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Funding: We acknowledge support from the European Commission (European Research Council grant 321305) and Marie Sklodowska-Curie Individual Fellowship grant 745776. We are also grateful to EPSRC for support from grants (EP/L017008/1 and EP/L012294/1). We investigated singlet exciton diffusion in three ITIC derivatives used as electron acceptors in organic photovoltaics (OPVs) by time-resolved photoluminescence volume quenching and exciton–exciton annihilation. The exciton diffusion coefficient was found to be in the range of 0.003–0.007 cm2 s−1 which leads to a three-dimensional exciton diffusion length of up to 31 nm. We fabricated solar cells using bulk heterojunctions of these acceptors with the electron donor PTB7-Th which showed ∼7% efficiency and large scale phase separation. Our results show that long range exciton diffusion and large domains offer significant advantages for OPVs. Publisher PDF

Funding: European Research Council (grant 321305); UK EPSRC for equipment grant (EP/L017008/1) and (EP/M508214/1) (OB). Exciton diffusion is an important part of light harvesting in organic photovoltaics (OPVs) because it enables excitons to reach the interface betweeen donor and acceptor and contribute to the photocurrent. Here we used simple and cost-effective techniques of thermal annealing and solvent vapour annealing to increase the exciton diffusion coefficient and exciton diffusion length in two liquid crystalline electron donor materials BQR and BTR. We found that the three-dimensional exciton diffusion length increased to ~40 nm upon annealing in both materials. Grazing-incidence wide angle X-ray scattering (GIWAXS) measurements show an increase of crystallite size to ~37 nm in both materials after thermal annealing. We determined an average domain size of these materials in the blends with PC71BM using diffusion-limited fluorescence quenching and found that it increased to 31 nm in BTR PC71BM blends and to 60 nm in BQR PC71BM blends. Our results provide understanding of how annealing improves device efficiency. Postprint

Authors thank the EPSRC for funding under grants EP/L012200/1 and EP/L012294/1. A new dual-chain oligothiophene-based organic semiconductor, EH-5T-TTC, is presented. The molecule contains two conjugated chains linked by a fused tetrathiocin core. X-ray crystallography reveals a boat conformation within the 8-membered sulfur heterocycle core and extensive π–π and intermolecular sulfur–sulfur interactions in the bulk, leading to a 2-dimensional structure. This unusual molecule has been studied as a ternary component in organic solar cell blends containing the electron donor PTB7-Th and both fullerene (PC71BM) and non-fullerene acceptors ITIC and EH-IDTBR. By incorporating EH-5T-TTC as a ternary component, the power conversion efficiency of the binary blends containing non-fullerene acceptor increases by 17% (from 7.8% to 9.2%) and by 85% for the binary blend with fullerene acceptor (from 3.3% to 6.3%). Detailed characterisation of the ternary blend systems implies that the ternary small molecule EH-5T-TTC functions differently in polymer:fullerene and polymer:non-fullerene blends and has dual functions of morphology modification and complementary spectral absorption. Publisher PDF

Over the last decade, 2,2″,7,7″-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (spiro-OMeTAD) has remained the hole transporting layer (HTL) of choice for producing high efficiency perovskite solar cells (PSCs). However, PSCs incorporating spiro-OMeTAD suffer significantly from dopant induced instability and non-ideal band alignments. Herein, a new approach is presented for tackling these issues using the functionality of organometallocenes to bind to Li+ dopant ions, rendering them immobile and reducing their impact on the degradation of PSCs. Consequently, significant improvements are observed in device stability under elevated temperature and humidity, conditions in which ion migration occurs most readily. Remarkably, PSCs prepared with ferrocene retain 70% of the initial power conversion efficiency (PCE) after a period of 1250 h as compared to only 8% in the control. Synergistically, it is also identified that ferrocene improves the hole extraction yield at the HTL interface and reduces interfacial recombination enabling PCEs to reach 23.45%. This work offers a pathway for producing highly efficient spiro-OMeTAD devices with conventional dopants via addressing the key challenge of dopant induced instability in leading PSCs.

Funding: This research was funded by European commission under FP7 LAMP project “Laser Induced Synthesis of Polymeric Nanocomposite Materials and Development of Micro-patterned Hybrid Light Emitting Diodes (LED) and Transistors (LET)” (Grant No. 247928) Many displays involve the use of color conversion layers. QDs are attractive candidates as color converters because of their easy processability, tuneable optical properties, high photoluminescence quantum yield, and good stability. Here, we show that emissive QDs with narrow emission range can be made in-situ in a polymer matrix, with properties useful for color conversion. This was achieved by blending the blue-emitting pyridine based polymer with a cadmium selenide precursor and baking their films at different temperatures. To achieve efficient color conversion, blend ratio and baking temperature/time were varied. We found that thermal decomposition of the precursor leads to highly emissive QDs whose final size and emission can be controlled using baking temperature/time. The formation of the QDs inside the polymer matrix was confirmed through morphological studies using atomic force microscopy (AFM) and transmission electron microscopy (TEM). Hence, our approach provides a cost-effective route to making highly emissive color converters for multi-color displays. Publisher PDF

The extraction of charge from perovskite solar cells requires charge diffusion to a charge extraction layer (e.g. PEDOT:PSS), followed by charge extraction. We present a method based on time-resolved luminescence to measure charge diffusion and extraction. We find that hole transfer from methylammonium lead iodide (MAPI) to PEDOT:PSS limits the hole extraction rate, and that faster extraction is obtained by using NiO as a hole extraction layer. In addition we observe a very high hole diffusion coefficient of 2.2 cm2/s in a solution-processed MAPI film that is independent of charge density, suggesting a band-like regime of hole transport.

Interface-mediated recombination losses between perovskite and charge transport layers are one of the main reasons that limit the device performance, in particular for the open-circuit voltage (VOC) of perovskite solar cells (PSCs). Here, functional molecular interface engineering (FMIE) is employed to retard the interfacial recombination losses. The FMIE is a facile solution-processed means that introducing functional molecules, the fluorene-based conjugated polyelectrolyte (CPE) and organic halide salt (OHS) on both contacts of the perovskite absorber layer. Through the FMIE, the champion PSCs with an inverted planar heterojunction structure show a remarkable high VOC of 1.18 V whilst maintaining a fill factor (FF) of 0.83, both of which result in improved power conversion efficiencies (PCEs) of 21.33% (with stabilized PCEs of 21.01%). In addition to achieving one of the highest PCEs in the inverted PSCs, the results also highlight the synergistic effect of these two molecules in improving device performance. Therefore, the study provides a straightforward avenue to fabricate highly efficient inverted PSCs.

This work was supported by the Engineering and Physical Sciences Research Council (grant EP/L017008/1 and studentship grant EP/M508214/1 to O. Blaszczyk) and the European Research Council (grant 321305). Dr L. K. Jagadamma acknowledges support from a Marie Skłodowska-Curie Individual Fellowship (European Commission) (MCIF: No. 745776). Small solar cells based on metal halide perovskites have shown a tremendous increase in efficiency in recent years. These huge strides in device performance make it important to understand processes such as accumulation and extraction of charge carriers to better address the scalability and stability challenges which have not been solved yet. In most studies to date it is unclear whether the limiting factor of charge extraction is charge transport in the bulk of the perovskite or transfer across the interface with the charge extracting layer, owing largely to the inaccessibility of buried interfaces. Separating bulk and interfacial effects on charge extraction can help the search for new charge extracting materials, improve understanding of charge transport in active layer materials and help optimise device performance; not only in the laboratory setting but also for commercial production. Here we present a method to unambiguously distinguish between bulk and interface effects on charge extraction dynamics which is based on time-resolved photoluminescence with different excitation density profiles. We use this method to study charge extraction from solution-deposited CH3NH3PbI3 films to NiO and PEDOT:PSS layers. We find that NiO shows faster hole extraction than PEDOT:PSS from the 300 nm thick perovskite film on the time scale of 300 ps which is independent of charge carrier density in the region of 1016-1017 cm-3 . The interface with NiO is found to only slightly limit charge extraction rate at charge densities exceeding 1016 cm-3 as the extraction rate is fast and does not decrease with time. This is in contrast to PEDOT:PSS where we find the charge extraction rate to be slower, decreasing with time and dependent on charge density in the region 1016-1017 cm-3 which we interpret as charge accumulation at the interface. Hence we find that charge extraction is severely limited by the interface with PEDOT:PSS. These findings are confirmed by transient absorption spectroscopy. A hole diffusion coefficient of D=(2.2 ±0.4) cm2/s was determined in the perovskite film that is independent of charge density. This indicates a band-like hole transport regime, not observed for solution processed films before. Our findings stress the importance of interface optimization in devices based on perovskite active layers as there is still room for improvement of the hole extraction rate even in the case of the superior NiO layer. Publisher PDF

We acknowledge support from EPSRC (grant number EP/L012294/1) and the European Research Council (grant number 321305). I. D. W. S. also acknowledges a Royal Society Wolfson Research Merit Award. Additives play an important role in modifying the morphology and phase separation of donor and acceptor molecules in bulk heterojunction (BHJ) solar cells. Here, we report triptycene (TPC) as a small-molecule additive for supramolecular control of phase separation and concomitant improvement of the power conversion efficiency (PCE) of PTB7 donor and fullerene acceptor-based BHJ polymer solar cells. An overall 60% improvement in PCE is observed for both PTB7:PC61BM and PTB7:PC71BM blends. The improved photovoltaic (PV) performance can be attributed to three factors: (a) TPC-induced supramolecular interactions with donor:acceptor components in the blends to realize a nanoscale phase-separated morphology; (b) an increase in the charge transfer state energy that lowers the driving force for electron transfer from donor to acceptor molecules; and (c) an increase in the charge carrier mobility. An improvement in efficiency using TPC as a supramolecular additive has also been demonstrated for other BHJ blends such as PBDB-T:PC71BM and P3HT:PCBM, implying the wide applicability of this new additive molecule. A comparison of the photostability of TPC as an additive for PTB7:PCBM solar cells to that of the widely used 1,8-diiodooctane additive shows ∼30% higher retention of PV performance for the TPC-added solar cells after 34 h of AM 1.5G illumination. The results obtained suggest that the approach of using additives that can promote supramolecular interactions to modify the length scale of phase separation between donor and acceptor is very promising and can lead to the development of highly efficient and stable organic photovoltaics. Postprint Postprint

The authors thank the European Research Council for financial support (EXCITON Grant 321305). We studied crystallinity and exciton harvesting in bulk heterojunctions of a semiconducting polymer PffBT4T-2OD and electron acceptor PC71BM which are used to make highly efficient organic solar cells. Grazing incidence wide-angle X-ray scattering (GIWAXS) shows that the size of crystalline domains of PffBT4T-2OD increases to ~18 nm in photovoltaic blends upon thermal annealing at 100 °C for 5 minutes. These domains are larger than the typical exciton diffusion lengths in conjugated polymers. Time-resolved fluorescence measurements show that exciton diffusion length in PffBT4T-2OD increases from ~14 to ~24 nm upon thermal annealing, which enables efficient charge generation in blends with large domains. Solar cells prepared using thermally annealed blends show higher photocurrent, open circuit voltage and fill factor compared to as spin-coated blends which indicates reduced recombination losses. Our results demonstrate the advantages of large crystalline domains in organic photovoltaics, providing exciton diffusion is sufficient. Postprint

Hybrid perovskites have received tremendous attention due to their exceptional photovoltaic and optoelectronic properties. Among the two widely used perovskite solar cell device architectures of n-ip and p-i-n, the latter is interesting in terms of its simplicity of fabrication and lower energy input. However this structure mostly uses PEDOT:PSS as a hole transporting layer which can accelerate the perovskite solar cell degradation. Hence the development of stable, inorganic hole extraction layers (HEL), without compromising the simplicity of device fabrication is crucial in this fast-growing photovoltaic field. Here we demonstrate a low temperature (~100 oC) solution - processed and ultrathin (~ 6 nm) NiO nanoparticle thin films as an efficient HEL for CH3NH3PbI3 based perovskite solar cells. We measure a power conversion efficiency (PCE) of 13.3 % on rigid glass substrates and 8.5 % on flexible substrates. A comparison with PEDOT:PSS based MAPbI3 solar cells (PCE ~ 7.9 %) shows that NiO based solar cells have higher short circuit current density and improved open circuit voltage (1.03V). Apart from the photovoltaic performance under 1 Sun, the efficient hole extraction property of NiO is demonstrated for indoor lighting as well with a PCE of 23.0 % for NiO based CH3NH3PbI2.9Cl0.1 p-i-n solar cells under compact fluorescent lighting. Compared to the perovskite solar cells fabricated on PEDOT:PSS HEL, better shelf-life stability is observed for perovskite solar cells fabricated on NiO HEL. Detailed microstructural and photophysical investigations imply uniform morphology, lower recombination losses, and improved charge transfer properties for CH3NH3PbI3 grown on NiO HEL., 19 pages

We thank the European Research Council (ERC) for financial support (EXCITON grant 321305). Data supporting this study is available at https://doi.org/10.17630/0e75f92d-6f8a-41be-ad45-ac6d1d890ee2. The singlet exciton diffusion length was measured in a small molecule electron donor material DR3TBDTT using fluorescence quenching at a planar interface with a cross-linked fullerene derivative. The one-dimensional exciton diffusion length was increased from ~16 to ~24 nm by annealing the film in carbon disulfide solvent vapor. Planar heterojunction solar cells were fabricated using bilayers of these materials and it was found that solvent vapor annealing increased the short circuit current density by 46%. This can be explained by improved exciton harvesting in the annealed bilayer. Postprint

The authors acknowledge financial support from FP7 project “Laser Induced Synthesis of Polymeric Nanocomposite Materials and Development of Micro‐patterned Hybrid Light Emitting Diodes (LED) and Transistors (LET)” – LAMP project (G.A. 247928). M.T.S., A.R., and I.D.W.S. acknowledge support from the European Research Council (EXCITON grant 321305). I.D.W.S. acknowledges a Royal Society Wolfson Research Merit Award. The authors are grateful to EPSRC for an equipment grant (EP/L017008/1). Exciton diffusion plays an important role in functional materials used in organic optoelectronic devices, such as solar cells, organic light emitting diodes, and lasers. Here we explore how exciton diffusion can be controlled in highly fluorescent blue‐emitting polyfluorene materials by changing the length and type of side chains. We find that the exciton diffusion coefficient (D) decreases from 1.2 × 10−3 cm2 s−1 to 0.2×10−3 cm2 s−1 when the side chain length is increased from 8 to 12 carbon atoms. Other changes to the side chains led to enhancement of D up to 1.6 × 10−3 cm2 s−1. Our results show that small adjustments to the molecular structure can be helpful for the future development of high‐brightness organic light emitting devices. Postprint Postprint

Inverted quantum dot sensitized solar cells using non-toxic CuInSxSe2–x nanocrystals deposited on mesoporous NiO demonstrate high hole injection rates of 10–8 s–1 and record efficiencies of 1.25%.., Recent progress in quantum dot (QD) sensitized solar cells has demonstrated the possibility of low-cost and efficient photovoltaics. However, the standard device structure based on n-type materials often suffers from slow hole injection rate, which may lead to unbalanced charge transport. We have fabricated efficient p-type (inverted) QD sensitized cells, which combine the advantages of conventional QD cells with p-type dye sensitized configurations. Moreover, p-type QD sensitized cells can be used in highly promising tandem configurations with n-type ones. QDs without toxic Cd and Pb elements and with improved absorption and stability were successfully deposited onto mesoporous NiO electrode showing good coverage and penetration according to morphological analysis. Detailed photophysical charge transfer studies showed that high hole injection rates (108 s–1) observed in such systems are comparable with electron injection in conventional n-type QD assemblies. Inverted solar cells fabricated with various QDs demonstrate excellent power conversion efficiencies of up to 1.25%, which is 4 times higher than the best values for previous inverted QD sensitized cells. Attempts to passivate the surface of the QDs show that traditional methods of reduction of recombination in the QD sensitized cells are not applicable to the inverted architectures.

Funding: European Research Council (grant number 321305) and the EPSRC (grant number EP/L017008/1). IDWS is a Royal Society Wolfson Research Merit award holder. Hybrid materials combining a wide bandgap metal oxide semiconductor, metal chalcogenide nanocrystals and molecular systems represent very attractive materials for fabricating devices with new function or improved photoelectrochemical performances. This study deals with sensitization of NiO, which is a p-type semiconductor, by quantum dots (QDs) of PbS with an average diameter of 3 nm. The PbS QDs were attached to the monocrystalline film of NiO by mercaptopropionic acid linker and were subsequently capped with methyl-pyridine naphthalene diimide (NDI) units to prepare quantum dot sensitized solar cells (p-QDSSCs) on NiO electrodes. Time-resolved photoluminescence measurements of the PbS emission were used to determine the rate constants for charge transfer from the PbS exciton to the NiO, cobalt based redox mediator and NDI. Notably, it was shown that NDI quenches the PbS exciton by electron transfer with a quite fast rate constant (6.9 x 107 s-1). The PbS QDs sensitized NiO films were finally used to fabricate solar cells with tris(4,4’-ditert-butyl-2,2’-bipyridine) cobalt(III/II) as redox mediator. It was observed that the presence of NDI on PbS improved the photovoltaic performance by 50% relative to that of cells without NDI, leading to a device with the following characteristics: Jsc = 5.75 mA/cm2, Voc = 226 mV, ff = 34% and PCE = 0.44%. This study demonstrates that photogalvanic processes can be a productive pathway to better performing sensitized p-type semiconductor for p-QDSSC. In other words, photoinduced electron transfer from the QDs towards the electrolyte rather than initial photoinduced charge injection into the p-type semiconductor can be a favorable operative mechanism in QD sensitized NiO films and might be exploited further for the construction of better performing solar cells or photocatalytic devices. Postprint Postprint

This paper was supported by Engineering and Physical Sciences Research Council (EPSRC) Grants No. EP/K503162/1, No. EP/M506631/1, No. EP/M025330/1, No. EP/L017008/1, No. EP/K022237/1, No. EP/K015540/1, and No. EP/I036079/1. RUS facilities in Cambridge were established through grants to M.A.C. from the EPSRC and the Natural Environment Research Council (Grants No. NE/B505738/1 and No. NE/F17081/1). A portion of this research used resources at the Spallation Neutron Source, a U.S. Department of Energy Office of Science User Facility operated by the Oak Ridge National Laboratory (ORNL). I.D.W.S. acknowledges funding from a Royal Society Wolfson research merit award. The rapid increase in power conversion efficiencies of photovoltaic devices incorporating lead halide perovskites has resulted in intense interest in the cause of their excellent properties. In the present paper, resonant ultrasound spectroscopy has been used to determine the elastic and anelastic properties of CH3NH3PbX3 (where X = Cl, Br, or I) and CD3ND3PbI3 perovskites in the 5-380 K temperature range. This is coupled with differential scanning calorimetry, variable temperature neutron powder diffraction, and variable temperature photoluminescence studies to provide insights into the underlying processes and structural instabilities in the crystal structure. By comparing measurements on CH3NH3PbI3 with the deuterated equivalent, it has been possible to distinguish processes which are related to the hydrogen bonding between the methylammonium cation and the perovskite framework. We observe that replacing hydrogen with deuterium has a significant impact on both the elastic and photophysical properties, which shows that hydrogen bonding plays a crucial role in the material performance. Temperature-dependent photoluminescence studies show that the light emission is unaffected by the tetragonal-orthorhombic phase transition, but a blueshift in the emission and a steep increase in photoluminescence quantum yield are seen at temperatures below 150 K. Finally, observations of peaks in acoustic loss occurring in CH3NH3PbCl3 have revealed freezing processes in the vicinity of ∼150-170 K, with activation energies in the range of 300 to 650 meV. These processes are attributed to freezing of the motion of methylammonium cations, and could explain the changes in photoluminescence seen in CH3NH3PbI3 at the same temperature. Postprint

Funding: European Research Council (grant 321305). IDWS acknowledges a Royal Society Wolfson Research Merit Award. We are grateful to EPSRC for equipment grant (EP/L017008/1) and for support of OB (EP/M508214/1). In organic photovoltaic blends, there is a trade-off between exciton harvesting and charge extraction because of the short exciton diffusion length. Developing a way of increasing exciton diffusion length would overcome this trade-off by enabling efficient light harvesting from large domains. In this work, we engineered (enhanced) both exciton diffusion length and domain size using solvent vapour annealing (SVA). We show that SVA can give a three-fold enhancement in exciton diffusion coefficient (D) and nearly a doubling of exciton diffusion length. It also increases the domain size, leading to enhancement of charge extraction efficiency from 63 to 89%. Usually larger domains would reduce exciton harvesting but this is overcome by the large increase in exciton diffusion, leading to a 20% enhancement in device efficiency. Postprint

VBK and ŽS appreciate funding from Center of Excellence (STIM) at the University of Split. This research was supported by STIM-REI, a project funded by European Union from European Structural and Investment Funds 2014–2020. Contract Number KK.01.1.1.01.0003. This work was supported by the National Science Centre under grants DEC-2013/10/A/ST4/00114 and DEC-2013/09/B/ST5/03417 and by a statutory activity subsidy from the Polish Ministry of Science and Higher Education for the Faculty of Chemistry of Wroclaw University of Science and Technology. We would like to acknowledge the financial support from the French-Croatian project “International Laboratory for Nano Clusters and Biological Aging, LIA NCBA”. IDWS acknowledges the support from a Royal Society Wolfson Research Merit Award. Thiolate-protected gold nanoclusters have recently attracted considerable attention due to their size-dependent luminescence characterized by a long lifetime and large Stokes shift. However, the optimization of nanocluster properties such as the luminescence quantum yield is still a challenge. We report here the transformation of Au25Capt18 (Capt labels captopril) nanoclusters occurring at low pH and yielding a product with a much increased luminescence quantum yield which we have identified as Au23Capt17. We applied a simple method of treatment with HCl to accomplish this transformation and we characterized the absorption and emission of the newly created ligated nanoclusters as well as their morphology. Based on DFT calculations we show which Au nanocluster size transformations can lead to highly luminescent species such as Au23Capt17. Postprint

This work was supported by the Agence Nationale de la Recherche, project QuePhélec (ANR-13-BS10-0011-01). MTS and IDWS are thankful to ERC for financial support for exciton diffusion project, grant number 321305. AKB and IDWS also acknowledge financial support from EPSRC programme grant: structured light, EP/J01771X. Control over the deposition of quantum dots (QDs) on nanostructured semiconductors is very important for the photovoltaic performance of QD sensitized solar cells. The best control is typically achieved using bifunctional molecular linkers, such as mercaptopropionic acid (MPA), to attach the QDs to metal oxides in a specific manner; however some materials, such as ZnO, are not compatible with these molecules due to their pH sensitivity. We have developed new linkers, mercaptophosphonic acids of different length, which allow efficient functionalization of ZnO nanowires and also mesoporous TiO2 without damaging their surface. Detailed XPS and contact angle studies of the mechanism of self-assembly of these acids show that their strong chelation of the oxide surface prevents protonic attack and etching. Using these linkers, we show that colloidal ternary quantum dots, CuInS2, can be conformally and homogeneously deposited on the functionalized metal oxides. Photophysical studies by means of time-resolved photoluminescence spectroscopy confirm efficient electron transfer from the QDs to the metal oxides with the rate and efficiency scaling with respect to the linker length and nature. The efficiency of the QD sensitized solar cells fabricated with such assemblies also strongly depends on the linkers used and follows the trends observed for the charge transfer. Postprint

The authors wish to thank the EPSRC for funding. PJS thanks the Royal Society for a Wolfson Research Merit Award. Star-shaped conjugated systems with varying oligofluorene arm length and substitution patterns of the central BODIPY core have been synthesised, leading to two families of compounds, T-B1-T-B4 and Y-B1-Y-B4, with T- and Y-shaped motifs, respectively. Thermal stability, cyclic voltammetry, absorption and photoluminescence spectroscopy of each member of these two families were studied in order to determine their suitability as emissive materials in photonic applications. Publisher PDF

We acknowledge support from EPSRC (grant number EP/L012294/1) and the European Research Council (grant number 321305). I.D.W.S. also acknowledges a Royal Society Wolfson Research Merit Award. VS acknowledges support from the Office of Naval Research NDSEG fellowship. Research data supporting this paper is available at doi http://dx.doi.org/10.17630/eadf56f3-8c70-47da-ac6d-67f2d78b3f74 Selective optimisation of light harvesting materials and interface properties has brought breakthroughs in power conversion efficiency (11-12 %) of organic photovoltaics (OPVs). However to translate this promising efficiency to economically viable applications, long term stability is a fundamental requirement. A number of degradation pathways, both extrinsic and intrinsic, reduce the long term stability of OPVs. Here, the photovoltaic properties of a highly efficient bulk heterojunction PTB7-Th:PC71BM blend were investigated as a function of thermal annealing. The changes in charge generation, separation, and transport due to thermal annealing were measured and related to changes in the microstructure and photovoltaic performance. A 30 % drop in power conversion efficiency of PTB7-Th:PC71BM blends upon thermal annealing at 150 oC was identified as mainly due to morphological instability induced by strong phase separation of donor and acceptor molecules of the blend films. Based on the insight gained from these investigations, enhanced thermal stability was demonstrated by replacing the PC71BM fullerene acceptor with the non-fullerene acceptor ITIC, for which power conversion efficiency dropped only by 9 % upon thermal annealing at 150 oC. Postprint

The authors thank the German BMBF for funding within the scope of the projects InnoProfile 2.2 (03IPT602X) and MEDOS (03EK3503A) as well as the European Commission within the scope of the Career Integration Grant (FP7, MSCA, 630864). I.D.W.S. and M.T.S. acknowledge support from the European Research Council (grant number 321305) and from EPSRC (grant number EP/L017008/1). I.D.W.S. also acknowledges a Royal Society Wolfson Research Merit Award. K.L. is a fellow of the Canadian Institute for Advanced Research (CIFAR). The research data supporting this publication can be accessed at https://doi.org/10.17630/af263bfb-620c-40a8-9929-86658e5187d3 A method for resolving the diffusion length of excitons and the extraction yield of charge carriers is presented based on the performance of organic bilayer solar cells and careful modeling. The technique uses a simultaneous variation of the absorber thickness and the excitation wavelength. Rigorously differing solar cell structures as well as independent photoluminescence quenching measurements give consistent results. Postprint Postprint

M.C, M.T.S, A.R and I.D.W.S acknowledge support from the European Research Council (EXCITON grant 321305). I.D.W.S acknowledges Royal Society Wolfson Research Merit Award. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515 The influence of various processing conditions on the singlet exciton diffusion is explored in films of a conjugated random copolymer poly-(3-hexylthiophene-co-3-dodecylthiophene) (P3HT-co-P3DDT) and correlated with the degree of crystallinity probed by grazing incidence X-ray scattering and with exciton bandwidth determined from absorption spectra. The exciton diffusion coefficient is deduced from exciton-exciton annihilation measurements and is found to increase by more than a factor of three when thin films are annealed using CS2 solvent vapour. A doubling of exciton diffusion coefficient is observed upon melt annealing at 200 °C and the corresponding films show about 50% enhancement in the degree of crystallinity. In contrast, films fabricated from polymer solutions containing a small amount of either solvent additive or nucleating agent show a decrease in exciton diffusion coefficient possibly due to formation of traps for excitons. Our results suggest that the enhancement of exciton diffusivity occurs because of increased crystallinity of alkyl-stacking and longer conjugation of aggregated chains which reduces the exciton bandwidth. Publisher PDF

ANR is gratefully acknowledged for the financial support of these researches through the QuePhelec project (n° ANR-13-BS10-0011-01). Région des Pays de la Loire and Nantes University for the project LUMOMAT are also acknowledged. We acknowledge support from the European Research Council (grant number 321305) and the EPSRC (grant number EP/L017008/1). IDWS is a Royal Society Wolfson Research Merit award holder. The research data supporting this publication can be accessed at http://dx.doi.org/10.17630/ddaebfb9-e127-43cb-9048-966a572b50ac. Quantum dots (QDs) are very attractive materials for solar cells due to their high absorption coefficients, size dependence and easy tunability of their optical and electronic properties due to quantum confinement. Particularly interesting are the PbS QDs owing to their broad spectral absorption until the long wavelengths, their easy processability and low cost. Here, we used control of the PbS QDs size to understand charge transfer processes at the interfaces of NiO semiconductor and explain the optimal QDs size in photovoltaic devices. Towards this goal, we have synthesized a series of PbS QDs with different diameters (2.8 A until 4A) and investigated charge transfer dynamics by time resolved spectroscopy and their ability to act as sensitizers in nanocrystalline NiO based solar cells using the cobalt tris(4,4'-diterbutyl-2,2'-bipyridine) complex as redox mediator. We found that PbS QDs with average diameter of 3.0 nm are optimal size in terms of efficient charge transfers and light harvesting efficiency for photovoltaic performances. Our study showed that an hole injection from PbS QDs to NiO valence band (VB) is an efficient process even with low injection driving force (0.3 eV) and occurs in 6-10 ns. Furthermore we found that the direct electrolyte reduction (photoinduced electron transfer to the cobalt redox mediator) also occurs in parallel to the hole injection with rate constant of similar magnitude (10-20 ns). In spite of its large driving force, the rate constant of the oxidative quenching of PbS by Co(III) diminishes more steeply than hole injection on NiO when the diameter of PbS increases. This is understood as the consequence of increasing the trap states that limit electron shift. We believe that our detailed findings will advance the future design of QD sensitized photocathodes. Postprint

Authors would like to acknowledge the EPSRC for financial support for the UP-VLC (EP/K00042X/1). PJS and IDWS also acknowledge Royal Society Wolfson Research Merit Awards. We report a study of blends of semiconducting polymers as saturated red color converters to replace commercial phosphors in hybrid LEDs for visible light communication (VLC). By blending two star-shaped organic semiconductor molecules, we found a near complete energy transfer (> 90% efficiency) from the green-emitting truxene-cored compound T4BT-B to the red-emitting boron dipyrromethene (BODIPY) cored materials. Furthermore, we have demonstrated the capability of these materials as fast color converters for VLC by measuring their intrinsic optical modulation bandwidth and data rate. The measured 3 dB modulation bandwidth of blends (~55 MHz) is more than 10 times higher than commercially available LED phosphors and also higher than the red-emitting BODIPY color converter alone in solution. The data rate achieved with this blend is 20 times higher than measured with a commercially available phosphor based color converter. Postprint

The authors acknowledge financial support from FP7 project “Laser Induced Synthesis of Polymeric Nanocomposite Materials and Development of Micro-patterned Hybrid Light Emitting Diodes (LED) and Transistors (LET)” – LAMP project (G.A. 247928). AKB and IDWS also acknowledge financial support from EPSRC Programme grant “Challenging the limits of photonics: Structured light” EP/J01771X/1. Conjugated polymer-semiconductor quantum dot (QD) composites are attracting increasing attention due to the complementary properties of the two classes of materials. We report a convenient method for in situ formation of QDs, and explore the conditions required for light emission of nanocomposite blends. In particular we explore the properties of nanocomposites of the blue emitting polymer poly[9,9-bis(3,5-di-tert-butylphenyl)-9H-fluorene] together with cadmium sulphide (CdS) and cadmium selenide (CdSe) precursors. We show the formation of emissive quantum dots of CdSe from thermally decomposed precursor. The dots are formed inside the polymer matrix and have a photoluminescence quantum yield of 7.5%. Our results show the importance of appropriate energy level alignment, and are relevant to the application of organic-inorganic systems in optoelectronic devices. Publisher PDF

We are grateful to the European Research Council (grant 321305), EPSRC (grants EP/J01771X/1, EP/L017008/1 and EP/M02105X/1) for financial support. IDWS acknowledges a Royal Society Wolfson Research Merit Award. GSH thanks the Natural Sciences and Engineering Research Council (NSERC) of Canada for funding. We show that the emission efficiency of blue-green phosphorescent emitters can be controlled through coupling of the excited state to vibrational modes. We controlled this vibrational coupling through choice of different ligands and as a result, complexes with CF3-groups on the ancillary ligand were essentially non-emissive (ΦPL < 1%), whereas with isosteric CH3-groups the complexes were strongly emissive (ΦPL > 50%). Emission of the complexes can be drastically improved (30 times higher ΦPL compared to degassed solution for the CF3-containing complexes) by blending them with an inert solid host such as PMMA, which mitigates metal-ligand vibrations. Solution-processed organic light-emitting diodes made from these materials showed efficiency as high as 6.3%. Postprint

Photoexcitation of carbon nanotubes generates excitons which decay by exciton-exciton annihilation at sufficient density. We examine this decay under conditions of one, few and many excitons per nanotube. A classic ID reaction-diffusion behaviour is observed, with decay limited by diffusion for t>3ps and by reaction for t

Two new heteroleptic iridium(III) complexes bearing an aryldiazoimidazole ligand are reported. These complexes differ structurally with respect to the protonation state of the imidazole ring, but can be independently accessed by varying the synthetic conditions. Their structures have been unequivocally confirmed by X-ray crystal structure analysis, with surprising differences in the structural parameters of the two complexes. The strongly absorbing nature of the free diazoimidazole ligand is enhanced in these iridium complexes, with the protonated cationic complex demonstrating extraordinarily strong panchromic absorption up to 700 nm. The absorption profile of the deprotonated neutral complex is blueshifted by about 100 nm and thus the interconversion between the two complexes as a function of the acidity/basicity of the environment can be readily monitored by absorption spectroscopy. Theoretical calculations revealed the origins of these markedly different absorption properties. Finally, the protonated analogue has been targeted as an acceptor material for organic photovoltaic (OPV) applications, and preliminary results are reported.

The influence of crystallinity on exciton diffusion and fullerene distribution was investigated by blending amorphous and semicrystalline copolymers. We measured exciton diffusion and fluorescence quenching in such blends by dispersing fullerene molecules into them. We find that the diffusion length is more than two times higher in the semicrystalline copolymer than in the amorphous copolymer. We also find that fullerene preferentially mixes into disordered regions of the polymer film. This shows that relatively small differences in molecular structure are important for exciton diffusion and fullerene distribution.

The authors thank EPSRC for fi nancial support from the UP-VLC project grant (EP/K00042X/1). P.J.S. and I.D.W.S. also acknowledge a Royal Society Wolfson Research Merit Award. Star-shaped organic semiconductors with boron dipyrromethene (BODIPY) cores are color-conversion materials for blue LED-based visible light communications. The difference between 0 and 1 bits is resolved in colour-converted data links at 100 Mb s−1. The BODIPY modulation bandwidth is eight times higher than that measured using conventional phosphor color converters. Publisher PDF

The authors thank EPSRC for financial support from UP-VLC Project Grant (EP/K00042X/1). Visible Light Communications (VLC) is a promising new technology which could offer higher data transmission rates than existing broadband RF/microwave wireless technologies. In this paper, we show that a blend of semiconducting polymers can be used to make a broadband, balanced color converter with a very high modulation bandwidth to replace commercial phosphors in hybrid LEDs for visible light communications. The resulting color converter exploits partial Förster energy transfer in a blend of the highly fluorescent green emitter BBEHP-PPV and orange-red emitting MEH-PPV. We quantify the efficiency of the photoinduced energy transfer from BBEHP-PPV to MEH-PPV, and demonstrate modulation bandwidths (electrical-electrical) of ∼200 MHz, which are 40 times higher than commercially available phosphor LEDs. Furthermore, the VLC data rate achieved with this blend using On-Off Keying (OOK) is many times (∼35) higher than that measured with a commercially available phosphor color converter. Postprint

Nanostructured composites of inorganic and organic materials are attracting extensive interest for electronic and optoelectronic device applications. Here we report a novel method for the fabrication and patterning of metal selenide nanoparticles in organic semiconductor films that is compatible with solution processable large area device manufacturing. Our approach is based upon the controlled in situ decomposition of a cadmium selenide precursor complex in a film of the electron transporting material 1,3,5-tris(N-phenyl-benzimidazol-2-yl)-benzene (TPBI) by thermal and optical methods. In particular, we show that the photoluminescence quantum yield (PLQY) of the thermally converted CdSe quantum dots (QDs) in the TPBI film is up to 15%. We also show that laser illumination can form the QDs from the precursor. This is an important result as it enables direct laser patterning (DLP) of the QDs. DLP was performed on these nanocomposites using a picosecond laser. Confocal microscopy shows the formation of emissive QDs after laser irradiation. The optical and structural properties of the QDs were also analysed by means of UV-Vis, PL spectroscopy and transmission electron microscopy (TEM). The results show that the QDs are well distributed across the film and their emission can be tuned over a wide range by varying the temperature or irradiated laser power on the blend films. Our findings provide a route to the low cost patterning of hybrid electroluminescent devices. This journal is © The Royal Society of Chemistry.

Exciton-exciton recombination in isolated semiconducting single-walled carbon nanotubes was studied using femtosecond transient absorption. Under sufficient excitation to saturate the optical absorption, we observed an abrupt transition between reaction- and diffusion- limited kinetics, arising from reactions between incoherent localized excitons with a finite probability of ~ 0.2 per encounter. This represents the first experimental observation of a crossover between classical and critical kinetics in a 1D coalescing random walk, which is a paradigm for the study of non- equilibrium systems., Accepted for Physical Review Letters. Title changed, and "exciton fusion" replaced by "exciton-exciton recombination". Present address of Prof Tom Brown added. 12 pages plus 3 figures

Silicon Photomultipliers (SiPM) are solid-state pixelated photodetectors. Lately these sensors have been investigated for Time of Flight Positron Emission Tomography (ToF-PET) applications, where very good coincidence time resolution of the order of hundreds of picoseconds imply spatial resolution of the order of cm in the image reconstruction. The very fast rise time typical of the avalanche discharge improves the time resolution, but can be limited by the readout electronics and the technology used to construct the device. In this work the parameters of the equivalent circuit of the device that directly affect the pulse shape, namely the quenching resistance and capacitance and the diode and parasitic capacitances, were calculated. The mean rise time obtained with different preamplifiers was also measured.