## Publications

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2017
Socratous, J., S. Watanabe, K. K. Banger, C. N. Warwick, R. Branquinho, P. Barquinha, R. Martins, E. Fortunato, and H. Sirringhaus, Physical Review B, vol. 95, no. 4: American Physical Society, pp. 045208, jan, 2017. AbstractWebsite

Despite the success of exploiting the properties of amorphous oxide semiconductors for device applications, the charge transport in these materials is still not clearly understood. The observation of a definite Hall voltage suggests that electron transport in the conduction band is free-electron-like. However, the temperature dependence of the Hall and field-effect mobilities cannot be explained using a simple bandlike model. Here, we perform gated Hall effect measurements in field-effect transistors, which allow us to make two independent estimates of the charge carrier concentration and determine the Hall factor providing information on the energy dependence of the relaxation time. We demonstrate that the Hall factor in a range of sputtered and solution-processed quaternary amorphous oxides, such as a-InGaZnO, is close to two, while in ternary oxides, such as InZnO, it is near unity. This suggests that quaternary elements like Ga act as strong ionized impurity scattering centers in these materials.

Salgueiro, D., A. Kiazadeh, R. Branquinho, L. Santos, P. Barquinha, R. Martins, and E. Fortunato, Journal of Physics D: Applied Physics, vol. 50, no. 6: IOP Publishing, pp. 065106, feb, 2017. AbstractWebsite

Chemical solution deposition is a low cost, scalable and high performance technique to obtain metal oxide thin films. Recently, solution combustion synthesis has been introduced as a chemical route to reduce the processing temperature. This synthesis method takes advantage of the chemistry of the precursors as a source of energy for localized heating. According to the combustion chemistry some organic solvents can have a dual role in the reaction, acting both as solvent and fuel. In this work, we studied the role of 2-methoxyethanol in solution based synthesis of ZTO thin films and its influence on the performance of ZTO TFTs. The thermal behaviour of ZTO precursor solutions confirmed that 2-methoxyethanol acts simultaneously as a solvent and fuel, replacing the fuel function of urea. The electrical characterization of the solution based ZTO TFTs showed a slightly better performance and lower variability under positive gate bias stress when urea was not used as fuel, confirming that the excess fuel contributes negatively to the device operation and stability. Solution based ZTO TFTs demonstrated a low hysteresis ($Δ$V = −0.3 V) and a saturation mobility of 4–5 cm2 V−1 s−1.

2016
Branquinho, R., A. Santa, E. Carlos, D. Salgueiro, P. Barquinha, R. Martins, and E. Fortunato, 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., 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, 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
Kiazadeh, A., D. Salgueiro, R. Branquinho, J. Pinto, H. L. Gomes, P. Barquinha, R. Martins, and E. Fortunato, APL Materials, vol. 3, no. 6: AIP Publishing, pp. 062804, jun, 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.

Ullaha, S., F. {De Matteis}, R. Branquinho, E. Fortunato, R. Martins, and I. Davoli, 2015 IEEE 15th International Conference on Nanotechnology (IEEE-NANO): IEEE, pp. 144–147, jul, 2015. 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.

Kololuoma, T., J. Leppäniemi, H. Majumdar, R. Branquinho, E. Herbei-Valcu, V. Musat, R. Martins, E. Fortunato, and A. Alastalo, J. Mater. Chem. C, vol. 3, no. 8, pp. 1776–1786, 2015. AbstractWebsite

We report a sol-gel approach to fabricate aluminum-oxy-hydroxide (AlOOH) -based inks for gravure printing of high-dielectric-constant nanocomposite films. By reacting 3-glycidoxypropyl- trimethoxysilane (GPTS) with aluminum-oxide-hydroxide (AlOOH) nanoparticles under constant bead milling, inks suitable for gravure printing were obtained. The calculated relative dielectric constant based on measured capacitances and film thicknesses for the gravure-printed GPTS:AlOOH nanocomposite varied between 7 and 11 at a 10 kHz frequency. The dielectric constant depended on the mixing ratio of the composite and was found to follow the Maxwell-Garnett ternary-system mixing rule indicating presence of micro/nanopores that affect the electrical properties of the fabricated films. Increasing leakage current with increasing AlOOH content was observed. High leakage current was reduced by printing two-layer films. The double-layered gravure-coated films exhibited similar capacitance density but clearly lower leakage current and less electrical breakdowns in comparison to single-layered films having comparable film compositions and film thicknesses. The best composite yielded a capacitance density of 109 ± 2 pF/mm2 at the 10 kHz frequency and a leakage current density of 60 ± 20 µA/cm2 at 0.5 MV/cm electric field as a single layer. The calculated relative dielectric constant at the 10 kHz frequency for this composition was 11.2 ± 0.5. Introduction

Alexa, A., N. Tigau, P. Alexandru, A. Pimentel, R. Branquinho, D. Salgueiro, T. Calmeiro, R. Martins, E. Fortunato, and V. Musat, 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.

Santos, L., D. Nunes, R. Branquinho, D. Salgueiro, P. Barquinha, R. Martins, and E. Fortunato, ACS applied materials {&} interfaces, vol. 7, no. 1, pp. 638–646, 2015. 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 × 106, threshold voltage (VTh) of 0.3–1.9 V, and mobility up to 1 cm2/(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.

Branquinho, R., D. Salgueiro, A. Santa, A. Kiazadeh, P. Barquinha, L. Í. Pereira, R. Martins, and E. Fortunato, Semicond. Sci. Technol., vol. 30: IOP Publishing, pp. 024007, 2015. AbstractWebsite

Solution based deposition has been recently considered as a viable option for low-cost flexible electronics. In this context research efforts have been increasingly centred on the development of suitable solution-processed materials for oxide based transistors. Nevertheless, the majority of synthetic routes reported require the use of toxic organic solvents. In this work we report on a new environmental friendly solution combustion synthesis route, using ethanol as solvent, for the preparation of indium/gallium free amorphous zinc-tin oxide (ZTO) thin film transistors (TFTs) including AlOx gate dielectric. The decomposition of ZTO and AlOx precursor solutions, electrical characterization and stability of solution processed ZTO/AlOx TFTs under gate-bias stress, in both air and vacuum atmosphere, were investigated. The devices demonstrated low hysteresis ($Δ$V = 0.23 V), close to zero turn on voltage, low threshold voltage (VT = 0.36 V) and a saturation mobility of 0.8 cm2 V−1 s−1 at low operation voltages. Ethanol based ZTO/AlOx TFTs are a promising alternative for applications in disposable, low cost and environmental friendly electronics.

2014
Branquinho, R., D. Salgueiro, L. Santos, P. Barquinha, L. Pereira, R. F. D. P. Martins, and E. Fortunato, ACS applied materials {&} interfaces, vol. 6: American Chemical Society, pp. 195592–9, oct, 2014. AbstractWebsite

Solution processing has been recently considered as an option when trying to reduce the costs associated to 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 cm2 V-1 s-1.

Veigas, B., R. Branquinho, J. V. Pinto, P. J. Wojcik, R. Martins, E. Fortunato, and P. V. Baptista, Biosensors and Bioelectronics, vol. 52: Elsevier, pp. 50–55, 2014. 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. ?? 2013 Elsevier B.V.

2013
Pinto, J. V., R. Branquinho, P. Barquinha, E. Alves, R. Martins, and E. Fortunato, IEEE/OSA Journal of Display Technology, vol. 9, no. 9, pp. 729–734, 2013. Abstract

We present the results obtained with an extended-gate ISFET totally based on amorphous oxides (GIZO as the semiconductor, {\textless}formula formulatype="inline"{\textgreater}{\textless}tex Notation="TeX"{\textgreater}{\$}{\{}hbox{\{}Ta{\}}{\}}{\_}{\{}2{\}}{\{}hbox{\{}O{\}}{\}}{\_}{\{}5{\}}{\{}hbox{\{}:SiO{\}}{\}}{\_}{\{}2{\}}{\$}{\textless}/tex{\textgreater} {\textless}/formula{\textgreater} as the dielectric and {\textless}formula formulatype="inline"{\textgreater}{\textless}tex Notation="TeX"{\textgreater}{\$}{\{}hbox{\{}Ta{\}}{\}}{\_}{\{}2{\}}{\{}hbox{\{}O{\}}{\}}{\_}{\{}5{\}}{\$}{\textless}/tex{\textgreater} {\textless}/formula{\textgreater} as the sensitive layer). A full characterization of the device was performed with constant ionic strength pH buffer solutions, revealing a sensitivity of 40 mV/pH with small hysteresis, and good linearity in the pH 4{&}{\#}x2013;pH 10 range buffer solutions. These results clearly show that it is possible to produce room-temperature disposable and low cost bio-sensors.

Branquinho, R., J. V. Pinto, T. Busani, P. Barquinha, L. Pereira, P. V. Baptista, R. Martins, and E. Fortunato, IEEE/OSA Journal of Display Technology, vol. 9, no. 9, pp. 723–728, 2013. AbstractWebsite

The effect of post-deposition annealing temperature on the pH sensitivity of room temperature RF sputtered Ta2O5 was investigated. Structural and morphological features of these films were analyzed before and after annealing at various temperatures. The deposited films are amorphous up to 600 °C and crystallize at 700 °C in an orthorhombic phase. Electrolyte-insulator-semiconductor (EIS) field effect based sensors with an amorphous Ta2O5 sensing layer showed pH sensitivity above 50 mV/pH. For sensors annealed above 200 °C pH sensitivity decreased with increasing temperature. Stabilized sensor response and maximum pH sensitivity was 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.

Ramos, A. M., S. Pereira, M. T. Cidade, G. Pereira, R. Branquinho, L. Pereira, R. Martins, and E. Fortunato, 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.

2011
Branquinho, R., B. Veigas, J. V. Pinto, R. Martins, E. Fortunato, and P. V. Baptista, Biosensors and Bioelectronics, vol. 28, no. 1: Elsevier B.V., pp. 44–49, 2011. AbstractWebsite

We present a new approach for real-time monitoring of PCR amplification of a specific sequence from the human c-MYC proto-oncogene using a Ta 2O 5 electrolyte-insulator-semiconductor (EIS) sensor. The response of the fabricated EIS sensor to cycle DNA amplification was evaluated and compared to standard SYBR-green fluorescence incorporation, showing it was possible to detect DNA concentration variations with 30mV/??M sensitivity. The sensor's response was then optimized to follow in real-time the PCR amplification of c-MYC sequence from a genomic DNA sample attaining an amplification profile comparable to that of a standard real-time PCR. Owing to the small size, ease of fabrication and low-cost, the developed Ta 2O 5 sensor may be incorporated onto a microfluidic device and then used for real-time PCR. Our approach may circumvent the practical and economical obstacles posed by current platforms that require an external fluorescence detector difficult to miniaturize and incorporate into a lab-on-chip system. ?? 2011 Elsevier B.V.

2008
Albuquerque, R., M. C. Neves, M. H. Mendonça, T. Trindade, and O. C. Monteiro, Colloids and Surfaces A: Physicochemical and Engineering Aspects, vol. 328, pp. 107–113, 2008. Abstract

The decolorization of aqueous solutions methylene blue (C.I. Basic Blue 9), due to the presence of nanocrystalline Bi2S3, supported on SiO2 submicron particles, was investigated here. For this decolorization process, two distinct characteristics, though related, associated to the role of SiO2/Bi2S3 were identified: (i) high methylene blue adsorption capability and (ii) photocatalytic activity to methylene blue photodecolorization. Effects of experimental parameters on the decolorization process, such as methylene blue and nanocomposite concentrations, pH and Bi2S3 particle size were investigated. The maximum adsorption ability of the SiO2/Bi2S3 was approximately 15.6 mg methylene blue per gram. The complete decolorization of a 16 ppm organic dye solution can be achieved, by an adsorption process, in an extremely short time (less than 5 min), using 1.6 g/L of SiO2/Bi2S3 nanocomposite. The study of the decolorization of the dye by an adsorption-photoassisted decolorization process was carried out by irradiation of a suspension prepared with 100 mL of methylene blue solution (8 ppm) and 50 mg of SiO2/Bi2S3. In these conditions the complete decolorization of the dye, adsorbed and in the solution, was achieved in 40 min. © 2008 Elsevier B.V. All rights reserved.

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, 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, 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.