Rodrigo Martins

A glass was made using bottom ash produced by a Portuguese municipal solid waste (MSW) incinerator. The bottom ash was the single batch material used in the formation of the glass, which was obtained through a conventional melt-quenching method. The glass was then converted to glass-ceramic for further recycling to construction materials. After submitting the glass samples to several heat treatments, between 820 and 1050°C and during different times, it was verified that the optimum heat treatment schedule for the ceramization of the glass was at 1000°C for 10h, as confirmed by microstructural observation and by X-ray diffraction. The major crystalline phases precipitated in the glass-ceramic were wollastonite (CaSiO3) and diopside (Ca(Mg,Al)(Si,Al)2O6). Microstructural analysis of the glass-ceramic revealed that the crystalline phases were present as dendrites and fiber-like structures that were homogeneously distributed in the material. The glassceramic showed good mechanical properties with a hardness of 5.6 MPa and a bending strength of 101 MPa. This material had a density of 2.8 gcm-3 and a thermal expansion coefficient of 9.10-6°C-1. The glass and the glass-ceramic showed an excellent chemical stability against leaching in acidic solution and in alkaline solution. In summary, both the glass and the glass-ceramic have good chemical and mechanical properties and can, therefore, be applied as construction materials.

This work presents a comparative study between MIS photodiodes produced using high quality amorphous silicon (a-Si:H), deposited by PECVD at 2Å/s, using 13.56 MHz frequency and polymorphous silicon (pm-Si) deposited at 3Å/s using a 27.12 MHz frequency. The results show that the pm-Si:H outperforms the a-Si:H MIS photodiodes by having a rectification ratio of 107, and photosensitivity at AM1.5 conditions of 107, under 1V reverse bias. Apart from that, the pm-Si:H photodiode presents a higher open circuit voltage and better fill factor than a-Si:H MIS photodiode. These results prove that quality devices can be produced at high growth rates by using pm-Si:H. In this work the photodiode performances were correlated to the films properties, aiming to determine the characteristics responsible for the performances exhibited by the pm-Si:H devices.

Gallium-doped zinc oxide (GZO) thin films have been deposited onto polyethylene naphthalate (PEN) substrates by r.f. magnetron sputtering at room temperature. The influence of the film thickness (from 70 to 890 nm) on the electrical, structural and morphological properties are presented. The lowest resistivity obtained was 5 × 10-4 Ω cm with a Hall mobility of 13.7 cm2/Vs and a carrier concentration of 8.6 × 1020 cm-3. These values were obtained by passivating the surface of the polymer with a thin silicon dioxide, so preventing the moisture and oxygen permeation inside the film. © 2003 Elsevier B.V. All rights reserved.

We report high performance ZnO thin film transistor (ZnO-TFT) fabricated by rf magnetron sputtering at room temperature with a bottom gate configuration. The ZnO-TFT operates in the enhancement mode with a threshold voltage of 19 V, a field effect mobility of 28 cm2/Vs, a gate voltage swing of 1.39 V/decade and an on/off ratio of 3×105. The ZnO-TFT present an average optical transmission (including the glass substrate) of 80% in the visible part of the spectrum. The combination of transparency, high field-effect mobility and room temperature processing makes the ZnO-TFT a very promising low cost optoelectronic device for the next generation of invisible and flexible electronics.

This work presents preliminary results in the study of a novel structure for a laser scanned photodiode (LSP) type of image sensor. In order to increase the signal output, a stacked p-i-n-p-i-n structure with an intermediate light-blocking layer is used. The image and the scanning beam are incident through opposite sides of the sensor and their absorption is kept in separate junctions by an intermediate light-blocking layer. As in the usual LSP structure the scanning beam-induced photocurrent is dependent on the local illumination conditions of the image. The main difference between the two structures arises from the fact that in this new structure the image and the scanner have different optical paths leading to an increase in the photocurrent when the scanning beam is incident on a region illuminated on the image side of the sensor, while a decreasing in the photocurrent was observed in the single junction LSP. The results show that the structure can be successfully used as an image sensor even though some optimization is needed to enhance the performance of the device. © 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.

Electrochromic coatings are used in a wide range of technical fields. This paper refers to the properties of amorphous Indium-tin-oxide (ITO) and WO 3 thin films obtained by dc-magnetron reactive sputtering in different oxygen partial pressures (PO2) at room temperature (RT). SEM, XRD and UV-Vis-NIR spectroscopy characterized the films prepared in terms of morphology, structure, and optical and electrical properties. The maximum of the optical transmittance in the visible range for the ITO and WO3 films was above 97% and 98%, respectively. These films were incorporated into ECDs (electrochromic devices) whose performance was assessed by optical methods.

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 work reports the use of undoped porous amorphous/nanocrystalline hydrogenated silicon (a/nc-Si:H) thin films produced by hot wire chemical vapour deposition (HW-CVD) as ethanol detector above 50ppm and as a primary fuel cell where a power of 4μW/cm2 was obtained in structures of the type glass/ITO/i-a-nc-Si:H/Al. The porous silicon looks like a sponge constituted by grains and cluster of grains that determines the type of surface morphology and the behaviour of the structure under the presence of vapour moisture. Apart from that, the detector/device performances will also depend on the type of interlayer and interfaces with the metal contacts. The sponge like structure adsorbs the OH groups in uncompensated bonds, which behave as donor-like carriers, leading to an increase in the current flowing through the material, directly dependent on the ethanol vapour pressure. The corresponding role of the components of the microstructure on this detector was investigated by spectroscopic impedance. The response time of the current of the sensor and its recovery time are in the range of 10-50s at room temperature. © 2004 Elsevier B.V. All rights reserved.

In this paper, we investigate the optoelectronic properties and the photodegradation of amorphous silicon films produced by the hot wire plasma assisted technique (HWPA-CVD). We observed that hydrogen dilution in the gas phase plays an important role in the time dependence of the photoconductivity, which is correlated with an enhancement of defect density. We also compare the degradation of these films with those produced by plasma enhanced and by hot wire chemical vapour deposition techniques (PECVD and HW-CVD) and we found lower time dependence for the photodegradation of the films produced by HWPA-CVD technique © 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.

In this work we present results of structural composition and morphological characteristics of polymorphous silicon (pm-Si:H) films deposited by PECVD at 13.56 and 27.12 MHz. In addition, the role of the excitation frequency on the growth rate will be also analyzed. The results show that by using the 27.12 MHz excitation frequency the hydrogen dilution in the plasma needed to produce pm-Si:H can be reduced by more than 50% as well as the rf power density, leading to an increase on the growth rate to values higher than 3 Å/s. Spectroscopic ellipsometry and Raman spectroscopy show that the 27.12 MHz pm-Si:H films are more ordered than the pm-Si:H films produced at 13.56 MHz, while the infrared spectroscopy show that the SiH2 concentration in the films is strongly reduced. AFM measurements reveal that the films produced at 27.12 MHz films are more structured, presenting also higher roughness. © 2004 Elsevier B.V. All rights reserved.

The aim of this work is to present a process able to allow a fast method to clean plasma enhanced chemical vapour deposition (PECVD) systems used to produce amorphous silicon films and their alloys, and a proper device patterning when required. In this work we propose to study CF4/O2 or SF6 as etchant gases at room temperature to perform cleaning and films patterning. The aim is to select the process that leads to a faster cleaning process without formation of residual contaminants or to anisotropic patterning of very thin layers. The influence of some plasma parameters, such as pressure (p), power (P) and flow (f) for the etchant gases used will be also analysed.

In this work we report the study of spectral response on large area amorphous silicon solar cells (30×40 cm2), deposited through plasma enhanced chemical vapour deposition technique (PECVD) at excitation frequencies of 27.12MHz. To perform this work, the solar cells were split in units of area of 0.126 cm2, which allows determining the device homogeneity over all the entire solar cell. Emphasis of this work is put the role of thickness and optical band gap of p-doped layer on the collection efficiency, spectral response, current density-voltage curves under standard condition and spectroscopy impedance. The results show that high transparent p-doped layer can be deposited at 42mW/cm2, which allows increasing the collection efficiency in 45%, at the blue region. The spectroscopy impedance performed showed to be efficient in analyzing the device shunt resistance, interfaces role on the device performances and the behaviour of the device depletion region, for the range of frequencies analysed.

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.

The fabrication of high field-effect mobility ZnO thin film transistor (ZnO-TFT) at room temperature by rf magnetron sputtering was discussed. The ZnO used was deposited onto borosilicate glass substrate with a thickness of 1 mm with 100 x 100 mm surface area, coated with a 200 nm sputtered ITO film. The hall mobilities of about 2 cm2 / V s and a carrier concentration of 3 x 1016cm-3 were measured for the films with lower resistivity. It was observed that the ZnO-TFT presented an average optical transmission of 80% in the visibility part of the spectrum.

A study of intrinsic zinc oxide thin film as ozone sensor based on the ultraviolet (UV) photoreduction and subsequent ozone re oxidation of zinc oxide as a fully reversible process was presented. It was found that the film described were produced by spray pyrolysis, dc and rf magnetron sputtering. The dc resistivity of the films changed more than eight orders of magnitude when exposed to an UV dose of 4 mW/cm2. Analysis shows that the porous and textured zinc oxide films produced by spray pyrolysis at low substrate exhibit an excellent ac impedance response.

Ga-doped polycrystalline zinc oxide (GZO) thin films have been deposited at high growth rates by rf magnetron sputtering. The dependence of electrical, optical and morphological properties on the rf power density were investigated. The lowest resistivity of 1.9×10-4 Ωcm was obtained for a rf power density of 9 W/cm2 and an argon sputtering pressure of 0.15 Pa at room temperature. The films are polycrystalline with a hexagonal structure and a strong crystallographic c-axis orientation (002) perpendicular to the substrate surface. The films present an overall transmittance in the visible spectra of about 85%. The low resistivity, accomplished with a high growth rate deposited at room temperature, enables the deposition of these films onto polymeric substrates for flexible optoelectronic devices and displays.

Gallium-doped zinc oxide films were prepared by rf magnetron sputtering at room temperature as a function of the substrate-target distance. The best results were obtained for a distance of 10 cm, where a resistivity as low as 2.7×10-4 Ωcm, a Hall mobility of 18 cm2/Vs and a carrier concentration of 1.3×1021 cm-3 were achieved. The films are polycrystalline presenting a strong crystallographic c-axis orientation (002) perpendicular to the substrate. The films present an overall transmittance in the visible part of the spectra of about 85 %, in average. The low resistivity, accomplished with a high growth rate deposited at RT, enables the deposition of these films onto polymeric substrates for flexible applications.

Amorphous undoped a-Si:H films have been produced by hot wire plasma assisted chemical vapour deposition (HWPA-CVD), which combines the hot wire chemical vapour deposition (HW-CVD) and plasma enhanced chemical vapour deposition techniques. In this work we analyse the dissociation mechanism of the gas during the film growth in both processes with a quadrupole mass spectrometer. Besides that, the energy delivered to the gas dissociation is determined and correlated with the films properties. Thus, based on the results of the dissociated species for each deposition condition and process, we explain why the growth rate is enhanced when the filament temperature rises in HW-CVD process and why it decreases as r.f. power is enhanced in HWPA-CVD process. © 2002 Elsevier Science B.V. All rights reserved.

In this work we present results of a study performed on MIS diodes with the following structure: substrate (glass) / Cr (2000Å) / a-Si:H n + (400Å) / a-Si:H i (5500Å) / oxide (0-40Å) / Au (100Å) to determine the influence of the oxide passivation layer grown by different techniques on the electrical performance of MIS devices. The results achieved show that the diodes with oxides grown using hydrogen peroxide present higher rectification factor (2×106) and signal to noise (S/N) ratio (1×107 at -1V) than the diodes with oxides obtained by the evaporation of SiO2, or by the chemical deposition of SiO 2 by plasma of HMDSO (hexamethyldisiloxane), but in the case of deposited oxides, the breakdown voltage is higher, 30V instead of 3-10 V for grown oxides. The ideal oxide thickness, determined by spectroscopic ellipsometry, is dependent on the method used to grow the oxide layer and is in the range between 6 and 20 Å. The reason for this variation is related to the degree of compactation of the oxide produced, which is not relevant for applications of the diodes in the range of ± 1V, but is relevant when high breakdown voltages are required.

Doped a/μc-Si:H films were produced in different starting deposition conditions by the hot wire chemical vapor deposition technique. In this paper, we show that by changing the initial onset deposition conditions of the process and maintaining the overall pressure, hydrogen dilution and filament temperature, it is possible to control the compactness of the films. As the films nucleation is the key parameter to produce compact films, we show that starting the process with hydrogen and progressively introducing the process gas enhances the compactness and improve the electrical properties of the films produced. © 2002 Elsevier Science B.V. All rights reserved.

Highly transparent and conductive ZnO:Ga thin films were produced by rf magnetron sputtering at room temperature on polyethylene naphthalate substrates. The films present a good electrical and optical stability, surface uniformity and a very good adhesion to the polymeric substrates. The lowest resistivity obtained was 5×10-4 Ωcm with a sheet resistance of 15 Ω/sqr and an average optical transmittance in the visible part of the spectra of 80%. It was also shown that by passivating the polymeric surface with a thin SiO2 layer, the electrical and structural properties of the films are improved nearly by a factor of 2.

In this paper, we present results concerning the thickness dependence (from 70 to 890 nm) of electrical, structural, morphological and optical properties presented by gallium-doped zinc oxide (GZO) deposited on polyethylene naphthalate (PEN) substrates by r.f. magnetron sputtering at room temperature. For thicknesses higher than 300 nm an independent correlation between the electrical, morphological, structural and optical properties are observed. The lowest resistivity obtained was 5 × 10-4 Ω cm with a sheet resistance of 15 Ω/□ and an average optical transmittance in the visible part of the spectra of 80%. It is also shown that by passivating the surface of the polymer by depositing a thin silicon dioxide layer the electrical and structural properties of the films are improved nearly by a factor of two. © 2003 Elsevier B.V. All rights reserved.