Rodrigo Martins

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.

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.

Position sensitive detectors (PSD) using hydrogenated amorphous silicon as the active layer have been widely proposed either with the p-i-n or the Schottky structure. In this case, the devices are tailored to respond to light in the range 620-650 nm. Little is known about the use of silicon carbide active layers in such devices, which is important when the detected light is in the blue region of the light spectrum. In this paper we present for the first time the electro-optical properties of the a-Six:C1-x:H/Pd and p-ic-n PSD, using a-Six:C1-x:H layers deposited by plasma enhanced chemical vapour deposition (PECVD). These sensors are able to distinguish the wavelength of the impinging visible radiation (from red to blue light). In addition, the sensors respond to light intensities as lower as 1 × 10-6 W cm-2 with a resolution better than 0.04 mm and a linearity between ±0.12% and ±0.8%. © 2002 Elsevier Science B.V. All rights reserved.

In this work, we report the electro-optical properties exhibited by ZnO:A1 thin films deposited by r.f. magnetron sputtering. The effect of the deposition parameters on the properties of the films were studied with the aim to determine the most suitable deposition conditions to obtain ZnO:Al thin films with a low resistivity and high transmittance, characteristics required for applications on optoelectronic devices. After annealing, the ZnO:Al thin films present a low resistivity (6.25 × 10-3 Ωcm) and a high transmittance (90%) when produced with a deposition pressure of 1.6 × 10-2 mbar and r.f. power of 150W. © 2002 Elsevier Science Ltd. All rights reserved.

The room temperature ozone sensing properties of polycrystalline undoped zinc oxide (ZnO) thin films have been investigated. ZnO thin films have been produced by the d.c. and r.f. magnetron sputtering technique as well as with spray pyrolysis with a variety of parameters. The as-grown films were brought to a high conducting state through a reversible photoreduction process by UV light exposure and were subsequently exposed to ozone resulting in a strong resistivity increase caused by re-oxidation. The magnitude of the effect was largest for the sputtered films, which exhibited resistivity changes of more than 8 orders of magnitude, whereas films deposited by spray pyrolysis showed changes of less than 3 orders of magnitude. XRD and AFM analysis of the films revealed that all films were microcrystalline. The film texture, however, was strongly related to the growth technique and the parameters used. Best results were achieved with r.f.-sputtered films, which have been deposited at high total pressures. These films exhibited a sensor response of 1.2 × 108. © 2002 Elsevier Science B.V. All rights reserved.

In this work we studied the influence of hydrogen dilution, rf power, and the filament and substrate temperatures on the electro-optical properties and composition of a-Si:H films produced by hot wire plasma assisted technique. The a-Si:H films were produced on Mylar substrates with growth rate of up to 37 Å/s, ημτ product of 1.6 × 10-7 cm2/V, photoconductivity to dark conductivity ratio of 1 × 104 (at AM1.5 radiation), and a dark conductivity of about 10-10 (Ω cm)-1 for substrate temperature of 130 °C, hydrogen dilution of 99%, filament temperature of 1700 °C, and rf power of 100 W. © 2002 Elsevier Science B.V. All rights reserved.

The most common techniques used to produce ZnO thin films are the spray pyrolysis and the magnetron sputtering techniques, low and high cost processes respectively. The aim of this work is to compare the properties of the films produced by these two techniques. The predominant difference observed was on the morphological properties. The films produced by spray pyrolysis have a rougher surface than the ones obtained by sputtering. Also the effect of the thermal annealing treatment is much more prononnced for the ZnO thin films produced by spray pyrolysis. After heat treatment films exhibit similar electrical properties and their application to optoelectronic devices is demonstrated.

In this work we present the results of a study on the uniformity of ZnO thin films produced by spray pyrolysis. The properties of the thin films depend essentially on the carrier gas pressure and gas flow used. The best films for optoelectronic applications were obtained with a carrier gas pressure of 2 bar and solution flow of 37 ml/min. The velocity of the nozzle affects essentially the uniformity of the ZnO thin films. However this important characteristic of the large area thin films is independent of the nature (doped and undoped) of the thin film and exhibits a high dependence on the variation of the temperature along the substrate. © 2001 Materials Research Society.

The performances of amorphous and nano-crystalline porous silicon thin films as gas detector are pioneer reported in this work. The films were produced by the hot wire chemical vapour deposition (HW-CVD). These films present a porous like-structure, which is due to the uncompensated bonds and oxidise easily in the presence of air. This behaviour is a problem when the films are used for solar cells or thin film transistors. For as gas detectors, the oxidation is a benefit, since the CO, H2 or O2 molecules replace the OH adsorbed group. In the present study we observe the behaviour of amorphous and nano-crystalline porous silicon thin films under the presence of ethanol, at room temperature. The data obtained reveal a change in the current values recorded by more than three orders of magnitude, depending on the film preparation condition. This current behaviour is due to the adsorption of the OH chemical group by the Si uncompensated bonds as can be observed in the infrared spectra. Besides that, the current response and its recover time are done in few seconds.

Flexible large area thin film position sensitive detectors based on amorphous silicon technology were prepared on polyimide substrates using the conventional plasma enhanced chemical vapor deposition technique. The sensors were characterized by spectral response, illuminated I-V characteristics position detectability measurements and atomic force microscopy. The obtained one-dimensional position sensors, 5-mm wide and 60-mm long, presented a maximum spectral response at 600 nm, an open circuit voltage of 0.6 V and a position detectability with a correlation of 0.9989 associated to a S.D. of 1×10-2, comparable to those produced on glass substrates.

In this work, we present the properties of n-type silicon films obtained by hot wire plasma assisted technique produced at different rf power and gas flow rate. The films were produced at a filament temperature of 2000°C and the rf power was varied from 0 W to 200 W while gas flow rate was varied from 15 to 100 sccm keeping rf power at 50 W. In this flow rate range, the growth rate of the films varied from 5Å/s to 250Å/s and the corresponding electrical room dark conductivity varied from 10-2 to 10(Ωcm)-1. On the other hand, we observed that the electrical conductivity increased from 2 to 6(Ωcm)-1, and the Hall mobility from 0.1 to 2 cm2/V.s as rf power change from 0 W to 200 W. The infrared, EDS and XPS analyses revealed the existence of oxygen incorporation, which is not related to post-deposition oxidation. The X-ray diffraction and μRaman data show the presence of Si crystals in the films structure and the SEM micrographs reveal a granular surface morphology with grain sizes lower than 60 nm.

In this work we present a study of the properties of ZnO thin films produced by spray pyrolysis and r.f. magnetron sputtering. Before the annealing treatment the properties of the films are very similar, which means that the films produced by both techniques could be used on optoelectronic devices. However spray pyrolysis is a more simple and cheap technique than sputtering, but with this last technique the thin films exhibit a higher uniformity. © 2001 Materials Research Society.

Thin films of SnO2 deposited by spray pyrolysis as a function of temperature and the carrier gas flow have been produced, in order to evaluate the adequate deposition parameters for application in optoelectronic devices. The characterisation was centred mainly onto the structural, electrical and optical properties of the films. The obtained results showed that the films produced at 450°C and a gas flow of 101/min (as deposited) present an average transmittance (visible spectrum) of 90% and a bulk resistivity of 3.2×10-3 Ωcm.

The aim of this work is to determine the role of different metal contacts on the performances of one-dimensional thin-film position-sensitive detectors produced by plasma-enhanced chemical vapour deposition, to be used in optical rulers for alignment applications. The device consists on an indium tin oxide/p-i-n structure where the metal contacts used were based on Al, Al + Cu and Ag. The results achieved show that the contact mainly influences the final sensor range by limiting the magnitude of the analogue signals recorded. In spite of soldering problems the Al contact was the contact that lead to better discrimination of the sensor, with a nonlinearity of ±0.8% and a fall-off parameter of 3.2 × 10-3 cm-1. The Al + Cu contact also exhibits good performances (nonlinearity, of ±1.1%; fall-off parameter, 1.4 × 10-2 cm-1) and should be chosen since it is much easier to solder but requires protection against oxidation. The integration of these sensors on the optical ruler lead to the production of a system with a response time below 0.5 ms, an accuracy better than ±1% and a mechanical precision of better than 0.25 mm in 100 mm, with a full-scale noise below ±0.1%.

This work aims to study the role of the r.f. electrode configuration on the plasma characteristics of a PECVD asymmetric reactor. The configurations used are the usual diode configuration, the triode configuration and a new configuration that we named short-circuited grid electrode (SGE). The plasma generated was characterized with the use of a Langmuir probe and an impedance probe. We demonstrate that the plasma parameters are highly dependent on the reactor geometry. The results achieved show that by changing the r.f. electrode configuration the DC self-bias varies from about 100 to close to 0 V. This variation causes changes in the ion bombardment of the reactor surfaces, which can affect the growing of the films deposited. We also demonstrate that for the SGE configuration the area seen by the plasma does not correspond to the exposed physical area of the electrode, and we suggest a model to explain this phenomenon.

The aim of this paper is to present results concerning the morphology, structure, mechanical and electrical characteristics of the new proposed Cu-Sn metallurgical alloy, which may be used in electronic joins. By proper choice of process temperature and pressure, Cu coated surfaces are soldered using Sn as pre-form. The main results achieved indicate that the formation of Cu3Sn phase begins at a temperature of about 473 K and that the Sn thickness (dSn) needed is slightly above 7 μm. Due to join wettability, higher temperatures (between 523 and 573 K) and dSn above 35 μm are required to form joins within the specifications of the electronic industry.

This work refers to the main electro-optical characteristics exhibited by large area indium tin oxide films (300 × 400 mm) produced by r.f. magnetron sputtering under different oxygen concentrations and deposition pressures. Besides that, the ageing effect on the electro-optical characteristics of the films produced was also analyzed. The results achieved show that the film transparency and conductivity were highly improved (more than four orders of magnitude) by first annealing them in air at 470°C, followed by a reannealed stage under vacuum, in a hydrogen atmosphere, at 350°C. The ageing tests show that film degradation occurs when the films are produced at oxygen concentrations above 10% and/or at deposition pressures above 1.2 × 10-2 mbar. © 1999 Elsevier Science S.A. All rights reserved.