Development of novel multi-substituted apatite nanophases with advanced functionalities for bone regeneration

In the field of bone substitutes is highly researched an innovative material able to fill gaps with high mechanical performances and able to stimulate cell response, permitting the complete restoration of the bone portion. In this respect, the synthesis of new bioactive materials able to mimic the compositional, morphological and mechanical features of bone is considered as the elective approach for effective tissue regeneration. Hydroxyapatite (HA) is the main component of the inorganic part of bone. Additionally ionic substitution can be performed in the apatite lattice producing different effects, depending from the selected ions. Magnesium, in substitution of calcium, and carbonate, in substitution of phosphate, extensively present in the biological bones, are able to improve properties naturally present in the apatitic phase, (i.e. biomimicry, solubility e osteoinductive properties). Other ions can be used to give new useful properties, like antiresorptive or antimicrobial properties, to the apatitic phase. This thesis focused on the development of hydroxyapatite nanophases with multiple ionic substitutions including gallium, or zinc ions, in association with magnesium and carbonate, with the purpose to provide double synergistic functionality as osteogenic and antibacterial biomaterial. Were developed bioactive materials based on Sr-substituted hydroxyapatite in the form of sintered targets. The obtained targets were treated with Pulsed Plasma Deposition (PED) resulting in the deposition of thin film coatings able to improve the roughness and wettability of PEEK, enhancing its osteointegrability. Were investigated heterogeneous gas-solid reactions, addressed to the biomorphic transformations of natural 3D porous structures into bone scaffolds with biomimetic composition and hierarchical organization, for application in load-bearing sites. The kinetics of the different reactions of the process were optimized to achieve complete and controlled phase transformation, maintaining the original 3-D morphology. Massive porous scaffolds made of ion-substituted hydroxyapatite and bone-mimicking structure were developed and tested in 3-D cell culture models.

Determination of local density of states in amorphous oxide semiconductors with Kelvin Probe Force Microscopy

Amorphous semiconductors are important materials as they can be deposited by physical deposition techniques on large areas and even on plastic substrates. Therefore, they are crucial for transistors in large active matrices for imaging and transparent wearable electronics. The most widely applied candidate for amorphous thin film transistors production is Indium Gallium Zinc Oxide (IGZO). It is attracting much interest because of its optical transparency, facile processing by sputtering deposition and notable improved charge carrier mobility with respect to hydrogenated amorphous silicon a-Si:H. Degradation of the device and long-term performance issues have been observed if IGZO thin film transistors are subjected to electrical stress, leading to a modification of IGZO channel properties and subthreshold slope. Therefore, it is of great interest to have a reliable and precise method to study the conduction band tail, and the density of states in amorphous semiconductors. The aim of this thesis is to develop a local technique using Kelvin Probe Force Microscopy to study the evolution of IGZO DOS properties. The work is divided into three main parts. First, solutions to the non-linear Poisson-Boltzmann equation of a metal-insulator-semiconductor junction describing the charge accumulation and its relation to DOS properties are elaborated. Second macroscopic techniques such as capacitance voltage (CV) measurements and photocurrent spectroscopy are applied to obtain a non-local estimate of band-tail DOS properties in thin film transistor samples. The third part of my my thesis is dedicated to the KPFM measurements. By fitting the data to the developed numerical model, important parameters describing the amorphous conduction band tail are obtained. The results are in excellent agreement with the macroscopic characterizations. KPFM result is comparable also with non-local optoelectronic characterizations, such as photocurrent spectroscopy.

Diffractive phase-shift lithography photomask operating in proximity printing mode

A phase shift proximity printing lithographic mask is designed, manufactured and tested. Its design is based on a Fresnel computer-generated hologram, employing the scalar diffraction theory. The obtained amplitude and phase distributions were mapped into discrete levels. In addition, a coding scheme using sub-cells structure was employed in order to increase the number of discrete levels, thus increasing the degree of freedom in the resulting mask. The mask is fabricated on a fused silica substrate and an amorphous hydrogenated carbon (a:C-H) thin film which act as amplitude modulation agent. The lithographic image is projected onto a resist coated silicon wafer, placed at a distance of 50 mu m behind the mask. The results show a improvement of the achieved resolution - linewidth as good as 1.5 mu m - what is impossible to obtain with traditional binary masks in proximity printing mode. Such achieved dimensions can be used in the fabrication of MEMS and MOEMS devices. These results are obtained with a UV laser but also with a small arc lamp light source exploring the partial coherence of this source. (C) 2010 Optical Society of America

Theoretical investigation of atomic and electronic structures of Ga(2)O(3)(ZnO)(6)

Transparent conducting oxides (TCO) are widely used in technological applications ranging from photovoltaics to thin-film transparent field-effect transistors. In this work we report a first-principles investigation, based on density-functional theory, of the atomic and electronic properties of Ga(2)O(3)(ZnO)(6) (GZO(6)), which is a promising candidate to be used as host oxide for wide band gap TCO applications. We identify a low-energy configuration for the coherent distribution of the Ga and Zn atoms in the cation positions within the experimentally reported orthorhombic GZO(6) structure. Four Ga atoms are located in four-fold sites, while the remaining 12 Ga atoms in the unit cell form four shared Ga agglomerates (a motif of four atoms). The Zn atoms are distributed in the remaining cation sites with effective coordination numbers from 3.90 to 4.50. Furthermore, we identify the natural formation of twin-boundaries in GZO(6), which can explain the zigzag modulations observed experimentally by high-resolution transmission electron microscopy in GZO(n) (n=9). Due to the intrinsic twin-boundary formation, polarity inversion in the ZnO tetrahedrons is present which is facilitated by the formation of the Ga agglomerates. Our analysis shows that the formation of fourfold Ga sites and Ga agglomerates are stabilized by the electronic octet rule, while the distribution of Ga atoms and the formation of the twin-boundary help alleviate excess strain. Finally we identify that the electronic properties of GZO(6) are essentially determined by the electronic properties of ZnO, i.e., there are slight changes in the band gap and optical absorption properties.

Low-temperature deposition of silicon oxide and silicon nitride by reactive magnetron sputtering

In this study, oxide and nitride films were deposited at room temperature through the reaction of silicon Sputtered by argon and oxygen ions or argon and nitrogen ions at 250 and 350 W with 0.67 Pa pressure. It was observed that for both thin films the deposition rates increase with the applied RF power and decrease with the increase of the gas concentration. The Si/O and Si/N ratio were obtained through RBS analyses and for silicon oxide the values changed from 0.42 to 0.57 and for silicon nitride the Values changed from 0.4 to 1.03. The dielectric constants were calculated through capacitance-voltage curves with the silicon oxide values varying from 2.4 to 5.5, and silicon nitride values varying from 6.2 to 6.7, which are good options for microelectronic dielectrics. (c) 2008 Elsevier Ltd. All rights reserved.

Numerical study of tensile tests conducted on systems with elastic-plastic films deposited onto elastic-plastic substrates

In this work, a series of two-dimensional plane-strain finite element analyses was conducted to further understand the stress distribution during tensile tests on coated systems. Besides the film and the substrate, the finite element model also considered a number of cracks perpendicular to the film/substrate interface. Different from analyses commonly found in the literature, the mechanical behavior of both film and substrate was considered elastic-perfectly plastic in part of the analyses. Together with the film yield stress and the number of film cracks, other variables that were considered were crack tip geometry, the distance between two consecutive cracks and the presence of an interlayer. The analysis was based on the normal stresses parallel to the loading axis (sigma(xx)), which are responsible for cohesive failures that are observed in the film during this type of test. Results indicated that some configurations studied in this work have significantly reduced the value of sigma(xx) at the film/substrate interface and close to the pre-defined crack tips. Furthermore, in all the cases studied the values of sigma(xx) were systematically larger at the film/substrate interface than at the film surface. (C) 2010 Elsevier B.V. All rights reserved.

PbO-GeO(2) rib waveguides for photonic applications

This work presents for the first time to our knowledge the fabrication and characterization of rib waveguides produced with PbO-GeO(2) (PGO) thin films. The target was manufactured using pure oxides ( 60 PbO-40 GeO(2), in wt%) and amorphous thin films were produced with the RF sputtering technique. PGO thin films present small absorption in the visible and in the near infrared and refractive index of similar to 2.0. The definition of the rib waveguide structure was made using conventional optical lithography followed by plasma etching, performed in a Reactive Ion Etching (RIE) reactor. Light propagation mode in the waveguide structure was analyzed using integrated optic simulation software. Optical loss measurements were performed to determine the propagation loss at 633 nm, for ribs with height of 70 nm and width of 3-5 mu m; experimental values around 2 dB/cm were found for the propagation loss and confirmed the theoretical calculations. The results obtained demonstrate that PGO thin films are potential candidates for application in integrated optics. Published by Elsevier B.V.

Comparison of oxidation efficiency of disperse dyes by chemical and photoelectrocatalytic chlorination and removal of mutagenic activity

Degradation of Disperse Orange 1, Disperse Red 1 and Disperse Red 13 dyes has been performed using electrochemical oxidation on Pt electrode, chemical chlorination and photoelectrochemical oxidation on Ti/TiO(2) thin film electrodes in NaCl or Na(2)SO(4) medium. 100% discoloration was obtained for all tested methods after 1 h of treatment. Faster color removal was obtained by photoelectrocatalytic oxidation in 0.1 mol L(-1) NaCl pH 4.0 under UV light and an applied potential of +1.0V (vs SCE reference electrode), which indicates also values around 60% of TOC removal. The conventional chlorination method and electrochemical oxidation on Pt electrode resulted in negligible reduction of TOC removal. All dyes showed positive mutagenic activity in the Salmonella/microsome assay with the strain TA98 in the absence and presence of S9 (exogenous metabolic activation). Nevertheless, there is complete reduction of the mutagenic activity after 1 h of photoelectrocatalytic oxidation, suggesting that this process would be good option to remove disperse azo dyes from aqueous media. (C) 2008 Elsevier Ltd. All rights reserved.

Mutagenic activity removal of selected disperse dye by photoeletrocatalytic treatment

The degradation of black dye commercial product (BDCP) composed of C.I. Disperse Blue 373, C.I. Disperse Orange 37, C.I. Disperse Violet 93 dyes was investigated by photoelectrocatalysis process. The dyes have shown high mutagenic activity with Salmonella strain YG1041 and TA98 with and without S9. Samples of BCPD dye submitted to conventional chlorination and photoelectrocatalytic oxidation were compared monitoring its products by HPLC using a diode array detector, spectrophotometry UV-vis, TOC removal, and mutagenicity potency. The photoelectrocatalytic method operating with Ti/TiO(2) as anode at +1.0 V and UV illumination presented fast oxidation of test solutions containing 10 mg L(-1) of dye in 0.1 mol L(-1) NaCl pH 4.0 leading to 100% of discoloration, 67% of mineralization, and negative response to all tested Salmonella strains. The formation of Cl(aEuro cent), CL(2) (aEuro cent) on photoelectrocatalytic medium improved the efficiency of the method in relation to conventional chlorination method that promoted 100% of discoloration, but only 8% of TOC removal and more mutagenic product.

Turbulent spots in boundary layers in a free-piston shock-tunnel flow

In this paper, experiments to detect turbulent spots in the transitional boundary layers, formed on a flat plate in a free-piston shock tunnel how, are reported. Experiments indicate that thin-film heat-transfer gauges are suitable for identifying turbulent-spot activity and can be used to identify parameters such as the convection rate of spots and the intermittency of turbulence.

Boundary-layer transition measurements in hypervelocity flows in a shock tunnel

Experiments to investigate the transition process in hypervelocity boundary layers were performed in the T4 free-piston shock tunnel. An array of thin-film heat-transfer gauges was used to detect the location and extent of the transitional region on a 1500 mm long x 120 turn wide flat plate, which formed one of the walls of a duct. The experiments were performed in a Mach 6 flow of air with 6- and 12-MJ/kg nozzle-supply enthalpies at unit Reynolds numbers ranging from 1.6 x 10(6) to 4.9 x 10(6) m(-1). The results show that the characteristics typical of transition taking place through the initiation, growth, and merger of turbulent spots are evident in the heat-transfer signals. A 2-mm-high excrescence located 440 turn from the leading edge was found to be capable of generating a turbulent wedge within an otherwise laminar boundary layer at a unit Reynolds number of 2.6 x 10(6) m(-1) at the 6-MJ/kg condition. A tripping strip, located 100 mm from the leading edge and consisting of a line 37 teeth of 2 rum height equally spaced and spanning the test surface, was also found to be capable of advancing the transition location at the same condition and at the higher enthalpy condition.

Piezoresistive sensors for force mapping of hip-prostheses

The success of artificial prosthetic replacements depends on the fixation of the artificial prosthetic component after being implanted in the thighbone. The materials for fixation are subject to mechanical stresses, which originate permanent deformations, incipient cracks and even fatigue fractures. This work shows the possibility of monitoring the mechanical stress over time in prosthesis. In this way, highly sensitive silicon thin-film piezoresistive sensors were developed attached to prosthesis and their results compared with commercial strain gauge sensors. Mechanical stress-strain experiments were performed in compressive mode, during 10,000 cycles. Experimental data was acquired at mechanical vibration frequencies of 0.5 Hz, 1 Hz and 5 Hz, and sent to a computer by means of a wireless link. The results show that there is a decrease in sensitivity of the thin-film silicon piezoresistive sensors when they are attached to the prosthesis, but this decrease does not compromise its monitoring performance. The sensitivity, compared to that of commercial strain gauges, is much larger due to their higher gauge factors (-23.5), when compared to the GFs of commercial sensors (2).

Neural Electrode Array Based on Aluminum: Fabrication and Characterization

A unique neural electrode design is proposed with 3 mm long shafts made from an aluminum-based substrate. The electrode is composed by 100 individualized shafts in a 10 × 10 matrix, in which each aluminum shafts are precisely machined via dicing-saw cutting programs. The result is a bulk structure of aluminum with 65 ° angle sharp tips. Each electrode tip is covered by an iridium oxide thin film layer (ionic transducer) via pulsed sputtering, that provides a stable and a reversible behavior for recording/stimulation purposes, a 40 mC/cm2 charge capacity and a 145 Ω impedance in a wide frequency range of interest (10 Hz-100 kHz). Because of the non-biocompatibility issue that characterizes aluminum, an anodization process is performed that forms an aluminum oxide layer around the aluminum substrate. The result is a passivation layer fully biocompatible that furthermore, enhances the mechanical properties by increasing the robustness of the electrode. For a successful electrode insertion, a 1.1 N load is required. The resultant electrode is a feasible alternative to silicon-based electrode solutions, avoiding the complexity of its fabrication methods and limitations, and increasing the electrode performance.

Photo-induced instability of nanocrystalline silicon TFTs

We examine the instability behavior of nanocrystalline silicon (nc-Si) thin-film transistors (TFTs) in the presence of electrical and optical stress. The change in threshold voltage and sub-threshold slope is more significant under combined bias-and-light stress when compared to bias stress alone. The threshold voltage shift (Delta V-T) after 6 h of bias stress is about 7 times larger in the case with illumination than in the dark. Under bias stress alone, the primary instability mechanism is charge trapping at the semiconductor/insulator interface. In contrast, under combined bias-and-light stress, the prevailing mechanism appears to be the creation of defect states in the channel, and believed to take place in the amorphous phase, where the increase in the electron density induced by electrical bias enhances the non-radiative recombination of photo-excited electron-hole pairs. The results reported here are consistent with observations of photo-induced efficiency degradation in solar cells.

Phototransistor with nanocrystalline Si/amorphous Si bilayer channel

We report a field-effect phototransistor with a channel comprising a thin nanocrystalline silicon transport layer and a thicker hydrogenated amorphous silicon absorption layer. The semiconductor and dielectric layers were deposited by radio-frequency plasma enhanced chemical vapor deposition. The phototransistor with channel length of 24 microns and photosensitive area of 1.4 mm(2) shows an off-current of about 1 pA, and high photoconductive gain in the subthreshold region. Measurements of the quantum efficiency at different incident light intensities and biasing conditions, along with spectral-response characteristics, and threshold voltage stability characterization demonstrate the feasibility of the phototransistor for low light level detection.