Soil characteristics of cryosols from two sites on King George Island, maritime Antarctica

This study presents soil temperature and moisture regimes from March 2008 to January 2009 for two active layer monitoring (CALM-S) sites at King George Island, Maritime Antarctica. The monitoring sites were installed during the summer of 2008 and consist of thermistors (accuracy of ±0.2 °C), arranged vertically with probes at different depths and one soil moisture probe placed at the bottommost layer at each site (accuracy of ± 2.5%), recording data at hourly intervals in a high capacity datalogger. The active layer thermal regime in the studied period for both soils was typical of periglacial environments, with extreme variation in surface temperature during summer resulting in frequent freeze and thaw cycles. The great majority of the soil temperature readings during the eleven month period was close to 0 °C, resulting in low values of freezing and thawing degree days. Both soils have poor thermal apparent diffusivity but values were higher for the soil from Fildes Peninsula. The different moisture regimes for the studied soils were attributed to soil texture, with the coarser soil presenting much lower water content during all seasons. Differences in water and ice contents may explain the contrasting patterns of freezing of the studied soils, being two-sided for the coarser soil and one-sided for the loamy soil. The temperature profile of the studied soils during the eleven month period indicates that the active layer reached a maximum depth of approximately 92 cm at Potter and 89 cm at Fildes. Longer data sets are needed for more conclusive analysis on active layer behaviour in this part of Antarctica.

Phytomass and soil carbon storage of different land cover classes in the Usa river basin

This study describes detailed partitioning of phytomass carbon (C) and soil organic carbon (SOC) for four study areas in discontinuous permafrost terrain, Northeast European Russia. The mean aboveground phytomass C storage is 0.7 kg C/m**2. Estimated landscape SOC storage in the four areas varies between 34.5 and 47.0 kg C/m**2 with LCC (land cover classification) upscaling and 32.5-49.0 kg C/m**2 with soil map upscaling. A nested upscaling approach using a Landsat thematic mapper land cover classification for the surrounding region provides estimates within 5 ± 5% of the local high-resolution estimates. Permafrost peat plateaus hold the majority of total and frozen SOC, especially in the more southern study areas. Burying of SOC through cryoturbation of O- or A-horizons contributes between 1% and 16% (mean 5%) of total landscape SOC. The effect of active layer deepening and thermokarst expansion on SOC remobilization is modeled for one of the four areas. The active layer thickness dynamics from 1980 to 2099 is modeled using a transient spatially distributed permafrost model and lateral expansion of peat plateau thermokarst lakes is simulated using geographic information system analyses. Active layer deepening is expected to increase the proportion of SOC affected by seasonal thawing from 29% to 58%. A lateral expansion of 30 m would increase the amount of SOC stored in thermokarst lakes/fens from 2% to 22% of all SOC. By the end of this century, active layer deepening will likely affect more SOC than thermokarst expansion, but the SOC stores vulnerable to thermokarst are less decomposed.

Oxygen Reduction Reaction on Pt Overlayers Deposited onto a Gold Film: Ligand, Strain, and Ensemble Effect

We study the oxygen reduction reaction (ORR), the catalytic process occurring at the cathode in fuel cells, on Pt layers prepared by electrodeposition onto an Au substrate. Using a nominal Pt layer by layer deposition method previously proposed, imperfect layers of Pt on Au are obtained. The ORR on deposited Pt layers decreases with increasing Pt thickness. In the submonolayer region, however, the ORR activity is superior to that of bulk Pt. Using density functional theory (DFT) calculations, we correlate the observed activity trend to strain, ligand, and ensemble effects. At submonolayer coverage certain atom configurations weaken the binding energies of reaction intermediates due to a ligand and ensemble effect, thus effectively increasing the ORR activity. At higher Pt coverage the activity is governed by a strain effect, which lowers the activity by decreasing the oxidation potential of water. This study is a nice example of how the influence of strain, ligand, and ensemble effects on the ORR can be deconvoluted.

Adaptive liquid-crystal phase-only passive devices

This PhD work is focused on liquid crystal based tunable phase devices with special emphasis on their design and manufacturing. In the course of the work a number of new manufacturing technologies have been implemented in the UPM clean room facilities, leading to an important improvement in the range of devices being manufactured in the laboratory. Furthermore, a number of novel phase devices have been developed, all of them including novel electrodes, and/or alignment layers. The most important manufacturing progress has been the introduction of reactive ion etching as a tool for achieving high resolution photolithography on indium-tin-oxide (ITO) coated glass and quartz substrates. Another important manufacturing result is the successful elaboration of a binding protocol of anisotropic conduction adhesives. These have been employed in high density interconnections between ITO-glass and flexible printed circuits. Regarding material characterization, the comparative study of nonstoichiometric silicon oxide (SiOx) and silica (SiO2) inorganic alignment layers, as well as the relationship between surface layer deposition, layer morphology and liquid crystal electrooptical response must be highlighted, together with the characterization of the degradation of liquid crystal devices in simulated space mission environment. A wide variety of phase devices have been developed, with special emphasis on beam steerers. One of these was developed within the framework of an ESA project, and consisted of a high density reconfigurable 1D blaze grating, with a spatial separation of the controlling microelectronics and the active, radiation exposed, area. The developed devices confirmed the assumption that liquid crystal devices with such a separation of components, are radiation hard, and can be designed to be both vibration and temperature sturdy. In parallel to the above, an evenly variable analog beam steering device was designed, manufactured and characterized, providing a narrow cone diffraction free beam steering. This steering device is characterized by a very limited number of electrodes necessary for the redirection of a light beam. As few as 4 different voltage levels were needed in order to redirect a light beam. Finally at the Wojskowa Akademia Techniczna (Military University of Technology) in Warsaw, Poland, a wedged analog tunable beam steering device was designed, manufactured and characterized. This beam steerer, like the former one, was designed to resist the harsh conditions both in space and in the context of the shuttle launch. Apart from the beam steering devices, reconfigurable vortices and modal lens devices have been manufactured and characterized. In summary, during this work a large number of liquid crystal devices and liquid crystal device manufacturing technologies have been developed. Besides their relevance in scientific publications and technical achievements, most of these new devices have demonstrated their usefulness in the actual work of the research group where this PhD has been completed. El presente trabajo de Tesis se ha centrado en el diseño, fabricación y caracterización de nuevos dispositivos de fase basados en cristal líquido. Actualmente se están desarrollando dispositivos basados en cristal líquido para aplicaciones diferentes a su uso habitual como displays. Poseen la ventaja de que los dispositivos pueden ser controlados por bajas tensiones y no necesitan elementos mecánicos para su funcionamiento. La fabricación de todos los dispositivos del presente trabajo se ha realizado en la cámara limpia del grupo. La cámara limpia ha sido diseñada por el grupo de investigación, es de dimensiones reducidas pero muy versátil. Está dividida en distintas áreas de trabajo dependiendo del tipo de proceso que se lleva a cabo. La cámara limpia está completamente cubierta de un material libre de polvo. Todas las entradas de suministro de gas y agua están selladas. El aire filtrado es constantemente bombeado dentro de la zona limpia, a fin de crear una sobrepresión evitando así la entrada de aire sin filtrar. Las personas que trabajan en esta zona siempre deben de estar protegidas con un traje especial. Se utilizan trajes especiales que constan de: mono, máscara, guantes de látex, gorro, patucos y gafas de protección UV, cuando sea necesario. Para introducir material dentro de la cámara limpia se debe limpiar con alcohol y paños especiales y posteriormente secarlos con nitrógeno a presión. La fabricación debe seguir estrictamente unos pasos determinados, que pueden cambiar dependiendo de los requerimientos de cada dispositivo. Por ello, la fabricación de dispositivos requiere la formulación de varios protocolos de fabricación. Estos protocolos deben ser estrictamente respetados a fin de obtener repetitividad en los experimentos, lo que lleva siempre asociado un proceso de fabricación fiable. Una célula de cristal líquido está compuesta (de forma general) por dos vidrios ensamblados (sándwich) y colocados a una distancia determinada. Los vidrios se han sometido a una serie de procesos para acondicionar las superficies internas. La célula se llena con cristal líquido. De forma resumida, el proceso de fabricación general es el siguiente: inicialmente, se cortan los vidrios (cuya cara interna es conductora) y se limpian. Después se imprimen las pistas sobre el vidrio formando los píxeles. Estas pistas conductoras provienen del vidrio con la capa conductora de ITO (óxido de indio y estaño). Esto se hace a través de un proceso de fotolitografía con una resina fotosensible, y un desarrollo y ataque posterior del ITO sin protección. Más tarde, las caras internas de los vidrios se acondicionan depositando una capa, que puede ser orgánica o inorgánica (un polímero o un óxido). Esta etapa es crucial para el funcionamiento del dispositivo: induce la orientación de las moléculas de cristal líquido. Una vez que las superficies están acondicionadas, se depositan espaciadores en las mismas: son pequeñas esferas o cilindros de tamaño calibrado (pocos micrómetros) para garantizar un espesor homogéneo del dispositivo. Después en uno de los sustratos se deposita un adhesivo (gasket). A continuación, los sustratos se ensamblan teniendo en cuenta que el gasket debe dejar una boca libre para que el cristal líquido se introduzca posteriormente dentro de la célula. El llenado de la célula se realiza en una cámara de vacío y después la boca se sella. Por último, la conexión de los cables a la célula y el montaje de los polarizadores se realizan fuera de la sala limpia (Figura 1). Dependiendo de la aplicación, el cristal líquido empleado y los demás componentes de la célula tendrán unas características particulares. Para el diseño de los dispositivos de este trabajo se ha realizado un estudio de superficies inorgánicas de alineamiento del cristal líquido, que será de gran importancia para la preparación de los dispositivos de fase, dependiendo de las condiciones ambientales en las que vayan a trabajar. Los materiales inorgánicos que se han estudiado han sido en este caso SiOx y SiO2. El estudio ha comprendido tanto los factores de preparación influyentes en el alineamiento, el comportamiento del cristal líquido al variar estos factores y un estudio de la morfología de las superficies obtenidas.

Nano-imprinted rear-side diffraction gratings for absorption enhancement in solar cells

As wafer-based solar cells become thinner, light-trapping textures for absorption enhancement will gain in importance. In this work, crystalline silicon wafers were textured with wavelength-scale diffraction grating surface textures by nanoimprint lithography using interference lithography as a mastering technology. This technique allows fine-tailored nanostructures to be realized on large areas with high throughput. Solar cell precursors were fabricated, with the surface textures on the rear side, for optical absorption measurements. Large absorption enhancements are observed in the wavelength range in which the silicon wafer absorbs weakly. It is shown experimentally that bi-periodic crossed gratings perform better than uni-periodic linear gratings. Optical simulations have been made of the fabricated structures, allowing the total absorption to be decomposed into useful absorption in the silicon and parasitic absorption in the rear reflector. Using the calculated silicon absorption, promising absorbed photocurrent density enhancements have been calculated for solar cells employing the nano-textures. Finally, first results are presented of a passivation layer deposition technique that planarizes the rear reflector for the purpose of reducing the parasitic absorption.

A fast XPS study of sulphate promoted propene decomposition over Pt{111}

SO2 oxidation has been followed by Fast XPS over Pt{111}. Preadsorbed oxygen reduces the low temperature saturation coverage of SO2 with respect to the clean surface. Heating a mixed O2/SO2 adlayer results in efficient oxidation of both upright and flat-lying SO2 molecules to surface-bound SO4. Sulphate decomposes above room temperature liberating gas-phase SO2 and SO3. Propene adsorbs molecularly at 100 K over clean Pt{111} and dehydrogenates above 250 K to form a stable propylidyne adlayer, which in turn decomposes above 400 K to form graphitic carbon. Preadsorbed surface sulphate enhances the sticking probability of propene via formation of an alkyl-sulphate complex. Thermal decomposition of this complex accounts for low temperature propene combustion and is accompanied by atomic sulpur deposition. Propylidyne forms as on clean Pt but is less reactive undergoing partial oxidation above 450 K with residual surface oxygen.

Radiation fluxes, soil heat flux, air temperature, soil temperature, soil moisture and vegetation at dwarf shrubs and wet sedges in Kytalyk, NE Siberia

Vegetation changes, such as shrub encroachment and wetland expansion, have been observed in many Arctic tundra regions. These changes feed back to permafrost and climate. Permafrost can be protected by soil shading through vegetation as it reduces the amount of solar energy available for thawing. Regional climate can be affected by a reduction in surface albedo as more energy is available for atmospheric and soil heating. Here, we compared the shortwave radiation budget of two common Arctic tundra vegetation types dominated by dwarf shrubs (Betula nana) and wet sedges (Eriophorum angustifolium) in North-East Siberia. We measured time series of the shortwave and longwave radiation budget above the canopy and transmitted radiation below the canopy. Additionally, we quantified soil temperature and heat flux as well as active layer thickness. The mean growing season albedo of dwarf shrubs was 0.15 ± 0.01, for sedges it was higher (0.17 ± 0.02). Dwarf shrub transmittance was 0.36 ± 0.07 on average, and sedge transmittance was 0.28 ± 0.08. The standing dead leaves contributed strongly to the soil shading of wet sedges. Despite a lower albedo and less soil shading, the soil below dwarf shrubs conducted less heat resulting in a 17 cm shallower active layer as compared to sedges. This result was supported by additional, spatially distributed measurements of both vegetation types. Clouds were a major influencing factor for albedo and transmittance, particularly in sedge vegetation. Cloud cover reduced the albedo by 0.01 in dwarf shrubs and by 0.03 in sedges, while transmittance was increased by 0.08 and 0.10 in dwarf shrubs and sedges, respectively. Our results suggest that the observed deeper active layer below wet sedges is not primarily a result of the summer canopy radiation budget. Soil properties, such as soil albedo, moisture, and thermal conductivity, may be more influential, at least in our comparison between dwarf shrub vegetation on relatively dry patches and sedge vegetation with higher soil moisture.

Vanadate conformation variations in vanadium pentoxide nanostructures

We report the comparative structural-vibrational study of nanostructures of nanourchins, nanotubes, and nanorods of vanadium oxide. The tube walls comprise layers of vanadium oxide with the organic surfactant intercalated between atomic layers. Both Raman scattering and infrared spectroscopies showed that the structure of nanourchins, nanotubes, and nanorods of vanadium oxide nanocomposite are strongly dependent on the valency of the vanadium, its associated interactions with the organic surfactant template, and on the packing mechanism and arrangement of the surfactant between vanadate layers. Accurate assignment of the vibrational modes to the V-O coordinations has allowed their comparative classification and relation to atomic layer structure. Although all structures are formed from the same precursor, differences in vanadate conformations due to the hydrothermal treatment and surfactant type result in variable degrees of crystalline order in the final nanostructure. The nanotube-containing nanourchins contain vanadate layers in the nanotubes that are in a distorted γ- V5+ conformation, whereas the the nanorods, by comparison, show evidence for V5+ and V4+ species-containing ordered VOx lamina.

Development of InAlN HEMTs for space application

This thesis investigates the emerging InAlN high electron mobility transistor (HEMT) technology with respect to its application in the space industry. The manufacturing processes and device performance of InAlN HEMTs were compared to AlGaN HEMTs, also produced as part of this work. RF gain up to 4 GHz was demonstrated in both InAlN and AlGaN HEMTs with gate lengths of 1 μm, with InAlN HEMTs generally showing higher channel currents (~150 c.f. 60 mA/mm) but also degraded leakage properties (~ 1 x 10-4 c.f. < 1 x 10-8 A/mm) with respect to AlGaN. An analysis of device reliability was undertaken using thermal stability, radiation hardness and off-state breakdown measurements. Both InAlN and AlGaN HEMTs showed excellent stability under space-like conditions, with electrical operation maintained after exposure to 9.2 Mrad of gamma radiation at a dose rate of 6.6 krad/hour over two months and after storage at 250°C for four weeks. Furthermore a link was established between the optimisation of device performance (RF gain, power handling capabilities and leakage properties) and reliability (radiation hardness, thermal stability and breakdown properties), particularly with respect to surface passivation. Following analysis of performance and reliability data, the InAlN HEMT device fabrication process was optimised by adjusting the metal Ohmic contact formation process (specifically metal stack thicknesses and anneal conditions) and surface passivation techniques (plasma power during dielectric layer deposition), based on an existing AlGaN HEMT process. This resulted in both a reduction of the contact resistivity to around 1 x 10-4 Ω.cm2 and the suppression of degrading trap-related effects, bringing the measured gate-lag close to zero. These discoveries fostered a greater understanding of the physical mechanisms involved in device operation and manufacture, which is elaborated upon in the final chapter.

Device Physics of Two-Dimensional Crystalline Materials

Thesis (Ph.D.)--University of Washington, 2016-07

Scaffolds porosos à base de fosfatos de cálcio para regeneração óssea

Graças ao aumento da esperança média de vida do ser humano, a engenharia de tecidos tem sido uma área alvo de enorme investigação. A utilização de estruturas tridimensionais porosas e biodegradáveis, denominadas de scaffolds, como matriz para a adesão e proliferação celular tem sido amplamente investigada. Existem atualmente diversas técnicas para a produção destas estruturas mas o grau de exigência tem vindo a aumentar, existindo ainda lacunas que necessitam ser preenchidas. A técnica de robocasting consiste numa deposição camada a camada de uma pasta coloidal, seguindo um modelo computorizado (CAD) e permite a produção de scaffolds com porosidade tamanho de poro e fração de porosidade controlados, boa reprodutibilidade, e com formas variadas, as quais podem ser idênticas às dos defeitos ósseos a preencher. O presente estudo teve como objetivo produzir scaffolds porosos à base de fosfatos de cálcio através de robocasting. Para tal, foram estudadas duas composições de pós à base de β-TCP, uma pura e outra co-dopada com estrôncio, zinco e manganês. Inicialmente os pós foram sintetizados pelo método de precipitação química por via húmida. Após a síntese, estes foram filtrados, secos, calcinados a 1000ºC e posteriormente moídos até possuírem um tamanho médio de partícula de cerca de 1,5 μm. Os pós foram depois peneirados com uma malha de 40μm e caracterizados. Posteriormente foram preparadas várias suspensões e avaliado o seu comportamento reológico, utilizando Targon 1128 como dispersante, Hidroxipropilmetilcelulose (HPMC) como ligante e polietilenimina (PEI) como agente floculante. Por fim, e escolhida a melhor composição para a formação da pasta, foram produzidos scaffolds com diferentes porosidades, num equipamento de deposição robótica (3D Inks, LLC). Os scaffolds obtidos foram secos à temperatura ambiente durante 48 horas, sinterizados a 1100ºC e posteriormente caracterizados por microscopia eletrónica de varrimento (SEM), avaliação dos tamanhos de poro, porosidade total e testes mecânicos. Ambas as composições estudadas puderam ser transformadas em pastas extrudíveis, mas a pasta da composição pura apresentou uma consistência mais próxima do ideal, tendo originado scaffolds de melhor qualidade em termos de microestrutura e de propriedades mecânicas.

The Atomic Structure Of A Bare Buffer Layer On Sic(0001) Chemically Resolved.

A chemical-specific photoelectron diffraction structure determination of a carbon rich buffer layer on SiC is reported. In addition to the long-range ripple of this surface, a local buckling in the hexagonal sublattice, which breaks the local range order symmetry, was unraveled.

Factors Controlling The Deposition Of Silk Fibroin Nanofibrils During Layer-by-layer Assembly.

The layer-by-layer technique has been used as a powerful method to produce multilayer thin films with tunable properties. When natural polymers are employed, complicated phenomena such as self-aggregation and fibrilogenesis can occur, making it more difficult to obtain and characterize high-quality films. The weak acid and base character of such materials provides multilayer systems that may differ from those found with synthetic polymers due to strong self-organization effects. Specifically, LbL films prepared with chitosan and silk fibroin (SF) often involve the deposition of fibroin fibrils, which can influence the assembly process, surface properties, and overall film functionality. In this case, one has the intriguing possibility of realizing multilayer thin films with aligned nanofibers. In this article, we propose a strategy to control fibroin fibril formation by adjusting the assembly partner. Aligned fibroin fibrils were formed when chitosan was used as the counterpart, whereas no fibrils were observed when poly(allylamine hydrochloride) (PAH) was used. Charge density, which is higher in PAH, apparently stabilizes SF aggregates on the nanometer scale, thereby preventing their organization into fibrils. The drying step between the deposition of each layer was also crucial for film formation, as it stabilizes the SF molecules. Preliminary cell studies with optimized multilayers indicated that cell viability of NIH-3T3 fibroblasts remained between 90 and 100% after surface seeding, showing the potential application of the films in the biomedical field, as coatings and functional surfaces.

Thermal diffusion in molecular dynamics simulations of thin film diamond deposition

Molecular dynamics simulations of carbon atom depositions are used to investigate energy diffusion from the impact zone. A modified Stillinger-Weber potential models the carbon interactions for both sp2 and sp3 bonding. Simulations were performed on 50 eV carbon atom depositions onto the (111) surface of a 3.8 x 3.4 x 1.0 nm diamond slab containing 2816 atoms in 11 layers of 256 atoms each. The bottom layer was thermostated to 300 K. At every 100th simulation time step (27 fs), the average local kinetic energy, and hence local temperature, is calculated. To do this the substrate is divided into a set of 15 concentric hemispherical zones, each of thickness one atomic diameter (0.14 nm) and centered on the impact point. A 50-eV incident atom heats the local impact zone above 10 000 K. After the initial large transient (200 fs) the impact zone has cooled below 3000 K, then near 1000 K by 1 ps. Thereafter the temperature profile decays approximately as described by diffusion theory, perturbed by atomic scale fluctuations. A continuum model of classical energy transfer is provided by the traditional thermal diffusion equation. The results show that continuum diffusion theory describes well energy diffusion in low energy atomic deposition processes, at distance and time scales larger than 1.5 nm and 1-2 ps, beyond which the energy decays essentially exponentially. (C) 1998 Published by Elsevier Science S.A. All rights reserved.