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Photovoltaics (PVs) are a critical technology for curbing growing levels of anthropogenic greenhouse gas emissions, and meeting increases in future demand for low-carbon electricity. In order to fulfil ambitions for net-zero carbon dioxide equivalent (CO2eq) emissions worldwide, the global cumulative capacity of solar PVs must increase by an order of magnitude from 0.9 TWp in 2021 to 8.5 TWp by 2050 according to the International Renewable Energy Agency, which is considered to be a highly conservative estimate. In 2020, the Henry Royce Institute brought together the UK PV community to discuss the critical technological and infrastructure challenges that need to be overcome to address the vast challenges in accelerating PV deployment. Herein, we examine the key developments in the global community, especially the progress made in the field since this earlier roadmap, bringing together experts primarily from the UK across the breadth of the photovoltaics community. The focus is both on the challenges in improving the efficiency, stability and levelized cost of electricity of current technologies for utility-scale PVs, as well as the fundamental questions in novel technologies that can have a significant impact on emerging markets, such as indoor PVs, space PVs, and agrivoltaics. We discuss challenges in advanced metrology and computational tools, as well as the growing synergies between PVs and solar fuels, and offer a perspective on the environmental sustainability of the PV industry. Through this roadmap, we emphasize promising pathways forward in both the short- and long-term, and for communities working on technologies across a range of maturity levels to learn from each other., Comment: 160 pages, 21 figures

The rising energy prices in Europe and the urgent need to address global warming have sparked a significant increase in the installation of domestic photovoltaic systems to harness solar energy. However, since solar energy is available only during daytime hours and its availability varies daily, effectively shifting energy use becomes crucial. Whilst batteries can assist in storing excess energy, their high prices hinder their widespread adoption. In this study, we explore the importance of load to maximise return on investment. We propose an incremental approach to fitting load profiles into the production envelope, allowing for practical implementation. We compare different meter resolutions: 1 second, 5 minutes, 15 minutes, and 1 hour. Our analysis reveals that making real-time decisions (per second) leads to significant energy savings of 16\% compared to hourly decisions. Furthermore, we explore three types of device management strategies: ON/OFF management independent of PV production, ON/OFF management based on the current PV production, ON/OFF management based on both current and forecasted PV production, utilising an optimal fit algorithm. Through our study, we demonstrate that our implementation of the third approach outperforms a standard management approach, resulting in more than 17% cost savings. This study provides insights into the optimisation of load-shifting strategies in domestic photovoltaic installations, highlighting the importance of load control and the potential benefits in maximising the utilisation of solar energy while minimising energy costs and environmental impact.

Metal halide perovskite solar cells have gained widespread attention due to their high efficiency and high defect tolerance. The absorbing perovskite layer is as a mixed electron-ion conductor that supports high rates of ion and charge transport at room temperature, but the migration of mobile defects can lead to degradation pathways. We combine experimental observations and drift-diffusion modelling to demonstrate a new framework to interpret surface photovoltage (SPV) measurements in perovskite systems and mixed electronic ionic conductors more generally. We conclude that the SPV in mixed electronic ionic conductors can be understood in terms of the change in electric potential at the surface associated with changes in the net charge within the semiconductor system. We show that by modifying the interfaces of perovskite bilayers, we may control defect migration behaviour throughout the perovskite bulk. Our new framework for SPV has broad implications for developing strategies to improve the stability of perovskite devices by controlling defect accumulation at interfaces. More generally, in mixed electronic conductors our framework provides new insights into the behaviour of mobile defects and their interaction with photoinduced charges, which are foundational to physical mechanisms in memristivity, logic, impedance, sensors and energy storage.

Space-charge-limited current (SCLC) measurements are used to estimate charge carrier mobilities and electronic trap densities of semiconductors by analysing the current density-voltage (JV) relationship for unipolar devices predicted by the Mott-Gurney (MG) law. However, the interpretation of SCLC measurements for metal-halide perovskites is problematic due to mobile ionic defects which redistribute to screen electrostatic fields in devices during measurements. To overcome this, an SCLC measurement protocol was recently suggested that minimises ionic charge redistribution by probing the current during millisecond voltage pulses superimposed on a background bias. Here, we use drift-diffusion simulations with mobile ions to assess the validity of the MG law for analysing both the standard and new protocol JV measurements. We simulated idealised perovskite devices with differing mobile ion densities and compared them with simulations and measurements of devices with typical contact materials. We found the validity region for the MG law is limited to perovskites with mobile ion densities lower than the device's equilibrium charge carrier density (<10^17 cm-3 for 400 nm thick methylammonium lead iodide films) and contacts with injection/extraction barriers <=0.1 eV. The latter limitation can be partially overcome by increasing the device thickness, whereas the former limitation cannot. This restricts the range of perovskite layer compositions and viable contact materials that can be reliably analysed with the MG law. Approaches such as estimating trap densities from the apparent voltage onset to trap-free SCLC regime should also be critically reviewed since they rely on the same potentially invalid assumptions as the MG law. Our results demonstrate that extracting meaningful and accurate values for metal halide perovskite material properties from SCLC maybe challenging, or often not possible., Comment: Main text 22 pages, supplementary materials 9 pages

Non-fullerene acceptors (NFAs) are excellent light harvesters, yet the origin of such high optical extinction is not well understood. In this work, we investigate the absorption strength of NFAs by building a database of time-dependent density functional theory (TDDFT) calculations of ~500 pi-conjugated molecules. The calculations are first validated by comparison with experimental measurements on liquid and solid state using common fullerene and non-fullerene acceptors. We find that the molar extinction coefficient ({\epsilon}_(d,max)) shows reasonable agreement between calculation in vacuum and experiment for molecules in solution, highlighting the effectiveness of TDDFT for predicting optical properties of organic pi-conjugated molecules. We then perform a statistical analysis based on molecular descriptors to identify which features are important in defining the absorption strength. This allows us to identify structural features that are correlated with high absorption strength in NFAs and could be used to guide molecular design: highly absorbing NFAs should possess a planar, linear, and fully conjugated molecular backbone with highly polarisable heteroatoms. We then exploit a random decision forest to draw predictions for {\epsilon}_(d,max) using a computational framework based on extended tight-binding Hamiltonians, which shows reasonable predicting accuracy with lower computational cost than TDDFT. This work provides a general understanding of the relationship between molecular structure and absorption strength in pi-conjugated organic molecules, including NFAs, while introducing predictive machine-learning models of low computational cost., Comment: 40 pages and 5 figures (main text)

Exchanging hydrophobic alkyl-based side chains to hydrophilic glycol-based side chains is a widely adopted method for improving mixed-transport device performance, despite the impact on solid state packing and polymer-electrolyte interactions being poorly understood. Presented here is a Molecular Dynamics (MD) force field for modelling alkoxylated and glycolated polythiophenes. The force field is validated against known packing motifs for their monomer crystals. MD simulations, coupled with X-ray Diffraction (XRD), show that alkoxylated polythiophenes will pack with a `tilted stack' and straight interdigitating side chains, whilst their glycolated counterpart will pack with a `deflected stack' and an s-bend side chain configuration. MD simulations reveal water penetration pathways into the alkoxylated and glycolated crystals - through the {\pi}-stack and through the lamellar stack respectively. Finally, the two distinct ways tri-ethylene glycol polymers can bind to cations are revealed, showing the formation of a meta-stable single bound state, or an energetically deep double bound state, both with a strong side chain length dependance. The minimum energy pathways for the formation of the chelates are identified, showing the physical process through which cations can bind to one or two side chains of a glycolated polythiophene, with consequences for ion transport in bithiophene semiconductors., Comment: 10 pages, 4 figures

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 the electric field in 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 screening/redistribution on time-scales 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 performed on typical solar cell structures and has potential to become a routine characterization tool for optimizing hybrid perovskite devices., Comment: 65 pages, 41 figures

Electricity access in refugee camps is often limited to critical operations for humanitarian agencies and typically powered by fossil fuel generators. We study the economic and environmental benefits that optimised fully renewable and diesel-hybrid mini-grid designs can provide in humanitarian settings by displacing diesel use. Considering the case study of Nyabiheke camp in Rwanda we found that these benefits are substantial, with savings up to 32% of total costs and 83% of emissions, and cost payback times ranging from 0.9 to 6.2 years. Despite of their different cost structures, we find that all hybridisation levels of the system provide cost and emission savings compared to the incumbent diesel system. We highlight how modelling tools can facilitate the introduction and progressive expansion of systems as well as inform operational considerations on the ground. This study demonstrates how financial resources, environmental objectives and operational timeframes will influence the most appropriate system design for humanitarian actors on a case-by-case basis.

The recent emergence of lead-halide perovskites as active layer materials for thin film semiconductor devices including solar cells, light emitting diodes, and memristors has motivated the development of several new drift-diffusion models that include the effects of both mobile electronic and ionic charge carriers. The aim of this work is to provide a comprehensive guide to Driftfusion, a versatile simulation tool built for simulating one-dimensional ordered semiconductor devices with mixed ionic-electronic conducting layers. Driftfusion enables users to model devices with multiple, distinct, material layers and up to four charge carrier species: electrons and holes by default plus up to two ionic species. The time-dependent carrier continuity equations are fully-coupled to Poisson's equation enabling transient optoelectronic device measurement protocols to be simulated. In addition to material and device-wide properties, users have direct access to adapt the physical models for carrier transport, generation and recombination. Furthermore, a graded-interface approach circumvents the requirement for boundary conditions at material interfaces and enables interface-specific properties, such as high rates of interfacial recombination, to be introduced., Comment: Main text: 30 pages, 17 figures, Supplemental information: 29 pages, 20 figures

We report the development of redox-active conjugated polymers with potential application to electrochemical energy storage. Side chain engineering enables processing of the polymer electrodes from solution, stability in aqueous electrolytes and efficient transport of ionic and electronic charge carriers. We synthesized a 3,3' dialkoxybithiophene homo polymer (p type polymer) with glycol side chains and prepared naphthalene 1,4,5,8-tetracarboxylic-diimide-dialkoxybithiophene (NDI gT2) copolymers (n type polymer) with either a glycol or zwitterionic side chain on the NDI unit. For the latter, we developed a post-functionalization synthesis to attach the polar zwitterion side chains to the polymer backbone to avoid challenges of purifying polar intermediates. We demonstrate fast and reversible charging of solution processed electrodes for both the p- and n type polymers in aqueous electrolytes, without using additives or porous scaffolds and for films up to micrometers thick. We apply spectroelectrochemistry as an in operando technique to probe the state of charge of the electrodes. This reveals that thin films of the p-type polymer and zwitterion n-type polymer can be charged reversibly with up to two electronic charges per repeat unit (bipolaron formation). We combine thin films of these polymers in a two-electrode cell and demonstrate output voltages of up to 1.4 V with high redox stability. Our findings demonstrate the potential of functionalizing conjugated polymers with appropriate polar side chains to improve specific capacity, reversibility and rate capabilities of polymer electrodes in aqueous electrolytes., Comment: Main text 16 pages including 6 figures + 49 pages of supporting information. arXiv admin note: substantial text overlap with arXiv:1711.10457

We present a detailed study of the structure-dynamics relationship of regio-regular and regio-random PEHT using different neutron scattering techniques. Deuteration is employed to modulate the coherent and incoherent cross-sections, allowing particularly to access both self-motions and collective dynamics of the materials. The measurements are underpinned by extensive quantitative calculations using classical MD, as well as first principles quantum chemistry. MD reproduced well the main structural features and slow motions, and shed light on differences in collective dynamics between Q-values linked with the $\pi-\pi$ stacking and the lamellar stacking, with the crystalline phase being the most impacted. On the other hand MD led to a limited description of molecular vibrations. In this context, first principles molecular calculations described well the high-energy vibrational features ( $>$ 900 cm$^{-1}$ ), while periodic calculations allowed to better describe the low- and mid-energy vibrational ranges ( 200-900 cm$^{-1}$ ). The mid-energy range is predominantly associated with both intra-molecular and inter-molecular mode coupling, which encloses information about both the polymer conformation and the polymer packing at short range. One of the outcomes of this study is the validation of the common assumption made that RRa-P3HT is a good approximation for the amorphous phase of RR-P3HT at the macroscopic level. The present work helps to clarify unambiguously the latter point which has been largely overlooked in the literature. We highlight the importance to complement optical spectroscopy techniques with inelastic neutron scattering. The latter offering the advantage of being insensitive to the delocalized $\pi$-electron system, and thus enabling to infer relevant quantities like conjugation lengths, for instance, impacting properties of conjugated polymer., Comment: Featured as ACS Editors' Choice. Featured on the Cover of the December 10, 2019 issue of Chemistry of Materials

High power conversion efficiency (PCE) inverted organic photovoltaics (OPVs) usually use thermally evaporated MoO3 as a hole transporting layer (HTL). Despite the high PCE values reported, stability investigations are still limited and the exact degradation mechanisms of inverted OPVs using thermally evaporated MoO3 HTL remain unclear under different environmental stress factors. In this study, we monitor the accelerated lifetime performance of non-encapsulated inverted OPVs using thiophene-based active layer materials and evaporated MoO3 under the ISOS D-2 protocol (heat conditions 65 {\deg}C). The investigation of degradation mechanisms presented focus on optimized P3HT:PC[70]BM-based inverted OPVs. Specifically, we present a systematic study on the thermal stability of inverted P3HT:PC[70]BM OPVs using solution processed PEDOT:PSS and evaporated MoO3 HTL. Using a series of measurements and reverse engineering methods we report that the P3HT:PC[70]BM/MoO3 interface is the main origin of failure of P3HT:PC[70]BM-based inverted OPVs under intense heat conditions.

Mobile ions in hybrid perovskite semiconductors introduce a new degree of freedom to electronic devices suggesting applications beyond photovoltaics. An intuitive device model describing the interplay between ionic and electronic charge transfer is needed to unlock the full potential of the technology. We describe the perovskite-contact interfaces as transistors which couple ionic charge redistribution to energetic barriers controlling electronic injection and recombination. This reveals an amplification factor between the out of phase electronic current and the ionic current. Our findings suggest a strategy to design thin film electronic components with large, tuneable, capacitor-like and inductor-like characteristics. The resulting simple equivalent circuit model, which we verified with time-dependent drift-diffusion simulations of measured impedance spectra, allows a general description and interpretation of perovskite solar cell behaviour., Comment: 12 pages main text, total 51 including supplementary information

The ideality factor determined by measuring the open circuit voltage (VOC) as function of light intensity is often used as a means to identify the dominant recombination mechanism in solar cells. However, applying this Suns-VOC technique to perovskite cells is problematic since the VOC evolves with time in a way which depends on the previously applied bias (Vpre), the light intensity, and the device architecture/processing. Here we show that the dominant recombination mechanism in two structurally similar CH3NH3PbI3 devices containing either mesoporous Al2O3 or TiO2 layers can be identified from the signature of the transient ideality factor following application of a forward bias, Vpre, to the device in the dark. The transient ideality factor, is measured by monitoring the temporal evolution of VOC at different light intensities. The initial values of the transient ideality were consistent with corresponding photoluminescence vs intensity as well as electroluminescence vs current density measurements. Time-dependent simulations of the measurement on modelled devices, which include the effects of mobile ionic charge, show that Shockley Read Hall (SRH) recombination through deep traps at the charge collection interfaces is dominant in both devices. Using transient photovoltage measurements superimposed on the evolving VOC of bifacial devices we further show that the charge collection interface extends throughout the mesoporous TiO2 layer, consistent with a transient ideality signature corresponding to SRH recombination in the bulk of the film. This information could not be inferred from an ideality factor determined from only steady-state VOC values. The method we have developed will be useful for identifying performance bottlenecks in new variants of perovskite devices by comparison with the transient ideality signatures we have predicted for a range of possible recombination schemes., Comment: Main manuscript and supporting information

We report a neutral salt water based battery which uses p-type and n-type solution processed polymer films as the cathode and the anode of the cell. The specific capacity of the electrodes (approximately 30 mAh cm-3) is achieved via formation of bipolarons in both the p-type and n-type polymers. By engineering ethylene glycol and zwitterion based side chains attached to the polymer backbone we facilitate rapid ion transport through the non-porous polymer films. This, combined with efficient transport of electronic charge via the conjugated polymer backbones, allowed the films to maintain constant capacity at high charge and discharge rates (>1000 C-rate). The electrodes also show good stability during electrochemical cycling (less than 30% decrease in capacity over >1000 cycles) and an output voltage up to 1.4 V. The performance of these semiconducting polymers with polar side-chains demonstrates the potential of this material class for fast-charging, water based electrochemical energy storage devices., Comment: Main paper 13 pages, included supporting information 49 pages

The GaAs/AlGaAs quantum well solar cell (QWSC) shows promise as a novel approach to higher efficiency solar cells but suffers from a poor short circuit current Jsc. We report on efforts to reduce this problem with the use of compositional grading and back surface mirroring. We present experimental quantum efficiency (QE) data on a range of compositionally graded QWSCs and devices in which the back surface of the cell is coated with a mirror, increasing the optical thickness of the quantum well layer in the long wavelength range. The experimental QE spectra are reproduced by a model which deals with arbitrary compositional profiles and optical cavities formed in the mirrored cells. The model is used to design an optimised QWSC, and projected Jsc values given. Applications including II-VI and tandem solar cells are considered., Comment: Proc. 2nd World Conf. and Exhibition on Photovoltaic Solar Energy Conversion, Vienna, Austria, 6-10 (1998) pp. 227-229. Proceedings available: http://bookshop.europa.eu/en/2nd-world-conference-on-photovoltaic-solar-energy-conversion.-proceedings-of-the-international-conference-held-at-vienna-austria-6-10-july-1998-volume-ii-pbCLNB18656/

We present Raman and terahertz absorbance spectra of methylammonium lead halide single crystals (MAPbX3, X = I, Br, Cl) at temperatures between 80 and 370 K. These results show good agreement with density-functional-theory phonon calculations.1 Comparison of experimental spectra and calculated vibrational modes enables confident assignment of most of the vibrational features between 50 and 3500 cm-1. Reorientation of the methylammonium cations, unlocked in their cavities at the orthorhombic-to-tetragonal phase transition, plays a key role in shaping the vibrational spectra of the different compounds. Calculations show that these dynamics effects split Raman peaks and create more structure than predicted from the independent harmonic modes. This explains the presence of extra peaks in the experimental spectra that have been a source of confusion in earlier studies. We discuss singular features, in particular the torsional vibration of the C-N axis, which is the only molecular mode that is strongly influenced by the size of the lattice. From analysis of the spectral linewidths, we find that MAPbI3 shows exceptionally short phonon lifetimes, which can be linked to low lattice thermal conductivity. We show that optical rather than acoustic phonon scattering is likely to prevail at room temperature in these materials., Comment: 40 pages (no supporting info uploaded)

Ionic migration has been proposed as a possible cause of photovoltaic current-voltage hysteresis in hybrid perovskite solar cells. However, a major objection to this hypothesis is that hysteresis can be reduced by changing the interfacial contact materials, which are unlikely to significantly influence the behaviour of ionic defects within the perovskite phase. Here we use transient optoelectronic measurements, combined with device simulations, to show that the primary effects of ionic migration can in fact be observed both in devices with hysteresis, and with hysteresis free type contact materials. The data indicate that electric-field screening, consistent with ionic migration, is similar or identical in both high and low hysteresis CH3NH3PbI3 cells. Simulation of the transients shows that hysteresis requires the combination of both mobile ionic charge and recombination near the contacts. Passivating contact recombination results in higher photogenerated charge concentrations at forward bias which screen the ionic charge, reducing hysteresis., Comment: 40 pages, main text + supporting information

All-organic-based photovoltaic solar cells have attracted considerable attention because of their low-cost processing and short energy payback time. In such systems the primary dissociation of an optical excitation into a pair of photocarriers has been recently shown to be extremely rapid and efficient, but the physical reason for this remains unclear. Here, two-dimensional photocurrent excitation spectroscopy, a novel non-linear optical spectroscopy, is used to probe the ultrafast coherent decay of photoexcitations into charge-producing states in a polymer:fullerene based solar cell. The two-dimensional photocurrent spectra are interpreted by introducing a theoretical model for the description of the coupling of the electronic states of the system to an external environment and to the applied laser fields. The experimental data show no cross-peaks in the two-dimensional photocurrent spectra, as predicted by the model for coherence times between the exciton and the photocurrent producing states of 20\,fs or less.

In high-performance solar cells based on polymeric semiconductors, the mechanism of photocarrier generation on $<100$-fs timescales is yet to be unravelled. In particular the dynamics of early-time electronic coupling between excitons on polymer chains and charge-transfer states need to be investigated in order to develop a detailed picture of ultrafast processes involved in photocurrent production. In this proceeding, we report preliminary measurements using a novel spectroscopy that can measure such correlations: two-dimensional coherent photocurrent excitation spectroscopy. This nonlinear technique measures off-diagonal spectral correlations in a two-dimensional photocurrent excitation spectrum. We interpret these sectroscopic measurements in light of recent theoretical predictions., Comment: 12 pages, 3 figures, EXCON 2015