Desenvolvimento de um biomaterial cerâmico baseado no sistema Li2O-SiO2 para restauração dentária

Dissertação para obtenção do Grau de Mestre em Engenharia Biomédica

Al-doped ZnO ceramic sputtering targets based on nanocrystalline powders produced by emulsion detonation synthesis – deposition and application as a transparent conductive oxide material

Transparent conducting oxides (TCOs) have been largely used in the optoelectronic industry due to their singular combination of low electrical resistivity and high optical transmittance. They are usually deposited by magnetron sputtering systems being applied in several devices, specifically thin film solar cells (TFSCs). Sputtering targets are crucial components of the sputtering process, with many of the sputtered films properties dependent on the targets characteristics. The present thesis focuses on the development of high quality conductive Al-doped ZnO (AZO) ceramic sputtering targets based on nanostructured powders produced by emulsion detonation synthesis method (EDSM), and their application as a TCO. In this sense, the influence of several processing parameters was investigated from the targets raw-materials synthesis to the application of sputtered films in optoelectronic devices. The optimized manufactured AZO targets present a final density above 99 % with controlled grain size, an homogeneous microstructure with a well dispersed ZnAl2O4 spinel phase, and electrical resistivities of ~4 × 10-4 Ωcm independently on the Al-doping level among 0.5 and 2.0 wt. % Al2O3. Sintering conditions proved to have a great influence on the properties of the targets and their performance as a sputtering target. It was demonstrated that both deposition process and final properties of the films are related with the targets characteristics, which in turn depends on the initial powder properties. In parallel, the influence of several deposition parameters in the film´s properties sputtered from these targets was investigated. The sputtered AZO TCOs showed electrical properties at room temperature that are superior to simple oxides and comparable to a reference TCO – indium tin oxide (ITO), namely low electrical resistivity of 5.45 × 10-4 Ωcm, high carrier mobility (29.4 cm2V-1s-1), and high charge carrier concentration (3.97 × 1020 cm-3), and also average transmittance in the visible region > 80 %. These superior properties allowed their successful application in different optoelectronic devices.

Structural, optical and magnetic properties of pulsed laser deposited Co-doped ZnO films

Zn1−xCoxO films with different Co concentrations (with x=0.00, 0.10, 0.15, and 0.30) were grown by pulsed laser deposition (PLD) technique. The structural and optical properties of the films were investigated by grazing incidence X-ray diffraction (GIXRD), Raman spectroscopy and photoluminescence (PL). The magnetic properties were measured by conventional magnetometry using a SQUID and simulated by ab-initio calculations using Korring–Khon–Rostoker (KKR) method combined with coherent potential approximation (CPA). The effect of Co-doping on the GIXRD and Raman peaks positions, shape and intensity is discussed. PL studies demonstrate that Co-doping induces a decrease of the bandgap energy and quenching of the UV emission. They also suggest the presence of Zn interstitials when x≥0.15. The 10% Co-doped ZnO film shows ferromagnetism at 390 K with a spontaneous magnetic moment ≈4×10−5 emu and coercive field ≈0.17 kOe. The origin of ferromagnetism is explained based on the calculations using KKR method.

Effect of annealing temperature on photoluminescence and resistive switching characteristics of ZnO/Al2O3 multilayer nanostructures

This work demonstrates the role of defects generated during rapid thermal annealing of pulsed laser deposited ZnO/Al2O3 multilayer nanostructures in presence of vacuum at different temperatures (Ta) (500–900 C) on their electrical conductance and optical characteristics. Photoluminescence (PL) emissions show the stronger green emission at Ta 600 C and violet–blue emission at TaP800 C, and are attributed to oxygen vacancies and zinc related defects (zinc vacancies and interstitials) respectively. Current–voltage (I–V) characteristics of nanostructures with rich oxygen vacancies and zinc related defects display the electroforming free resistive switching (RS) characteristics. Nanostructures with rich oxygen vacancies exhibit conventional and stable RS behavior with high and low resistance states (HRS/LRS) ratio 104 during the retention test. Besides, the dominant conduction mechanism of HRS and LRS is explained by trap-controlled-space-charge limited conduction mechanism, where the oxygen vacancies act as traps. On the other hand, nanostructures with rich zinc related defects show a diode-like RS behavior. The rectifying ratio is found to be sensitive on the zinc interstitials concentration. It is assumed that the rectifying behavior is due to the electrically formed interface layer ZnAl2O4 at the Zn defects rich ZnO crystals – Al2O3 x interface and the switching behavior is attributed to the electron trapping/de-trapping process at zinc vacancies.

The mineralogy and chemistry of the German and Portuguese tiles used to face a historic building in the Amazon region and their natural susceptibility to tropical weathering

During the 19th century, the most prominent buildings of the city of Belém were faced entirely with tiles manufactured in Portugal and Germany, which now exhibit distinct degrees of degradation. The Pinho mansion is one of the most important of these buildings and was selected for the investigation of the action of the tropical Amazonian climate on the degradation of the tiles. To achieve this objective, the tiles were mapped for organic and inorganic degradation, and samples were collected for analysis. The minerals were determined by XRD, the chemical composition by classical wet methods and SEM/EDS, and the microorganisms under the microscope. The results show that the German and Portuguese tiles are quite different in their composition. While both ceramic bodies are composed of SiO2 and Al2O3, CaO was found only in the Portuguese tile. The low Na2O and K2O contents indicate the addition of materials to reduce the fusion temperature. SiO2 and PbO are the main constituents of the glaze, with CoO and FeO being added as pigment. The ceramic body of the German tiles is constituted of quartz, mullite, and cristobalite, in contrast with the Portuguese tiles, which are made of quartz, gehlenite, diopside, calcite, and feldspars. The glazes are XRD-amorphous. The chemical and mineralogical differences between the German and Portuguese tiles indicate that they were produced from different raw materials under distinct thermal processes. The most prominent weathering-related modifications are the thin layers (German tiles), oxidation stains, dark stains, the detachment of the tile (Portuguese tiles), loss of the glaze and powdering of the ceramic body (Portuguese tiles) through the establishment of Cyanophyta and Bacillariophyta.. The distinct degradation patterns of the tiles exposed to the tropical Amazon climate are a consequence of their distinct mineralogy and chemistry.

MOVPE growth and characterisation of ZnO properties for optoelectronic applications

ZnO, Epitaxy, Metal organic vapor phase epitaxy, MOCVD, CVD, Semiconductor, Optoelectronics, X-ray diffraction, Cathodoluminescence, Microelectronics

Zum Fällungsprozess und Wachstum kugelförmiger SiO2-Partikel

Magdeburg, Univ., Fak. für Verfahrens- und Systemtechnik, Diss., 2008

Metallorganische Gasphasenepitaxie und Charakterisierung homoepitaktischer ZnO-Schichten

Magdeburg, Univ., Fak. für Naturwiss., Diss., 2009

Application of ZnO-Functionalised-Sepiolite in weaning piglet diets

The objective was to evaluate the effect of ZnO-Functionalised-Sepiolite (ZnO-Sepiolite) to fulfil Zn requirements and health status of weaning piglets. Pre-starter Basal Diet (BD, corn– soybean based, from weaning till 14 days on trial) was calculated to provide 27 mg Zn/kg feed from raw materials and had no added ZnO and no antibiotics or organic acids. Treatments during pre-starter period were: 1) BD+90% of NRC Zn requirements completed with ZnO (ZnO90); 2) BD+90% of NRC Zn requirements completed with ZnO-Sepiolite (ZnOS90); 3) BD+3000 mg ZnO/kg of diet (ZnO3000); 4) BD+150 mg added Zn/kg diet from ZnO-Sepiolite (ZnOS150). The starter feed (corn–soybean based, from 14 till 31 days on trial) was common for all piglets, and met 90% NRC Zn requirements by adding ZnO. Diarrhea affected more than 50% of the animals of ZnO90, ZnOS90 and ZnOS150, and 33% of the ZnO3000 animals. Animals from ZnOS90 tended (Pb0.10) to improve Gain to Feed ratio (G:F) compared to animals from ZnO90 (0.830 kg/kg vs. 0.811 kg/kg for G:F). Performance of animals from ZnO3000 was not significantly different from the other treatments, and was numerically similar to animals from ZnOS90. The inclusion of ZnO at 3000 mg/kg of feed in the pre-starter period numerically decreased P in serum at the end of this period, with no effect on Ca level; normal levels were restored after 2 weeks of feeding the same levels of Zn than other animals. Animals fed ZnOSepiolite diets had numerically higher serum Ca than ZnO90 and ZnO3000 at 12 days and higher than ZnO90 at 28 days. Serum Zn levels were significantly higher for ZnO3000 than the other treatments.

Reversible ferromagnetic switching in ZnO:(Co,Mn) powders

We report here on the magnetic properties of ZnO:Mn- and ZnO:Co-doped nanoparticles. We have found that the ferromagnetism of ZnO:Mn can be switched on and off by consecutive low-temperature annealings in O2 and N2, respectively, while the opposite phenomenology was observed for ZnO:Co. These results suggest that different defects (presumably n-type for ZnO:Co and p-type for ZnO:Mn) are required to induce a ferromagnetic coupling in each case. We will argue that ferromagnetism is likely to be restricted to a very thin, nanometric layer at the grain surface. These findings reveal and give insight into the dramatic relevance of surface effects to the occurrence of ferromagnetism in ZnO-doped oxides.

Low-loss rib waveguides containing Si nanocrystals embedded in SiO2

We report on the study and modeling of the structural and optical properties of rib-loaded waveguides working in the 600-900-nm spectral range. A Si nanocrystal (Si-nc) rich SiO2 layer with nominal Si excess ranging from 10% to 20% was produced by quadrupole ion implantation of Si into thermal SiO2 formed on a silicon substrate. Si-ncs were precipitated by annealing at 1100°C, forming a 0.4-um-thick core layer in the waveguide. The Si content, the Si-nc density and size, the Si-nc emission, and the active layer effective refractive index were determined by dedicated experiments using x-ray photoelectron spectroscopy, Raman spectroscopy, energy-filtered transmission electron microscopy, photoluminescence and m-lines spectroscopy. Rib-loaded waveguides were fabricated by photolithographic and reactive ion etching processes, with patterned rib widths ranging from 1¿to¿8¿¿m. Light propagation in the waveguide was observed and losses of 11dB/cm at 633 and 780 nm were measured, modeled and interpreted.

Size dependence of refractive index of Si nanoclusters embedded in SiO2

he complex refractive index of SiO2 layers containing Si nanoclusters (Si-nc) has been measured by spectroscopic ellipsometry in the range from 1.5 to 5.0 eV. It has been correlated with the amount of Si excess accurately measured by x-ray photoelectron spectroscopy and the nanocluster size determined by energy-filtered transmission electron microscopy. The Si-nc embedded in SiO2 have been produced by a fourfold Si+ ion implantation, providing uniform Si excess aimed at a reliable ellipsometric modeling. The complex refractive index of the Si-nc phase has been calculated by the application of the Bruggeman effective-medium approximation to the composite media. The characteristic resonances of the refractive index and extinction coefficient of bulk Si vanish out in Si-nc. In agreement with theoretical simulations, a significant reduction of the refractive index of Si-nc is observed, in comparison with bulk and amorphous silicon. The knowledge of the optical properties of these composite layers is crucial for the realization of Si-based waveguides and light-emitting devices.

Optical-geometrical effects on the photoluminescence spectra of Si nanocrystals embedded in SiO2

We demonstrate that thickness, optical constants, and details of the multilayer stack, together with the detection setting, strongly influence the photoluminescence spectra of Si nanocrystals embedded in SiO2. Due to multiple reflections of the visible light against the opaque silicon substrate, an interference pattern is built inside the oxide layer, which is responsible for the modifications in the measured spectra. This interference effect is complicated by the depth dependence of (i) the intensity of the excitation laser and (ii) the concentration of the emitting nanocrystals. These variations can give rise to apparent features in the recorded spectra, such as peak shifts, satellite shoulders, and even splittings, which can be mistaken as intrinsic material features. Thus, they can give rise to an erroneous attribution of optical bands or estimate of the average particle size, while they are only optical-geometrical artifacts. We have analyzed these effects as a function of material composition (Si excess fraction) and thickness, and also evaluated how the geometry of the detection setup affects the measurements. To correct the experimental photoluminescence spectra and extract the true spectral shape of the emission from Si nanocrystals, we have developed an algorithm based on a modulation function, which depends on both the multilayer sequence and the experimental configuration. This procedure can be easily extended to other heterogeneous systems.

White luminescence from Si+ and C+ ion-implanted SiO2 films

The microstructural and optical analysis of SiO2 layers emitting white luminescence is reported. These structures have been synthesized by sequential Si+ and C+ ion implantation and high-temperature annealing. Their white emission results from the presence of up to three bands in the photoluminescence (PL) spectra, covering the whole visible spectral range. The microstructural characterization reveals the presence of a complex multilayer structure: Si nanocrystals are only observed outside the main C-implanted peak region, with a lower density closer to the surface, being also smaller in size. This lack of uniformity in their density has been related to the inhibiting role of C in their growth dynamics. These nanocrystals are responsible for the band appearing in the red region of the PL spectrum. The analysis of the thermal evolution of the red PL band and its behavior after hydrogenation shows that carbon implantation also prevents the formation of well passivated Si/SiO2 interfaces. On the other hand, the PL bands appearing at higher energies show the existence of two different characteristics as a function of the implanted dose. For excess atomic concentrations below or equal to 10%, the spectra show a PL band in the blue region. At higher doses, two bands dominate the green¿blue spectral region. The evolution of these bands with the implanted dose and annealing time suggests that they are related to the formation of carbon-rich precipitates in the implanted region. Moreover, PL versus depth measurements provide a direct correlation of the green band with the carbon-implanted profile. These PL bands have been assigned to two distinct amorphous phases, with a composition close to elemental graphitic carbon or stoichiometric SiC.