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Description
Biogenic silica nanostructures, derived from diatoms, possess highly ordered porous hierarchical nanostructures and afford flexibility in design in large part due to the availability of a great variety of shapes, sizes, and symmetries. These advantages have been exploited for study of transport phenomena of ions and molecules towards the goal

Biogenic silica nanostructures, derived from diatoms, possess highly ordered porous hierarchical nanostructures and afford flexibility in design in large part due to the availability of a great variety of shapes, sizes, and symmetries. These advantages have been exploited for study of transport phenomena of ions and molecules towards the goal of developing ultrasensitive and selective filters and biosensors. Diatom frustules give researchers many inspiration and ideas for the design and production of novel nanostructured materials. In this doctoral research will focus on the following three aspects of biogenic silica: 1) Using diatom frustule as protein sensor. 2) Using diatom nanostructures as template to fabricate nano metal materials. 3) Using diatom nanostructures to fabricate hybrid platform.

Nanoscale confinement biogenetic silica template-based electrical biosensor assay offers the user the ability to detect and quantify the biomolecules. Diatoms have been demonstrated as part of a sensor. The sensor works on the principle of electrochemical impedance spectroscopy. When specific protein biomarkers from a test sample bind to corresponding antibodies conjugated to the surface of the gold surface at the base of each nanowell, a perturbation of electrical double layer occurs resulting in a change in the impedance.

Diatoms are also a new source of inspiration for the design and fabrication of nanostructured materials. Template-directed deposition within cylindrical nanopores of a porous membrane represents an attractive and reproducible approach for preparing metal nanopatterns or nanorods of a variety of aspect ratios. The nanopatterns fabricated from diatom have the potential of the metal-enhanced fluorescence to detect dye-conjugated molecules.

Another approach presents a platform integrating biogenic silica nanostructures with micromachined silicon substrates in a micro
ano hybrid device. In this study, one can take advantages of the unique properties of a marine diatom that exhibits nanopores on the order of 40 nm in diameter and a hierarchical structure. This device can be used to several applications, such as nano particles separation and detection. This platform is also a good substrate to study cell growth that one can observe the reaction of cell growing on the nanostructure of frustule.
ContributorsLin, Kai-Chun (Author) / Ramakrishna, B.L. (Thesis advisor) / Goryll, Michael (Thesis advisor) / Dey, Sandwip (Committee member) / Prasad, Shalini (Committee member) / Arizona State University (Publisher)
Created2014
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Description
In the last few years, significant advances in nanofabrication have allowed tailoring of structures and materials at a molecular level enabling nanofabrication with precise control of dimensions and organization at molecular length scales, a development leading to significant advances in nanoscale systems. Although, the direction of progress seems to follow

In the last few years, significant advances in nanofabrication have allowed tailoring of structures and materials at a molecular level enabling nanofabrication with precise control of dimensions and organization at molecular length scales, a development leading to significant advances in nanoscale systems. Although, the direction of progress seems to follow the path of microelectronics, the fundamental physics in a nanoscale system changes more rapidly compared to microelectronics, as the size scale is decreased. The changes in length, area, and volume ratios due to reduction in size alter the relative influence of various physical effects determining the overall operation of a system in unexpected ways. One such category of nanofluidic structures demonstrating unique ionic and molecular transport characteristics are nanopores. Nanopores derive their unique transport characteristics from the electrostatic interaction of nanopore surface charge with aqueous ionic solutions. In this doctoral research cylindrical nanopores, in single and array configuration, were fabricated in silicon-on-insulator (SOI) using a combination of electron beam lithography (EBL) and reactive ion etching (RIE). The fabrication method presented is compatible with standard semiconductor foundries and allows fabrication of nanopores with desired geometries and precise dimensional control, providing near ideal and isolated physical modeling systems to study ion transport at the nanometer level. Ion transport through nanopores was characterized by measuring ionic conductances of arrays of nanopores of various diameters for a wide range of concentration of aqueous hydrochloric acid (HCl) ionic solutions. Measured ionic conductances demonstrated two distinct regimes based on surface charge interactions at low ionic concentrations and nanopore geometry at high ionic concentrations. Field effect modulation of ion transport through nanopore arrays, in a fashion similar to semiconductor transistors, was also studied. Using ionic conductance measurements, it was shown that the concentration of ions in the nanopore volume was significantly changed when a gate voltage on nanopore arrays was applied, hence controlling their transport. Based on the ion transport results, single nanopores were used to demonstrate their application as nanoscale particle counters by using polystyrene nanobeads, monodispersed in aqueous HCl solutions of different molarities. Effects of field effect modulation on particle transition events were also demonstrated.
ContributorsJoshi, Punarvasu (Author) / Thornton, Trevor J (Thesis advisor) / Goryll, Michael (Thesis advisor) / Spanias, Andreas (Committee member) / Saraniti, Marco (Committee member) / Arizona State University (Publisher)
Created2011
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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

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.
ContributorsFirth, Peter (Author) / Holman, Zachary C (Thesis advisor) / Kozicki, Michael (Committee member) / Goryll, Michael (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Hydrogen is considered one of the most potential fuels due to its highest gravimetric energy density with no pollutant emission during the energy cycle. Among several techniques for hydrogen generation, the promising photoelectrochemical water oxidation is considered a long-term solar pathway by splitting water. The system contains a photoanode and

Hydrogen is considered one of the most potential fuels due to its highest gravimetric energy density with no pollutant emission during the energy cycle. Among several techniques for hydrogen generation, the promising photoelectrochemical water oxidation is considered a long-term solar pathway by splitting water. The system contains a photoanode and a cathode immersed in an aqueous electrolyte where charge separation takes place in the bulk of the semiconducting material on light absorption, leading to water oxidation/reduction at the surface of the photoelectrodes/cathode. It is imperative to develop materials that demonstrate high light absorption in the wide spectrum along with photoelectrochemical stability. N-type Monoclinic scheelite bismuth vanadate (BiVO4) is selected due to its incredible light absorption capabilities, direct bandgap (Eg ∼ 2.4-2.5 eV) and relatively better photoelectrochemical stability. However, BiVO4 encounters huge electron-hole recombination due to smaller diffusion lengths and positive conduction bands that cause slow charge dynamics and sluggish water oxidation kinetics. In order to improve the illustrated drawbacks, four strategies were discussed. Chapter 1 describe the fundamental understanding of photoelectrochemical cell and BiVO4. Chapter 2 illustrates details of the experimental procedure and state-of-the-art material characterization. Chapter 3 provide the impact of alkali metal placement in the crystal structure of BiVO4 systematically that exhibited ~20 times more performance than intrinsic BiVO4, almost complete bulk charge separation and enhancement in the diffusion length. Detailed characterization determined that the alkali metal getting placed in the interstitial void of BiVO4 lattice and multiple interbands formation enhanced the charge dynamics. Chapter 4 contains stoichiometric doping of Y3+ or Er3+ or Yb3+ at the Bi3+ site, leading to an extended absorption region, whereas non-stoichiometric W6+ doping at the V5+ site minimizes defects and increased charge carriers. To further enhance the performance, type-II heterojunction with WO3 along p-n junction with Fe:NiO enhance light absorption and charge dynamics close to the theoretical performance. Chapter 5 provides a comprehensive study of a uniquely developed sulfur modified Bi2O3 interface layer to facilitate charge dynamics and carrier lifetime improvement by effectively passivating the WO3/BiVO4 heterojunction interface. Finally, chapter 6 summarized the major findings, conclusion and outlook in developing BiVO4 as an efficient photoanode material.
ContributorsPrasad, Umesh (Author) / Kannan, Arunachala Mada (Thesis advisor) / Azeredo, Bruno (Committee member) / Chan, Candace (Committee member) / Segura, Sergio Garcia (Committee member) / Arizona State University (Publisher)
Created2021
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Description
In recent years, the scientific community around the synthesis and processing of nanoporous metals is striving to integrate them into powder metallurgy processes such as additive manufacturing since it has a potential to fabricate 3D hierarchical high surface area electrodes for energy applications. Recent research in dealloying – a versatile

In recent years, the scientific community around the synthesis and processing of nanoporous metals is striving to integrate them into powder metallurgy processes such as additive manufacturing since it has a potential to fabricate 3D hierarchical high surface area electrodes for energy applications. Recent research in dealloying – a versatile method for synthesizing nanoporous metals – emphasized the need in understanding its process-structure relationships to independently control the relative density, ligament and pore sizes with good process reproducibly. In this dissertation, a new understanding of the dealloying process is presented for synthesizing (i) nanoporous gold thin-films and (ii) nanoporous Cu spherical powders with an emphasis on understanding variability in their process-structure relationships and process scalability. First, this work sheds the light on the nature of the dealloying front and its percolation along the grain boundaries in nanocrystalline gold-silver thin films by studying the early stages of ligament nucleation. Additionally, this work analyses its variability by investigating new process variables such as (i) equilibration time and (ii) precursor aging and their impacts in achieving process reproducibility. The correlation of relative density with ligament size is contextualized with state-of-the-art data mining research. Second, this work provides a new methodology for large scale production of nanoporous Cu powder and demonstrates its integration with powder casting to fabricate porous conductive electrode. By understanding the influence of etching solution concentration and titration methodology on the structure and composition of nanoporous Cu, it was possible to fabricate precipitate-free powders at high throughputs. Further, the nature of oxygen incorporation into porous Cu powder was studied as a function of surface-to-volume ratio of powder in atmospheric conditions. To consolidate powders into parts via open-die casting, this work harvests Ostwald Ripening phenomena associated with thermal coarsening in nanoporous metals to weld them at low temperatures (approximately one-third of its melting temperature). This work represents a major step towards the integration of nanoporous Cu feedstocks into additive manufacturing.
ContributorsNiauzorau, Stanislau (Author) / Azeredo, Bruno (Thesis advisor) / Sieradzki, Karl (Committee member) / Song, Kenan (Committee member) / Chawla, Nikhilesh (Committee member) / Arizona State University (Publisher)
Created2022
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Description
The objective of this dissertation is to study the optical and radiative properties of inhomogeneous metallic structures. In the ongoing search for new materials with tunable optical characteristics, porous metals and nanowires provides an extensive design space to engineer its optical response based on the morphology-dependent phenomena.This dissertation firstly discusses

The objective of this dissertation is to study the optical and radiative properties of inhomogeneous metallic structures. In the ongoing search for new materials with tunable optical characteristics, porous metals and nanowires provides an extensive design space to engineer its optical response based on the morphology-dependent phenomena.This dissertation firstly discusses the use of aluminum nanopillar array on a quartz substrate as spectrally selective optical filter with narrowband transmission for thermophotovoltaic systems. The narrow-band transmission enhancement is attributed to the magnetic polariton resonance between neighboring aluminum nanopillars. Tuning of the resonance wavelengths for selective filters was achieved by changing the nanopillar geometry. It concludes by showing improved efficiency of Gallium-Antimonide thermophotovoltaic system by coupling the designed filter with the cell. Next, isotropic nanoporous gold films are investigated for applications in energy conversion and three-dimensional laser printing. The fabricated nanoporous gold samples are characterized by scanning electron microscopy, and the spectral hemispherical reflectance is measured with an integrating sphere. The effective isotropic optical constants of nanoporous gold with varying pore volume fraction are modeled using the Bruggeman effective medium theory. Nanoporous gold are metastable and to understand its temperature dependent optical properties, a lab-scale fiber-based optical spectrometer setup is developed to characterize the in-situ specular reflectance of nanoporous gold thin films at temperatures ranging from 25 to 500 oC. The in-situ and the ex-situ measurements suggest that the ii specular, diffuse, and hemispherical reflectance varies as a function of temperature due to the morphology (ligament diameter) change observed. The dissertation continues with modeling and measurements of the radiative properties of porous powders. The study shows the enhanced absorption by mixing porous copper to copper powder. This is important from the viewpoint of scalability to get end products such as sheets and tubes with the requirement of high absorptance that can be produced through three-dimensional printing. Finally, the dissertation concludes with recommendations on the methods to fabricate the suggested optical filters to improve thermophotovoltaic system efficiencies. The results presented in this dissertation will facilitate not only the manufacturing of materials but also the promising applications in solar thermal energy and optical systems.
ContributorsRamesh, Rajagopalan (Author) / Wang, Liping (Thesis advisor) / Azeredo, Bruno (Thesis advisor) / Phelan, Patrick (Committee member) / Yu, Hongbin (Committee member) / Rykaczewski, Konrad (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Solar energy has become one of the most popular renewable energy in human’s life because of its abundance and environment friendliness. To achieve high solar energy conversion efficiency, it usually requires surfaces to absorb selectivity within one spectral range of interest and reflect strongly over the rest of the spectrum.

Solar energy has become one of the most popular renewable energy in human’s life because of its abundance and environment friendliness. To achieve high solar energy conversion efficiency, it usually requires surfaces to absorb selectivity within one spectral range of interest and reflect strongly over the rest of the spectrum. An economic method is always desired to fabricate spectrally selective surfaces with improved energy conversion efficiency. Colloidal lithography is a recently emerged way of nanofabrication, which has advantages of low-cost and easy operation.

In this thesis, aluminum metasurface structures are proposed based on colloidal lithography method. High Frequency Structure Simulator is used to numerically study optical properties and design the aluminum metasurfaces with selective absorption. Simulation results show that proposed aluminum metasurface structure on aluminum oxide thin film and aluminum substrate has a major reflectance dip, whose wavelength is tunable within the near-infrared and visible spectrum with metasurface size. As the metasurface is opaque due to aluminum film, it indicates strong wavelength-selective optical absorption, which is due to the magnetic resonance between the top metasurface and bottom Al film within the aluminum oxide layer.

The proposed sample is fabricated based on colloidal lithography method. Monolayer polystyrene particles of 500 nm are successfully prepared and transferred onto silicon substrate. Scanning electron microscope is used to check the surface topography. Aluminum thin film with 20-nm or 50-nm thickness is then deposited on the sample. After monolayer particles are removed, optical properties of samples are measured by micro-scale optical reflectance and transmittance microscope. Measured and simulated reflectance of these samples do not have frequency selective properties and is not sensitive to defects. The next step is to fabricate the Al metasurface on Al_2 O_3 and Al films to experimentally demonstrate the selective absorption predicted from the numerical simulation.
ContributorsGuan, Chuyun (Author) / Wang, Liping (Thesis advisor) / Azeredo, Bruno (Committee member) / Wang, Robert (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Design and development of optical sensors for the detection of specific targets, e.g., ions, molecules, proteins, light polarizations, is one of the most essential research topics in the field of nanophotonics that paves the way for significant technological progressions in chemical and biomarker detections, polarimetric imaging and other sensing related

Design and development of optical sensors for the detection of specific targets, e.g., ions, molecules, proteins, light polarizations, is one of the most essential research topics in the field of nanophotonics that paves the way for significant technological progressions in chemical and biomarker detections, polarimetric imaging and other sensing related applications. In this dissertation, three designs of optical sensors based on plasmonic and dielectric nanostructures are thoroughly studied for the applications in chemicals, biomarkers and light polarization detection. Firstly, a plasmonic nanoantenna structure, which is composed of complementary anisotropic nanobars and nanoapertures featuring strong localized electric field enhancement at nanogap region, demonstrates both high sensitivity refractometric detection and specific infrared fingerprint detection for chemical sensing. Specifically, the sensor can probe monolayer thin octadecanethiol with a large resonance shift of 136 nm and all four characteristic infrared fingerprints detected. Secondly, a bio-inspired double-layered metasurface structure, which is made of dielectric nanoantenna and plasmonic nanogratings, mediates strong optical chirality and enables the selection of circularly polarized light handedness (extinction ratio ≥ 35) with high transmission efficiency (≥ 80%). The structure can be further integrated on-chip with linear polarizers for highly precise full-Stokes polarimetric detection with minimum transmission loss. Lastly, a gold nanoparticle based colorimetric assay is designed for high sensitivity, specificity and rapid detection of infectious diseases related biomarkers. The complete design workflows from critical reagents productions, rapid detection protocol to assay characterizations are extensively studied. Detection of Ebola virus disease biomarker, secreted glycoprotein, within 20 minutes are experimentally demonstrated with limit of detection down to ~40 pM and a broad detection range from 10 pM to 1 µM. The designs of the three sensors propose novel and versatile design concepts for the development of sensing devices in the detection of chemicals, biomarkers and light polarization. The efforts in the fundamental theoretical analysis and experimental demonstrations are expected to provide valuable contents to the optical sensor researches and to potentially inspire new sensor designs for broad sensing applications in the future.
ContributorsChen, Xiahui (Author) / Wang, Chao (Thesis advisor) / Zhao, Yuji (Committee member) / Wang, Liping (Committee member) / Goryll, Michael (Committee member) / Arizona State University (Publisher)
Created2021