Lucy Jessica F. Hart

Through remarkable advances in materials design, the efficiency of photovoltaic energy conversion in molecular materials has risen from 1% to over 20% within 2 decades. Some recent reports argue that charge photogeneration can occur directly in neat films of the best-performing molecular materials, and that this process may assist current generation in heterojunction devices. Here we address this assertion by combining experimental measurements of charge generation in single-component and heterojunction devices with a computational model of the generation and evolution of delocalized excited states in such systems. We identify key molecular parameters that are likely to assist charge generation in high-performance materials, including the exciton binding energy, reorganization energy, energetic disorder, electronic coupling and the molecular packing motif. We show that including state delocalization is critical to the results. While we find that charge generation in single domains is unlikely to drive photocurrent generation in low-offset heterojunctions, the same molecular parameters favour charge generation in both device architectures.

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.

This study examines the kinetic origins of the temperature dependence of photoelectrochemical water oxidation on nanostructured titania photoanodes. We observe that the photocurrent is enhanced at 50 °C relative to 20 °C, with this enhancement being most pronounced (by up to 70%) at low anodic potentials (<+0.6 V vs RHE). Over this low potential range, the photocurrent magnitude is largely determined by kinetic competition between water oxidation catalysis (WOC) and recombination between surface holes and bulk electrons (back electron-hole recombination, BER). We quantify the BER process by transient photocurrent analyses under pulsed irradiation. Remarkably, we find that the kinetics of BER (∼90 ms half-time) are independent of temperature. In contrast, the kinetics of WOC, determined from the analysis of the photoinduced absorption of accumulated surface holes, are found to accelerate up to 2-fold at 50 °C relative to 20 °C. We conclude that the enhanced photocurrent densities observed in the low-applied potential region result primarily from the accelerated WOC, reducing losses due to the competing BER pathway. At higher applied potentials (>+0.6 V vs RHE), a smaller (∼10%) enhancement in photocurrent density is observed at 50 °C relative to 20 °C. Photoinduced absorption studies, correlated with studies using triethanolamine as a hole scavenger, indicate that this more modest enhancement at anodic potentials primarily results from an enhanced charge separation efficiency. We conclude by discussing the implications of these results for the practical application of photoanodic WOC under solar irradiation, influenced by these temperature-independent and -dependent underlying kinetic processes.

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.

The charge carrier dynamics of SrTiO₃ are measured on fast (ps–ns) timescales, to reveal remarkably slow bimolecular recombination compared to alternative metal oxides commonly employed in photocatalytic applications.

Non‐fullerene acceptors (NFAs) have enabled power conversion efficiencies exceeding 19% in organic solar cells (OSCs). However, the open‐circuit voltage of OSCs remains low relative to their optical gap due to excessive non‐radiative recombination, and this now limits performance. Here, an important aspect of OSC design is considered, namely management of the triplet exciton population formed after non‐geminate charge recombination. By comparing the blends PM6:Y11 and PM6:Y6, it is shown that the greater crystallinity of the NFA domains in PM6:Y11 leads to a higher rate of triplet‐triplet annihilation (TTA). This is attributed to the four times larger ground state dipole moment of Y11 versus Y6, which improves the long range NFA out‐of‐plane ordering. Since TTA converts a fraction of the non‐emissive triplet states into bright singlet states, it has the potential to reduce non‐radiative voltage losses. Through a kinetic analysis of the recombination processes under 1‐Sun illumination, a framework is provided for determining the conditions under which TTA may improve OSC performance. If these could be satisfied, TTA has the potential to reduce non‐radiative voltage losses by up to several tens of millivolts.

Understanding the kinetic competition between charge extraction and recombination, and how this is impacted by mobile ions, remains a key challenge in perovskite solar cells (PSCs). Here, this issue is addressed by combining operando photoluminescence (PL) measurements, which allow the measurement of real‐time PL spectra during current–voltage (J–V) scans under 1‐sun equivalent illumination, with the results of drift‐diffusion simulations. This operando PL analysis allows direct comparison between the internal performance (recombination currents and quasi‐Fermi‐level‐splitting (QFLS)) and the external performance (J–V) of a PSC during operation. Analyses of four PSCs with different electron transport materials (ETMs) quantify how a deeper ETM LUMO induces greater interfacial recombination, while a shallower LUMO impedes charge extraction. Furthermore, it is found that a low ETM mobility leads to charge accumulation in the perovskite under short‐circuit conditions. However, thisalone cannot explain the remarkably high short‐circuit QFLS of over 1 eV which is observed in all devices. Instead, drift‐diffusion simulations allow this effect to be assigned to the presence of mobile ions which screen the internal electric field at short‐circuit and lead to a reduction in the short‐circuit current density by over 2 mA cm⁻² in the best device.