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Photophysical aggregates are ubiquitous in many solid-state microstructures adopted by conjugated polymers, in which $\pi$ electrons interact with those in other polymer chains or those in other chromophores along the chain. These interactions fundamentally define the electronic and optical properties of the polymer film. While valuable insight can be gained from linear excitation and photoluminescence spectra, nonlinear coherent excitation spectral lineshapes provide intricate understanding on the electronic couplings that define the aggregate and their fluctuations. Here, we discuss the coherent two-dimensional excitation lineshape of a model hairy-rod conjugated polymer. At zero population waiting time, we find a $\pi/2$ phase shift between the 0-0 and 0-1 vibronic peaks in the real and imaginary components of the complex coherent spectrum, as well as a dynamic phase rotation with population waiting time over timescales that are longer than the optical dephasing time. We conjecture that these are markers of relaxation of the photophysical aggregate down the tight manifold of the exciton band. These results highlight the potential for coherent spectroscopy via analysis of the complex spectral lineshape to become a key tool to develop structure-property relationships in complex functional materials., Comment: 9 manuscript pages plus supplementary material document. Submitted to the Journal of Chemical Physics

Polariton condensation relies on the macroscopic occupation of the lowest-energy polariton state beyond a critical density. The mechanisms driving the occupation and depopulation of this state all rely on multi-particle scattering, whose dynamics determine the extent to which condensates can form spontaneously. To pinpoint many-body processes hindering polariton condensation in two-dimensional metal-halide semiconductors, we examine the exciton-polariton dynamics in a Fabry-P\'erot microcavity over timescales involving polariton ($\bm{\ll 1}$\,ps) and exciton scattering ($\bm{\gg 1}$\,ps). We find enhanced nonlinear exciton-exciton interactions in the microcavity versus the bare semiconductor and ultrafast polariton scattering depopulating the lowest-energy polariton state. We posit that the complex scattering landscape between the exciton reservoir and polaritons limits the formation of polariton condensates in these semiconductors, and we discuss the generality of our conclusions for highly polar materials in which the lattice mediates multi-particle correlations., Comment: 27 pages, 6 figures, plus supplementary material document. Submitted for publication

In this work, we demonstrate the formation of a "red-phase" poly[2-methoxy, 5-(2'- ethyl-hexoxy)-1,4-phenylene vinylene-PPV] (MEH-PPV) embedded into a host matrix of highly entangled ultra-high molecular weight polystyrene (MEH-PPV/UHMW PS pseudogel) that allows the simple processing of the MEH-PPV solutions. We processed a "red-phase" in the gel, the gel shows that the features what have beed demonstrated in the solution can be observed in the processable gel for optoelectronics applications. [Yamagata, Hajime, and Hestand, Nicholas J. and Spano, Frank C. and Kohler, Anna and Scharsich, Christina and Hoffmann, Sebastian T. and Bassler, Heinz, The Journal of Chemical Physics, 2013, 139, 114903]

Frenkel excitons, the primary photoexcitations in organic semiconductors that are unequivocally responsible for the optical properties of this materials class, are predicted to form \emph{bound} exciton pairs, i.e., biexcitons. These are key intermediates, ubiquitous in many relevant photophysical processes; for example, they determine the exciton bimolecular annihilation dynamics in such systems. Deciphering the details of biexciton correlations is, thus, of utmost importance to understand the optical processes in these semiconductors. To date, however, due to their spectral ambiguity, there has been only scant direct evidence of bound biexcitons, limiting the insights that can be gained. Moreover, a quantum-mechanical basis describing biexciton correlation/stability has so far been lacking. By employing nonlinear coherent spectroscopy, we identify here bound biexcitons in a model polymeric semiconductor. We find, unexpectedly, that excitons with \emph{interchain} vibronic dispersion reveal \emph{intrachain} biexciton correlations and vice versa. Moreover, using a Frenkel exciton model, we can relate the biexciton binding energy to molecular parameters quantified by quantum chemistry, including the magnitude and sign of the exciton-exciton interaction the inter-site hopping energies. Therefore, our work promises a window towards general insights into the many-body electronic structure in polymeric semiconductors and beyond; e.g., other excitonic systems such as organic semiconductor crystals, molecular aggregates, photosynthetic light-harvesting complexes, or DNA., Comment: 4 figures and Supplementary Materials

Recent demonstrations of inverted thermal activation of charge mobility in polymer field-effect transistors have excited the interest in transport regimes not limited by thermal barriers. However, rationalization of the limiting factors to access such regimes is still lacking. An improved understanding in this area is critical for development of new materials, establishing processing guidelines, and broadening of the range of applications. Here we show that precise processing of a diketopyrrolopyrrole-tetrafluorobenzene-based electron transporting copolymer results in single crystal-like and voltage-independent mobility with vanishing activation energy above 280 K. Key factors are uniaxial molecular alignment and thermal annealing at temperatures within the melting endotherm of films. Experimental and computational evidence converge toward a picture of electrons being delocalized within crystalline domains of increased size. Residual energy barriers introduced by disordered regions are bypassed in the direction of molecular alignment by a more efficient interconnection of the ordered domains following the annealing process.

A series of donor-acceptor-donor (D-A-D) structured small-molecule compounds, with 3,3'-(ethane-1,2-diylidene)bis(indolin-2-one) (EBI) as a novel electron acceptor building block coupled with various electron donor end-capping moieties (thiophene, bithiophene and benzofuran), were synthesized and characterized. When the fused-ring benzofuran is combined to EBI (EBI-BF), the molecules displayed a perfectly planar conformation and afforded the best charge tranport properties among these EBI compounds with a hole mobility of up to 0.021 cm2 V-1 s-1. All EBI-based small molecules were used as donor material along with a PC61BM acceptor for the fabrication of solution-processed bulk-heterojunction (BHJ) solar cells. The best performing photovoltaic devices are based on the EBI derivative using the bithiophene end-capping moiety (EBI-2T) with a maximum power conversion efficiency (PCE) of 1.92%, owing to the broad absorption spectra of EBI-2T and the appropriate morphology of the BHJ. With the aim of establishing a correlation between the molecular structure and the thin film morphology, differential scanning calorimetry, atomic force microscopy and X-ray diffraction analysis were performed on neat and blend films of each material.

Typical device architectures in polymer-based optoelectronic devices, such as field effect transistors organic light emitting diodes and photovoltaic cells include sub-100 nm semiconducting polymer thin-film active layers, whose microstructure is likely to be subject to finite-size effects. The aim of this study was to investigate effect of the two-dimensional spatial confinement on the internal structure of the semiconducting polymer poly(9,9-dioctylfluorene) (PFO). PFO melts were confined inside the cylindrical nanopores of anodic aluminium oxide (AAO) templates and crystallized via two crystallization strategies, namely, in the presence or in the absence of a surface bulk reservoir located at the template surface. We show that highly textured semiconducting nanowires with tuneable crystal orientation can be thus produced. Moreover, our results indicate that employing the appropriate crystallization conditions extended-chain crystals can be formed in confinement. The results presented here demonstrate the simple fabrication and crystal engineering of ordered arrays of PFO nanowires; a system with potential applications in devices where anisotropic optical properties are required, such as polarized electroluminescence, waveguiding, optical switching, lasing, etc.

An oligomeric semiconductor containing three bisthiophenediketopyrrolopyrole units (Tri-BTDPP) was synthesized and characterized. Tri-BTDPP has a HOMO level of -5.34 eV, a broad absorption close to the near infrared region and a low band gap of 1.33 eV. Additionally, a promising hole mobility of 1 x 10-3 cm V-1 s-1 was achieved after thermal annealing at 150 C in organic field effect transistors (OFET). Organic photovoltaic (OPV) cells containing Tri-BTDPP and PC71BM as the donor/acceptor couple exhibited a power conversion efficiency (PCE) of 0.72%. Through an intensive study of the active layer using AFM, XRD, and DSC, it was found that Tri-BTDPP and PC71BM were unable to intermix effectively, resulting in oversized Tri-BTDPP crystalline phases and thus poor charge separation. Strategies to improve the OPV performance were thus proposed.

Poly(vinylidene fluoride) (PVDF) has long been regarded as an ideal piezoelectric plastic because it exhibits a large piezoelectric response and a high thermal stability. However, the realization of piezoelectric PVDF elements has proven to be problematic, amongst others, due to the lack of industrially-scalable methods to process PVDF into the appropriate polar crystalline forms. Here, we show that fully piezoelectric PVDF films can be produced via a single-step process that exploits the fact that PVDF can be molded at temperatures below its melting temperature, i.e. via solid-state-processing. We demonstrate that we thereby produce d_PVDF, the piezoelectric charge coefficient of which is comparable to that of biaxially stretched d_PVDF. We expect that the simplicity and scalability of solid-state processing combined with the excellent piezoelectric properties of our PVDF structures will provide new opportunities for this commodity polymer and will open a range of possibilities for future, large-scale, industrial production of plastic piezoelectric films

We measure the homogeneous excitation linewidth of regioregular poly(3-hexylthiophene), a model semicrystalline polymeric semiconductor, by means of two-dimensional coherent photoluminescence excitation spectroscopy. At a temperature of 8\,K, we find a linewidth that is always $\gtrsim 110$\,meV full-width-at-half-maximum, which is a significant fraction of the total linewidth. It displays a spectral dependence and is minimum near the 0--0 origin peak. We interpret this spectral dependence of the homogeneous excitation linewidth within the context of a weakly coupled aggregate model., Comment: 13 pages, 4 figures, Supplementary Material

In polymeric semiconductors, charge carriers are polarons, which means that the excess charge deforms the molecular structure of the polymer chain that hosts it. This effect results in distinctive signatures in the vibrational modes of the polymer. We probe polaron photo- generation dynamics at polymer:fullerene heterojunctions by monitoring its time-resolved resonance-Raman spectrum following ultrafast photoexcitation. We conclude that polarons emerge within 200 fs, which is nearly two orders of magnitude faster than exciton localisation in the neat polymer film. Surprisingly, further vibrational evolution on <50-ps timescales is modest, indicating that the polymer conformation hosting nascent polarons is not signif- icantly different from that in equilibrium. This suggests that charges are free from their mutual Coulomb potential, under which vibrational dynamics would report charge-pair relaxation. Our work addresses current debates on the photocarrier generation mechanism at organic semiconductor heterojunctions, and is, to our knowledge, the first direct probe of molecular conformation dynamics during this fundamentally important process in these materials., Comment: 33 pages, please download separately PDF files containing figures (3 figures) and supplementary information

The optoelectronic properties of macromolecular semiconductors depend fundamentally on their solid-state microstructure. For example, the molecular-weight distribution influences polymeric- semiconductor properties via diverse microstructures; polymers of low weight-average molecular weight (Mw) form unconnected, extended-chain crystals, usually of a paraffinic structure. Because of the non-entangled nature of the relatively short-chain macromolecules, this leads to a polycrystalline, one-phase morphology. In contrast, with high-Mw materials, where average chain lengths are longer than the length between entanglements, two-phase morphologies, comprised of crystalline moieties embedded in largely unordered (amorphous) regions, are obtained. We investigate charge photogeneration processes in neat regioregular poly(3-hexylthiophene) (P3HT) of varying Mw by means of time-resolved photoluminescence (PL) spectroscopy. At 10 K, PL originating from recombination of long-lived charge pairs decays over microsecond timescales. Both the amplitude and decay rate distribution depend strongly on Mw. In films with dominant one-phase chain-extended microstructures, the delayed PL is suppressed as a result of a diminished yield of photoinduced charges, and its decay is significantly faster than in two-phase microstructures. However, independent of Mw, charge recombination regenerates singlet excitons in torsionally disordered chains forming more strongly coupled photophysical aggregates than those in the steady-state ensemble, with delayed PL lineshape reminiscent of that in paraffinic morphologies at steady state. We conclude that highly delocalized excitons in disordered regions between crystalline and amorphous phases dissociate extrinsically with yield and spatial distribution that depend intimately upon microstructure., Comment: 19 pages, 4 figures

The electronic properties of macromolecular semiconductor thin films depend profoundly on their solid-state microstructure, which in turn is governed, among other things, by the processing conditions selected and the polymer chemical nature and molecular weight. Specifically, low-molecular-weight materials form crystalline domains of cofacially $\pi$-stacked molecules, while the usually entangled nature of higher molecular-weight polymers leads to microstructures comprised of molecularly ordered crystallites interconnected by amorphous regions. Here, we examine the interplay between extended exciton states delocalized along the polymer backbones and across polymer chains within the $\pi$-stack, depending on the structural development with molecular weight. We combine optical spectroscopies, thermal probes, and theoretical modeling, focusing on neat poly(3-hexylthiophene) (P3HT), one of the most extensively studied polymer semiconductors, of weight-average molecular weight of 3-450\,kg/mol. The spatial coherence within the chain is significantly reduced (by nearly 30\%). These observations give valuable structural information; they suggest that the macromolecules in aggregated regions of high-molecular-weight P3HT adopt a more planar conformation compared to low-molecular-weight materials. This results in the observed increase in intrachain exciton coherence. In contrast, shorter chains seem to lead to torsionally more disordered architectures. A rigorous, fundamental description of primary photoexcitations in $\pi$-conjugated polymers is hence developed: two-dimensional excitons are defined by the chain-length dependent molecular arrangement and interconnectivity of the conjugated macromolecules, leading to interplay between intramolecular and intermolecular spatial coherence., Comment: Submitted to Physical Review X on 6 June 2013, 38 pages, 10 figures

We probe charge photogeneration and subsequent recombination dynamics in neat regioregular poly(3-hexylthiophene) films over six decades in time by means of time-resolved photoluminescence spectroscopy. Exciton dissociation at 10K occurs extrinsically at interfaces between molecularly ordered and disordered domains. Polaron pairs thus produced recombine by tunnelling with distributed rates governed by the distribution of electron-hole radii. Quantum-chemical calculations suggest that hot-exciton dissociation at such interfaces results from a high charge-transfer character., Comment: 10 pages, 3 figures

We present a simple and inexpensive means to measure background-free photoinduced absorption spectra by implementing a dual optical modulation scheme. Our objective is to measure quasi-steady-state absorption spectra of long-lived photoexcitations, such as polarons and triplet excitons in organic semiconductors, when the photoluminescence of the sample is strong compared to the photoinduced absorption signal. In our instrument, we modulate a continuous-wave laser at a frequency $f_{pu}$ with a mechanical chopper before exciting the material. We measure the fractional change of transmission of the sample with a tuneable monochromatic probe source modulated at a frequency $f_{pr}$, and with a digital lockin amplifier at a reference frequency $f_{ref} = f_{pu} + f_{pr}$. We generate the reference sinusoidal wave for the lockin amplifier using a simple home-built electronic circuit that generates their sum-frequency signal. This scheme allows measurement of the fractional change of transmittance of the sample induced by the pump laser at a frequency $f_{pu} + f_{pr}$ without parasitic signal at a frequency $f_{pu}$, such as photoluminescence of the sample or pump-laser scatter. We demonstrate the power of this approach by measuring cleanly the photoinduced absorption spectrum of a highly luminescent semiconductor polymer, poly(9,9-dioctylfluorene-co-benzothiadiazole), at 10\,K. We compare this measurement favourably with that obtained by simple modulation of the pump laser after subtraction of the dominant photoluminescence background., Comment: 17 pages, 5 figures

Muon spin spectroscopy and in particular the avoided level crossing technique is introduced, with the aim of showing it as a very sensitive local probe for electron spin relaxation in organic semiconductors. Avoided level crossing data on TMS-pentacene at different temperatures are presented, and they are analysed to extract the electron spin relaxation rate, that is shown to increase on increasing the temperature from 0.02 MHz to 0.33 MHz at 3 K and 300 K respectively., Comment: International Conference TSN2010 "Trends in spintronics and nanomagnetism"