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Integration von Multi-Gate-Transistoren auf Basis einer 22 nm-TechnologieBaldauf, Tim 29 January 2014 (has links) (PDF)
Die kontinuierliche Skalierung der planaren MOSFETs war in den vergangenen 40 Jahren der Schlüssel, um die Bauelemente immer kleiner und leistungsfähiger zu gestalten. Hinzu kamen Techniken zur mechanischen Verspannung, Verfahren zur Kurzzeitausheilung, die in-situ-dotierte Epitaxie und neue Materialien, wie das High-k-Gateoxid in Verbindung mit Titannitrid als Gatemetall. Jedoch erschwerten Kurzkanaleffekte und eine zunehmende Streuung der elektrischen Eigenschaften die Verkleinerung der planaren Transistoren erheblich. Somit gelangten die planaren MOSFETs mit der aktuellen 28 nm-Technologie teilweise an die Grenzen ihrer Funktionalität. Diese Arbeit beschäftigt sich daher mit der Integration von Multi-Gate-Transistoren auf Basis einer 22 nm-Technologie, welche eine bessere Steuerfähigkeit des Gatekontaktes aufweisen und somit die Fortführung der Skalierung ermöglichen. Zudem standen die Anforderungen eines stabilen und kostengünstigen Herstellungsprozesses als Grundvoraussetzung zur Übernahme in die Volumenproduktion stets mit im Vordergrund. Die Simulationen der Tri-Gate-Transistoren stellten dabei den ersten Schritt hin zu einer Multi-Gate-Technologie dar. Ihre Prozessabfolge unterscheidet sich von den planaren Transistoren nur durch die Formierung der Finnen und bietet damit die Möglichkeit eines hybriden 22 nm-Prozesses. Am Beispiel der Tri-Gate-Transistoren wurden zudem die Auswirkungen der Kristallorientierung, der mechanischen Verspannung und der Überlagerungseffekte es elektrischen Feldes auf die Leistungsfähigkeit von Multi-Gate-Strukturen analysiert. Im nächsten Schritt wurden Transistoren mit vollständig verarmten Kanalgebieten untersucht. Sie weisen aufgrund einer niedrigen Kanaldotierung eine Volumeninversion, eine höhere Ladungsträgerbeweglichkeit und eine geringere Anfälligkeit gegenüber der zufälligen Dotierungsfluktuation auf, welche für leistungsfähige Multi-Gate-Transistoren entscheidende Kriterien sind. Zu den betrachteten Varianten zählen die planaren ultradünnen SOI-MOSFETs, die klassischen FinFETs mit schmalen hohen Finnen und die vertikalen Nanowire-Transistoren. Anschließend wurden die Vor- und Nachteile der verschiedenen Transistorstrukturen für eine mittel- bis langfristige industrielle Nutzung betrachtet. Dazu erfolgte eine Analyse der statistischen Schwankungen und eine Skalierung hin zur 14 nm-Technologie. Eine Zusammenfassung aller Ergebnisse und ein Ausblick auf die mögliche Übernahme der Konzepte in die Volumenproduktion schließen die Arbeit ab. / Within the past 40 years the continuous scaling of planar MOSFETs was key to shrink the devices and to improve their performance. Techniques like mechanical stressing, rapid thermal annealing and in-situ doped epitaxial growing as well as novel materials, such as high-k-gate-oxide in combination with titanium nitride as metal-gate, has been introduced. However, short-channel-effects and increased scattering of electrical proper-ties significantly complicate the scaling of planar transistors. Thus, the planar MOSFETs gradually reached their limits of functionality with the current 28 nm technology node. For that reason, this work focuses on integration of multi-gate transistors based on a 22 nm technology, which show an improved gate control and allow a continuous scaling. Furthermore, the requirements of a stable and cost-efficient process as decisive condition for mass fabrication were always taken into account. The simulations of the tri-gate transistors present the first step toward a multi-gate technology. The process sequence differs from the planar one solely by a fin formation and offers the possibility of a hybrid 22 nm process. Also, the impact of crystal orientation, mechanical stress and superposition of electrical fields on the efficiency of multi-gate structures were analyzed for the tri-gate transistors. In a second step transistors with fully depleted channel regions were studied. Due to low channel doping they are showing a volume inversion, a higher carrier mobility and a lower sensitivity to random doping fluctuations, which are essential criteria for powerful multi-gate transistors. Reviewed structure variants include planar ultra-thin-body-SOI-MOSFETs, classic FinFETs with a tall, narrow fins and vertical nanowire transistors. Then advantages and disadvantages of the considered transistor structures have been observed for a medium to long term industrial use. For this purpose, an analysis of statistical fluctuations and the scaling-down to 14 nm technology was carried out. A summary of all results and an outlook to the transfer of concepts into mass fabrication complete this work.
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Parametric studies of field-directed nanowire chaining for transparent electrodesAlsaif, Jehad 25 August 2017 (has links)
Transparent electrodes (TEs) have become important components of displays, touch
screens, and solar photovoltaic (PV) energy conversion devices. As electrodes, they
must be electrically conductive while being transparent. Transparent materials are
normally poor conductors and materials with high electrical conductivity, such as
metals, are typically not transparent. From the few candidate materials, indium
tin oxide (ITO) is currently the best available, but indium is an expensive material
and ITO cost has risen with increasing demand. Therefore, alternative materials
or methods are sought to encourage production needs of applications and help in
reducing their price. This thesis presents and discusses results of experimental work
for a method, field-directed chaining, to produce a TE device which is nanowire-based,
with a figure of merit FoM= 2.39 x10E-4
Ohm E-1, comparable to ITO but with potential
for far lower cost.
Using electric field-directed chaining, multiple parallel long chains of metal nanowires
are assembled on inexpensive transparent materials such as glass by field directed
nanowire chaining, using methods first demonstrated in our laboratory.
In this work, we have improved the fraction of functional chains, by tuning the
field/voltage, a key step in increasing the FoM and lowering the cost. The effect
of operating parameters on TE optical and electrical properties has been studied and identified as well. From experiments with twenty seven substrates, each with
a range of electric field and nanowire concentration, the highest light transmission
achieved is 78% and the lowest sheet resistance achieved is 100 Ohm/sq. Among all
the operating parameters, the electric field has the most significant influence on the
fraction of nanowire chains that are functional. In the operating range of electric field strength available to us, we observed a monotonic increase in the fraction of
functional nanowire chains. We found a counter-intuitive change in TE properties in
a sub-range of nanowire concentration, associated with a change in the structure of
chained patterns. / Graduate
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On the stability of carbon nanotube and titania nanowire based catalyst materials:from synthesis to applicationsRautio, A.-R. (Anne-Riikka) 08 March 2016 (has links)
Abstract
Degradation of the support and sintering of catalyst nanoparticles inherently leads to a loss of functionality of catalyst materials in converters and sensors. Malfunction in such devices may lead to serious economic and environmental damage. The quest for novel and sustainable catalyst materials with better durability is thus ongoing. In this thesis, one-dimensional nanomaterials such as carbon nanotubes and titanium dioxide nanowires are studied and compared to their conventional zero-dimensional counterparts in regard to their structural and functional stability. With the combination of several catalyst nanomaterials and supporting surfaces, aging properties of more than 70 different materials are assessed by the means of X-ray diffraction, transmission electron microscopy and energy-dispersive X-ray analyses. Although CNTs were shown to be thermally the most stable carbonaceous supports for metal nanoparticles, they are, similar to other carbon supports, more sensitive to high temperatures than metal oxide supports and can suffer deactivation by catalytic oxidation and gasification even at moderate temperatures. In addition, the irradiation of the samples with e-beams caused the most dramatic changes in CNT based materials, where nanosized deformities (voids, channels) were formed when either nanoparticles or defects were present. The prepared nanocompositions have been utilized successfully in three different applications including (i) synthesis of hydrogen from ethanol via a steam reforming reaction, (ii) hydrogenation of citral to form value added chemicals and (iii) the application of advanced electrode materials in electric double-layer capacitors. Both CNT and TiO₂ nanowire based nanomaterials were shown to outperform their conventional nano- and microparticle based counterparts in the studied catalytic reactions, i.e. in citral hydrogenation and steam reforming of ethanol, respectively. Furthermore, nanostructured CNTs obtained by catalytic partial oxidation of the material showed an increased specific surface area, which could be exploited in supercapacitor electrodes with enhanced specific capacitance. / Tiivistelmä
Katalyyttitukimateriaalin pilaantuminen ja katalyyttinanopartikkelien sintrautuminen johtavat siihen, että muuntajissa ja sensoreissa käytettävät katalyyttiset materiaalit eivät enää toimi, mikä voi aiheuttaa sekä vakavia taloudellisia haittoja että ympäristöhaittoja. Tämän vuoksi kehitetään uusia kestävämpiä katalyyttimateriaaleja. Tässä väitöskirjassa tutkittiin yksiulotteisia nanomateriaaleja, kuten hiilinanoputkia sekä titaanidioksidinanojohtimia ja verrattiin niiden rakenteellista ja toiminnallista stabiiliutta perinteisiin nollaulotteisiin vastineisiin. Erilaisten katalyyttinanomateriaalien ja tukimateriaalien yhdistelmien ikääntymistä arvioitiin röntgendiffraktion, läpäisyelektronimikroskopian ja energiadispersiivisen röntgenanalyysin avulla yli 70 erilaisesta näytteestä.
Vaikka hiilinanoputket osoittautuivat termisesti stabiileimmaksi hiilipohjaiseksi tukimateriaaliksi metallinanopartikkeleille, ne ovat kuten kaikki hiilimateriaalit, metallioksiditukimateriaaleja herkempiä korkeille lämpötiloille. Hiilinanoputkipohjaiset katalyytit voivat deaktivoitua katalyyttisen hapettumisen tai kaasuuntumisen vuoksi jo kohtalaisissa lämpötiloissa. Lisäksi elektronisäteellä säteilytetyt nanopartikkelit tai pintavirheitä sisältävät hiilinanoputkipohjaiset katalyytit olivat tutkituista nanomateriaaleista herkimpiä muodostamaan nanorakenteita (koloja, kanavia).
Valmistettuja nanokomposiitteja käytettiin onnistuneesti kolmessa eri sovelluksessa: i) vedyn valmistuksessa etanolista höyryreformointireaktiolla, ii) hienokemikaalien valmistuksessa sitraalin hydrauksella sekä iii) elektrodimateriaalina EDLC-kondensaattorissa. Sekä hiilinanoputki- sekä TiO₂-nanojohdinpohjaiset nanomateriaalit toimivat testatuissa katalyyttisissa reaktioissa (etanolin reformointi sekä sitraalin hydraus) paremmin kuin niiden perinteiset vastineet. Lisäksi superkondensaattorin ominaiskapasitanssia onnistuttiin nostamaan lisäämällä hiilinanoputkipohjaisen elektrodin ominaispinta-alaa katalyyttisella hapetusreaktiolla.
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Thermodynamics and Kinetics of Nucleation and Growth of Silicon NanowiresShakthivel, Dhayalan January 2014 (has links) (PDF)
Si nanowires have potential applications in a variety of technologies such as micro and nanoelectronics, sensors, electrodes and photovoltaic applications due to their size and specific surface area. Au particle-assisted vapour-liquid-solid or VLS growth method remains the dominant process for Si nanowire growth. A comprehensive kinetic model that addresses all experimental observations and provides a physico-chemical model of the VLS growth method is thus essential. The work done as part of this research is divided into two sections.
A steady state kinetic model was first developed for the steady state growth rate of Si nanowires using SiCl4 and SiH4 as precursors. The steady state refers to a balance between the rates of injection and ejection of Si into the Au droplet. This balance results in a steady state supersaturation under which wire growth proceeds. In particular evaporation and reverse reaction of Si from the Au droplet and modes of crystal growth for wire growth have been considered in detail for the first time. The model is able to account for both, the radius independent and radius dependent growth rates reported in the literature. It also shows that the radius dependence previously attributed to purely thermodynamic considerations could also as well be explained just by steady state kinetics alone. Expressions have been derived for the steady state growth rate that require the desolvation energy, activation energy for precursor dissociation and supersaturation prevalent in the particle as inputs for calculation.
In order to evaluate this model the incubation and growth of Si nanowires were studied on sapphire substrates in an indigenously built automated MOCVD reactor. Sapphire was chosen as the substrate, as opposed to Si which is commonly used, so as to ensure that the vapour phase is the only source of Si. A classical incubation period for nucleation, of the order of 4-8 minutes, was experimentally observed for the first time.
Using the change in this incubation period with temperature a value of 15kT was determined to be the desolvation energy for growth using SiH4. The steady state growth rate of Si nanowires were measured and compared with the predictions of the model using the values of activation energies so determined.
The thesis based on the current research work is organized as follows:
Chapter 1 introduces the research area followed by a brief outline of the overall work
Chapter 2 provides a summary of current literature, and puts the research described in this thesis in perspective. The diameter dependent growth rate of NWs which was initially solely attributed to the Gibbs-Thomson effect is first summarized. Experimental observations to the contrary are then highlighted. These contradictions provided the incentive for the research described in this thesis. Following a summary of the growth rate theories, the experimental observations on incubation available in the literature are summarized. All the other variants of the VLS method are also discussed.
Chapter 3 describes the design, construction and working of an indigenously built semi- automated CVD reactor. This CVD reactor was used to conduct the Si NW growth experiments over sapphire substrates.
Chapter 4 develops the physical chemistry model for Au catalyzed Si nanowire growth using SiCl4 and SiH4 precursors. The model originated from the contradictions present in the literature over the rate limiting step of the VLS growth mechanism and the steady state growth rate dependence on wire diameter. The development starts with explaining the thermodynamics of the steady state VLS process. The significance of the model lies in the detailed analysis of the all the atomistic process occurring during the VLS growth. In particular the evaporation and reverse reaction of Si from Au-Si droplet is explained in detail and possibly for the first time. Expressions for steady state growth rate by various modes, such as layer by layer growth (LL), by multilayer growth (ML) and growth by movement of a rough interface at the L-S growth interface are derived and presented.
Chapter 5 discusses the results which emerge out the kinetic model from the previous chapter. Under a single framework of equations, the model is successful in explaining both the diameter independent and diameter dependent growth of NWs. As one of the major outcomes of the model, the growth rates of Si NWs are predicted and trends in growth rate are found to agree with those experimentally observed. Growth rate dependencies on pressure and temperature are implicitly included in the equations derived. An estimate of supersaturation has been extracted for the first time using the framework of equations.
Chapter 6 contains the experimental results of the Si NW growth over sapphire substrates. An incubation period in the order of 3-8 minutes has been observed for Si NW growth on sapphire. The data has been compared with existing literature data and interpreted using classical transient nucleation theory. The incubation period data has been utilized to extract the kinetic parameter, QD, which is the desolvation enegy. These parameters and the measured steady state growth rates have been used to estimate the supersaturation existing in the droplet using the framework developed in chapters 4 and 5.
Chapter 7 summarizes the outcome of the current research and highlights the future directions for the research problem addressed in this thesis.
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Photochemical and Photoelectric Applications of II-VI Semiconductor NanomaterialsSugunan, Abhilash January 2010 (has links)
<p>In this work we investigated fabrication of semiconductor nanomaterials and evaluated their potential for photo-chemical and photovoltaic applications. We investigated two different II-VI semiconductor nanomaterial systems; (i) ZnO oriented nanowire arrays non-epitaxially grown from a substrate; and (ii) colloidal CdTe nanotetrapods synthesized by solution-based thermal decomposition of organo-metallic precursors. In both the cases our main focus has been optimizing material synthesis for improving potential applications based on photon-electron interactions.</p><p>We have studied the synthesis of vertically aligned ZnO nanowire arrays (NWA), by a wet chemical process on various substrates. The synthesis is based on epitaxial growth of ZnO seed-layer on a substrate in a chemical bath consisting of an aqueous solution of zinc nitrate and hexamethylenetetramine (HMT). We have suggested an additional role played by HMT during the synthesis of ZnO nanowire arrays. We have also extended this synthesis method to fabricate hierarchical nanostructures of nanofibers of poly-L-lactide acting as a substrate for the radially oriented growth of ZnO nanowires. The combination of high surface area of the nanofibrous substrate with the flexibility of the PLLA-ZnO hierarchical nanostructure enabled the proof-of-principle demonstration of a ‘continuous-flow’ water treatment system that could effectively decompose single and combination of known organic pollutants in water, as well as render common waterborne bacteria nonviable.</p><p>We have studied another chemical synthesis that is commonly used for size controlled synthesis of colloidal quantum dots, which was modified to obtain anisotropic nanocrystals mainly for CdE (E=S, Se, Te) compositions. In this work we demonstrate by use of oleic acid (instead of alkylphosphonic acids) it is possible to synthesize CdTe and CdSe nanotetrapods at much lower temperatures (~180 ºC) than what is commonly reported in the literature, with significantly different formation mechanism in the low-temperature reaction.</p><p>Finally, we have performed preliminary photoconduction measurements with CdTe nanotetrapods using gold ‘nanogap’ electrodes fabricated in-house, and obtain up to 100 times enhancement in current levels in the <em>I–V </em>measurements under illumination with a white light source.</p> / QC20100607
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Low temperature fabrication of one-dimensional nanostructures and their potential application in gas sensors and biosensorsGabrielyan, Nare January 2013 (has links)
Nanomaterials are the heart of nanoscience and nanotechnology. Research into nanostructures has been vastly expanding worldwide and their application spreading into numerous branches of science and technology. The incorporation of these materials in commercial products is revolutionising the current technological market. Nanomaterials have gained such enormous universal attention due to their unusual properties, arising from their size in comparison to their bulk counterparts. These nanosized structures have found applications in major devices currently under development including fuel cells, computer chips, memory devices, solar cells and sensors. Due to their aforementioned importance nanostructures of various materials and structures are being actively produced and investigated by numerous research groups around the world. In order to meet the market needs the commercialisation of nanomaterials requires nanomaterial fabrication mechanisms that will employ cheap, easy and low temperature fabrication methods combined with environmentally friendly technologies. This thesis investigates low temperature growth of various one-dimensional nanostructures for their potential application in chemical sensors. It proposes and demonstrates novel materials that can be applied as catalysts for nanomaterial growth. In the present work, zinc oxide (ZnO) and silicon (Si) based nanostructures have been fabricated using low temperature growth methods including hydrothermal growth for ZnO nanowires and plasma-enhanced chemical vapour deposition (PECVD) technique for Si nanostructures. The structural, optical and electrical properties of these materials have been investigated using various characterisation techniques. After optimising the growth of these nanostructures, gas and biosensors have been fabricated based on Si and ZnO nanostructures respectively in order to demonstrate their potential in chemical sensors. For the first time, in this thesis, a new group of materials have been investigated for the catalytic growth of Si nanostructures. Interesting growth observations have been made and theory of the growth mechanism proposed. The lowest growth temperature in the published literature is also demonstrated for the fabrication of Si nanowires via the PECVD technique. Systematic studies were carried out in order to optimise the growth conditions of ZnO and Si nanostructures for the production of uniformly shaped nanostructures with consistent distribution across the substrate. v The surface structure and distribution of the variously shaped nanostructures has been analysed via scanning electron microscopy. In addition, the crystallinity of these materials has been investigating using Raman and X-ray diffraction spectroscopies and transmission electron microscopy. In addition to the fabrication of these one-dimensional nanomaterials, their potential application in the chemical sensors has been tested via production of a glucose biosensor and an isopropyl alcohol vapour gas sensor based on ZnO and Si nanostructures respectively. The operation of the devices as sensors has been demonstrated and the mechanisms explored.
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Design and Fabrication of Nanostructures for the Enhancement of Photovoltaic DevicesPrevost, Richard M, III 19 May 2017 (has links)
In 2012 the net world electricity generation was 21.56 trillion kilowatt hours. Photovoltaics only accounted for only 0.1 trillion kilowatt hours, less than 1 % of the total power. Recently there has been a push to convert more energy production to renewable sources. In recent years a great deal of interest has been shown for dye sensitized solar cells. These devices use inexpensive materials and have reported efficiencies approaching 12% in the lab. Here methods have been studied to improve upon these, and other, devices. Different approaches for the addition of gold nanoparticles to TiO2 films were studied. These additions acted as plasmonic and light scattering enhancements to reported dye sensitized devices. These nanoparticle enhancements generated a 10% efficiency in device performance for dye sensitized devices. Quantum dot (QD) sensitized solar cells were prepared by successive ionic layer adsorption and reaction (SILAR) synthesis of QDs in mesoporous films as well as the chemical attachment of colloidal quantum dots using 3-mercaptopropionic acid (3-MPA). Methods of synthesizing a copper sulfide (Cu2S) counter electrode were investigated to improve the device performance. By using a mesoporous film of indium tin oxide nanoparticles as a substrate for SILAR growth of Cu2S catalyst, an increase in device performance was seen over that of devices using platinum. These devices did suffer from construction drawbacks. This lead to the development of 3D nanostructures for use in Schottky photovoltaics. These high surface area devices were designed to overcome the recombination problems of thin film Schottky devices. The need to deposit a transparent top electrode limited the success of these devices, but did lead to the development of highly ordered metal nanotube arrays. To further explore these nanostructures depleted heterojunction devices were produced. Along with these devices a new approach to depositing lead sulfide quantum dots was developed. This electrophoretic deposition technique uses an applied electric field to deposit nanoparticles onto a substrate. This creates the possibility for a low waste method for depositing nanocrystals onto nanostructured substrates.
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Interaction of sublevels in gated biased semiconductor nanowires / Interaktion av subband i nanotrådar med pålagd drivspänningKarlsson, Henrik January 2016 (has links)
Mesoscopic devices, such as nano-wires, are of interest for the next step in creating spintronic devices. With the ability to manipulate electrons and their spin, spintronic devices may be realised. To that end the different effects found in low-dimensional devices must be studied and understood. In this thesis the influence that lateral spin-orbit coupling (LSOC) has on a nanowire, with asymmetrical confinement potential, is studied. The nanowire is studied through a numerical approach, using the Hartree-Fock method with Dirac interactions to solve the eigenvalue problem of an idealised infinite nanowire. The nanowire has a split-gate that generates the electrostatic asymmetrical confinement potential. It is found that the lateral spin-orbit coupling has little to no effect without any longitudinal effects in the wire, such as source-drain bias. The electrons will spontaneously create spin-rows in the device due to spin polarization. The spin polarization is triggered by using LSOC, numerical noise or from a weak magnetic field. / Mesoskopiska anordningar, som nano-trådar, tros vara ett viktigt steg för att skapa spinnelektronik. För att kunna skapa spinnelektronik behövs kunskap om hur elektroner kan manipuleras. Generellt måste därför existerande fenomen i nanoelektronik studeras. I denna avhandling studeras hur ''lateral spin-orbit koppling'' (LSOC) influerar en nanotråd som har en asymmetrisk potentialbarriär. Hartree-Fock metoden, med Dirac potential för elektron-elektron interaktioner, användes för att beräkna energinivåerna för en idealisk, oändligt lång nanotråd. Nanotråden har en split-gate som alstrar den elektrostatiska, asymmetriska potentialbarriären. "Lateral spin-orbit koppling" visar sig ha minimal effekt då longitudinella effekter, exempelvis spänning, saknas. Elektronerna placerar sig spontant i spinn-rader i tråden vid spontan spinn polarisation. Spinn polarisationen sätts igång av LSOC, numeriska störningar eller från svagt pålagt magnetfält.
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The Effect Of Stationary UV Excitation On The Optical Behavior Of Electrochemically Self-Assembled Semiconductor NanowiresKatkar, Rajesh A. 01 January 2006 (has links)
In this work, we investigate the optical response of the semiconductor quantum wire array when excited by stationary UV light. The array is synthesized by selectively electro-depositing the semiconductor material in electrochemically self-assembled porous alumina templates. Our studies are based on the optical behavioral changes in CdS, ZnO, ZnSe and CdSe quantum wires of 50-, 25- and 10-nm diameters. We use a set of generalized Bloch equations to solve the interband polarization function of the semiconductors derived within the Hartree-Fock approximation, and theoretically model the UV excitation effect on the quantum wires. The solutions which consider the effects of screening, Coulomb interaction between the carriers and many body effects on excitons are generated for a quasi-equilibrium regime using a devised accelerated fixed point method. The solution technique is developed in Mathematica to iteratively solve this complex set of equations. The optical constants generated for individual quantum wires are incorporated into a finite-element electromagnetic wave simulator, HFSS, to investigate the full behavior of the array of wires. Theoretically calculated values of the dielectric permittivity of the un-excited quantum wires are shown to decrease progressively as the wire diameter reduces. We perform the experimental analysis using a pump-probe excitation scheme incorporated in a sensitive Michelson interferometer in a homodyne setup. We measure extremely small changes in the phase shift between the interfering IR probe beams and hence measure the refractive index changes caused by the UV pump. While the decreasing filling factor acts to reduce the optical activity in narrower wire arrays, the shifting of the DOS function with additional quantum confinement serves to increase it. These competing effects give rise to the size-dependent non-monotonic optical activity experimentally observed in ZnO, CdS and ZnSe nanowire arrays. The simulation results show a rapid increase in the changes in effective permittivity values of the individual quantum wires as diameter decreases. The substantial changes observed in the refractive index for the whole thin film array at intermediate wire diameter sizes may be suitable for optical phase shifting, intensity modulation and switching applications in integrated optical devices.
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Diagnostics and Degradation Investigations of Li-Ion Battery Electrodes using Single Nanowire Electrochemical CellsPalapati, Naveen kumar reddy, Palapati, Naveen kumar reddy 01 January 2016 (has links)
Portable energy storage devices, which drive advanced technological devices, are improving the productivity and quality of our everyday lives. In order to meet the growing needs for energy storage in transportation applications, the current lithium-ion (Li-ion) battery technology requires new electrode materials with performance improvements in multiple aspects: (1) energy and power densities, (2) safety, and (3) performance lifetime. While a number of interesting nanomaterials have been synthesized in recent years with promising performance, accurate capabilities to probe the intrinsic performance of these high-performance materials within a battery environment are lacking. Most studies on electrode nanomaterials have so far used traditional, bulk-scale techniques such as cyclic voltammetry, electrochemical impedance spectroscopy, and Raman spectroscopy. These approaches give an ensemble-average estimation of the electrochemical properties of a battery electrode and does not provide a true indication of the performance that is intrinsic to its material system. Thus, new techniques are essential to understand the changes happening at a single particle level during the operation of a battery. The results from this thesis solve this need and study the electrical, mechanical and size changes that take place in a battery electrode at a single particle level.
Single nanowire lithium cells are built by depositing nanowires in carefully designed device regions of a silicon chip using Dielectrophoresis (DEP). This work has demonstrated the assembly of several NW cathode materials like LiFePO4, pristine and acid-leached α-MnO2, todorokite – MnO2, acid and nonacid-leached Na0.44MnO2. Within these materials, α-MnO2 was chosen as the model material system for electrochemical experiments. Electrochemical lithiation of pristine α-MnO2 was performed inside a glove box. The volume, elasticity and conductivity changes were measured at each state-of-charge (SOC) to understand the performance of the material system. The NW size changes due to lithiation were measured using an Atomic Force Microscope (AFM) in the tapping mode. Electronic conductivity changes as a function of lithiation was also studied in the model α-MnO2 NWs and was found to decrease substantially with lithium loading. In other measurements involving a comparison between the alpha and todorokite phases of this material system, it was observed that the rate capability of these materials is limited not by the electronic but, by the ionic conductivity.
Mechanical degradation of a battery cathode represents an important failure mode, which results in an irreversible loss of capacity with cycling. To analyze and understand these degradation mechanisms, this thesis has tested the evolution of nanomechanical properties of a battery cathode. Specifically, contact-mode AFM measurements have focused on the SOC-dependent changes in the Young’s modulus and fracture strength of an α-MnO2 NW electrode, which are critical parameters that determine its mechanical stability. These changes have been studied at the end of the first discharge step, 1 full electrochemical cycle, and 20 cycles. The observations show an increase in Young’s modulus at low concentrations of lithium loading and this is attributed to the formation of new Li-O bonds within the tunnel-structured cathode. As the lithium loading increases further, the Young’s modulus was observed to reduce and this is hypothesized to occur due to the distortions of the crystal at high lithium concentrations. The experimental-to-theoretical fracture strength ratio, which points to the defect density in the crystal at a given stoichiometry, was observed to reduce with electrochemical lithium insertion / cycling. This capability has demonstrated lithiation-dependent mechanical property measurements for the first time and represents an important contribution since degradation models, which are currently in use for materials at any size scale, always assume constant values regardless of the change in stoichiometry.
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