Rodrigo Martins

The effect of annealing treatment (in the presence of different types of atmospheres) on the performances of zinc oxide thin films (intrinsic and doped with In and Al) prepared by spray pyrolysis have been studied, with the aim to determine more adequate conditions to improve the properties of the films. The results show that the annealing treatment leads to substantial changes in the structural, electrical and optical characteristics of ZnO thin films. The most significant improvements were obtained after annealing in forming gas (reduction atmosphere) at 200°C during 2 h. The ZnO:In film after heat treatment was the one that exhibited the lowest resistivity (p=5.2x10-2 ωcm) and a high transmittance (T=86%). © 2001 Elsevier Science Ltd. All rights reserved.

In this work we present preliminary results on the sensitivity to methane gas of zinc oxide thin films deposited by spray pyrolysis. It was found that using highly resistive (above 104 Ω cm) thin films and by performing the measurements at 200°C a sensitivity better than one order of magnitude was found to detect 2000 ppm of methane. A linear dependence on the sensitivity between 100 and 2000 ppm of methane was also obtained. © 2001 Elsevier Science Ltd. All rights reserved.

{In this work we report how it is possible to control the plasma regime near the substrate surface, from predominantly α to predominantly γ', passing trough and intermediate α-γ' regime, and simultaneously control the energy of the ions striking the substrate during a-Si:H deposition from a silane glow discharge in a modified triode type PECVD reactor. To do so, we apply a DC voltage (Vpol to a set of grids placed in front of the r.f. electrode and by doing this, we control the energy of the ions striking the substrate during the film's growth and the plasma regime near the substrate. Under a plasma of the γ' regime, the surface roughness is high and the films are poorly compact. In the α-γ' regime, the ion bombardment is moderate and the films are highly smooth and compact. In the α regime the ion bombardment is higher and so the films can become more compact but the surface roughness increases and the electrical properties deteriorate. The results achieved show that the best transport properties are achieved for the films deposited in the α-γ' regime corresponding to a Vpol of 38 V. Under this condition the films presented a dark conductivity, σd = 6.2×10-12 (Ωcm)-1, activation energy, ΔE ≈ 0.9 eV, hydrogen content

In this work a study of the influence of the annealing treatment (atmosphere and temperature) on the properties of zinc oxide thin films (intrinsic and doped with indium and aluminum) prepared by spray pyrolysis is presented. The result shows that the type of atmosphere (reduction or oxidant) has an important role in the changes observed in the structural, electrical and optical properties of the ZnO thin films. The ZnO thin film doped with indium, presents the lowest resistivity (ρ = 5.8×10-3 Ωcm) associated to a high transmittance (T = 86%), characteristics required for application on optoelectronic devices.

This paper presents results of the role of the oxygen concentration (CO) and the deposition pressure (pd) on structural and electrical properties of indium tin oxide films produced by r.f. magnetron sputtering. The films were annealed in air, followed by a reannealed stage in hydrogen, aiming to improve the film's transparency and conductivity. The results achieved show that the films texture grain size, structure and compactness is more influenced by CO than by pd, the same does not happen with the electrical properties.

The role of the deposition pressure and hydrogen dilution in the production of p-type Si:H films by hot wire chemical vapor deposition, was investigated. The system used permits to obtain uniform and homogeneous films properties over a 10cm×10cm substrate area. As heated filament we used Ta, since Ta filaments have longer life period without deteriorating than the W filaments ones. In this work, we show that the electrical properties of the films produced are dependent on the process gas pressure. In the pressure range of 13.3 Pa (0.1 Torr) to 66.5 Pa (0.5Torr), the film's coplanar electrical conductivity at room temperature varies by more than two orders of magnitude, for films produced at same hydrogen dilution and filament temperature, reaching values of about 0.1 (Ωcm)-1, at deposition pressures of about 40-53Pa (0.3-0.4Torr). On the other hand, the increase in hydrogen dilution (from 87% to 96%) promotes the surface roughness due to an enlargement of grain sizes in the direction of the {220} diffraction planes as observed by SEM micrographs without changing the crystalline fraction (48-50%) obtained by micro-Raman analysis.

This work analyse mainly the dissociation mechanism of the gas during the hot wire (HW) and hot wire plasma-assisted (HWPA) processes used to produce hydrogenated carbon films and silicon-carbide, using ethylene and silane as gas sources. The results show that ethylene is better decomposed by plasma-enhanced chemical vapour deposition (PECVD) than HW process. The data also show that the HWPA leads to a better carbon © incorporation than HW processes, when silicon carbide alloys are produced and, that the presence of atomic hydrogen (H) is beneficial for all processes. That is, the presence of the plasma and H lead to the formation of higher C radicals such as methylsilane (CH3SiH3), ethylsilane (C2H5SiH3) and silorane (C2H4SiH2), whose contributions are enhanced as the fraction of ethylene (Feth) in the gas mixture increases. © 2001 Published by Elsevier Science B.V.

We report in this paper the influence of the rf power on the properties of p-type silicon thin films produced by hot wire plasma assisted chemical vapor deposition (HWPA-CVD) technique, using a gas mixture containing SiH4, B2H6, CH4 and H2. The influence of the rf power in the film morphology, its structure and its composition has been determined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and infrared spectroscopy. The electrical dark conductivity, activation energy, optical band gap and growth rate values for the different rf power was also evaluated. The data achieved show that rf power rules the surface morphology, the film structure and its electrical characteristics. © 2001 Elsevier Science B.V. All rights reserved.

This paper presents the process conditions that lead to the production of nanostructured silicon films grown by plasma enhanced chemical vapour deposition close to the so-called gamma regime (powder formation), highly dense and with low density of bulk states. Thus, the powder management is one important issue to be addressed in this paper. As a general rule we observed that high quality films (low density of states and high μτ products) are obtained when films are grown under low ion bombardment at high hydrogen dilution and deposition pressure conditions, to allow the proper surface passivation and surface activation.

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 paper was to present results of the role of the d.c. grid bias on the silane plasma impedance and its I-V characteristics to grow undoped amorphous silicon (a-Si:H) films by plasma enhanced chemical vapour deposition (PECVD) in conditions where some nanoparticles can be formed in the growth region of the deposition process, under proper ion bombardment. The results achieved show that the performances of the films produced are dependent on the self bias voltage that can present photosensitivities of approximately 107 (two orders of magnitude larger than the one exhibited by films grown under conventional conditions) with density of states determined by the constant photocurrent method below 4×1015 cm-3. Apart from that, the films grown are less affected by light soaking than the conventional films.

This paper reports results on the role of high hydrogen dilution (above 80%) on the electro-optical and structural properties of boron doped silicon films produced by hot wire chemical vapor deposition (HW-CVD) technique, keeping constant the filament temperature. The structural, compositional, morphological, electrical and optical properties achieved show that the films present excellent homogeneity over the entire 10 x 10 cm deposited area. These results were obtained for films produced at gas pressures below 66.5 Pa, in spite of the high flow rate used. © 2001 Elsevier Science B.V. All rights reserved.

In this work, we report the optical and compositional properties of hydrogenated amorphous silicon carbide (a-SiC:H) thin films produced by plasma-enhanced chemical vapor deposition (PE-CVD), hot wire CVD (HW-CVD) and hot wire plasma-assisted CVD (HWPA-CVD) processes. The optical band gap of a-SiC:H films was controlled from 1.85 to 3.5 eV by varying the percentage of ethylene in the silane gas mixture from 3 to 100%. Adding a rf plasma to the hot wire process the carbon gas source dissociation is implemented leading to an increase in bulk carbon incorporation. This evidence is proved by the enhancement of the peak ascribed to the SiC stretching vibration mode, the reduction of the peak related to the SiH wagging modes, the decrease in the refractive index and the increase of optical band gap. The influence of hydrogen gas dilution on the properties of the films obtained by the different methods is also reported. © 2001 Elsevier Science B.V. All rights reserved.

This work deals with the study of the role of intra-gap density of states and films composition on the colour selection of the collection spectrum of glass/ITO/a-Six:C1-x:H/Al Schottky photodiodes produced in a conventional plasma-enhanced chemical vapour deposition (PECVD) system using as gas sources silane and a controlled mixtures of silane and methane. To do so, properties of the films were investigated, especially the one concerning the determination of the valence controllability of the films produced and the density of bulk states. Besides that, a PINIP device was also produced, using the a-Six:C1-x:layer that lead to the best Schottky diode performances. © 2001 Elsevier Science B.V. All rights reserved.

The process conditions of growing thin silicon films by plasma enhanced chemical vapour deposition (PECVD) were presented. The plasma impedance was found to monitor the powders in the PECVD systems and good quality silicon films were grown close to the plasma regime where the powders were formed. The silicon films exhibited properties which were interpreted based on a two-phase model where silicon nanostructures were embedded in a disordered network.

Sensitivity tests to reductive gases such as methane, hydrogen and ethane were performed on zinc oxide (ZnO) thin films. The highest value of sensitivity was obtained for the film with a high electrical resistivity and a low thickness. The variation of the operating temperature of the film leads to a significant change in the sensitivity of the sensor with an 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 hydrogen following by methane and than for ethane since the value of sensitivity obtained are higher and its variation with the gas concentration more pronounced.

Highly textured transparent conducting ZnO:Al thin films have been prepared by r.f. magnetron sputtering. The films were deposited on polyester (Mylar type D, 100 μm thickness) and glass substrates at room temperature. Surface stylus profiling, X-ray diffraction, scanning electron microscopy, transmission electron microscope and Hall effect measurements as a function of temperature, using the van der Pauw technique have characterized the films. The samples are polycrystalline with a hexagonal wurtzite structure and a strong crystallographic c-axis orientation (002) perpendicular to the substrate surface (columnar structure). The ZnO:Al thin films with a resistivity as low as 3.6×10-2 Ωcm have been obtained, as deposited. © 2001 Materials Research Society.

Highly textured transparent conducting ZnO:Al thin films have been prepared by r.f. magnetron sputtering. The films were deposited on polyester (Mylar type D, 100 μm thickness) and glass substrates at room temperature. Surface stylus profiling, X-ray diffraction, scanning electron microscopy, transmission electron microscope and Hall effect measurements as a function of temperature have been used to characterize the produced films. The samples are polycrystalline with a hexagonal wurtzke structure and a strong crystallographic c-axis orientation (002) perpendicular to the substrate surface (columnar structure). The ZnO:Al thin films with a resistivity as low 3.6×10-2 Ωcm have been obtained, as deposited.