Matching Items (50)

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Wet NanoBonding™: Catalyzing Molecular Cross-Bridges and Interphases Between Nanoscopically Smoothed Si-Based Surfaces and Tailoring Surface Energy Components

Description

Dry and steam NanoBonding™ are conceived and researched to bond Si-based surfaces, via nucleation and growth of a two-dimensional SiOxHy or hydrated SiOxHy interphase connecting surfaces at the nanoscale

Dry and steam NanoBonding™ are conceived and researched to bond Si-based surfaces, via nucleation and growth of a two-dimensional SiOxHy or hydrated SiOxHy interphase connecting surfaces at the nanoscale across macroscopic domains. The motivation is to create strong, long lasting, hermetically bonded sensors with their electronics for the development of an artificial pancreas and to bond solar cells to glass panels for robust photovoltaic technology. The first step in NanoBonding™ is to synthesize smooth surfaces with 20 nm wide atomic terraces via a precursor phase, ß-cSiO2 on Si(100) and oxygen-deficient SiOx on the silica using the Herbots-Atluri process and Entrepix’s spin etching. Smooth precursor phases act as geometric and chemical template to nucleate and grow macroscopic contacting domains where cross bridging occurs via arrays of molecular strands in the hydrated SiOxHy interphase. Steam pressurization is found to catalyze NanoBonding™ consistently, eliminating the need for direct mechanical compression that limits the size and shape of wafers to be bonded in turn, reducing the cost of processing. Total surface energy measurements via 3 Liquids Contact Angle Analysis (3L CAA) enables accurate quantitative analysis of the total surface energy and each of its components. 3L CAA at each step in the process shows that surface energy drops to 42.4 ± 0.6 mJ/m2 from 57.5 ± 1.4 mJ/m2 after the Herbots-Atluri clean of an “As Received” wafer. 3L CAA after steam pressurization Nanobonding™ shows almost complete elimination from 13.8 mJ/m2 ± 1.0 to 0.002 ±- 0.0002 mJ/m2 in the contribution of acceptors to the total free surface energy, and an increase from 0.2 ± .03 to 23.8± 1.6 mJ/m2 in the contribution of donors. This is consistent with an increase in hydroxylation of the ß-cSiO2 surface as a consistent precursor phase for cross-bridging. This research optimizes the use of glycerin, water, and α-bromo-naphtalene in the use of 3L CAA to effectively quantify the components of total free surface energy which helps to better understand the most consistent method for NanoBonding™.

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Created

Date Created
  • 2013-05

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Characterization of Liquid-Phase Exfoliated Two-Dimensional Nanomaterials Derived from Non-van der Waals Solids

Description

Liquid-phase exfoliation (LPE) is a straightforward and scalable method of producing two-dimensional nanomaterials. The LPE process has typical been applied to layered van der Waals (vdW) solids, such as graphite

Liquid-phase exfoliation (LPE) is a straightforward and scalable method of producing two-dimensional nanomaterials. The LPE process has typical been applied to layered van der Waals (vdW) solids, such as graphite and transition metal dichalcogenides, which have layers held together by weak van der Waals interactions. However, recent research has shown that solids with stronger bonds and non-layered structures can be converted to solution-stabilized nanosheets via LPE, some of which have shown to have interesting optical, magnetic, and photocatalytic properties. In this work, two classes of non-vdW solids – hexagonal metal diborides and boron carbide – are investigated for their morphological features, their chemical and crystallographic compositions, and their solvent preference for exfoliation. Spectroscopic and microscopic techniques are used to verify the composition and crystal structure of metal diboride nanosheets. Their application as mechanical fillers is demonstrated by incorporation into polymer nanocomposite films of polyvinyl alcohol and by successful integration into liquid photocurable 3D printing resins. Application of Hansen solubility theory to two metal diboride compositions enables extrapolation of their affinities for certain solvents and is also used to find solvent blends suitable for the nanosheets. Boron carbide nanosheets are examined for their size and thickness and their exfoliation planes are computationally analyzed and experimentally investigated using high-resolution transmission electron microscopy. The resulting analyses indicate that the exfoliation of boron carbide leads to multiple observed exfoliation planes upon LPE processing. Overall, these studies provide insight into the production and applications of LPE-produced nanosheets derived from non-vdW solids and suggest their potential application as mechanical fillers in polymer nanocomposites.

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Date Created
  • 2020

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Static behavior of chalcogenide based programmable metallization cells

Description

Nonvolatile memory (NVM) technologies have been an integral part of electronic systems for the past 30 years. The ideal non-volatile memory have minimal physical size, energy usage, and cost while

Nonvolatile memory (NVM) technologies have been an integral part of electronic systems for the past 30 years. The ideal non-volatile memory have minimal physical size, energy usage, and cost while having maximal speed, capacity, retention time, and radiation hardness. A promising candidate for next-generation memory is ion-conducting bridging RAM which is referred to as programmable metallization cell (PMC), conductive bridge RAM (CBRAM), or electrochemical metallization memory (ECM), which is likely to surpass flash memory in all the ideal memory characteristics. A comprehensive physics-based model is needed to completely understand PMC operation and assist in design optimization.

To advance the PMC modeling effort, this thesis presents a precise physical model parameterizing materials associated with both ion-rich and ion-poor layers of the PMC's solid electrolyte, so that captures the static electrical behavior of the PMC in both its low-resistance on-state (LRS) and high resistance off-state (HRS). The experimental data is measured from a chalcogenide glass PMC designed and manufactured at ASU. The static on- and off-state resistance of a PMC device composed of a layered (Ag-rich/Ag-poor) Ge30Se70 ChG film is characterized and modeled using three dimensional simulation code written in Silvaco Atlas finite element analysis software. Calibrating the model to experimental data enables the extraction of device parameters such as material bandgaps, workfunctions, density of states, carrier mobilities, dielectric constants, and affinities.

The sensitivity of our modeled PMC to the variation of its prominent achieved material parameters is examined on the HRS and LRS impedance behavior.

The obtained accurate set of material parameters for both Ag-rich and Ag-poor ChG systems and process variation verification on electrical characteristics enables greater fidelity in PMC device simulation, which significantly enhances our ability to understand the underlying physics of ChG-based resistive switching memory.

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Created

Date Created
  • 2014

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Photoluminescence enhancement of Ge quantum dots by exploiting the localized surface plasmon of epitaxial Ag islands

Description

This dissertation presents research findings regarding the exploitation of localized surface plasmon (LSP) of epitaxial Ag islands as a means to enhance the photoluminescence (PL) of Germanium (Ge) quantum dots

This dissertation presents research findings regarding the exploitation of localized surface plasmon (LSP) of epitaxial Ag islands as a means to enhance the photoluminescence (PL) of Germanium (Ge) quantum dots (QDs). The first step of this project was to investigate the growth of Ag islands on Si(100). Two distinct families of Ag islands have been observed. “Big islands” are clearly faceted and have basal dimensions in the few hundred nm to μm range with a variety of basal shapes. “Small islands” are not clearly faceted and have basal diameters in the 10s of nm range. Big islands form via a nucleation and growth mechanism, and small islands form via precipitation of Ag contained in a planar layer between the big islands that is thicker than the Stranski-Krastanov layer existing at room-temperature.

The pseudodielectric functions of epitaxial Ag islands on Si(100) substrates were investigated with spectroscopic ellipsometry. Comparing the experimental pseudodielectric functions obtained for Si with and without Ag islands clearly identifies a plasmon mode with its dipole moment perpendicular to the surface. This observation is confirmed using a simulation based on the thin island film (TIF) theory. Another mode parallel to the surface may be identified by comparing the experimental pseudodielectric functions with the simulated ones from TIF theory. Additional results suggest that the LSP energy of Ag islands can be tuned from the ultra-violet to the infrared range by an amorphous Si (α-Si) cap layer.

Heterostructures were grown that incorporated Ge QDs, an epitaxial Si cap layer and Ag islands grown atop the Si cap layer. Optimum growth conditions for distinct Ge dot ensembles and Si cap layers were obtained. The density of Ag islands grown on the Si cap layer depends on its thickness. Factors contributing to this effect may include the average strain and Ge concentration on the surface of the Si cap layer.

The effects of the Ag LSP on the PL of Ge coherent domes were investigated for both α-Si capped and bare Ag islands. For samples with low-doped substrates, the LSPs reduce the Ge dot-related PL when the Si cap layer is below some critical thickness and have no effect on the PL when the Si cap layer is above the critical thickness. For samples grown on highly-doped wafers, the LSP of bare Ag islands enhanced the PL of Ge QDs by ~ 40%.

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Created

Date Created
  • 2015

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A computational and theoretical study of conductance in hydrogen-bonded molecular junctions

Description

This thesis is devoted to the theoretical and computational study of electron transport in molecular junctions where one or more hydrogen bonds are involved in the process. While electron transport

This thesis is devoted to the theoretical and computational study of electron transport in molecular junctions where one or more hydrogen bonds are involved in the process. While electron transport through covalent bonds has been extensively studied, in recent work the focus has been shifted towards hydrogen-bonded systems due to their ubiquitous presence in biological systems and their potential in forming nano- junctions between molecular electronic devices and biological systems.

This analysis allows us to significantly expand our comprehension of the experimentally observed result that the inclusion of hydrogen bonding in a molecular junc- tion significantly impacts its transport properties, a fact that has important implications for our understanding of transport through DNA, and nano-biological interfaces in general. In part of this work I have explored the implications of quasiresonant transport in short chains of weakly-bonded molecular junctions involving hydrogen bonds. I used theoretical and computational analysis to interpret recent experiments and explain the role of Fano resonances in the transmission properties of the junction.

In a different direction, I have undertaken the study of the transversal conduction through nucleotide chains that involve a variable number of different hydrogen bonds, e.g. NH···O, OH···O, and NH···N, which are the three most prevalent hydrogen bonds in biological systems and organic electronics. My effort here has fo- cused on the analysis of electronic descriptors that allow a simplified conceptual and computational understanding of transport properties. Specifically, I have expanded our previous work where the molecular polarizability was used as a conductance de- scriptor to include the possibility of atomic and bond partitions of the molecular polarizability. This is important because it affords an alternative molecular descrip- tion of conductance that is not based on the conventional view of molecular orbitals as transport channels. My findings suggest that the hydrogen-bond networks are crucial in understanding the conductance of these junctions.

A broader impact of this work pertains the fact that characterizing transport through hydrogen bonding networks may help in developing faster and cost-effective approaches to personalized medicine, to advance DNA sequencing and implantable electronics, and to progress in the design and application of new drugs.

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Created

Date Created
  • 2017

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Inorganic and Organic Photovoltaic Materials for Powering Electrochromic Systems

Description

ABSTRACT

Autonomous smart windows may be integrated with a stack of active components, such as electrochromic devices, to modulate the opacity/transparency by an applied voltage. Here, we describe the processing

ABSTRACT

Autonomous smart windows may be integrated with a stack of active components, such as electrochromic devices, to modulate the opacity/transparency by an applied voltage. Here, we describe the processing and performance of two classes of visibly-transparent photovoltaic materials, namely inorganic (ZnO thin film) and fully organic (PCDTBT:PC70BM), for integration with electrochromic stacks.

Sputtered ZnO (2% Mn) films on ITO, with transparency in the visible range, were used to fabricate metal-semiconductor (MS), metal-insulator-semiconductor (MIS), and p-i-n heterojunction devices, and their photovoltaic conversion under ultraviolet (UV) illumination was evaluated with and without oxygen plasma-treated surface electrodes (Au, Ag, Al, and Ti/Ag). The MS Schottky parameters were fitted against the generalized Bardeen model to obtain the density of interface states (Dit ≈ 8.0×1011 eV−1cm−2) and neutral level (Eo ≈ -5.2 eV). These devices exhibited photoconductive behavior at λ = 365 nm, and low-noise Ag-ZnO detectors exhibited responsivity (R) and photoconductive gain (G) of 1.93×10−4 A/W and 6.57×10−4, respectively. Confirmed via matched-pair analysis, post-metallization, oxygen plasma treatment of Ag and Ti/Ag electrodes resulted in increased Schottky barrier heights, which maximized with a 2 nm SiO2 electron blocking layer (EBL), coupled with the suppression of recombination at the metal/semiconductor interface and blocking of majority carriers. For interdigitated devices under monochromatic UV-C illumination, the open-circuit voltage (Voc) was 1.2 V and short circuit current density (Jsc), due to minority carrier tunneling, was 0.68 mA/cm2.

A fully organic bulk heterojunction photovoltaic device, composed of poly[N-9’-heptadecanyl-2,7-carbazole-alt-5,5-(4’,7’-di-2-thienyli2’,1’,3’-benzothiadiazole)]:phenyl-C71-butyric-acidmethyl (PCDTBT:PC70BM), with corresponding electron and hole transport layers, i.e., LiF with Al contact and conducting
on-conducting (nc) PEDOT:PSS (with ITO/PET or Ag nanowire/PDMS contacts; the illuminating side), respectively, was developed. The PCDTBT/PC70BM/PEDOT:PSS(nc)/ITO/PET stack exhibited the highest performance: power conversion efficiency (PCE) ≈ 3%, Voc = 0.9V, and Jsc ≈ 10-15 mA/cm2. These stacks exhibited high visible range transparency, and provided the requisite power for a switchable electrochromic stack having an inkjet-printed, optically-active layer of tungsten trioxide (WO3), peroxo-tungstic acid dihydrate, and titania (TiO2) nano-particle-based blend. The electrochromic stacks (i.e., PET/ITO/LiClO4/WO3 on ITO/PET and Ag nanowire/PDMS substrates) exhibited optical switching under external bias from the PV stack (or an electrical outlet), with 7 s coloration time, 8 s bleaching time, and 0.36-0.75 optical modulation at λ = 525 nm. The devices were paired using an Internet of Things controller that enabled wireless switching.

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Created

Date Created
  • 2018

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Broken ergodicity and 1

Description

Fluctuations with a power spectral density depending on frequency as $1/f^\alpha$ ($0<\alpha<2$) are found in a wide class of systems. The number of systems exhibiting $1/f$ noise means it has

Fluctuations with a power spectral density depending on frequency as $1/f^\alpha$ ($0<\alpha<2$) are found in a wide class of systems. The number of systems exhibiting $1/f$ noise means it has far-reaching practical implications; it also suggests a possibly universal explanation, or at least a set of shared properties. Given this diversity, there are numerous models of $1/f$ noise. In this dissertation, I summarize my research into models based on linking the characteristic times of fluctuations of a quantity to its multiplicity of states. With this condition satisfied, I show that a quantity will undergo $1/f$ fluctuations and exhibit associated properties, such as slow dynamics, divergence of time scales, and ergodicity breaking. I propose that multiplicity-dependent characteristic times come about when a system shares a constant, maximized amount of entropy with a finite bath. This may be the case when systems are imperfectly coupled to their thermal environment and the exchange of conserved quantities is mediated through their local environment. To demonstrate the effects of multiplicity-dependent characteristic times, I present numerical simulations of two models. The first consists of non-interacting spins in $0$-field coupled to an explicit finite bath. This model has the advantage of being degenerate, so that its multiplicity alone determines the dynamics. Fluctuations of the alignment of this model will be compared to voltage fluctuations across a mesoscopic metal-insulator-metal junction. The second model consists of classical, interacting Heisenberg spins with a dynamic constraint that slows fluctuations according to the multiplicity of the system's alignment. Fluctuations in one component of the alignment will be compared to the flux noise in superconducting quantum interference devices (SQUIDs). Finally, I will compare both of these models to each other and some of the most popular models of $1/f$ noise, including those based on a superposition of exponential relaxation processes and those based on power law renewal processes.

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Created

Date Created
  • 2018

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Detection and surface reactivity of engineered nanoparticles in water

Description

Engineered nanoparticles (NPs) pose risk potentials, if they exist in water systems at significant concentrations and if they remain reactive to cause toxicity. Three goals guided this study: (1)

Engineered nanoparticles (NPs) pose risk potentials, if they exist in water systems at significant concentrations and if they remain reactive to cause toxicity. Three goals guided this study: (1) establishing NP detecting methods with high sensitivity to tackle low concentration and small sizes, (2) achieving assays capable of measuring NP surface reactivity and identifying surface reaction mechanisms, and (3) understanding the impact of surface adsorption of ions on surface reactivity of NPs in water.

The size detection limit of single particle inductively coupled plasma spectrometry (spICP-MS) was determined for 40 elements, demonstrating the feasibility of spICP-MS to different NP species in water. The K-means Clustering Algorithm was used to process the spICP-MS signals, and achieved precise particle-noise differentiation and quantitative particle size resolution. A dry powder assay based on NP-catalyzed methylene blue (MB) reduction was developed to rapidly and sensitively detect metallic NPs in water by measuring their catalytic reactivity.

Four different wet-chemical-based NP surface reactivity assays were demonstrated: “borohydride reducing methylene blue (BHMB)”, “ferric reducing ability of nanoparticles (FRAN)”, “electron paramagnetic resonance detection of hydroxyl radical (EPR)”, and “UV-illuminated methylene blue degradation (UVMB)”. They gave different reactivity ranking among five NP species, because they targeted for different surface reactivity types (catalytic, redox and photo reactivity) via different reaction mechanisms. Kinetic modeling frameworks on the assay outcomes revealed two surface electron transfer schemes, namely the “sacrificial reducing” and the “electrode discharging”, and separated interfering side reactions from the intended surface reaction.

The application of NPs in chemical mechanical polishing (CMP) was investigated as an industrial case to understand NP surface transformation via adsorbing ions in water. Simulation of wastewater treatment showed CMP NPs were effectively removed (>90%) by lime softening at high pH and high calcium dosage, but 20-40% of them remained in water after biomass adsorption process. III/V ions (InIII, GaIII, and AsIII/V) derived from semiconductor materials showed adsorption potentials to common CMP NPs (SiO2, CeO2 and Al2O3), and a surface complexation model was developed to determine their intrinsic complexation constants for different NP species. The adsorption of AsIII and AsV ions onto CeO2 NPs mitigated the surface reactivity of CeO2 NPs suggested by the FRAN and EPR assays. The impact of the ion adsorption on the surface reactivity of CeO2 NPs was related to the redox state of Ce and As on the surface, but varied with ion species and surface reaction mechanisms.

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Created

Date Created
  • 2018

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Advanced Characterization of Aerogel Films Deposited via Aerosol Impaction-Driven Assembly

Description

A new nanoparticle deposition technique, Aerosol Impaction-Driven Assembly (AIDA), was extensively characterized for material structures and properties. Aerogel films can be deposited directly onto a substrate with AIDA without the

A new nanoparticle deposition technique, Aerosol Impaction-Driven Assembly (AIDA), was extensively characterized for material structures and properties. Aerogel films can be deposited directly onto a substrate with AIDA without the long aging and drying steps in the sol-gel method. Electron microscopy, pore size analysis, thermal conductivity, and optical measurements show the nanoparticle (NP) films to be similar to typical silica aerogel. Haze of nanoparticle films modeled as scattering sites correlates strongly with pore size distribution. Supporting evidence was obtained from particle sizes and aggregates using electron microscopy and small-angle X-ray scattering. NP films showed interlayers of higher porosity and large aggregates formed by tensile film stress.

To better understand film stress and NP adhesion, chemical bonding analyses were performed for samples annealed up to 900 °C. Analysis revealed that about 50% of the NP surfaces are functionalized by hydroxyl (-OH) groups, providing for hydrogen bonding. Ellipsometric porosimetry was used to further understand the mechanical properties by providing a measure of strain upon capillary pressure from filling pores. Upon annealing to 200 °C, the films lost water resulting in closer bonding of NPs and higher Young’s modulus. Upon further annealing up to 900 °C, the films lost hydroxyl bonds while gaining siloxane bonds, reducing Young’s modulus. The application of ellipsometric porosimetry to hydrophilic coatings brings into question the validity of pore size distribution calculations for materials that hold onto water molecules and result in generally smaller calculated pore sizes.

Doped hydrogenated microcrystalline silicon was grown on crystalline silicon NPs, as a test case of an application for NP films to reduce parasitic absorption in silicon heterojunction solar cells. Parasitic absorption of blue light could be reduced because microcrystalline silicon has a mix of direct and indirect bandgap, giving lower blue absorption than amorphous silicon. Using Ultraviolet Raman spectroscopy, the crystallinity of films as thin as 13 nm was determined rapidly (in 1 minute) and non-destructively. A mono-layer of nanocrystals was applied as seeds for p-doped microcrystalline silicon growth and resulted in higher crystallinity films. Applications of the method could be explored for other nanocrystalline materials.

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Date Created
  • 2020

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Characterization of Solution-processed Metal Chalcogenide Precursor, Thin Film, and Nanocomposite for Thermoelectricity

Description

Satisfying the ever-increasing demand for electricity while maintaining sustainability and eco-friendliness has become a key challenge for humanity. Around 70% of energy is rejected as heat from different sectors. Thermoelectric

Satisfying the ever-increasing demand for electricity while maintaining sustainability and eco-friendliness has become a key challenge for humanity. Around 70% of energy is rejected as heat from different sectors. Thermoelectric energy harvesting has immense potential to convert this heat into electricity in an environmentally friendly manner. However, low efficiency and high manufacturing costs inhibit the widespread application of thermoelectric devices. In this work, an inexpensive solution processing technique and a nanostructuring approach are utilized to create thermoelectric materials. Specifically, the solution-state and solid-state structure of a lead selenide (PbSe) precursor is characterized by different spectroscopic techniques. This precursor has shown promise for preparing thermoelectric lead selenide telluride (PbSexTe1-x) thin films. The precursor was prepared by reacting lead and diphenyl diselenide in different solvents. The characterization reveals the formation of a solvated lead(II) phenylselenolate complex which deepens the understanding of the formation of these precursors. Further, using slightly different chemistry, a low-temperature tin(II) selenide (SnSe) precursor was synthesized and identified as tin(IV) methylselenolate. The low transformation temperature makes it compatible with colloidal PbSe nanocrystals. The colloidal PbSe nanocrystals were chemically treated with a SnSe precursor and subjected to mild annealing to form conductive nanocomposites. Finally, the room temperature thermoelectric characterization of solution-processed PbSexTe1-x thin films is presented. This is followed by a setup development for temperature-dependent measurements and preliminary temperature-dependent measurements on PbSexTe1-x thin films.

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Created

Date Created
  • 2020