Heavy-atom effects on intramolecular singlet fission in a conjugated polymer

A chief aim in singlet fission research is to develop new materials concepts for more efficient singlet fission. The typical approaches such as tuning π-overlap and charge-transfer interactions, enhancing delocalization, altering diradical character, or extending the conjugation length have profound effects simultaneously on the singlet and triplet energetics and the couplings between them. While these strategies have resulted in a handful of high-efficiency materials, the complex interplay of these factors makes systematic materials development challenging, and it would be useful to be able to selectively manipulate the properties and dynamics of just part of the singlet fission pathway. Here, we investigate the potential of heteroatom substitution as just such a selective tool. We explore the influence of heavy atoms within the main backbone of polythienylenevinylene and its selenophene and tellurophene derivatives. We find no significant effects on the prompt <300 fs intramolecular singlet fission dynamics but a clear heavy-atom effect on longer time scales

Excitation Energy Delocalization and Transfer to Guests within M(II)4L6 Cage Frameworks

We have prepared a series of M(II)4L6 tetrahedral cages containing one or the other of two distinct BODIPY moieties, as well as mixed cages that contain both BODIPY chromophores. The photophysical properties of these cages and their fullerene-encapsulated adducts were studied in depth. Upon cage formation, the charge-transfer character exhibited by the bis(aminophenyl)-BODIPY subcomponents disappeared. Strong excitonic interactions were instead observed between at least two BODIPY chromophores along the edges of the cages, arising from the electronic delocalization through the metal centers. This excited-state delocalization contrasts with previously reported cages. All cages exhibited the same progression from an initial bright singlet state (species I) to a delocalized dark state (species II), driven by interactions between the transition dipoles of the ligands, and subsequently into geometrically relaxed species III. In the case of cages loaded with C60 or C70 fullerenes, ultrafast host-to-guest electron transfer was observed to compete with the excitonic interactions, short-circuiting the I → II → III sequence

Effect of fullerene acceptor on the performance of solar cells based on PffBT4T-2OD

We have studied bulk-heterojunction (BHJ) solar cells composed of the polymer PffBT4T-2OD as electron donor and three different electron accepting fullerenes, namely PC71BM, PC61BM and indene-C60-bis-adduct (ICBA) in order to understand the impact of different fullerenes on the morphology and efficiency of the corresponding photovoltaic devices. Despite PffBT4T-2OD:ICBA devices being characterised by higher values of Voc, they display the lowest power conversion efficiency (PCE) due to their lower Jsc and FF values. We find that although all blend films have similar morphologies, X-ray scattering indicates a reduced degree of order within the fullerene domains in the ICBA-based film. Due to the high LUMO level of ICBA, the corresponding blends are characterised by a lower initial exciton dissociation and this associated with the reduced ordering within the ICBA domains results in increased geminate recombination of the photogenerated electrons in the fullerene-rich domains and a consequently reduced PCE of the corresponding devices

Tensor network simulation of multi-environmental open quantum dynamics via machine learning and entanglement renormalisation

The simulation of open quantum dynamics is a critical tool for understanding how the non-classical properties of matter might be functionalised in future devices. However, unlocking the enormous potential of molecular quantum processes is highly challenging due to the very strong and non-Markovian coupling of 'environmental' molecular vibrations to the electronic 'system' degrees of freedom. Here, we present an advanced but general computational strategy that allows tensor network methods to effectively compute the non-perturbative, real-time dynamics of exponentially large vibronic wave functions of real molecules. We demonstrate how ab initio modelling, machine learning and entanglement analysis can enable simulations which provide real-time insight and direct visualisation of dissipative photophysics, and illustrate this with an example based on the ultrafast process known as singlet fission

Optical‐mode structure of micropillar microcavities containing a fluorescent conjugated polymer

The light emission from a series of micropillar microcavities containing a fluorescent, red‐emitting conjugated polymer, is explored. Cavities are fabricated by defining two dielectric mirrors either side of a polymer active region. Focused ion‐beam (FIB) lithography is then used to etch pillar structures into the planar cavity having diameters between 1 and 11 µm. The photoluminescence (PL) emission of the cavities is characterized using real‐space tomographic and Fourier‐space imaging techniques, with emission shown to be quantized into a mode‐structure resulting from both vertical and lateral optical confinement within the pillar. The optical‐confinement effects which result in a blue‐shift of the fundamental mode as the pillar diameter is reduced is demonstrated, with a model applied to describe the energy and distribution of the confined optical modes

Efficient Radiative Pumping of Polaritons in a Strongly Coupled Microcavity by a Fluorescent Molecular Dye

KGaA, Weinheim.The optical properties of a series of strongly coupled microcavities containing the fluorescent molecular dye BODIPY-Br (bromine-substituted boron-dipyrromethene) dispersed into a transparent dielectric matrix are explored, with each cavity having a different exciton-photon detuning. Using temperature dependent emission, time-resolved spectroscopy, white-light reflectivity, and measurements of fluorescence quantum yield, the population of polaritons is explored along the lower polariton branch. It is found that both the cavity fluorescence quantum efficiency and the distribution of polariton states along the lower polariton branch is a function of exciton-photon detuning. Importantly, it is shown that in the most negatively detuned cavities, the emission quantum efficiency approaches that of a control (noncavity) film. A simple fitting model is developed, which is based upon direct radiative pumping of polariton states along the lower polariton branch and used it to obtain an excellent agreement with measured photoluminescence as a function of temperature and exciton-photon detuning, and qualitative agreement with the measured photoluminescence quantum efficiency. The radiative pumping mechanism indicates that to facilitate the formation of a nonequilibrium polariton condensate in strongly-coupled microcavities containing dispersed molecular dyes, it is important to utilize materials having high fluorescent quantum efficiency and fast radiative rates

Radiative pumping in a strongly coupled microcavity filled with a neat molecular film showing excimer emission

Strong light-matter interactions have attracted much attention as a means to control the physical/chemical properties of organic semiconducting materials with light-matter hybrids called polaritons. To unveil the processes under strong coupling, studies on the dynamics of polaritons are of particular importance. While highly condensed molecular materials with large dipole density are ideal to achieve strong coupling, the emission properties of such films often become a mixture of monomeric and excimeric components, making the role of excimers unclear. Here, we use amorphous neat films of a new bis(phenylethynyl anthracene) derivative showing only excimer emission and investigate the excited-state dynamics of a series of strongly coupled microcavities, with each cavity being characterised by a different exciton–photon detuning. A time-resolved photoluminescence study shows that the excimer radiatively pumps the lower polariton in the relaxation process and the decay profile reflects the density of states. The delayed emission derived from triplet–triplet annihilation is not sensitive to the cavity environment, possibly due to the rapid excimer formation. Our results highlight the importance of controlling intermolecular interactions towards rational design of organic exciton–polariton devices, whose performance depends on efficient polariton relaxation pathways

Untargeted effects in organic exciton-polariton transient spectroscopy : a cautionary tale

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 modelling 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

Emissive spin-0 triplet-pairs are a direct product of triplet–triplet annihilation in pentacene single crystals and anthradithiophene films

Singlet fission and triplet–triplet annihilation represent two highly promising ways of increasing the efficiency of photovoltaic devices. Both processes are believed to be mediated by a biexcitonic triplet-pair state, 1(TT). Recently however, there has been debate over the role of 1(TT) in triplet–triplet annihilation. Here we use intensity-dependent, low-temperature photoluminescence measurements, combined with kinetic modelling, to show that distinct 1(TT) emission arises directly from triplet–triplet annihilation in high-quality pentacene single crystals and anthradithiophene (diF-TES-ADT) thin films. This work demonstrates that a real, emissive triplet-pair state acts as an intermediate in both singlet fission and triplet–triplet annihilation and that this is true for both endo- and exothermic singlet fission materials

Intermolecular States in Organic Dye Dispersions: Excimers vs Aggregates

Rapid excited-state quenching in the solid state is a widespread limitation for organic chromophores. Even when molecules are dispersed in neutral host matrices, photoluminescence quantum yields decrease sharply with increased concentration, pointing to efficient intermolecular non-radiative decay pathways that remain poorly understood. Here we study the nature of the intermolecular states formed in dispersions of the prototypical BODIPY dyes. Using temperature-dependent and time-resolved photoluminescence measurements, we describe the processes of energy transfer into excimer states and, in materials with suitable chemical structure, excitonically coupled dimers. These dimer states exhibit remarkable near-unity quantum yield