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2023
Coelho, Beatriz J., Joana V. Pinto, Jorge Martins, Ana Rovisco, Pedro Barquinha, Elvira Fortunato, Pedro V. Baptista, Rodrigo Martins, and Rui Igreja. "{Parylene C as a Multipurpose Material for Electronics and Microfluidics}." Polymers. 15 (2023): 2277. AbstractWebsite

Poly(p-xylylene) derivatives, widely known as Parylenes, have been considerably adopted by the scientific community for several applications, ranging from simple passive coatings to active device components. Here, we explore the thermal, structural, and electrical properties of Parylene C, and further present a variety of electronic devices featuring this polymer: transistors, capacitors, and digital microfluidic (DMF) devices. We evaluate transistors produced with Parylene C as a dielectric, substrate, and encapsulation layer, either semitransparent or fully transparent. Such transistors exhibit steep transfer curves and subthreshold slopes of 0.26 V/dec, negligible gate leak currents, and fair mobilities. Furthermore, we characterize MIM (metal–insulator–metal) structures with Parylene C as a dielectric and demonstrate the functionality of the polymer deposited in single and double layers under temperature and AC signal stimuli, mimicking the DMF stimuli. Applying temperature generally leads to a decrease in the capacitance of the dielectric layer, whereas applying an AC signal leads to an increase in said capacitance for double-layered Parylene C only. By applying the two stimuli, the capacitance seems to suffer from a balanced influence of both the separated stimuli. Lastly, we demonstrate that DMF devices with double-layered Parylene C allow for faster droplet motion and enable long nucleic acid amplification reactions.

2022
Rovisco, Ana, Maria Morais, Rita Branquinho, Elvira Fortunato, Rodrigo Martins, and Pedro Barquinha. "{Microwave-Assisted Synthesis of Zn2SnO4 Nanostructures for Photodegradation of Rhodamine B under UV and Sunlight}." Nanomaterials. 12 (2022): 2119. AbstractWebsite

The contamination of water resources by pollutants resulting from human activities represents a major concern nowadays. One promising alternative to solve this problem is the photocatalytic process, which has demonstrated very promising and efficient results. Oxide nanostructures are interesting alternatives for these applications since they present wide band gaps and high surface areas. Among the photocatalytic oxide nanostructures, zinc tin oxide (ZTO) presents itself as an eco-friendly alternative since its composition includes abundant and non-toxic zinc and tin, instead of critical elements. Moreover, ZTO nanostructures have a multiplicity of structures and morphologies possible to be obtained through low-cost solution-based syntheses. In this context, the current work presents an optimization of ZTO nanostructures (polyhedrons, nanoplates, and nanoparticles) obtained by microwave irradiation-assisted hydrothermal synthesis, toward photocatalytic applications. The nanostructures' photocatalytic activity in the degradation of rhodamine B under both ultraviolet (UV) irradiation and natural sunlight was evaluated. Among the various morphologies, ZTO nanoparticles revealed the best performance, with degradation > 90% being achieved in 60 min under UV irradiation and in 90 min under natural sunlight. The eco-friendly production process and the demonstrated ability of these nanostructures to be used in various water decontamination processes reinforces their sustainability and the role they can play in a circular economy.

2021
{Henriques Ferreira}, Sofia, Ana Rovisco, Andreia dos Santos, Hugo Águas, Rui Igreja, Pedro Barquinha, Elvira Fortunato, and Rodrigo Martins. "{Porous ZnO Nanostructures Synthesized by Microwave Hydrothermal Method for Energy Harvesting Applications}." Nanopores. Eds. Sadia Ameen, Shaheer M. Akhtar, and Hyung-Shik Shin. IntechOpen, 2021. Abstract

Abstract Long-haul travel does not constitute an obstacle for tourists to travel and is fast gaining the attention of tourists in new and unique experiences. This study was conducted to identify the long-haul travel motivation by international tourists to Penang. A total of 400 respondents participated in this survey, conducted around the tourist attractions in Penang, using cluster random sampling. However, only 370 questionnaires were only used for this research. Data were analysed using SPSS software 22 version. The findings, ‘knowledge and novelty seeking' were the main push factors that drove long-haul travel by international tourists to Penang. Meanwhile, the main pull factor that attracts long- haul travel by international tourists to Penang was its ‘culture and history'. Additionally, there were partly direct and significant relationships between socio-demographic, trip characteristics and travel motivation (push factors and pull factors). Overall, this study identified the long-haul travel motivations by international tourists to Penang based on socio-demographic, trip characteristics and travel motivation and has indirectly helped in understanding the long-haul travel market particularly for Penang and Southeast Asia. This research also suggested for an effective marketing and promotion strategy in pro- viding useful information that is the key to attract international tourists to travel long distances. Keywords:

Ferreira, Sofia Henriques, Maria Morais, Daniela Nunes, Maria João Oliveira, Ana Rovisco, Ana Pimentel, Hugo Águas, Elvira Fortunato, and Rodrigo Martins. "{High UV and Sunlight Photocatalytic Performance of Porous ZnO Nanostructures Synthesized by a Facile and Fast Microwave Hydrothermal Method}." Materials. 14 (2021): 2385. AbstractWebsite

The degradation of organic pollutants in wastewaters assisted by oxide semiconductor nanostructures has been the focus of many research groups over the last decades, along with the synthesis of these nanomaterials by simple, eco-friendly, fast, and cost-effective processes. In this work, porous zinc oxide (ZnO) nanostructures were successfully synthesized via a microwave hydrothermal process. A layered zinc hydroxide carbonate (LZHC) precursor was obtained after 15 min of synthesis and submitted to different calcination temperatures to convert it into porous ZnO nanostructures. The influence of the calcination temperature (300, 500, and 700 °C) on the morphological, structural, and optical properties of the ZnO nanostructureswas investigated. All ZnO samples were tested as photocatalysts in the degradation of rhodamine B (RhB) under UV irradiation and natural sunlight. All samples showed enhanced photocatalytic activity under both light sources, with RhB being practically degraded within 60 min in both situations. The porous ZnO obtained at 700 °C showed the greatest photocatalytic activity due to its high crystallinity, with a degradation rate of 0.091 and 0.084 min−1 for UV light and sunlight, respectively. These results are a very important step towards the use of oxide semiconductors in the degradation of water pollutants mediated by natural sunlight.

{Isabel Bento Rovisco}, Ana, Rita Branquinho, Joana {Vaz Pinto}, Rodrigo Martins, Elvira Fortunato, and Pedro Barquinha. "{Hydrothermal Synthesis of Zinc Tin Oxide Nanostructures for Photocatalysis, Energy Harvesting and Electronics}." Novel Nanomaterials. IntechOpen, 2021. Abstract
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Rovisco, Ana, Rita Branquinho, Rodrigo Martins, Elvira Fortunato, and Pedro Barquinha. "{Microwave-Assisted Hydrothermal Synthesis of Zn2SnO4 Nanostructures for Photocatalytic Dye Degradation}." Materials Proceedings. 4 (2021): 92. AbstractWebsite

Zinc-tin oxide (ZTO) nanostructures appear as one of the most promising material systems for a new generation of nanodevices. In this work, a microwave-assisted hydrothermal synthesis to produce different shapes of Zn2SnO4 nanostructures (nanoparticles, octahedrons and nanoplates) is presented. Reproducible and homogeneous results were obtained with the advantage of reducing up to 20 h the synthesis time when compared to using a conventional oven. Furthermore, the photocatalytic activity of the Zn2SnO4 nanostructures in the degradation of rhodamine B under UV light was studied. Zn2SnO4 nanoparticles demonstrated better performance with >90% of degradation being achieved in 2.5 h.

dos Santos, Andreia, Filipe Sabino, Ana Rovisco, Pedro Barquinha, Hugo Águas, Elvira Fortunato, Rodrigo Martins, and Rui Igreja. "{Optimization of ZnO Nanorods Concentration in a Micro-Structured Polymeric Composite for Nanogenerators}." Chemosensors. 9 (2021): 27. AbstractWebsite

The growing use of wearable devices has been stimulating research efforts in the development of energy harvesters as more portable and practical energy sources alternatives. The field of piezoelectric nanogenerators (PENGs) and triboelectric nanogenerators (TENGs), especially employing zinc oxide (ZnO) nanowires (NWs), has greatly flourished in recent years. Despite its modest piezoelectric coefficient, ZnO is very attractive due to its sustainable raw materials and the facility to obtain distinct morphologies, which increases its multifunctionality. The integration of ZnO nanostructures into polymeric matrices to overcome their fragility has already been proven to be fruitful, nevertheless, their concentration in the composite should be optimized to maximize the harvesters' output, an aspect that has not been properly addressed. This work studies a composite with variable concentrations of ZnO nanorods (NRs), grown by microwave radiation assisted hydrothermal synthesis, and polydimethylsiloxane (PDMS). With a 25 wt % ZnO NRs concentration in a composite that was further micro-structured through laser engraving for output enhancement, a nanogenerator (NG) was fabricated with an output of 6 V at a pushing force of 2.3 N. The energy generated by the NG could be stored and later employed to power small electronic devices, ultimately illustrating its potential as an energy harvesting device.

Rovisco, Ana, Rita Branquinho, Jonas Deuermeier, Tomás Freire, Elvira Fortunato, Rodrigo Martins, and Pedro Barquinha. "{Shape Effect of Zinc-Tin Oxide Nanostructures on Photodegradation of Methylene Blue and Rhodamine B under UV and Visible Light}." ACS Applied Nano Materials. 4 (2021): 1149-1161. AbstractWebsite
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Silva, Carlos, Jorge Martins, Jonas Deuermeier, Maria Elias Pereira, Ana Rovisco, Pedro Barquinha, João Goes, Rodrigo Martins, Elvira Fortunato, and Asal Kiazadeh. "{Towards Sustainable Crossbar Artificial Synapses with Zinc-Tin Oxide}." Electronic Materials. 2 (2021): 105-115. AbstractWebsite

In this article, characterization of fully patterned zinc-tin oxide (ZTO)-based memristive devices with feature sizes as small as 25 µm2 is presented. The devices are patterned via lift-off with a platinum bottom contact and a gold-titanium top contact. An on/off ratio of more than two orders of magnitude is obtained without the need for electroforming processes. Set operation is a current controlled process, whereas the reset is voltage dependent. The temperature dependency of the electrical characteristics reveals a bulk-dominated conduction mechanism for high resistance states. However, the charge transport at low resistance state is consistent with Schottky emission. Synaptic properties such as potentiation and depression cycles, with progressive increases and decreases in the conductance value under 50 successive pulses, are shown. This validates the potential use of ZTO memristive devices for a sustainable and energy-efficient brain-inspired deep neural network computation.

2020
Martins, Jorge, Asal Kiazadeh, Joana V. Pinto, Ana Rovisco, Tiago Gonçalves, Jonas Deuermeier, Eduardo Alves, Rodrigo Martins, Elvira Fortunato, and Pedro Barquinha. "{Ta2O5/SiO2 Multicomponent Dielectrics for Amorphous Oxide TFTs}." Electronic Materials. 2 (2020): 1-16. AbstractWebsite

Co-sputtering of SiO2 and high-$ąppa$ Ta2O5 was used to make multicomponent gate dielectric stacks for In-Ga-Zn-O thin-film transistors (IGZO TFTs) under an overall low thermal budget (T = 150 °C). Characterization of the multicomponent layers and of the TFTs working characteristics (employing them) was performed in terms of static performance, reliability, and stability to understand the role of the incorporation of the high-$ąppa$ material in the gate dielectric stack. It is shown that inherent disadvantages of the high-$ąppa$ material, such as poorer interface properties and poor gate insulation, can be counterbalanced by inclusion of SiO2 both mixed with Ta2O5 and as thin interfacial layers. A stack comprising a (Ta2O5)x(SiO2)100 − x film with x = 69 and a thin SiO2 film at the interface with IGZO resulted in the best performing TFTs, with field-effect mobility (µFE) ≈ 16 cm2·V−1·s−1, subthreshold slope (SS) ≈ 0.15 V/dec and on/off ratio exceeding 107. Anomalous Vth shifts were observed during positive gate bias stress (PGBS), followed by very slow recoveries (time constant exceeding 8 × 105 s), and analysis of the stress and recovery processes for the different gate dielectric stacks showed that the relevant mechanism is not dominated by the interfaces but seems to be related to the migration of charged species in the dielectric. The incorporation of additional SiO2 layers into the gate dielectric stack is shown to effectively counterbalance this anomalous shift. This multilayered gate dielectric stack approach is in line with both the large area and the flexible electronics needs, yielding reliable devices with performance suitable for successful integration on new electronic applications.

Rovisco, Ana, Andreia dos Santos, Tobias Cramer, Jorge Martins, Rita Branquinho, Hugo Águas, Beatrice Fraboni, Elvira Fortunato, Rodrigo Martins, Rui Igreja, and Pedro Barquinha. "{Piezoelectricity Enhancement of Nanogenerators Based on PDMS and ZnSnO 3 Nanowires through Microstructuration}." ACS Applied Materials & Interfaces. 12 (2020): 18421-18430. AbstractWebsite

The current trend for smart, self-sustainable, and multifunctional technology demands for the development of energy harvesters based on widely available and environmentally friendly materials. In this context, ZnSnO3 nanostructures show promising potential because of their high polarization, which can be explored in piezoelectric devices. Nevertheless, a pure phase of ZnSnO3 is hard to achieve because of its metastability, and obtaining it in the form of nanowires is even more challenging. Although some groups have already reported the mixing of ZnSnO3 nanostructures with polydimethylsiloxane (PDMS) to produce a nanogenerator, the resultant polymeric film is usually flat and does not take advantage of an enhanced piezoelectric contribution achieved through its microstructuration. Herein, a microstructured composite of nanowires synthesized by a seed-layer free hydrothermal route mixed with PDMS (ZnSnO3@PDMS) is proposed to produce nanogenerators. PFM measurements show a clear enhancement of d33 for single ZnSnO3 versus ZnO nanowires (23 ± 4 pm/V vs 9 ± 2 pm/V). The microstructuration introduced herein results in an enhancement of the piezoelectric effect of the ZnSnO3 nanowires, enabling nanogenerators with an output voltage, current, and instantaneous power density of 120 V, 13 $μ$A, and 230 $μ$W·cm-2, respectively. Even using an active area smaller than 1 cm2, the performance of this nanogenerator enables lighting up multiple LEDs and other small electronic devices, thus proving great potential for wearables and portable electronics.

Bahubalindruni, Pydi Ganga, Pedro Barquinha, Bhawna Tiwari, Maria Pereira, Ana Santa, Jorge Martins, Ana Rovisco, Vitor Tavares, Rodrigo Martins, and Elvira Fortunato. "{Rail-to-Rail Timing Signals Generation Using InGaZnO TFTs for Flexible X-Ray Detector}." IEEE Journal of the Electron Devices Society. 8 (2020): 157-162. AbstractWebsite

This paper reports on-chip rail-to-rail timing signals generation thin-film circuits for the first time. These circuits, based on a-IGZO thin-film transistors (TFTs) with a simple staggered bottom gate structure, allow row and column selection of a sensor matrix embedded in a flexible radiation sensing system. They include on-chip clock generator (ring oscillator), column selector (shift register) and row-selector (a frequency divider and a shift register). They are realised with rail-to-rail logic gates with level-shifting ability that can perform inversion and NAND logic operations. These logic gates are capable of providing full output swing between supply rails, $V_{DD}$ and $V_{SS}$ , by introducing a single additional switch for each input in bootstrapping logic gates. These circuits were characterised under normal ambient atmosphere and show an improved performance compared to the conventional logic gates with diode connected load and pseudo CMOS counterparts. By using these high-performance logic gates, a complete rail-to-rail frequency divider is presented from measurements using D-Flip Flop. In order to realize a complete compact system, an on-chip ring oscillator (output clock frequency around 1 kHz) and a shift register are also presented from simulations, where these circuits show a power consumption of 1.5 mW and 0.82 mW at a supply voltage of 8 V, respectively. While the circuit concepts described here were designed for an X-ray sensing system, they can be readily expanded to other domains where flexible on-chip timing signal generation is required, such as, smart packaging, biomedical wearable devices and RFIDs.

2019
Rovisco, Ana, Rita Branquinho, Jorge Martins, Elvira Fortunato, Rodrigo Martins, and Pedro Barquinha. "{Growth Mechanism of Seed-Layer Free ZnSnO3 Nanowires: Effect of Physical Parameters}." Nanomaterials. 9 (2019): 1002. AbstractWebsite

ZnSnO3 semiconductor nanostructures have several applications as photocatalysis, gas sensors, and energy harvesting. However, due to its multicomponent nature, the synthesis is far more complex than its binary counter parts. The complexity increases even more when aiming for low-cost and low-temperature processes as in hydrothermal methods. Knowing in detail the influence of all the parameters involved in these processes is imperative, in order to properly control the synthesis to achieve the desired final product. Thus, this paper presents a study of the influence of the physical parameters involved in the hydrothermal synthesis of ZnSnO3 nanowires, namely volume, reaction time, and process temperature. Based on this study a growth mechanism for the complex Zn:Sn:O system is proposed. Two zinc precursors, zinc chloride and zinc acetate, were studied, showing that although the growth mechanism is inherent to the material itself, the chemical reactions for different conditions need to be considered.

Rovisco, Ana, Rita Branquinho, Jorge Martins, Elvira Fortunato, Rodrigo Martins, and Pedro Barquinha. "{Growth Mechanism of Seed-Layer Free ZnSnO3 Nanowires: Effect of Physical Parameters}." Nanomaterials. 9 (2019): 1002. Abstract

ZnSnO3 semiconductor nanostructures have several applications as photocatalysis, gas sensors, and energy harvesting. However, due to its multicomponent nature, the synthesis is far more complex than its binary counter parts. The complexity increases even more when aiming for low-cost and low-temperature processes as in hydrothermal methods. Knowing in detail the influence of all the parameters involved in these processes is imperative, in order to properly control the synthesis to achieve the desired final product. Thus, this paper presents a study of the influence of the physical parameters involved in the hydrothermal synthesis of ZnSnO3 nanowires, namely volume, reaction time, and process temperature. Based on this study a growth mechanism for the complex Zn:Sn:O system is proposed. Two zinc precursors, zinc chloride and zinc acetate, were studied, showing that although the growth mechanism is inherent to the material itself, the chemical reactions for different conditions need to be considered.

2018
Rovisco, Ana, Rita Branquinho, Jorge Martins, Maria João Oliveira, Daniela Nunes, Elvira Fortunato, Rodrigo Martins, and Pedro Barquinha. "{Seed-Layer Free Zinc Tin Oxide Tailored Nanostructures for Nanoelectronic Applications: Effect of Chemical Parameters}." ACS Applied Nano Materials. 1 (2018): 3986-3997. AbstractWebsite

Semiconductor nanowires are mostly processed by complex, expensive and high temperature methods. In this work, with the intent of developing zinc tin oxide nanowires (ZTO NWs) by low-cost and low-complexity processes, we show a detailed study on the influence of chemical parameters in the hydrothermal synthesis of ZTO nanostructures at temperatures of only 200 °C. Two different zinc precursors, the ratio between zinc and tin precursors, the concentration of the surfactant agent and of the mineralizer were studied. The type and the crystallinity of the nanostructures was found to be highly dependent on the used precursors and on the concentration of each reagent. Conditions for obtaining different ZTO nanostructures were achieved, namely Zn2SnO4 nanoparticles and ZnSnO3 nanowires with length ≈ 600 nm, with the latter being reported for the first time ever by hydrothermal methods without the use of seed layers. Optical and electrical properties were analyzed, being obtained band gaps of 3.60 and 3.46 eV, fo...

2017
Martins, Jorge, Pydi Bahubalindruni, Ana Rovisco, Asal Kiazadeh, Rodrigo Martins, Elvira Fortunato, and Pedro Barquinha. "{Bias Stress and Temperature Impact on InGaZnO TFTs and Circuits}." Materials. 10 (2017): 680. AbstractWebsite

This paper focuses on the analysis of InGaZnO thin-film transistors (TFTs) and circuits under the influence of different temperatures and bias stress, shedding light into their robustness when used in real-world applications. For temperature-dependent measurements, a temperature range of 15 to 85 • C was considered. In case of bias stress, both gate and drain bias were applied for 60 min. Though isolated transistors show a variation of drain current as high as 56% and 172% during bias voltage and temperature stress, the employed circuits were able to counteract it. Inverters and two-TFT current mirrors following simple circuit topologies showed a gain variation below 8%, while the improved robustness of a cascode current mirror design is proven by showing a gain variation less than 5%. The demonstration that the proper selection of TFT materials and circuit topologies results in robust operation of oxide electronics under different stress conditions and over a reasonable range of temperatures proves that the technology is suitable for applications such as smart food packaging and wearables.

2016
Bahubalindruni, Pydi Ganga, Asal Kiazadeh, Allegra Sacchetti, Jorge Martins, Ana Rovisco, Vitor Grade Tavares, Rodrigo Martins, Elvira Fortunato, and Pedro Barquinha. "{Influence of Channel Length Scaling on InGaZnO TFTs Characteristics: Unity Current-Gain Cutoff Frequency, Intrinsic Voltage-Gain, and On-Resistance}." Journal of Display Technology. 12 (2016): 515-518. AbstractWebsite
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Barrocas, B., S. Sério, A. Rovisco, Y. Nunes, and Melo M. E. Jorge. "{Removal of rhodamine 6G dye contaminant by visible light driven immobilized Ca1⿿Ln MnO3 (Ln = Sm, Ho; 0.1 ⿤x⿤ 0.4) photocatalysts}." Applied Surface Science. 360 (2016): 798-806. AbstractWebsite

Visible-light-driven Ca1-xLnxMnO3 (Ln=Sm, Ho; 0.1≤x≤0.4) films were grown by RF- magnetron sputtering onto fused silica substrates. The effects of Ca2+ substitution for Ho3+ or Sm3+ in Ca1-xLnxMnO3 on the structural, morphological and photocatalytic properties for Rhodamine 6G dye degradation under visible light irradiation were investigated. XRD showed a pure typical perovskite phase for all the prepared films, except for Ca0.9Ho0.1MnO3 and a decrease of the crystallite size with the increase of the amount of ion substituted. SEM and AFM revealed that the films surface is dense, with low roughness. UV-vis spectroscopy indicated for the two series band gaps in the range of 1.6 - 2.8eV, being lower for the films containing holmium. The results showed that some Ca1-xHoxMnO3 and Ca1-xSmxMnO3 films present higher photocatalytic activity for Rh6G degradation in comparison with TiO2 films and for the same x value the Ho-films exhibited higher photocatalytic activity. For both films series the maximal degradation rate was obtained for x=0.2; above this content the degradation percentage exhibits a decreasing trend with the increase of Ho or Sm substitution, except for x=0.4 in the case of Ho system, which is observed again an increase in the degradation rate. The Rh6G photocatalytic degradation followed a pseudo first-order reaction kinetics. XRD and SEM of the used photocatalysts evidenced high photochemical stability.

Kiazadeh, Asal, Henrique L. Gomes, Pedro Barquinha, Jorge Martins, Ana Rovisco, Joana V. Pinto, Rodrigo Martins, and Elvira Fortunato. "{Improving positive and negative bias illumination stress stability in parylene passivated IGZO transistors}." Applied Physics Letters. 109 (2016): 051606. AbstractWebsite
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2014
Barrocas, B., S. Sério, A. Rovisco, and M. E. {Melo Jorge}. "{Visible-Light Photocatalysis in Ca0.6Ho0.4MnO3 Films Deposited by RF-Magnetron Sputtering Using Nanosized Powder Compacted Target}." The Journal of Physical Chemistry C. 118 (2014): 590-597. AbstractWebsite

A novel immobilized Ca0.6Ho0.4MnO3 photocatalyst has been developed with high photocatalytic activity for Rhodamine 6G (Rh6G) photodegradation under visible light irradiation. The nanocrystalline Ca0.6Ho0.4MnO3 films were successfully deposited by RF-magnetron sputtering on unheated quartz glass substrates using Ca0.6Ho0.4MnO3 powder as sputtering target and its photocatalytic functionalities have been explored. The visible-light-responsive photocatalytic activity of Ca0.6Ho0.4MnO3 films was evaluated by the photodegradation of Rh6G aqueous solutions under visible light irradiation. The reusability of Ca0.6Ho0.4MnO3 films on fresh dye samples was studied, showing an efficient reuse, without decreasing the photocatalytic decolorization efficiency. Furthermore, X-ray diffraction of the reused films did not reveal additional phases indicating high photochemical stability of the films even after reusing them in successive runs. The photocatalytic efficiency of the nanocrystalline Ca0.6Ho0.4MnO3 films was further compared with TiO2 films also produced by sputtering and the results revealed a significant improvement in photocatalytic activity over TiO2 under visible light irradiation. Almost complete photodecolorization of a 5 ppm Rh6G solution was achieved in 4 h, while only 64% of dye degradation was observed in TiO2 photoassisted process. This work provides a feasible route to fabricate high-performance immobilized ABO3-based nanomaterials, and the finding opens up a new venue for designing visible light sensitive ternary compounds for photocatalytical applications. A novel immobilized Ca0.6Ho0.4MnO3 photocatalyst has been developed with high photocatalytic activity for Rhodamine 6G (Rh6G) photodegradation under visible light irradiation. The nanocrystalline Ca0.6Ho0.4MnO3 films were successfully deposited by RF-magnetron sputtering on unheated quartz glass substrates using Ca0.6Ho0.4MnO3 powder as sputtering target and its photocatalytic functionalities have been explored. The visible-light-responsive photocatalytic activity of Ca0.6Ho0.4MnO3 films was evaluated by the photodegradation of Rh6G aqueous solutions under visible light irradiation. The reusability of Ca0.6Ho0.4MnO3 films on fresh dye samples was studied, showing an efficient reuse, without decreasing the photocatalytic decolorization efficiency. Furthermore, X-ray diffraction of the reused films did not reveal additional phases indicating high photochemical stability of the films even after reusing them in successive runs. The photocatalytic efficiency of the nanocrystalline Ca0.6Ho0.4MnO3 films was further compared with TiO2 films also produced by sputtering and the results revealed a significant improvement in photocatalytic activity over TiO2 under visible light irradiation. Almost complete photodecolorization of a 5 ppm Rh6G solution was achieved in 4 h, while only 64% of dye degradation was observed in TiO2 photoassisted process. This work provides a feasible route to fabricate high-performance immobilized ABO3-based nanomaterials, and the finding opens up a new venue for designing visible light sensitive ternary compounds for photocatalytical applications.

Barrocas, B., S. Sério, A. Rovisco, Y. Nunes, A. I. de Sá, Silva M. I. da Pereira, and Melo M. E. Jorge. "{Characterization and electrochemical behaviour of nanostructured calcium samarium manganite electrodes fabricated by RF-Magnetron Sputtering}." Electrochimica Acta. 137 (2014): 99-107. AbstractWebsite

Ca1-xSmxMnO3 (0≤x≤0.4) films were successfully fabricated on Indium Tin Oxide (ITO) coated quartz glass substrates by radio frequency magnetron sputtering technique (RF- magnetron sputtering) from compacted nanosized powder targets, and subsequent annealing at 800°C in air, for 6h. X-ray diffraction shows a pure typical perovskite phase for x≥0.1. Scanning electron microscopy and atomic force microscopy revealed that the film surface is dense, with low roughness, depending on the Sm content, even though a few cracks were observed. Crystallite size was found to decrease with the Sm content. The electrodes were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS).The oxide electrode's capacitance was estimated using both techniques and the corresponding roughness factors evaluated. The values obtained from the two methods show a good agreement. A comparison between the voltammetric data and those referred in the literature allowed finding out that the redox reaction occurring at the electrode surface involves the pair Mn4+/Mn3+. EIS measurements confirm the voltammetric data and they also give additional information about the film porosity and the charge transfer resistance. This last parameter is associated with the oxidation and reduction of the pair Mn3+/Mn4+and after normalized by the roughness factor shows an increase with samarium content.