Scale up of microwave annealed FA0.83Cs0.17PbI1.8Br1.2 perovskite towards an industrial scale

ABSTRACT: Perovskite solar cells (PSCs) efficiency has rapidly increased from the initial 3.8 to recent 24.2%. This high efficiency has attracted serious worldwide researchers and industry attention due to their low material cost, and simple solution-based fabrication process. However, fundamental studies on PSCs are usually produced through lab-scale actions and carried out on small-area devices (≤1 cm2). Here we present the advances of up-scaling using microwave (MW) annealing of perovskite films on large area specimens (~16 cm2), looking forward the industrial-scale. Morphological, structural and optical characterization were performed to confirm the effectiveness of the scaled up MW annealing.info:eu-repo/semantics/publishedVersio

Diagnosis of pathologies in ancient (seventeenth-eighteenth centuries) decorative blue-and-white ceramic tiles : Green stains in the glazes of a panel depicting Lisbon prior to the 1755 earthquake

Decorative panels of ceramic glazed tiles comprise a valuable cultural heritage in Mediterranean countries. Their preservation requires the development of a systematic scientific approach. Exposure to an open-air environment allows for a large span of deterioration effects. Successfully overcoming these effects demands a careful identification of involved degradation processes. Among these, the development of micro-organisms and concomitant glaze surface staining is a very common effect observed in panels manufactured centuries ago. This paper describes a study on the nature of green stains appearing at the surface of blue-and-white tile glazes from a large decorative panel with more than one thousand tiles, called Vista de Lisboa that depicts the city before the destruction caused by the 1755 earthquake. The characterization of green-stained blue-and-white tile glazes was performed using non-destructive X-ray techniques (diffraction and fluorescence spectrometry) by directly irradiating the surface of small tile fragments, complemented by a destructive scanning electron microscopy (SEM) observation of one fragment. Despite the green staining, analytical X-ray data showed that no deterioration had occurred irrespective of the blue or white color, while complementary SEM-EDX data provided chemical evidence of microorganism colonization at the stained glaze surface

Charge transport and recombination of dye sensitized 1D nanostructured-TiO2 films prepared by reactive sputtering

Dye sensitized solar cells (DSCs) are governed by light absorption, charge injection, electron transport and recombination and electrolyte diffusion. One way to improve the efficiency of these devices is by the design of highly ordered nanostructured semiconductor materials.The advantages can be two-fold: Firstly charge transport within the metal-oxide can be enhanced and hence thicker films can be employed and secondly, the complete permeation with a solid-state hole-transport medium of the sensitized metal-oxide can be facilitated. Nanostructured materials should promote vectorial electron diffusion and have as few recombination sights as possible so as to further enhance electron lifetimes and electron collection efficiencies. These materials should also have a high surface area so as to allow for efficient dye-loading and hence light absorption. Highly ordered TiO2 nanostructured films were prepared by reactive sputtering and their charge transport characteristics evaluated in DSCs. These were compared to DSCs employing mesoporous TiO2 films prepared by doctor blade technique using commercial paste. Charge transport characteristics were evaluated by impedance spectroscopy (IS), incident photon to current conversion efficiencies (IPCE) and current-voltage (iV) curves under simulated AM1.5G irradiation. Film morphology and structural properties were evaluated by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively

Assessment of dye distribution in sensitized solar cells by microprobe techniques

Dye sensitized solar cells (DSCs) have received considerable attention once this technology offers economic and environmental advantages over conventional photovoltaic (PV) devices. The PV performance of a DSC relies on the characteristics of its photoanode, which typically consists of a nanocrystalline porous TiO2 film, enabled with a large adsorptive surface area. Dye molecules that capture photons from light during device operation are attached to the film nanoparticles. The effective loading of the dye in the TiO2 electrode is of paramount relevance for controlling and optimizing solar cell parameters. Relatively few methods are known today for quantitative evaluation of the total dye adsorbed on the film. In this context, microprobe techniques come out as suitable tools to evaluate the dye surface distribution and depth profile in sensitized films. Electron Probe Microanalysis (EPMA) and Ion Beam Analytical (IBA) techniques using a micro-ion beam were used to quantify and to study the distribution of the Ru organometallic dye in TiO2 films, making use of the different penetration depth and beam sizes of each technique. Different 1D nanostructured TiO2 films were prepared, morphologically characterized by SEM, sensitized and analyzed by the referred techniques. Dye load evaluation in different TiO2 films by three different techniques (PIXE, RBS and EPMA/WDS) provided similar results of Ru/Ti mass fraction ratio. Moreover, it was possible to assess dye surface distribution and its depth profile, by means of Ru signal, and to visualize the dye distribution in sample cross-section through X-ray mapping by EPMA/EDS. PIXE maps of Ru and Ti indicated an homogeneous surface distribution. The assessment of Ru depth profile by RBS showed that some films have homogeneous Ru depth distribution while others present different Ru concentration in the top layer (2 lm thickness). These results are consistent with the EPMA/EDS maps obtained

Microscopy techniques for dye distribution in DSCs nanocrystalline TiO2 films

Capture of sunlight has attracted an increasing interest in the scientific community and triggered the development of efficient and cheap photovoltaic devices. Amongst recent generation technologies for solar energy conversion, dye-sensitized solar cells (DSCs) show an optimal trade-off between high-conversion efficiency and low-cost manufacturing. For the last two decades, significant progress has been made and best energy conversion efficiency of the DSC at the laboratory scale has surpassed 12% [1]. A lot of work has focused on the enlargement of surface areas to enhance the amount of adsorbed dyes by reduction of nanoparticle sizes or utilization of novel structures. Nevertheless there remain some crucial details of DSC operation for which limited information is available, namely dye diffusion and adsorption, surface coverage and dye distribution throughout the nc-TiO2 film. Microprobe techniques can be powerful tools to evaluate the dye load, the dye distribution and dye depth profile in sensitized films. Electron Probe Microanalysis (EPMA) and Ion Beam Analytical (IBA) techniques using a micro-ion beam, namely micro-Particle Induced X-ray Emission ( PIXE) and Rutherford Backscattering Spectrometry (RBS), were used to quantify and to study the distribution of the ruthenium organometallic (N719) dye in TiO2 films, profiting from the different penetration depth and beam sizes of each technique. Two different types of films were prepared and sensitized, mesoporous nanoparticles and 1D nanostructured TiO2 films (figure 1). Despite the low concentration of Ru, the high sensitive analytical techniques used allowed to assess the Ru surface distribution and depth profile. Fig. 2 shows the PIXE maps of Ru and Ti indicating an homogeneous surface distribution. The same figure presents the RBS spectra obtained with a 2 MeV proton beam of the same sample showing that a good spectra fit is obtained considering only two sample layers: the first one with a 1.7 ìm thickness; the second one being the SiO2 substrate. The Ru RBS signal also shows that the dye has an homogeneous depth distribution. Due to the fine spatial resolution of the EPMA/WDS (Wavelength Dispersive Spectroscopy) technique it was possible to visualise the dye distribution in sample cross-section (with micrometer or submicrometer dimensions) as presented in Fig. 3 for the elemental mapping of a mesoporous nanoparticle TiO2 film. Dye load evaluation by two different techniques (ìPIXE and EPMA/WDS) provided similar results (Ru/Ti values around 0.5 %). The distribution analysis of the organometallic dye (N719) was done through ruthenium distribution via X-ray mapping. RBS was used to assess the ruthenium depth profile. This assessment can lead to a better understanding of the device performance

Dye assessment in nanostructured TiO2 sensitized films by microprobe techniques

Dye sensitized solar cells (DSCs) have received considerable attention once this technology offers economic and environmental advantages over conventional photovoltaic (PV) devices. The PV performance of a DSC relies on the characteristics of its photoanode, which typically consists of a nanocrystalline porous TiO2 film, enabled with a large adsorptive surface area. Dye molecules that capture photons from light during device operation are attached to the film nanoparticles. The effective loading of the dye in the TiO2 electrode is of utmost importance for controlling and optimizing solar cell parameters. Relatively few methods are known today for quantitative evaluation of the total dye adsorbed on the film. In this work, a new approach combining microprobe techniques namely, Ion Beam Analytical (IBA) techniques using a micro-ion beam (Rutherford Backscattering Spectrometry (RBS) and Particle Induced X-ray Emission (PIXE)) and Electron Probe Micro-Analysis (EPMA) was carried out to assess dye distribution and depth profile in TiO2 films and the dye load based on Ru/Ti mass ratio. Different 1D nanostructured TiO2 films were prepared, morphologically characterised by SEM, sensitized and analysed by the referred techniques. Dye load evaluation in different TiO2 films by three different techniques (PIXE, RBS and EPMA/ wavelength dispersive spectrometry (WDS)) provided similar results of Ru/Ti mass fraction ratio. Moreover, it was possible to assess dye surface distribution and its depth profile, by means of Ru signal, and to visualise the dye distribution in sample cross-section through X-ray mapping by EPMA/ energy dispersive spectrometry (EDS). PIXE maps of Ru and Ti indicated an homogeneous surface distribution. The assessment of ruthenium depth profile by RBS showed that some films have homogeneous Ru depth distribution while others present different Ru concentration in the top layer (2 ìm thickness). These results are consistent with the EPMA/EDS maps obtained. EPMA (WDS and EDS) together with IBA techniques proved to be powerful tools for functional materials characterisation and provided very promising results in the study of nanostructured TiO2 sensitized films

13 anos de monitorização da descarga do emissário submarino da Guia: integração na DQA

O Programa das Nações Unidas para o Ambiente define monitorização como “o processo de observação repetitivo com fins definidos, de um ou mais elementos do ambiente, de acordo com um planeamento prévio no espaço e no tempo, utilizando metodologias comparáveis para caracterização ambiental e colheita de dados”. A Directiva Quadro da Água (DQA), o instrumento orientador na União Europeia para gestão das águas superficiais interiores, águas de transição, águas costeiras e águas subterrâneas, suporta este conceito propondo, no entanto, três níveis para os programas de monitorização: (1) monitorização de vigilância orientada para a evolução a longo prazo; (2) operacional, orientada para zonas em risco de não atingir os objectivos de qualidade requeridos pela DQA; (3) de investigação orientada para a compreensão e quantificação dos processos responsáveis por excessos que levam ao incumprimento da DQA. Embora sejam os Estados-Membros quem devam adoptar estas medidas e cumprir os seus objectivos, o comportamento pró-activo de algumas empresas contribui significativamente para o cumprimento das exigências da DQA. A SANEST, Saneamento da Costa do Estoril, empresa gestora do Sistema de Saneamento da Costa do Estoril implementou um programa de monitorização da descarga do emissário submarino da Guia. Este programa deu continuidade ao iniciado em 1993, antes da entrada em funcionamento do sistema, e é o maior programa de monitorização a nível nacional em zonas costeiras, que inclui investigação detalhada a vários níveis. O progressivo aumento do número de parâmetros e a adaptação de metodologias, quer na ETAR quer no meio receptor, demonstra também a preocupação desta empresa pela salvaguarda e gestão sustentável dos recursos. Neste trabalho são apresentados os principais resultados do programa de monitorização referido, levado a cabo por Laboratórios de Estado e Universidades portugueses, que em conjunto cobrem os requisitos normativos nacionais e internacionais, em termos analíticos, e detêm o conhecimento necessário à componente de monitorização operacional, preconizada na DQA

Ultrafast Low-Temperature Crystallization of Solar Cell Graded Formamidinium-Cesium Mixed-Cation Lead Mixed-Halide Perovskites Using a Reproducible Microwave-Based Process

National Funds through FCT, Foundation for Science and Technology, under the projects ALTALUZ (PTDC/CTM-ENE/5125/2014) and SUPER SOLAR (PTDC/NAN-OPT/28430/2017). M.J.M. also acknowledges funding by FCT through the Grant SFRH/BPD/115566/2016.The control of morphology and crystallinity of solution-processed perovskite thin-films for solar cells is the key for further enhancement of the devices' power conversion efficiency and stability. Improving crystallinity and increasing grain size of perovskite films is a proven way to boost the devices' performance and operational robustness, nevertheless this has only been achieved with high-temperature processes. Here, we present an unprecedented low-temperature (<80 °C) and ultrafast microwave (MW) annealing process to yield uniform, compact, and crystalline FA 0.83 Cs 0.17 Pb(I (1-x) Br x ) 3 perovskite films with full coverage and micrometer-scale grains. We demonstrate that the nominal composition FA 0.83 Cs 0.17 PbI 1.8 Br 1.2 perovskite films annealed at 100 W MW power present the same band gap, similar morphology, and crystallinity of conventionally annealed films, with the advantage of being produced at a lower temperature (below 80 °C vs 185 °C) and during a very short period of time (∼2.5 min versus 60 min). These results open new avenues to fabricate band gap tunable perovskite films at low temperatures, which is of utmost importance for mechanically flexible perovskite cells and monolithic perovskite based tandem cells applications.authorsversionpublishe

Sub-Bandgap Sensitization of Perovskite Semiconductors via Colloidal Quantum Dots Incorporation

ABSTRACT: By taking advantage of the outstanding intrinsic optoelectronic properties of perovskite-based photovoltaic materials, together with the strong near-infrared (NIR) absorption and electronic confinement in PbS quantum dots (QDs), sub-bandgap photocurrent generation is possible, opening the way for solar cell efficiencies surpassing the classical limits. The present study shows an effective methodology for the inclusion of high densities of colloidal PbS QDs in a MAPbI3 (methylammonium lead iodide) perovskite matrix as a means to enhance the spectral window of photon absorption of the perovskite host film and allow photocurrent production below its bandgap. The QDs were introduced in the perovskite matrix in different sizes and concentrations to study the formation of quantum-confined levels within the host bandgap and the potential formation of a delocalized intermediate mini-band (IB). Pronounced sub-bandgap (in NIR) absorption was optically confirmed with the introduction of QDs in the perovskite. The consequent photocurrent generation was demonstrated via photoconductivity measurements, which indicated IB establishment in the films. Despite verifying the reduced crystallinity of the MAPbI3 matrix with a higher concentration and size of the embedded QDs, the nanostructured films showed pronounced enhancement (above 10-fold) in NIR absorption and consequent photocurrent generation at photon energies below the perovskite bandgap.info:eu-repo/semantics/publishedVersio