Effect of argon ion energy on the performance of silicon nitridemultilayer permeation barriers grown by hot-wire CVD on polymers

One of the authors (S.M.) acknowledges Direction des Relations Extérieures of Ecole Polytechnique for financial support.

Silicon nanowire arrays coupled with cobalt phosphide spheres as low-cost photocathodes for efficient solar hydrogen evolution

We demonstrate the first example of silicon nanowire array photocathodes coupled with hollow spheres of the emerging earth-abundant cobalt phosphide catalysts. Compared to bare silicon nanowire arrays, the hybrid electrodes exhibit significantly improved photoelectrochemical performance toward the solar-driven H2 evolution reaction.

Novas funcionalidades para dispositivos médicos invasivos com imagem

Tese de Doutoramento em Engenharia Eletrónica e de Computadores.

Dynamic wet etching of silicon through isopropanol alcohol evaporation

In this paper, Isopropanol (IPA) availability during the anisotropic etching of silicon in Potassium Hydroxide (KOH) solutions was investigated. Squares of 8 to 40 m were patterned to (100) oriented silicon wafers through DWL (Direct Writing Laser) photolithography. The wet etching process was performed inside an open HDPE (High Density Polyethylene) flask with ultrasonic agitation. IPA volume and evaporation was studied in a dynamic etching process, and subsequent influence on the silicon etching was inspected. For the tested conditions, evaporation rates for water vapor and IPA were determined as approximately 0.0417 mL/min and 0.175 mL/min, respectively. Results demonstrate that IPA availability, and not concentration, plays an important role in the definition of the final structure. Transversal SEM (Scanning Electron Microscopy) analysis demonstrates a correlation between microloading effects (as a consequence of structure spacing) and the angle formed towards the (100) plane.

Modulation of the secretome of hBMSCs by tailoring the macromolecular gradient in hydrogels to generate tissue-to-tissue interfaces

Tissue-to-tissue interfaces are commonly present in all tissues exhibiting structural, biological and chemical gradients serving a wide range of physiological functions. These interfaces are responsible for mediation of load transfer between two adjacent tissues. They are also important structures in sustaining the cellular communications to retain tissueâ s functional integration and homeostasis. [1] All cells have the capacity to sense and respond to physical and chemical stimulus and when cultured in three-dimensional (3D) environments they tend to perform their function better than in two-dimensional (2D) environments. Spatial and temporal 3D gradient hydrogels better resemble the natural environment of cells in mimicking their extracellular matrix. [2] In this study we hypothesize that differential functional properties can be engineered by modulation of macromolecule gradients in a cell seeded threedimensional hydrogel system. Specifically, differential paracrine secretory profiles can be engineered using human Bone Marrow Stem Cells (hBMSCâ s). Hence, the specific objectives of this study are to: assemble the macromolecular gradient hydrogels to evaluate the suitablity for hBMSCâ s encapsulation by cellular viability and biofunctionality by assessing the paracrine secretion of hBMSCâ s over time. The gradient hydrogels solutions were prepared by blend of macromolecules in one solution such as hyaluronic (HA) acid and collagen (Col) at different ratios. The gradient hydrogels were fabricated into cylindrical silicon moulds with higher ratio solutions assembled at the bottom of the mould and adding the two solutions consecutively on top of each other. The labelling of the macromolecules was performed to confirm the gradient through fluorescence microscopy. Additionally, AFM was conducted to assess the gradient hydrogels stiffness. Gradient hydrogels characterization was performed by HA and Col degradation assay, degree of crosslinking and stability. hBMSCâ s at P3 were encapsulated into each batch solution at 106 cells/ml solution and gradient hydrogels were produced as previously described. The hBMSCâ s were observed under confocal microscopy to assess viability by Live/Dead® staining. Cellular behaviour concerning proliferation and matrix deposition was also performed. Secretory cytokine measurement for pro-inflammatory and angiogenesis factors was carried out using ELISA. At genomic level, qPCR was carried out. The 3D gradient hydrogels platform made of different macromolecules showed to be a suitable environment for hBMSCâ s. The hBMSCâ s gradient hydrogels supported high cell survival and exhibited biofunctionality. Besides, the 3D gradient hydrogels demonstrated differentially secretion of pro-inflammatory and angiogenic factors by the encapsulated hBMSCâ s. References: 1. Mikos, AG. et al., Engineering complex tissues. Tissue Engineering 12,3307, 2006 2. Phillips, JE. et al., Proc Natl Acad Sci USA, 26:12170-5, 2008

Synthesis and characterization of novel 4H-pyran-4-ylidene indole-based heterocyclic systems for several optical applications

The development of organic materials displaying high two-photon absorption (TPA) has attracted much attention in recent years due to a variety of potential applications in photonics and optoelectronics, such as three-dimensional optical data storage, fluorescence imaging, two-photon microscopy, optical limiting, microfabrication, photodynamic therapy, upconverted lasing, etc. The most frequently employed structural motifs for TPA materials are donor–pi bridge–acceptor (D–pi–A) dipoles, donor–pi bridge–donor (D–pi–D) and acceptor–pi bridge-acceptor (A–pi–A) quadrupoles, octupoles, etc. In this work we present the synthesis and photophysical characterization of quadrupolar heterocyclic systems with potential applications in materials and biological sciences as TPA chromophores. Indole is a versatile building block for the synthesis of heterocyclic systems for several optoelectronic applications (chemosensors, nonlinear optical, OLEDs) due to its photophysical properties and donor electron ability and 4H-pyran-4-ylidene fragment is frequently used for the synthesis of red light-emitting materials. On the other hand, 2-(2,6-dimethyl-4H-pyran-4-ylidene)malononitrile (1) and 1,3-diethyl-dihydro-5-(2,6-dimethyl-4H-pyran-4-ylidene)-2-thiobarbituric (2) units are usually used as strong acceptor moieties for the preparation of π-conjugated systems of the push-pull type. These building blocks were prepared by Knoevenagel condensation of the corresponding ketone precursor with malononitrile or 1,3-diethyl-dihydro-2-thiobarbituric acid. The new quadrupolar 4H-pyran-4-ylidene fluorophores (3) derived from indole were prepared through condensation of 5-methyl-1H-indole-3-carbaldehyde with the acceptor precursors 1 and 2, in the presence of a catalytical amount of piperidine. The new compounds were characterized by the usual spectroscopic techniques (UV-vis., FT-IR and multinuclear NMR - 1H, 13C).

Surface plasmon resonance-coupled photoluminescence and resistive switching behavior of pulsed laser-deposited Ag:SiC nanocermet thin films

In this study, Ag:SiC nanocermets were prepared via rapid thermal annealing (RTA) of pulsed laser-deposited SiC/Ag/SiC trilayers grown on Si substrate. Atomic force microscope images show that silver nanoparticles (Ag NPs) are formed after RTA, and the size of NPs increases with increasing Ag deposition time (t Ag). Sharp dip observed in the reflectance spectra confirmed the existence of Ag surface plasmons (SPs). The infrared transmission spectra showed an intense and broad absorption band around 780–800 cm−1 that can be assigned to Si-C stretching vibration mode. Influence of t Ag on the spectral characteristics of SP-enhanced photoluminescence (PL) and electrical properties of silicon carbide (SiC) films has been investigated. The maximum PL enhancement by 5.5 times for Ag:SiC nanocermets is achieved when t Ag ≈ 50 s. This enhancement is due to the strong resonant coupling between SiC and the SP oscillations of the Ag NPs. Presence of Ag NPs in SiC also induces a forming-free resistive switching with switching ratio of 2 × 10−2. The analysis of I–V curves demonstrates that the trap-controlled space-charge-limited conduction with filamentary model is the governing mechanism for the resistive switching in nanocerment thin films.

Mechanical, fatigue and wear properties of sintered Carbon Nanotube-based functionally graded materials

Tese de Doutoramento Engenharia Mecânica

Estudo das propriedades físicas fundamentais de filmes finos intermetálicos do tipo Ti-Me (Me = Al, Au) na funcionalização de elétrodos - sensores para dispositivos biomédicos

Dissertação de mestrado integrado em Engenharia de Materiais

Controlled aggregation of gold nanoparticles in a di-ureasilmatrix. Optical and micro indentation investigation

Nanocomposite materials with an organic-inorganic urea-silicate (di-ureasil) based matrix containing gold nanoparticles (NPs) were synthesized and characterized by optical (UV/Vis) spectroscopy and indentation measurement. The urea silicate gels were obtained by reaction between silicon alkoxyde modified by isocyanate group and polyethylene glycol oligomer with amine terminal groups in presence of catalyst. The latter ensures the successful incorporation of citrate-stabilized gold NPs in the matrix. It is shown that using a convenient destabilizing agent (AgNO3) and governing the preparative conditions, the aggregation degree of gold NPs can be controlled. The developed synthesis procedure significantly simplifies the preparative procedure of gold/urea silicate nanocomposites, compared to the procedure using gold NPs, preliminary covered with silica shells. Mechanical properties of the prepared sample were characterised using depth sensing indentation methods (DSI) and an idea about the type of aggregation structures was suggested.

Titanium oxide adhesion layer for high temperature annealed Si/Si3N4/TiOx/Pt/LiCoO2 battery structures

This work describes the influence of a high annealing temperature of about 700C on the Si(substrate)/Si3N4/TiOx/Pt/LiCoO2 multilayer system for the fabrication of all-solid-state lithium ion thin film microbatteries. Such microbatteries typically utilize lithium cobalt oxide (LiCoO2) as cathode material with a platinum (Pt) current collector. Silicon nitride (Si3N4) is used to act as a barrier against Li diffusion into the substrate. For a good adherence between Si3N4 and Pt, commonly titanium (Ti) is used as intermediate layer. However, to achieve crystalline LiCoO2 the multilayer system has to be annealed at high temperature. This post-treatment initiates Ti diffusion into the Pt-collector and an oxidation to TiOx, leading to volume expansion and adhesion failures. To solve this adhesion problem, we introduce titanium oxide (TiOx) as an adhesion layer, avoiding the diffusion during the annealing process. LiCoO2, Pt and Si3N4 layers were deposited by magnetron sputtering and the TiOx layer by thermal oxidation of Ti layers deposited by e-beam technique. Asdeposited and annealed multilayer systems using various TiOx layer thicknesses were studied by scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) and x-ray photoelectron spectroscopy (XPS). The results revealed that an annealing process at temperature of 700C leads to different interactions of Ti atoms between the layers, for various TiOx layer thicknesses (25–45 nm).

Lithium-doped silk fibroin films for application in electrochromic devices

Silk fibroin (SF) is a commonly available natural biopolymer produced in specialized glands of arthropods, with a long history of use in textile production and also in health cares. The exceptional intrinsic properties of these fibers, such as self-assembly, machinability, biocompatibility, biodegradation or non-toxicity, offer a wide range of exciting opportunities [1]. It has long been recognized that silk can be a rich source of inspiration for designing new materials with tailored properties, enhanced performance and high added value for targeted applications, opening exciting new prospects in the domain of materials science and related technological fields, including bio-friendly integration, miniaturization and multifunctionalization. In recent years it has been demonstrated that fibroin is an excellent material for active components in optics and photonics devices. Progress in new technological fields such as optics, photonics and electronics are emerging [2,3]. The incorporation of polymer electrolytes as components of various devices (advanced batteries, smart windows, displays and supercapacitors) offers significant advantages with respect to traditional electrolytes, including enhanced reliability and improved safety. SF films are particularly attractive in this context. They have near-perfect transparency across the VIS range, surface flatness (together with outstanding mechanical robustness), ability to replicate patterned substrates and their thickness may be easily tailored from a few nanometers to hundreds of micrometers through spin-casting of a silk solution into subtract. Moreover, fibroin can be added to other biocomponents or salts in order to modify the biomaterial properties leading to optimized and total different functions. Preliminary tests performed with a prototype electrochromic device (ECD) incorporating SF films doped with lithium triflate and lithium tetrafluoroborate (LiTFSI and LiBF4, respectively) as electrolyte and WO3 as cathodic electrochromic layer, are extremely encouraging. Aiming to evaluate the performance of the ion conducting SF membranes doped with LiTFSI and LiBF4 (SF-Li), small ECDs with glass/ITO/WO3/SF-Li/CeO2-TiO2/ITO/glass configuration were assembled and characterized. The device exhibited, after 4500 cycles, the insertion of charge at -3.0 V reached –1.1 mC.cm-2 in 15 s. After 4500 cycles the window glass-staining, glass/ITO/WO3/Fibrin-Li salts electrolyte/CeO2-TiO2/ITO/glass configuration was reversible and featured a T  8 % at λ = 686 nm

Flexible organic–inorganic hybrid layer encapsulation for organic opto-electronic devices

In this work we produce and study the flexible organic–inorganic hybrid moisture barrier layers for the protection of air sensitive organic opto-electronic devices. The inorganic amorphous silicon nitride layer (SiNx:H) and the organic PMMA [poly (methyl methacrylate)] layer are deposited alternatingly by using hot wire chemical vapor deposition (HW-CVD) and spin-coating techniques, respectively. The effect of organic–inorganic hybrid interfaces is analyzed for increasing number of interfaces. We produce highly transparent (∼80% in the visible region) hybrid structures. The morphological properties are analysed providing a good basis for understanding the variation of the water vapor transmission rate (WVTR) values. A minimum WVTR of 4.5 × 10−5g/m2day is reported at the ambient atmospheric conditions for 7 organic/inorganic interfaces. The hybrid barriers show superb mechanical flexibility which confirms their high potential for flexible applications.

Bateria de lítio em filme fino: fabrico e caracterização do cátodo em substrato flexível

Dissertação de mestrado integrado em Engenharia Eletrónica Industrial e Computadores

High-aspect-ratio tridimensional electrode arrays for neural applications

Tese de Doutoramento em Engenharia Biomédica.