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At least 1,711 records · Page 95

Damping Off Terahertz Sound Modes of a Liquid upon Immersion of Nanoparticles

Here, the control of phonon propagation in nanoparticle arrays is one of the frontiers of nanotechnology, potentially enabling the discovery of materials with unknown functionalities for potential innovative applications. The exploration of the terahertz window appears quite promising as phonons in this range are the leading carriers of heat transport in insulators and their control is the key to implement devices for heat flow management. Unfortunately, this scientific field is still in its infancy, and even a basic topic such as the influence of floating nanoparticles on the terahertz phonon propagation of a colloidal suspension still eludes a firm answer. Shedding some light on this topic is the main motivation of the present work, which focuses an inelastic X-ray scattering (IXS) measurements on a dilute suspension of Au nanospheres in water. Measured spectra showed a nontrivial shape displaying multiple inelastic features that, based on a Bayesian inference analysis, we assign to phonon modes propagating throughout the nanoparticle interior. Surprisingly, the spectra bear no evidence of propagating modes, which are known to dominate the spectrum of pure water, owing to the scattering that these modes suffer from the sparse nanoparticles in suspension. In perspective, this finding may inspire simple routes to manipulate high-frequency acoustic propagation in hybrid—liquid and solid—materials.

74 ATOMIC AND MOLECULAR PHYSICS↗

Vertical Architecture Solution-Processed Quantum Dot Photodetectors with Amorphous Selenium Hole Transport Layer

Colloidal quantum dots (CQDs) provide wide spectral tunability and high absorption coefficients owing to quantum confinement and large oscillator strengths, which along with solution processability, allow a facile, low-cost, and room-temperature deposition technique for the fabrication of photonic devices. However, many solution-processed CQD photodetector devices demonstrate low specific-detectivity and slow temporal response. To achieve improved photodetector characteristics, limiting carrier recombination and enhancing photogenerated carrier separation are crucial. In this study, we develop and present an alternate vertical-stack photodetector wherein we use a solution-processed quantum dot photoconversion layer coupled to an amorphous selenium (a-Se) wide-bandgap charge transport layer that is capable of exhibiting single-carrier hole impact ionization and is compatible with active-matrix readout circuitry. This a-Se chalcogenide transport layer enables the fabrication of high-performance and reliable solution-processed quantum dot photodetectors, with enhanced charge extraction capabilities, high specific detectivity (D* ~ 0.5–5 × 10 12 Jones), fast 3 dB electrical bandwidth (3 dB BW ~ 22 MHz), low dark current density (J D ~ 5–10 pA/cm 2 ), low noise current (i n ~ 20–25 fW/Hz 1/2 ), and high linear dynamic range (LDR ~130–150 dB) across the measured visible electromagnetic spectrum (~405–656 nm).

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Carbon Nanotubes for Quantum Dot Photovoltaics with Enhanced Light Management and Charge Transport

Colloidal quantum dot (CQD)-based photovoltaics are an emerging low-cost solar cell technology with power conversion efficiencies exceeding 10%, i.e., high enough to be interesting for commercialization. Well-controlled and understood charge carrier transport through the device stack is required to make the next step in efficiency improvements. In this work, polymer-wrapped single-walled carbon nanotube (SWNT) films embedded in an insulating poly(methyl methacrylate) (PMMA) matrix and capped by a thermally evaporated Au electrode are investigated as a composite hole transport layer and optical spacer. Employing transient absorption spectroscopy we show that the SWNTs enhance the charge transfer rate from CQD to CQD, ZnO, or SWNT. In order to pinpoint the underlying mechanism for the improvement, we investigate the energetics of the junction by measuring the relative alignment of the band edges, using Kelvin probe and cyclic voltammetry. Measuring the external quantum efficiency and absorption we find that the improvement is not mainly from electronic improvements but from enhanced absorption of the CQD absorber. We demonstrate experimentally and theoretically, by employing a transfer-matrix model, that the transparent PMMA matrix acts as an optical spacer, which leads to an enhanced absorption in the absorber layer. Lastly, with these electronic and optical enhancements, the efficiency of the PbS CQD solar cells improved from 4.0% to 6.0%.

14 SOLAR ENERGY↗

Lead-Free Cs 4 CuSb 2 Cl 12 Layered Double Perovskite Nanocrystals

Concerns about the toxicity of lead-based perovskites have aroused great interest for the development of alternative lead-free perovskite-type materials. Recently, theoretical calculations predict that Pb 2+ cations can be substituted by a combination of Cu 2+ and Sb 3+ cations to form a vacancy-ordered layered double perovskite structure with superior optoelectronic properties. However, accessibilities to this class of perovskite-type materials remain inadequate, hindering their practical implementations in various applications. Here, we report the first colloidal synthesis of Cs 4 CuSb 2 Cl 12 perovskite-type nanocrystals (NCs). The resulting NCs exhibit a layered double perovskite structure with ordered vacancies and a direct bandgap of 1.79 eV. A composition-structure-property relationship has been established by investigating a series of Cs 4 Cu x Ag 2-2x Sb 2 Cl 12 perovskite-type NCs (0 ≤ x ≤ 1). The composition-induced crystal structure transformation, thus the electronic bandgap evolution has been explored by experimental observations and further confirmed by theoretical calculations. Taking advantages of both the unique electronic structure and solution processability, we demonstrate that the Cs 4 CuSb 2 Cl 12 NCs can be solution-processed as high-speed photodetectors with ultrafast photo-response and narrow bandwidth. We anticipate that our study will prompt future research to design and fabricate novel and high-performance lead-free perovskite-type NCs for a range of applications.

25 ENERGY STORAGE↗

Nanophotonic force microscopy: Characterizing particle–surface interactions using near-field photonics

Direct measurements of particle–surface interactions are important for characterizing the stability and behavior of colloidal and nanoparticle suspensions. Current techniques are limited in their ability to measure pico-Newton scale interaction forces on submicrometer particles due to signal detection limits and thermal noise. In this paper, we present a new technique for making measurements in this regime, which we refer to as nanophotonic force microscopy. Using a photonic crystal resonator, we generate a strongly localized region of exponentially decaying, near-field light that allows us to confine small particles close to a surface. From the statistical distribution of the light intensity scattered by the particle we are able to map out the potential well of the trap and directly quantify the repulsive force between the nanoparticle and the surface. Finally, as shown in this Letter, our technique is not limited by thermal noise, and therefore, we are able to resolve interaction forces smaller than 1 pN on dielectric particles as small as 100 nm in diameter.

36 MATERIALS SCIENCE↗

Diagnosing heterogeneous dynamics in single-molecule/particle trajectories with multiscale wavelets

In this study, we describe a simple automated method to extract and quantify transient heterogeneous dynamical changes from large data sets generated in single-molecule/particle tracking experiments. Based on wavelet transform, the method transforms raw data to locally match dynamics of interest. This is accomplished using statistically adaptive universal thresholding, whose advantage is to avoid a single arbitrary threshold that might conceal individual variability across populations. How to implement this multiscale method is described, focusing on local confined diffusion separated by transient transport periods or hopping events, with three specific examples: in cell biology, biotechnology, and glassy colloid dynamics. The discussion is generalized within the framework of continuous time random walk. This computationally efficient method can run routinely on hundreds of millions of data points analyzed within an hour on a desktop personal computer.

36 MATERIALS SCIENCE↗

Towards zero-threshold optical gain using charged semiconductor quantum dots

Colloidal semiconductor quantum dots are attractive materials for the realization of solution-processable lasers. However, their applications as optical-gain media are complicated by a non-unity degeneracy of band-edge states, because of which multiexcitons are required to achieve the lasing regime. This increases the lasing thresholds and leads to very short optical gain lifetimes limited by nonradiative Auger recombination. Here, we show that these problems can be at least partially resolved by employing not neutral but negatively charged quantum dots. By applying photodoping to specially engineered quantum dots with impeded Auger decay, we demonstrate a considerable reduction of the optical gain threshold due to suppression of ground-state absorption by pre-existing carriers. Moreover, by injecting approximately one electron per dot on average, we achieve a more than twofold reduction in the amplified spontaneous emission threshold, bringing it to the sub-single-exciton level. Furthermore, these measurements indicate the feasibility of ‘zero-threshold’ gain achievable by completely blocking the band-edge state with two electrons.

36 MATERIALS SCIENCE↗

The diversity of three-dimensional photonic crystals

Many butterflies, birds, beetles, and chameleons owe their spectacular colors to the microscopic patterns within their wings, feathers, or skin. When these patterns, or photonic crystals, result in the omnidirectional reflection of commensurate wavelengths of light, it is due to a complete photonic band gap (PBG). The number of natural crystal structures known to have a PBG is relatively small, and those within the even smaller subset of notoriety, including diamond and inverse opal, have proven difficult to synthesize. Here, we report more than 150,000 photonic band calculations for thousands of natural crystal templates from which we predict 351 photonic crystal templates – including nearly 300 previously-unreported structures – that can potentially be realized for a multitude of applications and length scales, including several in the visible range via colloidal self-assembly. With this large variety of 3D photonic crystals, we also revisit and discuss oft-used primary design heuristics for PBG materials.

54 ENVIRONMENTAL SCIENCES↗

Polar state reversal in active fluids

Spontaneous emergence of correlated states such as flocks and vortices is a prime example of collective dynamics and self-organization observed in active matter. In geometrically confined systems, the formation of globally correlated polar states proceeds through the emergence of a macroscopic steadily rotating vortex, which spontaneously selects a clockwise or counterclockwise global chiral state. In this work, we reveal that a global vortex formed by colloidal rollers exhibits polar state reversal and that a subsequent formation of the collective states upon re-energizing the system is not random. We combine experiments and simulations to elucidate how a combination of hydrodynamic and electrostatic interactions leads to hidden asymmetries in the local particle positional order, reflecting the chiral state of the system. These asymmetries can be exploited to systematically command subsequent polar states of active liquids through temporal control of the activity.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Grain boundary facilitated dissolution of nanocrystalline NpO 2 (s) from legacy waste processing

Dissolution of actinide dioxides, including neptunium dioxide (NpO 2 (s)), is paramount for the prediction of the environmental fate of nuclear materials. Quantifying dissolution rates, as well as understanding qualitative dissolution mechanisms, informs performance assessment for geologic disposal of spent nuclear fuel and management of legacy radioactive waste. The aim of this research was to measure the dissolution rate of nanocrystalline NpO 2 (s), produced through legacy nuclear waste processing, under oxidizing conditions, as well as to characterize surface alteration to the material. The solid phase was characterized using electron microscopy techniques (SEM/STEM) and X-ray photoelectron spectroscopy (XPS), indicating preferential dissolution of Np-hydroxide contained in the grain boundaries of NpO 2 (s) and fragmentation of grains from the matrix. The oxidative dissolution was monitored over 40 weeks, yielding a two-step kinetic dissolution model involving hydration of NpO 2 (s) and subsequent oxidation and dissolution of the hydroxide phase. Here, the proposed dissolution models for nanocrystalline NpO 2 (s) suggest that microstructural features such as grain boundaries are key factors affecting dissolution, including release of colloidal particles, and ultimately, environmental fate and transport of nuclear materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Synthesis of luminescent core/shell α-Zn 3 P 2 /ZnS quantum dots

Metal chalcogenide nanoparticles offer vast control over their optoelectronic properties via size, shape, composition, and morphology which has led to their use across fields including optoelectronics, energy storage, and catalysis. While cadmium and lead-based nanocrystals are prevalent in applications, concerns over their toxicity have motivated researchers to explore alternate classes of nanomaterials based on environmentally benign metals such as zinc and tin. The goal of this research is to identify material systems that offer comparable performance to existing metal chalcogenide systems from abundant, recyclable, and environmentally benign materials. With band gaps that span the visible through the infrared, II–V direct band gap semiconductors such as tetragonal zinc phosphide (α-Zn 3 P 2 ) are promising candidates for optoelectronics. To date, syntheses of α-Zn 3 P 2 nanoparticles have been hindered because of the toxicity of zinc and phosphorus precursors, surface oxidation, and defect states leading to carrier trapping and low photoluminescence quantum yield. Here, we report a colloidal synthesis of quantum confined α-Zn 3 P 2 nanoparticles from common phosphorus precursor tris(trimethylsilyl)phosphine and environmentally benign zinc carboxylates. Shelling of the nanoparticles with zinc sulfide is shown as a method of preventing oxidation and improving the optical properties of the nanoparticles. These results show a route to stabilizing α-Zn 3 P 2 nanoparticles for optoelectronic device applications.

25 ENERGY STORAGE↗

KOTOBUKI-1 apparatus for cryogenic coherent X-ray diffraction imaging

We have developed an experimental apparatus named KOTOBUKI-1 for use in coherent X-ray diffraction imaging experiments of frozen-hydrated non-crystalline particles at cryogenic temperature. For cryogenic specimen stage with small positional fluctuation for a long exposure time of more than several minutes, we here use a cryogenic pot cooled by the evaporation cooling effect for liquid nitrogen. In addition, a loading device is developed to bring specimens stored in liquid nitrogen to the specimen stage in vacuum. The apparatus allows diffraction data collection for frozen-hydrated specimens at 66 K with a positional fluctuation of less than 0.4 μm and provides an experimental environment to easily exchange specimens from liquid nitrogen storage to the specimen stage. The apparatus was developed and utilized in diffraction data collection of non-crystalline particles with dimensions of μm from material and biological sciences, such as metal colloid particles and chloroplast, at BL29XU of SPring-8. Recently, it has been applied for single-shot diffraction data collection of non-crystalline particles with dimensions of sub-μm using X-ray free electron laser at BL3 of SACLA.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Experimental investigation of magnetic anisotropy in spin vortex discs

We present experimental 2D vector vibrating sample magnetometer measurements to demonstrate the shape anisotropy effects occurring in micrometer-diameter supermalloy spin vortex discs. Measurements made for different disc sizes and orientations confirm the out-of-plane susceptibility is several orders of magnitude smaller than the in-plane susceptibility. These results validate with a high certitude that spin vortices with high diameter to thickness ratio retain in-plane-only magnetization, even when subjected to fields in the out-of-plane direction. These results contribute to further computational simulations of the dynamics of spin vortex structures in colloidal suspensions where external fields may be applied in any arbitrary direction.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Measuring kinetic energy changes in the mesoscale with low acquisition rates

We report on the measurement of the average kinetic energy changes in isothermal and non-isothermal quasistatic processes in the mesoscale, realized with a Brownian particle trapped with optical tweezers. Our estimation of the kinetic energy change allows to access to the full energetic description of the Brownian particle. Kinetic energy estimates are obtained from measurements of the mean square velocity of the trapped bead sampled at frequencies several orders of magnitude smaller than the momentum relaxation frequency. The velocity is tuned applying a noisy electric field that modulates the amplitude of the fluctuations of the position and velocity of the Brownian particle, whose motion is equivalent to that of a particle in a higher temperature reservoir. Additionally, we show that the dependence of the variance of the time-averaged velocity on the sampling frequency can be used to quantify properties of the electrophoretic mobility of a charged colloid. Our method could be applied to detect temperature gradients in inhomogeneous media and to characterize the complete thermodynamics of biological motors and of artificial micro and nanoscopic heat engines.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Three-body interactions in complex fluids: Virial coefficients from simulation finite-size effects

A simulation technique is described for quantifying the contribution of three-body interactions to the thermodynamical properties of coarse-grained representations of complex fluids. The method is based on a new approach for determining virial coefficients from the measured volume-dependent asymptote of a certain structural function. By comparing the third virial coefficient B{sub 3} for a complex fluid with that of an approximate coarse-grained model described by a pair potential, three body effects can be quantified. The strategy is applicable to both Molecular Dynamics and Monte Carlo simulation. Its utility is illustrated via measurements of three-body effects in models of star polymers and in highly size-asymmetrical colloid-polymer mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

“Rings of saturn-like” nanoarrays with high number density of hot spots for surface-enhanced Raman scattering

The Ag nanoparticles (NPs) surrounding triangular nanoarrays (TNAs) with high number density of surface-enhanced Raman scattering (SERS) hot spots (SERS hot spots ring) are prepared by a combination of NPs deposition and subsequent colloid lithography processing. Owing to the SERS hot spots ring, the Ag NPs surrounding TNAs have been proved an excellent candidate for ultrasensitive molecular sensing for their high SERS signal enhancing capacity in experiments and theories. The Ag NPs surrounding TNAs can be readily used for the quick detection of low concentrations of molecules related to food safety; herein, detection of melamine is discussed.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Measuring local volume fraction, long-wavelength correlations, and fractionation in a phase-separating polydisperse fluid

We dynamically simulate fractionation (partitioning of particle species) during spinodal gas-liquid separation of a size-polydisperse colloid, using polydispersity up to ∼40% and a skewed parent size distribution. We introduce a novel coarse-grained Voronoi method to minimise size bias in measuring local volume fraction, along with a variety of spatial correlation functions which detect fractionation without requiring a clear distinction between the phases. These can be applied whether or not a system is phase separated, to determine structural correlations in particle size, and generalise easily to other kinds of polydispersity (charge, shape, etc.). We measure fractionation in both mean size and polydispersity between the phases, its direction differing between model interaction potentials which are identical in the monodisperse case. These qualitative features are predicted by a perturbative theory requiring only a monodisperse reference as input. The results show that intricate fractionation takes place almost from the start of phase separation, so can play a role even in nonequilibrium arrested states. The methods for characterisation of inhomogeneous polydisperse systems could in principle be applied to experiment as well as modelling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural behavior and dynamics of an anomalous fluid between attractive and repulsive walls: Templating, molding, and superdiffusion

Confinement can modify the dynamics, the thermodynamics, and the structural properties of liquid water, the prototypical anomalous liquid. By considering a generic model for anomalous liquids, suitable for describing solutions of globular proteins, colloids, or liquid metals, we study by molecular dynamics simulations the effect that an attractive wall with structure and a repulsive wall without structure have on the phases, the crystal nucleation, and the dynamics of the fluid. We find that at low temperatures the large density of the attractive wall induces a high-density, high-energy structure in the first layer (“templating” effect). In turn, the first layer induces a “molding” effect on the second layer determining a structure with reduced energy and density, closer to the average density of the system. This low-density, low-energy structure propagates further through the layers by templating effect and can involve all the existing layers at the lowest temperatures investigated. Therefore, although the high-density, high-energy structure does not self-reproduce further than the first layer, the structured wall can have a long-range influence thanks to a sequence of templating, molding, and templating effects through the layers. We find that the walls also have an influence on the dynamics of the liquid, with a stronger effect near the attractive wall. In particular, we observe that the dynamics is largely heterogeneous (i) among the layers, as a consequence of the sequence of structures caused by the walls presence, and (ii) within the same layer, due to superdiffusive liquid veins within a frozen matrix of particles near the walls at low temperature and high density. Hence, the partial freezing of the first layer does not correspond necessarily to an effective reduction of the channel's section in terms of transport properties, as suggested by other authors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗