Robust singlet fission in pentacene thin films with tuned charge transfer interactions.

Singlet fission, the spin-allowed photophysical process converting an excited singlet state into two triplet states, has attracted significant attention for device applications. Research so far has focused mainly on the understanding of singlet fission in pure materials, yet blends offer the promise of a controlled tuning of intermolecular interactions, impacting singlet fission efficiencies. Here we report a study of singlet fission in mixtures of pentacene with weakly interacting spacer molecules. Comparison of experimentally determined stationary optical properties and theoretical calculations indicates a reduction of charge-transfer interactions between pentacene molecules with increasing spacer molecule fraction. Theory predicts that the reduced interactions slow down singlet fission in these blends, but surprisingly we find that singlet fission occurs on a timescale comparable to that in pure crystalline pentacene. We explain the observed robustness of singlet fission in such mixed films by a mechanism of exciton diffusion to hot spots with closer intermolecular spacings.

Structure formation in perfluoropentacene:diindenoperylene blends and its impact on transient effects in the optical properties studied in real-time during growth.

We discuss the result of the competing effects of favourable intermolecular interactions and steric incompatibilities due to the size mismatch of perfluoropentacene (PFP) and diindenoperylene (DIP) on the structure formation and associated optical properties in mixed films. Using real-time grazing incidence X-ray diffraction we investigate the size of coherently scattering islands l(s) as a function of film thickness and mixing ratio. We find that for PFP:DIP 1:2 blends l(s) is by a factor of ~4 smaller than in pure DIP films, while l(s) of the PFP:DIP 2:1 blends is not significantly reduced compared with pure PFP. Yet, we observe an increase in l(s) with film thickness for all of the samples, independent on the mixing ratio. In parallel with the structural characterization we investigate the evolution of the absorption spectra in the visible spectral range and its dependence on l(s) in situ during film growth using differential reflectance spectroscopy. We observe a surprisingly strong effect of changes in the structural order on the shape of ε(2, xy)(E), evident by a pronounced evolution of characteristic peaks in the thickness range from 1.6 nm to 9.6 nm. The combined results of the real-time experiments allow to identify the thickness dependent crystal grain size as the origin of the observed transient effects in the absorption spectra.

Mixing-induced anisotropic correlations in molecular crystalline systems.

We investigate the structure of mixed thin films composed of pentacene and diindenoperylene using x-ray reflectivity and grazing incidence x-ray diffraction. For equimolar mixtures we observe vanishing in-plane order coexisting with an excellent out-of-plane order, a yet unreported disordering behavior in binary mixtures of organic semiconductors, which are crystalline in their pure form. One approach to rationalize our findings is to introduce an anisotropic interaction parameter in the framework of a mean field model. By comparing the structural properties with those of other mixed systems, we discuss the effects of sterical compatibility and chemical composition on the mixing behavior, which adds to the general understanding of interactions in molecular mixtures.

Heart failure biomarkers: focus on interleukin-1 receptor-like 1-based blood tests.

Heart failure is a leading cause of morbidity and mortality in the Western world. It is often a progressive disease, and the pathophysiology behind this adverse development is not completely understood. Biomarkers are of increasing importance in heart failure research. Despite a growing number of candidate markers, only a select few have made it into clinical practice. Interleukin-1 receptor-like 1 (IL1RL1), also known as protein ST2, is the receptor for interleukin-33 (IL-33), a cytokine involved in T-cell-mediated immune responses. IL1RL1 expression is induced by cardiomyocyte stretch, and IL1RL1 may thus reflect the activity of two interacting processes in heart failure: inflammation and hemodynamic stress. In recent years, the soluble, truncated IL1RL1 isoform B has been shown to provide prognostic information in heart failure. Although ILRL1 isoform B does not seem to aid in the diagnosis of the disease, an elevated plasma/serum concentration of this marker is firmly associated with adverse outcome in patients with heart failure. This association has been established in different heart failure cohorts and is independent of age, etiology of heart failure and left ventricular function. Ultimately, the IL-33/IL1RL1 pathway may become a therapeutic target in heart failure.

Photoluminescence spectroscopy of pure pentacene, perfluoropentacene, and mixed thin films.

We report detailed temperature dependent photoluminescence (PL) spectra of pentacene (PEN), perfluoropentacene (PFP), and PEN:PFP mixed thin films grown on SiO(2). PEN and PFP are particularly suitable for this study, since they are structurally compatible for good intermixing and form a model donor/acceptor system. The PL spectra of PEN are discussed in the context of existing literature and compared to the new findings for PFP. We analyze the optical transitions observed in the spectra of PEN and PFP using time-dependent density functional theory calculations. Importantly, for the mixed PEN:PFP film we observe an optical transition in PL at 1.4 eV providing evidence for coupling effects in the blend. We discuss a possible charge-transfer (CT) and provide a tentative scheme of the optical transitions in the blended films.

Real-time changes in the optical spectrum of organic semiconducting films and their thickness regimes during growth.

We present real-time in situ studies of optical spectra during thin film growth of several prototype organic semiconductors (pentacene, perfluoropentacene, and diindenoperylene) on SiO2. These data provide insight into surface and interface effects that are of fundamental importance and of relevance for applications in organic electronics. With respect to the bulk, the different molecular environment and structural changes within the first few monolayers can give rise to significant optical changes. Similar to interface-driven phenomena in, e.g., magnetism, spectral changes as a function of thickness d are a very general effect, decaying as 1/d in the simplest approximation. We observe energy shifts of 50-100 meV, rather small changes of the exciton-phonon coupling, and new transitions in specific systems, which should be considered as general features of the growth of organics.