The tuning of optical resonances in nanoparticle assemblies is primarily achieved through the fundamental principle of plasmonic coupling. When the nanoparticles interact in close proximity, ...plasmonic coupling modes could be generated with energies sensitive to the type of nanoparticle assembly. By precise polymer-based gold nanorod functionalization, we produce Langmuir monolayers of gold nanorods and control, in situ, the ability of nanoparticles to hybridize, thereby regulating the optical response of the nanoparticles. This strategy enables an understanding of the hybridization phenomenon of gold nanorods in monolayer systems. In the long term, this work enables the investigation of in situ hybridization of nanoparticle systems with reduced particle numbers.
Molybdenum disulfide (MoS2), with its active edge sites, is a proposed alternative to platinum for catalyzing the hydrogen evolution reaction (HER). Recently, the inert basal plane of MoS2 was ...successfully activated and optimized with excellent intrinsic HER activity by creating and further straining sulfur (S) vacancies. Nevertheless, little is known about the HER kinetics of those S vacancies and the additional effects from elastic tensile strain. Herein, scanning electrochemical microscopy was used to determine the HER kinetic data for both unstrained S vacancies (formal potential E v 0 = −0.53 VAg/AgCl, electron-transfer coefficient αv = 0.4, electron-transfer rate constant k v 0 = 2.3 × 10–4 cm/s) and strained S vacancies (E sv 0= −0.53 VAg/AgCl, αsv = 0.4, k sv 0 = 1.0 × 10–3 cm/s) on the basal plane of MoS2 monolayers, and the strained S vacancy has an electron-transfer rate 4 times higher than that of the unstrained S vacancy. This study provides a general platform for measuring the kinetics of two-dimensional material-based catalysts.
The effect of variations in microbubble shell composition on microbubble resonance frequency is revealed through experiment. These variations are achieved by altering the mole fraction and molecular ...weight of functionalized polyethylene glycol (PEG) in the microbubble phospholipid monolayer shell and measuring the microbubble resonance frequency. The resonance frequency is measured via a chirp pulse and identified as the frequency at which the pressure amplitude loss of the ultrasound wave is the greatest as a result of passing through a population of microbubbles. For the shell compositions used herein, we find that PEG molecular weight has little to no influence on resonance frequency at an overall PEG mole fraction (0.01) corresponding to a mushroom regime and influences the resonance frequency markedly at overall PEG mole fractions (0.050-0.100) corresponding to a brush regime. Specifically, the measured resonance frequency was found to be 8.4, 4.9, 3.3 and 1.4 MHz at PEG molecular weights of 1000, 2000, 3000 and 5000 g/mol, respectively, at an overall PEG mole fraction of 0.075. At an overall PEG mole fraction of just 0.01, on the other hand, resonance frequency exhibited no systematic variation, with values ranging from 5.7 to 4.9 MHz. Experimental results were analyzed using the Sarkar bubble dynamics model. With the dilatational viscosity held constant (10(-8) N·s/m) and the elastic modulus used as a fitting parameter, model fits to the pressure amplitude loss data resulted in elastic modulus values of 2.2, 2.4, 1.6 and 1.8 N/m for PEG molecular weights of 1000, 2000, 3000 and 5000 g/mol, respectively, at an overall PEG mole fraction of 0.010 and 4.2, 1.4, 0.5 and 0.0 N/m, respectively, at an overall PEG mole fraction of 0.075. These results are consistent with theory, which predicts that the elastic modulus is constant in the mushroom regime and decreases with PEG molecular weight to the inverse 3/5 power in the brush regime. Additionally, these results are consistent with inertial cavitation studies, which revealed that increasing PEG molecular weight has little to no effect on inethe rtial cavitation threshold in the mushroom regime, but that increasing PEG molecular weight decreases inertial cavitation markedly in the brush regime. We conclude that the design and synthesis of microbubbles with a prescribed resonance frequency is attainable by tuning PEG composition and molecular weight.
Semiconducting MoTe2 is one of the few two-dimensional (2D) materials with a moderate band gap, similar to silicon. However, this material remains underexplored for 2D electronics due to ambient ...instability and predominantly p-type Fermi level pinning at contacts. Here, we demonstrate unipolar n-type MoTe2 transistors with the highest performance to date, including high saturation current (>400 μA/μm at 80 K and >200 μA/μm at 300 K) and relatively low contact resistance (1.2 to 2 kΩ·μm from 80 to 300 K), achieved with Ag contacts and AlO x encapsulation. We also investigate other contact metals (Sc, Ti, Cr, Au, Ni, Pt), extracting their Schottky barrier heights using an analytic subthreshold model. High-resolution X-ray photoelectron spectroscopy reveals that interfacial metal-Te compounds dominate the contact resistance. Among the metals studied, Sc has the lowest work function but is the most reactive, which we counter by inserting monolayer hexagonal boron nitride between MoTe2 and Sc. These metal-insulator-semiconductor (MIS) contacts partly depin the metal Fermi level and lead to the smallest Schottky barrier for electron injection. Overall, this work improves our understanding of n-type contacts to 2D materials, an important advance for low-power electronics.
We demonstrate the feasibility of covalently linking a single microbubble to a single, giant uni-lamellar vesicle (GUV). Such a combination of GUV plus microbubble might prove useful as a new drug ...delivery vehicle involving microbubble cavitation-induced sonoporation of the vesicle bilayer as a release mechanism. We therefore applied the well known methodology of passive cavitation detection to measure the influence of lipid shell chemistry on inertial cavitation thresholds for externally added microbubbles. We find that cavitation threshold changes significantly with changes in either molecular weight or mole fraction of poly(ethylene glycol), historically used to impede gas dissolution and microbubble coalescence. We attribute changes in cavitation threshold to changes in microbubble resonance frequency resulting from changes in microbubble shell bending elasticity. To further demonstrate the influence of shell chemistry on microbubble behavior, we describe how several common bubble phenomena – and some new – respond to changes in lipid chain length.
Two-dimensional (2D) semimetals beyond graphene have been relatively unexplored in the atomically thin limit. Here, we introduce a facile growth mechanism for semimetallic WTe2 crystals and then ...fabricate few-layer test structures while carefully avoiding degradation from exposure to air. Low-field electrical measurements of 80 nm to 2 μm long devices allow us to separate intrinsic and contact resistance, revealing metallic response in the thinnest encapsulated and stable WTe2 devices studied to date (3–20 layers thick). High-field electrical measurements and electrothermal modeling demonstrate that ultrathin WTe2 can carry remarkably high current density (approaching 50 MA/cm2, higher than most common interconnect metals) despite a very low thermal conductivity (of the order ∼3 Wm–1 K–1). These results suggest several pathways for air-stable technological viability of this layered semimetal.
•We present an optical method for measure the size distribution of microbubbles.•We measure the size distribution of microbubbles with different shell compositions.•Microbubble size distributions are ...monomodal and nearly Gaussian in shape.•Microbubble size distributions are insensitive to changes in shell composition.•Microbubble size is generally determined by the synthesis method.
The effect of modifying the shell composition of a population of microbubbles on their size demonstrated through experiment. Specifically, these variations include altering both the mole fraction and molecular weight of functionalized polymer, polyethylene glycol (PEG) in the microbubble phospholipid monolayer shell (1–15mol% PEG, and 1000–5000g/mole, respectively). The size distribution is measured with an unbiased image segmentation program written in MATLAB which identifies and sizes bubbles from micrographs. For a population of microbubbles with a shell composition of 5mol% PEG2000, the mean diameter is 1.42μm with a variance of 0.244μm. For the remainder of the shell compositions studied herein, we find that the size distributions do not show a statistically significant correlation to either PEG molecular weight or mole fraction. All the measured distributions are nearly Gaussian in shape and have a monomodal peak.
Ultrathin transition metal dichalcogenides (TMDCs) have recently been extensively investigated to understand their electronic and optical properties. Here we study ultrathin Mo0.91W0.09Te2, a ...semiconducting alloy of MoTe2, using Raman, photoluminescence (PL), and optical absorption spectroscopy. Mo0.91W0.09Te2 transitions from an indirect to a direct optical band gap in the limit of monolayer thickness, exhibiting an optical gap of 1.10 eV, very close to its MoTe2 counterpart. We apply tensile strain, for the first time, to monolayer MoTe2 and Mo0.91W0.09Te2 to tune the band structure of these materials; we observe that their optical band gaps decrease by 70 meV at 2.3% uniaxial strain. The spectral widths of the PL peaks decrease with increasing strain, which we attribute to weaker exciton–phonon intervalley scattering. Furthermore, strained MoTe2 and Mo0.91W0.09Te2 extend the range of band gaps of TMDC monolayers further into the near-infrared, an important attribute for potential applications in optoelectronics.
Two-dimensional (2D) materials have recently been incorporated into resistive memory devices because of their atomically thin nature, but their switching mechanism is not yet well understood. Here we ...study bipolar switching in MoTe2-based resistive memory of varying thickness and electrode area. Using scanning thermal microscopy (SThM), we map the surface temperature of the devices under bias, revealing clear evidence of localized heating at conductive “plugs” formed during switching. The SThM measurements are correlated to electro-thermal simulations, yielding a range of plug diameters (250 to 350 nm) and temperatures at constant bias and during switching. Transmission electron microscopy images reveal these plugs result from atomic migration between electrodes, which is a thermally-activated process. However, the initial forming may be caused by defect generation or Te migration within the MoTe2. This study provides the first thermal and localized switching insights into the operation of such resistive memory and demonstrates a thermal microscopy technique that can be applied to a wide variety of traditional and emerging memory devices.
Ultrasound contrast agents consist of microbubbles with diameters in the micrometer range. Excited by ultrasound, these bubbles exhibit highly nonlinear oscillation. While well developed physical ...models for microbubble oscillation exist, the efficiency of pulse sequences for sensitive microbubble detection is discussed based on simple mathematical models of general nonlinearity. Typically, Taylor series are used to model microbubble nonlinearity for the development of detection schemes. Recently, pulse sequences were proposed which exploit nonlinear memory of microbubbles, a property that cannot be modeled by a Taylor series but can be explained using a Volterra series. Therefore, this paper discusses and evaluates the usage of Volterra series for the modeling of the scattering behavior of contrast agent microbubbles. A numerically stable linear estimation algorithm is implemented to determine a third order Volterra model for a free gas bubble with a resting radius
r
0
=
1
μ
m
. For insonification pressures up to 100
kPa, the identified model allowed for a mean-square error of less than −16
dB with respect to the reference signal. Analysis of the response to narrowband signals showed that the achievable mean-square error is further reduced for the bandwidth available to typical ultrasound transducers used for clinical diagnostics.
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