DESIGN AND FABRICATION OF RESONANT GAS SENSOR FOR HIGH SENSITIVITY IN THE PRESENCE OF AIR DAMPING

Gas sensors have been used widely in different important area including industrial control, environmental monitoring, counter-terrorism and chemical production. Micro-fabrication offers a promising way to achieve sensitive and inexpensive gas sensors. Over the years, various MEMS gas sensors have been investigated and fabricated. One significant type of MEMS gas sensors is based on mass change detection and the integration with specific polymer. This dissertation aims to make contributions to the design and fabrication of MEMS resonant mass sensors with capacitance actuation and sensing that lead to improved sensitivity. To accomplish this goal, the research has several objectives: (1) Define an effective measure for evaluating the sensitivity of resonant mass devices; (2) Model the effects of air damping on microcantilevers and validate models using laser measurement system (3) Develop design guidelines for improving sensitivity in the presence of air damping; (4) Characterize the degree of uncertainty in performance arising from fabrication variation for one or more process sequences, and establish design guidelines for improved robustness. Work has been completed toward these objectives. An evaluation measure has been developed and compared to an RMS based measure. Analytic models of air damping for parallel plate that include holes are compared with a COMSOL model. The models have been used to identify cantilever design parameters that maximize sensitivity. Additional designs have been modeled with COMSOL and the development of an analytical model for Fixed-free cantilever geometries with holes has been developed. Two process flows have been implemented and compared. A number of cantilever designs have been fabricated and the uncertainty in process has been investigated. Variability from processing have been evaluated and characterized.

Suppression of the intrinsic stochastic pinning of domain walls in magnetic nanostripes

Nanofabrication has allowed the development of new concepts such as magnetic logic and race-track memory, both of which are based on the displacement of magnetic domain walls on magnetic nanostripes. One of the issues that has to be solved before devices can meet the market demands is the stochastic behaviour of the domain wall movement in magnetic nanostripes. Here we show that the stochastic nature of the domain wall motion in permalloy nanostripes can be suppressed at very low fields (0.6-2.7 Oe). We also find different field regimes for this stochastic motion that match well with the domain wall propagation modes. The highest pinning probability is found around the precessional mode and, interestingly, it does not depend on the external field in this regime. These results constitute an experimental evidence of the intrinsic nature of the stochastic pinning of domain walls in soft magnetic nanostripes

Movimiento de paredes de dominio magnético en nanohilos con defectos controlados

La investigación realizada en este trabajo de tesis se ha centrado en el estudio de la generación, anclaje y desenganche de paredes de dominio magnético en nanohilos de permalloy con defectos controlados. Las últimas tecnologías de nanofabricación han abierto importantes líneas de investigación centradas en el estudio del movimiento de paredes de dominio magnético, gracias a su potencial aplicación en memorias magnéticas del futuro. En el 2004, Stuart Parkin de IBM introdujo un concepto innovador, el dispositivo “Racetrack”, basado en un nanohilo ferromagnético donde los dominios de imanación representan los "bits" de información. La frontera entre dominios, ie pared magnética, se moverían en una situación ideal por medio de transferencia de espín de una corriente polarizada. Se anclan en determinadas posiciones gracias a pequeños defectos o constricciones de tamaño nanométrico fabricados por litografía electrónica. El éxito de esta idea se basa en la generación, anclaje y desenganche de las paredes de dominio de forma controlada y repetitiva, tanto para la lectura como para la escritura de los bits de información. Slonczewski en 1994 muestra que la corriente polarizada de espín puede transferir momento magnético a la imanación local y así mover paredes por transferencia de espín y no por el campo creado por la corriente. Desde entonces muchos grupos de investigación de todo el mundo trabajan en optimizar las condiciones de transferencia de espín para mover paredes de dominio. La fracción de electrones polarizados que viaja en un hilo ferromagnético es considerablemente pequeña, así hoy por hoy la corriente necesaria para mover una pared magnética por transferencia de espín es superior a 1 107 A/cm2. Una densidad de corriente tan elevada no sólo tiene como consecuencia una importante degradación del dispositivo sino también se observan importantes efectos relacionados con el calentamiento por efecto Joule inducido por la corriente. Otro de los problemas científico - tecnológicos a resolver es la diversidad de paredes de dominio magnético ancladas en el defecto. Los diferentes tipos de pared anclados en el defecto, su quiralidad o el campo o corriente necesarios para desenganchar la pared pueden variar dependiendo si el defecto posee dimensiones ligeramente diferentes o si la pared se ancla con un método distinto. Además, existe una componente estocástica presente tanto en la nucleación como en el proceso de anclaje y desenganche que por un lado puede ser debido a la naturaleza de la pared que viaja por el hilo a una determinada temperatura distinta de cero, así como a defectos inevitables en el proceso de fabricación. Esto constituye un gran inconveniente dado que según el tipo de pared es necesario aplicar distintos valores de corriente y/o campo para desenganchar la pared del defecto. Como se menciona anteriormente, para realizar de forma eficaz la lectura y escritura de los bits de información, es necesaria la inyección, anclaje y desenganche forma controlada y repetitiva. Esto implica generar, anclar y desenganchar las paredes de dominio siempre en las mismas condiciones, ie siempre a la misma corriente o campo aplicado. Por ello, en el primer capítulo de resultados de esta tesis estudiamos el anclaje y desenganche de paredes de dominio en defectos de seis formas distintas, cada uno, de dos profundidades diferentes. Hemos realizado un análisis estadístico en diferentes hilos, donde hemos estudiado la probabilidad de anclaje cada tipo de defecto y la dispersión en el valor de campo magnético aplicado necesario para desenganchar la pared. Luego, continuamos con el estudio de la nucleación de las paredes de dominio magnético con pulsos de corriente a través una linea adyacente al nanohilo. Estudiamos defectos de tres formas distintas e identificamos, en función del valor de campo magnético aplicado, los distintos tipos de paredes de dominio anclados en cada uno de ellos. Además, con la ayuda de este método de inyección que es rápido y eficaz, hemos sido capaces de generar y anclar un único tipo de pared minimizando el comportamiento estocástico de la pared mencionado anteriormente. En estas condiciones óptimas, hemos estudiado el desenganche de las paredes de dominio por medio de corriente polarizada en espín, donde hemos conseguido desenganchar la pared de forma controlada y repetitiva siempre para los mismos valores de corriente y campo magnético aplicados. Además, aplicando pulsos de corriente en distintas direcciones, estudiamos en base a su diferencia, la contribución térmica debido al efecto Joule. Los resultados obtenidos representan un importante avance hacia la explotación práctica de este tipo de dispositivos. ABSTRACT The research activity of this thesis was focused on the nucleation, pinning and depinning of magnetic domain walls (DWs) in notched permalloy nanowires. The access to nanofabrication techniques has boosted the number of applications based on magnetic domain walls (DWs) like memory devices. In 2004, Stuart Parkin at IBM, conceived an innovative concept, the “racetrack memory” based on a ferromagnetic nanowire were the magnetic domains constitute the “bits” of information. The frontier between those magnetic domains, ie magnetic domain wall, will move ideally assisted by a spin polarized current. DWs will pin at certain positions due to artificially created pinning sites or “notches” fabricated with ebeam lithography. The success of this idea relies on the careful and predictable control on DW nucleation and a defined pinning-depinning process in order to read and write the bits of information. Sloncsewski in 1994 shows that a spin polarized current can transfer magnetic moment to the local magnetization to move the DWs instead of the magnetic field created by the current. Since then many research groups worldwide have been working on optimizing the conditions for the current induced DW motion due to the spin transfer effect. The fraction of spin polarized electrons traveling through a ferromagnetic nanowire is considerably small, so nowadays the current density required to move a DW by STT exceeds 1 107 A/cm2. A high current density not only can produce a significant degradation of the device but also important effects related to Joule heating were also observed . There are other scientific and technological issues to solve regarding the diversity of DWs states pinned at the notch. The types of DWs pinned, their chirality or their characteristic depinning current or field, may change if the notch has slightly different dimensions, the stripe has different thickness or even if the DW is pinned by a different procedure. Additionally, there is a stochastic component in both the injection of the DW and in its pinning-depinning process, which may be partly intrinsic to the nature of the travelling DW at a non-zero temperature and partly due to the unavoidable defects introduced during the nano-fabrication process. This constitutes an important inconvenient because depending on the DW type different values of current of magnetic field need to be applied in order to depin a DW from the notch. As mentioned earlier, in order to write and read the bits of information accurately, a controlled reproducible and predictable pinning- depinning process is required. This implies to nucleate, pin and depin always at the same applied magnetic field or current. Therefore, in the first chapter of this thesis we studied the pinning and depinning of DW in six different notch shapes and two depths. An statistical analysis was conducted in order to determine which notch type performed best in terms of pinning probability and the dispersion measured in the magnetic field necessary to depin the magnetic DWs. Then, we continued studying the nucleation of DWs with nanosecond current pulses by an adjacent conductive stripe. We studied the conditions for DW injection that allow a selective pinning of the different types of DWs in Permalloy nanostripes with 3 different notch shapes. Furthermore, with this injection method, which has proven to be fast and reliable, we manage to nucleate only one type of DW avoiding its stochastic behavior mentioned earlier. Having achieved this optimized conditions we studied current induced depinning where we also achieved a controlled and reproducible depinning process at always the same applied current and magnetic field. Additionally, changing the pulse polarity we studied the joule heating contribution in a current induced depinning process. The results obtained represent an important step towards the practical exploitation of these devices.

Step and flash imprint lithography: Fabrication of patterned media for extremely high density magnetic data storage devices

Currently the data storage industry is facing huge challenges with respect to the conventional method of recording data known as longitudinal magnetic recording. This technology is fast approaching a fundamental physical limit, known as the superparamagnetic limit. A unique way of deferring the superparamagnetic limit incorporates the patterning of magnetic media. This method exploits the use of lithography tools to predetermine the areal density. Various nanofabrication schemes are employed to pattern the magnetic material are Focus Ion Beam (FIB), E-beam Lithography (EBL), UV-Optical Lithography (UVL), Self-assembled Media Synthesis and Nanoimprint Lithography (NIL). Although there are many challenges to manufacturing patterned media, the large potential gains offered in terms of areal density make it one of the most promising new technologies on the horizon for future hard disk drives. Thus, this dissertation contributes to the development of future alternative data storage devices and deferring the superparamagnetic limit by designing and characterizing patterned magnetic media using a novel nanoimprint replication process called "Step and Flash Imprint lithography". As opposed to hot embossing and other high temperature-low pressure processes, SFIL can be performed at low pressure and room temperature. Initial experiments carried out, consisted of process flow design for the patterned structures on sputtered Ni-Fe thin films. The main one being the defectivity analysis for the SFIL process conducted by fabricating and testing devices of varying feature sizes (50 nm to 1 μm) and inspecting them optically as well as testing them electrically. Once the SFIL process was optimized, a number of Ni-Fe coated wafers were imprinted with a template having the patterned topography. A minimum feature size of 40 nm was obtained with varying pitch (1:1, 1:1.5, 1:2, and 1:3). The Characterization steps involved extensive SEM study at each processing step as well as Atomic Force Microscopy (AFM) and Magnetic Force Microscopy (MFM) analysis.

Development of micro immunosensors to study genomic and proteomic biomarkers related to cancer and Alzheimer's disease

A report from the National Institutes of Health defines a disease biomarker as a “characteristic that is objectively measured and evaluated as an indicator of normal biologic processes, pathogenic processes, or pharmacologic responses to a therapeutic intervention.” Early diagnosis is a crucial factor for incurable disease such as cancer and Alzheimer’s disease (AD). During the last decade researchers have discovered that biochemical changes caused by a disease can be detected considerably earlier as compared to physical manifestations/symptoms. In this dissertation electrochemical detection was utilized as the detection strategy as it offers high sensitivity/specificity, ease of operation, and capability of miniaturization and multiplexed detection. Electrochemical detection of biological analytes is an established field, and has matured at a rapid pace during the last 50 years and adapted itself to advances in micro/nanofabrication procedures. Carbon fiber microelectrodes were utilized as the platform sensor due to their high signal to noise ratio, ease and low-cost of fabrication, biocompatibility, and active carbon surface which allows conjugation with biorecognition moieties. This dissertation specifically focuses on the detection of 3 extensively validated biomarkers for cancer and AD. Firstly, vascular endothelial growth factor (VEGF) a cancer biomarker was detected using a one-step, reagentless immunosensing strategy. The immunosensing strategy allowed a rapid and sensitive means of VEGF detection with a detection limit of about 38 pg/mL with a linear dynamic range of 0–100 pg/mL. Direct detection of AD-related biomarker amyloid beta (Aβ) was achieved by exploiting its inherent electroactivity. The quantification of the ratio of Aβ1-40/42 (or Aβ ratio) has been established as a reliable test to diagnose AD through human clinical trials. Triple barrel carbon fiber microelectrodes were used to simultaneously detect Aβ1-40 and Aβ1-42 in cerebrospinal fluid from rats within a detection range of 100nM to 1.2μM and 400nM to 1μM respectively. In addition, the release of DNA damage/repair biomarker 8-hydroxydeoxyguanine (8-OHdG) under the influence of reactive oxidative stress from single lung endothelial cell was monitored using an activated carbon fiber microelectrode. The sensor was used to test the influence of nicotine, which is one of the most biologically active chemicals present in cigarette smoke and smokeless tobacco.

Experimentally estimated dead space for GaAs and InP based planar Gunn diodes

The authors would like to thank the staff of the James Watt Nanofabrication Centre at the University of Glasgow for help in fabricating the devices which is reported in this paper. ‘Part of this work was supported by ESPRC through EP/H011862/ 1, and EP/H012966/1.

Resist-substrate interface tailoring for generating high density arrays of Ge and Bi2Se3 nanowires by electron beam lithography

The authors report a chemical process to remove the native oxide on Ge and Bi2Se3 crystals, thus facilitating high-resolution electron beam lithography (EBL) on their surfaces using a hydrogen silsesquioxane (HSQ) resist. HSQ offers the highest resolution of all the commercially available EBL resists. However, aqueous HSQ developers such as NaOH and tetramethylammonium hydroxide have thus far prevented the fabrication of high-resolution structures via the direct application of HSQ to Ge and Bi2Se3, due to the solubility of components of their respective native oxides in these strong aqueous bases. Here we provide a route to the generation of ordered, high-resolution, high-density Ge and Bi2Se3 nanostructures with potential applications in microelectronics, thermoelectric, and photonics devices.                         

Electron beam lithography assisted high-resolution pattern generation

This thesis details the top-down fabrication of nanostructures on Si and Ge substrates by electron beam lithography (EBL). Various polymeric resist materials were used to create nanopatterns by EBL and Chapter 1 discusses the development characteristics of these resists. Chapter 3 describes the processing parameters, resolution and topographical and structural changes of a new EBL resist known as ‘SML’. A comparison between SML and the standard resists PMMA and ZEP520A was undertaken to determine the suitability of SML as an EBL resist. It was established that SML is capable of high-resolution patterning and showed good pattern transfer capabilities. Germanium is a desirable material for use in microelectronic applications due to a number of superior qualities over silicon. EBL patterning of Ge with high-resolution hydrogen silsesquioxane (HSQ) resist is however difficult due to the presence of native surface oxides. Thus, to combat this problem a new technique for passivating Ge surfaces prior to EBL processes is detailed in Chapter 4. The surface passivation was carried out using simple acids like citric acid and acetic acid. The acids were gentle on the surface and enabled the formation of high-resolution arrays of Ge nanowires using HSQ resist. Chapter 5 details the directed self-assembly (DSA) of block copolymers (BCPs) on EBL patterned Si and, for the very first time, Ge surfaces. DSA of BCPs on template substrates is a promising technology for high volume and cost effective nanofabrication. The BCP employed for this study was poly (styrene-b-ethylene oxide) and the substrates were pre-defined by HSQ templates produced by EBL. The DSA technique resulted into pattern rectification (ordering in BCP) and in pattern multiplication within smaller areas.

Développement de procédés technologiques pour une intégration 3D monolithique de dispositifs nanoélectroniques sur CMOS

Résumé : Le transistor monoélectronique (SET) est un dispositif nanoélectronique très attractif à cause de son ultra-basse consommation d’énergie et sa forte densité d’intégration, mais il n’a pas les capacités suffisantes pour pouvoir remplacer complètement la technologie CMOS. Cependant, la combinaison de la technologie SET avec celle du CMOS est une voie intéressante puisqu’elle permet de profiter des forces de chacune, afin d’obtenir des circuits avec des fonctionnalités additionnelles et uniques. Cette thèse porte sur l’intégration 3D monolithique de nanodispositifs dans le back-end-of-line (BEOL) d’une puce CMOS. Cette approche permet d’obtenir des circuits hybrides et de donner une valeur ajoutée aux puces CMOS actuelles sans altérer le procédé de fabrication du niveau des transistors MOS. L’étude se base sur le procédé nanodamascène classique développé à l’UdeS qui a permis la fabrication de dispositifs nanoélectroniques sur un substrat de SiO2. Ce document présente les travaux réalisés sur l’optimisation du procédé de fabrication nanodamascène, afin de le rendre compatible avec le BEOL de circuits CMOS. Des procédés de gravure plasma adaptés à la fabrication de nanostructures métalliques et diélectriques sont ainsi développés. Le nouveau procédé nanodamascène inverse a permis de fabriquer des jonctions MIM et des SET métalliques sur une couche de SiO2. Les caractérisations électriques de MIM et de SET formés avec des jonctions TiN/Al2O3 ont permis de démontrer la présence de pièges dans les jonctions et la fonctionnalité d’un SET à basse température (1,5 K). Le transfert de ce procédé sur CMOS et le procédé d’interconnexions verticales sont aussi développés par la suite. Finalement, un circuit 3D composé d’un nanofil de titane connecté verticalement à un transistor MOS est réalisé et caractérisé avec succès. Les résultats obtenus lors de cette thèse permettent de valider la possibilité de co-intégrer verticalement des dispositifs nanoélectroniques avec une technologie CMOS, en utilisant un procédé de fabrication compatible.

HIGH VOLTAGE ELECTROPHORETIC DEPOSITION FOR ELECTROCHEMICAL ENERGY STORAGE AND OTHER APPLICATIONS

High voltage electrophoretic deposition (HVEPD) has been developed as a novel technique to obtain vertically aligned forests of one-dimensional nanomaterials for efficient energy storage. The ability to control and manipulate nanomaterials is critical for their effective usage in a variety of applications. Oriented structures of one-dimensional nanomaterials provide a unique opportunity to take full advantage of their excellent mechanical and electrochemical properties. However, it is still a significant challenge to obtain such oriented structures with great process flexibility, ease of processing under mild conditions and the capability to scale up, especially in context of efficient device fabrication and system packaging. This work presents HVEPD as a simple, versatile and generic technique to obtain vertically aligned forests of different one-dimensional nanomaterials on flexible, transparent and scalable substrates. Improvements on material chemistry and reduction of contact resistance have enabled the fabrication of high power supercapacitor electrodes using the HVEPD method. The investigations have also paved the way for further enhancements of performance by employing hybrid material systems and AC/DC pulsed deposition. Multi-walled carbon nanotubes (MWCNTs) were used as the starting material to demonstrate the HVEPD technique. A comprehensive study of the key parameters was conducted to better understand the working mechanism of the HVEPD process. It has been confirmed that HVEPD was enabled by three key factors: high deposition voltage for alignment, low dispersion concentration to avoid aggregation and simultaneous formation of holding layer by electrodeposition for reinforcement of nanoforests. A set of suitable parameters were found to obtain vertically aligned forests of MWCNTs. Compared with their randomly oriented counterparts, the aligned MWCNT forests showed better electrochemical performance, lower electrical resistance and a capability to achieve superhydrophpbicity, indicating their potential in a broad range of applications. The versatile and generic nature of the HVEPD process has been demonstrated by achieving deposition on flexible and transparent substrates, as well as aligned forests of manganese dioxide (MnO2) nanorods. A continuous roll-printing HVEPD approach was then developed to obtain aligned MWCNT forest with low contact resistance on large, flexible substrates. Such large-scale electrodes showed no deterioration in electrochemical performance and paved the way for practical device fabrication. The effect of a holding layer on the contact resistance between aligned MWCNT forests and the substrate was studied to improve electrochemical performance of such electrodes. It was found that a suitable precursor salt like nickel chloride could be used to achieve a conductive holding layer which helped to significantly reduce the contact resistance. This in turn enhanced the electrochemical performance of the electrodes. High-power scalable redox capacitors were then prepared using HVEPD. Very high power/energy densities and excellent cyclability have been achieved by synergistically combining hydrothermally synthesized, highly crystalline α-MnO2 nanorods, vertically aligned forests and reduced contact resistance. To further improve the performance, hybrid electrodes have been prepared in the form of vertically aligned forest of MWCNTs with branches of α-MnO2 nanorods on them. Large- scale electrodes with such hybrid structures were manufactured using continuous HVEPD and characterized, showing further improved power and energy densities. The alignment quality and density of MWCNT forests were also improved by using an AC/DC pulsed deposition technique. In this case, AC voltage was first used to align the MWCNTs, followed by immediate DC voltage to deposit the aligned MWCNTs along with the conductive holding layer. Decoupling of alignment from deposition was proven to result in better alignment quality and higher electrochemical performance.

Doped nanostructured semiconductors produced by cold plasma combined with heat

The potential of combining cold plasma and thermal treatment for the nanofabrication of advances semiconductors was investigated.