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Herein, we present two novel organic semiconducting polymers synthesised from an ancient dye. By employing cross-conjugation within the polymer backbone as a synthetic strategy, we are able to engineer optical gaps such that the novel materials absorb over the entire visible spectrum. The cross-conjugated polymers exhibited relatively high n-type charge transport performance in organic field-effect transistors, a rare characteristic for this type of polymer. Quantum chemical calculations provide insight into this behaviour, suggesting that, whilst conjugation along the HOMO is indeed inhibited via molecular design, these materials possess highly delocalized LUMOs, facilitating high n-type charge transport.

Exciton-polaritons are quasiparticles with mixed photon and exciton character that demonstrate rich quantum phenomena, novel optoelectronic devices and the potential to modify chemical properties of materials. Organic semiconductors are of current interest for their room-temperature polariton formation. However, within organic optoelectronic devices, it is often the 'dark' spin-1 triplet excitons that dominate operation. These triplets have been largely ignored in treatments of polariton physics. Here we demonstrate polariton population from the triplet manifold via triplet-triplet annihilation, leading to polariton emission that is longer-lived (>microseconds) even than exciton emission in bare films. This enhancement arises from spin-2 triplet-pair states, formed by singlet fission or triplet-triplet annihilation, feeding the polariton. This is possible due to state mixing, which -in the strong coupling regime- leads to sharing of photonic character with states that are formally non-emissive. Such 'photonic sharing' offers the enticing possibility of harvesting or manipulating even states that are formally dark.

Vezie, Michelle S. et al., The specific optical absorption of an organic semiconductor is critical to the performance of organic optoelectronic devices. For example, higher light-harvesting efficiency can lead to higher photocurrent in solar cells that are limited by sub-optimal electrical transport. Here, we compared over 40 conjugated polymers, and found that many different chemical structures share an apparent maximum in their extinction coefficients. However, a diketopyrrolopyrrole-thienothiophene copolymer shows remarkably high optical absorption at relatively low photon energies. By investigating its backbone structure and conformation with measurements and quantum chemical calculations, we find that the high optical absorption can be explained by the high persistence length of the polymer. Accordingly, we demonstrate high absorption in other polymers with high theoretical persistence length. Visible light harvesting may be enhanced in other conjugated polymers through judicious design of the structure., M.S.V. and S. F. are grateful to the Engineering and Physical Sciences Research Council (EPSRC) for a doctoral training award and a CDT studentship (EP/G037515/1) respectively. G.P. and S.C.H. acknowledge the University of Cyprus for funding through the internal grant "ORGANIC". B.D., A.G. and M.C.Q. acknowledge financial support from the Ministerio de Economía y Competitividad of Spain through projects CSD2010–00044 (Consolider NANOTHERM), SEV-2015_0496 and MAT2012–37776 and the European Research Council through project ERC CoG648901. I.M., R.S.A. and I.McC. acknowledge support from the European Commission FP7 Project ArtESun (604397). J.N. is grateful to the Royal Society for a Wolfson Merit Award, and acknowledges financial support from EPSRC grants EP/K030671/1, EP/K029843/1 and EP/J017361/1. The authors thank Dr. Isabel Alonso for performing supplementary ellipsometric measurements; we thank Prof. Thomas Kirchartz, Dr. Jarvist Moore Frost, Dr. Christian Müller and Dr. Isabel Alonso for helpful discussions.

The control and optimization of interfacial charge transfer processes is crucial to the design of efficient perovskite solar cells. Herein, we measure the yield and kinetics of hole transfer across the methylammonium lead triiodide perovskite|polymeric hole transport material heterojunction, as a function of the interfacial energy offset, ∆E between the highest occupied molecular orbital of the hole transport material and the valence band of the perovskite. A combination of steady-state and time-resolved photoluminescence, along with transient absorption spectroscopy revealed that only a small driving energy (∆E~0.07eV) is required to induce highly efficient hole transfer. The findings of this paper suggest that further improvements in the open-circuit voltage, and so the power conversion efficiency, of perovskite solar cells could be achieved by incorporating hole transport materials that provide an interfacial energy offset in the range 0 < ∆E < 0.18eV.

A series of polyfluorene-based polymers with a range of weight percentages (w/w) of a platinum(II)-containing porphyrin, 5,15-dimesityl-10,20-diphenylporphyrinato platinum(II) (MPP(Pt)), were synthesised and incorporated into organic light-emitting diodes. All polymers showed emission predominantly in the red/NIR region with only those polymers with porphyrin w/w of less than 2% showing residual tails at wavelengths lower than 600 nm, indicating increased emission from the porphyrin as w/w increases. The 2% loading of MPP(Pt) gave the highest efficiency LED (0.48%) and light output (2630 mW/m2).

Resonance Raman Spectroscopy (RRS) is employed in this study to examine the influence of molecular weight on the optical response of a diketopyrrolopyrrole polymer (DPP-TT-T) in solution. The vibronic structure observed for the ground state absorption of this polymer is found to vary with molecular weight and solvent. Resonance Raman Intensity Analysis (RRIA) revealed that the absorption spectra can be described by at least two dipole-allowed transitions and the vibronic structure variation is due to differing contributions from linear and curved segments of the polymer. © 2016 SPIE. 9923 Sponsors: The Society of Photo-Optical Instrumentation Engineers (SPIE) Conference code: 125526

© The Royal Society of Chemistry 2017. Conventional solar cells absorb photons with energy above the bandgap of the active layer while sub-bandgap photons are unharvested. One way to overcome this loss is to capture the low energy light in the triplet state of a molecule capable of undergoing triplet-triplet annihilation (TTA), which pools the energy of two triplet states into one high energy singlet state that can then be utilized. This mechanism underlies the function of an organic intermediate band solar cell (IBSC). Here, we report a solid-state organic IBSC that shows enhanced photocurrent derived from TTA that converts sub-bandgap light into charge carriers. Femtosecond resolution transient absorption spectroscopy and delayed fluorescence spectroscopy provide evidence for the triplet sensitization and upconversion mechanisms, while external quantum efficiency measurements in the presence of a broadband background light demonstrate that sub-bandgap performance enhancements are achievable in this device. The solid-state architecture introduced in this work serves as an alternative to previously demonstrated solution-based IBSCs, and is a compelling model for future research efforts in this area.

Singlet fission is a multiexciton generation process, where one singlet exciton is absorbed and two triplet excitons are produced. The potential of more efficient photovoltaic devices utilizing singlet fission materials has attracted wide interests for tuneable, stable organic chromophores with suitable excited‐state ordering. The strict energetic requirements hinder the exploration of novel organic materials, and most well‐known singlet fission materials, linear acenes, are considered to be unstable in their excited states. To solve the stability issue, excited‐state aromaticity provides a feasible research option, from which a few chromophores have been designed and studied. This review describes indolonaphthyridine (IND) derivative chromophores and discusses their ability to undergo singlet fission with superior ambient stability. Deepened theoretical analysis taking into account the excited‐state Hückel‐aromatic and diradical characters rationalizes the special properties of these chromophores. Moreover, the improved understanding of the aromatic character enables us to outline a feasible design strategy suitable for other scaffolds undergo singlet fission and excited‐state aromaticity. Hopefully, this review can light a fire on the way toward various novel singlet fission chromophores designed based on the excited‐state aromatic view.

Engineering the molecular structure of conjugated polymers is key to advancing the field of organic electronics. In this work, we synthesized a molecularly encapsulated version of the naphthalene diimide bithiophene copolymer PNDIT2, which is among the most popular high charge mobility organic semiconductors in n-type field-effect transistors and non-fullerene acceptors in organic photovoltaic blends. The encapsulating macrocycles shield the bithiophene units while leaving the naphthalene diimide units available for intermolecular interactions. With respect to PNDIT2, the encapsulated counterpart displays an increased backbone planarity. Molecular encapsulation prevents preaggregation of the polymer chains in common organic solvents, while it permits π-stacking in the solid state and promotes thin film crystallinity through an intermolecular-lock mechanism. Consequently, n-type semiconducting behavior is retained in field-effect transistors, although charge mobility is lower than in PNDIT2 due to the absence of the fibrillar microstructure that originates from preaggregation in solution. Hence, molecularly encapsulating conjugated polymers represent a promising chemical strategy to tune the molecular interaction in solution and the backbone conformation and to consequently control the nanomorphology of casted films without altering the electronic structure of the core polymer.

Intermolecular interactions play a fundamental role on the performance of conjugated materials in organic electronic devices, as they heavily influence their optoelectronic properties. Synthetic control over the solid state properties of organic optoelectronic materials is crucial to access real life applications. Perylene diimides (PDIs) are one of the most highly studied classes of organic fluorescent dyes. In the solid state, π-π stacking suppresses their emission, limiting their use in a variety of applications. Here, we report the synthesis of a novel PDI dye that is encapsulated by four alkylene straps. X-ray crystallography indicates that intermolecular π-π stacking is completely suppressed in the crystalline state. This is further validated by the photophysical properties of the dye in both solution and solid state and supported by theoretical calculations. However, we find that the introduction of the encapsulating "arms" results in the creation of charge-transfer states which modify the excited state properties. This article demonstrates that molecular encapsulation can be used as a powerful tool to tune intermolecular interactions and thereby gain an extra level of control over the solid state properties of organic optoelectronic materials.

Funder: Royal Society; Id: http://dx.doi.org/10.13039/501100000288, Funder: Winton Programme for the Physics of Sustainability, Conjugated polymers are an important class of chromophores for optoelectronic devices. Understanding and controlling their excited state properties, in particular, radiative and non‐radiative recombination processes are among the greatest challenges that must be overcome. We report the synthesis and characterization of a molecularly encapsulated naphthalene diimide‐based polymer, one of the most successfully used motifs, and explore its structural and optical properties. The molecular encapsulation enables a detailed understanding of the effect of interpolymer interactions. We reveal that the non‐encapsulated analogue P(NDI‐2OD‐T) undergoes aggregation enhanced emission; an effect that is suppressed upon encapsulation due to an increasing π‐interchain stacking distance. This suggests that decreasing π‐stacking distances may be an attractive method to enhance the radiative properties of conjugated polymers in contrast to the current paradigm where it is viewed as a source of optical quenching.

Transitioning to electrified transport requires improvements in sustainability, energy density, power density, lifetime, and approved the cost of lithium-ion batteries, with significant opportunities remaining in the development of next-generation cathodes. This presents a highly complex, multiparameter optimization challenge, where developments in cathode chemical design and discovery, theoretical and experimental understanding, structural and morphological control, synthetic approaches, and cost reduction strategies can deliver performance enhancements required in the near- and longer-term. This multifaceted challenge requires an interdisciplinary approach to solve, which has seen the establishment of numerous academic and industrial consortia around the world to focus on cathode development. One such example is the Next Generation Lithium-ion Cathode Materials project, FutureCat, established by the UK’s Faraday Institution for electrochemical energy storage research in 2019, aimed at developing our understanding of existing and newly discovered cathode chemistries. Here, we present our perspective on persistent fundamental challenges, including protective coatings and additives to extend lifetime and improve interfacial ion transport, the design of existing and the discovery of new cathode materials where cation and cation-plus-anion redox-activity can be exploited to increase energy density, the application of earth-abundant elements that could ultimately reduce costs, and the delivery of new electrode topologies resistant to fracture which can extend battery lifetime.

Efficient charge photogeneration in conjugated polymers typically requires the presence of a second component to act as electron acceptor. Here, we report a novel low band-gap conjugated polymer with a donor/orthogonal acceptor motif: poly-2,6-(4,4-dihexadecyl-4H-cyclopenta [2,1-b:3,4-b′]dithiophene)-alt-2,6-spiro [cyclopenta[2,1-b:3,4-b′]dithiophene-4,9′-fluorene]-2′,7′-dicarbonitrile, referred to as PCPDT-sFCN. The role of the orthogonal acceptor is to spatially isolate the LUMO from the HOMO, allowing for negligible exchange energy between electrons in these orbitals and minimising the energy gap between singlet and triplet charge transfer states. We employ ultrafast and microsecond transient absorption spectroscopy to demonstrate that, even in the absence of a separate electron acceptor, PCPDT-sFCN shows efficient charge photogeneration in both pristine solution and film. This efficient charge generation is a result of an isoenergetic singlet/triplet charge transfer state equilibrium acting as a reservoir for charge carrier formation. Furthermore, clear evidence of enhanced triplet populations, which form in less than 1 ps, is observed. Using group theory, we show that this ultrafast triplet formation is due to highly efficient, quantum mechanically allowed intersystem crossing between the bright, initially photoexcited local singlet state and the triplet charge transfer state. Remarkably, the free charges that form via the charge transfer state are extraordinarily long-lived with millisecond lifetimes, possibly due to the stabilisation imparted by the spatial separation of PCPDT-sFCN's donor and orthogonal acceptor motifs. The efficient generation of long-lived charge carriers in a pristine polymer paves the way for single-material applications such as organic photovoltaics and photodetectors., The spatial separation of PCPDT-sFCN's donor and orthogonal acceptor motifs allows efficient photogeneration of extraordinarily long-lived charge carriers in the pristine polymer, providing an important step towards single-material optoelectronics.

Conjugated polymers with intense solid-state emission are vital for the development of next-generation optoelectronic devices. In particular, it remains extremely challenging to construct π-conjugated systems that emit in the red region of the electromagnetic spectrum and also retain their optical properties and intense photoluminescence in the solid state. In this article we report the synthesis and characterization of three novel diketopyrrolopyrrole-based conjugated polymers, with systematic variation of the covalent encapsulation density. Through control of the distance and density of encapsulation, our red-emitting polymers demonstrate that aggregation-caused quenching can be mostly eliminated, culminating in the most efficient solid-state photoluminescence from red conjugated polymers to date.

We present the synthesis of a novel diphenylanthracene (DPA) based semiconducting polymer. The polymer is solubilised by alkoxy groups attached directly to a DPA monomer, meaning the choice of co-monomer is not limited to exclusively highly solubilising moieties. Interestingly, the polymer shows a red-shifted elecroluminescence maximum (510 nm) when compared to its photoluminescence maximum (450 nm) which we attribute to excimer formation. The novel polymer was utilised as a host for a covalently-linked platinum(ii) complexed porphyrin dopant. Emission from these polymers was observed in the NIR and again showed almost a 100 nm red shift from photoluminescence to electroluminescence. This work demonstrates that utilising highly aggregating host materials is an effective tool for inducing red-shifted emission in OLEDs.