Synthesis of Composition-Tunable Ag-Cu Bimetallic Nanoparticles Through Plasma-Driven Solution Electrolysis.

Bimetallic nanomaterials have shown great potential across various fields of application. However, the synthesis of many bimetallic particles can be challenging due to the immiscibility of their constituent metals. In this study, we present a synthetic strategy to produce compositionally tunable silver-copper (Ag-Cu) bimetallic nanoparticles using plasma-driven liquid surface chemistry.

In Vivo Optical Clearing of Mammalian Brain.

Established methods for imaging the living mammalian brain have, to date, taken optical properties of the tissue as fixed; we here demonstrate that it is possible to modify the optical properties of the brain itself to significantly enhance at-depth imaging while preserving native physiology. Using a small amount of any of several biocompatible materials to raise the refractive index of solutions superfusing the brain prior to imaging, we could increase several-fold the signals from the deepest cells normally visible and, under both one-photon and two-photon imaging, visualize cells previously too dim to see. The enhancement was observed for both anatomical and functional fluorescent reporters across a broad range of emission wavelengths.

Nonthermal Plasma Synthesis of Metallic Ti Nanocrystals.

Nanoscale metallic titanium (Ti) offers unique energetic and biocompatible characteristics for the aerospace and biomedical industries. A rapid and sustainable method to form purified Ti nanocrystals is still in demand due to their high oxygen affinity. Herein, we report the production of highly purified Ti nanoparticles with a nonequilibrium face center cubic (FCC) structure from titanium tetrachloride (TiCl) via a capacitively coupled plasma (CCP) route.

Silver Nanoparticle Synthesis in Glycerol by Low-Pressure Plasma-Driven Electrolysis: The Roles of Free Electrons and Photons.

Low-temperature plasmas in and in contact with liquids have emerged as a catalyst-free approach for the selective, electrode-free, and green synthesis of novel materials. For the synthesis of nanomaterials, short-lived solvated electrons have been proposed to be the critical reducing species, while the role of ultraviolet (UV) photons from plasma is less explored. Here, we demonstrate that UV radiation contributes ∼70% of the integral plasma effect in synthesizing silver (Ag) nanoparticles within a glycerol solution.

Capacitively coupled nonthermal plasma synthesis of aluminum nanocrystals for enhanced yield and size control.

Uniform-size, non-native oxide-passivated metallic aluminum nanoparticles (Al NPs) have desirable properties for fuel applications, battery components, plasmonics, and hydrogen catalysis. Nonthermal plasma-assisted synthesis of Al NPs was previously achieved with an inductively coupled plasma (ICP) reactor, but the low production rate and limited tunability of particle size were key barriers to the applications of this material. This work focuses on the application of capacitively coupled plasma (CCP) to achieve improved control over Al NP size and a ten-fold increase in yield.

Inductively Coupled Nonthermal Plasma Synthesis of Size-Controlled γ-AlO Nanocrystals.

Gamma alumina (γ-AlO) is widely used as a catalyst and catalytic support due to its high specific surface area and porosity. However, synthesis of γ-AlO nanocrystals is often a complicated process requiring high temperatures or additional post-synthetic steps. Here, we report a single-step synthesis of size-controlled and monodisperse, facetted γ-AlO nanocrystals in an inductively coupled nonthermal plasma reactor using trimethylaluminum and oxygen as precursors.

A Single-Step Bottom-up Approach for Synthesis of Highly Uniform Mie-Resonant Crystalline Semiconductor Particles at Visible Wavelengths.

Optically Mie-resonant crystalline silicon nanoparticles have long attracted interest for their unique scattering behaviors. Here, we report a bottom-up nonthermal plasma process that produces highly monodisperse particles, with diameters controllable between 60 and 214 nm, by temporarily electrostatically trapping nanoparticles inside a continuous-flow plasma reactor. The particle size is tuned by adjusting the gas residence time in the reactor.

Observation of suppressed diffuson and propagon thermal conductivity of hydrogenated amorphous silicon films.

Hydrogenated amorphous silicon (a-Si:H) has drawn keen interest as a thin-film semiconductor and superb passivation layer in high-efficiency silicon solar cells due to its low cost, low processing temperature, high compatibility with substrates, and scalable manufacturing. Although the impact of hydrogenation on the structural, optical, and electronic properties of a-Si:H has been extensively studied, the underlying physics of its impact on the thermal properties is still unclear. Here, we synthesize a-Si:H films with well-controlled hydrogen concentrations using plasma-enhanced chemical vapor deposition and systematically study the thermal conductivity of these a-Si:H films using time-domain thermoreflectance.

Broadband, Angle- and Polarization-Invariant Antireflective and Absorbing Films by a Scalable Synthesis of Monodisperse Silicon Nanoparticles.

Optically induced magnetic resonances (OMRs) are highly tunable scattering states that cannot be reproduced in systems that only support electric resonances, such as in metals, lossy, or low-index materials. Despite offering unique scattering and coupling behavior, the study of OMRs in thin films has been limited by synthesis and simulation constraints. We report on the absorption and scattering response of OMR-based thin films composed of monodisperse crystalline silicon nanoparticles synthesized using a scalable nonthermal plasma growth technique and tractable simulation framework.

Distance-dependent resonance energy transfer in alkyl-terminated Si nanocrystal solids.

Understanding and controlling the energy transfer between silicon nanocrystals is of significant importance for the design of efficient optoelectronic devices. However, previous studies on silicon nanocrystal energy transfer were limited because of the strict requirements to precisely control the inter-dot distance and to perform all measurements in air-free environments to preclude the effect of ambient oxygen. Here, we systematically investigate the distance-dependent resonance energy transfer in alkyl-terminated silicon nanocrystals for the first time.

Band Gap Tuning of Films of Undoped ZnO Nanocrystals by Removal of Surface Groups.

Transparent conductive oxides (TCOs) are widely used in optoelectronic devices such as flat-panel displays and solar cells. A significant optical property of TCOs is their band gap, which determines the spectral range of the transparency of the material. In this study, a tunable band gap range from 3.

Water-Soluble Luminescent Silicon Nanocrystals by Plasma-Induced Acrylic Acid Grafting and PEGylation.

Luminescent silicon nanocrystals are promising nanomaterials for biomedical applications due to their unique optical properties and biocompatibility. Here, we demonstrate a two-step surface modification approach coupling gas-phase and liquid-phase methods to synthesize PEGylated acrylic acid grafted silicon nanocrystals with near-infrared emission in water and biological media. First, acrylic acid grafted silicon nanocrystals are synthesized by an all-gas-phase approach on a millisecond time scale, omitting high temperature and postpurification processes.

Predicting plasma conditions necessary for synthesis of γ-AlO nanocrystals.

Nonthermal plasma (NTP) offers a unique synthesis environment capable of producing nanocrystals of high melting point materials at relatively low gas temperatures. Despite the rapidly growing material library accessible through NTP synthesis, designing processes for new materials is predominantly empirically driven. Here, we report on the synthesis of both amorphous alumina and γ-Al2O3 nanocrystals and present a simple particle heating model that is suitable for predicting the plasma power necessary for crystallization.

Inductively coupled nonthermal plasma synthesis of aluminum nanoparticles.

Metallic nanoparticles of aluminum (Al), a nontoxic and earth-abundant element, are relevant to plasmonic and energetic applications. However, monodisperse Al nanoparticles are difficult to synthesize using all gas-phase approaches, especially in the 10 to 20 nm size range; yet, many applications require particles of this size due to their enhanced properties. Here, an inductive nonthermal plasma reactor fed with aluminum trichloride (AlCl) and Ar is used to synthesize single-crystal aluminum nanoparticles.

Ion attachment rates and collection forces on dust particles in a plasma sheath with finite ion inertia and mobility.

Ion attachment and ion drag to dust particles near the edge of a nonthermal plasma sheath are of interest to better understand how particles become trapped in such sheath regions. While electron-particle collisions in plasmas and sheaths can often be described by orbital motion limited theory, quantification of ion transport about dust particles in collisional sheath regions requires a distinct modeling approach. In this work, the dimensionless ion attachment coefficients and dimensionless collection forces on negatively charged particles are calculated using ion trajectory models accounting for an external electric field in a collisional sheath, ion inertia, and finite ion mobility.

Aluminum Oxide Nanoparticle Films Deposited from a Nonthermal Plasma: Synthesis, Characterization, and Crystallization.

Aluminum oxide, both in amorphous and crystalline forms, is a widely used inorganic ceramic material because of its chemical and structural properties. In this work, we synthesized amorphous aluminum oxide nanoparticles using a capacitively coupled nonthermal plasma utilizing trimethylaluminum and oxygen as precursors and studied their crystallization and phase transformation behavior through postsynthetic annealing. The use of two reactor geometries resulted in amorphous aluminum oxide nanoparticles with similar compositions but different sizes.

Nonthermal Plasma-Enhanced Chemical Vapor Deposition of Two-Dimensional Molybdenum Disulfide.

Molybdenum disulfide (MoS) is being studied for a wide range of applications including lithium-ion batteries and hydrogen evolution reaction catalysts. In this paper, we present a single-step nonthermal plasma-enhanced chemical vapor deposition (PECVD) process for the production of two-dimensional MoS. This method provides an alternative route to established CVD and plasma synthesis routes.

Bright Silicon Nanocrystals from a Liquid Precursor: Quasi-Direct Recombination with High Quantum Yield.

Silicon nanocrystals (SiNCs) with bright bandgap photoluminescence (PL) are of current interest for a range of potential applications, from solar windows to biomedical contrast agents. Here, we use the liquid precursor cyclohexasilane (SiH) for the plasma synthesis of colloidal SiNCs with exemplary core emission. Through size separation executed in an oxygen-shielded environment, we achieve PL quantum yields (QYs) approaching 70% while exposing intrinsic constraints on efficient core emission from smaller SiNCs.

Poly(methyl methacrylate) Films with High Concentrations of Silicon Quantum Dots for Visibly Transparent Luminescent Solar Concentrators.

Silicon quantum dots (Si QDs) are attractive, nontoxic luminophores for luminescent solar concentrators (LSCs). Here, we produced Si QD/poly(methyl methacrylate) (PMMA) films on glass by doctor-blading polymer solutions and achieved films with low light scattering at an order of magnitude higher Si QD weight fraction than has been achieved previously in the bulk. We suggest that the fast solidification rate of films as compared to slow bulk polymerization is an enabling factor in avoiding large agglomerates within the nanocomposites.

Probing Dopant Locations in Silicon Nanocrystals via High Energy X-ray Diffraction and Reverse Monte Carlo Simulation.

Understanding the locations of dopant atoms in ensembles of nanocrystals is crucial to controlling the dopants' function. While electron microscopy and atom probe tomography methods allow investigation of dopant location for small numbers of nanocrystals, assessing large ensembles has remained a challenge. Here, we are using high energy X-ray diffraction (HE-XRD) and structure reconstruction via reverse Monte Carlo simulation to characterize nanocrystal structure and dopant locations in ensembles of highly boron and phosphorus doped silicon nanocrystals (Si NCs).

Synthesis of PEG-grafted boron doped Si nanocrystals.

Silicon nanocrystals are intriguing materials for biomedical imaging applications because of their unique optical properties and biological compatibility. We report a new surface functionalization route to synthesize biological buffer soluble and colloidally stable silicon nanocrystals, which is enabled by surface boron doping. Harnessing the distinctive Lewis acidic boron surface sites, postsynthetic modifications of plasma synthesized boron doped nanocrystals were carried out with polyethylene glycol (PEG-OH) ligands in dimethyl sulfoxide under photochemical conditions.

Aerosol-Phase Synthesis and Processing of Luminescent Silicon Nanocrystals.

Silicon quantum dots are attractive materials for luminescent devices and bioimaging applications. For these light-emitting applications, higher photoluminescence efficiency is desired in order to achieve better device performance. Nonthermal plasma synthesis successfully allows for the continuous production of silicon nanocrystals, but postprocessing is necessary to improve photoluminescence quantum yields so that nanocrystals can be used for luminescence applications.

Metal-insulator transition in a semiconductor nanocrystal network.

Many envisioned applications of semiconductor nanocrystals (NCs), such as thermoelectric generators and transparent conductors, require metallic (nonactivated) charge transport across an NC network. Although encouraging signs of metallic or near-metallic transport have been reported, a thorough demonstration of nonzero conductivity, σ, in the 0 K limit has been elusive. Here, we examine the temperature dependence of σ of ZnO NC networks.

Variable range hopping conduction in ZnO nanocrystal thin films.

Zinc oxide (ZnO) nanocrystal films are of interest for new applications in thin film transistors and as transparent conductive oxides. Previous work has concentrated on achieving highly conductive, metallic films. This work focusses on the less explored insulating to semi-insulating regime, which enables obtaining deeper insights into the roles of surface states and defect states trapped at the nanocrystal interfaces.