Monitorização e otimização da deposição de filmes de óxidos mistos por RF-sputtering

Dissertação para obtenção do Grau de Mestre em Engenharia FísicaEste trabalho descreve a produção e caracterização de filmes de óxidos mistos depositados por pulverização catódica de rádio frequência assistida por magnetrão a partir de alvos de pó compactado, para utilização como elétrodos em aplicações ambientais. Os óxidos mistos utilizados como alvos apresentam a composição geral Ca1-xAxMnO3, com A=Sm ou Ho e 0≤x≤0,4 e já se encontravam previamente preparados pelo método de auto-combustão. Os filmes foram depositados em dois tipos de substratos, substratos de fused silica (não condutores) e substratos de quartzo com filme de ITO pré-depositado (condutores) e, posteriormente, submetidos a tratamento térmico, a T=800ºC ao ar durante 6 horas, para promover a formação de um filme cristalino. Os filmes foram caracterizados por difração de raios-X (XRD), microscopia eletrónica de varrimento (SEM) e microscopia de forças atómicas (AFM). A caracterização estrutural revelou que praticamente todos os filmes após o tratamento térmico cristalizam numa estrutura tipo perovskite, à exceção dos filmes produzidos a partir de alvos de CaMnO3 e de Ca0,9Ho0,1MnO3, que apresentam maioritariamente a fase Ca2Mn3O8. A partir da análise das imagens obtidas por SEM e por AFM, verificou-se que, de um modo geral, as superfícies são pouco rugosas e apresentam uma morfologia semelhante. A caracterização por AFM mostrou ainda que os valores de rugosidade média, Rrms, são superiores para os filmes depositados em substrato de quartzo com filme de ITO. É ainda de salientar que com este trabalho se conseguiu desenvolver elétrodos de filmes de óxidos mistos com boa aderência e estabilidade mecânica revelando que a técnica de pulverização catódica (sputtering) é uma alternativa bastante promissora para a produção de elétrodos de óxidos mistos comparativamente com os métodos normalmente utilizados. Esta tese é constituída por 5 capítulos. O Capítulo I refere-se à introdução do trabalho, na qual se pretende dar a conhecer as motivações do projeto realizado e, ainda, expor alguns conceitos sobre os óxidos mistos utilizados e fundamentos sobre a Física de Plasmas, de modo a clarificar o processo de pulverização catódica como técnica para a deposição de filmes. No Capítulo II, Técnicas de Caracterização, são apresentados os conceitos básicos e princípios de funcionamento das técnicas utilizadas para a caracterização dos filmes obtidos (XRD, AFM e SEM) e o procedimento utilizado.No Capítulo III descreve-se o procedimento experimental associado ao desenvolvimento dos filmes, bem como o sistema de deposição em que se trabalhou. O Capítulo IV refere-se à apresentação e à análise dos resultados obtidos na caracterização dos filmes através das várias técnicas utilizadas.O Capítulo V corresponde à apresentação das conclusões obtidas ao longo da realização do trabalho. Por fim, são ainda apresentadas as perspetivas futuras para este projeto.Fundação para a Ciência e Tecnologia - PTDC/AAC-AMB/103112/200

Microwave-Assisted Hydrothermal Synthesis of Zn2SnO4 Nanostructures for Photocatalytic Dye Degradation

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.publishersversionpublishe

Desenvolvimento de uma metodologia para promover a sua implementação em Portugal

As entidades públicas estão entre os grandes consumidores ao nível europeu, despendendo mais de 1,5 mil milhões de euros, anualmente, em compras públicas de produtos e serviços. A integração de critérios ambientais no processo de contratação pública permite, segundo a Estratégia Nacional para as Compras Públicas Ecológicas 2008-2010 (Resolução do Conselho de Ministros n.º 65/2007), “estabelecer uma interligação entre as várias acções e políticas comunitárias, possibilitando uma abordagem das questões ambientais mais abrangente e sustentável”. O presente estudo apresenta dois objectivos distintos: 1) analisar o ponto de situação da administração pública quanto às compras públicas ecológicas, seleccionando para tal dois organismos representativos: o Ministério da Educação e o Ministério da Saúde; e 2) desenvolver uma metodologia prática, para a implementação de compras públicas ecológicas, um “guia” para aquisições ambientalmente adequadas de apoio à decisão, permitindo ao utilizador cumprir os objectivos da Estratégia Nacional de Compras Públicas Ecológicas, desempenhando um papel decisivo ao ser protagonizador e promotor de comportamentos sustentáveis. A análise das práticas ao nível dos Ministérios torna-se então fundamental, uma vez que estes órgãos de poder central e fazedores de políticas públicas podem ser indutores de mudanças comportamentais, isto é podem servir de exemplo de boas práticas a outros sectores da sociedade

Microwave-Assisted Synthesis of Zn2SnO4 Nanostructures for Photodegradation of Rhodamine B under UV and Sunlight

Funding Information: This work is funded by National Funds through FCT—Portuguese Foundation for Science and Technology, Reference UIDB/50025/2020-2023. This work also received funding from the European Community’s H2020 program under grant agreement No. 716510 (ERC-2016-StG TREND) and No. 101008701 (EMERGE). Publisher Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland.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.publishersversionpublishe

effect of physical parameters

POCI-01-0145-FEDER-007688. SFRH/BD/131836/2017. SFRH/BD/122286/2016.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.publishersversionpublishe

High UV and sunlight photocatalytic performance of porous ZnO nanostructures synthesized by a facile and fast microwave hydrothermal method

Funding Information: Funding: This work is funded by National Funds through FCT-Portuguese Foundation for Science and Technology, reference UIDB/50025/2020-2023 and FCT/MCTES. This work also received funding from the European Community’s H2020 program under grant agreement No. 787410 (ERC-2018-AdG DIGISMART), No. 716510 (ERC-2016-StG TREND) and No. 952169 (SYNERGY, H2020-WIDESPREAD-2020-5, CSA). S. H. F. acknowledges FCT for the AdvaMTech PhD program scholarship PD/BD/114086/2015 and IDS-FunMat-INNO-2 project FPA2016/EIT/EIT RawMaterials Grant Agreement 17184. M.J.O. acknowledges FCT for the scholarship SFRH/BD/132057/2017 and MIT Portugal PhD Program.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.publishersversionpublishe

Rail-to-Rail Timing Signals Generation Using InGaZnO TFTs for Flexible X-Ray Detector

ECR/2017/000931 POCI-01-0145-FEDER-007688This 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.publishersversionpublishe

Seed-Layer Free Zinc Tin Oxide Tailored Nanostructures for Nanoelectronic Applications: Effect of Chemical Parameters

POCI-01-0145-FEDER-007688Semiconductor 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 degrees C. Two different zinc precursors, the ratio between zinc and tin precursors, and the concentration of the surfactant agent and of the mineralizer were studied. The type and the crystallinity of the nanostructures were 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 similar to 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, obtaining band gaps of 3.60 and 3.46 eV for ZnSnO3 and Zn2SnO4, respectively, and a resistivity of 1.42 k Omega.cm for single ZnSnO3 nanowires, measured using nanomanipulators after localized deposition of Pt electrodes by e-beam assisted gas decomposition. The low-temperature hydrothermal methods explored here proved to be a low-cost, reproducible, and highly flexible route to obtain multicomponent oxide nanostructures, particularly ZTO NWs. The diversity of the synthesized ZTO structures has potential application in next-generation nanoscale devices such as field effect nanotransistors, nanogenerators, resistive switching memories, gas sensors, and photocatalysis.proofpublishe

Improving positive and negative bias illumination stress stability in parylene passivated IGZO transistors

The impact of a parylene top-coating layer on the illumination and bias stress instabilities of indium-gallium-zinc oxide thin-film transistors (TFTs) is presented and discussed. The parylene coating substantially reduces the threshold voltage shift caused by continuous application of a gate bias and light exposure. The operational stability improves by 75%, and the light induced instability is reduced by 35%. The operational stability is quantified by fitting the threshold voltage shift with a stretched exponential model. Storage time as long as 7 months does not cause any measurable degradation on the electrical performance. It is proposed that parylene plays not only the role of an encapsulation layer but also of a defect passivation on the top semiconductor surface. It is also reported that depletion-mode TFTs are less sensitive to light induced instabilities. This is attributed to a defect neutralization process in the presence of free electrons. Published by AIP Publishing