CONTROL OF AVERAGE SPACING OF OMCVD GROWN GOLD NANOPARTICLES

Metallic nanostructures and their applications is a rapidly expanding field. Nobel metals such as silver and gold have historically been used to demonstrate plasmon effects due to their strong resonances, which occur in the visible part of the electromagnetic spectrum. Localized surface plasmon resonance (LSPR) produces an enhanced electromagnetic field at the interface between a gold nanoparticle (Au NP) and the surrounding dielectric. This enhanced field can be used for metal-dielectric interface- sensitive optical interactions that form a powerful basis for optical sensing. In addition to the surrounding material, the LSPR spectral position and width depend on the size, shape, and average spacing between these particles. Au NP LSPR based sensors depict their highest sensitivity with optimized parameters and usually operate by investigating absorption peak shifts. The absorption peak of randomly deposited Au NPs on surfaces is mostly broad. As a result, the absorption peak shifts, upon binding of a material onto Au NPs might not be very clear for further analysis. Therefore, novel methods based on three well-known techniques, self-assembly, ion irradiation, and organo-metallic chemical vapour deposition (OMCVD) are introduced to control the average-spacing between Au NPs. In addition to covalently binding and other advantages of OMCVD grown Au NPs, interesting optical features due to their non- spherical shapes are presented. The first step towards the average-spacing control is to uniformly form self- assembled monolayers (SAMs) of octadecyltrichlorosilane (OTS) as resists for OMCVD Au NPs. The formation and optimization of the OTS SAMs are extensively studied. The optimized resist SAMs are ion-irradiated by a focused ion beam (FIB) and ions generated by a Tandem accelerator. The irradiated areas are refilled with 3-mercaptopropyl- trimethoxysilane (MPTS) to provide nucleation sites for the OMCVD Au NP growth. Each step during sample preparation is monitored by using surface characterization methods such as contact angle measurements, ellipsometry, X-ray photoelectron iii spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), Rutherford backscattering spectroscopy (RBS), UV-Visible spectroscopy, and time-of-flight secondary ion mass spectroscopy (ToF-SIMS)

Synthesis and characterization of silicon dioxide thin films by low pressure chemical vapor deposition

Ditertiarybutylsilane ( DTBS ) and oxygen have been used as precursors to produce silicon dioxide films by low pressure chemical vapor deposition. These films were synthesized in the temperature range of 600°C to 800°C at constant pressure, and at different gas flow composition. The films were found to be uniform with a composition that varied with deposition temperature and gas flow ratio. The growth rate was found to follow an Arrhenius behavior with an apparent activation energy of 2.62 kcal/mol. The growth rate was seen to increase with higher distance between wafers and to vary as a function of square root of the 0, flow rate. The refractive index of the films were found to be 1.462 at deposition temperature 600°C and increased with higher temperature. The stresses were very low tensile in the films and tended to be compressive with increasing deposition temperature

Chemical vapor deposition and characterization of polysilanes polymer based thin films and their applications in compound semiconductors and silicon devices

As the semiconductors industry is moving toward nanodevices, there is growing need to develop new materials and thin films deposition processes which could enable strict control of the atomic composition and structure of thin film materials in order to achieve precise control on their electrical and optical properties. The accurate control of thin film characteristics will become increasingly important as the miniaturization of semiconductor devices continue. There is no doubt that chemical synthesis of new materials and their self assembly will play a major role in the design and fabrication of next generation semiconductor devices. The objective of this work is to investigate the chemical vapor deposition (CVD) process of thin film using a polymeric precursor as a source material. This process offers many advantages including low deposition cost, hazard free working environment, and most importantly the ability to customize the polymer source material through polymer synthesis and polymer functionalization. The combination between polymer synthesis and CVD process will enable the design of new generation of complex thin film materials with a wide range of improved chemical, mechanical, electrical and optical properties which cannot be easily achieved through conventional CVD processes based on gases and small molecule precursors. In this thesis we mainly focused on polysilanes polymers and more specifically poly(dimethylsilanes). The interest in these polymers is motivated by their distinctive electronic and photonic properties which are attributed to the delocalization of the [sigma]-electron along the Si-Si backbone chain. These characteristics make polysilane polymers very promising in a broad range of applications as a dielectric, a semiconductor and a conductor. The polymer-based CVD process could be eventually extended to other polymer source materials such as polygermanes, as well as and a variety of other inorganic and hybrid organic-inorganic polymers. This work has demonstrated that a polysilane polymeric source can be used to deposit a wide range of thin film materials exhibiting similar properties with conventional ceramic materials such as silicon carbide (SiC), silicon oxynitride (SiON), silicon oxycarbide (SiOC) silicon dioxide (SiO[subscript 2]) and silicon nitride (Si[subscipt 3]N[subscript 4]). The strict control of the deposition process allows precise control of the electrical, optical and chemical properties of polymer-based thin films within a broad range. This work has also demonstrated for the first time that poly(dimethylsilmaes) polymers deposited by CVD can be used to effectively passivate both silicon and gallium arsenide MOS devices. This finding makes polymer-based thin films obtained by CVD very promising for the development of high-[kappa] dielectric materials for next generation high-mobility CMOS technology

Porous Low-Dielectric-Constant Material for Semiconductor Microelectronics

To provide high speed, low dynamic power dissipation, and low cross-talk noise for microelectronic circuits, low-dielectric-constant (low-k) materials are required as the inter- and intra-level dielectric (ILD) insulator of the back-end-of-line interconnects. Porous low-k materials have low-polarizability chemical compositions and the introducing porosity in the film. Integration of porous low-k materials into microelectronic circuits, however, poses a number of challenges because the composition and porosity affected the resistance to damage during integration processing and reduced the mechanical strength, thereby degrading the properties and reliability. These issues arising from porous low-k materials are the subject of the present chapter

Durability of Nanosized Oxygen-Barrier Coatings on Polymers

Research on silicon oxide thin films developed as gas-barrier protection for polymer-based components is reviewed, with attention paid to the relations between (i) coating defects, cohesive strength and internal stress state, and (ii) interfacial interactions and related adhesion to the substrate. The deposition process of the oxide from a vapor or a plasma phase leads in both cases to the formation of covalent bonds between the two materials, with high adhesion levels. The oxide coating contains nanoscopic defects and microscopic flaws, and their respective effect on the barrier performance and mechanical resistance of the coating is analyzed. Potential improvements are discussed, including the control of internal stresses in the coating during deposition. Controlled levels of compressive internal stresses in the coating are beneficial to both the barrier performance and the mechanical reliability of the coated polymer. An optimal coating thickness, with low oxygen permeation and high cohesive strength, is determined from experimental and theoretical analyses of the failure mechanisms of the coating under mechanical load. These investigations are found relevant to tailor the interactions and stress state in the interfacial region, in order to improve the reliability of the coating/substrate assembly

Covalent functionalization of silicon nitride surfaces for anti-biofouling and bioselective capture

Microsieves – microengineered membranes – have been introduced in microfiltration technology as a new generation of inorganic membranes. The thin membranes are made of silicon nitride (SixN4), which gives the membranes outstanding features, such as chemical inertness and high mechanical strength. Microsieves have very well-defined pore size and pore shape, with an extremely homogeneous size distribution and high porosity. As a result, high-flux performance and excellent selectivity may be achieved. However, biofouling issues exert limitations on the application of microsieves in filtration and diagnostics. Surface functionalization was found to be a feasible way to minimize biofouling, but also to achieve biorecognition in microbiological applications. The aim of this thesis is to improve microsieve performance in biological applications by means of surface functionalization with organic coatings for protein repellence and selective capture of microorganisms. In this thesis, SixN4 surfaces were functionalized with organic monolayers via stable Si C and N-C linkages. Coatings to render SixN4 surfaces protein repellent were studied in depth by two approaches: grafting of ethylene oxide monolayers onto the surface (Chapter 2); and grafting of zwitterionic polymers from the surface (Chapter 3). UV induced surface modification with oligo(ethylene oxide) chains with three (EO3) and six (EO6) units and the detailed characterization of these modified surfaces are described in Chapter 2. Successful attachment of EO3 and EO6 on SixN4 surfaces was achieved. The modified surfaces exhibit excellent protein repellence in bovine serum albumin (BSA) solution (~ 94%), but only moderate (~ 80%) protein repulsion was observed in fibrinogen (FIB) solution. This observation motivated the study towards grafting zwitterionic polymer brushes from SixN4 surfaces for improved protein repellence. A new method to grow zwitterionic polymers from monolayers containing tertiary bromides, via atom transfer radical polymerization (ATRP) was developed. The zwitterionic polymer coated surfaces showed excellent protein repellence in FIB solution (> 99%), while exhibiting very stable performance in PBS during one week, i.e., unchanged thickness, no hydrolysis of the polymers occurred and protein repellence in FIB solution remained constant. The use of microsieves as detection platform for microorganisms was explored in Chapter 4. Microorganisms can be caught by microsieves whose pore sizes are smaller than the microorganisms while allowing an easy flow-through of other components. However, detection capacity of microsieves is severely hampered by fouling issues. To avoid this problem, the use of microsieves with pore sizes larger than the microorganisms, in combination with immobilized antibodies was investigated in Chapter 4. Anti Salmonella antibodies were immobilized onto epoxide monolayers on microsieve surfaces by reaction with the primary amines present in the antibody. The antibody-coated microsieves showed excellent detection of Salmonella with high sensitivity and selectivity, significantly improving detection efficiency in crude biological samples, and reducing analysis times. The capture efficiency of Salmonella in milk samples was, however, found to be lower than that achieved in buffered solution. Most likely, this is due to nonspecific adsorption of milk proteins on the antibody-coated microsieves. In addition, the use of a blocking solution before incubation with microorganism solution remained an essential step in order to avoid the occurrence of interfering background fluorescence. In order to minimize these problems, the incorporation of antibodies on top of protein-repellent zwitterionic polymers coated on SixN4 surfaces was studied in Chapter 5. Anti-Salmonella antibodies were immobilized on zwitterionic polymer brushes coated SixN4 surfaces through the bromide moieties retained at the end of the polymer chain after ATRP. Antibody-functionalized zwitterionic polymers adsorbed only minimal amounts of FIB, indicating excellent protein repellence of the modified surfaces. Moreover, anti-Salmonella antibodies immobilized onto zwitterionic surfaces exhibit highly selective capture and improved sensitivity, as compared to antibodies on epoxide coated surfaces. This achievement offers a new approach that enables highly sensitive and selective detection of microorganism, while minimizing nonspecific adsorption of proteins that are not of interest. In Chapter 6, an overview is given of the most important findings presented in the thesis. Recommendations, as well as additional ideas on how to bring this research into industrial application are discussed. </p

Development of a new chemical sensor based on plasma polymerized polypyrrole films

La present tesis contribueix a donar una nova visió dins de l'àrea de modificació de superfícies, la qual implica la nanoestructuració de substrats fent servir la tècnica d'auto-assemblatge per a dipositar sobre aquests un polímer conductor mitjançant deposició química en fase vapor per plasma. L'ús de polímers conductors ha despertat un creixent interès en el desenvolupament de sensors químics per a l'anàlisi de gasos en aplicacions d'enginyeria electrònica. La contínua reducció de mida en aquests dispositius ha encoratjat la proposta d'un mètode alternatiu per aconseguir estructures de rang nanomètric, així com per solucionar problemes com la falta d'adherència entre substrat i polímer, disminuir els límits de detecció o escurçar els temps de resposta.En aquesta investigació s'ha treballat amb monocapes amb un grup pirrol terminal per tal de potenciar la nucleació i creixement de pel·lícules de polipirrol polimeritzades mitjançant plasma. A més, les monocapes han aportat millores en l'adhesió interfacial de l'estructura polímer/metall. Així mateix, s'han dopat les pel·lícules primes de polipirrol per tal d'obtenir la seva forma conductora, les propietats elèctriques de les quals permeten utilitzar-ho com a sensor químic. La seva exposició a un vapor comporta canvis en la conductivitat del polímer, a través dels quals es pot identificar i quantificar l'esmentat analit.L'auto-assemblatge i la deposició del polímer són els factors claus en aquesta investigació. Per tant, s'han utilitzat diverses tècniques de caracterització de superfícies com XPS, TOF-SIMS, FT-IR o SEM, per estudiar les seves propietats físiques i químiques. Igualment, l'ús de l'AFM ha estat de gran ajut per investigar el procés de nucleació i la topografia de les pel·lícules. A més, la tècnica de les quatre puntes ha proporcionat una excel·lent eina per realitzar mesures de conductivitat a les pel·lícules primes. Finalment, les pel·lícules polimeritzades per plasma han mostrat una gran sensibilitat al diòxid de carboni, demostrant la seva capacitat per ser utilitzades com a sensors químics.La presente tesis contribuye a dar una nueva visión dentro del área de modificación de superficies, la cual implica la nanoestructuración de sustratos utilizando la técnica de auto-ensamblado para depositar sobre éstos un polímero conductor mediante deposición química en fase vapor por plasma. El uso de polímeros conductores ha despertado un creciente interés en el desarrollo de sensores químicos para el análisis de gases en aplicaciones de ingeniería electrónica. La continua reducción de tamaño en estos dispositivos ha alentado la propuesta de un método alternativo para conseguir estructuras de rango nanométrico, así como para solucionar problemas tales como la falta de adherencia entre sustrato y polímero, disminuir los límites de detección o acortar los tiempos de respuesta.En esta investigación se ha trabajado con monocapas con un grupo pirrol terminal para potenciar la nucleación y crecimiento de películas de polipirrol polimerizadas mediante plasma. Además, las monocapas han aportado mejoras en la adhesión interfacial de la estructura polímero/metal. Asimismo, se han dopado las películas delgadas de polipirrol para obtener su forma conductora, cuyas propiedades eléctricas permiten utilizarlo como sensor químico. Su exposición a un vapor conlleva cambios en la conductividad del polímero, a través de los cuales se puede identificar y cuantificar dicho analito.El auto-ensamblaje y la deposición del polímero son los factores claves en esta investigación. Por lo tanto, se han utilizado diversas técnicas de caracterización de superficies, como XPS, TOF-SIMS, FT-IR o SEM, para estudiar sus propiedades físicas y químicas. Igualmente, el uso del AFM ha sido de gran valor para investigar el proceso de nucleación y la topografía de las películas. Además, la técnica de las cuatro puntas ha proporcionado una excelente herramienta para realizar medidas de conductividad en películas delgadas. Finalmente, las películas polimerizadas por plasma han mostrado una gran sensibilidad al dióxido de carbono, con lo cual han demostrado su capacidad para ser utilizados como sensores químicos.This thesis contributes a new insight into surface modification involving substrates nanostructuration by self-assembly to deposit on them a conducting polymer through plasma enhanced chemical vapor deposition. The use of conducting polymers has gained growing interest in the development of chemical sensor arrays for gas analysis in electronic engineering applications. The size reduction in these devices has encouraged the proposal of an alternative method to achieve structures at nanometer range, as well as overcoming problems like lack of adhesion between substrate and polymer, lower limits of detection or shorten response times.The investigation has dealt with the use of pyrrole terminated monolayers to enhance the nucleation and growth of polypyrrole plasma polymerized films. In addition, monolayers provide an improvement in the interfacial adhesion of the polymer/metal structure. Furthermore, polymeric thin films have been doped to obtain the conducting form of polypyrrole, of which electric properties enable to use it as a chemical sensor. Exposure to vapors leads to changes in polymer conductivity, by which analytes can be identified and quantified.Self-assembly and polymer deposition are key factors in this research, as a consequence surface characterization techniques, such as XPS, TOF-SIMS, FT-IR or SEM, have been employed to study their physical and chemical characteristics. Especially interesting have been the use of AFM to investigate the nucleation process and the film topography. Moreover, the four-point probe technique has provided an excellent tool to perform conductivity measurements on thin films. Besides, plasma polymerized films have shown a high sensitivity to carbon dioxide in order to demonstrate their aptitudes to be utilized as a chemical sensor

Development of biofunctional and biocompatible surfaces for biodiagnostic applications utilising plasma enhanced chemical vapour deposition

Plasma enhanced chemical vapour deposition was investigated for the deposition of biofunctional thin films onto surfaces in the fabrication of biomedical diagnostic devices. Two major aspects of the deposited films were assessed for their applicability in new diagnostic systems. The first relates to the functionality of the surface. The functionality of the surface relates to the ability of specific surface functional groups to be deposited stably and in a manner that will allow for biomolecular adhesion. Biomolecular adhesion is an important feature of surfaces requiring immobilisation of a detection agent, especially in liquid throughput devices. A comprehensive characterisation of the films developed herein was carried out. Following on from work previously undertaken by members of our research group, the films developed have shown a high degree of stability of the density of surface functional groups after exposure to aqueous conditions similar to those employed by liquid throughput devices. I found that the densities of these surface groups are superior to films created through liquid chemical deposition. Processes developed as part of this work were tailored for optimal manufacturability, e.g. the removal of heating apparatus required by the aminopropyltriethoxysilane monomer by installing a complimentary tetraethyl orthosilicate and allylamine process. Secondly, I investigated surface wettability and developed a novel process for surface wettability control using atetraethyl orthosilicate and acrylic acid film stack. The plasma polymerised acrylic acid film was employed to react with the underlying organosilicon matrix, causing a shift in the surface characteristics. The polymeric acrylic acid network was shown to have a wearing effect on the organosilicon, catalysed by environmental water vapour. This process was subsequently controlled for the purpose of wettability control of the surface. As the underlying organosilicon layer is reduced, the increasingly oxygen rich interface becomes more hydrophilic, giving specific and stable control over the surfaces‟ water contact angle. As the fluidic interaction with a surface is generally of high importance in microfluidics, control of this provides a method of improving the workability of novel fluidic systems with materials that previously showed unfavourable characteristics