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2016
Branquinho, R., A. Santa, E. Carlos, D. Salgueiro, P. Barquinha, R. Martins, and E. Fortunato, "{Solution Combustion Synthesis: Applications in Oxide Electronics}", Developments in Combustion Technology: InTech, pp. 397–417, oct, 2016. Abstract

Oxide-based electronics have been well established as an alternative to silicon technology; however, typical processing requires complex, high-vacuum equipment, which is a major drawback, particularly when targeting low-cost applications. The possibility to deposit the materials by low-cost techniques such as inkjet printing has drawn tremendous interest in solution processible materials for electronic applications; however, high processing temperatures still required. To overcome this issue, solution combustion synthesis has been recently pursued. Taking advantage of the exothermic nature of the reaction as a source of energy for localized heating, the precursor solutions can be converted into oxides at lower process temperatures. Theoretically, this can be applied to any metal ions to produce the desired oxide, opening unlimited possibilities to materials' composition and combinations. Solution combustion synthesis has been applied for the production of semiconductor thin films based on ZnO, In2O3, SnO2 and combinations of these oxides, and also for high $ąppa$ dielectrics (Al2O3). All of which are required for numerous electronic devices and applications such as fully oxide-based thin-film transistors (TFTs). The properties of produced thin films are highly dependent on the precursor solution characteristics; hence, the influence of several processing parameters; organic fuel, solvent and annealing temperature was studied. Although precursor solution degradation/oxide formation mechanisms are not yet fully understood, particularly for thin films, we demonstrate that high-performance devices are obtained with combustion solution-based metal oxide thin films. The results clearly show that solution combustion synthesis is becoming one of the most promising methods for low-temperature flexible electronics.

Lorenz, M., M. S. {Ramachandra Rao}, T. Venkatesan, E. Fortunato, P. Barquinha, R. Branquinho, D. Salgueiro, R. Martins, E. Carlos, A. Liu, et al., "{The 2016 oxide electronic materials and oxide interfaces roadmap}", Journal of Physics D: Applied Physics, vol. 49, no. 43: IOP Publishing, pp. 433001, nov, 2016. AbstractWebsite

Oxide electronic materials provide a plethora of possible applications and offer ample opportunity for scientists to probe into some of the exciting and intriguing phenomena exhibited by oxide systems and oxide interfaces. In addition to the already diverse spectrum of properties, the nanoscale form of oxides provides a new dimension of hitherto unknown phenomena due to the increased surface-to-volume ratio. Oxide electronic materials are becoming increasingly important in a wide range of applications including transparent electronics, optoelectronics, magnetoelectronics, photonics, spintronics, thermoelectrics, piezoelectrics, power harvesting, hydrogen storage and environmental waste management. Synthesis and fabrication of these materials, as well as processing into particular device structures to suit a specific application is still a challenge. Further, characterization of these materials to understand the tunability of their properties and the novel properties that evolve due to their nanostructured nature is another facet of the challenge. The research related to the oxide electronic field is at an impressionable stage, and this has motivated us to contribute with a roadmap on 'oxide electronic materials and oxide interfaces'. This roadmap envisages the potential applications of oxide materials in cutting edge technologies and focuses on the necessary advances required to implement these materials, including both conventional and novel techniques for the synthesis, characterization, processing and fabrication of nanostructured oxides and oxide-based devices. The contents of this roadmap will highlight the functional and correlated properties of oxides in bulk, nano, thin film, multilayer and heterostructure forms, as well as the theoretical considerations behind both present and future applications in many technologically important areas as pointed out by Venkatesan. The contributions in this roadmap span several thematic groups which are represented by the following authors: novel field effect transistors and bipolar devices by Fortunato, Grundmann, Boschker, Rao, and Rogers; energy conversion and saving by Zaban, Weidenkaff, and Murakami; new opportunities of photonics by Fompeyrine, and Zuniga-Perez; multiferroic materials including novel phenomena by Ramesh, Spaldin, Mertig, Lorenz, Srinivasan, and Prellier; and concepts for topological oxide electronics by Kawasaki, Pentcheva, and Gegenwart. Finally, Miletto Granozio presents the European action 'towards oxide-based electronics' which develops an oxide electronics roadmap with emphasis on future nonvolatile memories and the required technologies. In summary, we do hope that this oxide roadmap appears as an interesting up-to-date snapshot on one of the most exciting and active areas of solid state physics, materials science, and chemistry, which even after many years of very successful development shows in short intervals novel insights and achievements.

Carlos, E., R. Branquinho, A. Kiazadeh, P. Barquinha, R. Martins, and E. Fortunato, "{UV-Mediated Photochemical Treatment for Low-Temperature Oxide-Based Thin-Film Transistors}", ACS Applied Materials {&} Interfaces, vol. 8, no. 45: American Chemical Society, pp. 31100–31108, nov, 2016. AbstractWebsite

Solution processing of amorphous metal oxides has lately been used as an option to implement in flexible electronics, allowing a reduction of the associated costs and high performance. However, the research has focused more on the semiconductor layer rather than on the insulator layer, which is related to the stability and performance of the devices. This work aims to evaluate amorphous aluminum oxide thin films produced by combustion synthesis and the influence of far-ultraviolet (FUV) irradiation on the properties of the insulator on thin-film transistors (TFTs) using different semiconductors, in order to have compatibility with flexible substrates. An optimized dielectric layer was obtained for an annealing of 30 min assisted by FUV exposure. These thin films were applied in gallium–indium–zinc oxide TFTs as dielectrics showing the best results for TFTs annealed at 180 °C with FUV irradiation: good reproducibility with a subthreshold slope of 0.11 ± 0.01 V dec –1 and a turn-on voltage of −0.12 ± 0.05 V...

2015
Alexa, A., N. Tigau, P. Alexandru, A. Pimentel, R. Branquinho, D. Salgueiro, T. Calmeiro, R. Martins, E. Fortunato, and V. Musat, "{Morphological and optical characterization of transparent thin films obtained at low temperature using ZnO nanoparticles}", Journal of Optoelectronic and Advanced Materials, vol. 17, no. 9, pp. 1288–1295, 2015. Abstract

Transparent metal oxides thin films are a class of inorganic conductors and semiconductors with significant importance for use in portable electronics, displays, flexible electronics, multi-functional windows and solar cells. Due to the recent development of transparent and flexible electronics, there is a growing interest in depositing metal-oxide thin-film on plastic substrates that can offer flexibility, lighter weight, and potentially lead to cheaper manufacturing by allowing printing and roll- to-roll processing. The plastic substrates, however, limit device processing to below 200oC. In this context, the deposition of high-performance semiconductor thin films from dispersions of pre-prepared oxide nanoparticles at temperatures below 200oC represents a potential key route. This paper reports on the preparation of ZnO transparent thin films using solution- processed nanoparticles (NPs) precipitated from zinc acetate alcoholic solution with potassium hydroxide. The nanoparticles size distribution, microstructure and crystallinity were measured by dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The thin films were deposited by spin-coating onto soda lima glass substrate, using a dispersion of 1wt{%} ZnO NPs. The morphology of the films annealed at 120 and 180oC, observed by atomic force microscopy and cross-section scanning electron microscopy, shows columnar grains with diameter ranging between 20 and 70 nm, depending on the conditions of depositions. Optical measurements indicated high transparency, between 85 and 94 {%}, in the visible range, a direct nature of band-to-band transitions and band gap values between 3,22 and 3,32 eV. The refractive index and extinction coefficient have been calculated from optical transmittance and reflectance spectra.

2013
Ramos, A. M., S. Pereira, M. T. Cidade, G. Pereira, R. Branquinho, L. Pereira, R. Martins, and E. Fortunato, "{Preparation and characterization of cellulose nanocomposite hydrogels as functional electrolytes}", Solid State Ionics, vol. 242: Elsevier B.V., pp. 26–32, 2013. AbstractWebsite

In this work Laponite was combined with a modified abundant natural polymer, (caboxymethyl cellulose), acrylic sodium salt polymer and lithium perchlorate aiming to produce inexpensive and sustainable nanocomposite electrolytes for functional electrochemical devices. Optical, electrochemical, structural, morphological and rheological characterization was performed in order to evaluate their properties and potential advantages as electrolyte. It was verified that the addition of Laponite led to an ionic conductivity at room temperature (25 C) in the range of 6 to 9 ?? 10- 5 Scm - 1 this value being then determined by the composition of the nanocomposite. These electrolytes were applied to electrochromic devices using evaporated nickel oxide thin film as the electrochromic layer. The devices exhibited a significant transmittance modulation that exceeds 45 {%} at 600 nm. ?? 2013 Elsevier B.V.

2005
Liu, H. R., P. T. Gomes, S. I. Costa, T. M. Duarte, R. Branquinho, A. C. Fernandes, J. C. W. Chien, R. P. Singh, and M. M. Marques, "{Highly active new $\alpha$-diimine nickel catalyst for the polymerization of $\alpha$-olefins}", Journal of Organometallic Chemistry, vol. 690, pp. 1314–1323, 2005. Abstract

A new silylated $\alpha$-diimine ligand, bis[N,N′-(4-tert-butyl- diphenylsilyl-2,6-diisopropylphenyl)imino]acenaphthene 3, and its corresponding Ni(II) complex, {\{}bis[N,N′-(4-tert-butyl-diphenylsilyl-2,6- diisopropylphenyl)imino]acenaphthene{\}}dibromonickel 4, have been synthesized and characterized. The crystal structures of 3 and 4 were determined by X-ray crystallography. In the solid state, complex 4 is a dimer with two bridging Br ligands linking the two nickel centers, which have square pyramidal geometries. Complex 4, activated either by diethylaluminum chloride (DEAC) or methylaluminoxane (MAO) produces very active catalyst systems for the polymerization of ethylene and moderately active for the polymerization of propylene. The activity values are in the order of magnitude of 107 g PE (mol Ni [E] h)-1 for the polymerization of ethylene and of 105 g PP (mol Ni [P] h)-1 for the polymerization of propylene. NMR analysis shows that branched polyethylenes (PE) are obtained at room or higher temperatures and almost linear PE is obtained at 0°C with 4/DEAC. © 2004 Elsevier B.V. All rights reserved.

2004
Martins, A. M., R. Branquinho, J. Cui, A. R. Dias, T. M. Duarte, J. Fernandes, and S. S. Rodrigues, "{Syntheses and structures of molybdenum and tungsten pentabenzylcyclopentadienyl complexes: New chlorination reactions}", Journal of Organometallic Chemistry, vol. 689, pp. 2368–2376, 2004. Abstract

[M(CpBz)(CO)3CH3] (M=Mo, 2a, W, 2b; CpBz=C5(CH2Ph)5) have been prepared and reacted with PCl5 and PhI · Cl2. Depending on the metal and on the chlorinating reagent used [Mo(CpBz) ($η$2-COCH3)Cl3], 3, [W(CpBz)Cl4], 4, [Mo(CpBz)(CO)3Cl], 5 and [Mo(CpBz)Cl4], 6 have been obtained. The molecular structures of all compounds are reported and two conformations have been characterised for the benzyl substituents. In complexes 2a, 2b and 5 one phenyl ring bends towards the metals while in 3 and 4 the five phenyls point opposite to the metals. © 2004 Elsevier B.V. All rights reserved.