Piers R. F. Barnes

As lab-scale perovskite solar cells (PSCs) approach their efficiency limits, reproducing this performance in large-area, manufacturable devices remains challenging. Here, we show that printing interlayers of metal oxide nanoparticles, specifically Al₂O₃ and SnO₂, can systematically control the morphology and interfacial energetics of solution-processed PC₆₁BM electron transport layers (ETLs) in flexible roll-to-roll printed PSCs. These nanoparticle interlayers enhance ETL uniformity, reduce pinholes, and increase shunt resistance, improving power conversion efficiencies (PCEs) and reducing device failure rates by 50%. Through a combination of systematic device characterization, morphological, spectroscopic and energetic analysis, coupled with drift-diffusion simulations, the distinct roles of insulating (Al₂O₃) and semiconducting (SnO₂) nanoparticle interlayers in mediating carrier extraction and recombination are elucidated. Al₂O₃ suppresses interfacial recombination and improves device reproducibility, albeit with some penalty in short-circuit current, whereas SnO₂ enhances electronic coupling and charge extraction, delivering a champion PCE of 11.0% (active area: 0.5 cm²). Incorporating SnO₂ interlayers into larger-area modules (active area: 7.2 cm²) further demonstrates the robustness of this strategy under manufacturing-relevant conditions. Together, these results provide an important framework for nanoparticle-mediated interface engineering and establish a simple, effective, and scalable route to improving both performance and yield in printed large-area PSCs.

Surface passivation in perovskite solar cells can enhance device efficiency, yet incomplete interfacial functionality poses challenges to long-term reliability. Here we present a strategic interfacial engineering approach using sodium heptafluorobutyrate to fully functionalize the perovskite surface. Sodium heptafluorobutyrate acts as an ion shield that tunes the perovskite surface work function and increases the defect formation energy, resulting in an improved interface with the electron transport layer that minimizes recombination and boosts electron extraction under operation. We find that a sodium-heptafluorobutyrate-functionalized perovskite surface promotes a uniform, compact C ₆₀ layer that effectively blocks ion diffusion and stabilizes the device stack. This approach allows p–i–n perovskite solar cells to achieve a record power conversion efficiency (PCE) of 27.02% (certified 26.96% with a maximum-power-point-tracking PCE of 26.61%). Devices with an active area of 1 cm ² deliver a PCE of 25.95%. Perovskite solar cells retain 100% of their initial efficiency following 1,200 h of continuous 1-sun illumination at the maximum power point. Devices also demonstrate exceptional thermal stability, retaining 92% of the initial PCE when ageing at 85 °C for 1,800 h and 94% after 200 thermal cycles between –40 °C and +85 °C.

Conjugated polymers (CPs) with polar side chains can conduct electronic and ionic charges simultaneously, making them promising for bioelectronics, electrocatalysis and energy storage. Recent work showed that adding alkyl spacers between CP backbones and polar side chains improved electronic charge carrier mobility, reduced swelling and enhanced stability, without compromising ion transport. However, how alkyl spacers impact polymer backbone conformation and, subsequently, electronic properties remain unclear. In this work, we design two oxy‐bithiophene‐based CP series, each featuring progressively extended alkyl spacer lengths and two distinct molecular weight (MW) distributions. Using operando characterisations, we evaluate the (spectro)electrochemical and swelling properties of the polymer thin films, and their performance in organic field‐effect transistors and organic electrochemical transistors. Surprisingly, alkyl spacers negatively impact the hole mobility of our polymers, with higher MW amplifying this effect. Using molecular dynamics simulations, we show that it is thermodynamically favourable for adjacent non‐polar alkyl spacers to aggregate in polar electrolytes, leading to backbone twisting. Further spectroscopic measurements corroborate this prediction. Our findings demonstrate the active interactions between side chain structure, MW and electrolyte/solvent polarity in influencing polymer performance, underscoring the importance of considering solvation environment effects on polymer conformation when designing new mixed conducting CPs for electrochemical applications.

Conjugated polymers (CPs) with polar side chains can conduct electronic and ionic charges simultaneously, making them promising for bioelectronics, electrocatalysis and energy storage. Recent work showed that adding alkyl spacers between CP backbones and polar side chains improved electronic charge carrier mobility, reduced swelling and enhanced stability, without compromising ion transport. However, how alkyl spacers impact polymer backbone conformation and, subsequently, electronic properties remain unclear. In this work, we design two oxy‐bithiophene‐based CP series, each featuring progressively extended alkyl spacer lengths and two distinct molecular weight (MW) distributions. Using operando characterisations, we evaluate the (spectro)electrochemical and swelling properties of the polymer thin films, and their performance in organic field‐effect transistors and organic electrochemical transistors. Surprisingly, alkyl spacers negatively impact the hole mobility of our polymers, with higher MW amplifying this effect. Using molecular dynamics simulations, we show that it is thermodynamically favourable for adjacent non‐polar alkyl spacers to aggregate in polar electrolytes, leading to backbone twisting. Further spectroscopic measurements corroborate this prediction. Our findings demonstrate the active interactions between side chain structure, MW and electrolyte/solvent polarity in influencing polymer performance, underscoring the importance of considering solvation environment effects on polymer conformation when designing new mixed conducting CPs for electrochemical applications.

Herein, we investigate the effect of mobile ions on steady-state perovskite solar cell performance and show that they can lead to significant increases in open circuit voltage and improve device tolerance to interfacial energetic misalignments.

Many recent advances in metal halide perovskite solar cell (PSC) performance are attributed to surface treatments which passivate interfacial trap states, minimise charge recombination and boost photovoltages. Surprisingly, these photovoltages exceed the cells' built-in potentials, often with large energetic offsets reported between the perovskite and transport layer semiconductor band edges - contradicting standard photovoltaic design principles. Here we show that this tolerance to energetic offsets results from mixed ionic/electronic conduction in the perovskite layer. Combining drift-diffusion simulations with experiments probing the current-voltage performance of PSCs as a function of ion distribution, we demonstrate that electrostatic redistribution of ionic charge reduces surface recombination currents at steady-state, increasing the photovoltage by tens to hundreds of millivolts. Thus, mobile ions can reduce the sensitivity of photovoltage to energetic misalignments at perovskite/transport layer interfaces, benefitting overall efficiency. Building on these insights, we show how photovoltaic design principles are modified to account for mobile ions.

Ionic charge transport is a ubiquitous language of communication in biological systems. As such, bioengineering is in constant need of innovative, soft, and biocompatible materials that facilitate ionic conduction. Low molecular weight gelators (LMWGs) are complex self-assembled materials that have received increasing attention in recent years. Beyond their biocompatible, self-healing, and stimuli responsive facets, LMWGs can be viewed as a "solid" electrolyte solution. In this work, we investigate 3,4-ethylenedioxythiophene (EDOT) as a capping group for a small peptide library, which we use as a system to understand the relationship between modes of assembly and charge transport in supramolecular gels. Through a combination of techniques including small-angle neutron scattering (SANS), NMR-based Van't Hoff analysis, atomic force microscopy (AFM), rheology, four-point probe, and electrochemical impedance spectroscopy (EIS), we found that modifications to the peptide sequence result in distinct assembly pathways, thermodynamic parameters, mechanical properties, and ionic conductivities. Four-point probe conductivity measurements and electrochemical impedance spectroscopy suggest that ionic conductivity is approximately doubled by programmable gel assemblies with hollow cylinder morphologies relative to gels containing solid fibers or a control electrolyte. More broadly, it is hoped this work will serve as a platform for those working on charge transport of aqueous soft materials in general.

Conventional spectroscopies are not sufficiently selective to comprehensively understand the behaviour of trapped carriers in perovskite solar cells, particularly under their working conditions. Here we use infrared optical activation spectroscopy (i.e., pump-push-photocurrent), to observe the properties and real-time dynamics of trapped carriers within operando perovskite solar cells. We compare behaviour differences of trapped holes in pristine and surface-passivated FA_0.99Cs_0.01PbI₃ devices using a combination of quasi-steady-state and nanosecond time-resolved pump-push-photocurrent, as well as kinetic and drift-diffusion models. We find a two-step trap-filling process: the rapid filling (~10 ns) of low-density traps in the bulk of perovskite, followed by the slower filling (~100 ns) of high-density traps at the perovskite/hole transport material interface. Surface passivation by n-octylammonium iodide dramatically reduces the number of trap states (~50 times), improving the device performance substantially. Moreover, the activation energy (~280 meV) of the dominant hole traps remains similar with and without surface passivation.

Electric fields arising from the distribution of charge in metal-halide perovskite solar cells are critical for understanding the many weird and wonderful optoelectronic properties displayed by these devices. Mobile ionic defects are thought to accumulate at interfaces to screen electric fields within the bulk of the perovskite semiconductor on application of external bias, but tools are needed to directly probe the dynamics of this process. Here, we show that electroabsorption measurements allow the electric field within the active layer to be tracked as a function of frequency or time. The magnitude of the electroabsorption signal, corresponding to the strength of the electric field in the perovskite layer, falls off for externally applied low-frequency voltages or at long times following voltage steps. Our observations are consistent with drift-diffusion simulations, impedance spectroscopy, and transient photocurrent measurements. They indicate charge redistribution on timescales ranging from 10 ms to 100 s, depending on the device interlayer material, perovskite composition, dominant charged defect, and illumination conditions. The method can be used on typical solar-cell structures and has the potential to become a routine characterization tool for optimizing hybrid perovskite devices.