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Zubizarreta, C, Berasategui EG, Bayon R, Galindo ER, Barros R, Gaspar D, Nunes D, Calmeiro T, Martins R, Fortunato E, Barriga J.  2014.  {Evaluation of the optoelectronic properties and corrosion behavior of Al2O3-doped ZnO films prepared by dc pulsed magnetron sputtering}. JOURNAL OF PHYSICS D-APPLIED PHYSICS. 47, Number 48 Abstract
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Zanarini, S, Garino N, Nair JR, Francia C, Wojcik PJ, Pereira L, Fortunato E, Martins R, Bodoardo S, Penazzi N.  2014.  {Contrast Enhancement in Polymeric Electrochromic Devices Encompassing Room Temperature Ionic Liquids}. International Journal of Electrochemical Science. 9:1650–1662., Number 4 Abstract
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Wojcik, PJ, Santos L, Pereira L, Martins R, Fortunato E.  2015.  {Tailoring nanoscale properties of tungsten oxide for inkjet printed electrochromic devices}. Nanoscale. 7:1696–1708., Number 5: Royal Society of Chemistry AbstractWebsite

This paper focuses on the engineering procedures governing the synthesis of tungsten oxide nanocrystals and the formulation of printable dispersions for electrochromic applications. By that means, we aim to stress the relevancy of a proper design strategy that results in improved physicochemical properties of nanoparticle loaded inks. In the present study inkjet printable nanostructured tungsten oxide particles were successfully synthesized via hydrothermal processes using pure or acidified aqueous sol-gel precursors. Based on the proposed scheme, the structure and morphology of the nanoparticles were tailored to ensure the desired printability and electrochromic performance. The developed nanomaterials with specified structures effectively improved the electrochemical response of printed films, resulting in 2.5 times higher optical modulation and 2 times faster coloration time when compared with pure amorphous films.

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Vicente, A, Águas H, Mateus T, Araújo A, Lyubchyk A, Siitonen S, Fortunato E, Martins R.  2015.  {Solar cells for self-sustainable intelligent packaging}. J. Mater. Chem. A. 3:13226–13236., Number 25 AbstractWebsite
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Veigas, B, Fortunato E, Baptista PV.  2015.  {Field Effect Sensors for Nucleic Acid Detection: Recent Advances and Future Perspectives}, jan. Sensors. 15:10380–10398., Number 5: Multidisciplinary Digital Publishing Institute AbstractWebsite

In the last decade the use of field-effect-based devices has become a basic structural element in a new generation of biosensors that allow label-free DNA analysis. In particular, ion sensitive field effect transistors (FET) are the basis for the development of radical new approaches for the specific detection and characterization of DNA due to FETs' greater signal-to-noise ratio, fast measurement capabilities, and possibility to be included in portable instrumentation. Reliable molecular characterization of DNA and/or RNA is vital for disease diagnostics and to follow up alterations in gene expression profiles. FET biosensors may become a relevant tool for molecular diagnostics and at point-of-care. The development of these devices and strategies should be carefully designed, as biomolecular recognition and detection events must occur within the Debye length. This limitation is sometimes considered to be fundamental for FET devices and considerable efforts have been made to develop better architectures. Herein we review the use of field effect sensors for nucleic acid detection strategies—from production and functionalization to integration in molecular diagnostics platforms, with special focus on those that have made their way into the diagnostics lab.

Veigas, B, Branquinho R, Pinto JV, Wojcik PJ, Martins R, Fortunato E, Baptista PV.  2014.  {Ion sensing (EIS) real-time quantitative monitorization of isothermal DNA amplification}. Biosensors and Bioelectronics. 52:50–55. AbstractWebsite

Field-effect-based devices are becoming a basic structural element in a new generation of microbiosensors. Reliable molecular characterization of DNA and/or RNA is of paramount importance for disease diagnostics and to follow up alterations in gene expression profiles. The use of such devices for point-of-need diagnostics has been hindered by the need of standard or real-time PCR amplification procedures. The present work focuses on the development of a tantalum pentoxide (Ta2O5) based sensor for the real-time label free detection of DNA amplification via loop mediated isothermal amplification (LAMP) allowing for quantitative analysis of the cMYC proto-oncogene. The strategy based on the field effect sensor was tested within a range of 1×108–1011 copies of target DNA, and a linear relationship between the log copy number of the initial template DNA and threshold time was observed allowing for a semi-quantitative analysis of DNA template. The concept offers many of the advantages of isothermal quantitative real-time DNA amplification in a label free approach and may pave the way to point-of-care quantitative molecular analysis focused on ease of use and low cost.

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Ullaha, S, Matteis DF, Branquinho R, Fortunato E, Martins R, Davoli I.  2015.  {A combination of solution synthesis solution combustion synthesis for highly conducting and transparent Aluminum Zinc Oxide thin films}. 2015 IEEE 15th International Conference on Nanotechnology (IEEE-NANO). :144–147. Abstract

Aluminum Zinc Oxide has been extensively investigated as a cheap alternative to transparent conducting tin oxide films for electronic and optoelectronic applications. Thin films of Aluminum Zinc Oxide have been developed successfully through a combination of solution combustion synthesis and solution synthesis. Zn(NO3)3·6H2O as metal source was dissolved in 2-methoxyethanol as solvent through combustion synthesis with Urea as fuel while dopant source of AlCl3·6H2O was mixed separately in solvent to avoid aluminum oxide formation in the films. Precursor solutions were obtained mixing Zn {&} Al separate solutions in 9:1, 8:2, and 7:3 ratios respectively with oxide, fuel and dopant concentrations of 0.5, 0.25, 0.1, and 0.05 M. The film stacks have been prepared through spin-coating with heating at 400°C for 10 minutes after each deposition to remove residuals and evaporate solvents. Thermal annealing in oven at 600°C for 1 hour followed by rapid thermal annealing at 500°C {&} 600°C first in vacuum and then in N2-5{%}H2 environment respectively for 10 minutes each reduced the resistivity of film stacks. Film stack with 10 layers for an average thickness of 0.5$μ$m gave the best Hall Effect resistivity of 3.2 × 10-2 $Ømega$-cm in the case of 0.5M solution with Zn:Al mixing ratio of 9:1 for RTA annealings at 600°C with an average total transparency of 80 {%} in the wavelength range of 400-1200 nm. The results show a clear trend that increasing the amount of ingredients resistivity could further be decreased.

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Santos, L, Wojcik P, Pinto JV, Elangovan E, Viegas J, Pereira LÍ, Martins R, Fortunato E.  2015.  {Structure and Morphologic Influence of WO 3 Nanoparticles on the Electrochromic Performance of Dual-Phase a -WO 3 /WO 3 Inkjet Printed Films}, feb. Advanced Electronic Materials. 1:n/a–n/a., Number 1-2 AbstractWebsite
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Santos, L, Neto JP, Crespo A, Nunes D, Costa N, Fonseca IM, Barquinha P, Pereira LÍ, Silva J, Martins R, Fortunato E.  2014.  {WO3 Nanoparticle-Based Conformable pH Sensor}. ACS Applied Materials {&} Interfaces. 6:12226–12234., Number 15 AbstractWebsite

pH is a vital physiological parameter that can be used for disease diagnosis and treatment as well as in monitoring other biological processes. Metal/metal oxide based pH sensors have several advantages regarding their reliability, miniaturization, and cost-effectiveness, which are critical characteristics for in vivo applications. In this work, WO3 nanoparticles were electrodeposited on flexible substrates over metal electrodes with a sensing area of 1 mm2. These sensors show a sensitivity of ?56.7 ± 1.3 mV/pH, in a wide pH range of 9 to 5. A proof of concept is also demonstrated using a flexible reference electrode in solid electrolyte with a curved surface. A good balance between the performance parameters (sensitivity), the production costs, and simplicity of the sensors was accomplished, as required for wearable biomedical devices.

Santos, L, Nunes D, Calmeiro T, Branquinho R, Salgueiro D, Barquinha P, Pereira LÍ, Martins R, Fortunato E.  2015.  {Solvothermal synthesis of gallium-indium-zinc-oxide nanoparticles for electrolyte-gated transistors.}, jan. ACS applied materials {&} interfaces. 7:638–46., Number 1 AbstractWebsite

Solution-processed field-effect transistors are strategic building blocks when considering low-cost sustainable flexible electronics. Nevertheless, some challenges (e.g., processing temperature, reliability, reproducibility in large areas, and cost effectiveness) are requirements that must be surpassed in order to achieve high-performance transistors. The present work reports electrolyte-gated transistors using as channel layer gallium-indium-zinc-oxide nanoparticles produced by solvothermal synthesis combined with a solid-state electrolyte based on aqueous dispersions of vinyl acetate stabilized with cellulose derivatives, acrylic acid ester in styrene and lithium perchlorate. The devices fabricated using this approach display a ION/IOFF up to 1 × 10(6), threshold voltage (VTh) of 0.3-1.9 V, and mobility up to 1 cm(2)/(V s), as a function of gallium-indium-zinc-oxide ink formulation and two different annealing temperatures. These results validates the usage of electrolyte-gated transistors as a viable and promising alternative for nanoparticle based semiconductor devices as the electrolyte improves the interface and promotes a more efficient step coverage of the channel layer, reducing the operating voltage when compared with conventional dielectrics gating. Moreover, it is shown that by controlling the applied gate potential, the operation mechanism of the electrolyte-gated transistors can be modified from electric double layer to electrochemical doping.

Santos, L, Silveira CM, Elangovan E, Neto JP, Nunes D, Pereira LÍ, Martins R, Viegas J, Moura JJG, Todorovic S, Almeida GM, Fortunato E.  2016.  {Synthesis of WO3 nanoparticles for biosensing applications}, feb. Sensors and Actuators B: Chemical. 223:186–194. AbstractWebsite
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Rodrigues, J, Mata D, Pimentel A, Nunes D, Martins R, Fortunato E, Neves AJ, Monteiro T, Costa FM.  2015.  {One-step synthesis of ZnO decorated CNT buckypaper composites and their optical and electrical properties}, may. Materials Science and Engineering: B. 195:38–44. AbstractWebsite
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Rodrigues, J, Cerqueira AFR, Sousa MG, Santos NF, Pimentel A, Fortunato E, da Cunha AF, Monteiro T, Costa FM.  Submitted.  {Exploring the potential of laser assisted flow deposition grown ZnO for photovoltaic applications}. Materials Chemistry and Physics. AbstractWebsite

Zinc oxide (ZnO) is a widely studied wide band gap semiconductor with applications in several fields, namely to enhance solar cells efficiency. Its ability to be grown in a wide variety of nanostructured morphologies, allowing the designing of the surface area architecture constitutes an important advantage over other semiconductors. Laser assisted flow deposition (LAFD) is a recently developed growth method, based on a vapour-solid mechanism, which proved to be a powerful approach in the production of ZnO micro/nanostructures with different morphologies as well as high crystallinity and optical quality. In the present work we report the use of the LAFD technique to grow functional ZnO nanostructures (nanoparticles and tetrapods) working as nano templates to improve the dye-sensitized solar cells (DSSCs) efficiency. The structural and morphological characterization of the as-grown ZnO crystals were performed by X-ray diffraction and electron microscopy, respectively, and the optical quality was assessed by photoluminescence spectroscopy. DSSCs were produced using a combination of these nanostructures, which were subsequently sensitized with N719 dye. An efficiency of ∼3{%} was achieved under simulated AM 1.5 illumination conditions for a dye loading time of 1 h.

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Pimentel, A, Nunes D, Duarte P, Rodrigues J, Costa FM, Monteiro T, Martins R, Fortunato E.  2014.  {Synthesis of Long ZnO Nanorods under Microwave Irradiation or Conventional Heating}. The Journal of Physical Chemistry C. 118:14629–14639., Number 26 AbstractWebsite

The present work reports the synthesis of zinc oxide (ZnO) nanostructures produced either under microwave irradiation using low cost domestic microwave equipment or by conventional heating, both under hydrothermal conditions. X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, room/low temperature photoluminescence, and Raman spectroscopy have been used to investigate the structure, morphology, and optical properties of the produced ZnO nanorods. Identical structures with aspect ratio up to 13 have been achieved for both synthesis routes displaying similar final properties. The hexagonal wurtzite structure has been identified, and a red-orange emission has been detected in the presence of UV irradiation for all the conditions studied. Thermal stability of the as-prepared nanostructures has been evaluated through thermogravimetric measurements revealing an increase of superficial defects. The as-prepared ZnO nanorods were tested as UV sensors on paper substrate, which led to fast response (30 s) and rapid recovery (100 s) times, as well as sensitivity up to 10 indicating that these materials may have a high potential in low cost, disposable UV photodetector applications.

Pimentel, A, Ferreira S, Nunes D, Calmeiro T, Martins R, Fortunato E.  2016.  {Microwave Synthesized ZnO Nanorod Arrays for UV Sensors: A Seed Layer Annealing Temperature Study}. Materials. 9:299., Number 4 AbstractWebsite
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Pereira, L, Gaspar D, Guerin D, a Delattre, Fortunato E, Martins R.  2014.  {The influence of fibril composition and dimension on the performance of paper gated oxide transistors}. Nanotechnology. 25:94007., Number 9 AbstractWebsite

Paper electronics is a topic of great interest due the possibility of having low-cost, disposable and recyclable electronic devices. The final goal is to make paper itself an active part of such devices. In this work we present new approaches in the selection of tailored paper, aiming to use it simultaneously as substrate and dielectric in oxide based paper field effect transistors (FETs). From the work performed, it was observed that the gate leakage current in paper FETs can be reduced using a dense microfiber/nanofiber cellulose paper as the dielectric. Also, the stability of these devices against changes in relative humidity is improved. On other hand, if the pH of the microfiber/nanofiber cellulose pulp is modified by the addition of HCl, the saturation mobility of the devices increases up to 16 cm 2 V −1 s −1 , with an I ON / I OFF ratio close to 10 5 .

Pereira, S, Gonçalves A, Correia N, Pinto J, Pereira LÍ, Martins R, Fortunato E.  2014.  {Electrochromic behavior of NiO thin films deposited by e-beam evaporation at room temperature}. Solar Energy Materials and Solar Cells. 120, Part:109–115. AbstractWebsite

In this work we report the role of thickness on electrochromic behavior of nickel oxide (NiO) films deposited by e-beam evaporation at room temperature on ITO-coated glass. The structure and morphology of films with thicknesses between 100 and 500 nm were analyzed and then correlated with electrochemical response and transmittance modulation when immersed in 0.5 M LiClO4–PC electrolyte. The NiO exhibits an anodic coloration, reaching for the thickest film a transmittance modulation of 66{%} between colored and bleached state, at 630 nm, with a color efficiency of 55 cm2 C−1. Very fast switch between states was obtained, where coloration and bleaching times are 3.6 s cm−2 and 1.4 s cm−2, respectively.

Pavan, M, Rühle S, Ginsburg A, Keller DA, Barad H-N, Sberna PM, Nunes D, Martins R, Anderson AY, Zaban A, Fortunato E.  2015.  {TiO2/Cu2O all-oxide heterojunction solar cells produced by spray pyrolysis}, jan. Solar Energy Materials and Solar Cells. 132:549–556. AbstractWebsite

Here we present for the first time a TiO2/Cu2O all-oxide heterojunction solar cell entirely produced by spray pyrolysis onto fluorine doped tin oxide (FTO) covered glass substrates, using silver as a back contact. A combinatorial approach was chosen to investigate the impact of the TiO2 window layer and the Cu2O light absorber thicknesses. We observe an open circuit voltage up to 350mV and a short circuit current density which is strongly dependent of the Cu2O thickness, reaching a maximum of {\~{}}0.4mA/cm2. Optical investigation reveals that a thickness of 300nm spray pyrolysis deposited Cu2O is sufficient to absorb most photons with an energy above the symmetry allowed optical transition of 2.5eV, indicating that the low current densities are caused by strong recombination in the absorber that consists of small Cu2O grains.

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Nunes, D, Calmeiro TRR, Nandy S, Pinto JVV, Pimentel A, Barquinha P, Carvalho PAA, Walmsley JCC, Fortunato E, Martins R.  2016.  {Charging effects and surface potential variations of Cu-based nanowires}, nov. Thin Solid Films. 601:45–53. 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 {\textgreater} WFCu {\textgreater} WFCu2O.

Nunes, D, Pimentel A, Barquinha P, Carvalho PA, Fortunato E, Martins R.  2014.  {Cu2O polyhedral nanowires produced by microwave irradiation}. JOURNAL OF MATERIALS CHEMISTRY C. 2:6097–6103., Number 30 Abstract
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Nunes, D, Santos L, Duarte P, Pimentel A, Pinto JV, Barquinha P, Carvalho PA, Fortunato E, Martins R.  2015.  {Room temperature synthesis of Cu₂O nanospheres: optical properties and thermal behavior.}, feb. Microscopy and microanalysis : the official journal of Microscopy Society of America, Microbeam Analysis Society, Microscopical Society of Canada. 21:108–19., Number 1 AbstractWebsite

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.

Nandy, S, Gonçalves G, Pinto JV, Busani T, Figueiredo V, Pereira LÍ, {Paiva Martins} RF, Fortunato E.  2013.  {Current transport mechanism at metal-semiconductor nanoscale interfaces based on ultrahigh density arrays of p-type NiO nano-pillars.}. Nanoscale. 5:11699–709., Number 23 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.

Nandy, S, Thapa R, Kumar M, Som T, Bundaleski N, Teodoro OMND, Martins R, Fortunato E.  2015.  {Efficient Field Emission from Vertically Aligned Cu2O1-delta(111) Nanostructure Influenced by Oxygen Vacancy}. ADVANCED FUNCTIONAL MATERIALS. 25:947–956., Number 6 Abstract
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Marques, AC, Santos L, Costa MN, Dantas JM, Duarte P, Gonçalves A, Martins R, Salgueiro CA, Fortunato E.  2015.  {Office paper platform for bioelectrochromic detection of electrochemically active bacteria using tungsten trioxide nanoprobes.}, jan. Scientific reports. 5:9910. AbstractWebsite

Electrochemically active bacteria (EAB) have the capability to transfer electrons to cell exterior, a feature that is currently explored for important applications in bioremediation and biotechnology fields. However, the number of isolated and characterized EAB species is still very limited regarding their abundance in nature. Colorimetric detection has emerged recently as an attractive mean for fast identification and characterization of analytes based on the use of electrochromic materials. In this work, WO3 nanoparticles were synthesized by microwave assisted hydrothermal synthesis and used to impregnate non-treated regular office paper substrates. This allowed the production of a paper-based colorimetric sensor able to detect EAB in a simple, rapid, reliable, inexpensive and eco-friendly method. The developed platform was then tested with Geobacter sulfurreducens, as a proof of concept. G. sulfurreducens cells were detected at latent phase with an RGB ratio of 1.10 ± 0.04, and a response time of two hours.

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Lyubchyk, A, Vicente A, Soule B, Alves PU, Mateus T, Mendes MJ, Águas H, Fortunato E, Martins R.  2016.  {Mapping the Electrical Properties of ZnO-Based Transparent Conductive Oxides Grown at Room Temperature and Improved by Controlled Postdeposition Annealing}, jan. Advanced Electronic Materials. 2:n/a–n/a., Number 1 AbstractWebsite
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