Effect of reaction time on the particle size of ZnO and ZnO : Ce obtained by a sol-gel method

In this work particles of ZnO of size range 33-56 Angstrom were prepared by a sol-gel method. The effect of reaction time on the particle size of ZnO or ZnO:Ce was investigated by transmission electron microscopy measurements, UV-vis absorption and luminescence spectroscopy. A linear increase of the mean particle size is observed as a function of reaction time. The cerium-doped particles are bigger than the pure ZnO ones obtained at the same reaction time. A shift to lower energy at the maximum of the bands is observed in all absorption, emission and excitation spectra as a function of particle growth. From the absorption spectra the optical energy gap values (Eg) for these particles were determined. In the quantum size regime, Eg was found to decrease with particle growth.

Using shifts in the electronic emission curve to evaluate polymer surface degradation

The polymer surface degradation and/or modification evolution of Teflon FEP and Mylar C films caused by a low energy electron beam were analyzed using a new method that consists in measuring the second crossover energy shift in the electronic emission curve. Upon prolonged irradiation, the second crossover energy shifts irreversibly to lower values in Teflon FEP but to higher values in Mylar C, indicating distinct mechanisms of surface degradation for the two polymers. The method represents a relatively inexpensive way to monitor early stages of surface degradation since the secondary electron emission comes from a maximum depth below the geometric surface of 100 mn in insulators. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Influence of the temperature on the nucleation of silver nanoparticles in Tm3+/Yb3+ codoped PbO-GeO2 glasses

The influence of the temperature on the nucleation of silver nanoparticles (NPs) in Tm3+/Yb3+ codoped PbO-GeO2 glasses was studied in this work. The infrared-to-visible frequency upconversion (UC) luminescence of Tm3+ ions was used to probe the NPs nucleation and the results were correlated with the increase of the heat-treatment temperature. Emission spectra in the blue-red region were measured by exciting the samples with a cw 980 nm diode laser in resonance with the Yb3+ transition (F-2(7/2) -> F-2(5/2)). The results were correlated with transmission electron microscopy measurements and revealed the different behavior of the nucleation process as a function of temperature.The enhanced UC emission in the visible region is attributed to the increased local field in the proximity of the silver NPs combined with the Yb3+ -> Tm3+ energy transfer. (C) 2010 Elsevier B.V. All rights reserved.

Defect-induced photoluminescence of powdered silica glass

Visible photoluminescence was generated in standard soda-lime-silica glass powder, mechanically milled in a high-energy attrition mill. The broad emission band maximum shows a linear dependence on the exciting wavelength, suggesting the possibility to tune the PL emission. The photoluminescence was attributed to defect generation related to unsatisfied chemical bonds due to the high surface area. Raman scattering and ultraviolet-visible optical reflectance measurements corroborate this assertion. Transmission electron microscopy measurements indicate that the powder is composed by nanocrystallites with about 10-20 nanometers immersed in an amorphous media.

Nanoparticle characterization of Er-doped SnO2 pellets obtained with different pH of colloidal suspension

SnO2:2 at. %Er xerogel samples were obtained by sol-gel technique from colloidal suspensions with distinct pHs. The evaluation of critical regions inside the nanocrystallite is fundamental for the interpretation of the influence of pH on the emission data. In this way, the nanocrystal depletion layer thickness was obtained with the help of photoluminescence, Raman, X-ray diffraction, and field-emission gun scanning electron microscopy measurements. It was observed that acid suspensions (pH < 7) lead to high surface disorder in which a larger number of cross-linked bonds Sn-O-Sn among nanoparticles are present. For these samples, the nanoparticle depletion layer is larger as compared to samples obtained from other pH. Photoluminescence measurement in the near infrared region indicates that the emission intensity of the transition 4I13/2 → 4I15/2 is also influenced by the pH of the starting colloidal suspension, generating peaks more or less broadened, depending on location of Er3+ ions in the SnO2 lattice (high or low symmetry sites). © 2013 AIP Publishing LLC.

Laser emission of a Nd-doped mixed tellurite and zinc oxide glass

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Mylar Secondary Emission-energy Distribution and Yields

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Mikroskopische Untersuchung der ferroelektrischen Elektronenemission von der freien Oberfläche von Triglyzinsulfat

In dieser Arbeit wurden erstmalig orts- und energieaufgelöste Untersuchungen der ferroelektrischen Elektronenemission (FEE) durchgeführt. Als Modellsystem diente Triglyzinsulfat (TGS). Als spektromikroskopische Methode kam die Emissions-Elektronenmikroskopie zum Einsatz. Typische Schaltfelder betrugen 2 kV/mm, angelegt wurde eine sinusoïdale Wechselspannung mit 300 Hz. Die Temperatur, bei der die FEE verschwindet (32°C), liegt unterhalb der Curie-Temperatur des TGS (TC=49°C). Dieser Unterschied kann auf den Einfluss des Extraktionsfeldes des Emissions-Elektronenmikroskops (1 kV/mm) zurückgeführt werden. Oberhalb der Curie-Temperatur konnte keine Emission beobachtet werden. Die Elektroden vor und nach der Messung waren identisch, d.h. nicht zerstört, wie man es erwarten würde, wenn ein Oberflächenplasma gezündet wurde. Bei ca. 150 V/mm beginnt die Intensität der beobachteten Emission Schwankungen aufzuweisen. Dies könnte die Ursache in dem Einsatz von ersten Zündungen eines Mikroplasmas mit destruktiver Wirkung haben. Die ortsintegrierte Energieverteilung weist bei Spannungsamplituden bis 300 V zwei Maxima auf. Dies deutet auf zwei Emissionsmechanismen hin, einen sekundären (ca. 10 eV) und einen primären (ca. 13 bis 45 eV) Effekt. Die Hochenergie-Abschneidekanten korrelieren im Bereich bis 200 V bis auf wenige eV mit der angelegten Spannungsamplitude. Die Messung der ortsaufgelösten Energieverteilung zeigt, dass die primäre Emission aus den Bereichen ohne Elektrode stammt. Sie wird der FEE zugeschrieben. Diese Elektronen können– auf Grund der lokalen Felder – auf die Elektroden beschleunigt werden und hier sekundäre Prozesse auslösen (niederenergetischer Bereich des Spektrums). Dies wird durch die lokalen Spektren dieser Bereiche bestätigt.

Synthesis and characterization of new discotic polycyclic aromatic hydrocarbons and related pyrolytic nanostructures

Diskotische Hexa-peri-hexabenzocoronene (HBC) als molekulare, definierte graphitische Substrukturen sind bereits seit langem Gegenstand von Untersuchungen zu der Delokalisierung von π-Elektronen. In dieser Arbeit wurden zusätzlich Platin-Komplexe in das periphere Substitutionsmuster von HBC eingeführt. Dies führte zu einer Verbesserung der Emission von dem angeregten Triplett-Zustand in den Singulett-Grundzustand mit einer zusätzlichen Verlängerung der Lebensdauer des angeregten Zustandes. Zusätzlich erlaubte diese Konfiguration ein schnelles Intersystem-Crossing mittels einer verstärkten Spin-Orbit Kopplung, die sowohl bei tiefen Temperaturen, als auch bei Raumtemperatur exklusiv zu Phosphoreszenz (T1→S0) führte. Das Verständniss über solche Prozesse ist auch essentiell für die Entwicklung verbesserter opto-elektronischer Bauteile. Die Erstellung von exakt definierten molekularen Strukturen, die speziell für spezifische Interaktionen hergestellt wurden, machten eine Inkorporation von hydrophoben-hydrophilen, wasserstoffverbrückten oder elektrostatischen funktionalisierten Einheiten notwendig, um damit den supramolekularen Aufbau zu kontrollieren. Mit Imidazolium-Salzen funktionalisierte HBC Derivate wurden zu diesem Zwecke hergestellt. Eine interessante Eigenschaft dieser Moleküle ist ihre Amphiphilie. Dies gestattete die Untersuchung ihrer Eigenschaften in einem polaren Solvens und sowohl der Prozessierbarkeit als auch der Faserbildung auf Siliziumoxid-Trägern. Abhängig vom Lösungsmittel und der gewählten Konditionen konnten hochkristalline Fasern erhalten werden. Durch eine Substitution der HBCs mit langen, sterisch anspruchsvollen Seitenketten, konnte durch eine geeignete Prozessierung eine homöotrope Ausrichtung auf Substraten erreicht werden, was dieses Material interessant für photovoltaische Applikationen macht. Neuartige Polyphenylen-Metall-Komplexe mit diskotischen, linearen und dendritischen Geometrien wurden mittels einer einfachen Reaktion zwischen Co2(CO)8 und Ethinyl-Funktionalitäten in Dichlormethan hergestellt. Nach der Pyrolyse dieser Komplexe ergaben sich unterschiedliche Kohlenstoff-Nanopartikel, inklusive Nanoröhren, graphitischen Nanostäben und Kohlenstoff/Metall Hybrid Komplexe, die durch Elektronenmikroskopie untersucht wurden. Die resultierenden Strukturen waren dabei abhängig von der Zusammensetzung und Struktur der Ausgangssubstanzen. Anhand dieser Resultate ergeben sich diverse Möglichkeiten, um den Mechanismus, der zur Herstellung graphitischer Nanopartikel führt, besser zu verstehen.

High-density metallic nano-emitter arrays and their field emission characteristics

We report the fabrication and field emission properties of high-density nano-emitter arrays with on-chip electron extraction gate electrodes and up to 106 metallic nanotips that have an apex curvature radius of a few nanometers and a the tip density exceeding 108 cm−2. The gate electrode was fabricated on top of the nano-emitter arrays using a self-aligned polymer mask method. By applying a hot-press step for the polymer planarization, gate–nanotip alignment precision below 10 nm was achieved. Fabricated devices exhibited stable field electron emission with a current density of 0.1 A cm−2, indicating that these are promising for applications that require a miniature high-brightness electron source.

Thermal, stress, and traps effects in AlGaN/GaN HEMTs

GaN y AlN son materiales semiconductores piezoeléctricos del grupo III-V. La heterounión AlGaN/GaN presenta una elevada carga de polarización tanto piezoeléctrica como espontánea en la intercara, lo que genera en su cercanía un 2DEG de grandes concentración y movilidad. Este 2DEG produce una muy alta potencia de salida, que a su vez genera una elevada temperatura de red. Las tensiones de puerta y drenador provocan un stress piezoeléctrico inverso, que puede afectar a la carga de polarización piezoeléctrica y así influir la densidad 2DEG y las características de salida. Por tanto, la física del dispositivo es relevante para todos sus aspectos eléctricos, térmicos y mecánicos. En esta tesis se utiliza el software comercial COMSOL, basado en el método de elementos finitos (FEM), para simular el comportamiento integral electro-térmico, electro-mecánico y electro-térmico-mecánico de los HEMTs de GaN. Las partes de acoplamiento incluyen el modelo de deriva y difusión para el transporte electrónico, la conducción térmica y el efecto piezoeléctrico. Mediante simulaciones y algunas caracterizaciones experimentales de los dispositivos, hemos analizado los efectos térmicos, de deformación y de trampas. Se ha estudiado el impacto de la geometría del dispositivo en su auto-calentamiento mediante simulaciones electro-térmicas y algunas caracterizaciones eléctricas. Entre los resultados más sobresalientes, encontramos que para la misma potencia de salida la distancia entre los contactos de puerta y drenador influye en generación de calor en el canal, y así en su temperatura. El diamante posee une elevada conductividad térmica. Integrando el diamante en el dispositivo se puede dispersar el calor producido y así reducir el auto-calentamiento, al respecto de lo cual se han realizado diversas simulaciones electro-térmicas. Si la integración del diamante es en la parte superior del transistor, los factores determinantes para la capacidad disipadora son el espesor de la capa de diamante, su conductividad térmica y su distancia a la fuente de calor. Este procedimiento de disipación superior también puede reducir el impacto de la barrera térmica de intercara entre la capa adaptadora (buffer) y el substrato. La muy reducida conductividad eléctrica del diamante permite que pueda contactar directamente el metal de puerta (muy cercano a la fuente de calor), lo que resulta muy conveniente para reducir el auto-calentamiento del dispositivo con polarización pulsada. Por otra parte se simuló el dispositivo con diamante depositado en surcos atacados sobre el sustrato como caminos de disipación de calor (disipador posterior). Aquí aparece una competencia de factores que influyen en la capacidad de disipación, a saber, el surco atacado contribuye a aumentar la temperatura del dispositivo debido al pequeño tamaño del disipador, mientras que el diamante disminuiría esa temperatura gracias a su elevada conductividad térmica. Por tanto, se precisan capas de diamante relativamente gruesas para reducer ele efecto de auto-calentamiento. Se comparó la simulación de la deformación local en el borde de la puerta del lado cercano al drenador con estructuras de puerta estándar y con field plate, que podrían ser muy relevantes respecto a fallos mecánicos del dispositivo. Otras simulaciones se enfocaron al efecto de la deformación intrínseca de la capa de diamante en el comportamiento eléctrico del dispositivo. Se han comparado los resultados de las simulaciones de la deformación y las características eléctricas de salida con datos experimentales obtenidos por espectroscopía micro-Raman y medidas eléctricas, respectivamente. Los resultados muestran el stress intrínseco en la capa producido por la distribución no uniforme del 2DEG en el canal y la región de acceso. Además de aumentar la potencia de salida del dispositivo, la deformación intrínseca en la capa de diamante podría mejorar la fiabilidad del dispositivo modulando la deformación local en el borde de la puerta del lado del drenador. Finalmente, también se han simulado en este trabajo los efectos de trampas localizados en la superficie, el buffer y la barrera. Las medidas pulsadas muestran que tanto las puertas largas como las grandes separaciones entre los contactos de puerta y drenador aumentan el cociente entre la corriente pulsada frente a la corriente continua (lag ratio), es decir, disminuir el colapse de corriente (current collapse). Este efecto ha sido explicado mediante las simulaciones de los efectos de trampa de superficie. Por su parte, las referidas a trampas en el buffer se enfocaron en los efectos de atrapamiento dinámico, y su impacto en el auto-calentamiento del dispositivo. Se presenta también un modelo que describe el atrapamiento y liberación de trampas en la barrera: mientras que el atrapamiento se debe a un túnel directo del electrón desde el metal de puerta, el desatrapamiento consiste en la emisión del electrón en la banda de conducción mediante túnel asistido por fonones. El modelo también simula la corriente de puerta, debida a la emisión electrónica dependiente de la temperatura y el campo eléctrico. Además, también se ilustra la corriente de drenador dependiente de la temperatura y el campo eléctrico. ABSTRACT GaN and AlN are group III-V piezoelectric semiconductor materials. The AlGaN/GaN heterojunction presents large piezoelectric and spontaneous polarization charge at the interface, leading to high 2DEG density close to the interface. A high power output would be obtained due to the high 2DEG density and mobility, which leads to elevated lattice temperature. The gate and drain biases induce converse piezoelectric stress that can influence the piezoelectric polarization charge and further influence the 2DEG density and output characteristics. Therefore, the device physics is relevant to all the electrical, thermal, and mechanical aspects. In this dissertation, by using the commercial finite-element-method (FEM) software COMSOL, we achieved the GaN HEMTs simulation with electro-thermal, electro-mechanical, and electro-thermo-mechanical full coupling. The coupling parts include the drift-diffusion model for the electron transport, the thermal conduction, and the piezoelectric effect. By simulations and some experimental characterizations, we have studied the device thermal, stress, and traps effects described in the following. The device geometry impact on the self-heating was studied by electro-thermal simulations and electrical characterizations. Among the obtained interesting results, we found that, for same power output, the distance between the gate and drain contact can influence distribution of the heat generation in the channel and thus influence the channel temperature. Diamond possesses high thermal conductivity. Integrated diamond with the device can spread the generated heat and thus potentially reduce the device self-heating effect. Electro-thermal simulations on this topic were performed. For the diamond integration on top of the device (top-side heat spreading), the determinant factors for the heat spreading ability are the diamond thickness, its thermal conductivity, and its distance to the heat source. The top-side heat spreading can also reduce the impact of thermal boundary resistance between the buffer and the substrate on the device thermal behavior. The very low electrical conductivity of diamond allows that it can directly contact the gate metal (which is very close to the heat source), being quite convenient to reduce the self-heating for the device under pulsed bias. Also, the diamond coated in vias etched in the substrate as heat spreading path (back-side heat spreading) was simulated. A competing mechanism influences the heat spreading ability, i.e., the etched vias would increase the device temperature due to the reduced heat sink while the coated diamond would decrease the device temperature due to its higher thermal conductivity. Therefore, relative thick coated diamond is needed in order to reduce the self-heating effect. The simulated local stress at the gate edge of the drain side for the device with standard and field plate gate structure were compared, which would be relevant to the device mechanical failure. Other stress simulations focused on the intrinsic stress in the diamond capping layer impact on the device electrical behaviors. The simulated stress and electrical output characteristics were compared to experimental data obtained by micro-Raman spectroscopy and electrical characterization, respectively. Results showed that the intrinsic stress in the capping layer caused the non-uniform distribution of 2DEG in the channel and the access region. Besides the enhancement of the device power output, intrinsic stress in the capping layer can potentially improve the device reliability by modulating the local stress at the gate edge of the drain side. Finally, the surface, buffer, and barrier traps effects were simulated in this work. Pulsed measurements showed that long gates and distances between gate and drain contact can increase the gate lag ratio (decrease the current collapse). This was explained by simulations on the surface traps effect. The simulations on buffer traps effects focused on illustrating the dynamic trapping/detrapping in the buffer and the self-heating impact on the device transient drain current. A model was presented to describe the trapping and detrapping in the barrier. The trapping was the electron direct tunneling from the gate metal while the detrapping was the electron emission into the conduction band described by phonon-assisted tunneling. The reverse gate current was simulated based on this model, whose mechanism can be attributed to the temperature and electric field dependent electron emission in the barrier. Furthermore, the mechanism of the device bias via the self-heating and electric field impact on the electron emission and the transient drain current were also illustrated.

The 3-D Structure of Polycrystalline Diamond Film by Electron Backscattering Diffraction (EBSD)

A lithographic method was used to produce polycrystalline diamond films having highly defined surface geometry, showing an array of diamond tips for possible application as a field emitter device. The films grown in this study used microwave plasma assisted chemical vapour deposition (MACVD) on a silicon substrate; the substrate was then dissolved away to reveal the surface features on the diamond film. It is possible to align the crystallite direction and affect the electron emission properties using a voltage bias to enhance the nucleation process and influence the nuclei to a preferred orientation. This study focuses on the identification of the distribution of crystal directions in the film, using electron backscattering diffraction (EBSD) to identify the crystallographic character of the film surface. EBSD allows direct examination of the individual diamond grains, grains boundaries and the crystal orientation of each individual crystallite. The EBSD maps of the bottom (nucleation side) of the films, following which a layer of film is ion-milled away and the mapping process repeated. The method demonstrates experimentally that oriented nucleation occurs and the thin sections allow the crystal texture to be reconstructed in 3-D. (C) 2003 Elsevier B.V. All rights reserved.

Design, Fabrication, and Characterization of Carbon Nanotube Field Emission Devices for Advanced Applications

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.

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.

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.

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.

A study at high energy-resolution and at low primary energies of the secondary emission from (100) tungsten

This work was supported by the Joint Services Electronics Program (U.S. Army, U.S. Navy, and U.S. Air Force) under Contract No. DA 28 043 AMC 00073(E).

Carbon dioxide emissions from diesel and compressed natural gas buses during acceleration

Motor vehicle emission factors are generally derived from driving tests mimicking steady state conditions or transient drive cycles. However, neither of these test conditions completely represents real world driving conditions. In particular, they fail to determine emissions generated during the accelerating phase – a condition in which urban buses spend much of their time. In this study we analyse and compare the results of time-dependant emission measurements conducted on diesel and compressed natural gas (CNG) buses during an urban driving cycle on a chassis dynamometer and we derive power-law expressions relating carbon dioxide (CO2) emission factors to the instantaneous speed while accelerating from rest. Emissions during acceleration are compared with that during steady speed operation. These results have important implications for emission modelling particularly under congested traffic conditions.