Rita Branquinho

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.