Manuel J. Mendes Website

{\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}

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.

Metal nanoparticles and diffractive nanostructures are widely studied for enhancing light trapping efficiency in thin-film solar cells. Both have achieved high performance enhancements, but there are very few direct comparisons between the two. Also, it is difficult to accurately determine the parasitic absorption of metal nanoparticles. Here, we assess the light trapping efficiencies of both approaches in an identical absorber configuration. We use a 240 nm thick amorphous silicon slab as the absorber layer and either a quasi-random supercell diffractive nanostructure or a layer of self-assembled metal nanoparticles for light trapping. Both the plasmonic and diffractive structures strongly enhance the absorption in the red/near-infrared regime. At longer wavelengths, however, parasitic absorption becomes evident in the metal nanoparticles, which reduces the overall performance of the plasmonic approach. We have formulated a simple analytical model to assess the parasitic absorption and effective reflectivity of a plasmonic reflector and to demonstrate good agreement with the experimental data.

In order to enhance infrared light absorption in sub-bandgap transitions in an intermediate band solar cell, the scattered near-field potential from uncoated and coated metallic nanoparticles with a spheroidal shape is calculated with the electrostatic model. The absorption enhancement produced at the surface plasmon frequency of the nanoparticles can be of several orders of magnitude in some cases.

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).

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.

The spectra of localized surface plasmon resonances (LSPRs) in self-assembled silver nanoparticles (NPs), prepared by solid-state dewetting of thin films, are discussed in terms of their structural properties. We summarize the dependences of size and shape of NPs on the fabrication conditions with a proposed structural-phase diagram. It was found that the surface coverage distribution and the mean surface coverage (SC) size were the most appropriate statistical parameters to describe the correlation between the morphology and the optical properties of the nanostructures. The results are interpreted with theoretical predictions based on Mie theory. The broadband scattering efficiency of LSPRs in the nanostructures is discussed towards application as plasmon-enhanced back reflectors in thin-film solar cells.

A colloidal deposition technique is presented to construct long-range ordered hybrid arrays of self-assembled quantum dots and metal nanoparticles. Quantum dots are promising for novel opto-electronic devices but, in most cases, their optical transitions of interest lack sufficient light absorption to provide a significant impact in their implementation. A potential solution is to couple the dots with localized plasmons in metal nanoparticles. The extreme confinement of light in the near-field produced by the nanoparticles can potentially boost the absorption in the quantum dots by up to two orders of magnitude. In this work, light extinction measurements are employed to probe the plasmon resonance of spherical gold nanoparticles in lead sulfide colloidal quantum dots and amorphous silicon thin-films. Mie theory computations are used to analyze the experimental results and determine the absorption enhancement that can be generated by the highly intense near-field produced in the vicinity of the gold nanoparticles at their surface plasmon resonance. The results presented here are of interest for the development of plasmon-enhanced colloidal nanostructured photovoltaic materials, such as colloidal quantum dot intermediate-band solar cells.

Abstract.  The concept of intermediate band solar cell (IBSC) is, apparently, simple to grasp. However, since the idea was proposed, our understanding has improved and some concepts can now be explained more clearly than when the concept was initially introduced. Clarifying these concepts is important, even if they are well known for the advanced researcher, so that research efforts can be driven in the right direction from the start. The six pieces of this work are: Does a miniband need to be formed when the IBSC is implemented with quantum dots? What are the problems for each of the main practical approaches that exist today? What are the simplest experimental techniques to demonstrate whether an IBSC is working as such or not? What is the issue with the absorption coefficient overlap and the Mott's transition? What would the best system be, if any?

Nowadays there is a strong demand for intelligent packaging to provide comfort, welfare and security to owners, vendors and consumers by allowing them to know the contents and interact with the goods. This is of particular relevance for low cost, fully disposable and recyclable products, such as identification tags and medical diagnostic tests, and devices for analysis and/or quality control in food and pharmaceutical industries. However, the increase of complexity and processing capacity requires continuous power and can be addressed by the combined use of a small disposable battery, charged by a disposable solar cell, which is able to work under indoor lighting. Herein, we show a proof-of-concept of the pioneering production of thin-film amorphous silicon (a-Si:H) solar cells with an efficiency of 4{%} by plasma enhanced chemical vapour deposition (PECVD) on liquid packaging cardboard (LPC), which is commonly used in the food and beverage industries. Such accomplishment put us one step closer to this revolution by providing a flexible, renewable and extremely cheap autonomous energy packaging system. Moreover, such Si thin films take advantage of their good performance at low-light levels, which also makes them highly desirable for cheap mobile indoor applications.

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 present development of non-wafer-based photovoltaics (PV) allows supporting thin film solar cells on a wide variety of low-cost recyclable and flexible substrates such as paper, thereby extending PV to a broad range of consumer-oriented disposable applications where autonomous energy harvesting is a bottleneck issue. However, their fibrous structure makes it challenging to fabricate good-performing inorganic PV devices on such substrates. The advances presented here demonstrate the viability of fabricating thin film silicon PV cells on paper coated with a hydrophilic mesoporous layer. Such layer can not only withstand the cells production temperature (150 °C), but also provide adequate paper sealing and surface finishing for the cell's layers deposition. The substances released from the paper substrate are continuously monitored during the cell deposition by mass spectrometry, which allows adapting the procedures to mitigate any contamination from the substrate. In this way, a proof-of-concept solar cell with 3.4{%} cell efficiency (41{%} fill factor, 0.82 V open-circuit voltage and 10.2 mA cm−2 short-circuit current density) is attained, opening the door to the use of paper as a reliable substrate to fabricate inorganic PV cells for a plethora of indoor applications with tremendous impact in multi-sectorial fields such as food, pharmacy and security.

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.

The application of diffraction gratings to solar cells is a promising approach to superseding the light trapping limits of conventional Lambertian structures. In this paper a mathematical formalism is derived for calculating the absorption that can be expected in a solar cell equipped with a diffraction grating, which can be applied to any lattice geometry and grating profile. Furthermore, the formalism is used to calculate the upper limit of total absorption that can theoretically be achieved using a diffraction grating. The derived formalism and limits are valid when the solar cell thickness is greater than the coherence length of the illuminating solar spectrum. Comparison is made to the upper limit achievable using an angularly selective Rugate filter, which is also calculated. Both limits are found to be considerably higher than the Lambertian limit within the range of sunlight concentration factors practically employed in photovoltaic systems (1–1000×). The upper limit of absorption using the diffraction grating is shown to be equal to the thermodynamic limit for all absorbances and concentration factors. The limit for the Rugate filter is generally lower, but tends to the thermodynamic limit for lower cell absorbances. Copyright © 2011 John Wiley {&} Sons, Ltd.