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2004
Zhang, S.a b, Xu Liao Martins Fortunate Zeng Hu Kong Y. a X. a. "Characterization of polymorphous silicon thin film and solar cells." Materials Science Forum. 455-456 (2004): 77-80. AbstractWebsite

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).

Zhang, S., Raniero Fortunato Pereira Martins Canhola Ferreira Nedev Águas Martins L. E. L. "Characterization of silicon carbide thin films prepared by VHF-PECVD technology." Journal of Non-Crystalline Solids. 338-340 (2004): 530-533. AbstractWebsite

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.

Raniero, L., Pereira Zhang Ferreira Águas Fortunato Martins L. S. I. "Characterization of the density of states of polymorphous silicon films produced at 13.56 and 27.12 MHz using CPM and SCLC techniques." Journal of Non-Crystalline Solids. 338-340 (2004): 206-210. AbstractWebsite

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.

i Martins, R.a, Águas Ferreira Fortunato Raniero Roca Cabarrocas H. a I. a. "Composition, structure and optical characteristics of polymorphous silicon films deposited by PECVD at 27.12 MHz." Materials Science Forum. 455-456 (2004): 100-103. AbstractWebsite

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.

Martins, R.a, Costa Águas Soares Marques Ferreira Borges Fortunato D. a H. a. "Detection limits of a nip a-Si:H linear array position sensitive detector." Materials Research Society Symposium Proceedings. Vol. 808. 2004. 507-512. Abstract

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%.

Zhang, S.a b, Liao Xu Martins Fortunato Kong X. a Y. a. "The diphasic nc-Si/a-Si:H thin film with improved medium-range order." Journal of Non-Crystalline Solids. 338-340 (2004): 188-191. AbstractWebsite

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.

Fernandes, M.a, Vieira Martins M. a R. b. "Dynamic characterization of large area image sensing structures based on a-SiC:H." Materials Science Forum. 455-456 (2004): 86-90. AbstractWebsite

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.

Águas, H.a, Pereira Ferreira Ramos Viana Andreu Vilarinho Fortunato Martins L. a I. a. "Effect of an interfacial oxide layer in the annealing behaviour of Au/a-Si:H MIS photodiodes." Journal of Non-Crystalline Solids. 338-340 (2004): 810-813. AbstractWebsite

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.

Aguas, H.a, Pereira Ferreira Ramos Viana Andreu Vilarinho Fortunato Martins L. a I. a. "Effect of annealing on gold rectifying contacts in amorphous silicon." Materials Science Forum. 455-456 (2004): 96-99. AbstractWebsite

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.

Águas, H., Raniero Pereira Fortunato Martins L. L. E. "Effect of the discharge frequency and impedance on the structural properties of polymorphous silicon." Thin Solid Films. 451-452 (2004): 264-268. AbstractWebsite

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.

Águas, H., Perreira Silva Fortunato Martins L. R. J. C. "Effect of the tunnelling oxide growth by H2O2 oxidation on the performance of a-Si:H MIS photodiodes." Materials Science and Engineering B: Solid-State Materials for Advanced Technology. 109 (2004): 256-259. AbstractWebsite

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.

Águas, H.a, Goullet Pereira Fortunato Martins A. b L. a. "Effect of the tunnelling oxide thickness and density on the performance of MIS photodiodes." Thin Solid Films. 451-452 (2004): 361-365. AbstractWebsite

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.

Paula, A.S., Canejo Martins Braz Fernandes J. P. H. G. "Effect of thermal cycling on the transformation temperature ranges of a Ni-Ti shape memory alloy." Materials Science and Engineering A. 378 (2004): 92-96. AbstractWebsite

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.

Fortunate, E., Gonçalves De Carvalho Pimentel Lavareda Marques Martins A. C. N. "Enhancement of the electrical properties of ITO deposited on polymeric substrates by using a ZnO buffer layer." Materials Research Society Symposium Proceedings. Vol. 814. 2004. 231-236. Abstract

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%.

Ferreira, I., Fortunato Martins E. R. "Ethanol vapour detector based in porous a-Si:H films produced by HW-CVD technique." Sensors and Actuators, B: Chemical. 100 (2004): 236-239. AbstractWebsite

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.

Grimmeiss, H.a, Martins Duart R. b J. M. "Excellence in European universities." Materials Today. 7 (2004): 56-60. AbstractWebsite

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.

Fortunato, E., Pereira Águas Ferrira Martins L. H. I. "Flexible position sensitive photodetectors based on a-Si:H heterostructures." Sensors and Actuators, A: Physical. 116 (2004): 119-124. AbstractWebsite

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.

Raniero, L.a, Martins Águas Zang Ferreira Pereira Fortunato Boufendi R. a H. a. "Growth of polymorphous/nanocrystalline silicon films deposited by PECVD at 13.56 MHz." Materials Science Forum. 455-456 (2004): 532-535. AbstractWebsite

This paper aims to characterize the growth process of polymorphous/ nanocrystalline silicon (pm-Si:H) films produced by PECVD at 13.56 MHz. The emphasis is in determining the plasma parameters that allow to control the conditions where pm/nc-Si:H can be obtained under high hydrogen dilution, where the only varied parameter is the silane gas flow, fixing rf power, deposition pressure and substrate temperature. The data achieved show that good pm/nc-Si:H films are produced at 240 Pa using a silane gas flow of 5sccm (dilution 1:70) to which it corresponds films with photosensitivities exceeding 106, optical gaps close to 1.80 eV and 18 at% hydrogen contents. The data also show that under certain deposition conditions the pm-Si:H films peel-off.

Fortunato, E., Pimentel Pereira Gonçalves Lavareda Águas Ferreira Carvalho Martins A. L. A. "High field-effect mobility zinc oxide thin film transistors produced at room temperature." Journal of Non-Crystalline Solids. 338-340 (2004): 806-809. AbstractWebsite

In this paper we present the first results of thin film transistors produced completely at room temperature using ZnO as the active channel and silicon oxynitride as the gate dielectric. The ZnO-based thin film transistors (ZnO-TFT) present an average optical transmission (including the glass substrate) of 84% in the visible part of the spectrum. The ZnO-TFT operates in the enhancement mode with a threshold voltage of 1.8 V. A field effect mobility of 70 cm2/Vs, a gate voltage swing of 0.68 V/decade and an on-off ratio of 5×105 were obtained. The combination of transparency, high field-effect mobility and room temperature processing makes the ZnO-TFT very promising for the next generation of invisible and flexible electronics. © 2004 Elsevier B.V. All rights reserved.

Fortunato, E., Pimentel Gonçalves Marques Martins A. A. A. "High mobility nanocrystalline indium zinc oxide deposited at room temperature." Materials Research Society Symposium Proceedings. Vol. 811. 2004. 437-442. Abstract

In this paper we present results of indium doped zinc oxide deposited at room temperature by rf magnetron sputtering, with electron mobility as high as 60 cm2/Vs. The films present a resistivity as low as 5×10 -4 Ωcm with an optical transmittance of 85%. The structure of these films look-like polymorphous (mixed of different amorphous and nanocrystalline phases from different origins) as detected from XRD patterns (no clear peak exists) with a high smooth surface, as detected from SEM micrographs, highly important to ensure long life time when used in display devices.

Fortunato, E.a, Assunção Gonçalves Marques Águas Pereira Ferreira Vilarinho Martins V. a A. a. "High quality conductive gallium-doped zinc oxide films deposited at room temperature." Thin Solid Films. 451-452 (2004): 443-447. AbstractWebsite

Transparent and highly conducting gallium-doped zinc oxide films were successfully deposited by rf sputtering at room temperature. The lowest resistivity achieved was 2.6×10-4 Ω cm for a thickness of 1100 nm (sheet resistance ≈1.6 Ω/sq), with a Hall mobility of 18 cm2/Vs and a carrier concentration of 1.3×1021 cm-3. The films are polycrystalline with a hexagonal structure and a strongly preferred orientation along the c-axis. A linear dependence between the mobility and the crystallite size was obtained. The films present a transmittance in the visible spectra between 80 and 90% and a refractive index of approximately 2, which is very close to the value reported for bulk material. © 2003 Elsevier B.V. All rights reserved.

Barquinha, P., Pereira Águas Fortunato Martins L. H. E. "Influence of the deposition conditions on the properties of titanium oxide produced by r.f. magnetron sputtering." Materials Science in Semiconductor Processing. 7 (2004): 243-247. AbstractWebsite

This work refers to the electro-optical and structural characteristics of titanium oxide (TiOx) thin films produced by radio frequency (r.f.) magnetron sputtering that present promising performances for gate dielectric applications, alone or in mixed tandem structures, such as with Al yOz films, taking advantage of its high dielectric constant. Films produced with a O2/Ar ratio between 0.1 and 0.15 present an improved stochiometry and density where the resistivity overcomes 1011 Ω cm and the fixed charge density decreases below 10 12 cm-2. The deposition pressure influences greatly the growth rate that seems to be a determinant factor dictating the films properties. © 2004 Elsevier Ltd. All rights reserved.

b c Nedev, N.a b, Beshkov Fortunato Georgiev Ivanov Raniero Zhang Martins G. a E. b. "Influence of the rapid thermal annealing on the properties of thin a-Si films." Materials Science Forum. 455-456 (2004): 108-111. AbstractWebsite

The variation of the structure, morphology and the electrical properties of thin amorphous silicon films caused by Rapid Thermal Annealing is studied. The films annealed at 1200°C for 2 minutes change their structure to polycrystalline and as a result their resistivity decreases by 4 orders of magnitude. Due to the small thickness of the as deposited amorphous silicon the obtained poly-Si is strongly irregular and has many discontinuities in its texture.

Fernandes, M.a, Vieira Rodrigues Martins M. a I. a. "Large area image sensing structures based on a-SiC:H: A dynamic characterization." Sensors and Actuators, A: Physical. 113 (2004): 360-364. AbstractWebsite

In recent works large area hydrogenated amorphous silicon p-i-n structures with low conductivity doped layers were proposed as single element image sensors. The working principle of this type of sensor 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. In order to evaluate the sensor capabilities is necessary to perform a response time characterization. This work focuses on the transient response of such sensor and on the influence of the carbon contents of the doped layers. In order to evaluate the response time a set of devices with different percentage of carbon incorporation in the doped layers is analyzed by measuring the scanner-induced photocurrent under different bias conditions. © 2004 Elsevier B.V. All rights reserved.

Martins, R., Fortunato Ferreira Dias E. I. C. "Materials Science Forum: Preface." Materials Science Forum. 455-456 (2004): ix-x. AbstractWebsite
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