Electrochemical Impedance Spectroscopy of All-Perovskite Tandem Solar Cells.

This work explores electrochemical impedance spectroscopy to study recombination and ionic processes in all-perovskite tandem solar cells. We exploit selective excitation of each subcell to enhance or suppress the impedance signal from each subcell, allowing study of individual tandem subcells. We use this selective excitation methodology to show that the recombination resistance and ionic time constants of the wide gap subcell are increased with passivation.

Substitution of lead with tin suppresses ionic transport in halide perovskite optoelectronics.

Despite the rapid rise in the performance of a variety of perovskite optoelectronic devices with vertical charge transport, the effects of ion migration remain a common and longstanding Achilles' heel limiting the long-term operational stability of lead halide perovskite devices. However, there is still limited understanding of the impact of tin (Sn) substitution on the ion dynamics of lead (Pb) halide perovskites. Here, we employ scan-rate-dependent current-voltage measurements on Pb and mixed Pb-Sn perovskite solar cells to show that short circuit current losses at lower scan rates, which can be traced to the presence of mobile ions, are present in both kinds of perovskites.

Ionic Accumulation as a Diagnostic Tool in Perovskite Solar Cells: Characterizing Band Alignment with Rapid Voltage Pulses.

Despite record-breaking devices, interfaces in perovskite solar cells are still poorly understood, inhibiting further progress. Their mixed ionic-electronic nature results in compositional variations at the interfaces, depending on the history of externally applied biases. This makes it difficult to measure the band energy alignment of charge extraction layers accurately.

Graphite-protected CsPbBr perovskite photoanodes functionalised with water oxidation catalyst for oxygen evolution in water.

Metal-halide perovskites have been widely investigated in the photovoltaic sector due to their promising optoelectronic properties and inexpensive fabrication techniques based on solution processing. Here we report the development of inorganic CsPbBr-based photoanodes for direct photoelectrochemical oxygen evolution from aqueous electrolytes. We use a commercial thermal graphite sheet and a mesoporous carbon scaffold to encapsulate CsPbBr as an inexpensive and efficient protection strategy.

Microseconds, milliseconds and seconds: deconvoluting the dynamic behaviour of planar perovskite solar cells.

Perovskite solar cells (PSC) are shown to behave as coupled ionic-electronic conductors with strong evidence that the ionic environment moderates both the rate of electron-hole recombination and the band offsets in planar PSC. Numerous models have been presented to explain the behaviour of perovskite solar cells, but to date no single model has emerged that can explain both the frequency and time dependent response of the devices. Here we present a straightforward coupled ionic-electronic model that can be used to explain the large amplitude transient behaviour and the impedance response of PSC.

An investigation of anode and cathode materials in photomicrobial fuel cells.

Photomicrobial fuel cells (p-MFCs) are devices that use photosynthetic organisms (such as cyanobacteria or algae) to turn light energy into electrical energy. In a p-MFC, the anode accepts electrons from microorganisms that are either growing directly on the anode surface (biofilm) or are free floating in solution (planktonic). The nature of both the anode and cathode material is critical for device efficiency.

Iron reduction by the cyanobacterium Synechocystis sp. PCC 6803.

Synechocystis sp. PCC 6803 uptakes iron using a reductive mechanism, similar to that exhibited by many other microalgae. Various bio-electrochemical technologies have made use of this reductive cellular capacity, but there is still a lack of fundamental understanding of cellular reduction rates under different conditions.

Polymerization of low molecular weight hydrogelators to form electrochromic polymers.

We present a method for the polymerization of low molecular weight hydrogelators to form polymers with unique structures. Carbazole-protected amino acids are shown to form hydrogels by self-assembly into fibrous structures. We show that is possible to directly electropolymerize the hydrogels.

A small-scale air-cathode microbial fuel cell for on-line monitoring of water quality.

The heavy use of chemicals for agricultural, industrial and domestic purposes has increased the risk of freshwater contamination worldwide. Consequently, the demand for efficient new analytical tools for on-line and on-site water quality monitoring has become particularly urgent. In this study, a small-scale single chamber air-cathode microbial fuel cell (SCMFC), fabricated by rapid prototyping layer-by-layer 3D printing, was tested as a biosensor for continuous water quality monitoring.

Trapping of redox-mediators at the surface of Chlorella vulgaris leads to error in measurements of cell reducing power.

The reduction of the redox mediator ferricyanide, [Fe(CN)6](3-), by a range of algal and bacterial species, is frequently measured to probe plasma membrane ferrireductase activity or to quantify the reducing power of algal/bacterial biofilms and suspensions. In this study we have used rotating disk electrochemistry (RDE) to investigate the reduction of ferricyanide by the model organism Chlorella vulgaris. Importantly, we have seen that the diffusion limited current due to the oxidation of ferrocyanide, [Fe(CN)6](4-), at the electrode decreased linearly as C.

Surface nucleated growth of dipeptide fibres.

We report the surface nucleated growth of self-assembled dipeptide films. The seeding-layer was a thin dipeptide film with a globular structure. Placing the seeding-layer in contact with dipeptide led to growth of fibres overnight.

Surface morphology and surface energy of anode materials influence power outputs in a multi-channel mediatorless bio-photovoltaic (BPV) system.

Bio-photovoltaic cells (BPVs) are a new photo-bio-electrochemical technology for harnessing solar energy using the photosynthetic activity of autotrophic organisms. Currently power outputs from BPVs are generally low and suffer from low efficiencies. However, a better understanding of the electrochemical interactions between the microbes and conductive materials will be likely to lead to increased power yields.

Sensing of pathogenic bacteria based on their interaction with supported bilayer membranes studied by impedance spectroscopy and surface plasmon resonance.

Pathogenic bacteria secrete various virulence factors, including toxins, lipases and proteases that allow them to infect, breakdown and colonize host tissue. Among various modes of action that the pathogenic bacteria use to damage the host, pore formation (by pore forming toxins (PFTs)) and lipid hydrolysis (by phospholipases) modes are common in damaging the eukaryotic cell membrane. PFTs in their monomeric form are extracellular diffusible and able to form hydrophilic pores in cell membrane while phospholipases cleaves and hydrolyzes the ester bonds of most phospholipids in cell membrane.

Directed self-assembly of dipeptides to form ultrathin hydrogel membranes.

The dipeptide amphiphile Fmoc-Leu-Gly-OH has been induced to self-assemble into thin surface-supported hydrogel gel films and gap-spanning hydrogel membranes. The thickness can be closely controlled, giving films/membranes from tens of nanometers to millimeters thick. SEM and TEM have confirmed that the dipeptides self-assemble to form fibers, with the membranes resembling a dense "mat" of entangled fibers.

The interaction of serum albumin with cholesterol containing lipid vesicles.

In this paper, the interaction of both human blood serum (the primary fraction of which is serum albumin) and pure human serum albumin (HSA) with surface immobilised lipid vesicles was measured by combined Surface Plasmon Resonance (SPR) and Surface Plasmon enhanced Fluorescence (SPEFS), and fluorescence microscopy. It was found that both blood serum and HSA showed specific binding to vesicles which contained cholesterol, resulting in increased membrane permeability and release of encapsulated fluorescent dye. This effect was not seen with heat inactivated blood serum, heat inactivated HSA or in vesicles not containing cholesterol.

Anti-fouling characteristics of surface-confined oligonucleotide strands bioconjugated on streptavidin platforms in the presence of nanomaterials.

This work describes our studies on the molecular design of interfacial architectures suitable for DNA sensing which could resist non-specific binding of nanomaterials commonly used as labels for amplifying biorecognition events. We observed that the non-specific binding of bio-nanomaterials to surface-confined oligonucleotide strands is highly dependent on the characteristics of the interfacial architecture. Thiolated double stranded oligonucleotide arrays assembled on Au surfaces evidence significant fouling in the presence of nanoparticles (NPs) at the nanomolar level.

Surface plasmon resonance-enhanced fluorescence implementation of a single-step competition assay: demonstration of fatty acid measurement using an anti-fatty acid monoclonal antibody and a Cy5-labeled fatty acid.

The development of a single-step, separation-free method for measurement of low concentrations of fatty acid using a surface plasmon resonance-enhanced fluorescence competition assay with a surface-bound antibody is described. The assay behavior was unexpectedly complex. A nonlinear coverage-dependent self-quenching of emission from surface-bound fluorescent label was deduced from the response kinetics and attributed to a surface plasmon-mediated energy transfer between adsorbed fluorophores, modified by the effects of plasmon interference.

A Comparative Plasmonic Study of Nanoporous and Evaporated Gold Films.

Previously, we have reported that nanoporous gold (NPG) films prepared by a chemical dealloying method have distinctive plasmonic properties, i.e., they can simultaneously support localized and propagating surface plasmon resonance modes (l-SPR and p-SPR, respectively).

Attachment and phospholipase A2-induced lysis of phospholipid bilayer vesicles to plasma-polymerized maleic anhydride/SiO2 multilayers.

This article describes a method by which intact vesicles can be chemically attached to hydrolyzed maleic anhydride films covalently bound to plasma-polymerized SiO2 on Au substrates. Surface plasmon field-enhanced fluorescence spectroscopy (SPFS) combined with surface plasmon resonance spectroscopy (SPR) was used to monitor the activation of plasma-deposited maleic anhydride (pp-MA) film with EDC/NHS and the subsequent coupling of lipid vesicles. The vesicles were formed from a mixture of phosphatidylcholine and phosphatidylethanolamine lipids, with a water-soluble fluorophore encapsulated within.

How important is the back reaction of electrons via the substrate in dye-sensitized nanocrystalline solar cells?

The role of the conducting glass substrate (fluorine-doped tin oxide, FTO) in the back reaction of electrons with tri-iodide ions in dye-sensitized nanocrystalline solar cells (DSCs) has been investigated using thin-layer electrochemical cells that are analogues of the DSCs. The rate of back reaction is dependent on the type of FTO and the thermal treatment. The results show that this back-reaction route cannot be neglected in DSCs, particularly at lower light intensities, where it is the dominant route for the back transfer of electrons to tri-iodide.