Manuel J. Mendes Website

The interaction of light with wavelength-sized photonic nanostructures is highly promising for light management applied to thin-film photovoltaics. Several light trapping effects come into play in the wave optics regime of such structures that crucially depend on the parameters of the photonic and absorbing elements. Thus, multi-parameter optimizations employing exact numerical models, as performed in this work, are essential to determine the maximum photocurrent enhancement that can be produced in solar cells.Generalized spheroidal geometries and high-index dielectric materials are considered here to model the design of the optical elements providing broadband absorption enhancement in planar silicon solar cells. The physical mechanisms responsible for such enhancement are schematized in a spectral diagram, providing a deeper understanding of the advantageous characteristics of the optimized geometries. The best structures, composed of TiO2 half-spheroids patterned on the cells' top surface, yield two times higher photocurrent (up to 32.5 mA/cm2 in 1.5 $μ$m thick silicon layer) than the same devices without photonic schemes.These results set the state-of-the-art closer to the theoretical Lambertian limit. In addition, the considered light trapping designs are not affected by the traditional compromise between absorption enhancement versus current degradation by recombination, which is a key technological advantage.

© 2016 WILEY-VCH Verlag GmbH {&} Co. KGaA, Weinheim 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, H2and Ar atmospheres, and H2and 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 $\rho$ ≈ 2.6–3.5 × 10−4$Ømega$cm, 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 ($\rho$ ≈ 10−4$Ømega$cm and transmittance in VIS range of 90{%}) employing much more earth-abundant materials.

Indium tin oxide (ITO) is the current standard state-of-the-art transparent conductive oxide (TCO), given its remarkable optical and electrical properties. However, the scarcity of indium carries an important drawback for the long-term application due to its intensive use in many optoelectronic devices such as displays, solar cells, and interactive systems. Zinc oxide-based TCOs can be a cost-effective and viable alternative, but the limitations imposed by their transmittance versus resistivity tradeoff still keep them behind ITO. In this work, an in-depth study of the structural and compositional material changes induced by specific postannealing treatments is presented, based on aluminum zinc oxide (AZO) and hydrogenated AZO (AZO:H) thin films grown by rf-magnetron sputtering at room temperature that allows an extensive understanding of the films' electrical/structural changes and the ability to tune their physical parameters to yield increasingly better performances, which put them in line with the best ITO quality standards. The present investigation comprises results of thermal annealing at atmospheric pressure, vacuum, forming gas, H2 and Ar atmospheres and plasmas. Overall the study being performed leads to a decrease in resistivity above 40{%}, reaching $\rho$ ≈ 3 × 10−4 $Ømega$ cm, with an average optical transmittance in the visible region around 88{%}. Such results are equivalent to the properties of state-of-the-art ITO.

© 2017 by the authors. In the present study, zinc oxide (ZnO) nanorods (NRs) with a hexagonal structure have been synthesized via a hydrothermal method assisted by microwave radiation, using specialized cardboard materials as substrates. Cardboard-type substrates are cost-efficient and robust paper-based platforms that can be integrated into several opto-electronic applications for medical diagnostics, analysis and/or quality control devices. This class of substrates also enables highly-sensitive Raman molecular detection, amiable to several different operational environments and target surfaces. The structural characterization of the ZnO NR arrays has been carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical measurements. The effects of the synthesis time (5-30 min) and temperature (70-130 °C) of the ZnO NR arrays decorated with silver nanoparticles (AgNPs) have been investigated in view of their application for surface-enhanced Raman scattering (SERS) molecular detection. The size and density of the ZnO NRs, as well as those of the AgNPs, are shown to play a central role in the final SERS response. A Raman enhancement factor of 7 × 105was obtained using rhodamine 6 G (RG6) as the test analyte; a ZnO NR array was produced for only 5 min at 70 °C. This condition presents higher ZnO NR and AgNP densities, thereby increasing the total number of plasmonic "hot-spots", their volume coverage and the number of analyte molecules that are subject to enhanced sensing.

© 2017 The growing interest in exploring thin film technologies to produce low cost devices such as n-i-p silicon solar cells, with outstanding performances and capability to address the highly relevant energy market, turns the optimization of their fabrication process a key area of development. The usual one-dimensional analysis of the involved parameters makes it difficult and time consuming to find the optimal set of conditions. To overcome these difficulties, the combination of experimental design and statistical analysis provides the tools to explore in a multidimensional fashion the interactions between fabrication parameters and expected experimental outputs. Design of Experiment and Multivariate Analysis are demonstrated here for the optimization of: (1) the low temperature deposition (150 °C) of high quality intrinsic amorphous silicon (i-a-Si:H); and (2) the matching of the n-, i-, and p-silicon layers thickness to maximize the efficiency of thin film solar cells. The multiple regression method applied, validated through analysis of variance and evaluated against exact numerical simulations, is shown to predict the overall intrinsic layer properties and the devices performance. The results confirm that experimental design and statistical data analysis are effective approaches to improve, within a minimum time frame and high certainty, the properties of silicon thin films, and subsequently the layer structure of solar cells.

Paper substrates, coated with ZnO nanorods (NRs) decorated with Ag nanoparticles (NPs), allowed the production of inexpensive, highly-performing and extremely reproducible three-dimensional (3D) SERS platforms. The ZnO NRs were synthesized by a simple, fast and low-temperature hydrothermal method assisted by microwave radiation and made SERS-active by decorating them with a dense array of silver nanoparticles deposited via a single-step thermal evaporation technique. Using Rhodamine 6G (R6G) as a probe molecule, with an amount down to 10-9 M, the SERS substrates allowed a Raman signal enhancement of 107. The contribution of the inter-Ag-NPs gaps for 3D geometry, ZnO NRs orientation and the large sensing area allowed by theNRscaffolds, were determinant factors for the significant Raman enhancement observed. The results demonstrate that plasmonic nanorod forests, covered with Ag NPs, are efficient SERS substrates with the advantages of being recyclable, flexible, lightweight, portable, biocompatible and extremely low-cost.

© 2017 Elsevier B.V. Ultrasonic spray pyrolysis deposition of ZnO-based materials offers an attractive high-throughput low-cost route towards industrial production of high-quality transparent conductive oxide (TCO) thin-films. In this work, undoped and aluminium-doped ZnO films have been grown employing ultrasonic spray pyrolysis at relatively low-temperate (300 °C), followed by a post-annealing treatment. The role of Al concentration in the starting solution, as well as the rapid thermal annealing (RTA) atmosphere, were investigated and correlated to the morphological, structural, electrical and optical properties of the films. The remarkable enhancement of electrical conductivity attained here is mainly ascribed to the combined effects of: (1) homogenous incorporation of Al3+into the ZnO matrix, which enhances crystal quality providing higher electronic mobility; and (2) the RTA which releases the localized electrons caused by oxygen absorption and thereby increases the free carrier density. Under optimum deposition conditions, a low resistivity and a high optical transmittance around 4 × 10−3$Ømega$ cm and 87{%}, respectively, were obtained. The application of the RTA post-process after low temperature growth has several advantages relative to the direct growth at high temperature (usually 400–575 °C), such as shorter growth time and lower cost associated to the spray pyrolysis equipment requirements and usage. The results suggest that the electrical and optical properties of the ZnO:Al films can be further improved for solar cell applications by controlling the temperature of the post-deposition annealing in reducing atmosphere.

The employment of printing techniques as cost-effective methods to fabricate low cost, flexible, disposable and sustainable solar cells is intimately dependent on the substrate properties and the adequate electronic devices to be powered by them. Among such devices, there is currently a growing interest in the development of user-oriented and multipurpose systems for intelligent packaging or on-site medical diagnostics, which would greatly benefit from printable solar cells as their energy source for autonomous operation. This chapter first describes and analyzes different types of cellulose-based substrates for flexible and cost effective optoelectronic and bio devices to be powered by printed solar cells. Cellulose is one of the most promising platforms for green recyclable electronics and it is fully compatible with large-scale printing techniques, although some critical requirements must be addressed. Paper substrates exist in many forms. From common office paper, to packaging cardboard used in the food industry, or nanoscale engineered cellulose (e.g. bacterial cellulose). However, it is the structure and content of paper that determines its end use. Secondly, proof-of-concept of optoelectronic and bio devices pro-duced by inkjet printing are described and show the usefulness of solar cells as a power source or as a chemical reaction initiator for sensors.

© 2018 The Authors The use of disposable recyclable, eco-friendly, sustainable and low-cost devices with multiple functions is becoming a demand in the emerging area of the Internet of Things as a way to decrease the degree of complexity of the electronic circuits required to serve a plethora of applications. Moreover, for low-cost disposable applications, it is relevant the systems to be recyclable. The idea beyond the present study concerns to exploit our imagination with simple questions such as: What happens if it is possible to have a simple and universal device architecture, easy to implement on paper substrates, but capable to provide different multiple functionalities? It would be possible to have a common template for electronic systems on paper that would be then easily customized depending on the final application? The present study answers to these demands by reporting the physics and electronics behavior of a multigate paper transistor where paper is simultaneously the substrate and the dielectric, while a metal-oxide-semiconductor (IGZO) is used as the active channel. Moreover, the same device is able to present logic functionalities simply by varying the amplitude and frequency of the input gate signals. These transistors operate at drain voltages of 1 V with low power, exhibiting ION/IOFF{\textgreater} 104and a mobility ≈2 cm2V−1s−1, serving the specifications for a broad range of smart disposable low power electronics. To sustain all this, an analytical compact model was developed able to precisely reproduce the response of paper-based dual-gate FETs and provide full understanding of their unique and innovative operational characteristics.

In this work, we highlight the influence of three different sol stabilizers, namely diethanolamine (DEA), Ammonium Hydroxide (NH4OH), and Nitric Acid (HNO3), on the optical and structural properties of spin-coated zinc oxide (ZnO) thin films. The XRD patterns related to all films exhibit a hexagonal crystal structure with a preferential orientation along the (0 0 2) direction. However an additional {\textless}100{\textgreater} peak arises when the films are prepared with DEA and NH4OH showing a better crystallinity than that displayed by HNO3-prepared films. The elaborated films show a high transparency reaching 80{%} for DEA-prepared films. The analysis of the transmittance and the reflectance measurements confirms a direct band-to-band transition. Depending on the sol stabilizer, the optical band gap energy is varying from 3.16 to 3.22 eV. The relatively wide band-gap of DEA-prepared ZnO films is correlated to their high crystallinity. Room temperature photoluminescence spectra indicate strong UV emission at around 377 nm originated from nearby band-edge transitions. Yet, the use of DEA as a stabilizer leads to a net intensity increase of the blue peak emission.

The copper zinc tin sulfide (CZTS) compound is a promising candidate as an alternative absorber material for thin-film solar cells. In this study, we investigate the direct formation of Cu1.92ZnSnx(Sb1-x)S4 compounds [CZT(A)S], with x=1, 0.85, 0.70, and 0.50, via a mechanochemical synthesis (MCS) approach, starting from powders of the corresponding metals, zinc sulfide, and sulfur. The thermal stability of the CZT(A)S compounds was evaluated in detail by in situ synchrotron high-energy x-ray diffraction measurements up to 700 °C. The CZT(A)S compounds prepared via MCS revealed a sphalerite-type crystal structure with strong structural stability over the studied temperature range. The contribution of the MCS to the formation of such a structure at room temperature is analyzed in detail. Additionally, this study provides insights into the MCS of CZTS-based compounds: the possibility of a large-scale substitution of Sn by Sb and the production of single phase CZT(A)S with a Cu-poor/Zn-poor composition. A slight increase in the band gap from 1.45 to 1.49-1.51 eV was observed with the incorporation of Sb, indicating that these novel compounds can be further explored for thin-film solar cells.

{\textless}p{\textgreater}Opto-electronics on/with paper is fostering a novel generation of flexible and recyclable devices for sunlight harvesting and intelligent optical sensing.{\textless}/p{\textgreater}

{\textless}h2{\textgreater}Summary{\textless}/h2{\textgreater}{\textless}p{\textgreater}Recent trends in photovoltaics demand ever-thin solar cells to allow deployment in consumer-oriented products requiring low-cost and mechanically flexible devices. For this, nanophotonic elements in the wave-optics regime are highly promising, as they capture and trap light in the cells' absorber, enabling its thickness reduction while improving its efficiency. Here, novel wavelength-sized photonic structures were computationally optimized toward maximum broadband light absorption. Thin-film silicon cells were the test bed to determine the best performing parameters and study their optical effects. Pronounced photocurrent enhancements, up to 37{%}, 27{%}, and 48{%}, respectively, in ultra-thin (100- and 300-nm-thick) amorphous, and thin (1.5-$μ$m) crystalline silicon cells are demonstrated with honeycomb arrays of semi-spheroidal dome or void-like elements patterned on the cells' front. Also importantly, key advantages in the electrical performance are anticipated, since the photonic nano/micro-nanostructures do not increase the cell roughness, therefore not contributing to recombination, which is a crucial drawback in state-of-the-art light-trapping approaches.{\textless}/p{\textgreater}

A fast method is presented to fabricate plasmonic light trapping structures in just ten minutes ({\textgreater}5 × faster than the present state of art), with excellent light scattering properties. The structures are composed of silver nanoparticles (Ag NPs) deposited by thermal evaporation and self-assembled using a rapid thermal annealing (RTA) system. The effect of the RTA heating rate on the NPs production reveals to be crucial to the decrease of the annealing process. The Ag NPs are integrated in thin film silicon solar cells to form a plasmonic back reflector (PBR) that causes a diffused light reflectivity in the near-infrared (600–1100 nm wavelength region). In this configuration the thicknesses of the AZO spacer/passivating layers between NPs and rear mirror, and between NPs and silicon layer, play critical roles in the near-field coupling of the reflected light towards the solar cell absorber, which is investigated in this work. The best spacer thicknesses were found to be 100 and 60 nm, respectively, for Ag NPs with preferential sizes of about 200 nm. The microcrystalline silicon ($μ$c-Si:H) solar cells deposited on such improved PBR demonstrate an overall 11{%} improvement on device efficiency, corresponding to a photocurrent of 24.4 mA/cm2 and an efficiency of 6.78{%}, against 21.79 mA/cm2 and 6.12{%}, respectively, obtained on flat structures without NPs.

One of the most promising approaches to produce industrial-compatible Transparent Conducting Materials (TCMs) with excellent characteristics is the fabrication of TCO/metal/TCO multilayers. In this article, we report on the electro-optical properties of a novel high-performing TCO/metal/TCO structure in which the intra-layer is a micro-structured metallic grid instead of a continuous thin film. The grid is obtained by evaporation of Ag through a mask of polystyrene colloidal micro-spheres deposited by the Langmuir-Blodgett method and partially dry-etched in plasma. IZO/Ag grid/IZO structures with different thicknesses and mesh dimensions have been fabricated, exhibiting excellent electrical characteristics (sheet resistance below 10 $Ømega$/□) and particularly high optical transmittance in the near-infrared spectral region as compared to planar (unstructured) TCM multilayers. Numerical simulations were also used to highlight the role of the Ag mesh parameters on the electrical properties.

CO2 capture and utilization (CCU) technologies are being immensely researched as means to close the anthropogenic carbon cycle. One approach known as artificial photosynthesis uses solar energy from photovoltaics (PV), carbon dioxide and water to generate hydrocarbon fuels, being methane (CH4) a preferential target due to the already in place infrastructures for its storage, distribution and consumption. Here, a model is developed to simulate a direct (1-step) solar methane production approach, which is studied in two scenarios: first, we compare it against a more conventional 2-step methane production route, and second, we apply it to address the energetic needs of concept buildings with usual space and domestic hot water heating requirements. The analysed 2-step process consists in the PV-powered synthesis of an intermediate fuel – syngas – followed by its conversion to CH4 via a Fischer–Tropsch (methanation) process. It was found that the 1-step route could be adequate to a domestic, small scale use, potentially providing energy for a single-family house, whilst the 2-step can be used in both small and large scale applications, from domestic to industrial uses. In terms of overall solar-to-CH4 energy efficiency, the 2-step method reaches 13.26{%} against the 9.18{%} reached by the 1-step method. Next, the application of the direct solar methane technology is analysed for domestic buildings, in different European locations, equipped with a combination of solar thermal collectors (STCs) and PV panels, in which the heating needs that cannot be fulfilled by the STCs are satisfied by the combustion of methane synthesized by the PV-powered electrolyzers. Various combinations of situations for a whole year were studied and it was found that this auxiliary system can produce, per m2 of PV area, in the worst case scenario 23.6 g/day (0.328 kWh/day) of methane in Stockholm, and in the best case scenario 47.4 g/day (0.658 kWh/day) in Lisbon.

Combined perovskite/crystalline-silicon four-terminal tandem solar cells promise {\textgreater}30{%} efficiencies. Here we propose all-thin-film double-junction architectures where high-bandgap perovskite top cells are coupled to ultrathin c-Si bottom cells enhanced with light trapping. A complete optoelectronic model of the devices was developed and applied to determine the optimal intermediate layers, which are paramount to maximize the cells' photocurrent. It was ascertained that by replacing the transparent conductive oxides by grid-based metallic contacts in the intermediate positions, the parasitic absorption is lowered by 30{%}. Overall, a 29.2{%} efficiency is determined for ∼2 um thick tandems composed of the optimized interlayers and improved with Lambertian light trapping.

The optical properties of localized surface plasmon resonances (LSPR) sustained by self-assembled silver nanoparticles are of great interest for enhancing light trapping in thin film photovoltaics. First, we report on a systematic investigation of the structural and the optical properties of silver nanostructures fabricated by a solid-state dewetting process on various substrates. Our study allows to identify fabrication conditions in which circular, uniformly spaced nanoparticles are obtainable. The optimized NPs are then integrated into plasmonic back reflector (PBR) structures. Second, we demonstrate a novel procedure, involving a combination of opto-electronic spectroscopic techniques, allowing for the quantification of useful and parasitic absorption in thin photovoltaic absorber deposited on top of the PBR. We achieve a significant broadband useful absorption enhancement of 90{%} for 0.9 µm thick $μ$c-Si:H film and demonstrate that optical losses due to plasmonic scattering are insignificant below 730 nm. Finally, we present a successful implementation of a plasmonic light trapping scheme in a thin film a-Si:H solar cell. The quantum efficiency spectra of the devices show a pronounced broadband enhancement resulting in remarkably high short circuit current densities (Jsc).