the size-dependent evolution of magnetism, colossal magnetoresistance, and nanoscale phase separation.

We report scanned probe investigations on the ferroelectric properties of individual single-crystalline barium titanate nanowires. We show that nonvolatile electric polarization can be reproducibly induced and manipulated on these nanowires, thereby demonstrating that nanowires as small as 10 nm in diameter retain ferroelectricity. The coercive field for polarization reversal is determined to be ∼7 kV/cm, and the retention time for the induced polarization exceeds 5 days. These nanowires should provide promising materials for fundamental investigations on nanoscale ferroelectricity, and they may also be useful in nanoscale nonvolatile memory applications.

The question of the nature and stability of polar ordering in nanoscale ferroelectrics is examined with colloidal nanocrystals of germanium telluride (GeTe). We provide atomic-scale evidence for room-temperature polar ordering in individual nanocrystals using aberration-corrected transmission electron microscopy and demonstrate a reversible, size-dependent polar-nonpolar phase transition of displacive character in nanocrystal ensembles. A substantial linear component of the distortion is observed, which is in contrast with theoretical reports predicting a toroidal state.

Single component and multicomponent nanocrystal (NC) solids represent an exciting new form of condensed matter, as they can potentially capture not only the quantum features of the individual building blocks but also novel collective properties through coupling of NC components. Unlike bulk semiconductors, however, there is no current theory for how introduction of dopants will impact the electronic structure and transport properties of NC solids. Empirically, it is known that in semiconductor NC systems, mixing two different materials of NCs electronically dopes the film. However, it has been challenging to connect the macroscopic measurements of doping effects on transport behavior to a microscopic understanding of how the identity, placement, and abundance of dopants impact these measurements. In this Letter, we report the first temperature-dependent thermopower measurements in doped and undoped NC solids. In combination with temperature-dependent electrical conductivity measurements, how the doping affects the carrier concentration as well as mobility is explored exclusively. These complementary measurements serve as a unique electronic spectroscopy tool to quantitatively reveal the energetics of carriers and electronic states in NC solids.