Rodrigo Martins

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.

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.

The present work focuses on a qualitative analysis of localised I-V characteristics based on the nanostructure morphology of highly dense arrays of p-type NiO nano-pillars (NiO-NPs). Vertically aligned NiO-NPs have been grown on different substrates by using a glancing angle deposition (GLAD) technique. The preferred orientation of as grown NiO-NPs was controlled by the deposition pressure. The NiO-NPs displayed a polar surface with a microscopic dipole moment along the (111) plane (Tasker's type III). Consequently, the crystal plane dependent surface electron accumulation layer and the lattice disorder at the grain boundary interface showed a non-uniform current distribution throughout the sample surface, demonstrated by a conducting AFM technique (c-AFM). The variation in I-V for different points in a single current distribution grain (CD-grain) has been attributed to the variation of Schottky barrier height (SBH) at the metal-semiconductor (M-S) interface. Furthermore, we observed that the strain produced during the NiO-NPs growth can modulate the SBH. Inbound strain acts as an external field to influence the local electric field at the M-S interface causing a variation in SBH with the NPs orientation. This paper shows that vertical arrays of NiO-NPs are potential candidates for nanoscale devices because they have a great impact on the local current transport mechanism due to its nanostructure morphology. © 2013 The Royal Society of Chemistry.

This work reports the production of ceramic targets based on nanostructured Al-doped ZnO (AZO) powders for sputtering applications. The nanostructured powder is obtained by a new patented process based on the detonation of an emulsion containing both Zn and Al metal precursors in the final proportion of 98:2wt% (ZnO:Al 2O 3), through which the Al contains is highly uniform distributed over ZnO. Due to the nanostructured powder characteristics, the targets can be sintered at substantially lower temperatures (1150-1250°C) by conventional sintering, contributing to production costs reduction of ceramic targets and consequently the costs of photovoltaic and displays industries. Electrical resistivity values around 3.0-7.0×10 -3Ωcm have been obtained depending on final microstructure of the targets. The electro-optical properties of the films produced at room temperature with thicknesses around 360nm, besides being highly uniform exhibit a resistivity of about 1×10 -3Ωcm and a transmittance in the visible range above 90%. © 2012 Elsevier Ltd.

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.

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.

In this paper, we report the environmental, optical, and gate bias stress stability of amorphous zinc-tin-oxide (ZTO) thin-film transistors (TFTs) fabricated by sol-gel spin-coating method. The ZTO TFTs showed excellent environmental and optical stability. The threshold voltage stability of ZTO TFTs was sensitive to both positive and negative gate bias stress. Maximum threshold voltage shifting of +1.9 and -3.2 V was observed under a gate bias stress of +10 and -10 V, respectively, with no significant change to subthreshold swing value. © 2006 IEEE.

The effects of zinc concentration on the performance of solution processed amorphous indium gallium zinc oxide (a-IGZO) thin film transistors (TFTs) have been investigated using high-k aluminum titanium oxide as gate dielectric. The x-ray diffraction results confirmed that all the IGZO channel layers are amorphous. The performance of a-IGZO TFTs were investigated in the linear regime operation. Highest linear field-effect mobility of 5.8 cm2 /V s with an Ion / Ioff ratio of 6× 107 and subthreshold swing of 0.28 V/dec were obtained for the a-IGZO (311) TFTs. The obtained performance of the a-IGZO TFTs is very promising for low-voltage display applications. © 2010 American Institute of Physics.

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.

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.

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

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

In this work, we present 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.

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.

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.

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 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.

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.

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.

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.

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.

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.

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.