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2000
Martins, R., A̧guas Ferreira Fortunato Guimares H. I. E. "Towards the improvement of the stability of a-Si:H pin devices." Solar Energy. 69 (2000): 257-262. AbstractWebsite

This paper deals with a new process to improve the stability of a-Si:H pin solar cells deposited in a single batch process by proper passivation of the interfaces. The process consists in removing partially a deposited sacrificial oxide layer grown between the p/i or i/n interfaces by SF6 etching. This layer is an absorber of defects and impurities that are introduced in the interfaces, mainly from the chamber walls and the substrate surface. The results achieved in laboratory samples lead to devices in which the fill factor and short circuit current density were improved respectively towards 75% and 16.5 mA cm-2, with a final working efficiency of about 9.5%. © 2001 Elsevier Science Ltd. All rights reserved.

Águas, H., Cabrita Tonello Nunes Fortunato Martins A. P. P. "Two step process for the growth of a thin layer of silicon dioxide for tunnelling effect applications." Materials Research Society Symposium - Proceedings. Vol. 619. 2000. 179-184. Abstract

In today's main crystalline silicon (c-Si) applications in MOS (metal-oxide-silicon), MIS (metal-insulator-semiconductor) or SIS (Semiconductor-Insulator-Semiconductor), the growing of the oxide layer plays the main role, dictating the device performances, in particular if it has to be grown by a low temperature process. Of fundamental importance is the SiO2 interface with the c-Si. A very low defect density interface is desirable so that the number of trapping states can be reduced and the devices performance optimised. A two step low temperature oxidation process is proposed. The process consists of growing first a layer of oxide by a wet process and then treating the grown oxide with an oxygen plasma. The oxygen ions from the plasma bombard the oxide causing compaction of the oxide and a decrease in the interface roughness and defect density. Infrared spectroscopy and spectroscopic ellipsometry measurements were performed on the samples to determine the oxide thickness, optical and structural properties. SIS structures were built and capacitance measurements were performed under dark and illuminated conditions from which were inferred the interface defect density and correlated with the oxide growth process.

1999
Fortunato, E., Malik Martins A. R. "Amorphous silicon thin films applied to photochemical sensors." Vacuum. 52 (1999): 41-44. AbstractWebsite

The present paper describes the properties of a photochemical sensor based on amorphous silicon MIS (Metal-Insulator-Semiconductor) diodes. The structure of the sensors used in this work are based on glass/Cr/a-SiH(n +)/a-Si:H(i)SiOx/Pd, where the amorphous silicon layers have been deposited by conventional plasma r.f. techniques. The proposed photochemical sensors present a 2-3 orders of magnitude change in the saturation current and a decrease of up to 40% on the open circuit voltage when in the presence of 400 ppm of hydrogen. The overall performance of these sensors, associated with the low cost fabrication technology, suggests that, in the near future, it will be possible to use them in several industrial applications. © 1998 Elsevier Science Ltd. All rights reserved.

Fortunato, E., Soares Teodoro Guimarães Mendes Águas Silva Martins F. P. N. "Characteristics of a linear array of a-Si:H thin film position sensitive detector." Thin Solid Films. 337 (1999): 222-225. AbstractWebsite

The increasing demand in automation processes in finishing techniques also calls for automatic measurement and inspection methods. These methods ought to be installed as close as possible to the production process and they ought to measure the values needed in a safe and fast way, without disturbing the process itself. Simultaneously they should be free of wear and insensitive against mechanical perturbations. This approach can be reached by proper combination of the laser triangulation technique with an array of linear position sensitive detectors, able to supply information about the surface finishing of an object. This is the aim of this paper that envisages to present experimental results of the performances exhibited by such an array constituting 128 elements. The analogue information supplied by this array is processed by an analogue/digital converter, directly coupled to the array and whose information is computer processed, concerning the recognition of patterns and the processing of information collected over the object to be inspected. © 1999 Elsevier Science S.A. All rights reserved.

Nunes, P.a, Malik Fernandes Fortunato Vilarinho Martins A. a B. a. "Influence of the doping and annealing atmosphere on zinc oxide thin films deposited by spray pyrolysis." Vacuum. 52 (1999): 45-49. AbstractWebsite

Undoped and doped (indium and aluminium) zinc oxide (ZnO) thin films have been prepared by spray pyrolysis, and the effect of the doping and annealing atmosphere on the electrical, optical and structural properties of the produced films has been investigated. The deposited films have a high resistivity. Annealing the films in an argon atmosphere or under vacuum leads to a substantial reduction of the electrical resistivity of the films and to an increase on the degree of cristallinity of the deposited material. The most pronounced changes were observed in the films annealed in Argon. The results also indicate that doping highly influences the electrical and structural properties of the films, which is more pronounced in the films doped with Indium. © 1998 Elsevier Science Ltd. All rights reserved.

Ferreira, I., Aguas Mendes Fernandes Fortunato Martins H. L. F. "Influence of the H2 dilution and filament temperature on the properties of P doped silicon carbide thin films produced by hot-wire technique." Materials Research Society Symposium - Proceedings. Vol. 507. 1999. 831-836. Abstract

This work deals with the role of hydrogen dilution and filament temperature on the morphology, structure and electrical properties of nanocrystalline boron doped silicon carbide thin films produced by hot-wire technique. The structural and morphological data obtained by XRD, SEM and micro-Raman show that for filament temperatures and hydrogen dilutions above 2100 °C and 90%, respectively, the surface morphology of the films is granular with a needle shape, while for lower filament temperatures and hydrogen dilutions the surface morphology gets honeycomb like. The SIMS analysis reveals that films produced with filament temperatures of about 2200 °C and hydrogen dilution of 99% present a higher hydrogen and carbon incorporation than the films produced at lower temperatures and hydrogen dilutions. These results agree with the electrical and optical characteristics recorded that show that the films produced exhibit optical gaps in the range from 1.8 to 2 eV and transverse conductivities ranging from 10-1 S/cm to 10-3 S/cm, consistent with the degree of films crystallinity and carbon incorporation recorded.

Ferreira, I., Fernandas Martins B. R. "Nanocrystalline silicon carbon doped films prepared by hot wire technique." Vacuum. 52 (1999): 147-152. AbstractWebsite

In this work we present data concerning the structure, composition and electro-optical performances of nanocrystalline silicon carbide doped films produced at the different filament temperatures and hydrogen dilution ratios. The XRD spectra reveal the presence of the typical Si peaks ascribed to (111) (220) and (311) diffraction planes, where no traces of the carbon peaks were found. The average grain sizes ranges from 10 nm to 30 nm, depending on the temperature of filament and hydrogen dilution used. We observed an enhancement of the peak ascribed to the (220) plane when high H dilution rates are used, meaning that the film starts being textured. The infrared data reveal the typical silicon carbide modes and a hydrogen content that varies from 3% to 1%, with the increase of the filament temperature. Besides that, the IR spectra show the typical SiO2 and SiO modes, associated to the oxide species that are mainly incorporated in the surface of the films and can be removed by proper wet etching. The planar conductivity is enhanced as the temperature of the filament is increased, being the highest conductivity achieved in the range of 0.2 (Ωcm)-1 and almost non activated. © 1998 Elsevier Science Ltd. All rights reserved.

Gonçalves, C.a, Ferreira Fortunato Ferreira Martins Marvão Martins Harder Oppelt J. a E. a. "New metallurgical systems for electronic soldering applications." Sensors and Actuators, A: Physical. 74 (1999): 70-76. AbstractWebsite

The aim of this paper is to present results on a new soldering process based on the low-temperature solidification of intermetallic phases from the system Cu-Sn-Cu which can be employed to form a heat-resistant die-attach as well as signal and power electric contacts. Because of the total transformation into intermetallic phase, the working temperature of the bond formed is several hundred degrees Celsius higher than the process temperature (around 250°C). This process leads to a homologous temperature T/Tm of about 0.3 compared to 0.7 in the case of soft SnAg solder alloy. Therefore a better reliability of the proposed bonding process is achievable. Results of the match of the predicted volume fraction of the intermetallic forms and the experimentally measured contact volume would be also discussed, for contacts formed in power diodes.

Baía, I.a, Quintela Mendes Nunes Martins M. b L. a. "Performances exhibited by large area ITO layers produced by r.f. magnetron sputtering." Thin Solid Films. 337 (1999): 171-175. AbstractWebsite

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.

Martins, R., Ferreira Fernandas Fortunato I. B. E. "Performances of a-Si:H films produced by hot wire plasma assisted technique." Vacuum. 52 (1999): 203-208. AbstractWebsite

This work reports on the performances of undoped and doped amorphous/nanocrystalline silicon films grown by hot wire plasma assisted technique. The structure (including the presence of several nanoparticles with sizes ranging from 5 nm to 50 nm), composition (oxygen and hydrogen content) and transport properties of the films are highly dependent on the temperature of the filament and on the hydrogen dilution. The undoped films grown under low r.f. power (≈4mWcm-2) and filament temperatures around 1850 K present dark conductivities below 10-10 Scm-1, optical gaps of about 1.6 eV and photosensitivities above 105, (under AM 1.5 light intensities), with almost no traces of oxygen content. For the n- and the p-doped silicon films also fabricated under the same conditions the conductivities obtained are of about 10-2Scm-1 and 10-5Scm-1, respectively. © 1998 Elsevier Science Ltd. All rights reserved.

Ferreira, I., Aguas Mendes Fernandes Fortunato Martins H. L. F. "Performances of nano/amorphous silicon films produced by hot wire plasma assisted technique." Materials Research Society Symposium - Proceedings. Vol. 507. 1999. 607-612. Abstract

This work reports on the performances of undoped and n doped amorphous/nano-crystalline silicon films grown by hot wire plasma assisted technique. The film's structure (including the presence of several nanoparticles with sizes ranging from 5 nm to 50 nm), the composition (oxygen and hydrogen content) and the transport properties are highly dependent on the filament temperature and on the hydrogen dilution. The undoped films grown under low r.f. power (≈4 mWcm-2) and with filament temperatures around 1850 °K have dark conductivities below 10-10 Scm-1, optical gaps of about 1.5 eV and photo-sensitivities above 105, (under AM1.5), with almost no traces of oxygen content. N-doped silicon films were also fabricated under the same conditions which attained conductivities of about 10-2 Scm-1.

Nunes, P.a, Fernandes Fortunato Vilarinho Martins B. a E. a. "Performances presented by zinc oxide thin films deposited by spray pyrolysis." Thin Solid Films. 337 (1999): 176-179. AbstractWebsite

The effect of doping and annealing atmosphere on the performances of zinc oxide thin films prepared by spray pyrolysis have been studied. The results show that the way doping influences the electrical and structural properties depends also on the characteristics of the doping element. Annealing the as-deposited films in an inert atmosphere leads to a substantial reduction in the resistivity of the films deposited and to an increase on the degree of film's crystallinity. © 1999 Elsevier Science S.A. All rights reserved.

Fortunato, E., Martins R. "Role of the collecting resistive layer on the static characteristics of 2D a-Si:H thin film position sensitive detector." Materials Research Society Symposium - Proceedings. Vol. 507. 1999. 303-308. Abstract

The aim of this work is to present an analytical model able to interpret the role of the thin collecting resistive layer on the static performances exhibited by 2D amorphous silicon hydrogenated pin thin film position sensitive detectors. In addition, experimental results concerning the device linearity and spatial resolution are presented and checked against the predicted values of the analytical model proposed.

Ferreira, I., Águas Mendes Martins H. L. R. "Role of the hot wire filament temperature on the structure and morphology of the nanocrystalline silicon p-doped films." Applied Surface Science. 144-145 (1999): 690-696. AbstractWebsite

Nanocrystalline p-doped silicon films were deposited at low substrate temperatures (around 200°C) in a hot wire reactor. In this paper we present the results on the role of the hydrogen dilution and filament temperature on the film's structure, composition, morphology and transport properties. The film's structure changes from honeycomb-like to a granular needle shape as the filament temperature changes from about 2000°C and hydrogen dilution 87%, to values above 2100°C and hydrogen dilution 90%, respectively. The nanocrystalline silicon-based films produced have optical gaps varying from 1.6 to 1.95 eV, with conductivities up to 0.2 S cm-1 and grain sizes (obtained by X-ray diffraction) in the range of 10-30 nm. © 1999 Elsevier Science B.V. All rights reserved.

b Martins, R.a b, Fortunato E. a. "Role of the resistive layer on the performances of 2D a-Si:H thin film position sensitive detectors." Thin Solid Films. 337 (1999): 158-162. AbstractWebsite

The aim of this work is to present an analytical model which can to interpret the role of the collecting resistive layer on the static performances exhibited by 2D amorphous silicon hydrogenated p-i-n thin film position sensitive detectors. In addition, experimental results concerning the device linearity and spatial resolution are presented and checked against the predicted values of the analytical model proposed. © 1999 Elsevier Science S.A. All rights reserved.

Fantoni, A.a, Vieira Martins M. b R. a. "Simulation of hydrogenated amorphous and microcrystalline silicon optoelectronic devices." Mathematics and Computers in Simulation. 49 (1999): 381-401. AbstractWebsite

This paper is concerned with the modelling and simulation of amorphous and microcrystalline silicon optoelectronic devices. The physical model and its mathematical formulation are extensively described. Its numerical reduction is also discussed together with the presentation of a computer program dedicated to the simulation of the electrical behaviour of such devices. This computer program, called ASCA (Amorphous Silicon Solar Cells Analysis), is capable of simulating, on one- and two-dimensional domains, the internal electrical behaviour of multi-layer structures, homojunctions and heterojunctions under simple or complex spectra illumination and externally applied biases. The applications of the simulator presented in this work are the analysis of μc/a-Si:H p-i-n photovoltaic cell in thermal equilibrium and illuminated by monochromatic light and the AMI.5 solar spectrum, with and without polarisation. We also study the appearance within the device of lateral components of the electric field and current density vectors when the illumination is not uniform. © 1999 IMACS/Elsevier Science B.V. All rights reserved.

Grigore, L.a, Meghea Grigore Martins A. b O. c. "Thermodynamic properties of ternary aqueous electrolyte solutions." Physics and Chemistry of Liquids. 37 (1999): 409-428. AbstractWebsite

In previous papers the mean excess chemical potential, μ1(E), in ternary systems of the type I sulphate + II sulphate + H2O, at 25°C was determined. Results obtained for systems with CuSO4(I), and ZnSO4(I) respectively, pointed out an obvious disparity between their behaviours. They show the existence of some important association phenomena partially accounting for the substantial deviations from ideal behaviour. The ternary sulphate systems (CuSO4 + Me(I,II)SO4 + H2O; ZnSO4 + Me(I,II)SO4 + H2O) studied were characterized against the binaries of the same ionic strength, experimental data being obtained using both e.m.f. and spectrophotometric methods. Deviations from the ideal behaviour were discussed in terms of thermodynamic excess functions and association constants. A comparative study between the results obtained with the two above mentioned methods is presented. In previous papers the mean excess chemical potential, μ1 E, in ternary systems of the type I sulphate+II sulphate+H2O, at 25 °C was determined. Results obtained for systems with CuSO4(I), and ZnSO4(I) respectively, pointed out an obvious disparity between their behaviours. They show the existence of some important association phenomena partially accounting for the substantial deviations from ideal behaviour. The ternary sulphate systems (CuSO4+MeI, IISO4+H2O; ZnSO4+MeI, IISO4+H2O) studied were characterized against the binaries of the same ionic strength, experimental data being obtained using both e.m.f. and spectrophotometric methods. Deviations from the ideal behaviour were discussed in terms of thermodynamic excess functions and association constants. A comparative study between the results obtained with the two above mentioned methods is presented.

Fantoni, A.a, Vieira Martins M. b R. a. "Transport properties in microcrystalline silicon solar cells under AM1.5 illumination analyzed by two-dimensional numerical simulation." Solid-State Electronics. 43 (1999): 1709-1714. AbstractWebsite

Microcrystalline silicon is a two-phase material. Its composition can be interpreted as a series of grains of crystalline silicon imbedded in an amorphous silicon tissue, with a high concentration of dangling bonds in the transition regions. In this paper, results for the transport properties of a μc-Si:H p-i-n junction obtained by means of two-dimensional numerical simulation are reported. The role played by the boundary regions between the crystalline grains and the amorphous matrix is taken into account and these regions are treated similar to a heterojunction interface. The device is analyzed under AM1.5 illumination and the paper outlines the influence of the local electric field at the grain boundary transition regions on the internal electric configuration of the device and on the transport mechanism within the μc-Si:H intrinsic layer.

Fantoni, A.a, Vieira Martins M. b R. a. "Transport properties of μc-Si:H analyzed by means of numerical simulation." Thin Solid Films. 337 (1999): 109-112. AbstractWebsite

Microcrystalline silicon is a two-phase material. Its composition can be interpreted as grains of crystalline silicon imbedded in an amorphous silicon tissue, with a high concentration of danglind bonds in the transition regions. In this paper, results obtained by means of numerical simulations about the transport properties of a μc-Si:H p-i-n junction are reported. The role played by the boundary regions between the crystalline grains and the amorphous matrix is taken in account, and these regions are treated similarly to a heterojunction interface. The influence of the local electric field at the grains boundary transition regions on the internal electric configuration of the device is outlined under illumination and applied external bias. © 1999 Elsevier Science S.A. All rights reserved.

1998
Fortunato, E.a, Malik Sêco Ferreira Martins A. a A. b. "Amorphous silicon sensors: From photo to chemical detection." Journal of Non-Crystalline Solids. 227-230 (1998): 1349-1353. AbstractWebsite

This paper reports the performances of metal/insulator/semiconductor devices, simultaneously sensitive to hydrogen and to the visible region of the spectrum. The sensors used in this work are based on glass/Cr/a-SiH(n+)/a-Si:H(i)/SiOx/Pd structures, where the amorphous silicon was deposited by conventional r.f. techniques and the oxide grown thermally (in air) or chemically (in hydrogen peroxide). The proposed sensors present a response of ∼ 3 orders of magnitude change in the saturation current when in the presence of 400 ppm of hydrogen and an open circuit voltage that decreases in the presence of hydrogen, with a maximum spectral response at 500 nm. These sensors were also compared with equivalent crystalline silicon devices whose oxides were prepared exactly in the same conditions as the ones used for the a-Si:H devices. © 1998 Elsevier Science B.V. All rights reserved.

Malik, A., Nunes Martins R. R. "Cubic to hexagonal phase transition in spray deposited tin-doped indium oxide films." Materials Research Society Symposium - Proceedings. Vol. 481. 1998. 599-605. Abstract

This work's aim is to report for the first time the cubic to hexagonal phase transition in tin-doped In2O3 films with a Sn/In atomic ratio of 0.03, fabricated at low temperature and normal pressure from alcoholic solution of InCl3 and SnCl4. The performed X-ray diffraction measurements show a difference between crystallographic symmetry of thin (100 nm) and thick (400 nm) films prepared in the same conditions: the structure of thick films can be related to high pressure In2O3 hexagonal system with a preferred orientation of c-axis parallel to the substrate surface, while thin films present a cubic symmetry with columnar (400) grain orientation. Phase transition nature is connected with non-axial tensile deformation of indium oxide grid due to insertion of chlorine ions in the position of two diagonally opposite oxygen vacancies in In2O3 network.

b b b b b Martins, R.a b, Maçarico Ferreira Nunes Bicho Fortunato A. a I. a. "Investigation of the amorphous to microcrystalline phase transition of thin film silicon produced by PECVD." Thin Solid Films. 317 (1998): 144-148. AbstractWebsite

We have deposited by Plasma Enhanced Chemical Vapour Deposition phosphorus doped amorphous and microcrystalline silicon films, as a function of the RF power (10-300 W), using a PH3/(SiH4 + H2 + He)mixture. It was found that films microcrystallization occurs for powers above 130 W, where a clear phase transition occurs. The microcrystalline films produced present high dark conductivities and optical band gaps, where the crystalline volume fraction is above 25%, as revealed by micro Raman spectroscopy. The Hall mobility have been also determined for amorphous and microcrystalline films, as a function of temperature, in the range 280-340 K. The data show that for the microcrystalline films the conduction is mainly in the extended states of the microcrystals, confirming also the double sign anomaly. That is, for n-type films, the sign is positive for the amorphous case while it is negative for the microcrystalline case. © 1998 Elsevier Science S.A.

Malik, A., Martins R. "Light-controlled switching transients in MIS silicon structures with multichannel insulator: physical processes and new device modelling." Materials Research Society Symposium - Proceedings. Vol. 490. 1998. 257-262. Abstract

We present the modelling of a new two-terminal and low-voltage operating optoelectronic device based on MIS silicon structure with multichannel insulator and having as gate a transparent metallic tin-doped indium oxide (ITO) layer deposited by spray pyrolysis technique over the insulator layer. ITO layer has a multiple non-rectifier electrical contact with silicon substrate, in the SiO2 channel's region. Construction details of the process, together with its operating characteristics are given. The devices developed do not require external active electronic components (transistors, microschemes) to execute their functions and to transform analogue input optical signals to digital output form, highly important for a wide range of optoelectronic applications.

Malik, A., Martins R. "Metal oxide/silicon heterostructures: New solutions for different optoelectronic applications." Materials Research Society Symposium - Proceedings. Vol. 487. 1998. 375-380. Abstract

In this paper we report the success in fabricating FTO/Si surface-barrier photodiodes produced by spray pyrolysis deposition technique, under ambient conditions. Three types of photodetectors for low-voltage-bias operation were developed based on high-resistivity silicon: 1. X-Ray detectors with energy resolution of 16.5% at 661.5 keV (137Cs source), consisting of surface-barrier PIN photodiode with an active area of 50 mm2 operating at 5 V reverse bias, scintillator based on monocrystalline Bi4Ge3O12 and preamplifier (noise of 250 e- RMS.); 2. Fast-response surface-barrier FTO/n–n+ silicon epitaxial photodiodes, operating at 10 V bias with rise times of 2 ns at λ = 0.85 μm; 3. Radiation-resistant drift epitaxial surface-barrier PIN photodiodes for unbiased operating conditions, with an exponential impurity distribution in a 8 μm thick epitaxial layer. A built-in electrical field due to the carrier concentration distribution in the epitaxial layer provides a considerable improvement in the `critical fluence' value (3×1014 cm-2) for neutron irradiation.

Malik, A.a, Sêco Fortunato Martins A. c E. b. "Microcrystalline thin metal oxide films for optoelectronic applications." Journal of Non-Crystalline Solids. 227-230 (1998): 1092-1095. AbstractWebsite

We report the properties and optoelectronic applications of transparent and conductive indium and tin oxide films prepared by the spray pyrolysis method and doped with Sn or F, respectively. The film properties have been measured using X-ray diffraction, optical and electrical absorption. As examples of applications we produced a set of selective optical detectors for different spectral regions, covering the wavelength range from 0.25 to 1.1 μm, based on metal oxide-semiconductor heterostructures and using different substrates such as: GaP, GaSe, AlxGa1-xAs, GaAs and Si. The fabricated devices exhibit several features such as: production simplicity, high quantum efficiency, uniform sensitivity over the entire active area and a high response speed. Finally, we present a high quantum efficiency and solar blind monocrystalline zinc sulphide optical sensor fabricated by spray deposition as an alternative to the ultraviolet-enhanced SiC and GaN photodetectors and the performances of a solar cell. © 1998 Elsevier Science B.V. All rights reserved.