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Journal Article
Ceia, T. F., A. G. Silva, C. S. Ribeiro, J. V. Pinto, M. H. Casimiro, A. M. Ramos, and J. Vital, "PVA composite catalytic membranes for hyacinth flavour synthesis in a pervaporation membrane reactor", Catalysis Today, vol. 236, pp. 98-107, 2014. Abstract
Alves, E., R. C. da Silva, J. V. Pinto, T. Monteiro, B. Savoini, D. Caceres, R. Gonzalez, and Y. Chen, "Radiation-damage recovery in undoped and oxidized Li doped MgO crystals implanted with lithium ions", Nuclear Instruments & Methods in Physics Research Section B-Beam Interactions with Materials and Atoms, vol. 206, pp. 148-152, 2003. AbstractWebsite
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
Cruz, M. M., J. V. Pinto, R. C. da Silva, E. Alves, R. Gonzalez, and M. Godinho, "Relaxation behaviour of Co and Ni implanted into MgO", Journal of Magnetism and Magnetic Materials, vol. 316, issue 2, pp. E776-E778, 2007. AbstractWebsite
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

Gonçalves, A., J. Resende, A. C. Marques, J. V. Pinto, D. Nunes, A. Marie, R. Gonçalves, L. Pereira, R. Martins, and E. Fortunato, "Smart optically active VO nanostructured layers applied in roof-type ceramic tiles for energy efficiency", Solar Energy Materials & Solar Cells, vol. 150, pp. 1-9, 2016.
Pinto, J. V., R. C. da Silva, E. Alves, M. J. Soares, T. Monteiro, and R. Gonzalez, "Stability and optical activity of Er implanted MgO", Nuclear Instruments & Methods in Physics Research Section B-Beam Interactions with Materials and Atoms, vol. 218, pp. 128-132, 2004. AbstractWebsite
Santos, L., P. Wojcik, J. V. Pinto, E. Elangovan, J. Viegas, L. Í. Pereira, R. Martins, and E. Fortunato, "Structure and Morphologic Influence of WO3 Nanoparticles on the Electrochromic Performance of Dual-Phase a-WO3/WO3 Inkjet Printed Films", Advanced Electronic Materials, pp. n/a-n/a, 2015. AbstractWebsite

The optimization of tungsten trioxide (WO3) nanoparticles produced via hydrothermal synthesis for application in electrochromic (EC) devices is reported. The structure and morphology of the nanoparticles are controlled by changing the acidity of the aqueous solvent added to the sol-gel precursor (peroxopolytungstic acid) during synthesis. Orthorhombic hydrated WO3 nanorods or monoclinic WO3 nanoslabs are obtained when HCl is added, while synthesis only in aqueous medium results in a mixture of both types of polymorphs. Dual-phase thin films are processed by inkjet printing deposition of the nanoparticles in flexible polyethylene terephthalate substrate with indium tin oxide coating (ITO PET) followed by the deposition of the precursor solution. When compared with purely amorphous tungsten oxide films, the dual phase ones present higher optical densities and improved capacity, and cyclability stability. The best results, obtained for orthorhombic hydrated nanoparticles (ortho-WO3·0.33H2O), are due to its high surface area and improved conductivity. Additionally, the ex situ X-ray diffraction (XRD) lithiation studies show evidence of a higher distortion of the monoclinic when compared with the orthorhombic crystallographic structure, which contribute to the inferior EC performance. These results validate the use of inkjet printing deposition with low processing temperatures for EC dual-phase thin films containing optimized nanoparticles which are compatible with low-cost substrates.

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
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. Fülöp, G. Gervino, L. Gialanella, a. Guglielmetti, C. Gustavino, G. Gyurky, a. Loiano, G. Imbriani, P. a. 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 and Methods in Physics Research, Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, vol. 489, pp. 160–169, 2002. Abstract

For the study of astrophysically relevant capture reactions in the underground laboratory LUNA a new setup of high sensitivity has been implemented. The setup includes a windowless gas target, a 4$π$ BGO summing crystal, and beam calorimeters. The setup has been recently used to measure the d(p,$\gamma$)3He cross-section for the first time within its solar Gamow peak, i.e. down to 2.5keV c.m. energy. The features of the optimized setup are described. © 2002 Elsevier Science B.V. All rights reserved.

Otero, V., M. F. Campos, J. V. Pinto, M. Vilarigues, L. Carlyle, and M. J. Melo, "{Barium, zinc and strontium yellows in late 19th-early 20th century oil paintings}", Heritage Science, vol. 5, no. 1, 2017. Abstract

© 2017 The Author(s). This work focuses on the study of the 19th century yellow chromate pigments based on barium (BaCrO4), zinc (4ZnCrO4K2O3H2O) and strontium (SrCrO4). These pigments, which are reported to shift in hue and darken, have been found in 19th century artworks. A better understanding of their historic manufacture will contribute to the visual/chemical interpretation of change in these colours. Research was carried out on the Winsor & Newton (W&N) 19th century archive database providing a unique insight into their manufacturing processes. One hundred and three production records were found, 69% for barium, 25% for zinc and 6% for strontium chromates, mainly under the names Lemon, Citron and Strontian Yellow, respectively. Analysis of the records shows that each pigment is characterised by only one synthetic pathway. The low number of records found for the production of strontium chromate suggests W&N was not selling this pigment formulation on a large scale. Furthermore, contrary to what the authors have discovered for W&N chrome yellow pigments, extenders were not added to these pigment formulations, most probably due to their lower tinting strength (TS). The latter was calculated in comparison to pure chrome yellow (PbCrO4, 100% TS) resulting in 92% for barium, 65% for zinc potassium and 78% for strontium chromate pigments. This indicates that W&N was probably using extenders primarily to adjust pigment properties and not necessarily as a means to reduce their costs. Pigment reconstructions following the main methods of synthesis were characterised by complementary analytical techniques: Fibre optic reflectance spectroscopy, X-ray diffraction, micro-Raman and micro-Fourier transform infrared spectroscopies. These pigments can be clearly distinguished on the basis of their infrared CrO42-asymmetric stretching fingerprint profile (between 1000 and 700 cm-1) and of their Raman CrO42-stretching bands (850-950 cm-1). This enabled their identification in historic paint samples: a tube of late 19th century W&N Lemon Yellow oil paint and micro-samples from paintings by three Portuguese painters, António Silva Porto (1850-1893), João Marques de Oliveira (1853-1927) and Amadeo de Souza-Cardoso (1887-1918). The good correlation found between the reconstructions and historic samples validates their use as reference materials for future photochemical studies.

Correia, R., J. Deuermeier, M. R. Correia, J. {Vaz Pinto}, J. Coelho, E. Fortunato, and R. Martins, "{Biocompatible Parylene-C Laser-Induced Graphene Electrodes for Microsupercapacitor Applications}", ACS Applied Materials {&} Interfaces, vol. 14, no. 41: American Chemical Society, pp. 46427–46438, oct, 2022. AbstractWebsite
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

Kardarian, K., D. Nunes, P. {Maria Sberna}, A. Ginsburg, D. A. Keller, J. {Vaz Pinto}, J. Deuermeier, A. Y. Anderson, A. Zaban, R. Martins, and E. Fortunato, "{Effect of Mg doping on Cu2O thin films and their behavior on the TiO2/Cu2O heterojunction solar cells}", Solar Energy Materials and Solar Cells, vol. 147, pp. 27–36, apr, 2016. AbstractWebsite

Abstract The present work shows the effect of magnesium doping on structural, optoelectrical and electrical properties of Cu2O thin films prepared by spray pyrolysis. The variation in the concentration of Mg shows significant impact on the final thin film properties, whereas the film doped with 0.5 at{%} of Mg exhibited major property improvements in comparison with the undoped thin film and among the other concentrations tested. This condition was further applied for the deposition of an absorber layer in a heterojunction solar cell array with a gradient in thicknesses of active layers to investigate the impact of changing thicknesses on the PV parameters of the solar cell. TiO2 was used as a window layer and the 0.5 at{%} Cu2O doped film as an absorber layer. The produced heterojunction solar cell array was further exposed to a rapid thermal annealing treatment. The I–V measurements show an open circuit voltage of up to 365 mV and a short circuit current density, which is dependent on absorber layer thickness, and reaches to a maximum value of 0.9 mA/cm2.

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.

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
Otero, V., J. V. V. Pinto, L. Carlyle, M. Vilarigues, M. Cotte, and M. J. J. Melo, "{Nineteenth century chrome yellow and chrome deep from Winsor & NewtonTM}", Studies in Conservation, vol. 62, no. 3, pp. 123–149, 2017. AbstractWebsite

The Winsor & NewtonTM (W&N) nineteenth century archive database includes digitised images of hand- written instructions and workshop notes for the manufacture of their artists' materials. For the first time, all 183 production records for yellow lead chromate pigments were studied and evaluated. They revealed that W&N produced essentially three pigment types: lemon/pale based on mixed crystals of lead chromate and lead sulphate [Pb(Cr,S)O4]; middle on pure monoclinic lead chromate [PbCrO4]; and deep that contains the latter admixed with basic lead chromate [Pb2CrO5]; accounting for 53, 22, and 21% of the production, respectively. Production records for primrose (4%) were also included since the formulation results in mixed crystals with a high percentage of lead sulphate, which, according to the literature, leaves it more prone to degradation. Each pigment type is characterised by only one or two main synthetic pathways; process variations reveal a systematic and thorough search for a high-quality durable product. A comparison of the chemical composition of pigment reconstructions with early W&N oil paint tubes showed that their records entitled ‘pale' and ‘lemon' correlated with the pigment in their tube labelled chrome yellow and, ‘middle' and ‘deep' with the label chrome deep. Lemon and middle pigment formulations were made into oil paints to assess their relative photo-stability. The degradation process was followed by colorimetry and was studied by synchrotron radiation-based techniques. Based on the X-ray absorption spectroscopy data, the possibility for creating a stability index for chrome yellows is discussed. Keywords:

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.

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.

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.

Coelho, J., R. F. Correia, S. Silvestre, T. Pinheiro, A. C. Marques, R. M. P. Correia, J. V. Pinto, E. Fortunato, and R. Martins, "{Paper-based laser-induced graphene for sustainable and flexible microsupercapacitor applications}", Microchimica Acta, vol. 190, no. 1, pp. 1–10, 2023. Abstract

Laser-induced graphene (LIG) is as a promising material for flexible microsupercapacitors (MSCs) due to its simple and cost-effective processing. However, LIG-MSC research and production has been centered on non-sustainable polymeric substrates, such as polyimide. In this work, it is presented a cost-effective, reproducible, and robust approach for the preparation of LIG structures via a one-step laser direct writing on chromatography paper. The developed strategy relies on soaking the paper in a 0.1 M sodium tetraborate solution (borax) prior to the laser processing. Borax acts as a fire-retardant agent, thus allowing the laser processing of sensitive substrates that other way would be easily destroyed under the high-energy beam. LIG on paper exhibiting low sheet resistance (30 $Ømega$ sq−1) and improved electrode/electrolyte interface was obtained by the proposed method. When used as microsupercapacitor electrodes, this laser-induced graphene resulted in specific capacitances of 4.6 mF cm−2 (0.015 mA cm−2). Furthermore, the devices exhibit excellent cycling stability (> 10,000 cycles at 0.5 mA cm−2) and good mechanical properties. By connecting the devices in series and parallel, it was also possible to control the voltage and energy delivered by the system. Thus, paper-based LIG-MSC can be used as energy storage devices for flexible, low-cost, and portable electronics. Additionally, due to their flexible design and architecture, they can be easily adapted to other circuits and applications with different power requirements. Graphical Abstract: [Figure not available: see fulltext.]

Pinheiro, A., A. Ruivo, M. Ferro, J. V. Pinto, J. Deuermeier, T. Mateus, A. Santa, M. J. Mendes, R. Martins, S. Gago, C. A. T. Laia, and Á. Hugo, {Parylene-Sealed Perovskite Nanocrystals Down-Shifting Layer for Luminescent Spectral Matching in Thin Film Photovoltaics}, , 2023. Abstract
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
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.

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