In this dissertation, I present that at a vacuum of 3×10-7 Torr, residual O2, CO2, H2 and Ar exposure do not significantly degrade the field emission (FE) properties of ZnO nanorods, but N2 exposure significantly does. I propose that this could be due to the dissociation of N2 into atomic nitrogen species and the reaction of such species with ZnO. I also present the effects of O2, CO2, H2O, N2, H2, and Ar residual gas exposure on the FE properties of GaN and ZnS nanostructure. A brief review of growth of ZnO, GaN and ZnS is provided. In addition, Cs deposition on GaN nanostructures at ultra-high vacuum results in 30% decrease in turn-on voltage and 60% in work function. The improvement in FE properties could be due to a Cs-induced space-charge layer at the surface that reduces the barrier for FE and lowers the work function. I describe a new phenomenon, in which the resistivity of CVD-grown graphene increases to a higher saturated value under light exposure, and depends on the wavelength of the light—the shorter the wavelength, the higher the resistivity. First-principle calculations and theoretical analysis based on density functional theory show that (1) a water molecule close to a graphene defect is easier to be split than that of the case of no defect existing and (2) there are a series of meta-stable partially disassociated states for an interfacial water molecule. Calculated disassociation energies are from 2.5 eV to 4.6 eV, that match the experimental observation range of light wavelength from visible to 254 nm UV light under which the resistivity of CVD-grown graphene is increased.

The current technological age is embodied by a constant push for increased performance and efficiency of electronic devices. This push is particularly observable for technologies that comprise free electron sources, which are used in various technologies including electronic displays, x-ray sources, telecommunication equipment, and spacecraft propulsion. Performance of these systems can be increased by reducing weight and power consumption, but is often limited by a bulky electron source with a high energy demand. Carbon nanotubes (CNTs) show favorable properties for field electron emission (FE) and performance as electron sources. This dissertation details the developments of a uniquely designed Spindt type CNT field emission array (CFEA), from initial concept to working prototype, to specifically prevent electrical shorting of the gate. The CFEA is patent pending in the United States. Process development enabled fabrication of a CFEA with a yield of up to 82%. Furthermore, a novel oxygen plasma etch process was developed to reverse shorting after CNT synthesis. CFEA testing demonstrates FE with a current density of up to 293 μA/cm² at the anode and 1.68 mA/cm² at the gate, with lifetimes in excess of 100 hours. A detailed analysis of eighty tested CFEAs revealed three distinct types of damage. Surprisingly, about half of the damaged chips are not electrically shorted, indicating that the CFEAs are very robust. Potential applications of this technology as cathodes for spacecraft electric propulsion were explored. Exposure to an operating electric propulsion thruster showed no significant effect or damage to the CFEAs, marking the first experimental study of CNT field emitters in an electric propulsion environment. A second effort in spacecraft propulsion is a collaboration with the Air Force Institute of Technology (AFIT). CFEAs are the payload on an AFIT developed Cube Satellite, called ALICE, to test electron emission in the space environment. ALICE has passed flight tests and is awaiting launch scheduled for 5 December 2013.

The first comprehensive discovery of carbon nanotubes (CNTs) by S. Iijima in 1991 sparked a huge scientific interest in investigating its unique structure and attractive properties. A multitude of potential applications of CNTs in modern science and technology has been envisaged very early after their discovery. While a few applications are realized on a commercial scale, many are still constrained to laboratory investigations for a constant improvement to meet the service needs. Moreover, some studies are still aimed at further understanding the very growth mechanism. The work reported in this thesis deals with two main topics: The first part of the thesis was aimed at investigating the influence of various supported catalyst precursors on the growth morphology of multiwalled CNTs (MWCNTs) by low-temperature thermal CVD (chemical vapour deposition). The results were explained with the help of thermodynamic calculations of equilibrium phases formed during the reduction reactions inside the CVD reactor. Striking an equilibrium between the respective oxide phase and the metallic phase of the active catalyst species forms the basis for a vertically aligned growth of CNTs. A new class of supported catalysts based on manganese oxide (MnO) was developed. It has been shown that such a method of thermodynamic analysis paves the way for a theoretical assessment of CNT growth morphology. Second part of the thesis is devoted to the growth and field emission characterization of large-array MWCNTs on diverse substrate materials. One of the burgeoning areas of research involves the application of CNTs as electron field emitters in x-ray computed tomography or display technologies. Although several research groups investigated the field emission behaviour of CNTs on different substrate materials, those studies carry at least two important drawbacks: Firstly, a vast majority of the publications report the emission characteristics of individual CNT or an individual vertically aligned CNT (VACNT) bundle. By measuring so, the electric field shielding effects between various CNTs in an array would not be accounted for. Therefore, in this work, large-area emitters grown on stainless steel, copper, molybdenum and silicon substrates were subjected to emission measurements under similar pulsed operation mode, so that a direct comparison would be possible. Entangled CNTs on stainless steel showed a poor emission current density, but a long-term stable emission of 10 mA for more than 96 hours (4 days). The emission current density of CNTs on Cu and Mo was further low, but the threshold field (ETh) on the former was desirably low (~2 V µm-1). Secondly, the existing literature concerning emission characteristics of large-area CNT emitters reports either a high emission current density (Jmax) or a good long-term stability, but fails to demonstrate both simultaneously. It was shown in this work that VACNTs grown on a specific patterned Si substrate displayed an excellent combination of emission current density (5.78 A cm-2) along with a long-term stable emission of 40 mA current for ~730 hours at 10% duty cycle (effective emission time: 73 hours). Based on these results, a hypothesis emphasizing a new parameter, the ratio of the cumulative area of the CNTs to that of the substrate (ACNTs/Asubstrate), was put forth to explain the emission efficiency of large-area emitters. This hypothesis needs further verification by means of simulations. / Iijimas Publikation über Kohlenstoffnanoröhren (CNT) im Jahre 1991 löste ein großes wissenschaftliches Interesse daran aus, die einzigartige Struktur von CNTs und deren attraktive Eigenschaften zu untersuchen. Schon kurz nach der Entdeckung von CNTs wurde das große Potential von CNTs für die moderne Naturwissenschaft und vielfältige Anwendungen erkannt. Einige solcher Anwendungen wurden bereits verwirklicht, viele andere sind gegenwärtig noch im Entwicklungstadium. Auch die Wachstumsmechanismen von CNTs werden momentan weiter untersucht. Die hier vorgelegte Doktorarbeit behandelt zwei Hauptthemen: Der erste Teil widmet sich der Untersuchung des Wachstums von mehrwandigen Kohlenstoffnanoröhren (MWCNTs) durch thermische chemische Gasphasenabscheidung (CVD) bei niedrigen Temperaturen, wobei besonders der Einfluss verschiedener Katalysatormaterialien auf die Nanoröhren-Morphologie im Mittelpunkt steht. Die Ergebnisse können erklärt werden mit Hilfe von thermodynamischen Berechnungen der Gleichgewichtsphasen, die sich während der Reduktionsreaktionen im CVD-Reaktor bilden. Ein Wachstum von senkrecht ausgerichteten CNTs hängt ab von einem Gleichgewicht zwischen der Oxidphase und der metallischen Phase der aktiven Katalysatorkomponenten. Im Rahmen dieser Arbeit wurde eine neue Klasse von Zweikomponenten-Katalysatoren auf der Grundlage von Manganoxid (MnO) entwickelt. Es kann gezeigt werden, dass eine thermodynamische Analyse als Grundlage für eine theoretische Beurteilung des CNT-Wachstumsmechanismus dienen kann. Der zweite Teil der Doktorarbeit ist dem Wachstum von ausgedehnten MWCNT-Anordnungen sowie der Untersuchung der Feldemissionscharakteristik dieser Proben gewidmet, wobei verschiedene Substratmaterialien berücksichtigt wurden. Die Anwendung von CNTs als Elektronen-Feldemitter für Computertomographie und für Bildschirme ist ein attraktives und wachsendes Forschungsgebiet. Zwar wurde das Feldemissionsverhalten von CNTs auf verschiedenen Substraten bereits von mehreren Forschergruppen untersucht, jedoch sind mit diesen Studien Unzulänglichkeiten verbunden: Erstens behandelt die Mehrzahl der Publikationen die Emissionscharakteristik von individuellen CNTs oder von individuellen senkrecht ausgerichteten CNT-Bündeln. Dabei wurden allerdings elektrostatische Abschirmeffekte durch benachbarte CNTs nicht berücksichtigt. Daher wurden im Rahmen dieser Arbeit großflächige Emitter auf Edelstahl-, Kupfer-, Molybdän- und Siliziumsubstraten hergestellt und hinsichtlich ihrer Emissionscharakteristik im gepulsten Regime untersucht, so dass ein direkter Vergleich zwischen den Proben auf verschiedenen Substraten möglich ist. Gegenseitig umschlungene CNTs auf Edelstahl zeigten eine geringe Emissionsstromdichte, dafür war die Emission jedoch langzeitstabil mit 10 mA über mehr als 96 Stunden (vier Tage). Die Emissionsstromdichte von CNTs auf Cu und Mo war ebenfalls niedrig, allerdings im Falle von Cu-Substraten verbunden mit einem vorteilhaft niedrigen Feldschwellwert (ETh) von etwa 2 V µm-1. Zweitens berichtet die vorhandene Literatur über großflächige CNT-Emitter mit einer hohen Emissionsstromdichte (Jmax) oder einer guten Langzeitstabilität, beides gleichzeitig wird allerdings in diesen Arbeiten nicht gezeigt. In der vorliegenden Arbeit werden senkrecht ausgerichtete CNTs auf speziellen strukturierten Si-Substraten vorgestellt, die eine ausgezeichnete Kombination von Emissionsstromdichte (5,78 A/cm2) und einem über 730 Stunden langzeitstabilen Emissionsstrom von 40 mA aufweist, wobei die Arbeitsphase 10 % und damit die effektive Emissionszeit 73 Stunden beträgt. Auf Grundlage dieser Ergebnisse kann ein neuer Erklärungsansatz vorgestellt werden: Das Verhältnis von aufsummierter CNT-Fläche zur Substratfläche (ACNTs/Asubstrate) wird als neuer Parameter eingeführt und zur Erklärung der Emissionseffizienz von großflächigen Emittern verwendet. Diese Arbeitshypothese sollte durch Simulationsrechnungen verifiziert werden.

The first comprehensive discovery of carbon nanotubes (CNTs) by S. Iijima in 1991 sparked a huge scientific interest in investigating its unique structure and attractive properties. A multitude of potential applications of CNTs in modern science and technology has been envisaged very early after their discovery. While a few applications are realized on a commercial scale, many are still constrained to laboratory investigations for a constant improvement to meet the service needs. Moreover, some studies are still aimed at further understanding the very growth mechanism. The work reported in this thesis deals with two main topics: The first part of the thesis was aimed at investigating the influence of various supported catalyst precursors on the growth morphology of multiwalled CNTs (MWCNTs) by low-temperature thermal CVD (chemical vapour deposition). The results were explained with the help of thermodynamic calculations of equilibrium phases formed during the reduction reactions inside the CVD reactor. Striking an equilibrium between the respective oxide phase and the metallic phase of the active catalyst species forms the basis for a vertically aligned growth of CNTs. A new class of supported catalysts based on manganese oxide (MnO) was developed. It has been shown that such a method of thermodynamic analysis paves the way for a theoretical assessment of CNT growth morphology. Second part of the thesis is devoted to the growth and field emission characterization of large-array MWCNTs on diverse substrate materials. One of the burgeoning areas of research involves the application of CNTs as electron field emitters in x-ray computed tomography or display technologies. Although several research groups investigated the field emission behaviour of CNTs on different substrate materials, those studies carry at least two important drawbacks: Firstly, a vast majority of the publications report the emission characteristics of individual CNT or an individual vertically aligned CNT (VACNT) bundle. By measuring so, the electric field shielding effects between various CNTs in an array would not be accounted for. Therefore, in this work, large-area emitters grown on stainless steel, copper, molybdenum and silicon substrates were subjected to emission measurements under similar pulsed operation mode, so that a direct comparison would be possible. Entangled CNTs on stainless steel showed a poor emission current density, but a long-term stable emission of 10 mA for more than 96 hours (4 days). The emission current density of CNTs on Cu and Mo was further low, but the threshold field (ETh) on the former was desirably low (~2 V µm-1). Secondly, the existing literature concerning emission characteristics of large-area CNT emitters reports either a high emission current density (Jmax) or a good long-term stability, but fails to demonstrate both simultaneously. It was shown in this work that VACNTs grown on a specific patterned Si substrate displayed an excellent combination of emission current density (5.78 A cm-2) along with a long-term stable emission of 40 mA current for ~730 hours at 10% duty cycle (effective emission time: 73 hours). Based on these results, a hypothesis emphasizing a new parameter, the ratio of the cumulative area of the CNTs to that of the substrate (ACNTs/Asubstrate), was put forth to explain the emission efficiency of large-area emitters. This hypothesis needs further verification by means of simulations. / Iijimas Publikation über Kohlenstoffnanoröhren (CNT) im Jahre 1991 löste ein großes wissenschaftliches Interesse daran aus, die einzigartige Struktur von CNTs und deren attraktive Eigenschaften zu untersuchen. Schon kurz nach der Entdeckung von CNTs wurde das große Potential von CNTs für die moderne Naturwissenschaft und vielfältige Anwendungen erkannt. Einige solcher Anwendungen wurden bereits verwirklicht, viele andere sind gegenwärtig noch im Entwicklungstadium. Auch die Wachstumsmechanismen von CNTs werden momentan weiter untersucht. Die hier vorgelegte Doktorarbeit behandelt zwei Hauptthemen: Der erste Teil widmet sich der Untersuchung des Wachstums von mehrwandigen Kohlenstoffnanoröhren (MWCNTs) durch thermische chemische Gasphasenabscheidung (CVD) bei niedrigen Temperaturen, wobei besonders der Einfluss verschiedener Katalysatormaterialien auf die Nanoröhren-Morphologie im Mittelpunkt steht. Die Ergebnisse können erklärt werden mit Hilfe von thermodynamischen Berechnungen der Gleichgewichtsphasen, die sich während der Reduktionsreaktionen im CVD-Reaktor bilden. Ein Wachstum von senkrecht ausgerichteten CNTs hängt ab von einem Gleichgewicht zwischen der Oxidphase und der metallischen Phase der aktiven Katalysatorkomponenten. Im Rahmen dieser Arbeit wurde eine neue Klasse von Zweikomponenten-Katalysatoren auf der Grundlage von Manganoxid (MnO) entwickelt. Es kann gezeigt werden, dass eine thermodynamische Analyse als Grundlage für eine theoretische Beurteilung des CNT-Wachstumsmechanismus dienen kann. Der zweite Teil der Doktorarbeit ist dem Wachstum von ausgedehnten MWCNT-Anordnungen sowie der Untersuchung der Feldemissionscharakteristik dieser Proben gewidmet, wobei verschiedene Substratmaterialien berücksichtigt wurden. Die Anwendung von CNTs als Elektronen-Feldemitter für Computertomographie und für Bildschirme ist ein attraktives und wachsendes Forschungsgebiet. Zwar wurde das Feldemissionsverhalten von CNTs auf verschiedenen Substraten bereits von mehreren Forschergruppen untersucht, jedoch sind mit diesen Studien Unzulänglichkeiten verbunden: Erstens behandelt die Mehrzahl der Publikationen die Emissionscharakteristik von individuellen CNTs oder von individuellen senkrecht ausgerichteten CNT-Bündeln. Dabei wurden allerdings elektrostatische Abschirmeffekte durch benachbarte CNTs nicht berücksichtigt. Daher wurden im Rahmen dieser Arbeit großflächige Emitter auf Edelstahl-, Kupfer-, Molybdän- und Siliziumsubstraten hergestellt und hinsichtlich ihrer Emissionscharakteristik im gepulsten Regime untersucht, so dass ein direkter Vergleich zwischen den Proben auf verschiedenen Substraten möglich ist. Gegenseitig umschlungene CNTs auf Edelstahl zeigten eine geringe Emissionsstromdichte, dafür war die Emission jedoch langzeitstabil mit 10 mA über mehr als 96 Stunden (vier Tage). Die Emissionsstromdichte von CNTs auf Cu und Mo war ebenfalls niedrig, allerdings im Falle von Cu-Substraten verbunden mit einem vorteilhaft niedrigen Feldschwellwert (ETh) von etwa 2 V µm-1. Zweitens berichtet die vorhandene Literatur über großflächige CNT-Emitter mit einer hohen Emissionsstromdichte (Jmax) oder einer guten Langzeitstabilität, beides gleichzeitig wird allerdings in diesen Arbeiten nicht gezeigt. In der vorliegenden Arbeit werden senkrecht ausgerichtete CNTs auf speziellen strukturierten Si-Substraten vorgestellt, die eine ausgezeichnete Kombination von Emissionsstromdichte (5,78 A/cm2) und einem über 730 Stunden langzeitstabilen Emissionsstrom von 40 mA aufweist, wobei die Arbeitsphase 10 % und damit die effektive Emissionszeit 73 Stunden beträgt. Auf Grundlage dieser Ergebnisse kann ein neuer Erklärungsansatz vorgestellt werden: Das Verhältnis von aufsummierter CNT-Fläche zur Substratfläche (ACNTs/Asubstrate) wird als neuer Parameter eingeführt und zur Erklärung der Emissionseffizienz von großflächigen Emittern verwendet. Diese Arbeitshypothese sollte durch Simulationsrechnungen verifiziert werden.

The ability to pattern in the nanoscale to drill holes, to draw lines, to make circles, or more complicated shapes that span a few atoms in width is the main driver behind current efforts in the rapidly growing area of nanomanufacturing. In applications ranging from the microprocessor industry to biomedical science, there is a constant need to develop new tools and processes that enable the shrinking of devices. For this and more applications, nanomanufacturing using electron beams offers a window of opportunity as a top-down approach since electrons, unlike light, have a wavelength that is in the order of the atomic distance. Though the technology based on electron beams has been available for more than twenty years, new concepts are constantly being explored and developed based on fundamental approaches. As such, a tool that utilizes electron field-emission from carbon nanotubes was proposed to accomplish such feats. A full numerical analysis of electron field-emission from carbon nanotubes for nanomachining applications is presented. The different aspects that govern the process of electron field-emission from carbon nanotubes using the finite element method are analyzed. Extensive modeling is carried here to determine what the effect of different carbon nanotube geometries have on their emission profiles, what energy transport processes they are subject to, and establish what the potential experimental parameters are for nanomachining. This dissertation builds on previous efforts based on Monte Carlo simulations to determine electron deposition profiles inside metals, but takes them to next level by considering realistic emission scenarios. A hybrid numerical approach is used that combines the two-temperature model with Molecular Dynamics to study phase change and material removal in depth. The use of this method, allows the determination of the relationship between the amount of energy required to remove a given number of atoms from a metallic workpiece and the number of carbon nanotubes and their required settings in order to achieve nanomachining. Finally, the grounds for future work in this area are provided, including the need for novel electron focusing systems, as well as the extension of the hybrid numerical approach to study different materials.

Nanomanufacturing is an active research area in academia and industry due to the ever-growing demands for precision surface modifications of thin films or substrates with nanoscale features. Conventional lithographic techniques face many challenges as they approach their fundamental limits. Consequently, new nanomanufacturing tools, fabrication techniques, and precision instruments are being explored and developed to meet these challenges. It has been hypothesized that direct-write nanolithography might be achieved by using a field-emitted electron beam for nanomachining. This dissertation moves this research one step closer by developing a precision instrument that can enable the integration of direct-write nanolithography by a field-emitted electron beam with dimensional metrology by scanning tunneling microscopy. First, field emission from two prospective electron sources, a carbon nanotube field emitter and a sharp tungsten field emitter, is characterized at distances ranging from sub-micrometer to a few micrometers. Also, the design and construction of a low thermal drift piezoelectric linear motor is described for tip-sample approach. Experiments indicate that: the step size is highly repeatable with a standard deviation of less than 1.2 nm and the thermal stability is better than 40 nm/◦C. Finally, the design and construction of the instrument are presented. Experiments indicate that: the instrument is operating properly in scanning tunneling microscope mode with a resolution of less than 2 Å.

<p>Carbon nanotubes (CNTs) have recently emerged as promising candidates for electron field emission (FE) cathodes in integrated FE devices. These nanostructured carbon materials possess exceptional properties and their synthesis can be thoroughly controlled. Their integration into advanced electronic devices, including not only FE cathodes, but sensors, energy storage devices, and circuit components, has seen rapid growth in recent years. The results of the studies presented here demonstrate that the CNT field emitter is an excellent candidate for next generation vacuum microelectronics and related electron emission devices in several advanced applications.</p><p> The work presented in this study addresses determining factors that currently confine the performance and application of CNT-FE devices. Characterization studies and improvements to the FE properties of CNTs, along with Micro-Electro-Mechanical Systems (MEMS) design and fabrication, were utilized in achieving these goals. Important performance limiting parameters, including emitter lifetime and failure from poor substrate adhesion, are examined. The compatibility and integration of CNT emitters with the governing MEMS substrate (i.e., polycrystalline silicon), and its impact on these performance limiting parameters, are reported. CNT growth mechanisms and kinetics were investigated and compared to silicon (100) to improve the design of CNT emitter integrated MEMS based electronic devices, specifically in vacuum microelectronic device (VMD) applications.</p><p> Improved growth allowed for design and development of novel cold-cathode FE devices utilizing CNT field emitters. A chemical ionization (CI) source based on a CNT-FE electron source was developed and evaluated in a commercial desktop mass spectrometer for explosives trace detection. This work demonstrated the first reported use of a CNT-based ion source capable of collecting CI mass spectra. The CNT-FE source demonstrated low power requirements, pulsing capabilities, and average lifetimes of over 320 hours when operated in constant emission mode under elevated pressures, without sacrificing performance. Additionally, a novel packaged ion source for miniature mass spectrometer applications using CNT emitters, a MEMS based Nier-type geometry, and a Low Temperature Cofired Ceramic (LTCC) 3D scaffold with integrated ion optics were developed and characterized. While previous research has shown other devices capable of collecting ion currents on chip, this LTCC packaged MEMS micro-ion source demonstrated improvements in energy and angular dispersion as well as the ability to direct the ions out of the packaged source and towards a mass analyzer. Simulations and experimental design, fabrication, and characterization were used to make these improvements.</p><p> Finally, novel CNT-FE devices were developed to investigate their potential to perform as active circuit elements in VMD circuits. Difficulty integrating devices at micron-scales has hindered the use of vacuum electronic devices in integrated circuits, despite the unique advantages they offer in select applications. Using a combination of particle trajectory simulation and experimental characterization, device performance in an integrated platform was investigated. Solutions to the difficulties in operating multiple devices in close proximity and enhancing electron transmission (i.e., reducing grid loss) are explored in detail. A systematic and iterative process was used to develop isolation structures that reduced crosstalk between neighboring devices from 15% on average, to nearly zero. Innovative geometries and a new operational mode reduced grid loss by nearly threefold, thereby improving transmission of the emitted cathode current to the anode from 25% in initial designs to 70% on average. These performance enhancements are important enablers for larger scale integration and for the realization of complex vacuum microelectronic circuits.</p> / Dissertation

La recherche sur les sources d'électrons modulées en temps connaît actuellement un vif intérêt, notamment dans le domaine des sciences fondamentales ou pour certaines applications exigeantes. C'est dans ce contexte que ce travail exploratoire sur l'émission de champ (EC) photo-assistée de nanofils de silicium s'inscrit. Nous explorons dans un premier temps les caractéristiques émissives de ces nanofils semi-conducteurs présentant un régime de saturation très prononcé, très sensible à la température et à la lumière, et encore jamais observé pour de telles structures à température ambiante. Le rôle important joué par la surface dans la saturation est prouvé par des traitements in-situ ayant des conséquences radicales sur les caractéristiques courant-tension de l'EC. Grâce à des cycles de passivation à l'hydrogène nous avons pu montrer le rôle des liaisons pendantes à l'interface matériau/oxyde dans la saturation et basculer de façon réversible entre un comportement quasi-métallique et semiconducteur. Nous étudions ensuite la réponse de ces émetteurs à une excitation optique modulée en temps. Leur réponse est attribuée à la photoconduction due à l'absorption directe : les effets thermiques peuvent être exclus à ces puissances laser. Nous avons alors mis en évidence la présence de deux constantes de temps associées à l'éclairement et la relaxation de l'échantillon. Le rôle des états pièges en surface prend là encore une part importante dans le temps de réponse de l'échantillon en limitant celui-ci à quelques dizaines de microsecondes seulement. Enfin nous avons mis en évidence un effet complètement nouveau en EC sous éclairage laser : une double résistance différentielle négative. Dans les dispositifs à semiconducteurs, cet effet est généralement associé à des oscillations de courant à haute fréquence et ouvre la perspective vers des sources EC compactes et auto-oscillantes à très hautes fréquences / There is currently a notable rise in research on time modulated electron sources for new fundamental science and for several demanding applications. Our exploratory work on photo-assisted field emission (FE) from silicon nanowires falls within this context. We first explore FE characteristics of these semiconducting nanowires, which are very sensitive to temperature and light and present a very pronounced current saturation regime, never observed before on such structures. The strong influence of surface states on the saturation regime is proven by in-situ treatments, which radically alter the FE current-voltage characteristics. H-passivation cycles reveal the role of dangling bonds at material/oxide interface in the saturation regime and allow to reversibly switch between a quasi-metal and semiconductor behavior. We then study the response of these emitters to a time modulated optical excitation. The response is attributed to direct absorption photoconduction after excluding thermal effects at these laser powers. The existence of two time constants associated with illumination and relaxation time is shown. The role of the surface state traps again plays an important part in the response time, limiting it to some tens of microseconds. Finally, a completely new effect in FE under laser illumination is identified : a double negative differential resistance. In semiconductor devices this effect is usually associated with high frequency current oscillations and thus opens perspectives toward compact and high frequency self-oscillating FE sources

<p>Large scale and cost-efficient synthesis of carbon nanostructured materials has garnered tremendous interest over the last decade owing to their plethora of engineering and bio-science applications. One promising method is roll-to-roll radio frequency chemical vapor deposition and this work presents a computational investigation of the capacitively coupled radio frequency plasma in such a system. The system operates at moderate pressures (less than 30 mbar) with an 80 kHz square wave voltage input. The computational model aids the understanding of plasma properties and α-γ transition parameters which strongly influence the nanostructure deposition characteristics in the system. One dimensional argon and hydrogen plasma models are developed to characterize the effects of input voltage, gas pressure, frequency, and waveform on the plasma properties. A hybrid mode which displays the characteristics of both α and γ discharges is found to exist for the low cycle frequency 80 kHz square wave voltage input due to the high frequency harmonics associated with a square waveform. The threshold voltage at which the transition between the different regimes occurs is higher for hydrogen than for argon owing to its diatomic nature. Collision radiative modeling is performed to predict the argon emission intensity in the discharge gap. The results are found to lie within 16% of the optical emission spectroscopy measurements with better agreement at the center of the discharge, where the measurement uncertainty is low and the emission by ions is not significant. A quasi-zero dimensional steady state chemistry model which uses the hydrogen plasma properties as inputs predicts high concentrations of C₂H, C₂H₂, C₂H₃⁺, C₂H₄⁺and C₂H₆⁺during carbon nanostructure deposition.</p> <p> </p> <p>Carbon nanostructures are popularly used as field emitters. Field emission based microplasma actuators generate highly non-neutral surface discharges that can be used to heat, pump, and mix the flow through microchannels and offer an innovative solution to the problems associated with microcombustion. They provide a constant source of heat to counter the large heat loss through the combustor surface, they aid in flow transport at low Reynolds numbers without the use of moving parts, and they provide a constant supply of radicals to promote chain branching reactions. This work presents two actuator concepts for the generation of field emission microplasma, one with offset electrodes and the other with planar electrodes. They operate at input voltages in the 275 to 325 V range at a frequency of 1 GHz which is found to be the most suitable value for flow enhancement. The momentum and energy imparted by the charged particles to the neutrals as modeled by 2D Particle-In-Cell with Monte Carlo Collisions (PIC/MCC) are applied to actuate flow in microchannels using 2D Computational Fluid Dynamics modeling. The planar electrode configuration is found to be more suitable for the purpose of heating, igniting and mixing the flow, as well as improving its residence time through a 10 mm long microcombustor. The combustion of hydrogen and air with the help of 4 such actuators, each with a power consumption of 47.5 mW/cm, generates power with an efficiency of 28.8%. Coating the electrode surface with carbon nanostructures improves the combustion efficiency by a factor of 2.5 and reduces the input voltage by a factor of 6.5. Such microcombustors can be applied to all battery based systems requiring micropower generation with the ultimate goal of “generating power on a chip'”.</p>

Um dos desafios mais importantes para a indústria de bens eletrônicos de consumo é o desenvolvimento de um dispositivo mostrador de informação (display) que tenda aos requisitos de alta qualidade de imagem, grande área, baixo consumo de energia e baixo custo. O display de comissão de campo (field emission display, ou FED) representa a tecnologia com maior potencial para atender a estes requisitos. No entanto a baixa durabilidade e a baixa confiabilidade dos protótipos baseados em emissores metálicos impedem que esta tecnologia entre no mercado. Neste trabalho, investigam-se duas abordagens que podem representar urna solução para estas deficiências: a melhora do vácuo na câmara de emissão e o emprego de nanotubos de carbono como emissores. No que se refere a melhora das propriedades de vácuo num FED, este trabalho propõe um novo tipo de emissor baseado em uma membrana porosa. Cálculos teóricos referentes as propriedades de vácuo e ao fator de amplificação do campo eletrostático são apresentados para esta nova configuração, sendo proposto um modelo para determinar o limite superior do fator de amplificação do campo. No que se refere a parte experimental, e demonstrado que membranas porosas de diamante de fato funcionam como emissores, de acordo com a proposta. O desempenho destas membranas e comparado com o de condutores metálicos planos, com e sem um recobrimento de diamond-like carbon. São apresentadas imagens dos spots de emissão em poros, e um estudo da estabilidade de emissão de longo prazo e realizado. No que se refere aos nanotubos de carbono este trabalho propõe um novo processo de tratamento dos nanotubos em arco de plasma que resulta em melhora das propriedades de emissão destas estruturas. Um estudo da estabilidade de emissão dos nanotubos também e apresentado, sendo que uma degradação sistemática da emissão e relatada para o caso de nanotubos mono-parede (single-wall). / One of the most important challenges to the electronics industry is the production of a flat panel display which fulfills the requirements of high quality image, large area low power and low cost. Field Emission Display (FED) is the technology in best conditions to face these requirements. However, the short lifetime and low reliability of FED prototypes based on metallic emitters are hindering this technology to get into the market. In this work we investigate two different approaches that could represent a solution for these problems: improvement of the vacuum characteristics inside the emission chamber and use of carbon nanotubes as emitters. With respect to the improvement of vacuun in a FED, this work proposes a new type of emitter based on a porous diamond membrane. Theoretical calculations referent to the vacuum properties and referent to electrostatic field enhancement factor are presented. A new model is proposed to determine the superior limit for the eletrostatic field enhancement factor in a porous emitter. With respect to the experimental part of this work, we show that diamond porous membranes indeed emit electrons, according to the original proposition. The emission performance of these membranes is compared to the performance of flat metalic emitters, coated or Dot with diamond-like carbon. Images of emission spots in pores and a study of the long term membrane emission stability are presented. With respect to carbon nanotubes this work presents a. new treatment process, under plasma arc, that resulted in emission improvement. A study all emission stability of nanotubes is also presented, and systematical emission decay is reported for single-wall nanotubes.