Rodrigo Martins

It is shown that the electronic properties of amorphous germanium (a-Ge) prepared by the glow-discharge decomposition of germane can be controlled systematically by substitutional phosphorus doping from the gas phase. Specimens with different doping levels have' been investigated by conductivity, thermoelectric power and Hall effect measurements in a temperature range between 160 and 450 K. The dependence of conductivity on doping level is qualitatively similar to that in a-Si, but the range of control is limited in a-Ge by the smaller mobility gap. Also the larger overall density of gap states in this material reduces the doping sensitivity. The above transport measurements and their temperature dependence can be interpreted in a quantitatively consistent manner- by a two-path model in which conduction takes place in the extended states and in another path through the localized states. As 111 a-Si, the photoconductivity of glow-discharge Ge can be appreciably sensitized by phosphorus doping. The μτ product deduced from such experiments on a-Ge and a-Si are compared for different preparation techniques. The data show that irrespective of the presence of hydrogen the method of deposition remains an important factor in determining the density of gap states. © 1979 Taylor & Francis Ltd.

The aim of the present work was to study the optical properties of amorphous hydrogenated silicon films produced by capacitive and inductive r.f. glow discharge in a 3%SiH4-Ar gas mixture. The effect of the application of static electric and magnetic fields during the film formation on the photoconductivity, photoactivation energy, recombination mechanisms and optical gap was thoroughly investigated. Films prepared in a capacitively or inductively coupled discharge show bias-dependent photoconductivities, which reach about 10-4 Ω-1 cm-1 for an inductive discharge with a negative bias and about 10-5 Ω-1 cm-1 for a capacitive discharge with a positive bias. The optical gap is of the order of 1.55 eV for capacitive films and is bias dependent for inductive films (1.45-1.85 eV). A superimposed magnetic field (of about 1 kG) increases the photoconductivity by one order of magnitude for both deposition methods. The optical gap is field dependent for inductive films (1.6-1.8 eV) and is about 1.6 eV for capacitive films. The main recombination mechanism at a moderate photon flux (less than 1014 cm-2 s-1) is monomolecular for all deposition conditions. The photoactivation energy lies between 0.1 and 0.2 eV for capacitive films and is about 0.1 eV for inductive films. It was also found that, by using suitable crossed electric and magnetic fields, it was possible to control the density and nature of the defect states in the films. These are correlated with the type of hydrogenated silicon species and with the amount of hydrogen incorporated into the films, which markedly influence the film properties. © 1982.

Doped and undoped a-Si:H and a-SiC:H films were deposited by R. F. decomposition of silane and silane/methane mixtures respectively, in a two consecutive (decomposition and deposition) chambers glow discharge capacitively coupled system. Their electro-optical properties were extensively investigated through dark conductivity, photoconductivity, spectral response, optical absorption, R. F. transmission spectra, electron spin ressonance and CxV MOS measurements.

The influence of U.V. light on the transport properties of a-Si : H films during its growth in a r.f. double chamber system was investigated by conductivity, optical absorption, I.R. absorption, spectral photoconductivity and X-ray diffraction measurements. It was concluded that the presence of U.V. light during the deposition process controls the way how hydrogen is incorporated in the structure as well as the impurity atoms. The microcrystalline films investigated present sharp peaks in the I.R. spectra. Both boron and phosphorus doped films show conductivities higher than 10 S cm-1 and estimated crystalline sizes of the order of 80 Å. © 1987.

Experimental results on structure defects in microcrystalline (μc) n- and p-doped μc-S1-x:Cx:H films deposited on alkali-free glass substrates by spatial plasma separation1 and obtained by electron paramagnetic resonance (EPR) are presented. The technique used for subtracting the substrate effect on recorded spectra is also discussed as well as its quantification. The microscopic structure of intrinsic defects and impurity states and their role in transport mechanisms are studied and correlated with the composition of their films. These results are also related to transport properties of deposited films in order to observe the role of dopant centres, located at conduction band tails, in controlling the electrical properties. © 1989.

Microcrystalline phosphorus-doped hydrogenated silicon alloy films were deposited in a remote plasma CVD (chemical vapor deposition) system. The film properties were studied as a function of RF power density and hydrogen concentration in the reaction gas mixture. The properties of the deposited films are extremely sensitive to the RF power density in the studied range of 250 mW/cm2 to 625 mW/cm2. Very low values of electrical resistivity were obtained. For an RF power density of 500 mW/cm2, ρ = 3 × 10-2 Ω-cm, while ρ = 1.9 × 103 Ω-cm for 625 mW/cm2, indicating the predominance of the amorphous tissue over the microcrystalline phase. High doping efficiencies which can be correlated to large grain size are indicated by the very low values of the activation energy as low as 30 meV for 500 mW/cm2, that were obtained.

One of the main problems in producing large area amorphous silicon devices concerns films uniformity. In this paper we present data concerning the role of reactor geometry and design and on the film performances as well as the problems related to mechanical mismatches in scaling up the reactor size. © 1991 Elsevier Science Publishers B.V. All rights reserved.

In this paper we report results concerning the effect of the TCO interface on hydrogenated amorphous silicon (a-Si:H) p-i-n homojunction solar cells. Its correlation with dark current density-voltage (J-V) characteristics and spectral response, before and after while light-soaking degradation, is analysed. From this study, we conclude that the properties and stability of these devices are not only influenced by the a-Si:H film properties, but also by the properties of the transparent conductive electrode and its interface with the a-Si:H layer.

This paper deals with the engineering aspects related to the rf energy coupling in Plasma Enhanced Chemical Vapour Deposition (PECVD) processes, in a diode-type unit in which an extra grid is used. The main emphasis is given in the determination of the real power delivered to the gas and comparing it with the total power losses, besides determining the best way to control the powder formed during the process. © 1994.

The influence of different TCOs (SnO2 and ITO) on the photoelectrical properties of 1-D position sensitive detectors based on p-i-n structures was studied. A strong cross-contamination in the p-layer and contamination in the i-layer reduce the quality of the device. Numerical analysis of TCO/p-i-n structure also revealed a strong increase in defect states at the p-layer surface which can be attributed to the reduction of TCO. ITO seems to be less appropriate for a front TCO, although the spectral response of the p-i-n structure under reverse bias is not significantly affected by the conditions at the TCO/p heterojunction.

In this work we present the results of a study concerning the role of the properties of zinc oxide thin films deposited by spray pyrolysis on its sensitivity to methane or ethane. It was found that using highly resistive thin layers leads to an increase in the film sensitivity. The variation of the operating temperature of the film leads to a significant change in the sensitivity of the sensor and the ideal operating temperature dependence of the gas used. The sensitivity of the ZnO thin films changes linear with the increase of the gas concentration. However these films seem to be more appropriated for the detection of methane than for ethane since the value of sensitivity obtained are higher and its variation with the gas concentration more pronounced. After the annealing treatment performed the films sensitivity decreases.

The influence of doping on the properties of zinc oxide thin films deposited by spray pyrolysis has been studied. The results show that the doping affects the properties of the films, mainly the electrical ones, function of its concentration and nature. The most significative improvement were observed for films doped with 1 at.% of indium exhibiting a resistivity of 1.9 × 10-1 Ω m associated to a transmittance of 86%, characteristics required for applications on the optoelectronic devices. © 2001 Elsevier Science Ltd. All rights reserved.

In this work we studied the influence of the dopant elements and concentration on the properties of ZnO thin film deposited by spray pyrolysis. The results show that the doping affects the thin films properties mainly the electrical ones, function of dopant concentration and nature. The most important changes were observed for films doped with 1at% of indium which exhibit a resistivity of 1.9 × 10-1 Ωcm associated with a transmitance of 90%. After the annealing treatment, the resistivity of the film decreases to 5.9 × 10-3 Ωcm without significative changes in the optical properties. The films were also used to produce amorphous silicon solar cells where the best results were obtained for ZnO:In. © 2002 Elsevier Science Ltd. All rights reserved.

Where a-Si:H pin devices are concerned, one of the main obstacles regarding improved performance is device stability, usually attributed to adverse behaviour at various interfaces within the device. Several attempts have been made to overcome this problem, such as the use of blocking layers at the interfaces. Although these have led to some improvements in device performance, most of the problems associated with device stability remain. This is mainly due to the defects at the interfaces, since the blocking layers (silicon alloys with carbon, nitrogen or oxygen) usually have a high density of bulk states, in comparison to intrinsic a-Si:H films. In this paper, we present a method that seems to be capable of improving device stability. It consists of performing a controlled removal of oxide interlayers at the interfaces, by an appropriate etching process. This enables the production of highly smoothed interfaces, and reduces possible cross-contamination of the i-layer from the adjacent doped layers. This amounts to a new design of typical pin devices, in which thin absorber layers are placed at the p/i and i/n interfaces. Their purpose is to trap most of the impurity atoms diffused from the doped layers, after which they are removed by appropriate etching. The fabrication of the absorbers (sacrificial layers), the nature of the etching and the tailoring of the defect profile at the interfaces will be discussed, including the performance exhibited by the resulting devices. © 2002 Elsevier Science B.V. All rights reserved.

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.

It is experimentally known that the linearity and sensitivity of the position sensitive detectors (PSD) are dependent on the resistance of the collecting layer and of the load resistance, mainly if the detection is based on the measurement of the photo-lateral voltage. To determine the value of the load resistance to be used in metal - insulator - semiconductor (MIS) PSDs structures that lead to the maximum value of sensitivity and linearity, we propose an electrical model through which it is able to simulate the proper sensor response and how the load resistance influence the results obtained. This model is valid for PSDs where the resistance of the collecting resistive layer is quite low (≤ 500 Ω), leading to a low output impedance. Under these conditions we conclude that the value of the load resistance should be of about 1 kΩ in order to achieve a good compromise between the linearity and the sensitivity of the PSD. This result is in agreement with the set of experiments performed. © 2005 Materials Research Society.

In this work, the relation between oxidant/monomer ratio and the electrical conductivity of polypyrrole was studied using different ratios. We achieved a maximum value for electrical conductivity of 7.5 S/cm for a ratio of 2:1. We also developed a chemical dip-coating process to produce the cathode layer in tantalum capacitors. We obtained capacitances of about 80 μF after 8 cycles using the sequence Monomer/Oxidant.