Rodrigo Martins

In this work, we develop a simple and eco-friendly water-inducement method for high-k yttrium oxide (YOx) dielectric. To prepare YOx thin films at low temperature, yttrium nitrate and deionized water were used as the source materials. No toxic organic materials were required in the YOx coating process. The YOx thin film annealed at 350 °C showed a low leakage current density of 2 × 10-9 A/cm2 at 5 MV/cm and a large areal-capacitance of 448 nF/cm2 at 1 kHz. On the basis of its implementation as the gate dielectric, the fully-water-induced In2O3 TFT based on YOx exhibited a high field-effect mobility of 15.98 cm2/Vs, excellent subthreshold swing of 75 mV/dec, an on/off current ratio of 6 × 106, and a negligible hysteresis of 50 mV. The as-fabricated TFT operated at a low voltage (∼1.5 V) and showed high drain current drive capability, enabling oxide TFT with a water-induced high-k dielectric for use in backplane electronics for low-power mobile display applications. © 2015 Elsevier B.V. All rights reserved.

Solution-processed p-type oxide semiconductors have recently attracted increasing interests for the applications in low-cost optoelectronic devices and low-power consumption complementary metal-oxide-semiconductor circuits. In this work, p-type nickel oxide (NiOx) thin films were prepared using low-temperature solution process and integrated as the channel layer in thin-film transistors (TFTs). The electrical properties of NiOx TFTs, together with the characteristics of NiOx thin films, were systematically investigated as a function of annealing temperature. By introducing aqueous high-k aluminum oxide (Al2O3) gate dielectric, the electrical performance of NiOx TFT was improved significantly compared with those based on SiO2 dielectric. Particularly, the hole mobility was found to be 60 times enhancement, quantitatively from 0.07 to 4.4 cm2/V s, which is mainly beneficial from the high areal capacitance of the Al2O3 dielectric and high-quality NiOx/Al2O3 interface. This simple solution-based method for producing p-type oxide TFTs is promising for next-generation oxide-based electronic applications. © 2016 Author(s).

Here, a simple, nontoxic, and inexpensive "water-inducement" technique for the fabrication of oxide thin films at low annealing temperatures is reported. For water-induced (WI) precursor solution, the solvent is composed of water without additional organic additives and catalysts. The thermogravimetric analysis indicates that the annealing temperature can be lowered by prolonging the annealing time. A systematic study is carried out to reveal the annealing condition dependence on the performance of the thin-film transistors (TFTs). The WI indium-zinc oxide (IZO) TFT integrated on SiO2 dielectric, annealed at 300 °C for 2 h, exhibits a saturation mobility of 3.35 cm2 V-1 s-1 and an on-to-off current ratio of ≈108. Interestingly, through prolonging the annealing time to 4 h, the electrical parameters of IZO TFTs annealed at 230 °C are comparable with the TFTs annealed at 300 °C. Finally, fully WI IZO TFT based on YOx dielectric is integrated and investigated. This TFT device can be regarded as "green electronics" in a true sense, because no organic-related additives are used during the whole device fabrication process. The as-fabricated IZO/YOx TFT exhibits excellent electron transport characteristics with low operating voltage (≈1.5 V), small subthreshold swing voltage of 65 mV dec-1 and the mobility in excess of 25 cm2 V-1 s-1. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-k alkaline lithium oxide (LiOx) thin films are fabricated by spin-coating method. The LiOx thin films are annealed at different temperatures and characterized by various techniques. An optimized LiOx dielectric is achieved at an annealing temperature of 300 °C and exhibits wide bandgap of ≈5.5 eV, smooth surface, relatively permittivity of ≈6.7, and low leakage current density. The as-fabricated LiOx thin films are integrated, as gate dielectrics, in both n-channel indium oxide (In2O3) and p-channel cupric oxide (CuO) transistors. The optimized In2O3/LiOx thin-film transistor (TFT) exhibits high performance and high stability, such as Ion/Ioff of 107, electron mobility of 5.69 cm2 V−1 s−1, subthreshold swing of 70 mV dec−1, negligible hysteresis, and threshold voltage shift of 0.1 V under bias stress for 1.5 h. Meanwhile, the p-channel CuO TFT based on LiOx dielectric shows high Ion/Ioff of 105 and hole mobility of 1.72 cm2 V−1 s−1. All the electrical performances are achieved at an ultra-low operating voltage of 2 V. Considering the simple procedure, the moderate annealing temperature, and the low power consumption merits, these outstanding characteristics represent a significant advance toward the development of battery compatible and portable electronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

A quantitative study of the dynamics of threshold-voltage shifts with time in gallium-indium zinc oxide amorphous thin-film transistors is presented using standard analysis based on the stretched exponential relaxation. For devices using thermal silicon oxide as gate dielectric, the relaxation time is 3× 105 s at room temperature with activation energy of 0.68 eV. These transistors approach the stability of the amorphous silicon transistors. The threshold voltage shift is faster after water vapor exposure suggesting that the origin of this instability is charge trapping at residual-water-related trap sites. © 2009 American Institute of Physics.

Hall effect measurements are one of the most powerful techniques for obtaining information about the conduction mechanism in polycrystalline semiconductor materials, which is the basis for understanding semiconductor gas sensors. In order to investigate the correlation between the microscopic characteristics and the macroscopic performances exhibited by undoped tin oxide gas sensors deposited by spray pyrolysis, Hall effect measurements were performed at different temperatures, from room temperature up to 500 K, and in the presence of two different atmospheres, air and methane. From these measurements, it was possible to infer the potential barrier and its dependence with the used atmosphere. The obtained results were analysed in terms of the oxygen mechanism at grain boundaries on the basis of the grain boundary-trapping model. In the presence of methane gas, the electrical resistivity decreases due to the lowering of the inter-grain boundary barrier height.

Hall effect measurements have been used to evaluate the conduction mechanism, exhibited by tin oxide thin film gas sensors deposited by spray pyrolysis. Two experiments have been carried out: (i) Hall measurements in air and (ii) in the presence of methane (first results reported), both as a function of temperature. From the measurements performed it was possible to infer the potential barrier and its dependence with the atmosphere used. The results obtained for the carrier concentration and mobility have been analysed in the light of the oxygen diffusion mechanism at grain boundaries by using the grain boundary-trapping model. In the presence of the methane gas the electrical resistivity decreases due to the lowering of the inter-grain boundary barrier height. © 2001 Published by Elsevier Science Ltd.

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. Guest editors: M S Ramachandra Rao and Michael Lorenz. © 2016 IOP Publishing Ltd.

We have investigated the electrical properties of metal-semiconductor field-effect transistors (MESFET) based on amorphous oxide semiconductor channels. All functional parts of the devices were sputter-deposited at room temperature. The influence on the electrical properties of a 150 °C annealing step of the gallium-indium-zinc-oxide channel is investigated. The MESFET technology offers a simple route for processing of the transistors with excellent electrical properties such as low subthreshold swing of 112 mV/decade, gate sweep voltages of 2.5 V, and channel mobilities up to 15 cm2 /V s. © 2010 American Institute of Physics.

The post-deposition modification of ZnO-based transparent conductive oxides (TCOs) can be the key to produce thin films with optoelectronic properties similar to indium tin oxide (ITO), but at a much lower cost. Here, we present electro-optical results achieved for post-deposition annealing of Al–Zn–O (AZO), AZO:H, Ga–Zn–O:H (GZO:H), and Zn–O:H (ZNO:H) thin films deposited by RF sputtering at room temperature. These studies comprise results of thermal annealing at atmospheric pressure, vacuum, forming gas, H2 and Ar atmospheres, and H2 and Ar plasmas, which lead to significant enhancement of their electro-optical properties, which are correlated to morphological and structural improvements. The post-deposition annealing leads to an enhancement in resistivity above 40% for AZO, AZO:H, and GZO:H, reaching ρ ≈ 2.6–3.5 × 10−4 Ωcm, while ZnO:H showed a lower improvement of 13%. The averaged optical transmittance in the visible region is about 89% for the investigated TCOs. Such results match the properties of state-of-art ITO (ρ ≈ 10−4 Ωcm and transmittance in VIS range of 90%) employing much more earth-abundant materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The p/i interface plays a major role in the conversion efficiency of nanocrystalline silicon (nc-Si:H) solar cells. Under plasma-enhanced chemical vapor deposition (PECVD) of the intrinsic (i) nc-Si:H layer, ion bombardment can severely affect the underlying p-doped layer and degrade the solar cell performance. The core of the present work is to investigate the effect of light and heavy ion bombardment on the structural modifications of the p-layer during the p/i interface formation. The properties of the nc-Si:H materials deposited under distinct conditions are analyzed and correlated to the deposition rate and the resulting cell efficiency. To recreate the ion bombardment during the initial stages of the i-layer deposition on the p-layer, hydrogen plasma treatment was performed for 30 s (light ion bombardment), after which a flux of silane was introduced into the deposition chamber in order to initiate the heavy ion bombardment and growth of an ultra-thin (5 nm) i-layer. The structural changes of the p-type nc-Si:H layers were observed by spectroscopic ellipsometry. The obtained results confirm that detrimental structural modifications (e.g. partial amorphization of the sub-surface region and bulk) occur in the p-layer, caused by the ion bombardment. To minimize this effect, a protective buffer layer is investigated able to improve the performance of the solar cells fabricated under increased growth rate conditions. © 2015 Elsevier B.V. All rights reserved.

Results are presented which are geared towards an understanding of the influence of powder formation during film growth. Plasma chemistry is correlated with the morphology, structure (inferred through infrared spectroscopy, scanning electron microscopy and X-ray diffraction) electro-optical and density of states of intrinsic films deposited under continuous and power modulated operation. Results show that for modulation frequencies where no powder formation occurs and low substrate temperatures T (150°C), silane decomposition gives rise to the growth of inhomogeneous films while in the high modulation frequency regime, at the same temperature, the anions and powder are trapped resulting in films with high deposition rates and low defect density.

The special Professor Walter E. Spear commemoration issue of the Philosophical Magazine, published in October 2009, contains papers which cover the numerous relevant issues, driven by commercial applications, primarily solar energy and displays. Kocka reviews the complex microstructure of crystallites embedded in the amorphous silicon tissue, the transport mechanism is determined by the conductive grains and influenced by the passivation through H at the grain boundaries. Hugger and co-researchers report on transient photocapacitance spectroscopy and drive-level capacitance profiling as a way of elucidating the fundamental electronic properties of hydrogenated ncSi. Tawada recounts the history of a-Si:H pin heterojunction solar cells, emphasizing the role of the p-type silicon carbide layer in the improvement of the device. Schubert and colleagues focus their work on the production of flexible PV modules with many applications in the architectural arena or integrated into clothing.

We present the modelling of a new two-terminal and low-voltage operating optoelectronic device based on MIS silicon structure with multichannel insulator and having as gate a transparent metallic tin-doped indium oxide (ITO) layer deposited by spray pyrolysis technique over the insulator layer. ITO layer has a multiple non-rectifier electrical contact with silicon substrate, in the SiO2 channel's region. Construction details of the process, together with its operating characteristics are given. The devices developed do not require external active electronic components (transistors, microschemes) to execute their functions and to transform analogue input optical signals to digital output form, highly important for a wide range of optoelectronic applications.

UV-enhanced monocrystalline zinc sulphide optical sensors with high quantum efficiency have been developed by spray deposition of heavy fluorine-doped tin oxide (FTO) thin films onto the surface of zinc sulphide monocrystals as an alternative to the UV-enhanced high-efficiency silicon photodetectors commonly used in precise radiometric and spectroscopic measurements as well as to new sensors based on SiC and GaN. The fabricated sensors have an unbiased internal quantum efficiency that is nearly 100% from 250 to 320 nm, and the typical sensitivity at 250 nm is 0.15 A W-1. The sensors are insensitive to solar radiation in conditions on the earth and can be used as solar blind photodetectors for precision UV measurements under direct solar illumination for both terrestrial and space applications. © 1998 Elsevier Science S.A. All rights reserved.

High quantum efficiency, UV-enhanced monocrystalline zinc sulphide optical sensors for precise radiometric and spectroscopic measurements have been developed by spray deposition of heavy fluorinedoped tin oxide thin films with carrier concentration near 1021 cm-3 onto the surface of zinc sulphide monocrystals as an alternative to the UV-enhanced silicon photodetectors as well as to new detectors based on SiC and GaN. The fabricated sensors have an unbiased internal quantum efficiency that was nearly 100% from 250 to 320 nm, and the typical sensitivity at 290 nm is 0.15 A/W. The sensors were insensitive to solar radiation in earth's conditions and can be used as solar blind photodetectors for precision UV-measurements under direct solar illumination, both terrestrial and space applications.

In this paper we report the success in fabricating FTO/Si surface-barrier photodiodes produced by spray pyrolysis deposition technique, under ambient conditions. Three types of photodetectors for low-voltage-bias operation were developed based on high-resistivity silicon: 1. X-Ray detectors with energy resolution of 16.5% at 661.5 keV (137Cs source), consisting of surface-barrier PIN photodiode with an active area of 50 mm2 operating at 5 V reverse bias, scintillator based on monocrystalline Bi4Ge3O12 and preamplifier (noise of 250 e- RMS.); 2. Fast-response surface-barrier FTO/n–n+ silicon epitaxial photodiodes, operating at 10 V bias with rise times of 2 ns at λ = 0.85 μm; 3. Radiation-resistant drift epitaxial surface-barrier PIN photodiodes for unbiased operating conditions, with an exponential impurity distribution in a 8 μm thick epitaxial layer. A built-in electrical field due to the carrier concentration distribution in the epitaxial layer provides a considerable improvement in the `critical fluence' value (3×1014 cm-2) for neutron irradiation.

We have developed new types of functional and smart optical silicon sensors, based on ITO/multichannel insulator/silicon structures, which are able to execute electronic functions such as amplifying the photocurrent (without avalanche multiplication), transforming the input optical signal into a radio frequency output signal and transforming the analogue input optical signal to a digital output form, without external active electronic components. These new functional optical sensors allow a substantial simplification of the registration of optical signals as well as of the electronic scheme to be used. © 1998 Elsevier Science S.A. All rights reserved.

We report the properties and optoelectronic applications of transparent and conductive indium and tin oxide films prepared by the spray pyrolysis method and doped with Sn or F, respectively. The film properties have been measured using X-ray diffraction, optical and electrical absorption. As examples of applications we produced a set of selective optical detectors for different spectral regions, covering the wavelength range from 0.25 to 1.1 μm, based on metal oxide-semiconductor heterostructures and using different substrates such as: GaP, GaSe, AlxGa1-xAs, GaAs and Si. The fabricated devices exhibit several features such as: production simplicity, high quantum efficiency, uniform sensitivity over the entire active area and a high response speed. Finally, we present a high quantum efficiency and solar blind monocrystalline zinc sulphide optical sensor fabricated by spray deposition as an alternative to the ultraviolet-enhanced SiC and GaN photodetectors and the performances of a solar cell. © 1998 Elsevier Science B.V. All rights reserved.

We have developed new types of functional and smart optical silicon sensors, based on ITO/multichannel insulator/silicon structures, which are able to execute electronic functions such as amplifying the photocurrent (without avalanche multiplication), transforming the input optical signal into a radio frequency output signal and transforming the analogue input optical signal to a digital output form, without external active electronic components. These new functional optical sensors allow as substantial simplification of the registration of optical signals as well as of the electronic scheme to be used.

This work's aim is to report for the first time the cubic to hexagonal phase transition in tin-doped In2O3 films with a Sn/In atomic ratio of 0.03, fabricated at low temperature and normal pressure from alcoholic solution of InCl3 and SnCl4. The performed X-ray diffraction measurements show a difference between crystallographic symmetry of thin (100 nm) and thick (400 nm) films prepared in the same conditions: the structure of thick films can be related to high pressure In2O3 hexagonal system with a preferred orientation of c-axis parallel to the substrate surface, while thin films present a cubic symmetry with columnar (400) grain orientation. Phase transition nature is connected with non-axial tensile deformation of indium oxide grid due to insertion of chlorine ions in the position of two diagonally opposite oxygen vacancies in In2O3 network.

This work reports the structure and electro-optical characteristics of different metal oxide films obtained by spray pyrolysis on heated glass substrates, aiming their application in optoelectronic devices. The results show that this technique leads to thin films with properties ranging from dielectric to degenerate semiconductors, offering the following advantages: simplicity, low cost, high productivity and the possibility of covering large areas, highly important for large area device applications.

UV-enhanced monocrystalline zinc sulphide optical sensors with high quantum efficiency have been developed by spray deposition of heavy fluorine-doped tin oxide (FTO) thin films onto the surface of zinc sulphide monocrystals as an alternative to the UV-enhanced high-efficiency silicon photodetectors commonly used in precise radiometric and spectroscopic measurements as well as to new sensors based on SiC and GaN. The fabricated sensors have an unbiased internal quantum efficiency that is nearly 100% from 250 to 320 nm, and the typical sensitivity at 250 nm is 0.15 A W-1. The sensors are insensitive to solar radiation in conditions on the earth and can be used as solar blind photodetectors for precision UV measurements under direct solar illumination for both terrestrial and space applications.

We present a set of high-efficiency optical sensors for the spectral range from 0.25 to 1.1 μm based on metal oxide-semiconductor heterostructures using different substrates: GaP, GaSe, AlxGa1-xAs, GaAs and Si. A set of several transparent conductive metal oxide films such as indium, tin and zinc oxides fabricated by the spray pyrolysis method and its doping procedure has been investigated. The results show that heavily doped indium and tin oxide films are preferable as the active transparent conductive electrode in heterojunction surface-barrier structures. The fabricated sensors exhibit several features such as process simplicity, high quantum efficiency, uniformity of sensitivity over the active area and a high response speed. Such sensors can be used for precision measurements in different scientific and technical applications.

A new high quantum efficiency gallium phosphide Schottky photodiode has been developed by spray deposition of heavily doped tin oxide films on n-type epitaxial structures, as an alternative to the conventional Schottky photodiodes using a semitransparent gold electrode. It is shown that fluorine-doped tin oxide films are more effective as transparent electrodes than tin-doped indium oxide films. The proposed photodiodes have a typical responsivity near 0.33 A W-1 at 440 nm and an unbiased internal quantum efficiency close to 100%, in the range from 250 to 450 nm. The model used to calculate the internal quantum efficiency (based on the optical constants of tin oxide films and gallium phosphide epitaxial layers) is found to be in good agreement with the experimental results. The data show that the quantum efficiency is strongly dependent on the thickness of the transparent electrode, owing to optical interference effects. The noise equivalent power for 440 nm is 2.7 × 10-15 W Hz-1/2, which indicates that these photodiodes can be used for accurate measurements in the short-wavelength range, even in the presence of stronger infrared background radiation.