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Branquinho, R, Salgueiro D, Santos L??dia, Barquinha P, Pereira L??s, Martins R, Fortunato E.  2014.  {Aqueous combustion synthesis of aluminum oxide thin films and application as gate dielectric in GZTO solution-based TFTs}. ACS Applied Materials and Interfaces. 6:19592–19599., Number 22 Abstract

Solution processing has been recently considered as an option when trying to reduce the costs associated with deposition under vacuum. In this context, most of the research efforts have been centered in the development of the semiconductors processes nevertheless the development of the most suitable dielectrics for oxide based transistors is as relevant as the semiconductor layer itself. In this work we explore the solution combustion synthesis and report on a completely new and green route for the preparation of amorphous aluminum oxide thin films; introducing water as solvent. Optimized dielectric layers were obtained for a water based precursor solution with 0.1 M concentration and demonstrated high capacitance, 625 nF cm(-2) at 10 kHz, and a permittivity of 7.1. These thin films were successfully applied as gate dielectric in solution processed gallium-zinc-tin oxide (GZTO) thin film transistors (TFTs) yielding good electrical performance such as subthreshold slope of about 0.3 V dec(-1) and mobility above 1.3 cm(2) V(-1) s(-1).

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.

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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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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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.

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.

Fernandes, M, Leones R, Costa AMS, Silva MM, Pereira S, Mano JF, Fortunato E, Rego R, {de Zea Bermudez} V.  2015.  {Electrochromic devices incorporating biohybrid electrolytes doped with a lithium salt, an ionic liquid or a mixture of both}. Electrochimica Acta. 161:226–235.: Elsevier Ltd 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.

Barquinha, P, Pereira S, Pereira LÍ, Wojcik P, Grey P, Martins R, Fortunato E.  2015.  {Flexible and Transparent WO 3 Transistor with Electrical and Optical Modulation}, may. Advanced Electronic Materials. 1:n/a–n/a., Number 5 AbstractWebsite
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Kiazadeh, A, Gomes HL, Barquinha P, Martins J, Rovisco A, Pinto JV, Martins R, Fortunato E.  2016.  {Improving positive and negative bias illumination stress stability in parylene passivated IGZO transistors}. APPLIED PHYSICS LETTERS. 109, Number 5 Abstract
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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.

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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Gaspar, D, Fernandes SN, de Oliveira AG, Fernandes JG, Grey P, Pontes RV, Pereira L, Martins R, Godinho MH, Fortunato E.  2014.  {Nanocrystalline cellulose applied simultaneously as the gate dielectric and the substrate in flexible field effect transistors}. Nanotechnology. 25:94008., Number 9 AbstractWebsite

Cotton-based nanocrystalline cellulose (NCC), also known as nanopaper, one of the major sources of renewable materials, is a promising substrate and component for producing low cost fully recyclable flexible paper electronic devices and systems due to its properties (lightweight, stiffness, non-toxicity, transparency, low thermal expansion, gas impermeability and improved mechanical properties). Here, we have demonstrated for the first time a thin transparent nanopaper-based field effect transistor (FET) where NCC is simultaneously used as the substrate and as the gate dielectric layer in an ‘interstrate' structure, since the device is built on both sides of the NCC films; while the active channel layer is based on oxide amorphous semiconductors, the gate electrode is based on a transparent conductive oxide. Such hybrid FETs present excellent operating characteristics such as high channel saturation mobility ({\textgreater}7 cm 2 V −1 s −1 ), drain–source current on/off modulation ratio higher than 10 5 , enhancement n-type operation and subthreshold gate voltage swing of 2.11 V/decade. The NCC film FET characteristics have been measured in air ambient conditions and present good stability, after two weeks of being processed, without any type of encapsulation or passivation layer. The results obtained are comparable to ones produced for conventional cellulose paper, marking this out as a promising approach for attaining high-performance disposable electronics such as paper displays, smart labels, smart packaging, RFID (radio-frequency identification) and point-of-care systems for self-analysis in bioscience applications, among others.

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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Kiazadeh, A, Salgueiro D, Branquinho R, Pinto J, Gomes HL, Barquinha P, Martins R, Fortunato E.  2015.  {Operational stability of solution based zinc tin oxide/SiO2 thin film transistors under gate bias stress}, jun. APL Materials. 3:062804., Number 6 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, 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.

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, 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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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.

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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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.

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 .

Aguas, H, Mateus T, Vicente A, Gaspar D, Mendes MJ, Schmidt WA, Pereira L, Fortunato E, Martins R.  2015.  {Thin Film Silicon Photovoltaic Cells on Paper for Flexible Indoor Applications}, jun. ADVANCED FUNCTIONAL MATERIALS. 25:3592–3598., Number 23 Abstract
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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.

Branquinho, R, Salgueiro D, Santa A, Kiazadeh A, Barquinha P, Pereira L, Martins R, Fortunato E.  2015.  {Towards environmental friendly solution-based ZTO/AlOx TFTs}. SEMICONDUCTOR SCIENCE AND TECHNOLOGY. 30, Number 2, SI Abstract
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