Publications

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2022
Firmino, R., E. Carlos, J. V. Pinto, J. Deuermeier, R. Martins, E. Fortunato, P. Barquinha, and R. Branquinho, "{Solution Combustion Synthesis of Hafnium-Doped Indium Oxide Thin Films for Transparent Conductors}", Nanomaterials, vol. 12, no. 13, pp. 2167, jun, 2022. AbstractWebsite

{\textless}p{\textgreater}Indium oxide (In2O3)-based transparent conducting oxides (TCOs) have been widely used and studied for a variety of applications, such as optoelectronic devices. However, some of the more promising dopants (zirconium, hafnium, and tantalum) for this oxide have not received much attention, as studies have mainly focused on tin and zinc, and even fewer have been explored by solution processes. This work focuses on developing solution-combustion-processed hafnium (Hf)-doped In2O3 thin films and evaluating different annealing parameters on TCO's properties using a low environmental impact solvent. Optimized TCOs were achieved for 0.5 M{%} Hf-doped In2O3 when produced at 400 °C, showing high transparency in the visible range of the spectrum, a bulk resistivity of 5.73 × 10−2 $Ømega$.cm, a mobility of 6.65 cm2/V.s, and a carrier concentration of 1.72 × 1019 cm−3. Then, these results were improved by using rapid thermal annealing (RTA) for 10 min at 600 °C, reaching a bulk resistivity of 3.95 × 10 −3 $Ømega$.cm, a mobility of 21 cm2/V.s, and a carrier concentration of 7.98 × 1019 cm−3, in air. The present work brings solution-based TCOs a step closer to low-cost optoelectronic applications.{\textless}/p{\textgreater}

2017
Goswami, S., S. Nandy, A. N. Banerjee, A. Kiazadeh, G. R. Dillip, J. V. Pinto, S. W. Joo, R. Martins, and E. Fortunato, "{“Electro-Typing” on a Carbon-Nanoparticles-Filled Polymeric Film using Conducting Atomic Force Microscopy}", Advanced Materials, vol. 29, no. 47, 2017. Abstract

© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Next-generation electrical nanoimprinting of a polymeric data sheet based on charge trapping phenomena is reported here. Carbon nanoparticles (CNPs) (waste carbon product) are deployed into a polymeric matrix (polyaniline) (PANI) as a charge trapping layer. The data are recorded on the CNPs-filled polyaniline device layer by “electro-typing” under a voltage pulse (VET, from ±1 to ±7 V), which is applied to the device layer through a localized charge-injection method. The core idea of this device is to make an electrical image through the charge trapping mechanism, which can be “read” further by the subsequent electrical mapping. The density of stored charges at the carbon–polyaniline layer, near the metal/polymer interface, is found to depend on the voltage amplitude, i.e., the number of injected charge carriers. The relaxation of the stored charges is studied by different probe voltages and for different devices, depending on the percolation of the CNPs into the PANI. The polymeric data sheet retains the recorded data for more than 6 h, which can be refreshed or erased at will. Also, a write–read–erase–read cycle is performed for the smallest “bit” of stored information through a single contact between the probe and the device layer.

2016
Nunes, D., A. Pimentel, J. V. Pinto, T. R. Calmeiro, S. Nandy, P. Barquinha, L. Pereira, P. A. Carvalho, E. Fortunato, and R. Martins, "{Photocatalytic behavior of TiO2 films synthesized by microwave irradiation}", Catalysis Today, vol. 278, 2016. Abstract

© 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
Morais, A. R. C., J. V. Pinto, D. Nunes, L. B. Roseiro, M. C. Oliveira, E. Fortunato, and R. Bogel-Łukasik, "{Imidazole: Prospect Solvent for Lignocellulosic Biomass Fractionation and Delignification}", ACS Sustainable Chemistry {&} Engineering: American Chemical Society, dec, 2015. AbstractWebsite
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Nunes, D., A. Pimentel, J. V. Pinto, T. R. Calmeiro, S. Nandy, P. Barquinha, L. Pereira, P. A. Carvalho, E. Fortunato, and R. Martins, "Photocatalytic behavior of TiO2 films synthesized by microwave irradiation", Catalysis Today, 2015. 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.

Nunes, D., L. Santos, P. Duarte, A. Pimentel, J. V. Pinto, P. Barquinha, P. A. Carvalho, E. Fortunato, and R. Martins, "Room Temperature Synthesis of Cu2O Nanospheres: Optical Properties and Thermal Behavior", Microscopy and Microanalysis, vol. 21, issue 01, pp. 11, 2015. Abstract

The present work reports a simple and easy wet chemistry synthesis of cuprous oxide (Cu2O) nanospheres at room temperature without surfactants and using different precursors. Structural characterization was carried out by X-ray diffraction, transmission electron microscopy, and scanning electron microscopy coupled with focused ion beam and energy-dispersive X-ray spectroscopy. The optical band gaps were determined from diffuse reflectance spectroscopy. The photoluminescence behavior of the as-synthesized nanospheres showed significant differences depending on the precursors used. The Cu2O nanospheres were constituted by aggregates of nanocrystals, in which an on/off emission behavior of each individual nanocrystal was identified during transmission electron microscopy observations. The thermal behavior of the Cu2O nanospheres was investigated with in situ X-ray diffraction and differential scanning calorimetry experiments. Remarkable structural differences were observed for the nanospheres annealed in air, which turned into hollow spherical structures surrounded by outsized nanocrystals. FAU - Nunes, Daniela

Nunes, D., T. R. Calmeiro, S. Nandy, J. V. Pinto, A. Pimentel, P. Barquinha, P. A. Carvalho, J. C. Walmsley, E. Fortunato, and R. Martins, "{Charging effects and surface potential variations of Cu-based nanowires}", Thin Solid Films: Elsevier B.V., pp. 1–9, 2015. AbstractWebsite

The presentwork reports charging effects and surface potential variations in pure copper, cuprous oxide and cu- pric 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 throughmicrowave irradiation and cupric oxide nanowireswere obtained via furnace annealing in at- mospheric conditions. Structural characterization of the nanowireswas carried out byX-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 sub- strate polarization increased with the applied bias. Cu2O and CuO nanowires behaved distinctively during the EFMmeasurements in accordancewith their band gap energies. Thework functions(WF) of the Cu-based nano- wires, obtained by KPFM measurements, yieldedWFCuO N WFCu N WFCu2O

Kiazadeh, A., D. Salgueiro, R. Branquinho, J. Pinto, H. L. Gomes, P. Barquinha, R. Martins, and E. Fortunato, "{Operational stability of solution based zinc tin oxide/SiO2 thin film transistors under gate bias stress}", APL Materials, vol. 3, no. 6, pp. 062804, 2015. AbstractWebsite

In this study, we report solution-processed amorphous zinc tin oxide transistors exhibiting high operational stability under positive gate bias stress, translated by a recoverable threshold voltage shift of about 20{%} of total applied stress voltage. Under vacuum condition, the threshold voltage shift saturates showing that the gate-bias stress is limited by trap exhaustion or balance between trap filling and emptying mechanism. In ambient atmosphere, the threshold voltage shift no longer saturates, stability is degraded and the recovering process is impeded. We suggest that the trapping time during the stress and detrapping time in recovering are affected by oxygen adsorption/desorption processes. The time constants extracted from stretched exponential fitting curves are ≈106 s and 105 s in vacuum and air, respectively.

Nunes, D., A. Pimentel, J. V. Pinto, T. R. Calmeiro, S. Nandy, P. Barquinha, L. Pereira, P. A. Carvalho, E. Fortunato, and R. Martins, "{Photocatalytic behavior of TiO2 films synthesized by microwave irradiation}", Catalysis Today: Elsevier B.V., 2015. AbstractWebsite
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2014
Veigas, B., R. Branquinho, J. V. Pinto, P. J. Wojcik, R. Martins, E. Fortunato, and P. V. Baptista, "Ion sensing (EIS) real-time quantitative monitorization of isothermal DNA amplification", Biosensors and Bioelectronics, 2014. Abstract
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2013
Nandy, S., G. Goncalves, J. V. Pinto, T. Busani, V. Figueiredo, L. Pereira, R. F. Paiva Martins, and E. Fortunato, "Current transport mechanism at metal-semiconductor nanoscale interfaces based on ultrahigh density arrays of p-type NiO nano-pillars", Nanoscale, vol. 5, issue 23, pp. 11699-11709, 2013. AbstractWebsite

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.

Pinto, J. V., R. Branquinho, P. Barquinha, E. Alves, R. Martins, and E. Fortunato, "Extended-Gate ISFETs Based on Sputtered Amorphous Oxides", Journal of Display Technology, vol. 9, issue 9, pp. 729-734, 2013. AbstractWebsite
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Figueiredo, V., J. V. Pinto, J. Deuermeier, R. Barros, E. Alves, R. Martins, and E. Fortunato, "p-Type CuxO Thin-Film Transistors Produced by Thermal Oxidation", Journal of Display Technology, vol. 9, issue 9, pp. 6, 2013. AbstractWebsite
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Branquinho, R., J. V. Pinto, T. Busani, P. Barquinha, L. Pereira, P. Viana Baptista, R. Martins, and E. Fortunato, "Plastic Compatible Sputtered Ta2O5 Sensitive Layer for Oxide Semiconductor TFT Sensors", Display Technology, Journal of, vol. 9, issue 9, pp. 723-728, 2013. Abstract

The effect of post-deposition annealing temperature on the pH sensitivity of room temperature RF sputtered Ta2O5 was investigated. Structural and morphological features of these films were analyzed before and after annealing at various temperatures. The deposited films are amorphous up to 600 °C and crystallize at 700 °C in an orthorhombic phase. Electrolyte-insulator-semiconductor (EIS) field effect based sensors with an amorphous Ta2O5 sensing layer showed pH sensitivity above 50 mV/pH. For sensors annealed above 200 °C pH sensitivity decreased with increasing temperature. Stabilized sensor response and maximum pH sensitivity was achieved after low temperature annealing at 200 °C, which is compatible with the use of polymeric substrates and application as sensitive layer in oxides TFT-based sensors.

Santos, R., J. Loureiro, A. Nogueira, E. Elangovan, J. V. Pinto, J. P. Veiga, T. Busani, E. Fortunato, R. Martins, and I. Ferreira, "Thermoelectric properties of V2O5 thin films deposited by thermal evaporation", Applied Surface Science, vol. 282, pp. 590-594, 2013. AbstractWebsite
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Cruz, M. M., R. C. Silva, J. V. Pinto, R. P. Borges, N. Franco, and A. Casaca, "{Formation of oriented nickel aggregates in rutile single crystals by Ni implantation}", Journal of Magnetism and Magnetic Materials, vol. 340: Elsevier, pp. 102–108, 2013. AbstractWebsite

The magnetic and electrical properties of Ni implanted single crystalline TiO2 rutile were studied for nominal implanted fluences between 0.5?1017 cm−2 and 2.0?1017 cm−2 with 150 keV energy, corre- sponding to maximum atomic concentrations between 9 at{%} and 27 at{%} at 65 nm depth, in order to study the formation of metallic oriented aggregates. The results indicate that the as implanted crystals exhibit superparamagnetic behavior for the two higher fluences, which is attributed to the formation of nanosized nickel clusters with an average size related with the implanted concentration, while only paramagnetic behavior is observed for the lowest fluence. Annealing at 1073 K induces the aggregation of the implanted nickel and enhances the magnetization in all samples. The associated anisotropic behavior indicates preferred orientations of the nickel aggregates in the rutile lattice consistent with Rutherford backscattering spectrometry—channelling results. Electrical conductivity displays anisotropic behavior but no magnetoresistive effects were detected.

Figueiredo, V., J. V. Pinto, J. Deuermeier, R. Barros, E. Alves, R. Martins, and E. Fortunato, "{p-Type Cu O Thin-Film Transistors Produced by Thermal Oxidation}", Journal of Display Technology, vol. 9, no. 9, pp. 735–740, 2013. Abstract

Thin-films of copper oxide Cu O were produced by thermal oxidation of metallic copper (Cu) at different tempera- tures (150–450 C). The films produced at temperatures of 200, 250 and 300 C showed high Hall motilities of 2.2, 1.9 and 1.6 cm V s , respectively. Single Cu O phases were obtained at 200 Cand its conversion toCuO starts at 250 C. For lower thick- nesses 40 nm, the films oxidized at 250 Cshowed a complete conversion to CuO phase. Successful thin-film transistors (TFTs) were produce by thermal oxidation of a 20 nm Cu film, obtaining p-type Cu O (at 200 C) and CuO (at 250 C) with On/Off ratios of 6 10 and 1 10 , respectively.

Branquinho, R., J. V. Pinto, T. Busani, P. Barquinha, L. Pereira, P. V. Baptista, R. Martins, and E. Fortunato, "{Plastic Compatible Sputtered Ta O Sensitive Layer for Oxide Semiconductor TFT Sensors}", Journal of Display Technology, vol. 9, no. 9, pp. 723–728, 2013. Abstract

The effect of post-deposition annealing temperature on the pH sensitivity of room temperature RF sputtered Ta O was investigated. Structural and morphological features of these films were analyzed before and after annealing at various tem- peratures. The deposited films are amorphous up to 600 Cand crystallize at 700 C in an orthorhombic phase. Electrolyte-insu- lator-semiconductor (EIS) field effect based sensors with an amor- phousTa O sensing layer showed pHsensitivity above 50 mV/pH. For sensors annealed above 200 C pH sensitivity decreased with increasing temperature. Stabilized sensor response andmaximum pHsensitivitywas achieved after low temperature annealing at 200 C, which is compatible with the use of polymeric substrates and application as sensitive layer in oxides TFT-based sensors

2012
Figueiredo, V., E. Elangovan, R. Barros, J. V. Pinto, T. Busani, R. Martins, and E. Fortunato, "{p-Type Cu x O Films Deposited at Room Temperature for Thin-Film Transistors}", Journal of Display Technology, vol. 8, no. 1, pp. 41–47, 2012. Abstract

Thin-films of copper oxide @Cu OA were sputtered from a metallic copper (Cu) target and studied as a function of oxygen partial pressure @O??A. A metallic Cu film with cubic structure obtained from 0{%} O?? has been transformed to cubic CuPO phase for the increase in O?? to 9{%} but then changed to monoclinic CuO phase (for O?? PS7). The variation in crystallite size (calculated from x-ray diffraction data) was further substantiated by the variation in grain size (surface microstruc- tures). The Cu O films produced with O?? ranging between 9{%} and 75{%} showed p-type behavior, which were successfully applied to produce thin-film transistors.

2011
Branquinho, R., B. Veigas, J. V. Pinto, R. Martins, E. Fortunato, and P. V. Baptista, "Real-time monitoring of PCR amplification of proto-oncogene c-MYC using a Ta2O5 electrolyte-insulator-semiconductor sensor", Biosensors & Bioelectronics, vol. 28, issue 1, pp. 44-49, 2011. Abstract
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2007
Borges, R. P., J. V. Pinto, R. C. da Silva, A. P. Goncalves, M. M. Cruz, and M. Godinho, "Ferromagnetism in ZnO doped with Co by ion implantation", Journal of Magnetism and Magnetic Materials, vol. 316, issue 2, pp. E191-E194, 2007. AbstractWebsite
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2002
Raiola, F., P. Migliardi, G. Gyurky, M. Aliotta, A. Formicola, R. Bonetti, C. Broggini, L. Campajola, P. Corvisiero, H. Costantini, J. Cruz, A. D'Onofrio, Z. Fulop, G. Gervino, L. Gialanella, A. Guglielmetti, G. Imbriani, C. Gustavino, A. P. Jesus, M. Junker, R. W. Kavanagh, P. G. P. Moroni, A. Ordine, J. V. Pinto, P. Prati, V. Roca, J. P. Ribeiro, D. Rogalla, C. Rolfs, M. Romano, F. Schumann, D. Schurmann, E. Somorjai, F. Strieder, F. Terrasi, H. P. Trautvetter, and S. Zavatarelli, "Enhanced electron screening in d(d, p)t for deuterated Ta", European Physical Journal A, vol. 13, issue 3, pp. 377-382, 2002. AbstractWebsite
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Casella, C., H. Costantini, A. Lemut, B. Limata, R. Bonetti, C. Broggini, L. Campajola, P. Corvisiero, J. Cruz, A. D'Onofrio, A. Formicola, Z. Fulop, G. Gervino, L. Gialanella, A. Guglielmetti, C. Gustavino, G. Gyurky, G. Imbriani, A. P. Jesus, M. Junker, A. Ordine, J. V. Pinto, P. Prati, J. P. Ribeiro, V. Roca, D. Rogalla, C. Rolfs, M. Romano, C. Rossi-Alvarez, F. Scheumann, E. Somorjai, O. Straniero, F. Strieder, F. Terrasi, H. P. Tratuvetter, S. Zavatarelli, and L. Collaboration, "First measurement of the d(p, gamma)He-3 cross section down to the solar Gamow peak", Nuclear Physics A, vol. 706, issue 1-2, pp. 203-216, 2002. AbstractWebsite
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Casella, C., H. Costantini, A. Lemut, B. Limata, D. Bemmerer, R. Bonetti, C. Broggini, L. Campajola, P. Cocconi, P. Corvisiero, J. Cruz, A. D'Onofrio, A. Formicola, Z. Fulop, G. Gervino, L. Gialanella, A. Guglielmetti, C. Gustavino, G. Gyurky, A. Loiano, G. Imbriani, A. P. Jesus, M. Junker, P. Musico, A. Ordine, F. Parodi, M. Parolin, J. V. Pinto, P. Prati, J. P. Ribeiro, V. Roca, D. Rogalla, C. Rolfs, M. Romano, C. Rossi-Alvarez, A. Rottura, F. Schuemann, E. Somorjai, F. Strieder, F. Terrasi, H. P. Trautvetter, A. Vomiero, and S. Zavatarelli, "A new setup for the underground study of capture reactions", Nuclear Instruments & Methods in Physics Research Section a-Accelerators Spectrometers Detectors and Associated Equipment, vol. 489, issue 1-3, pp. 160-169, 2002. AbstractWebsite
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Mateus, R., A. P. Jesus, B. Braizinha, J. Cruz, J. V. Pinto, and J. P. Ribeiro, "Proton-induced gamma-ray analysis of lithium in thick samples", Nuclear Instruments & Methods in Physics Research Section B-Beam Interactions with Materials and Atoms, vol. 190, pp. 117-121, 2002. AbstractWebsite
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