Matching Items (8)
Filtering by
- All Subjects: Nanoparticles
- Creators: Holman, Zachary C
- Creators: Buttry, Daniel A
Description
Gold-silver alloy nanoparticles (NPs) capped with adenosine 5'-triphosphate were synthesized by borohydride reduction of dilute aqueous metal precursors. High-resolution transmission electron microscopy showed the as-synthesized particles to be spherical with average diameters ~4 nm. Optical properties were measured by UV-Visible spectroscopy (UV-Vis), and the formation of alloy NPs was verified across all gold:silver ratios by a linear shift in the plasmon band maxima against alloy composition. The molar absorptivities of the NPs decreased non-linearly with increasing gold content from 2.0 x 108 M-1 cm-1 (fÉmax = 404 nm) for pure silver to 4.1 x 107 M-1 cm-1 (fÉmax = 511 nm) for pure gold. The NPs were immobilized onto transparent indium-tin oxide composite electrodes using layer-by-layer (LbL) deposition with poly(diallyldimethylammonium) acting as a cationic binder. The UV-Vis absorbance of the LbL film was used to calculate the surface coverage of alloy NPs on the electrode. Typical preparations had average NP surface coverages of 2.8 x 10-13 mol NPs/cm2 (~5% of cubic closest packing) with saturated films reaching ~20% of ccp for single-layer preparations (1.0 ~ 10-12 mol NPs/cm2). X-ray photoelectron spectroscopy confirmed the presence of alloy NPs in the LbL film and showed silver enrichment of the NP surfaces by ~9%. Irreversible oxidative dissolution (dealloying) of the less noble silver atoms from the NPs on LbL electrodes was performed by cyclic voltammetry (CV) in sulfuric acid. Alloy NPs with higher gold content required larger overpotentials for silver dealloying. Dealloying of the more-noble gold atoms from the alloy NPs was also achieved by CV in sodium chloride. The silver was oxidized first to cohesive silver chloride, and then gold dealloyed to soluble HAuCl4- at higher potentials. Silver oxidation was inhibited during the first oxidative scan, but subsequent cycles showed typical, reversible silver-to-silver chloride voltammetry. The potentials for both silver oxidation and gold dealloying also shifted to more oxidizing potentials with increasing gold content, and both processes converged for alloy NPs with >60% gold content. Charge-mediated electrochemistry of silver NPs immobilized in LbL films, using Fc(meOH) as the charge carrier, showed that 67% of the NPs were electrochemically inactive.
ContributorsStarr, Christopher A (Author) / Buttry, Daniel A (Thesis advisor) / Petuskey, William (Committee member) / Jones, Anne (Committee member) / Arizona State University (Publisher)
Created2014
Description
Waste heat energy conversion remains an inviting subject for research, given the renewed emphasis on energy efficiency and carbon emissions reduction. Solid-state thermoelectric devices have been widely investigated, but their practical application remains challenging because of cost and the inability to fabricate them in geometries that are easily compatible with heat sources. An intriguing alternative to solid-state thermoelectric devices is thermogalvanic cells, which include a generally liquid electrolyte that permits the transport of ions. Thermogalvanic cells have long been known in the electrochemistry community, but have not received much attention from the thermal transport community. This is surprising given that their performance is highly dependent on controlling both thermal and mass (ionic) transport. This research will focus on a research project, which is an interdisciplinary collaboration between mechanical engineering (i.e. thermal transport) and chemistry, and is a largely experimental effort aimed at improving fundamental understanding of thermogalvanic systems. The first part will discuss how a simple utilization of natural convection within the cell doubles the maximum power output of the cell. In the second part of the research, some of the results from the previous part will be applied in a feasibility study of incorporating thermogalvanic waste heat recovery systems into automobiles. Finally, a new approach to enhance Seebeck coefficient by tuning the configurational entropy of a mixed-ligand complex formation of copper sulfate aqueous electrolytes will be presented. Ultimately, a summary of these results as well as possible future work that can be formed from these efforts is discussed.
ContributorsGunawan, Andrey (Author) / Phelan, Patrick E (Thesis advisor) / Buttry, Daniel A (Committee member) / Mujica, Vladimiro (Committee member) / Chan, Candace K. (Committee member) / Wang, Robert Y (Committee member) / Arizona State University (Publisher)
Created2015
Description
In the nano-regime many materials exhibit properties that are quite different from their bulk counterparts. These nano-properties have been shown to be useful in a wide range of applications with nanomaterials being used for catalysts, in energy production, as protective coatings, and in medical treatment. While there is no shortage of exciting and novel applications, the world of nanomaterials suffers from a lack of large scale manufacturing techniques. The current methods and equipment used for manufacturing nanomaterials are generally slow, expensive, potentially dangerous, and material specific. The research and widespread use of nanomaterials has undoubtedly been hindered by this lack of appropriate tooling. This work details the effort to create a novel nanomaterial synthesis and deposition platform capable of operating at industrial level rates and reliability.
The tool, referred to as Deppy, deposits material via hypersonic impaction, a two chamber process that takes advantage of compressible fluids operating in the choked flow regime to accelerate particles to up several thousand meters per second before they impact and stick to the substrate. This allows for the energetic separation of the synthesis and deposition processes while still behaving as a continuous flow reactor giving Deppy the unique ability to independently control the particle properties and the deposited film properties. While the ultimate goal is to design a tool capable of producing a broad range of nanomaterial films, this work will showcase Deppy's ability to produce silicon nano-particle films as a proof of concept.
By adjusting parameters in the upstream chamber the particle composition was varied from completely amorphous to highly crystalline as confirmed by Raman spectroscopy. By adjusting parameters in the downstream chamber significant variation of the film's density was achieved. Further it was shown that the system is capable of making these adjustments in each chamber without affecting the operation of the other.
The tool, referred to as Deppy, deposits material via hypersonic impaction, a two chamber process that takes advantage of compressible fluids operating in the choked flow regime to accelerate particles to up several thousand meters per second before they impact and stick to the substrate. This allows for the energetic separation of the synthesis and deposition processes while still behaving as a continuous flow reactor giving Deppy the unique ability to independently control the particle properties and the deposited film properties. While the ultimate goal is to design a tool capable of producing a broad range of nanomaterial films, this work will showcase Deppy's ability to produce silicon nano-particle films as a proof of concept.
By adjusting parameters in the upstream chamber the particle composition was varied from completely amorphous to highly crystalline as confirmed by Raman spectroscopy. By adjusting parameters in the downstream chamber significant variation of the film's density was achieved. Further it was shown that the system is capable of making these adjustments in each chamber without affecting the operation of the other.
ContributorsFirth, Peter (Author) / Holman, Zachary C (Thesis advisor) / Kozicki, Michael (Committee member) / Goryll, Michael (Committee member) / Arizona State University (Publisher)
Created2015
Description
Semiconductor nanostructures are promising building blocks for light management in thin silicon solar cells and silicon-based tandems due their tunable optical properties. The present dissertation is organized along three main research areas: (1) characterization and modeling of III-V nanowires as active elements of solar cell tandems, (2) modeling of silicon nanopillars for reduced optical losses in ultra-thin silicon solar cells, and (3) characterization and modeling of nanoparticle-based optical coatings for light management.
First, the recombination mechanisms in polytype GaAs nanowires are studied through photoluminescence measurements coupled with rate equation analysis. When photons are absorbed in polytype nanowires, electrons and holes quickly thermalize to the band-edges of the zinc-blende and wurtzite phases, recombining indirectly in space across the type-II offset. Using a rate equation model, different configurations of polytype defects along the nanowire are investigated, which compare well with experiment considering spatially indirect recombination between different polytypes, and defect-related recombination due to twin planes and other defects. The presented analysis is a path towards predicting the performance of nanowire-based solar cells.
Following this topic, the optical mechanisms in silicon nanopillar arrays are investigated using full-wave optical simulations in comparison to measured reflectance data. The simulated electric field energy density profiles are used to elucidate the mechanisms contributing to the reduced front surface reflectance. Strong forward scattering and resonant absorption are observed for shorter- and longer- aspect ratio nanopillars, respectively, with the sub-wavelength periodicity causing additional diffraction. Their potential for light-trapping is investigated using full-wave optical simulation of an ultra-thin nanostructured substrate, where the conventional light-trapping limit is exceeded for near-bandgap wavelengths.
Finally, the correlation between the optical properties of silicon nanoparticle layers to their respective pore size distributions is investigated using optical and structural characterization coupled with full-wave optical simulation. The presence of
scattering is experimentally correlated to wider pore size distributions obtained from nitrogen adsorption measurements. The correlation is validated with optical simulation of random and clustered structures, with the latter approximating experimental. Reduced structural inhomogeneity in low-refractive-index nanoparticle inter-layers at the metal/semiconductor interface improves their performance as back reflectors, while reducing parasitic absorption in the metal.
First, the recombination mechanisms in polytype GaAs nanowires are studied through photoluminescence measurements coupled with rate equation analysis. When photons are absorbed in polytype nanowires, electrons and holes quickly thermalize to the band-edges of the zinc-blende and wurtzite phases, recombining indirectly in space across the type-II offset. Using a rate equation model, different configurations of polytype defects along the nanowire are investigated, which compare well with experiment considering spatially indirect recombination between different polytypes, and defect-related recombination due to twin planes and other defects. The presented analysis is a path towards predicting the performance of nanowire-based solar cells.
Following this topic, the optical mechanisms in silicon nanopillar arrays are investigated using full-wave optical simulations in comparison to measured reflectance data. The simulated electric field energy density profiles are used to elucidate the mechanisms contributing to the reduced front surface reflectance. Strong forward scattering and resonant absorption are observed for shorter- and longer- aspect ratio nanopillars, respectively, with the sub-wavelength periodicity causing additional diffraction. Their potential for light-trapping is investigated using full-wave optical simulation of an ultra-thin nanostructured substrate, where the conventional light-trapping limit is exceeded for near-bandgap wavelengths.
Finally, the correlation between the optical properties of silicon nanoparticle layers to their respective pore size distributions is investigated using optical and structural characterization coupled with full-wave optical simulation. The presence of
scattering is experimentally correlated to wider pore size distributions obtained from nitrogen adsorption measurements. The correlation is validated with optical simulation of random and clustered structures, with the latter approximating experimental. Reduced structural inhomogeneity in low-refractive-index nanoparticle inter-layers at the metal/semiconductor interface improves their performance as back reflectors, while reducing parasitic absorption in the metal.
ContributorsVulic, Natasa (Author) / Goodnick, Stephen M (Thesis advisor) / Honsberg, C. (Christiana B.) (Committee member) / Holman, Zachary C (Committee member) / Smith, David J. (Committee member) / Arizona State University (Publisher)
Created2019
Description
High photoluminescence (PL) quantum yields reported from amorphous (a-Si) and crystalline (c-Si) nanoparticles have opened up lots of possibilities for use of silicon in optical applications such as light emitting diodes (LEDs), photonics and solar cells with added processing and cost benefits. However, the PL response and the mechanisms behind it are highly dependent on the matrix in which the nanoparticles are grown and on the growth method. While, the bottom-up approach for deposition of free standing nanoparticles seem to be perfectly suited for large area deposition for LED and solar cell applications, the dominant growth techniques (laser ablation and pyrolysis) have been shown to suffer from limitations in control over size distribution of nanoparticles and the requirement of equipment capable of withstanding high temperature. This led to the exploration of plasma based synthesis methods in this work.
Towards this effort, the development and automation of a novel tool “Anny” for synthesis of silicon nanoparticles using non-thermal plasma chamber is reported. These nanoparticles are then accelerated due to choked flow through a nozzle leading to substrate independent deposition. The nanoparticle properties are characterized against precursor gas flow rates and RF power to identify the optimum growth conditions for a stable, continuous deposition. It is found that amorphous nanoparticles offer a wide variety of chamber conditions for growth with a high throughput, stable plasma for continuous, long term operations.
The quantum confinement model for crystalline and spatial confinement models for amorphous nanoparticles in our size regime (6-8nm) are suggested for free standing nanoparticles and we report a high PL output from well passivated amorphous nanoparticles.
The PL output and its dependence on stability of surface hydrogen passivation is explored using Fourier Transform Infrared spectroscopy (FTIR). It is shown that the amorphous nanoparticles have a better and more stable passivation compared to crystalline nanoparticles grown under similar conditions. Hence, we show a-Si nanoparticles as exciting alternatives for optical applications to c-Si nanoparticles.
Towards this effort, the development and automation of a novel tool “Anny” for synthesis of silicon nanoparticles using non-thermal plasma chamber is reported. These nanoparticles are then accelerated due to choked flow through a nozzle leading to substrate independent deposition. The nanoparticle properties are characterized against precursor gas flow rates and RF power to identify the optimum growth conditions for a stable, continuous deposition. It is found that amorphous nanoparticles offer a wide variety of chamber conditions for growth with a high throughput, stable plasma for continuous, long term operations.
The quantum confinement model for crystalline and spatial confinement models for amorphous nanoparticles in our size regime (6-8nm) are suggested for free standing nanoparticles and we report a high PL output from well passivated amorphous nanoparticles.
The PL output and its dependence on stability of surface hydrogen passivation is explored using Fourier Transform Infrared spectroscopy (FTIR). It is shown that the amorphous nanoparticles have a better and more stable passivation compared to crystalline nanoparticles grown under similar conditions. Hence, we show a-Si nanoparticles as exciting alternatives for optical applications to c-Si nanoparticles.
ContributorsGarg, Prateek (Author) / Holman, Zachary C (Thesis advisor) / Zhang, Yong H (Committee member) / Bertoni, Mariana (Committee member) / Arizona State University (Publisher)
Created2015
Description
Nanomaterials exhibit unique properties that are substantially different from their bulk counterparts. These unique properties have gained recognition and application for various fields and products including sensors, displays, photovoltaics, and energy storage devices. Aerosol Deposition (AD) is a relatively new method for depositing nanomaterials. AD utilizes a nozzle to accelerate the nanomaterial into a deposition chamber under near-vacuum conditions towards a substrate with which the nanomaterial collides and adheres. Traditional methods for designing nozzles at atmospheric conditions are not well suited for nozzle design for AD methods.
Computational Fluid Dynamics (CFD) software, ANSYS Fluent, is utilized to simulate two-phase flows consisting of a carrier gas (Helium) and silicon nanoparticles. The Cunningham Correction Factor is used to account for non-continuous effects at the relatively low pressures utilized in AD.
The nozzle, referred to herein as a boundary layer compensation (BLC) nozzle, comprises an area-ratio which is larger than traditionally designed nozzles to compensate for the thick boundary layer which forms within the viscosity-affected carrier gas flow. As a result, nanoparticles impact the substrate at velocities up to 300 times faster than the baseline nozzle.
Computational Fluid Dynamics (CFD) software, ANSYS Fluent, is utilized to simulate two-phase flows consisting of a carrier gas (Helium) and silicon nanoparticles. The Cunningham Correction Factor is used to account for non-continuous effects at the relatively low pressures utilized in AD.
The nozzle, referred to herein as a boundary layer compensation (BLC) nozzle, comprises an area-ratio which is larger than traditionally designed nozzles to compensate for the thick boundary layer which forms within the viscosity-affected carrier gas flow. As a result, nanoparticles impact the substrate at velocities up to 300 times faster than the baseline nozzle.
ContributorsHoffman, Trent (Author) / Holman, Zachary C (Thesis advisor) / Herrmann, Marcus (Committee member) / Kozicki, Michael (Committee member) / Arizona State University (Publisher)
Created2017
Description
Neurological disorders are difficult to treat with current drug delivery methods due to their inefficiency and the lack of knowledge of the mechanisms behind drug delivery across the blood brain barrier (BBB). Nanoparticles (NPs) are a promising drug delivery method due to their biocompatibility and ability to be modified by cell penetrating peptides, such as transactivating transciptor (TAT) peptide, which has been shown to increase efficiency of delivery. There are multiple proposed mechanisms of TAT-mediated delivery that also have size restrictions on the molecules that can undergo each BBB crossing mechanism. The effect of nanoparticle size on TAT-mediated delivery in vivo is an important aspect to research in order to better understand the delivery mechanisms and to create more efficient NPs. NPs called FluoSpheres are used because they come in defined diameters unlike polymeric NPs that have a broad distribution of diameters. Both modified and unmodified 100nm and 200nm NPs were able to bypass the BBB and were seen in the brain, spinal cord, liver, and spleen using confocal microscopy and a biodistribution study. Statistically significant differences in delivery rate of the different sized NPs or between TAT-modified and unmodified NPs were not found. Therefore in future work a larger range of diameter size will be evaluated. Also the unmodified NPs will be conjugated with scrambled peptide to ensure that both unmodified and TAT-modified NPs are prepared in identical fashion to better understand the role of size on TAT targeting. Although all the NPs were able to bypass the BBB, future work will hopefully provide a better representation of how NP size effects the rate of TAT-mediated delivery to the CNS.
ContributorsCeton, Ricki Ronea (Author) / Stabenfeldt, Sarah (Thesis director) / Sirianni, Rachael (Committee member) / Harrington Bioengineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Water-soluble, adenosine triphosphate (ATP)-stabilized palladium nanoparticles have been synthesized by reduction of palladium salt in the presence of excess ATP. They have been characterized by electron microscopy, energy dispersive X-ray spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, and X-ray diffraction in order to determine particle size, shape, composition and crystal structure. The particles were then subsequently attached to a glassy carbon electrode (GCE) in order to explore their electrochemical properties with regard to hydrogen insertion in 1 M sodium hydroxide. The particles were found to be in the size range 2.5 to 4 nm with good size dispersion. The ATP capping ligand allowed the particles to be air-stable and re-dissolved without agglomeration. It was found that the NPs could be firmly attached to the working electrode via cycling the voltage repeatedly in a NP/phosphate solution. Further electrochemical experiments were conducted to investigate the adsorption and absorption of hydrogen in the NPs in 1 M sodium hydroxide. Results for cyclic voltammetry experiments were consistent with those for nanostructured and thin-film palladium in basic solution. Absorbed hydrogen content was analyzed as a function of potential. The maximum hydrogen:Pd ratio was found to be ~0.7, close the theoretical maximum value for β phase palladium hydride.
ContributorsLamb, Timothy (Author) / Buttry, Daniel A (Thesis advisor) / Yarger, Jeffery (Committee member) / Ros, Alexandra (Committee member) / Arizona State University (Publisher)
Created2013