Manuel J. Mendes

Self-assembled silver nanoparticles for plasmon-enhanced solar cell back reflectors: correlation between structural and optical properties

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.

Self-organized colloidal quantum dots?and metal nanoparticles for plasmon-enhanced intermediate-band 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.

Highly efficient nanoplasmonic SERS on cardboard packaging substrates

This work reports on highly efficient surface enhanced Raman spectroscopy (SERS) constructed on low-cost, fully recyclable and highly reproducible cardboard plates, which are commonly used as disposable packaging material. The active optical component is based on plasmonic silver nanoparticle structures separated from the metal surface of the cardboard by a nanoscale dielectric gap. The SERS response of the silver (Ag) nanoparticles of various shapes and sizes were systematically investigated, and a Raman enhancement factor higher than 106 for rhodamine 6G detection was achieved. The spectral matching of the plasmonic resonance for maximum Raman enhancement with the optimal local electric field enhancement produced by 60 nm-sized Ag NPs predicted by the electromagnetic simulations reinforces the outstanding results achieved. Furthermore, the nanoplasmonic SERS substrate exhibited high reproducibility and stability. The SERS signals showed that the intensity variation was less than 5%, and the SERS performance could be maintained for up to at least 6 months.

Experimental quantification of useful and parasitic absorption of light in plasmon-enhanced thin silicon films for solar cells application

A combination of photocurrent and photothermal spectroscopic techniques is applied to experimentally quantify the useful and parasitic absorption of light in thin hydrogenated microcrystalline silicon (μc-Si:H) films incorporating optimized metal nanoparticle arrays, located at the rear surface, for improved light trapping via resonant plasmonic scattering. The photothermal technique accounts for the total absorptance and the photocurrent signal accounts only for the photons absorbed in the μc-Si:H layer (useful absorptance); therefore, the method allows for independent quantification of the useful and parasitic absorptance of the plasmonic (or any other) light trapping structure. We demonstrate that with a 0.9 μm thick absorber layer the optical losses related to the plasmonic light trapping in the whole structure are insignificant below 730 nm, above which they increase rapidly with increasing illumination wavelength. An average useful absorption of 43% and an average parasitic absorption of 19% over 400–1100 nm wavelength range is measured for μc-Si:H films deposited on optimized self-assembled Ag nanoparticles coupled with a flat mirror (plasmonic back reflector). For this sample, we demonstrate a significant broadband enhancement of the useful absorption resulting in the achievement of 91% of the maximum theoretical Lambertian limit of absorption.

Ag and Sn Nanoparticles to Enhance the Near-Infrared Absorbance of a-Si:H Thin Films

Silver (Ag) and tin (Sn) nanoparticles (NPs) were deposited by thermal evaporation onto heated glass substrates with a good control of size, shape and surface coverage. This process has the advantage of allowing the fabrication of thin-film solar cells with incorporated NPs without vacuum break, since it does not require chemical processes or post-deposition annealing. The X-ray diffraction, TEM and SEM properties are correlated with optical measurements and amorphous silicon hydrogenated (a-Si:H) films deposited on top of both types of NPs show enhanced absorbance in the near-infrared. The results are interpreted with electromagnetic modelling performed with Mie theory. A broad emission in the near-infrared region is considerably increased after covering the Ag nanoparticles with an a-Si:H layer. Such effect may be of interest for possible down-conversion mechanisms in novel photovoltaic devices.

Colloidal-lithographed TiO2 photonic nanostructures for solar cell light trapping

Dielectric-based photonic structures, composed of a lossless but high refractive index material, are currently among the preferential solutions for light management in thin film photovoltaics, as they allow broadband manipulation of sunlight to strongly boost the absorptance in the thin solar cell layers. In this work, we present an innovative colloidal lithography nanofabrication method that allows the precise engineering of wavelength-sized features, with the materials and geometries appropriate for efficient light trapping when implemented on the front surface of the cells. The method is developed here with TiO2 nanostructures tested on amorphous-silicon absorber thin films coated on the rear side by a metallic reflector. It is a simple, low-cost and scalable approach consisting of 4 main steps: (1) deposition of periodic close-packed arrays of polystyrene colloids which act as the mask; (2) shaping the particles and increasing their spacing via dry etching; (3) infiltration of TiO2 into the inter-particle spaces and (4) removal of the polystyrene particles to leave only the structured TiO2 layer. The resultant array of wavelength-sized features acts as a nanostructured high-index anti-reflection coating, which not only suppresses the reflected light at short wavelengths but also increases the optical path length of the longer wavelengths, via light scattering, within the absorber. The optical results have been compared with numerical electromagnetic computations to provide a deeper understanding of the physical mechanisms responsible for absorptance enhancement in the cells. A notorious 27.3% enhancement in the cell photocurrent is anticipated with the fabricated structures, relative to conventional anti-reflection coatings.

Multifunctional cellulose-paper for light harvesting and smart sensing applications

A novel generation of flexible opto-electronic smart applications is now emerging, incorporating photovoltaic and sensing devices driven by the desire to extend and integrate such technologies into a broad range of low cost and disposable consumer products of our everyday life and as a tool to bring together the digital and physical worlds. Several flexible polymeric materials are now under investigation to be used as mechanical supports for such applications. Among them, cellulose, the most abundant organic polymer on the Earth, commonly used in the form of paper, has attracted much research interest due to the advantages of being recyclable, flexible, lightweight, biocompatible and extremely low-cost, when compared to other materials. Cellulose substrates can be found in many forms, from the traditional micro-cellulose paper used for writing, printing and food/beverage packaging (e.g. liquid packaging cardboard), to the nano-cellulose paper which has distinct structural, optical, thermal and mechanical properties that can be tailored to its end use. The present article reviews the state-of-the-art related to the integration and optimization of photonic structures and light harvesting technologies on paper-based platforms, for applications such as Surface Enhanced Raman Scattering (SERS), supporting remarkable 107 signal enhancement, and photovoltaic solar cells reaching ∼5% efficiency, for power supply in standalone applications. Such paper-supported technologies are now possible due to innovative coatings that functionalize the paper surfaces, together with advanced light management solutions (e.g. wave-optical light trapping structures and NIR-to-visible up-converters). These breakthroughs open the way for an innovative class of disposable opto-electronic products that can find widespread use and bring important added value to existing commercial products. By making these devices ubiquitous, flexible and conformable to any object or surface, will also allow them to become part of the core of the Internet of Things (IoT) revolution, which demands systems’ mobility and self-powering functionalities to satisfy the requirements of comfort and healthcare of the users.

3D ZnO/Ag Surface-Enhanced Raman Scattering on Disposable and Flexible Cardboard Platforms

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 × 105 was obtained using rhodamine 6 G (R6G) 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.

Optoelectronics and Bio Devices on Paper Powered by Solar Cells

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 produced by inkjet printing are described and show the usefulness of solar cells as a power source or as a chemical reaction initiator for sensors.