Rodrigo Martins

In this work, we investigate the role of amorphous silicon (a-Si:H) thin films deposited by a plasma enhanced chemical vapor deposition (PECVD) technique on porous silicon (PS) to facilitate its water vapor and oxygen gas sensing properties using its electrical response. Overall we notice a rectifying behavior from a-Si:H/PS heterojunction device, where a current enhancement of one and four orders of magnitude was observed in the presence of oxygen gas and water vapor, in comparison with atmospheric air at room temperature, respectively. The photoluminescence (PL) investigation of PS shows a slight blue shift in the PL emission band from 1.72 to 1.77 eV and the intensity of the PL is enhanced by a factor of 5.4 with increase of porosity from 21% to 77%. This PL emission may originate from the O-Si-H related absorbance bands. Alternatively, quenching of the PL intensity was observed after a-Si:H films were deposited on PS specimens. Besides, micro-Raman and atomic force microscopic (AFM) analyse were carried out to understand the structure and morphological features of the PS and a-Si:H/PS specimens. © 2007 Elsevier B.V. All rights reserved.

In the present work, the spectroscopic ellipsometry (1.5 - 5.5 eV) was used to investigate the effects of current density induced microstructural variations and their influence on the electronic states of as-prepared and a-Si:H coated porous silicon (PS). The pseudodielectric responses of the low and high current densities (5 and 40 mA/cm2) were analyzed using a multilayer model within the effective medium approximation. The FTIR investigation reveals me enhancement of surface oxide (Si-Ox) layer with current density and the improvement of the Si-Hx band after a-Si:H coating.

In this work Spectroscopic Ellipsometry (SE) was used to study metal induced crystallization (MIC) on amorphous silicon films in order to analyze the influence of different annealing conditions on their structural properties. The variation of the metal thickness has shown to be determinant on the time needed to full crystallize silicon films. Films of 100 nm thickness crystallize after 2h at 500°C using 1 nm of Ni deposited on it. When reducing the average metal thickness down to 0.05 nm the same silicon film will need almost 10 hours to be totally crystallized. Using a new approach on the modelling procedure of the SE data we show to be possible to determine the Ni remaining inside the crystallized films. The method consists in using Ni as reference on the Bruggeman Effective Medium Approximation (BEMA) layer that will simulated the optical response of the crystallized silicon. Silicon samples and metal layers with different thicknesses were analyzed and this new method has shown to be sensible to changes on the initial metal/silicon ratio. The nickel distribution inside the silicon layers was independently measured by Rutherford Backscattering Spectroscopy (RBS) to check the data obtained from the proposed approach. © 2006 Materials Research Society.

In the production of porous silicon (PS) to optoelectronic application one of the most significant constrains is the surface defects passivation. In the present work we investigate, gallium-doped zinc oxide (GZO) thin films deposited by rf magnetron sputtering at room temperature on PS obtained with different etching times. The X-ray diffraction (XRD), Fourier transform infrared (FTIR) and atomic force microscopy (AFM) analysis have been carried out to understand the effect of GZO films coating on PS. Further, the XRD analysis suggests the formation of a good crystalline quality of the GZO films on PS. From AFM investigation we observe that the surface roughness increases after GZO film coating. The photoluminescence (PL) measurements on PS and GZO films deposited PS shows three emission peaks at around 1.9 eV (red-band), 2.78 eV (blue-band) and 3.2 eV (UV-band). PL enhancement in the blue and ultraviolet (UV) region has been achieved after GZO films deposition, which might be originated from a contribution of the near-band-edge recombination from GZO. © 2007 Elsevier B.V. All rights reserved.

In this work, HfO2 was deposited by r.f. sputtering at room temperature and then annealed for different times at 200°C in a forming gas atmosphere. After annealing for 2 hours the HfO2 layers present a reduction on the flat band voltage of about 1 V, relatively to the as deposited film, decreasing from -2.23V down to -1.28 V. This means an improvement of the interface properties and a reduction on the oxide charge density from 1.33×1012 cm-2 to 7.62×1011 cm -2. The dielectric constant reaches a maximum of 18.3 after 5h annealing due to film's densification. When annealing for longer times such as 10h a small degradation of the electrical properties is observed. After 10h annealing the dielectric constant, flat band voltage and fixed charge density are respectively, 14.9, -2.96 V and 1.64×1012 cm-2 and the leakage current also increases due to film's crystallization.

The aim of this work is to study the electrical characteristics of polycrystalline silicon (poly-Si) thin film transistors (TFTs) using spectroscopic impedance technique, where the poly-Si active layer was obtained by metal induced crystallization of amorphous silicon. From the study performed a theoretical model that fitted the impedance data is proposed, in order to obtain the separate contributions of each region that constitutes the TFT namely the channel, non accumulated region and contacts. © 2006 Elsevier B.V. All rights reserved.

In this work hafnium oxide (HfO2) was deposited by r.f. magnetron sputtering at room temperature and then annealed at 200 °C in forming gas (N2+H2) and oxygen atmospheres, respectively for 2, 5 and 10 h. After 2 h annealing in forming gas an improvement in the interface properties occurs with the associated flat band voltage changing from -2.23 to -1.28 V. This means a reduction in the oxide charge density from 1.33×1012 to 7.62×1011 cm-2. After 5 h annealing only the dielectric constant improves due to densification of the film. Finally, after 10 h annealing we notice a degradation of the electrical film's properties, with the flat band voltage and fixed charge density being -2.96 V and 1.64×1012 cm-2, respectively. Besides that, the leakage current also increases due to crystallization. On the other hand, by depositing the films at 200 °C or annealing it in an oxidizing atmosphere no improvements are observed when comparing these data to the ones obtained by annealing the films in forming gas. Here the flat band voltage is more negative and the hysteresis on the C-V plot is larger than the one recorded on films annealed in forming gas, meaning a degradation of the interfacial properties. © 2006 Elsevier Ltd. All rights reserved.

In this work, the optical and structural properties of high k materials such as tantalum oxide and titanium oxide were studied by spectroscopic ellipsometry, where a Tauc-Lorentz dispersion model based in one (amorphous films) or two oscillators (microcrystalline films) was used. The samples were deposited at room temperature by radio frequency magnetron sputtering and then annealed at temperatures from 100 to 500 °C. Concerning the tantalum oxide films, the increase of the annealing temperature, up to 500 °C does not change the amorphous nature of the films, increasing, however, their density. The same does not happen with the titanium oxide films that are microcrystalline, even when deposited at room temperature. Data concerning the use of a four-layer model based on one and two Tauc-Lorentz dispersions is also discussed, emphasizing its use for the detection of an amorphous incubation layer, normally present on microcrystalline films grown by sputtering. © 2006 Elsevier B.V. All rights reserved.

This work focuses on the role of the native oxide layer (SiO2) on the nickel (Ni)-assisted crystallization of amorphous silicon (a-Si). In some samples, the native oxide was removed using a HF-diluted solution before Ni layers with 0.5 nm be deposited on a-Si. The results show that the presence of a thin SiO2 layer of about 3 nm between the a-Si and the Ni delays the crystallization process. Ellipsometry data show that, after annealing for 5 h at 500 °C, the HF-cleaned sample presents a crystalline fraction of 88%, while the one with the native oxide has only 35%. This difference disappears after 20 h where both samples present similar crystalline fraction. These facts are also reflected on the film's electrical properties, where the activation energy for samples annealed for 5 h rises from 0.42 eV to 0.55 eV, when the oxide layer is removed. After 20 h and 30 h, the activation energy is around 0.55 eV for both kinds of samples, meaning that films with similar electrical properties are now obtained. However, the XRD data suggest the presence of some structural differences attributed to slight differences on the crystallization process. © 2005 Elsevier B.V. All rights reserved.

In this work metal induced crystallization (MIC) using nickel (Ni) was employed to obtain poly-Si by crystallization of amorphous films for application as active layer in TFTs. Ni layers with thicknesses of 0.5 nm, 1 nm and 2 nm were used to crystallize the silicon. The TFTs were produced with a bottom gate configuration using a multi-layer Al2O3/TiO2 insulator produced by atomic layer deposition (ALD) as gate dielectric. The best performances of the TFT produced were obtained when using very thin Ni layers for the crystallization. This is attributed to a lower metal contamination and to the enhancement of grain size, as a result of the lower nucleation density achieved, when using the thinnest Ni layer. Devices that exhibit effective mobility of 45.5 cm2V-1s-1 and an on/off ratio of 5.55×104 were produced using a 0.5 nm Ni layer to crystallize the active channel area.

In this paper we present the effect of thickness on the electrical and optical properties of intrinsic/nondoped zinc oxide thin films deposited at room temperature by radio frequency magnetron sputtering, able to be used as a semiconductor material on electronic devices, like for example ozone gas sensors and ultraviolet detectors. These films are polycrystalline with a c-axis preferential orientation parallel to the substrate. The films present a resistivity that varies from 5.0 × 104 Ω cm to 1.0 × 109 Ω cm with an optical visible transmittance of 85%. The sensor response exceeds more than five orders of magnitude when exposed to UV light recovering to the initial state in the presence of ozone. © 2006 Elsevier B.V. All rights reserved.

The aim of this work is to present a spectroscopic ellipsometry study focused on the annealing time effect on nickel metal induced crystallization of amorphous silicon thin films. For this purpose silicon layers with 80 and 125 nm were used on the top of which a 0.5 nm Ni thick layer was deposited. The ellipsometry simulation using a Bruggemann Effective Medium Approximation shows that films with 80 nm reach a crystalline fraction of 72% after 1 h annealing, appearing to be full crystallized after 2 h. No significant structural improvement is detected for longer annealing times. On the 125 nm samples the crystalline volume fraction after 1 h is only around 7%, requiring 5 h to get a similar crystalline fraction than the one achieved with the thinner film. This means that the time required for full crystallization will be strongly determined by the Si layer thickness. Using a new fitting approach the Ni content within the films was also determined by SE and related to the silicon film thickness. © 2006 Elsevier B.V. All rights reserved.

In this paper we present results of intrinsic/non doped zinc oxide films deposited at room temperature by rf magnetron sputtering able to be used as a truly semiconductor on electronic devices like ozone gas sensors and ultra-violet detectors. The produced films are polycrystalline with a c-axis preferential orientation parallel to the substrate. The films' resistivity varies from 4.0×10-2 Ωcm to 1.0×10-9 Ωcm, depending on the deposition conditions used (rf power density and oxygen partial pressure), which turns not affecting the optical properties (in average a transmittance of around 85 % and an optical band gap of about 3.44 eV, independent of the deposition conditions used). When exposed to UV light the sensor response based on these films may exceed more than 5 orders of magnitude, recovering to the initial state in the presence of ozone. The sensitivity of the films is improved when the oxygen partial pressure increases and the rf power density used decreases, due to changes on the structural properties of the films. © 2006 Materials Research Society.

In this work, metal induced crystallization using nickel was employed to obtain polycrystalline silicon by crystallization of amorphous films for thin film transistor applications. The devices were produced through only one lithographic process with a bottom gate configuration using a new gate dielectric consisting of a multi-layer of aluminum oxide/titanium oxide produced by atomic layer deposition. The best results were obtained for TFTs with the active layer of poly-Si crystallized for 20 h at 500 °C using a nickel layer of 0.5 nm where the effective mobility is 45.5 cm2 V-1 s-1. The threshold voltage, the on/off current ratio and the sub-threshold voltage are, respectively, 11.9 V, 5.55×104 and 2.49 V/dec. © 2005 Elsevier B.V. All rights reserved.

In this work we have focused our attention on the role of the gas mixture (O2/Ar) used during HfO2 thin film processing by r.f. magnetron sputtering, to produce dielectrics with suitable characteristics to be used as gate dielectric. Increasing the O2/Ar ratio from 0 to 0.2, the films properties (optical gap, permittivity, resistivity and compactness) are improved. At these conditions, films with a band gap around 5 eV were produced, indicating a good stoichiometry. Also the flat band voltage has a reduction of almost three times indicating also a reduction of the same order on the fixed charge density at the semiconductor-insulator interface. The dielectric constant is around 16 which is very good, since the surface of the silicon where the HfO2 films were deposited contains a SiO 2 layer of about 3 nm that gives an effective dielectric constant above 20, close to the HfO2 stoichiometric value (∼25). Further increase on the O2/Ar ratio does not produce significant improvements. © 2004 Elsevier B.V. All rights reserved.

In this work metal induced crystallization was studied using aluminium and gold deposited over 150 nm amorphous silicon films grown by LPCVD. Aluminium and gold layers with thickness between 1 and 5 nm were deposited on the silicon films and after that, the samples were annealed at 500°C from 5 up to 30 h. When the crystallization is induced through a gold layer, the Si crystalline fraction is higher than when using aluminium. For samples crystallized for 30 h at 500°C with 2 nm of metal a crystalline fraction of 57.5% was achieved using gold and only 38.7% when using aluminium. © 2005 Springer Science + Business Media, Inc.

The aim of this work is to optimize the metal/silicon ratio on nickel metal induced crystallization of silicon. For this purpose amorphous silicon layers with 80, 125 and 220 nm thick were used on the top of which 0.5 nm of Ni was deposited and annealed during the required time to full crystallize the a-Si. The data show that the 80 nm a-Si layer reaches a crystalline fraction of 95.7% (as detected by spectroscopic ellipsometry) after annealed for only 2 hours. No significant structural improvement is detected by ellipsometry neither by XRD when annealing the films for longer times. However, on 125 nm thick samples, after annealing for 2 hours the crystalline fraction is only 59.7%, reaching a similar value to the one with 80 nm only after 5 hours, with a crystalline fraction of 92.2%. Here again no significant improvements were achieved by using longer annealing times. Finally, the 220 nm thick a-Si sample is completely crystallized only after 10 hours annealing. These data clear suggest that the crystallization of thicker a-Si layers requires thicker Ni films to be effective for short annealing times. A direct dependence of the crystallization time on the metal/silicon ratio was observed and estimated. © 2005 Materials Research Society.

In this paper we present results of intrinsic/non-doped zinc oxide deposited at room temperature by radio frequency magnetron sputtering able to be used as a semiconductor material on electronic devices, like for example ozone gas sensors, ultra-violet detectors and thin film transistors. These films present a resistivity as high as 2.5×108 Ω cm with an optical transmittance of 90%. Concerning the structural properties, these films are polycrystalline presenting a uniform and very smooth surface. © 2005 Elsevier B.V. All rights reserved.

Shape memory alloys (SMA) represents a class of metallic materials that has the capability of recovering a previously defined initial shape when subject to an adequate thermomechanical treatment. The present work aims to study the influence of thermal cycles on the transition temperatures of a Ni-Ti alloy. In this system, small variations around the equiatomic composition give rise to significant transformation temperature variations ranging from 173 to 373 K. SMA usually presents the shape memory effect after an annealing treatment at ca. 973 K. The optimisation of the thermomechanical treatment will allow to "tune" the material to different transformation temperature ranges from the same starting material, just by changing the processing conditions. Differential scanning calorimeter (DSC) and in situ high-temperature X-ray diffraction (XRD) have been used to identify the transformation temperatures and the phases that are present after different thermal cycles. The results concerning a series of thermal cycles with different heating and cooling rates (from 1.67×10-2 to 1.25×10-1 K/s) and different holding temperatures (from 473 to 1033 K) are presented. © 2004 Elsevier B.V. All rights reserved.

The search for new dielectric materials to be used in metal-insulator- semiconductor (MIS) structures to replace the silicon oxide (SiO2) has been growing up. The aim is to have materials with high dielectric constants that could allow the use of thicker films and so, to reduce the role of leakage currents that happens in devices using very thin SiO2 layers or to allow the MIS devices to support high currents, besides having a retain memory effect. In this work, we present data concerning the production of hafnium oxide (HfO2) thin films by radio frequency (rf) sputtering that present suitable characteristics to be used as a gate dielectric, taking advantage of its high dielectric constant and stoichiometry reached under certain deposition conditions. Data concerning the role of the deposition parameters in the films structure and in the electrical properties of the films produced using capacitance-voltage (C-V) and current-voltage (I-V) measurements will be shown, together with data concerning the degree of films' compactness measured by spectroscopic ellipsometry (SE). © 2003 Elsevier B.V. All rights reserved.

The aim of this paper is to study the role of gold (Au) induced crystallization on amorphous silicon (a-Si) films produced by low pressure chemical vapor deposition (LPCVD) at low process temperatures (550 °C) to allow the use of glass substrates. Concerning the crystallization process Au was deposited by e-beam thermal evaporation over the silicon (Si), using different metal thickness, from 5 to 100 Å. The samples were then annealed at 450, 500 and 550 °C and the crystallization time was changed from 5 up to 30 h. The structure of the films was analyzed by X-ray diffraction (XRD) and spectroscopic ellipsometry (SE) while electrical conductivity measurements were performed to obtain the electrical properties of the films produced, namely the activation energy (EA) and how it changes with the Au thickness used. The data achieved show that the increase of the metal layer thickness decreases the time needed to get full crystallization. However this leads to lower conduction activation energy (EA) meaning that there is also an increase of Au incorporation that leads to the production of doped films. © 2004 Elsevier B.V. All rights reserved.

The aim of this paper is to study the role of different metals (aluminium, molybdenum, nickel and titanium) in inducing crystallization in films produced by LPCVD at high and low temperature processes and to compare the structural, morphological, optical and electrical properties of the various films produced. This work envisages the use of the most suitable conditions that lead to the production of films for optoelectronic applications such as solar cells. © 2003 Elsevier B.V. All rights reserved.

This paper deals with the role the substrate on the structure of undoped and n-doped polycrystalline silicon (poly-Si) films produced by Low Pressure Chemical Vapour Deposition (LPCVD). The structural and electrical properties of the films deposited on glass, glass covered with molybdenum (Mo), oxidised crystalline silicon and oxidised crystalline silicon covered with Mo were analysed using X-ray diffraction and Spectroscopic Ellipsometry, dark conductivity and Hall effect measurements. Undoped poly-Si films deposited over Mo present modifications in the crystalline structure relatively to those deposited on the other substrates. The presence of Mo changes the preferential growth orientation, enhancing the Si {111} grains orientation, leading to more compact films. The electrical measurements also confirm that the films grown on Mo substrates present better characteristics. Some differences are also observed during the initial growth stages when using glass or oxidised silicon. Very thin n-doped films present a less effective doping effect when deposited on oxidised silicon than the ones deposited on glass substrates.

Silicon nitride films were produced on glass and crystalline silicon substrates using r.f. magnetron sputtering to select the best process conditions (substrate temperature, gas pressure and r.f. power) to grow dielectrics for device applications such as low temperature thin film transistors, where special care has to be taken concerning the film's compactness and bulk defects. The films produced were analysed by different techniques such as ultra violet - visible - near infrared spectroscopy Fourier transformed infrared spectroscopy and capacitance measurements, aiming to correlate the films properties with its composition and degree of compactness. The role of the deposition pressure is notorious since films deposited at high pressures are more compact, presenting low oxygen incorporation after deposition. The increase of the substrate temperature up to 373 °K has the same effect, not changing the film's amorphous structure. These data will be discussed aiming to produce films with the required compactness and stoichiometry to grow very thin insulating layers (<10 nm) to be used in MIS structures or devices like thin film transistors.