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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).

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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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.

Liu, A, Liu GX, Zhu HH, Xu F, Fortunato E, Martins R, Shan FK.  2014.  {Fully Solution-Processed Low-Voltage Aqueous In2O3 Thin-Film Transistors Using an Ultrathin ZrOx Dielectric}. ACS Applied Materials {&} Interfaces. 6:17364–17369., Number 20 AbstractWebsite

We reported here ?aqueous-route? fabrication of In2O3 thin-film transistors (TFTs) using an ultrathin solution-processed ZrOx dielectric thin film. The formation and properties of In2O3 thin films under various annealing temperatures were intensively examined by thermogravimetric analysis, Fourier transform infrared spectroscopy, and atomic force microscopy. The solution-processed ZrOx thin film followed by sequential UV/ozone treatment and low-temperature thermal-annealing processes showed an amorphous structure, a low leakage-current density (?1 ? 10?9 A/cm2 at 2 MV/cm), and a high breakdown electric field (?7.2 MV/cm). On the basis of its implementation as the gate insulator, the In2O3 TFTs based on ZrOx annealed at 250 °C exhibit an on/off current ratio larger than 107, a field-effect mobility of 23.6 cm2/V·s, a subthreshold swing of 90 mV/decade, a threshold voltage of 0.13 V, and high stability. These promising properties were obtained at a low operating voltage of 1.5 V. These results suggest that ?aqueous-route? In2O3 TFTs based on a solution-processed ZrOx dielectric could potentially be used for low-cost, low-temperature-processing, high-performance, and flexible devices.

Liu, GX, Liu A, Shan FK, Meng Y, Shin BC, Fortunato E, Martins R.  2014.  {High-performance fully amorphous bilayer metal-oxide thin film transistors using ultra-thin solution-processed ZrOx dielectric}. Applied Physics Letters. 105:113509., Number 11 AbstractWebsite

In this study, we report high-performance amorphous In2O3/InZnO bilayer metal-oxide (BMO) thin-film transistor (TFT) using an ultra-thin solution-processed amorphous ZrOx dielectric. A thin layer of In2O3 offers a higher carrier concentration, thereby maximizing the charge accumulation and yielding high carrier mobility. A thick amorphous layer of InZnO controls the charge conductance resulting in low off-state current and suitable threshold voltage. As a consequence, the BMO TFT showed higher filed-effect mobility (37.9 cm2/V s) than single-layer InZnO TFT (7.6 cm2/V s). Apart from that we obtain an on/off current ratio of 109, a subthreshold swing voltage of 120 mV/decade, and a voltage shift ≤ 0.4 V under positive bias stress for 2.5 h, for a gate voltage of 3 V and drain voltage of 1 V. These data demonstrate that the BMO TFT has great potential for a broad range of applications as switching low-power transistors.

Deuermeier, J, Wardenga HF, Morasch J, Siol S, Nandy S, Calmeiro T, Martins R, Klein A, Fortunato E.  2016.  {Highly conductive grain boundaries in copper oxide thin films}, jun. JOURNAL OF APPLIED PHYSICS. 119, Number 23 Abstract
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Bahubalindruni, PG, Kiazadeh A, Sacchetti A, Martins J, Rovisco A, Tavares VG, Martins R, Fortunato E, Barquinha P.  2016.  {Influence of Channel Length Scaling on InGaZnO TFTs Characteristics: Unity Current-Gain Cutoff Frequency, Intrinsic Voltage-Gain, and On-Resistance}, jun. JOURNAL OF DISPLAY TECHNOLOGY. 12:515–518., Number 6 Abstract
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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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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.

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.

Cramer, T, Sacchetti A, Lobato MT, Barquinha P, Fischer V, Benwadih M, Bablet J, Fortunato E, Martins R, Fraboni B.  2016.  {Radiation-Tolerant Flexible Large-Area Electronics Based on Oxide Semiconductors}, jul. ADVANCED ELECTRONIC MATERIALS. 2, Number 7 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.

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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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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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.

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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Besleaga, C, Stan GE, Pintilie I, Barquinha P, Fortunato E, Martins R.  2016.  {Transparent field-effect transistors based on AlN-gate dielectric and IGZO-channel semiconductor}. Applied Surface Science. 379:270–276. AbstractWebsite

The degradation of thin-film transistors (TFTs) caused by the self-heating effect constitutes a problem to be solved for the next generation of displays. Aluminum nitride (AlN) is a viable alternative for gate dielectric of TFTs due to its good thermal conductivity, matching coefficient of thermal expansion to indium–gallium–zinc-oxide, and excellent stability at high temperatures. Here, AlN thin films of different thicknesses were fabricated by a low temperature reactive radio-frequency magnetron sputtering process, using a low cost, metallic Al target. Their electrical properties have been thoroughly assessed. Furthermore, the 200 nm and 500 nm thick AlN layers have been integrated as gate-dielectric in transparent TFTs with indium–gallium–zinc-oxide as channel semiconductor. Our study emphasizes the potential of AlN thin films for transparent electronics, whilst the functionality of the fabricated field-effect transistors is explored and discussed.

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.