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Spray coating is an industrially mature technique used to deposit thin films that combines high throughput with the ability to coat nonplanar surfaces. Here, we explore the use of ultrasonic spray coating to fabricate perovskite solar cells (PSCs) over rigid, nonplanar surfaces without problems caused by solution dewetting and subsequent "run-off". Encouragingly, we find that PSCs can be spray-coated using our processes onto glass substrates held at angles of inclination up to 45° away from the horizontal, with such devices having comparable power conversion efficiencies (up to 18.3%) to those spray-cast onto horizontal substrates. Having established that our process can be used to create PSCs on surfaces that are not horizontal, we fabricate devices over a convex glass substrate, with devices having a maximum power conversion efficiency of 12.5%. To our best knowledge, this study represents the first demonstration of a rigid, curved perovskite solar cell. The integration of perovskite photovoltaics onto curved surfaces will likely find direct applications in the aerospace and automotive sectors.

High temperature post-deposition annealing of hybrid lead halide perovskite thin films—typically lasting at least 10 min—dramatically limits the maximum roll-to-roll coating speed, which determines solar module manufacturing costs. While several approaches for “annealing-free” perovskite solar cells (PSCs) have been demonstrated, many are of limited feasibility for scalable fabrication. Here, this work has solvent-engineered a high vapor pressure solvent mixture of 2-methoxy ethanol and tetrahydrofuran to deposit highly crystalline perovskite thin-films at room temperature using gas-quenching to remove the volatile solvents. Using this approach, this work demonstrates p-i-n devices with an annealing-free MAPbI3 perovskite layer achieving stabilized power conversion efficiencies (PCEs) of up to 18.0%, compared to 18.4% for devices containing an annealed perovskite layer. This work then explores the deposition of self-assembled molecules as the hole-transporting layer without annealing. This work finally combines the methods to create fully annealing-free devices having stabilized PCEs of up to 17.1%. This represents the state-of-the-art for annealing-free fabrication of PSCs with a process fully compatible with roll-to-roll manufacture.

This study uses a laser patterning setup to write defect structures into a conjugated polymer microcavity. We show that the defect enhances optical confinement and reduces the lasing threshold.

Non‐radiative energy transfer between spatially‐separated molecules in a microcavity can occur when an excitonic state on both molecules are strongly‐coupled to the same optical mode, forming so‐called “hybrid” polaritons. Such energy transfer has previously been explored when thin‐films of different molecules are relatively closely spaced (≈100 nm). In this manuscript, we explore strong‐coupled microcavities in which thin‐films of two J‐aggregated molecular dyes were separated by a spacer layer having a thickness of up to 2 μm. Here, strong light‐matter coupling and hybridisation between the excitonic transition is identified using white‐light reflectivity and photoluminescence emission. We use steady‐state spectroscopy to demonstrate polariton‐mediated energy transfer between such coupled states over “mesoscopic distances”, with this process being enhanced compared to non‐cavity control structures., Ultralong‐range polariton‐assisted energy transfer was achieved in a microcavity containing two J‐aggregate cyanine dyes. The two dyes were separated by a distance of up to 2 μm using a polymeric spacer layer. Here, it was confirmed that hybrid middle polariton (MP) states, composed of a mixture between the cavity photon modes and the different exciton states, act as a route for efficient ultralong‐range energy transfer to energetically lower‐lying states.

Over the past decade, remarkable progress has advanced the field of perovskite solar cells to the forefront of thin film solar technologies. The stoichiometry of the perovskite material is of paramount importance as it determines the optoelectronic properties of the absorber and hence the device performance. However, little published work has focused on the synthesis of fully stoichiometric precursor materials of high purity and at high yield. Here, we report a low-cost, energy-efficient, and solvent-free synthesis of the lead iodide precursor by planetary ball milling. With our synthetic approach, we produce low-oxygen, single or multiple polytypic phase PbI2 with tunable stoichiometry. We determine the stoichiometry and the polytypes present in our synthesized materials and further compare them to commercially available materials, using X-ray diffraction, X-ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy. Both the stoichiometric PbI2 we synthesized and a substoichiometric commercially available PbI2 (where the iodide content is below the optimum Pb:I atomic ratio of 1:2) were used to grow methylammonium lead iodide microcrystals (which corrects the iodide content). Perovskite solar cells were then produced using stoichiometric and substoichiometric PbI2 mixed with an equimolar amount of methylammonium iodide and compared to devices produced from re-dissolved microcrystals. The photoactive perovskite layer deposition was processed in air, enabled by the use of a single low-toxicity solvent (dimethyl sulfoxide) combined with vacuum-assisted solvent evaporation. We find that the device performance is strongly dependent upon the stoichiometry of the lead iodide precursor, reaching champion efficiencies over 17%, with no obvious correlation with its polytypic phases. This work highlights the critical role of PbI2 stoichiometry in hybrid perovskites as well as demonstrating synthesis methods and perovskite layer fabrication protocols suitable for low-cost solar energy harvesting.

Strong coupling to the electronic or vibronic transitions of an organic semiconductor has been extensively studied in microcavity structures in which a molecular film is placed between two closely spaced mirrors. Recent experiments suggest that such strong coupling can be used to modify chemical reactions; however, the geometry of conventional microcavity structures makes such studies difficult as they limit the ability of molecules to interact with their local environment. Here, we show that optical strong coupling to a molecular film can be achieved even when such molecules are located on the surface of a dielectric slab. We then show that such molecules on the surface of the slab can undergo facile interactions with molecules in their surrounding environment, and evidence a reversible protonation/deprotonation reaction by exposing a surface-bound porphyrin to an acidic or basic vapor. Although our proof-of-principle measurements do not evidence any change in reaction rates, we believe our structures represent a promising system in which to explore polariton-driven chemical phenomena.

Over the past six years, researchers have investigated the use of spray coating to fabricate perovskite solar cells (PSCs), with the aim of demonstrating its viability as an industrial manufacturing process. This spotlight on applications outlines the key benefits of this coating technology and summarizes progress made to date, with attention focused on varied efforts to control the crystallization and uniformity of the perovskite layer. The emerging understanding of processes required to create smooth, dense spray-cast perovskite films has recently led to the demonstration of fully spray-cast PSCs with a power conversion efficiency of 19.4%.

Exciton-polaritons in 2D lattice geometries now attract considerable attention as systems in which to explore new physics. However, such structures are relatively difficult to fabricate as this can...

Ethylhexyloxy-functionalised pyrene (PEH) was prepared and copolymerised with both dithienyl-benzo[c]-[1], [2], [5]thiadiazole and dibithiophenyl-benzo[c]-[1], [2], [5]thiadiazole via a Stille coupling polymerisation method to yield PPEH-DTBT-8 and PPEH-DT2BT-8, respectively. A comparative study was conducted to assess the impact of substituting thiophene for bithiophene repeat units upon the resulting properties of the conjugated polymers. PPEH-DT2BT-8 which has bithiophene spacers between pyrene and benzothiadiazole repeat units, exhibited a narrower optical and electrochemical band gap relative to PPEH-DTBT-8; a consequence of the incorporating bithiophene spacer units which promote intramolecular charge transfer between the electron donating and electron accepting moieties. Both PPEH-DTBT-8 and PPEH-DT2BT-8 showed deep HOMO levels of -5.54 and -5.50 eV, respectively. The polymers possess good thermal stabilities with degradation temperatures in excess of 310 °C. The photovoltaic performance of the two polymers was studied by fabricating bulk heterojunction (BHJ) photovoltaic devices using PC70BM as the acceptor. PPEH-DTBT-8 and PPEH-DT2BT-8 demonstrated efficiencies of 0.33 and 1.83%, respectively. The higher efficiency of PPEH-DT2BT-8 can be attributed to vastly improved FF and Jsc values.

Description, In a major step toward the development of a quantum battery, superabsorption has been achieved in an organic microcavity., The rate at which matter emits or absorbs light can be modified by its environment, as markedly exemplified by the widely studied phenomenon of superradiance. The reverse process, superabsorption, is harder to demonstrate because of the challenges of probing ultrafast processes and has only been seen for small numbers of atoms. Its central idea—superextensive scaling of absorption, meaning larger systems absorb faster—is also the key idea underpinning quantum batteries. Here, we implement experimentally a paradigmatic model of a quantum battery, constructed of a microcavity enclosing a molecular dye. Ultrafast optical spectroscopy allows us to observe charging dynamics at femtosecond resolution to demonstrate superextensive charging rates and storage capacity, in agreement with our theoretical modeling. We find that decoherence plays an important role in stabilizing energy storage. Our work opens future opportunities for harnessing collective effects in light-matter coupling for nanoscale energy capture, storage, and transport technologies.

Recent advances in heterojunction and interfacial engineering of perovskite solar cells (PSCs) have enabled great progress in developing highly efficient and stable devices. Nevertheless, the effect of halide choice on the formation mechanism, crystallography, and photoelectric properties of the low-dimensional phase still requires further detailed study. In this work, we present key insights into the significance of halide choice when designing passivation strategies comprising large organic spacer salts, clarifying the effect of anions on the formation of quasi-2D/3D heterojunctions. To demonstrate the importance of halide influences, we employ novel neo-pentylammonium halide salts with different halide anions (neoPAX, X=I, Br, or Cl). We find that regardless of halide selection, iodide-based (neoPA)2(FA)(n-1)PbnI(3n+1) phases are formed above the perovskite substrate, while the added halide anions diffuse and passivate the perovskite bulk. In addition, we also find the halide choice has an influence on the degree of dimensionality (n). Comparing the three halides, we find that chloride-based salts exhibit superior crystallographic, enhanced carrier transport, and extraction compared to the iodide and bromide analogs. As a result, we report high power conversion efficiency in quasi-2D/3D PSCs, which are optimal when using chloride salts, reaching up to 23.35%, and improving long-term stability.

Two-Dimensional Electronic Spectroscopy reveals an ultrafast energy delocalization between 2μm distanced donor/acceptor molecules confined in a microcavity. This mechanism is promoted by the formation of hybrid-polariton states that induces a coupling in the entire system.

Funder: Equal Opportunities Foundation Hong Kong, Funder: University of Surrey; Id: http://dx.doi.org/10.13039/501100003513, Funder: DCSA3 scholarship, Funder: Royal Society; Id: http://dx.doi.org/10.13039/501100000288, Funder: European Research Council; Id: http://dx.doi.org/10.13039/501100000781, Successful manipulation of halide perovskite surfaces is typically achieved via the interactions between modulators and perovskites. Herein, it is demonstrated that a strong‐interaction surface modulator is beneficial to reduce interfacial recombination losses in inverted (p‐i‐n) perovskite solar cells (IPSCs). Two organic ammonium salts are investigated, consisting of 4‐hydroxyphenethylammonium iodide and 2‐thiopheneethylammonium iodide (2‐TEAI). Without thermal annealing, these two modulators can recover the photoluminescence quantum yield of the neat perovskite film in contact with fullerene electron transport layer (ETL). Compared to the hydroxyl‐functionalized phenethylammonium moiety, the thienylammonium facilitates the formation of a quasi‐2D structure onto the perovskite. Density functional theory and quasi‐Fermi level splitting calculations reveal that the 2‐TEAI has a stronger interaction with the perovskite surface, contributing to more suppressed non‐radiative recombination at the perovskite/ETL interface and improved open‐circuit voltage (VOC) of the fabricated IPSCs. As a result, the VOC increases from 1.11 to 1.20 V (based on a perovskite bandgap of 1.63 eV), yielding a power conversion efficiency (PCE) from ≈20% to 21.9% (stabilized PCE of 21.3%, the highest reported PCEs for IPSCs employing poly[N, N′′‐bis(4‐butylphenyl)‐N, N′′‐bis(phenyl)benzidine] as the hole transport layer, alongside the enhanced operational and shelf‐life stability for unencapsulated devices.

Strong light–matter coupling to form exciton– and vibropolaritons is increasingly touted as a powerful tool to alter the fundamental properties of organic materials. It is proposed that these states and their facile tunability can be used to rewrite molecular potential energy landscapes and redirect photophysical pathways, with applications from catalysis to electronic devices. Crucial to their photophysical properties is the exchange of energy between coherent, bright polaritons and incoherent dark states. One of the most potent tools to explore this interplay is transient absorption/reflectance spectroscopy. Previous studies have revealed unexpectedly long lifetimes of the coherent polariton states, for which there is no theoretical explanation. Applying these transient methods to a series of strong-coupled organic microcavities, we recover similar long-lived spectral effects. Based on transfer-matrix modeling of the transient experiment, we find that virtually the entire photoresponse results from photoexcitation effects other than the generation of polariton states. Our results suggest that the complex optical properties of polaritonic systems make them especially prone to misleading optical signatures and that more challenging high-time-resolution measurements on high-quality microcavities are necessary to uniquely distinguish the coherent polariton dynamics.

Solvent vapour annealing (SVA) is a common post-processing technique used to increase the average grain size of lead halide perovskite films and thus enhance device performance. The prevailing wisdom is that large grain perovskite films lead to enhanced stability, however, we observed the reverse in CH3NH3PbI3 (MAPbI3) with dimethylformamide vapour treatment compared to non-SVA controls. Using a range of microstructural characterisation techniques, we reveal that SVA is not a chemically benign grain-growth process, but leads to substantial stoichiometric changes in the perovskite films. Intrinsic material degradation is investigated under external loading with in situ X-ray scattering, and combined with lifetime testing on full devices. We show that the operational stability of SVA devices greatly depends on the initial stoichiometry of the MAPbI3 with PbI2-excess compositions being least stable. However, the incorporation of excess organic-halides in the precursor solution helps to mitigate the deleterious effects of SVA on device stability. This work critically re-evaluates current thinking around grain structure and stoichiometry in achieving long-term stability for perovskite solar cells.

The use of processing additives to optimize the active layer morphology in organic solar cells (OSCs) is a simple and impactful way to improve photovoltaic performance. However, the retention of high boiling point liquid additives affects the stability and lifetime of OSCs, necessitating the development of volatilizable additives that can improve efficiency at no cost of the long-term device stability. In this study, three novel volatilizable solid additives, INB-1F, INB-3F, and INB-5F, with different degrees of fluorination, are rationally designed, synthesized and added into photovoltaic solutions to fabricate OSCs. These additives evaporate upon moderate thermal annealing and exhibit higher volatility as the number of fluorine atoms increases. Our device studies show that these additives can enhance the efficiency of PBDB-T-2F:BTP-4F binary cells from 15.2% to 16.5%, and that of PBDB-T-2F:IT-4F from 12.1% to 13.4%. Molecular dynamics simulations reveal attractive interactions between these additives and the non-fullerene acceptor BTP-4F, leading to enhanced intermolecular π–π stacking among BTP-4Fs, which is a favorable morphological change that we attribute to the origin of the enhanced performance and long-term stability. Our work presents a novel strategy to design new solid additives to replace liquid additives toward efficient and stable OSCs.

Metal–organic framework nanosheets (MONs) are an emerging class of two-dimensional materials whose diverse and readily tunable structures make them ideal for use in optoelectronic applications. Here, liquid exfoliation is used to synthesize ultrathin zinc-porphyrin based MONs with electronic and optical properties ideally suited for incorporation into a polythiophene–fullerene (P3HT–PCBM) organic solar cell. Remarkably, the addition of MONs to the photoactive layer of a photovoltaic device results in a power conversion efficiency of 5.2%, almost twice that for reference devices without nanosheets with a simultaneous improvement of Jsc, Voc and FF. Our analysis indicates that the complimentary electronic, optical and structural properties of the MONs allows them to act as a surface to template the crystallization of P3HT leading to a doubling of the absorbance, a tenfold increase in hole mobility and reduced grain size. These results demonstrate the potential of MONs as a tunable class of two-dimensional materials for enhancing the performance of a broad range of organic solar cells and other electronic devices.

The insufficient phase separation between polymer donors and nonfullerene acceptors (NFAs) featuring low structural order disrupts efficient charge transport and increases charge recombination, consequently limiting the maximum achievable power conversion efficiency (PCE) of organic solar cells (OSCs). Herein, an NFA IT-M has been added as the third component into the PBDB-T:m-INPOIC OSCs and is shown to effectively tune the phase separation between donor and acceptor molecules, although all components in the ternary system exhibit low degrees of structural order. The incorporation of 10 wt % IT-M into a PBDB-T:m-INPOIC binary host blend appreciably increases the length scale of phase separation, creating continuous pathways that increase and balance charge transport. This leads to an enhanced photovoltaic performance from 12.8% in the binary cell to 13.9% for the ternary cell with simultaneously improved open-circuit voltage, short-circuit current, and fill factor. This work highlights the beneficial role of ternary components in controlling the morphology of the active layer for high-performance OSCs.

The chemical structure of non-fullerene acceptors (NFAs) affects their light-harvesting capabilities, energy levels and molecular orders, all of which play a crucial role in determining the efficiency of organic solar cells (OSCs). In this work, we have systematically investigated a series of ladder-type NFAs having different carbon-oxygen-bridged electron-donating cores, and revealed the effects of core structures and film casting conditions on molecular ordering and performance of OSCs. We found that NFAs containing the thieno [3,2-b]thiophene centered, 6 or 8 fused rings (i.e. COi6DFIC, COi8DFIC) exhibit narrower optical band gaps than NFAs containing the benzene centered, 5 or 7 fused rings (i.e. COi5DFIC, COi7DFIC). NFAs containing less fused rings in the carbon-oxygen-bridged core (i.e. COi5DFIC and COi6DFIC) exhibit edge-on molecular orientation in the blends with face-on oriented PTB7-Th donor, and result in low device efficiency. Although NFAs containing more fused rings (i.e. COi7DFIC and COi8DFIC) possess a pronounced flat-on lamellar crystalline structure in the pure state, the crystallization can be reduced when blending with PTB7-Th and under hot-substrate casting, while the lamella in COi8DFIC can be effectively suppressed to form face-on H- and J-type aggregates, leading to enhanced efficiency.

Organic photovoltaic (OPV) cells have recently undergone a rapid increase in power conversion efficiency (PCE) under AM1.5G conditions, as certified by the National Renewable Energy Laboratory (NREL), which have jumped from 11.5% in October 2017 to 18.2% in December 2020. However, the NREL certified PCE of large area OPV modules is still lagging far behind (11.7% in July 2020). Additionally, there has been a rapidly growing interest in the use of OPVs for dim light indoor applications, with reported PCE of some large area (≥1 cm2) devices, under 1000 lux, well above 20%. The transition of OPV from the lab to the market requires the development of effective manufacturing processes that can scale‐up laboratory‐scale devices into large area devices, without sacrificing performance and simultaneously minimizing associated manufacturing costs. This review article focuses on four important challenges that OPV technology has to face to achieve a reliable lab‐to‐fab transfer, namely: i) The upscaling of indium‐tin‐oxide (ITO)‐based single cells and the interconnection of single cells into large area modules; ii) the development of alternatives to vacuum processing; iii) the development of alternatives to ITO‐based substrates; and iv) strategies for improving the lifetime of large area OPV devices.

Celebrating the life of Alasdair Campbell.

Two-dimensional semiconducting transition metal dichalcogenides embedded in optical microcavities in the strong exciton-photon coupling regime may lead to promising applications in spin and valley addressable polaritonic logic gates and circuits. One significant obstacle for their realization is the inherent lack of scalability associated with the mechanical exfoliation commonly used for fabrication of two-dimensional materials and their heterostructures. Chemical vapor deposition offers an alternative scalable fabrication method for both monolayer semiconductors and other two-dimensional materials, such as hexagonal boron nitride. Observation of the strong light-matter coupling in chemical vapor grown transition metal dichalcogenides has been demonstrated so far in a handful of experiments with monolayer molybdenum disulfide and tungsten disulfide. Here we instead demonstrate the strong exciton-photon coupling in microcavities composed of large area transition metal dichalcogenide/hexagonal boron nitride heterostructures made from chemical vapor deposition grown molybdenum diselenide and tungsten diselenide encapsulated on one or both sides in continuous few-layer boron nitride films also grown by chemical vapor deposition. These transition metal dichalcogenide/hexagonal boron nitride heterostructures show high optical quality comparable with mechanically exfoliated samples, allowing operation in the strong coupling regime in a wide range of temperatures down to 4 Kelvin in tunable and monolithic microcavities, and demonstrating the possibility to successfully develop large area transition metal dichalcogenide based polariton devices.

Quantum batteries harness the unique properties of quantum mechanics to enhance energy storage compared to conventional batteries. In particular, they are predicted to undergo superextensive charging, where batteries with larger capacity actually take less time to charge. Up until now however, they have not been experimentally demonstrated, due to the challenges in quantum coherent control. Here we implement an array of two-level systems coupled to a photonic mode to realise a Dicke quantum battery. Our quantum battery is constructed with a microcavity formed by two dielectric mirrors enclosing a thin film of a fluorescent molecular dye in a polymer matrix. We use ultrafast optical spectroscopy to time resolve the charging dynamics of the quantum battery at femtosecond resolution. We experimentally demonstrate superextensive increases in both charging power and storage capacity, in agreement with our theoretical modelling. We find that decoherence plays an important role in stabilising energy storage, analogous to the role that dissipation plays in photosynthesis. This experimental proof-of-concept is a major milestone towards the practical application of quantum batteries in quantum and conventional devices. Our work opens new opportunities for harnessing collective effects in light-matter coupling for nanoscale energy capture, storage, and transport technologies, including the enhancement of solar cell efficiencies.

Publisher's version (útgefin grein), Bose-Einstein condensates of exciton-polaritons in inorganic semiconductor microcavities are known to possess strong interparticle interactions attributed to their excitonic component. The interactions play a crucial role in the nonlinear dynamics of such systems and can be witnessed as the energy blueshifts of polariton states. However, the localised nature of Frenkel excitons in strongly coupled organic microcavities precludes interparticle Coulomb exchange-interactions that change mechanisms of the nonlinearity and blueshifts accordingly. In this report, we unravel the origins of blueshifts in organic polariton condensates. We examine the possible contributions: intracavity optical Kerr-effect, gain-induced frequency-pulling, polariton interactions and effects related to saturation of optical transitions for weakly- and strongly-coupled molecules. We conclude that blueshifts in organic polariton condensates arise from the interplay of the saturation effects and intermolecular energy migration. Our model predicts the commonly observed step-like increase of both the emission energy and degree of linear polarization at the polariton condensation threshold., We thank Professor Nikolay Gippius for helpful discussions. A.Z. and A.B. acknowledge financial support from the Russian Scientific Foundation (RSF) grant No. 18-72-00227. O.K. and I.S. acknowledge support from the Government of the Russian Federation (projects 14.Y26.31.0015 and 3.2614.2017/4.6) and ITMO Fellowship Program. We also acknowledge partial funding from the UK EPSRC via Programme Grant “Hybrid Polaritonics” EP/M025330/1.

Optimizing the components and morphology within the photoactive layer of organic solar cells (OSCs) can significantly enhance their power conversion efficiency (PCE). A new A-D-A type non-fullerene acceptor IDMIC-4F is designed and synthesized in this work, and is employed as the third component to prepare high performance ternary solar cells. IDMIC-4F can form fibrils after solution casting, and the presence of this fibrillar structure in the PBDB-T-2F:BTP-4F host confines the growth of donors and acceptors into fine domains, as well as acting as transport channels to enhance electron mobility. Single junction ternary devices incorporating 10 wt% IDMIC-4F exhibit enhanced light absorption and balanced carrier mobility, and achieve a maximum PCE of 16.6% compared to 15.7% for the binary device, which is a remarkable efficiency for OSCs reported in literature. This non-fullerene acceptor fibril network strategy is a promising method to improve the photovoltaic performance of ternary OSCs.

The addition of alkali metal halides to hybrid perovskite materials can significantly impact their crystallisation and hence their performance when used in solar cell devices. Previous work on the use of potassium iodide (KI) in active layers to passivate defects in triple-cation mixed-halide perovskites has been shown to enhance their luminescence efficiency and reduce current–voltage hysteresis. However, the operational stability of KI passivated perovskite solar cells under ambient conditions remains largely unexplored. By investigating perovskite solar cell performance with SnO2 or TiO2 electron transport layers (ETL), we propose that defect passivation using KI is highly sensitive to the composition of the perovskite–ETL interface. We reconfirm findings from previous reports that KI preferentially interacts with bromide ions in mixed-halide perovskites, and – at concentrations >5 mol% in the precursor solution – modifies the primary absorber composition as well as leading to the phase segregation of an undesirable secondary non-perovskite phase (KBr) at high KI concentration. Importantly, by studying both material and device stability under continuous illumination and bias under ambient/high-humidity conditions, we show that this secondary phase becomes a favourable degradation product, and that devices incorporating KI have reduced stability.

Back-contact perovskite solar cells are fabricated by depositing methylammonium lead iodide perovskite into micron-sized grooves, with opposite walls of each groove being coated with either n- or p-type selective contacts. V-Shaped grooves are created by embossing a polymeric substrate, with the different charge-selective electrodes deposited onto the walls of the groove using a directional evaporation technique. We show that individual grooves act as photovoltaic devices, having a power conversion efficiency of up to 7.3%. By series-connecting multiple grooves, we create integrated micro-modules that build open circuit voltages up to nearly 15 V and power conversion efficiencies over 4%. The devices created are fully flexible, do not include rare metals, and are processed using techniques applicable to roll-to-roll processing.

Mixed-halide perovskites prepared from methylammonium iodide and lead chloride (MAPbI 3-x Cl x ) precursors are becoming increasingly well understood, however the effect of non-stoichiometry in this system is still not clear. Here, we create MAPbI 3-x Cl x perovskites from starting mixtures containing an excess of MAI, and study them using a variety of structural and optical probes. Using grazing incidence X-ray scattering (GIWAXS) we demonstrate the existence of non-perovskite structures, and show that addition of hydroiodic acid (HI) also leads to similar low-dimensional phase formation. Photoluminescence spectroscopy performed at cryogenic temperatures indicates the existence of multiple emissive states between 510 nm and 605 nm resulting from a low dimensional phase (LDP) or multiple phases. By mapping the distribution of luminescence across the surface with submicron resolution, we found strong co-localisation of LDP emissive states. At certain blend ratios, emission is seen from both LDP states and methylammonium lead iodide perovskite (around 770 nm). Photoluminescence excitation spectroscopy of mixed-phase films reveals energy transfer, or a cascade, between different LDP states, but this process only occurs inefficiently to the surrounding perovskite. Time-resolved photoluminescence measurements demonstrate that LDP excited-state lifetimes decrease as a function of increasing temperature; a process consistent with a thermally-activated charge transfer process. Our work suggests that non-stoichiometric materials prepared via this processing route can lead to the formation of metastable LDPs with unique material properties that merit further investigation.

We report the need for careful selection of anti-solvents for Sn-based perovskite solar cells fabricated through the commonly used anti-solvent method, compared to their Pb-based counterparts. This, in combination with the film processing conditions used, enables the complete removal of unwanted Sn4+ dopants, through engineering the anti-solvent method for Sn-based perovskites. Using a Cs0.05(FA0.83MA0.17)0.95Pb0.5Sn0.5I3 perovskite, charge carrier mobilities of 32 ± 3 cm2 V−1 s−1 (the highest reported for such systems through the optical-pump terahertz probe technique) together with ∼28 mA cm−2 short circuit current densities are achieved. A champion efficiency of 11.6% was obtained for solvent extraction using toluene (an 80% enhancement in efficiency compared to the other anti-solvents) which is further improved to 12.04% following optimised anti-solvent wash and thermal treatment. Our work highlights the importance of anti-solvents in managing defects for high efficiency low bandgap perovskite materials and develops the potential for all-perovskite tandem solar cells.

Nickel oxide (NiO) and titanium dioxide (TiO2) charge-extraction layers are fabricated under a partial pressure of O2 from nickel and titanium metals using a reactive electron-beam evaporation process. Using such materials, inverted architecture perovskite solar cells incorporating a NiO hole-transport layer achieve power conversion efficiencies up to 15.8%, whilst standard architecture devices using a TiO2 electron-transport layer achieve a power conversion efficiency up to 13.9%. Critically, we find that such metal oxides can be deposited at high speed (nm s−1) and at low substrate-temperature, and do not require a high-temperature anneal step after deposition, making reactive electron-beam evaporation compatible with roll-to-roll processing on sensitive flexible polymeric substrates.

We use ultrasonic spray-coating to sequentially deposit thin films of tin oxide, a triple-cation perovskite and spiro-OMeTAD, allowing us fabricate perovskite solar cells (PSCs) with a champion reverse scan power conversion efficiency (PCE) of 19.4% on small-area substrates. We show that the use of spray-deposition permits us to rapidly (>80 mm s−1) coat 25 mm × 75 mm substrates that were divided into a series of devices each with an active area of 15.4 mm2, yielding an average PCE of 10.3% and a peak PCE of 16.3%. By connecting seven 15.4 mm2 devices in parallel on a single substrate, we create a device having an effective active area of 1.08 cm2 and a PCE of 12.7%. This work demonstrates the possibility for spray-coating to fabricate high efficiency and low-cost perovskite solar cells at speed.

We explore the generation of anti-Stokes fluorescence from strongly coupled organic dye microcavities following resonant ground-state excitation. We observe polariton emission along the lower polariton branch, with our results indicating that this process involves a return to the exciton reservoir and the absorption of thermal energy from molecules in a vibrationally excited ground-state. We speculate that the generation of a population of "hot" polaritons is enhanced by the fact that the cavity supresses the emission of Stokes-shifted fluorescence, as it is located energetically below the cut-off frequency of the cavity.