I. Reactively sputtered Ti-Si-N thin films for diffusion barrier applications. II. Oxidation, diffusion and crystallization of an amorphous Zr_(60)Al_(15)Ni_(25) alloy.

Films of Ti-Si-N obtained by reactively sputtering a TiSi_2, a Ti_5Si_3, or a Ti_3Si target are either amorphous or nanocrystalline in structure. The atomic density of some films exceeds 10^23 at./cm^3. The room-temperature resistivity of the films increases with the Si and the N content. A thermal treatment in vacuum at 700 °C for 1 hour decreases the resistivity of the Ti-rich films deposited from the Ti_5Si_3 or the Ti_3Si target, but increases that of the Si-rich films deposited from the TiSi_2 target when the nitrogen content exceeds about 30 at. %.

Ti_(34)Si_(23)N_(43) deposited from the Ti_5Si_3 target is an excellent diffusion barrier between Si and Cu. This film is a mixture of nanocrystalline TiN and amorphous SiN_x. Resistivity measurement from 80 K to 1073 K reveals that this film is electrically semiconductor-like as-deposited, and that it becomes metal-like after an hour annealing at 1000 °C in vacuum. A film of about 100 nm thick, with a resistivity of 660 µΩcm, maintains the stability of Si n+p shallow junction diodes with a 400 nm Cu overlayer up to 850 °C upon 30 min vacuum annealing. When used between Si and Al, the maximum temperature of stability is 550 °C for 30 min. This film can be etched in a CF_4/O_2 plasma.

The amorphous ternary metallic alloy Zr_(60)Al_(15)Ni_(25) was oxidized in dry oxygen in the temperature range 310 °C to 410 °C. Rutherford backscattering and cross-sectional transmission electron microscopy studies suggest that during this treatment an amorphous layer of zirconium-aluminum-oxide is formed at the surface. Nickel is depleted from the oxide and enriched in the amorphous alloy below the oxide/alloy interface. The oxide layer thickness grows parabolically with the annealing duration, with a transport constant of 2.8x10^(-5) m^2/s x exp(-1.7 eV/kT). The oxidation rate is most likely controlled by the Ni diffusion in the amorphous alloy.

At later stages of the oxidation process, precipitates of nanocrystalline ZrO_2 appear in the oxide near the interface. Finally, two intermetallic phases nucleate and grow simultaneously in the alloy, one at the interface and one within the alloy.

Nanophotonic Light Trapping In Thin Solar Cells

Over the last several decades there have been significant advances in the study and understanding of light behavior in nanoscale geometries. Entire fields such as those based on photonic crystals, plasmonics and metamaterials have been developed, accelerating the growth of knowledge related to nanoscale light manipulation. Coupled with recent interest in cheap, reliable renewable energy, a new field has blossomed, that of nanophotonic solar cells.

In this thesis, we examine important properties of thin-film solar cells from a nanophotonics perspective. We identify key differences between nanophotonic devices and traditional, thick solar cells. We propose a new way of understanding and describing limits to light trapping and show that certain nanophotonic solar cell designs can have light trapping limits above the so called ray-optic or ergodic limit. We propose that a necessary requisite to exceed the traditional light trapping limit is that the active region of the solar cell must possess a local density of optical states (LDOS) higher than that of the corresponding, bulk material. Additionally, we show that in addition to having an increased density of states, the absorber must have an appropriate incoupling mechanism to transfer light from free space into the optical modes of the device. We outline a portfolio of new solar cell designs that have potential to exceed the traditional light trapping limit and numerically validate our predictions for select cases.

We emphasize the importance of thinking about light trapping in terms of maximizing the optical modes of the device and efficiently coupling light into them from free space. To further explore these two concepts, we optimize patterns of superlattices of air holes in thin slabs of Si and show that by adding a roughened incoupling layer the total absorbed current can be increased synergistically. We suggest that the addition of a random scattering surface to a periodic patterning can increase incoupling by lifting the constraint of selective mode occupation associated with periodic systems.

Lastly, through experiment and simulation, we investigate a potential high efficiency solar cell architecture that can be improved with the nanophotonic light trapping concepts described in this thesis. Optically thin GaAs solar cells are prepared by the epitaxial liftoff process by removal from their growth substrate and addition of a metallic back reflector. A process of depositing large area nano patterns on the surface of the cells is developed using nano imprint lithography and implemented on the thin GaAs cells.

Nanofabrication for On-Chip Optical Levitation, Atom-Trapping, and Superconducting Quantum Circuits

Researchers have spent decades refining and improving their methods for fabricating smaller, finer-tuned, higher-quality nanoscale optical elements with the goal of making more sensitive and accurate measurements of the world around them using optics. Quantum optics has been a well-established tool of choice in making these increasingly sensitive measurements which have repeatedly pushed the limits on the accuracy of measurement set forth by quantum mechanics. A recent development in quantum optics has been a creative integration of robust, high-quality, and well-established macroscopic experimental systems with highly-engineerable on-chip nanoscale oscillators fabricated in cleanrooms. However, merging large systems with nanoscale oscillators often require them to have extremely high aspect-ratios, which make them extremely delicate and difficult to fabricate with an "experimentally reasonable" repeatability, yield and high quality. In this work we give an overview of our research, which focused on microscopic oscillators which are coupled with macroscopic optical cavities towards the goal of cooling them to their motional ground state in room temperature environments. The quality factor of a mechanical resonator is an important figure of merit for various sensing applications and observing quantum behavior. We demonstrated a technique for pushing the quality factor of a micromechanical resonator beyond conventional material and fabrication limits by using an optical field to stiffen and trap a particular motional mode of a nanoscale oscillator. Optical forces increase the oscillation frequency by storing most of the mechanical energy in a nearly loss-less optical potential, thereby strongly diluting the effects of material dissipation. By placing a 130 nm thick SiO₂ pendulum in an optical standing wave, we achieve an increase in the pendulum center-of-mass frequency from 6.2 to 145 kHz. The corresponding quality factor increases 50-fold from its intrinsic value to a final value of Q_m = 5.8(1.1) x 10⁵, representing more than an order of magnitude improvement over the conventional limits of SiO₂ for a pendulum geometry. Our technique may enable new opportunities for mechanical sensing and facilitate observations of quantum behavior in this class of mechanical systems. We then give a detailed overview of the techniques used to produce high-aspect-ratio nanostructures with applications in a wide range of quantum optics experiments. The ability to fabricate such nanodevices with high precision opens the door to a vast array of experiments which integrate macroscopic optical setups with lithographically engineered nanodevices. Coupled with atom-trapping experiments in the Kimble Lab, we use these techniques to realize a new waveguide chip designed to address ultra-cold atoms along lithographically patterned nanobeams which have large atom-photon coupling and near 4π Steradian optical access for cooling and trapping atoms. We describe a fully integrated and scalable design where cold atoms are spatially overlapped with the nanostring cavities in order to observe a resonant optical depth of d₀ ≈ 0.15. The nanodevice illuminates new possibilities for integrating atoms into photonic circuits and engineering quantum states of atoms and light on a microscopic scale. We then describe our work with superconducting microwave resonators coupled to a phononic cavity towards the goal of building an integrated device for quantum-limited microwave-to-optical wavelength conversion. We give an overview of our characterizations of several types of substrates for fabricating a low-loss high-frequency electromechanical system. We describe our electromechanical system fabricated on a Si₃N₄ membrane which consists of a 12 GHz superconducting LC resonator coupled capacitively to the high frequency localized modes of a phononic nanobeam. Using our suspended membrane geometry we isolate our system from substrates with significant loss tangents, drastically reducing the parasitic capacitance of our superconducting circuit to ≈ 2.5$ fF. This opens up a number of possibilities in making a new class of low-loss high-frequency electromechanics with relatively large electromechanical coupling. We present our substrate studies, fabrication methods, and device characterization.

Photoelectrochemistry of GaAs and Si liquid junctions

A quantitative study has been performed on the stability of GaAs surfaces in a 0.10 M K₂Se-0.01 M K₂Se₂ aqueous solution. In this electrolyte, n-type GaAs electrodes displayed significant photocorrosion in competition with faradaic charge transfer to Se^2-. Chemisorption of group VIIIB metal ions onto the GaAs surfaces yielded improved current-voltage behavior of the GaAs photoanodes, and also resulted in a significant reduction in photocorrosion. This behavior implies that the chemisorbed metal ions act to increase the rate of hole transfer to the Se^2- species. Related experiments on n-GaAs, pGaAs, and Sn-doped In₂O₃ electrodes in Te^2-/- aqueous solutions have also been performed.

The majority carrier (electrons) transfer rate constant at a highly doped n⁺-Si/Co(Cp)₂Cl-methanol junction has been measured directly using the chronoamperometry electrochemical technique. The reduction reaction rate of Co(Cp)₂+ was 0.03 cm-s^-1 at the Si electrode, and was more than 100 times slower than at a hanging mercury electrode. The slower rate was attributed to the smaller optical and static dielectric constants, and the lower density of electrons of the semiconductor. The experimental results were compared to the Marcus theory of charge transfer.

The unique properties of high purity Si/liquid junctions have been investigated under illumination conditions in which the photogenerated carrier concentration exceeds the dopant concentration. Under these high injection conditions, negligible electric fields exist at the semiconductor/liquid interface, and carrier motion is driven by diffusion. Studies of the current-voltage properties of the Si in methanol solutions containing various redox couples suggested that high efficiency photoelectrochemical cells could be established through selective collection of carriers at the semiconductor/liquid junction. The quasi-Fermi levels of electrons and holes were measured directly against the solution potential. Steady-state and transient photovoltage measurements, and theoretical modeliug of the carrier transport, generation, and recombination dynamics indicated that the quasi-Fermi levels were flat across the semiconductor sample. The recombination velocities at the Si/liquid junctions have also been measured, and were shown to vary with the solution potential following the Shockley-Read-Hall theory on recombination.

Experiments using an artificial stream to investigate the seasonal growth of chalk-stream algae

Research into the production ecology of chalk streams using a large artificial recirculating stream is described. Physical chemical processes including calcium and inorganic phosphate levels, and exchange of gaseous carbon dioxide in both a simple closed system and a circulating system with gravel substrate have been monitored in both light and dark conditions. Further experiments were concerned with the seasonal changes in algal growth over the gravel substrate with constant water velocities and replenishment. The algal population, composed mainly of the diatoms Achnanthes minutissima, Meridion circulare, Nitzschia fonticola and Synedra ulna reached a peak in mid May and declined rapidly during June. Concentrations of phosphate phosphorus fell as the diatoms grew but was not thought to limit growth. Silicate concentrations followed the diatom cycle closely but never fell below 0.8 mg/l Si. It is possible that one of the nutrients may have been limiting the rate of growth due to steep diffusion gradients through the algal mat. In the last summer and autumn a hard calcareous crust composed of the green alga Gongrosira incrustans and the blue green alga Homeothrix varians , developed. The channel stream is compared with the natural conditions found in chalk streams.

A hora da estrela: uma narrativa que se desdobra sobre si mesma, tecendo e destecendo retratos do(s) outro(s) e retratos de si

Muito já se disse sobre Clarice Lispector, muito há, no entanto, a se dizer ainda. Com este nosso trabalho, ousamos trilhar um caminho que nos parece duplamente pouco explorado: por um lado, nos debruçamos sobre as pausas, as lacunas, as suspensões do dizer que se materializam em cortes no fio discursivo da literatura clariceana; mais especificamente nas interrupções que comparecem por meio de travessões, parênteses e aí estendemos para a interrogação em A Hora da Estrela. Por outro lado, trazemos, para este nosso objetivo, uma abordagem discursiva, isto é, temos como suporte teórico-metodológico a Análise de Discurso cujos autores basilares são Pêcheux e Orlandi. Esta autora, ao deslocar o estudo da pontuação do campo da gramática para o domínio do discurso, considera a pontuação como o lugar em que o sujeito trabalha seus pontos de subjetivação, o modo como interpreta (Orlandi, 2005). A pontuação, vista discursivamente, abre fendas do não-dizer no dizer, trabalhando sua (in)completude. Os travessões, os parênteses e a interrogação, em Clarice, rompem repetida e sucessivamente a linearidade da língua expondo seus vazios, seus meandros, seus impasses. Analisaremos o funcionamento discursivo desses três sinais de pontuação no dizer do narrador de A Hora da Estrela, assim como investigaremos as posições-sujeito do narrador que se delineiam em cada funcionamento desses sinais: posição-sujeito de narrador onipotente/onisciente, posição-sujeito de narrador impotente e posição-sujeito de narrador vacilante. Para nosso trabalho, apoiamo-nos também nas reflexões teóricas acerca da heterogeneidade da língua, propostas por Authier-Revuz e trazemos o conceito de enunciação vacilante formulado por Paulillo. Podemos dizer que, nas incisas desta novela clariceana, jogam posições-sujeito que se polemizam, que se equivocam. Essas posições refletem uma narrativa que ora descreve a possibilidade de narrar, de descrever o outro, ora confessa a impossibilidade de capturar esse outro pela palavra: narrador vacilante, narrativa vacilante

Paths Towards High Efficiency Silicon Photovoltaics

While photovoltaics hold much promise as a sustainable electricity source, continued cost reduction is necessary to continue the current growth in deployment. A promising path to continuing to reduce total system cost is by increasing device efficiency. This thesis explores several silicon-based photovoltaic technologies with the potential to reach high power conversion efficiencies. Silicon microwire arrays, formed by joining millions of micron diameter wires together, were developed as a low cost, low efficiency solar technology. The feasibility of transitioning this to a high efficiency technology was explored. In order to achieve high efficiency, high quality silicon material must be used. Lifetimes and diffusion lengths in these wires were measured and the action of various surface passivation treatments studied. While long lifetimes were not achieved, strong inversion at the silicon / hydrofluoric acid interface was measured, which is important for understanding a common measurement used in solar materials characterization.

Cryogenic deep reactive ion etching was then explored as a method for fabricating high quality wires and improved lifetimes were measured. As another way to reach high efficiency, growth of silicon-germanium alloy wires was explored as a substrate for a III-V on Si tandem device. Patterned arrays of wires with up to 12% germanium incorporation were grown. This alloy is more closely lattice matched to GaP than silicon and allows for improvements in III-V integration on silicon.

Heterojunctions of silicon are another promising path towards achieving high efficiency devices. The GaP/Si heterointerface and properties of GaP grown on silicon were studied. Additionally, a substrate removal process was developed which allows the formation of high quality free standing GaP films and has wide applications in the field of optics.

Finally, the effect of defects at the interface of the amorphous silicon heterojuction cell was studied. Excellent voltages, and thus efficiencies, are achievable with this system, but the voltage is very sensitive to growth conditions. We directly measured lateral transport lengths at the heterointerface on the order of tens to hundreds of microns, which allows carriers to travel towards any defects that are present and recombine. This measurement adds to the understanding of these types of high efficiency devices and may aid in future device design.

Memória, imaginação e transpiração no processo de fabricação do passado: a ficcionalização de si em Infância e Angústia, de Graciliano Ramos

O objetivo deste trabalho é investigar a proposta literária do escritor alagoano Graciliano Ramos que conceituamos como ficcionalização de si, a qual consiste na utilização de observação, experiência, imaginação e transpiração como ingredientes da elaboração ficcional. Para atingir a tal objetivo, buscamos traçar um breve panorama político-cultural da década de 1930, no sentido de situar a formação ideológica e a produção mais significativa do autor Caetés (1933), S. Bernardo (1934), Angústia (1936) e Vidas Secas (1938). Prosseguimos com a construção de um amplo painel sobre o papel da memória na escrita de si, concluindo sobre a impossibilidade da fidelidade absoluta na reprodução do real, uma vez que esta passa necessariamente pela subjetividade da linguagem, o que lhe confere um inegável caráter ficcional. Conceituamos autobiografia e refletimos sobre as profundas alterações percebidas no gênero autobiográfico, inserindo a produção de Graciliano Ramos no contexto memorialista. Defendemos a ideia de que o escritor antecipa, na década de 30, o que na década de 70 será denominado como autoficção. Construída a fundamentação teórica necessária, passamos a analisar e discutir trechos do romance Angústia, em contraponto com Infância. Confrontando as leituras destas obras, pudemos perceber o aproveitamento ficcional de acontecimentos traumáticos da infância do autor narrados em Infância na elaboração da fase infantil do personagem Luís da Silva, de Angústia