Photonic Properties of Thin Films Composed of Gallium Nitride Quantum Dots Synthesized by Nonequilibrium Plasma Aerotaxy.

Gallium nitride quantum dots (GaN QDs) are a promising material for optoelectronics, but the synthesis of freestanding GaN QDs remains a challenge. To date, the size-dependent photonic properties of freestanding GaN QDs have not been reported. Here, we examine the photonic properties exhibited by thin films composed of GaN QDs synthesized by nonequilibrium plasma aerotaxy. Each film exhibited two photoluminescence peaks after exposure to ambient air. The first peak was in the ultraviolet spectral region, and the second peak was in the visible region. Both peak positions depended on the QD size. Our findings, supported by transient absorption spectroscopy experiments, suggest that conduction band to valence band recombination was the cause of the ultraviolet photoluminescence and that recombination between the conduction band and an acceptor level was the cause of visible photoluminescence. Furthermore, we show that coating the surface of fresh QDs with Al2O3 suppressed the visible region photoluminescence, corroborating the conclusion that the photoactive defect was caused by oxidation in air.

Effects of Halides on Organic Compound Degradation during Plasma Treatment of Brines.

Plasma has been proposed as an alternative strategy to treat organic contaminants in brines. Chemical degradation in these systems is expected to be partially driven by halogen oxidants, which have been detected in halide-containing solutions exposed to plasma. In this study, we characterized specific mechanisms involving the formation and reactions of halogen oxidants during plasma treatment. We first demonstrated that addition of halides accelerated the degradation of a probe compound known to react quickly with halogen oxidants (i.e., para-hydroxybenzoate) but did not affect the degradation of a less reactive probe compound (i.e., benzoate). This effect was attributed to the degradation of para-hydroxybenzoate by hypohalous acids, which were produced via a mechanism involving halogen radicals as intermediates. We applied this mechanistic insight to investigate the impact of constituents in brines on reactions driven by halogen oxidants during plasma treatment. Bromide, which is expected to occur alongside chloride in brines, was required to enable halogen oxidant formation, consistent with the generation of halogen radicals from the oxidation of halides by hydroxyl radical. Other constituents typically present in brines (i.e., carbonates, organic matter) slowed the degradation of organic compounds, consistent with their ability to scavenge species involved during plasma treatment.

Plasma parameters and the reduction potential at a plasma-liquid interface.

Nonthermal plasmas in contact with liquids have been shown to generate a variety of reactive species capable of initiating reduction-oxidation (redox) reactions at the electrochemically active plasma-liquid interface. In conventional electrochemical cells, selective redox chemistry is achieved by controlling the reduction potential at the solid electrode-electrolyte interface by applying a bias via an external circuit. In the case of plasma-liquid systems, an analogous means of tuning the reduction potential near the interface has not clearly been identified. When treated as a floating surface, the liquid is expected to adopt a net negative charge to balance the flux of hot electrons and relatively cold positive ions. The reduction potential near the plasma-liquid interface is hypothesized to be proportional to the floating potential, which can be approximated using an analytical model provided the plasma parameters are known. Herein, we present a framework for correlating the electron density and electron temperature of a noble gas plasma jet to the reduction potential near the plasma-liquid interface. The plasma parameters were acquired for an argon atmospheric plasma jet in contact with an aqueous solution by means of laser Thomson scattering. The reduction potential was determined using identical reference electrodes to measure the potential difference between the plasma-liquid interface and bulk solution. Interestingly, the measured reduction potentials near the plasma-liquid interface were found to be in good agreement with the model-predicted values determined using the plasma parameters obtained from the Thomson scattering experiments.

Predicting plasma conditions necessary for synthesis of γ-Al2O3 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. The heating model only requires the composition, temperature, and pressure of the background gas along with the reactor geometry to calculate the temperature of particles suspended in the plasma as a function of applied power. Complete crystallization of the nanoparticle population was observed when applied power was greater than the threshold where the calculated particle temperature is equal to the crystallization temperature of amorphous alumina.

Highly Conductive Sb-SnO2 Nanocrystals Synthesized by Dual Nonthermal Plasmas.

Nonthermal plasma synthesis of transparent conducting oxide nanocrystals can offer advantages, for example, ligand-free surfaces, over traditionally used colloidal synthesis methods. When it comes to multicomponent (doped) metal oxide nanocrystal synthesis, uniform distribution of different metal elements and suppressing surface segregation of secondary resistive phases have been concerns. Specifically, surface segregation of resistive secondary phases reduces the electrical conductivity of nanocrystal assemblies. In this work, we demonstrate a nonthermal dual-plasma synthesis method capable of forming Sb-SnO2 (ATO) nanocrystals with a uniform composition distribution and apparently insignificant surface segregation of the dopant. A drastic increase in conductivity was observed in ATO thin films comprised of nanocrystals formed using a dual-plasma configuration compared to nanocrystals formed using a single-plasma configuration. The conductivity values of as-deposited porous films comprised of ATO nanocrystals, prepared using the dual-plasma approach, were on the order of 0.1 S cm-1, which to our knowledge is the highest conductivity reported to-date for that type of high surface area material. Annealing the films comprised of ATO nanocrystals at 500 °C for 2 h in air increased the conductivity and improved ambient stability, without significantly affecting the crystallite size.

Measurement of sub-2 nm stable clusters during silane pyrolysis in a furnace aerosol reactor.

The initial stages of particle formation are important in several industrial and environmental systems; however, the phenomenon is not completely understood due to the inability to measure cluster size distributions. A high resolution differential mobility analyzer with an electrometer was used to map out the early stages of Si particle formation from pyrolysis of SiH4 in a furnace aerosol reactor. We detected for the first time subnanometer stable clusters from silane pyrolysis, and the diameter was measured to be about 0.7 nm. This diameter is within the range of probable sizes that the reported families of critical silane clusters could have based on their actual molecular structure. The size distributions of negative clusters are also mapped out. In addition, gas chromatography mass spectrometry, and transmission electron microscopy characterizations of the clusters and primary particles are used to assess their mechanistic roles in aerosol dynamics of the initial stages of particle formation.

Aerosol-synthesized siliceous nanoparticles: impact of morphology and functionalization on biodistribution.

INTRODUCTION: Siliceous nanoparticles (NPs) have been extensively studied in nanomedicine due to their high biocompatibility and immense biomedical potential. Although numerous technologies have been developed, the synthesis of siliceous NPs for biomedical applications mainly relies on a few core technologies predominantly intended to produce spherical-shaped NPs. METHODS: In this context, the impact of different morphologies of siliceous NPs on biodistribution in vivo is limited. In the present study, we developed a novel technique based on an aerosol silane reactor to produce sintered silicon NPs of similar size but different surface areas due to distinct spherical subunits. Silica-converted particles were functionalized for radiolabeling with copper-64 (64Cu) to systematically analyze their behavior in the passive targeting of A431 tumor xenografts in mice after intravenous injection. RESULTS: While low nonspecific uptake was observed in most organs, the majority of particles were accumulated in the liver, spleen, and lung. Depending on the morphologies and function-alization, significant differences in the uptake profiles of the particles were observed. In terms of tumor uptake, spherical shapes with lower surface areas showed the highest accumulation and tumor-to-blood ratios of all investigated particles. CONCLUSION: This study highlights the importance of shape and fuctionalization of siliceous NPs on organ and tumor accumulation as significant factors for biomedical applications.

Contact Radius and the Insulator-Metal Transition in Films Comprised of Touching Semiconductor Nanocrystals.

Nanocrystal assemblies are being explored for a number of optoelectronic applications such as transparent conductors, photovoltaic solar cells, and electrochromic windows. Majority carrier transport is important for these applications, yet it remains relatively poorly understood in films comprised of touching nanocrystals. Specifically, the underlying structural parameters expected to determine the transport mechanism have not been fully elucidated. In this report, we demonstrate experimentally that the contact radius, between touching heavily doped ZnO nanocrystals, controls the electron transport mechanism. Spherical nanocrystals are considered, which are connected by a circular area. The radius of this circular area is the contact radius. For nanocrystals that have local majority carrier concentration above the Mott transition, there is a critical contact radius. If the contact radius between nanocrystals is less than the critical value, then the transport mechanism is variable range hopping. If the contact radius is greater than the critical value, the films display behavior consistent with metallic electron transport.

High electron mobility in thin films formed via supersonic impact deposition of nanocrystals synthesized in nonthermal plasmas.

Thin films comprising semiconductor nanocrystals are emerging for applications in electronic and optoelectronic devices including light emitting diodes and solar cells. Achieving high charge carrier mobility in these films requires the identification and elimination of electronic traps on the nanocrystal surfaces. Herein, we show that in films comprising ZnO nanocrystals, an electron acceptor trap related to the presence of OH on the surface limits the conductivity. ZnO nanocrystal films were synthesized using a nonthermal plasma from diethyl zinc and oxygen and deposited by inertial impaction onto a variety of substrates. Surprisingly, coating the ZnO nanocrystals with a few nanometres of Al2O3 using atomic layer deposition decreased the film resistivity by seven orders of magnitude to values as low as 0.12 Ω cm. Electron mobility as high as 3 cm(2) V(-1) s(-1) was observed in films comprising annealed ZnO nanocrystals coated with Al2O3.

Plasma synthesis of stoichiometric Cu2S nanocrystals stabilized by oleylamine.

Nonthermal plasmas can produce high quality nanocrystals in a continuous process without requiring solvents. A nonthermal plasma process is demonstrated to synthesize stoichiometric Cu2S nanocrystals, which show no signs of oxidation by spectrophotometry after 2 months in the ambient when stabilized with oleylamine and dispersed in toluene.

Stabilizing Cu2S for photovoltaics one atomic layer at a time.

Stabilizing Cu2S in its ideal stoichiometric form, chalcocite, is a long-standing challenge that must be met prior to its practical use in thin-film photovoltaic (PV) devices. Significant copper deficiency, which results in degenerate p-type doping, might be avoided by limiting Cu diffusion into a readily formed surface oxide and other adjacent layers. Here, we examine the extent to which PV-relevant metal-oxide over- and underlayers may stabilize Cu2S thin films with desirable semiconducting properties. After only 15 nm of TiO2 coating, Hall measurements and UV-vis-NIR spectroscopy reveal a significant suppression of free charge-carrier addition that depends strongly on the choice of deposition chemistry. Remarkably, the insertion of a single atomic layer of Al2O3 between Cu2S and TiO2 further stabilizes the active layer for at least 2 weeks, even under ambient conditions. The mechanism of this remarkable enhancement is explored by in situ microbalance and conductivity measurements. Finally, photoluminescence quenching measurements point to the potential utility of these nanolaminate stacks in solar-energy harvesting applications.

Highly active oxide photocathode for photoelectrochemical water reduction.

A clean and efficient way to overcome the limited supply of fossil fuels and the greenhouse effect is the production of hydrogen fuel from sunlight and water through the semiconductor/water junction of a photoelectrochemical cell, where energy collection and water electrolysis are combined into a single semiconductor electrode. We present a highly active photocathode for solar H(2) production, consisting of electrodeposited cuprous oxide, which was protected against photocathodic decomposition in water by nanolayers of Al-doped zinc oxide and titanium oxide and activated for hydrogen evolution with electrodeposited Pt nanoparticles. The roles of the different surface protection components were investigated, and in the best case electrodes showed photocurrents of up to -7.6 mA cm(-2) at a potential of 0 V versus the reversible hydrogen electrode at mild pH. The electrodes remained active after 1 h of testing, cuprous oxide was found to be stable during the water reduction reaction and the Faradaic efficiency was estimated to be close to 100%.

Influence of plasmonic Au nanoparticles on the photoactivity of Fe2O3 electrodes for water splitting.

An experimental study of the influence of gold nanoparticles on α-Fe(2)O(3) photoanodes for photoelectrochemical water splitting is described. A relative enhancement in the water splitting efficiency at photon frequencies corresponding to the plasmon resonance in gold was observed. This relative enhancement was observed only for electrode geometries with metal particles that were localized at the semiconductor-electrolyte interface, consistent with the observation that minority carrier transport to the electrolyte is the most significant impediment to achieving high efficiencies in this system.