Quantifying the role of experimental parameters on the growth of metal nanocrystals is crucial when designing synthesis protocols that yield specific structures. Here, the effect of temperature on the growth kinetics of radiolytically-formed branched palladium (Pd) nanocrystals is investigated by tracking their evolution using liquid cell transmission electron microscopy (TEM) and applying a temperature-dependent radiolysis model. At early times, kinetics consistent with growth limited is measured by the surface reaction rate, and it is found that the growth rate increases with temperature.
View Article and Find Full Text PDFACS Appl Bio Mater
August 2022
The erosion of tooth enamel is a common oral disease. The erosion pattern and location and the effects of nanoscale chemical composition on the erosion susceptibility of enamel have been well documented. However, the enamel remineralization accompanied by erosion and its underlying physicochemical mechanisms still remain poorly understood.
View Article and Find Full Text PDFCalcium oxalate monohydrate (COM) crystal is the most common crystalline component of human kidney stones. The molecular-scale inhibitory mechanisms of COM crystal growth by urinary biomolecules such as citrate and osteopontin adsorbed onto the crystal surface are now well understood. However, the pathways by which dissolved calcium and oxalate ions are incorporated into the molecular step of the COM crystal surface, leading to COM crystal growth-a prerequisite to be elucidated for developing effective therapeutics to inhibit COM stones-remain unknown.
View Article and Find Full Text PDFCdS has been known to be one of the best junction partners for Cu(In,Ga)Se (CIGS) in CIGS solar cells. However, the use of thick CdS buffer decreases the short-circuit current density of CIGS solar cells. There are two obstacles that limit the use of ultrathin CdS.
View Article and Find Full Text PDFWe report the systematic investigation of the surface optical phonon modes in Au-catalyzed GaAs nanowires grown on an Au pre-patterned GaAs(111)B substrate using -Raman spectroscopy. We employed electron-beam dose rate as a control parameter during the substrate patterning step for adjusting the nanowire base diameter and coverage, which are independent from the nanowire growth conditions. We have experimentally studied the effect of the fill factor and average diameter on the surface optical phonon modes and explained the red-shift and broadening of the surface optical phonon frequencies by employing the dielectric continuum model.
View Article and Find Full Text PDFWe report the relation between the catalyst patterning conditions and the intensity of the 1st order Raman active modes in Au-catalyzed GaAs nanowire bundles. We fabricated e-beam lithographically Au-patterned GaAs(111)B substrates by varying the patterning conditions (e-beam dose rate, dot-size and interdot-spacings), and grew GaAs nanowires via vapor-liquid-solid process using a solid-source molecular beam epitaxy. To understand the effects of the substrate preparation conditions and resulting morphologies on the optical characteristics of 1st order transverse optical and longitudinal optical phonon modes of GaAs, we characterized the nanowire bundles using complementary -Raman spectroscopy and scanning electron microscopy as a function of the e-beam dose rate (145-595 C/cm²), inter-dot spacing (100 and 150 nm) and pattern size (100 and 150 nm).
View Article and Find Full Text PDFWe report optical phonon vibration modes in ensembles of self-catalyzed InP/InAs/InP multi core-shell one-dimensional nanostructures (nanopillars and nanocones) grown on InP(111)B substrates using liquid indium droplets as a catalyst via metal-organic chemical vapor deposition. We characterized the Raman vibration modes of InAs E(TO), InAs A(TO), InAs E(LO), InP E(TO), InP A(LO), and InP E(LO) from the ensemble of as-grown nanostructures. We also identified second-order Raman vibration modes, associated with InP E(2TO), E(LO+TO), and E(2LO), in the InP/InAs/InP core-shell nanopillars and nanocones.
View Article and Find Full Text PDFPrecise control over the size and morphology of the Au spiky nanoparticle (SNP) is essential to obtain narrow and tunable surface plasmon resonance (SPR). However, these challenges require a fundamental understanding of the particle growth mechanism and kinetics as well as its morphological transition, which can only be achieved by real-time observation at nanometer resolution. Here, we report in situ liquid cell transmission electron microscopy studies of single and multiple Au SNP growth at various conditions of such parameters as size and dose rate of electron beam and HAuCl solution concentration.
View Article and Find Full Text PDFWe report the effect of morphology and substrate of self-catalyzed indium phosphide (InP) nanostructures on phonon vibration modes. Using liquid indium as a catalyst, we grew self-catalyzed InP nanocones and nanopillars on single crystal substrates of InP(111)B, Si(111), and Si(100) via metal-organic chemical vapor epitaxy. Due to crystal symmetry breaking in one-dimensional nanostructure, longitudinal-optical (LO) and transverse-optical (TO) phonon modes are clearly resolved with the strong anisotropic behavior.
View Article and Find Full Text PDFLithium metal is an ideal material for high-energy, cost-effective rechargeable energy storage systems. The thermodynamically unfavorable solid-liquid interface between the lithium metal and organic electrolyte necessitates the formation of an interlayer (SEI) which is known to have significant impact on lithium morphologies. Less well understood is the impact of the current collector substrate on the morphology of electrodeposited lithium.
View Article and Find Full Text PDFThe use of liquid cell electron microscopy as a quantitative probe of nanomaterial structures and reactions requires an accurate understanding of how the sample is altered by the imaging electron beam. In particular, changes in the chemical environment due to beam-induced radiolysis can strongly affect processes such as solution-phase nanocrystal synthesis or electrochemical deposition. It is generally assumed that beam effects are uniform throughout the irradiated liquid.
View Article and Find Full Text PDFThe performance of many electrochemical energy storage systems can be compromised by the formation of metal dendrites during charging. Additives in the electrolyte represent a useful strategy to mitigate dendrite formation, but understanding the mechanisms involved requires knowledge of the nanoscale effects of additives during electrochemical deposition. Here we quantify the effects of an inorganic additive on the morphology of an evolving electrochemical growth front, using liquid cell electron microscopy to provide the necessary spatial and temporal resolution.
View Article and Find Full Text PDFControl of interfacial morphology in electrochemical processes is essential for applications ranging from nanomanufacturing to batteries. Here, we quantify the evolution of an electrochemical growth front, using liquid cell electron microscopy to access unexplored length and time scales. During galvanostatic deposition of copper from an acidic electrolyte, we find that the growth front initially evolves consistent with kinetic roughening theory.
View Article and Find Full Text PDFWe develop a solution-based nanoscale patterning technique for site-specific deposition and dissolution of metallic nanocrystals. Nanocrystals are grown at desired locations by electron beam-induced reduction of metal ions in solution, with the ions supplied by dissolution of a nearby electrode via an applied potential. The nanocrystals can be "erased" by choice of beam conditions and regrown repeatably.
View Article and Find Full Text PDFWe report the growth of vertical <111>-oriented InAs x P1-x (0.11 ≤ x ≤ 0.27) nanowires via metal-organic chemical vapor deposition in the presence of indium droplets as catalysts on InP(111)B substrates at 375 °C.
View Article and Find Full Text PDF[Purpose] This study investigated the effects of Nordic walking on physical functions and depression in frail people aged 70 years and above. [Subjects] Twenty frail elderly individuals ≥70 years old were assigned to either a Nordic walking group (n=8) or general exercise group (n=10). [Methods] The duration of intervention was equal in both groups (3 sessions/week for 12 weeks, 60 min/session).
View Article and Find Full Text PDFMeasurements of solution-phase crystal growth provide mechanistic information that is helpful in designing and synthesizing nanostructures. Here, we examine the model system of individual Au nanocrystal formation within a defined liquid geometry during electron beam irradiation of gold chloride solution, where radiolytically formed hydrated electrons reduce Au ions to solid Au. By selecting conditions that favor the growth of well-faceted Au nanoprisms, we measure growth rates of individual crystals.
View Article and Find Full Text PDFWe report the plasmon-assisted photocurrent enhancement in Ag-nanoparticles (Ag-NPs) embedded PEDOT:PSS/P3HT:PCBM organic solar cells, and systematically investigate the causes of the improved optical absorption based on a cylindrical Ag-NPs optical model which is simulated with a 3-Dimensional finite difference time domain (FDTD) method. The proposed cylindrical Ag-NPs optical model is able to explain the optical absorption enhancement by the localized surface plasmon resonance (LSPR) modes, and to provide a further understanding of Ag-NPs shape parameters which play an important role to determine the broadband absorption phenomena in plasmonic organic solar cells. A significant increase in the power conversion efficiency (PCE) of the plasmonic solar cell was experimentally observed and compared with that of the solar cells without Ag-NPs.
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