Rodrigo Martins

Despite of a growing interest in this material, until now the studies on polymorphous silicon (pm-Si:H) have been performed on small laboratory reactors working at 13.56 MHz. Envisaging an industrial application of pm-Si:H, the technology was transferred to a large area plasma enhanced chemical vapour deposition reactor (25 × 40 cm2) working at excitation frequencies of 13.56 and 27.12 MHz. The plasma was characterized by impedance probe measurements and the films were characterized by spectroscopic ellipsometry, infrared spectroscopy and hydrogen evolution experiments, which are techniques that allow a rapid and reliable identification of pm-Si:H structure. Conductivity measurements were also performed to determine their transport properties. The results show that scaling up using the 13.56 MHz was successfully done and pm-Si:H films were deposited at a growth rate of ≈ 12 nm/min. Moreover, by using the 27.12 MHz excitation frequency the growth rate was even further increased to above 18 nm/min, as desired for industrial production. © 2002 Elsevier Science B.V. All rights reserved.

This paper describes, for the first time, a method of producing polymorphous silicon (pm-Si:H) films by plasma-enhanced (PE) CVD, using an excitation frequency of 27.12 MHz. The aim is to produce, at high growth rates, nanostructured films that are more stable than the conventional amorphous or polymorphous silicon films grown by PECVD at 13.56 MHz. The processing data show that, at 27.12 MHz, the pm-Si:H films are produced close to the transition region from amorphous to microcrystalline silicon films, at a growth rate of about 0.3 nm s-1, using pressures above 160 Pa. Apart from that, the analysis of the exodiffusion, spectroscopic ellipsometry (SE), and micro Raman data reveal that these films are more dense and compact than the polymorphous films grown at 13.56 MHz.

This paper describes, for the first time, a method of producing polymorphous silicon (pm-Si:H) films by plasma-enhanced (PE) CVD, using an excitation frequency of 27.12 MHz. The aim is to produce, at high growth rates, nanostructured films that are more stable than the conventional amorphous or polymorphous silicon films grown by PECVD at 13.56 MHz. The processing data show that, at 27.12 MHz, the pm-Si:H films are produced close to the transition region from amorphous to microcrystalline silicon films, at a growth rate of about 0.3 nms-1, using pressures above 160 Pa. Apart from that, the analysis of the exodiffusion, spectroscopic ellipsometry (SE), and micro Raman data reveal that these films are more dense and compact than the polymorphous films grown at 13.56 MHz.

This work refers to a study performed on polymorphous silicon (pm-Si:H) at excitation frequencies of 13.56 and 27.12 MHz in a large area PECVD reactor. The plasma was characterised by impedance probe measurements, aiming to identify the plasma conditions that lead to produce pm-Si:H films. The films produced were characterised by spectroscopic ellipsometry, infrared and Raman spectroscopy and hydrogen exodiffusion experiments, which are techniques that permit the structural characterisation of the pm-Si films and to study the possible differences between the films deposited at 13.56 and 27.12 MHz. Conductivity measurements were also performed to determine the transport properties of the films produced. The set of data obtained show that the 27.12 MHz pm-Si:H can be grown at higher rates with less hydrogen dilution and power density, being the resulting films denser, chemically more stable and with improved performances than the pm-Si:H films grown at 13.56 MHz.

In this work, spectroscopic ellipsometry was used to characterise oxide films produced by anodic oxidation of amorphous silicon using an ethylene glycol (0.04 M KNO3) solution. The data obtained show that the growth of the oxide is not only a function of the voltage applied, but also of the current density and of the time process. An empiric model based on a power law is proposed for the growth of the oxide using, as parameters, the voltages and the time process. The oxide produced shows porosity of approximately 12%, which can be reduced down to 6% under well-controlled growth conditions. © 2002 Elsevier Science B.V. All rights reserved.

In this paper, we present the preliminary results concerning the deposition of highly transparent and conductive gallium-doped zinc oxide (GZO) deposited on transparent flexible substrate based on cellulose derivatives. Prior to the deposition of the GZO film, the surface of the polymer have been coated with a thin silicon dioxide (SiO2) layer deposited by thermal evaporation assisted by an electron gun. By doing this surface treatment, we succeeded in depositing highly conductive and transparent GZO with an electrical resistivity of 2.0 × 10-3 Ω cm and an average optical transmittance in the visible part of the spectrum (400-700 nm) of 70% by r.f. magnetron sputtering at room temperature. Besides the optoelectronic properties, the films are mechanically stable with a polycrystalline structure with a strong preferred (002) orientation, parallel to the substrate. © 2003 Elsevier B.V. All rights reserved.

Thick films of cordierite-based glass ceramics were prepared by aqueous tape casting from suspensions containing 80-wt% solids. The weight proportions of cordierite/glass ranged from 70/30 to 30/70 in order to investigate the effect of glass content on the rheological behaviour and on the microstructures and properties of the green tapes. Suspensions with 50 to 60-wt% glass content exhibited the lowest viscosity values among all the slurries investigated, while the green tape containing 30-wt% glass presented homogenous microstructures at both top and bottom surfaces, contrarily to the observations for the other compositions. The green densities increased with glass content. The sintered tapes (1150°C, 2h) containing 50 to 60-wt% glass exhibited the lowest values for the dielectric constant (∼5.2) and dielectric loss (∼0.002) at 1MHz.

This work reports a technique to obtain electronic grade intrinsic amorphous silicon using the plasma enhanced chemical vapour deposition technique at 13.56 MHz. The batch processing method consists of igniting the plasma process through a neutral gas such as hydrogen or helium and only feeding the carrier gas containing the species to be decomposed into the reactor when the plasma is stabilized. By doing so, no surface damage is induced in the first deposited layers and so a more compacted and stable film is produced, compared to amorphous films grown by conventional methods. The best deposition conditions to produce films with good transport properties for optoelectronic applications are: temperature ≈ 473 K, 60 < pressure 87 Pa, power density of 32 mW/cm2 and flow of silane ≈ 10 sccm. The growth rate and the microstructure factor are 1.5 Å/s and 3.3×10-2, respectively, while the activation energy ≈ 0.8 eV; dark conductivity at room temperature ≈ 4.37×10-10 (ωcm)-1; photosensiti-vity ≈ 5.02×l06; density of states ≈ 6.6×1015 cm-3; bonded hydrogen concentration ≈ 20 at% and optical band gap ≈ 1.75 eV.

Polymorphous silicon (pm-Si:H) films have been prepared by a new regime of plasma enhanced chemical vapour deposition in the region adjacent of phase transition from amorphous to microcrystalline state. Comparing to the conventional amorphous silicon (a-Si:H), the pm-Si:H has higher photoconductivity (σph), better stability, and a broader light spectral response range in the longer wavelength range. It can be found from Raman spectra that there is a notable improvement in the medium range order. There are a blue shift for the stretching mode of IR. spectra and a red shift for the wagging mode. The shifts are attributed to the variation of the microstructure. By using pm-Si:H film as intrinsic layer, a p-i-n junction solar cell was prepared with the initial efficiency of 8.51% and a stabilized efficiency of 8.01% (AM1.5, 100mw/cm2) at room temperature (T R).

A series of hydrogenated amorphous silicon carbide films were prepared by plasma enhanced chemical vapor deposition (PECVD) using a gas mixture of silane, methane, and hydrogen as the reactive source and an excitation frequency of 27.12 MHz. Compared to the typical radio frequency deposition technique, the very high plasma excitation frequency increases the density of the electrons and decreases the electron temperature, which helps the dissociation of the SiH4 and CH4, and reduces the energetic ion impact on the growth surface of the thin film. Thus, dense-films with lower bulk density of states and higher growth rate are expected, as confirmed by spectroscopic ellipsometry data. Apart from that, a substantial reduction of bulk defects is achieved, allowing an improvement of the valence controllability (widening of the optical gap from about 1.9 to 3.6 eV). In this work results concerning the microstuctural and photoelectronic properties of the silicon carbide films will be discussed in detail, correlating them with the deposition process conditions used as well as with the gas phase composition of the mixtures used. © 2004 Elsevier B.V. All rights reserved.

The aim of this paper is to compare the density of bulk states (DOS) of polymorphous silicon (pm-Si:H) films produced by plasma enhanced chemical vapor deposition at 13.56 and 27.12 MHz using the constant photocurrent method and the space charge limited current (SCLC) technique. The data achieved revealed that the set of films produced present similar DOS. Apart from that, data concerning the correlation of the deposition conditions that lead to the production of pm-Si:H as well as their characteristics, such as the hydrogen content and how hydrogen is bonded, will be discussed, giving special emphasis to the set of mechanical stresses developed. By doing so we could get a better understanding of the nature of hydrogen bonding in pm-Si:H films as well as to determine the role of the excitation frequency on the film's performances, where films with amounts of hydrogen around 20 at.% can have DOS as low as 8 × 10 14 cm-3 with Urbach energies in the range of 41-50 meV. © 2004 Elsevier B.V. All rights reserved.

This paper presents data concerning the composition structure and optical characteristics of polymorphous silicon films produced by plasma enhanced chemical vapour deposition at 27.12 MHz and determined respectively by infrared spectrometry, micro Raman, exodiffusion and spectroscopic ellipsometry measurements. When compared to the pm-Si:H films produced at 13.56 MHz, the films produced at 27.12 MHz present hydrogen contents in the range of 21 at%, the sharp peak ascribed to the exodifusion measurements is shifted towards high temperatures and the imaginary part of the dielectric function 〈ε2〉 is larger and shifted to high energies. Apart from that the peaks of the infrared spectra ascribed to the stretching modes shift towards high wave numbers and the half width of the micro Raman peaks shrinks, meaning that the films produced at 27.12 MHz are more compact and dense.

This paper presents results of the spatial and frequency detection limits of an integrated array of 32 one-dimensional amorphous silicon thin film position sensitive detectors with a nip structure, under continuous and pulsed laser operation conditions. The data obtained show that 0.45×0.06 cm arrays, occupying a total active area of about 1 cm2 have a spatial resolution better than 10 μm (modulation transfer function of about 0.2), with a cut-off frequency of about 6.8 KHz. Besides that, under pulsed laser conditions the device non-linearity has its minimum (about 1.6%), for a frequency of about 200Hz. Up to the limits of the cut-off frequency, the device non-linearity increases to values above 4%.

A series of silicon film samples were prepared by plasma enhanced chemical vapor deposition (PECVD) near the threshold from amorphous to nanocrystalline state by adjusting the plasma parameters and properly increasing the reactions between the hydrogen plasma and the growing surface. The microstucture of the films was studied by micro-Raman and Fourier transform infrared (FTIR) spectroscopy. The influences of the hydrogen dilution ratio of silane (R H = [H2]/[SiH4]) and the substrate temperature (Ts) on the microstructural and photoelectronic properties of silicon films were investigated in detail. With the increase of RH from 10 to 100, a notable improvement in the medium-range order (MRO) of the films was observed, and then the phase transition from amorphous to nanocrystalline phase occurred, which lead to the formation of diatomic hydrogen complex, H 2 * and their congeries. With the increase of T s from 150 to 275 °C, both the short-range order and the medium range order of the silicon films are obviously improved. The photoconductivity spectra and the light induced changes of the films show that the diphasic nc-Si/a-Si:H films with fine medium-range order present a broader light spectral response range in the longer wavelength and a lower degradation upon illumination than conventional a-Si:H films. © 2004 Elsevier B.V. All rights reserved.

The working principle of silicon p-i-n structures with low conductivity (σd) doped layers as single element image sensors is based on the modulation, by the local illumination conditions of the photocurrent generated by a light beam scanning the active area of the device. A higher sensitivity is achieved using a wide band gap a-Si:C alloy in the doped layers, improving the light penetration into the intrinsic semiconductor and reducing the lateral currents in the structure, which are responsible by an image smearing effect observed in sensors with high σd doped layers. This work focuses on the transient response of such sensor and on the role of the carbon (C) content of the doped layers. A set of devices with different percentage of C incorporation in the doped layers is analyzed by measuring the scanner-induced photocurrent under different bias conditions, (ranging from -1.5V to 1V) in order to evaluate the response time.

This work presents a study on the effect of an interfacial silicon oxide layer placed between Au and a-Si:H MIS (metal-insulator-semiconductor) photodiodes in their performances, by stopping the Au diffusion towards the a-Si:H. The results show that the Au diffuses very easily to the oxide free a-Si:H surface, even at room temperature, degrading the photodiode performance. On the other hand, the MIS photodiodes with the interfacial oxide show an improvement of their characteristics after annealing, function of its thickness, and degree of film's compactness. This effect is associated with the presence of oxide of thicknesses ≥5 Å at the Au/a-Si:H interface that prevents the Au diffusion and improves the photodiode characteristics, which does not happen when the interfacial oxide is absent. © 2004 Elsevier B.V. All rights reserved.

This work presents a study performed on several Au contacts deposited by evaporation on oxide free and oxidised (5-20Å of oxide) a-Si:H surfaces. The characterisation of the films was performed on as deposited, aged and annealed at 150°C structures. SIMS and RBS measurements show that the Au diffuses very easily on oxide free a-Si:H surfaces, even at room temperature, resulting in the formation of an oxide at the device surface that acquires a blue colour instead of the gold colour of the contacts. This was also visible in the SEM pictures of the cross section of the structures produced and on the changes of the surface morphology observed by AFM measurements. On the other hand, when the Au is deposited on oxidised a-Si:H surfaces, the results show that the oxide prevents the Au from diffusing and the nature of the contact is preserved. That is, better rectifying and stability performances are obtained in MIS like structures than in Schottky structures.

This work presents a study performed on the deposition of pm-Si:H by plasma enhanced chemical vapor deposition using excitation frequencies of 13.56 and 27.12 MHz, where the interest of increasing the excitation frequency relies on higher plasma dissociation and reduced energy of ion bombardment, thus allowing the deposition of superior grade material at higher growth rates. The plasma impedance, which allows the monitoring of particle formation in the plasma, was correlated to the film properties, characterized by spectroscopic ellipsometry and hydrogen exodiffusion experiments. The set of data obtained show that by using the 27.12-MHz excitation frequency the hydrogen dilution and the r.f. power density needed to produce pm-Si:H can be reduced. Growth rates above 3.1 Å/s were obtained, the films being more dense and chemically more stable than those obtained with the standard 13.56 MHz. © 2003 Elsevier B.V. All rights reserved.

In this work metal-insulator-semiconductor (MIS) photodiodes with a structure: Cr/a-Si:H(n+)/a-Si:H(i)/oxide/Au were studied, where the main objective was to determine the influence of the oxide layer on the performance of the devices. The results achieved show that their performance is a function of both oxide thickness and oxide density. The a-Si:H oxidation method used was the immersion in H2O2 solution. By knowledge of the oxide growth process it was possible to fabricate photodiodes exhibiting an open circuit voltage of 0.65V and short circuit current density under AM1.5 illumination of 11mA/cm2, with a response times less than 1μs for load resistance <400Ω, and a signal to noise ratio of 1×107. © 2003 Elsevier B.V. All rights reserved.

In this work we present results of a study performed on metal-insulator-semiconductor (MIS) diodes with the following structure: substrate (glass)/Cr (2000 Å)/a-Si:H n+(400 Å)/a-Si:H i (5500 Å)/oxide (0-40 Å)/Au (100 Å) 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 (1×10 7 at -1 V) than the diodes with oxides obtained by the evaporation of SiO2, or by the chemical deposition of SiO2 by plasma of hexamethyldisiloxane. However, in the case of deposited oxides, the breakdown voltage is higher, 30 V 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 ±1 V, but is relevant when high breakdown voltages are required. © 2003 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.

In this paper we present the effect of the insertion of a non-doped nanocrystalline zinc oxide/buffer layer on the electrical, optical and structural properties of indium tin oxide produced at room temperature by radio frequency plasma enhanced reactive thermal evaporation on polymeric substrates. The electrical resistivity of the ITO films is reduced by more than two orders of magnitude (4.5×10-1 to 2.9×10-3 Ωcm). From the Hall effect measurements it is observed that the large decrease associated to the electrical resistivity, is due to the increase associated to the Hall mobility. Concerning the optical properties no effect was observed, being the transmittance in the visible and near the infra red region always higher than 80%.

In this work, we show the possibility to use undoped porous silicon (PS) thin films produced by hot wire chemical vapour deposition technique (HW-CVD) as ethanol detector. Silicon thins films produced by HW-CVD technique, under certain deposition conditions, have a porous structure [Vacuum 52 (1999) 147]. Therefore, in the presence of an alcohol, the OH group is adsorbed by the uncompensated bonds behaving as donor-like carriers leading to an increase in the current flowing through the material. This current enhancement is bias dependent in glass/ITO/i-a-Si:H/Al sensor and increases as the ethanol vapour pressure increases from 10-1mbar to atmospheric pressure. The response time of the current of the sensor and its recovery time are in the range of 10-50s at room temperature. Ethanol quantities above 50ppm can be detected. © Published by Elsevier B.V.

The need to improve the efficiency of the European university system is discussed. It is considered possible to increase university funding by letting students pay for their education. It is suggested that European universities raise more money for research from private sources by selling services. It is found appropriate to strive for excellence at the level of specific departments or schools to begin with.

This work describes the fabrication and characterization of an improved version of large area (5mm×80mm with an active length of 70mm) flexible position sensitive detectors deposited onto polymeric substrates (polyimide-Kapton® VN). The new configuration presented by the sensor is based on a heterostructure of a-Si:H/ZnO:Al. The sensors were characterized by spectral response, photocurrent dependence as a function of light intensity and position detection measurements. The set of data obtained on one-dimensional position sensitive detectors based on the heterostructure show excellent performances with a maximum spectral response of 0.12A/W at 500nm and a non-linearity of ±10% over 70mm length. The produced sensors present a non-linearity higher than those ones produced on glass substrates, due to the different thermal coefficients exhibited by the polymer and the amorphous silicon film. In order to prove this behaviour, it was measured the defect density obtained by the constant photocurrent method on amorphous silicon deposited on polymeric substrates bended with different radius of curvature. © 2004 Elsevier B.V. All rights reserved.