Photoexcitation dynamics in regioregular and regiorandom polythiophene films

Journal ArticleUsing a variety of optical probes techniques we studied the photoexcitation dynamics in thin films of poly-3-hexyl thiophene with regioregular order that forms lamellae structures with increased interchain interaction, as well as regiorandom order that keeps a chainlike morphology. In regiorandom films we found that intrachain excitons with correlated induced absorption and stimulated emission bands are the primary excitations; they give rise to a moderately strong photoluminescence band. In regioregular films, on the contrary, we found that the primary excitations are excitons with a much larger interchain component; this results in lack of stimulated emission, vanishing intersystem crossing, and very weak photoluminescence band. In regioregular films we also measured photogenerated geminate polaron pairs with ultrafast dynamics that are precursor to long-lived polaron excitations

Ultrafast spectroscopy of excitons in single-walled carbon nanotubes

Journal ArticleWe studied the femtosecond dynamics of photoexcitations in films containing semiconducting and metallic single-walled carbon nanotubes (SWNTs), using various pump-probe wavelengths and intensities.We found that confined excitons and charge carriers with subpicosecond dynamics dominate the ultrafast response in semiconducting and metallic SWNTs, respectively. Surprisingly, we also found from the exciton excited state absorption bands and multiphoton absorption resonances in the semiconducting nanotubes that transitions between subbands are allowed; this unravels the important role of electron-electron interaction in SWNT optics

Ultrafast dynamics of excitons and solitons in disubstituted polyacetylene

Journal ArticleWe studied the ultrafast photoexcitation dynamics in disubstituted polyacetylene (DPA). We found two distinctively different relaxation channels for the photogenerated excitons; ionic and covalent pathways. In DPA films the photogenerated odd-parity (Bu) excitons that are responsible for the high photoluminescence quantum efficiency follow the ionic relaxation pathway. During the hot exciton thermalization process, however, a fraction of the Bu excitons undergo a phonon-assisted transition to the covalent 2Ag state, which consequently decomposes into two neutral soliton-antisoliton pairs that are subject to ultrafast recombination or dissociate into stable neutral solitons. In DPA solutions the ionic channel remains unchanged, however, the covalent channel becomes ineffective due to the different hot exciton thermalization pathways

Investigating the retention of intermediate-mass black holes in star clusters using N-body simulations

Contrary to supermassive and stellar-mass black holes (SBHs), the existence of intermediate-mass black holes (IMBHs) with masses ranging between 10^{2-5} Msun has not yet been confirmed. The main problem in the detection is that the innermost stellar kinematics of globular clusters (GCs) or small galaxies, the possible natural loci to IMBHs, are very difficult to resolve. However, if IMBHs reside in the centre of GCs, a possibility is that they interact dynamically with their environment. A binary formed with the IMBH and a compact object of the GC would naturally lead to a prominent source of gravitational radiation, detectable with future observatories. We use N-body simulations to study the evolution of GCs containing an IMBH and calculate the gravitational radiation emitted from dynamically formed IMBH-SBH binaries and the possibility that the IMBH escapes the GC after an IMBH-SBH merger. We run for the first time direct-summation integrations of GCs with an IMBH including the dynamical evolution of the IMBH with the stellar system and relativistic effects, such as energy loss in gravitational waves (GWs) and periapsis shift, and gravitational recoil. We find in one of our models an intermediate mass-ratio inspiral (IMRI), which leads to a merger with a recoiling velocity higher than the escape velocity of the GC. The GWs emitted fall in the range of frequencies that a LISA-like observatory could detect, like the European eLISA or in mission options considered in the recent preliminary mission study conducted in China. The merger has an impact on the global dynamics of the cluster, as an important heating source is removed when the merged system leaves the GC. The detection of one IMRI would constitute a test of GR, as well as an irrefutable proof of the existence of IMBHs.Comment: Accepted for publication by A&A, minor modification

Ultrafast Pulse Radiolysis Using a Terawatt Laser Wakefield Accelerator

We report the first ultrafast pulse radiolysis transient absorption spectroscopy measurements from the Terawatt Ultrafast High Field Facility (TUHFF) at Argonne National Laboratory. TUHFF houses a 20 TW Ti:sapphire laser system that generates 2.5 nC sub-picosecond pulses of multi-MeV electrons at 10 Hz using laser wakefield acceleration. The system has been specifically optimized for kinetic measurements in a pump-probe fashion. This requires averaging over many shots which necessitates stable, reliable generation of electron pulses. The latter were used to generate excess electrons in pulse radiolysis of liquid water and concentrated solutions of perchloric acid. The hydronium ions in the acidic solutions react with the hydrated electrons resulting in the rapid decay of the transient absorbance at 800 nm on the picosecond time scale. Time resolution of a few picoseconds has been demonstrated. The current time resolution is determined primarily by the physical dimensions of the sample and the detection sensitivity. Subpicosecond time resolution can be achieved by using thinner samples, more sensitive detection techniques and improved electron beam quality.Comment: submitted to J. Appl. Phys. 5 figures, 23 page

Structure, Photophysics and the Order-Disorder Transition to the Beta Phase in Poly(9,9-(di -n,n-octyl)fluorene)

X-ray diffraction, UV-vis absorption and photoluminescence (PL) spectroscopy have been used to study the well-known order-disorder transition (ODT) to the beta phase in poly(9,9-(di n,n-octyl)fluorene)) (PF8) thin film samples through combination of time-dependent and temperature-dependent measurements. The ODT is well described by a simple Avrami picture of one-dimensional nucleation and growth but crystallization, on cooling, proceeds only after molecular-level conformational relaxation to the so called beta phase. Rapid thermal quenching is employed for PF8 studies of pure alpha phase samples while extended low-temperature annealing is used for improved beta phase formation. Low temperature PL studies reveal sharp Franck-Condon type emission bands and, in the beta phase, two distinguishable vibronic sub-bands with energies of approximately 199 and 158 meV at 25 K. This improved molecular level structural order leads to a more complete analysis of the higher-order vibronic bands. A net Huang-Rhys coupling parameter of just under 0.7 is typically observed but the relative contributions by the two distinguishable vibronic sub-bands exhibit an anomalous temperature dependence. The PL studies also identify strongly correlated behavior between the relative beta phase 0-0 PL peak position and peak width. This relationship is modeled under the assumption that emission represents excitons in thermodynamic equilibrium from states at the bottom of a quasi-one-dimensional exciton band. The crystalline phase, as observed in annealed thin-film samples, has scattering peaks which are incompatible with a simple hexagonal packing of the PF8 chains.Comment: Submitted to PRB, 12 files; 1 tex, 1 bbl, 10 eps figure

Triplet Exciton Generation in Bulk-Heterojunction Solar Cells based on Endohedral Fullerenes

Organic bulk-heterojunctions (BHJ) and solar cells containing the trimetallic nitride endohedral fullerene 1-[3-(2-ethyl)hexoxy carbonyl]propyl-1-phenyl-Lu3N@C80 (Lu3N@C80-PCBEH) show an open circuit voltage (VOC) 0.3 V higher than similar devices with [6,6]-phenyl-C[61]-butyric acid methyl ester (PC61BM). To fully exploit the potential of this acceptor molecule with respect to the power conversion efficiency (PCE) of solar cells, the short circuit current (JSC) should be improved to become competitive with the state of the art solar cells. Here, we address factors influencing the JSC in blends containing the high voltage absorber Lu3N@C80-PCBEH in view of both photogeneration but also transport and extraction of charge carriers. We apply optical, charge carrier extraction, morphology, and spin-sensitive techniques. In blends containing Lu3N@C80-PCBEH, we found 2 times weaker photoluminescence quenching, remainders of interchain excitons, and, most remarkably, triplet excitons formed on the polymer chain, which were absent in the reference P3HT:PC61BM blends. We show that electron back transfer to the triplet state along with the lower exciton dissociation yield due to intramolecular charge transfer in Lu3N@C80-PCBEH are responsible for the reduced photocurrent

Charge transfer dynamics in conjugated polymer/MoS2 organic/2D heterojunctions

Heterojunctions between organic and two-dimensional (2D) semiconductors show promising applications in ultrathin electronic and optoelectronic devices, including field-effect transistors, light-emitting diodes, and photovoltaics. These organic/2D heterojunctions form ideal interfaces due to the lack of dangling bonds at the surfaces of the neat (i.e., individual) materials and their propensity to interact via van der Waals forces. Despite this, organic/2D heterojunction devices have had relatively low quantum efficiencies, suggesting limitations on the charge transport within these devices. Understanding the charge transfer dynamics across organic/2D semiconductor interfaces at fundamental time scales is an important part of overcoming these limitations. In this work, we investigate the photoexcited charge carrier dynamics in organic/2D heterojunctions comprised of large-area monolayer MoS2 and solution-deposited organic semiconducting conjugated polymer thin-films. Using photoluminescence and femtosecond transient absorption spectroscopy, we compare the efficiencies of charge transfer for three different conjugated polymer/MoS2 heterojunctions: P3HT, PCDTBT, and PTB7. We show that electron transfer occurs from MoS2 to P3HT in under 9 ps, and from MoS2 to PCDTBT or PTB7 in under 120 fs. Despite this, we demonstrate that the P3HT/MoS2 heterojunction is the most efficient because the transferred charges have an order-of-magnitude increase in their lifetimes, giving rise to enhanced photoluminescence. This work will help guide designs of future organic/2D heterojunctions using scalable fabrication technologies

Carbon nanotubes for ultrafast fibre lasers

Carbon nanotubes (CNTs) possess both remarkable optical properties and high potential for integration in various photonic devices. We overview, here, recent progress in CNT applications in fibre optics putting particular emphasis on fibre lasers. We discuss fabrication and characterisation of different CNTs, development of CNT-based saturable absorbers (CNT-SA), their integration and operation in fibre laser cavities putting emphasis on state-of-the-art fibre lasers, mode locked using CNT-SA. We discuss new design concepts of high-performance ultrafast operation fibre lasers covering ytterbium (Yb), bismuth (Bi), erbium (Er), thulium (Tm) and holmium (Ho)-doped fibre lasers