Phase controlled SERS enhancement

Surface-enhanced Raman spectroscopy (SERS) has attracted increasing interest for chemical and biochemical sensing. Several studies have shown that SERS intensities are significantly increased when an optical interference substrate composed of a dielectric spacer and a reflector is used as a supporting substrate. However, the origin of this additional enhancement has not been systematically studied. In this paper, high sensitivity SERS substrates composed of self-assembled core-satellite nanostructures and silica-coated silicon interference layers have been developed. Their SERS enhancement is shown to be a function of the thickness of silica spacer on a more reflective silicon substrate. Finite difference time domain modeling is presented to show that the SERS enhancement is due to a spacer contribution via a sign change of the reflection coefficients at the interfaces. The magnitude of the local-field enhancement is defined by the interference of light reflected from the silica-air and silica-silicon interfaces, which constructively added at the hot spots providing a possibility to maximize intensity in the nanogaps between the self-assembled nanoparticles by changing the thickness of silica layer. The core-satellite assemblies on a 135\u2009nm silica-coated silicon substrate exhibit a SERS activity of approximately 13 times higher than the glass substrate

Dye regeneration and charge recombination in dye-sensitized solar cells with ferrocene derivatives as redox mediators

Ferrocene compounds are promising redox shuttles for application in dye-sensitized solar cells (DSCs). Chemical modification of the cyclopentadienyl rings is easily achievable affording almost unlimited variation of the redox properties. This allows fine-tuning of the driving force for dye-regeneration and optimization of the energy conversion efficiency of DSCs. Herein, six ferrocene derivatives have been chosen for investigation which cover the large redox potential range of 0.85 V, by virtue of simple alkylation and halogenation of the cyclopentadienyl ring, and enable improved matching of the energy levels of the sensitizer and the electrolyte. Although the focus of this work was to examine the effect of the redox potential on charge transfer processes, DSCs were fabricated which achieved high energy conversion efficiencies of over 5%. Charge transfer reactions were studied to reveal the dependence of the dye regeneration rate, recombination losses and recombination pathways on the reaction driving force. An increase in redox potential led to a higher efficiency due to higher open circuit potentials until a threshold is reached. At this threshold, the driving force for dye regeneration (18 kJ DE ¼ 0.19 V) becomes too small for efficient device operation, leading to rapid recombination between the oxidized dye and electrons in the TiO2 conduction band. As a result of this work guidelines can be formulated to aid the selection of redox couples for a particular sensitizer in order to maximize the utilization of incident solar energy

Dipole-field-assisted charge extraction in metal-perovskite-metal back-contact solar cells

Hybrid organic-inorganic halide perovskites are low-cost solution-processable solar cell materials with photovoltaic properties that rival those of crystalline silicon. The perovskite films are typically sandwiched between thin layers of hole and electron transport materials, which efficiently extract photogenerated charges. This affords high-energy conversion efficiencies but results in significant performance and fabrication challenges. Herein we present a simple charge transport layer-free perovskite solar cell (PSC), comprising only a perovskite layer with two interdigitated gold back-contacts. Charge extraction is achieved via self-assembled molecular monolayers (SAMs) and their associated dipole fields at the metal/perovskite interface. Photovoltages of approximately 600 mV generated by SAM-modified PSCs are equivalent to the built-in potential generated by individual dipole layers. Efficient charge extraction results in photocurrents of up to 12.1 mA/cm2 under simulated sunlight, despite a large electrode spacing.Comment: 18 pages, 5 figure

Can Laminated Carbon Challenge Gold? Toward Universal, Scalable, and Low-Cost Carbon Electrodes for Perovskite Solar Cells

While perovskite solar cell (PSC) efficiencies are soaring at a laboratory scale, these are most commonly achieved with evaporated gold electrodes, which would present a significant expense in large-scale production. This can be remedied through the use of significantly cheaper carbon electrodes that, in contrast to metals, also do not migrate through the device. To this end, the present work investigates simple-to-prepare aluminum-supported carbon electrodes derived from commercially available, inexpensive materials that can be applied onto various hole-transporting materials and enable photovoltaic performances on par with those provided by gold electrodes. Successful integration of the new carbon-based electrode into flexible devices produced by a roll-to-roll printing technology by both pressing and lamination is demonstrated. However, temperature cycling durability tests reveal that the use of carbon electrodes based on commercial pastes is hindered by incompatibility of adhesive additives with the key components of the PSCs under heating. Resolving this issue, tailor-made graphite electrodes devoid of damaging additives are introduced, which improve the PSC stability under temperature cycling test protocol to the level provided by benchmark gold electrodes. The study highlights current challenges in developing laminated carbon electrodes in PSCs and proposes strategies toward the resolution thereof.This work was funded by the Australian Centre for Advanced Photovoltaics and Australian Renewable Energy Agency. A.N.S. also acknowledges the financial support from the Australian Research Council (Centre of Excellence CE140100012; Future Fellowship FT200100317). Monash Centre for Electron Microscopy (MCEM) and Melbourne Centre for Nano fabrication (MCN) are acknowledged for providing access to their facilities. The authors are grateful to Dr T. Zhang, A. Surmiak, Dr. N. Peris, Dr. D. Senevirathna, and Dr. N. Pai from Monash University for the experimental support throughout this study

Negative Control of RpoS Synthesis by the sRNA ReaL in Pseudomonas aeruginosa

Pseudomonas aeruginosa (Pae) is an opportunistic human pathogen, able to resist host defense mechanisms and antibiotic treatment. In Pae, the master regulator of stress responses RpoS (σS) is involved in the regulation of quorum sensing and several virulence genes. Here, we report that the sRNA ReaL translationally silences rpoS mRNA, which results in a decrease of the RpoS levels. Our studies indicated that ReaL base-pairs with the Shine-Dalgarno region of rpoS mRNA. These studies are underlined by a highly similar transcription profile of a rpoS deletion mutant and a reaL over-expressing strain

Solution processable direct bandgap copper-silver-bismuth iodide photovoltaics : compositional control of dimensionality and optoelectronic properties

Altres ajuts: SRR acknowledges the support from "laCaixa" Foundation (ID 100010434; LCF/BQ/PI20/11760024). Open access publishing facilitated by Monash University, as part of the Wiley - Monash University agreement via the Council of Australian University Librarians.The search for lead-free alternatives to lead-halide perovskite photovoltaic materials resulted in the discovery of copper(I)-silver(I)-bismuth(III) halides exhibiting promising properties for optoelectronic applications. The present work demonstrates a solution-based synthesis of uniform CuAgBiI thin films and scrutinizes the effects of x on the phase composition, dimensionality, optoelectronic properties, and photovoltaic performance. Formation of pure 3D CuAgBiI at x = 1, 2D CuAgBiI at x = 2, and a mix of the two at 1 < x < 2 is demonstrated. Despite lower structural dimensionality, CuAgBiI has broader optical absorption with a direct bandgap of 1.89 ± 0.05 eV, a valence band level at -5.25 eV, improved carrier lifetime, and higher recombination resistance as compared to CuAgBiI. These differences are mirrored in the power conversion efficiencies of the CuAgBiI and CuAgBiI solar cells under 1 sun of 1.01 ± 0.06% and 2.39 ± 0.05%, respectively. The latter value is the highest reported for this class of materials owing to the favorable film morphology provided by the hot-casting method. Future performance improvements might emerge from the optimization of the CuAgBiI layer thickness to match the carrier diffusion length of ≈40-50 nm. Nonencapsulated CuAgBiI solar cells display storage stability over 240 days

Balancing charge extraction for efficient back-contact perovskite solar cells by using an embedded mesoscopic architecture

As the performance of organic–inorganic halide perovskite solar cells approaches their practical limits, the use of back-contact architectures, which eliminate parasitic light absorption, provides an effective route toward higher device efficiencies. However, a poor understanding of the underlying device physics has limited further performance improvements. Here a mesoporous charge-transporting layer is introduced into quasi-interdigitated back-contact perovskite devices and the charge extraction behavior with an increased interfacial contact area is studied. The results show that the incorporation of a thin mesoporous titanium dioxide layer significantly shortens the charge-transfer lifetime and results in more efficient and balanced charge extraction dynamics. A high short-circuit current density of 21.3 mA cm–2 is achieved using a polycrystalline perovskite layer on a mesoscopic quasi-interdigitated back-contact electrode, a record for this type of device architecture.The authors are grateful for the financial support by the Australian Centre for Advanced Photovoltaics (ACAP), the Australian Renewable Energy Agency (ARENA), and the Australian Research Council (ARC) ARC Centre of Excellence in Exciton Science (ACEx: CE170100026). This work was performed in part at the Melbourne Centre for Nanofabrication (MCN) in the Victorian Node of the Australian National Fabrication Facility (ANFF). Q.O. acknowledges the support from the ARC Centre of Excellence in Future Low-Energy Electronics Technologies (FLEET).Peer reviewe

Back-contact perovskite solar cell fabrication via microsphere lithography

Back-contact electrodes for hybrid organic-inorganic perovskite solar cells (PSCs) eliminate the parasitic absorption losses caused by the transparent conductive electrodes that are inherent to conventional sandwich-architecture devices. However, the fabrication methods for these unconventional architectures rely heavily on expensive photolithography, which limits scalability. Herein, we present an alternative cost-effective microfabrication technique in which the conventional photolithography process is replaced by microsphere lithography in which a close-packed polystyrene microsphere monolayer acts as the patterning mask for the honeycomb-shaped electrodes. A comprehensive comparison between photolithography and microsphere lithography fabrication techniques was conducted. Using microsphere lithography, we achieve highly efficient devices having a stabilized power conversion efficiency (PCE) of 8.6%, twice the reported value using photolithography. Microsphere lithography also enabled the fabrication of the largest back-contact PSC to date, having an active area of 0.75 cm2 and a stabilized PCE of 2.44%.This work was financially supported by the Australian Government through the Australian Renewable Energy Agency (ARENA) the Australian Centre for Advanced Photovoltaics (ACAP) and the Australian Research Council (ARC, DE220100154). This work was performed in part at the Melbourne Centre for Nanofabrication (MCN) in the Victorian Node of the Australian National Fabrication Facility (ANFF). The authors acknowledge use of facilities within the Monash Centre for Electron Microscopy (MCEM). The authors acknowledge use of facilities within the Flexible Electronics Laboratory (FEL) at the Commonwealth Scientific and Industrial Research Organisation (CSIRO), Clayton site. S.R.R. acknowledges the support from “la Caixa” Foundation (ID 100010434). Fellowship code LCF/BQ/PI20/11760024.Peer reviewe