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c Olziersky, A.a, Barquinha Vilà Magana Fortunato Morante Martins P. b A. a. "Role of Ga 2O 3-In 2O 3-ZnO channel composition on the electrical performance of thin-film transistors." Materials Chemistry and Physics. 131 (2011): 512-518. AbstractWebsite

In this work we present a study aiming to determine the role of Ga2O3-In2O3-ZnO (GIZO) channel layer composition on the electrical performance and stability exhibited by thin-film transistors (TFTs). The GIZO films were obtained by magnetron sputtering using ceramic targets of different compositions (Ga:In:Zn = 2:2:1, 2:2:2, 2:4:1 and 2:4:2 at.). Structural analysis corroborates the fully amorphous character of the GIZO deposited layers. For the target compositional range used we observe a Zn deficiency on the produced films, which affects the In/Ga atomic concentration ratios. Resistivity and mobility are found to show a general trend against the measured In/Ga ratio that reveals the role played by In and Ga cations on the transport mechanisms. Targets with increased In concentrations (2:4:1 and 2:4:2) allow to obtain the best TFT performances with field effect mobilities reaching values of 53.0 and 51.7cm2 V-1 s-1, respectively. In addition, the In-richer GIZO compositions result in considerably more stable TFTs, especially under positive gate bias stress conditions. Finally, it is verified that by using a target with a slightly lower In atomic composition (2:4:2 in comparison to 2:4:1), good stability and mobility can be achieved with potentially lower material costs.© 2011 Elsevier B.V. All rights reserved.

Oliveira, M.a, Liang Almeida Vistas Gonçalves Martins D. a J. a. "A path to renewable Mg reduction from MgO by a continuous-wave Cr:Nd:YAG ceramic solar laser." Solar Energy Materials and Solar Cells. 155 (2016): 430-435. AbstractWebsite

The first successful ablation of magnesium oxide through a home-made continuous-wave Cr:Nd:YAG ceramic solar laser is reported. A stationary heliostat-parabolic mirror solar energy collection and concentration system was used. A stable continuous-wave laser output power of 19.2 W was attained with laser beam brightness figure of merit 7.6 times higher than that of the previous scheme, enabling therefore the direct ablation of pure magnesium by our solar-pumped laser with only 1.6 m2 effective collection area. This could be an important step towards renewable magnesium production, offering multiple advantages, such as reducing agent avoidance, in relation to that of the previous Fresnel lens Cr:Nd:YAG continuous-wave solar laser system. © 2016 Elsevier B.V.

O'Brien, S.a, Çopuroglu Tassie Nolan Hamilton Povey Pereira Martins Fortunato Pemble M. a P. b. "The effect of dopants on the morphology, microstructure and electrical properties of transparent zinc oxide films prepared by the sol-gel method." Thin Solid Films. 520 (2011): 1174-1177. AbstractWebsite

The influence of doping on the morphology, physical and electrical properties of zinc oxide produced by the sol-gel method was examined. Undoped zinc oxide was observed to form relatively porous films. Addition of an Al dopant influenced the sheet resistance, but did not result in a change in morphology, examined by atomic force microscopy when compared to undoped films. In the case of electrical measurements, undoped ZnO films were extremely resistive. A minimum dopant concentration of 2 at.%. Al was required to produce materials which were more conductive, as observed by sheet resistance measurements, which were shown to vary with annealing temperature. The versatile nature of sol-gel processing was demonstrated by selective ink-jet deposition of sol-gel droplets which were annealed to form oxide materials. © 2011 Elsevier B.V. All rights reserved.

O'Brien, S.a, Nolan Çopuroglu Hamilton Povey Pereira Martins Fortunato Pemble M. G. a M. "Zinc oxide thin films: Characterization and potential applications." Thin Solid Films. 518 (2010): 4515-4519. AbstractWebsite

Zinc oxide (ZnO) has attracted recent interest for a range of applications, including use as a transparent conductive oxide (TCO) and in gas sensor devices. This paper compares ZnO films grown using two methods designed for the production of thin films, namely sol-gel and aerosol assisted chemical vapour deposition (AACVD) for potential use in sensor and TCO applications. Materials produced by the sol-gel route were observed to be amorphous when annealed at 350 °C, but were crystalline when annealed at higher temperatures and had a relatively open grain structure when compared to the AACVD films. Electrical characterization showed that materials were highly resistive, but that their properties varied considerably when the measurements were performed in vacuum or in air. This behaviour was rapidly reversible and reproducible for room temperature measurement. In contrast materials grown by aerosol-assisted CVD were non-porous, polycrystalline and conductive. Measured electrical properties did not vary with changing measurement atmosphere. These differences are discussed in terms of the structural characterisation of the films and some comments are made regarding the suitability of both approaches for the growth of ZnO thin film sensor materials. © 2009 Elsevier B.V. All rights reserved.

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de Nunes de Carvalho, C., Nijs Ferreira Fortunato Martins J. M. M. I. "Improvement of the ITO-p interface in a-Si:H solar cells using a thin SiO intermediate layer." Materials Research Society Symposium - Proceedings. Vol. 420. 1996. 861-865. Abstract

The use of ITO thin films on glass/ITO/p-i-n/metal amorphous silicon solar cells is reviewed. It is suggested a new application for silicon monoxide thin films on the ITO-p interface, as an intermediate layer, to minimize the ITO thin film deterioration process, during the early stage of exposure to a silane plasma rich in hydrogen. The thickness of the silicon monoxide thin films is chosen not to worsen the optical and electrical properties of the ITO thin films. The ITO-p interface is optimized (due to impurities diffusion decrease), leading to an overall improvement of the device performance.

Nunes, P., Marques Fortunato Martins A. E. R. "Performances presented by large area ZnO thin films deposited by spray pyrolysis." Materials Research Society Symposium Proceedings. Vol. 685. 2001. 152-157. Abstract

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.

Nunes, P., Fortunato Martins E. R. "Influence of the post-treatment on the properties of ZnO thin films." Thin Solid Films. 383 (2001): 277-280. AbstractWebsite

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.

Nunes, P., Costa Fortunato Martins D. E. R. "Performances presented by zinc oxide thin films deposited by r.f. magnetron sputtering." Vacuum. 64 (2002): 293-297. AbstractWebsite

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.

Nunes, P.a, Fortunato Vilarinho Martins E. a P. b. "Effect of different dopants on the properties of ZnO thin films." International Journal of Inorganic Materials. 3 (2001): 1211-1213. AbstractWebsite

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

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.

Nunes, P., Braz Fernandes Silva Fortunato Martins F. M. R. J. "Structural characterisation of zinc oxide thin films produced by spray pyrolysis." Key Engineering Materials. 230-232 (2002): 599-602. AbstractWebsite

In this work, we present a study of the effect of temperature, type and concentration of the dopant on the structural characteristics of ZnO thin films produced by spray pyrolysis; the crystallite size has been determined from profile peak shape analysis. These results are compared to the electrical characterisation performed on these materials. The effect of the dopant on the properties of ZnO thin films depends on its characteristics, mainly its ionic radius. Al, Ga and In have been studied as dopants, the best one being In, since it leads to the lowest resistivity.

c Nunes, D.a, Pimentel Pinto Calmeiro Nandy Barquinha Pereira Carvalho Fortunato Martins A. a J. V. "Photocatalytic behavior of TiO2 films synthesized by microwave irradiation." Catalysis Today. 278 (2016): 262-270. AbstractWebsite

Titanium dioxide was synthesized on glass substrates from titanium (IV)isopropoxide and hydrochloride acid aqueous solutions through microwave irradiation using as seed layer either fluorine-doped crystalline tin oxide (SnO2:F) or amorphous tin oxide (a-SnOx). Three routes have been followed with distinct outcome: (i) equimolar hydrochloride acid/water proportions (1HCl:1water) resulted in nanorod arrays for both seed layers; (ii) higher water proportion (1HCl:3water) originated denser films with growth yield dependent on the seed layer employed; while (iii) higher acid proportion (3HCl:1water) hindered the formation of TiO2. X-ray diffraction (XRD) showed that the materials crystallized with the rutile structure, possibly with minute fractions of brookite and/or anatase. XRD peak inversions observed for the materials synthesized on crystalline seeds pointed to preferred crystallographic orientation. Electron diffraction showed that the especially strong XRD peak inversions observed for TiO2 grown from the 1HCl:3water solution on SnO2:F originated from a [001] fiber texture. Transmittance spectrophotometry showed that the materials with finer structure exhibited significantly higher optical band gaps. Photocatalytic activity was assessed from methylene blue degradation, with the 1HCl:3water SnO2:F material showing remarkable degradability performance, attributed to a higher exposure of (001) facets, together with stability and reusability. © 2015 Elsevier B.V.

Nunes, P., Fortunato Martins E. R. "Influence of the annealing conditions on the properties of ZnO thin films." International Journal of Inorganic Materials. 3 (2001): 1125-1128. AbstractWebsite

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.

c Nunes, D.a, Calmeiro Nandy Pinto Pimentel Barquinha Carvalho Walmsley Fortunato Martins T. R. a S. "Charging effects and surface potential variations of Cu-based nanowires." Thin Solid Films. 601 (2016): 45-53. AbstractWebsite

The present work reports charging effects and surface potential variations in pure copper, cuprous oxide and cupric oxide nanowires observed by electrostatic force microscopy (EFM) and Kelvin probe force microscopy (KPFM). The copper nanowires were produced by wet synthesis, oxidation into cuprous oxide nanowires was achieved through microwave irradiation and cupric oxide nanowires were obtained via furnace annealing in atmospheric conditions. Structural characterization of the nanowires was carried out by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. During the EFM experiments the electrostatic field of the positive probe charged negatively the Cu-based nanowires, which in turn polarized the SiO2 dielectric substrate. Both the probe/nanowire capacitance as well as the substrate polarization increased with the applied bias. Cu2O and CuO nanowires behaved distinctively during the EFM measurements in accordance with their band gap energies. The work functions (WF) of the Cu-based nanowires, obtained by KPFM measurements, yielded WFCuO > WFCu > WFCu2O. © 2015 Elsevier B.V.

Nunes, P., Fortunato Vilarinho Martins E. P. R. "Effect of deposition conditions upon gas sensitivity of zinc oxide thin films deposited by spray pyrolysis." Solid State Phenomena. 80-81 (2001): 151-154. AbstractWebsite

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

Nunes, P., Fortunato Martins Vilarinho E. R. P. "Properties presented by ZnO thin films deposited by magnetron sputtering and spray pyrolysis." Key Engineering Materials. 230-232 (2002): 424-427. AbstractWebsite

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.

Nunes, P., Fortunato Martins E. R. "Properties of ZnO thin films deposited by spray pyrolysis and magnetron sputtering." Materials Research Society Symposium Proceedings. Vol. 685. 2001. 128-133. Abstract

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.

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.

Nunes, P., Fortunato Lopes Martins E. A. R. "Influence of the deposition conditions on the gas sensitivity of zinc oxide thin films deposited by spray pyrolysis." International Journal of Inorganic Materials. 3 (2001): 1129-1131. AbstractWebsite

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.

Nunes, P., Fortunato Vilarinho Martins E. P. R. "Properties presented by tin oxide thin films deposited by spray pyrolysis." Solid State Phenomena. 80-81 (2001): 139-144. AbstractWebsite

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.

Nunes, P.a, Fortunato Tonello Braz Fernandes Vilarinho Martins E. a P. a. "Effect of different dopant elements on the properties of ZnO thin films." Vacuum. 64 (2002): 281-285. AbstractWebsite

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

Nunes, P., Fortunato Martins E. R. "Thin film combustible gas sensors based on zinc oxide." Materials Research Society Symposium - Proceedings. Vol. 666. 2001. F521-F526. Abstract

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.

Nolan, M.G.a, Hamilton Obrien Bruno Pereira Fortunato Martins Povey Pemble J. A. a S. "The characterisation of aerosol assisted CVD conducting, photocatalytic indium doped zinc oxide films." Journal of Photochemistry and Photobiology A: Chemistry. 219 (2011): 10-15. AbstractWebsite

Indium doped, and undoped, zinc oxide films were deposited using aerosol assisted chemical vapour deposition (AACVD) at atmospheric pressure on glass substrates. Electrical measurements (I-V) showed a reduction in resistivity following the addition of indium, and XRD analysis revealed an associated switch to c-axis preferred crystal orientation. The ability of the films to oxidise organic material on their surface was analysed using stearic acid as the model contaminant under ultra-violet (UV, 365 nm) irradiation. The In-doped films displayed a greater rate of organic decomposition, which we attribute to the formation of a platelet surface structure having a larger surface area than the undoped films, on which the UV generated electrons and holes may react to form active photocatalytic species. In addition we suggest that the switch to c-axis crystal orientation may reduce the electron-hole pair recombination rate at the grain boundaries, due to an improvement in crystallinity and related reduction in carrier scattering losses, leading to an increase in photocatalytic organic decomposition rate. © 2011 Elsevier B.V. All rights reserved.

de Nijs, J.M.M.a, Carvalho Santos Martins C. b M. b. "A thin SiO layer as a remedy for the indium reduction at the In2O3/μc-Si:C:H interface." Applied Surface Science. 52 (1991): 339-342. AbstractWebsite

The reduction of the In2O3 caused by the deposition of μc-Si:C:H by means of plasma-enhanced CVD, is considerably diminished if a thin (50 Å) silicon monoxide layer is applied as a diffusion barrier. The amount of reduced indium diminishes by a factor three while the amount of silicon oxide is also less, although SiO was added on purpose. First results on an amorphous silicon In2O3/pi junction show that the SiO layer benefits the opto-electrical characteristics. © 1991.

b Neves, N.a b, Barros Antunes Ferreira Calado Fortunato Martins R. a E. a. "Sintering behavior of nano- and micro-sized ZnO powder targets for rf magnetron sputtering applications." Journal of the American Ceramic Society. 95 (2012): 204-210. AbstractWebsite

In this work, the nonisothermal sintering behavior of as-received commercial high purity ZnO micrometric (m-ZnO), submicrometric (sm-ZnO) and nanometric (n-ZnO) powders was studied. The sintering behavior for sputtering target production was evaluated by changing the green density of samples from 62% of theoretical density (TD) to 35%. We observed that for n-ZnO powder, the maximum shrinkage rate (MSR) temperature (T MSR) was not affected by the green density, and that it was reached at lower temperatures (∼710°C) compared with m-ZnO and sm-ZnO powders. For these powders, the temperature of MSR increased from 803°C to 934°C and from 719°C to 803°C as TD changed from 62% to 35% TD, respectively. Small grain size (∼0.560 μm) and high density targets were obtained for n-ZnO when sintered at temperatures below the T MSR. Heating rate from 1°C to 15°C/min led to lower activation energy for n-ZnO (∼201 ± 3 kJ/mol) than for the submicrometric (sm-ZnO) (∼332 ± 20 kJ/mol) and micrometric (m-ZnO) (∼273 ± 9 kJ/mol) powders. Using the model proposed by Bannister and Woolfrey, an n value of 0.75 was found, which was correlated with a combination of viscous flow and volume diffusion mechanisms that should control the initial stage of n-ZnO sintering. No significant differences were observed for n-ZnO powder in terms of density when the size of targets (scale-up effect) was increased, while in the case of m-ZnO and sm-ZnO, a delay in the densification was observed, which was related to the higher sinterability of n-ZnO powder. Two inches ZnO ceramic targets with different particle sizes and final densities were used in an rf magnetron sputtering system to produce ZnO films under the same deposition conditions. Films with thickness around 100 nm and good uniformity were produced using those targets, and no variation was observed in the optical and morphological properties. However, low electrical resistivity (1.4 Omega;·cm) films were obtained with n-ZnO targets, which could be explained in terms of a nonstoichiometric Zn:O composition of the started powders. © 2011 The American Ceramic Society.