Photoinduced Energy Transfer in Linear Guest-Host Chromophores: A Computational Study.

Polymer-based guest-host systems represent a promising class of materials for efficient light-emitting diodes. The energy transfer from the polymer host to the guest is the key process in light generation. Therefore, microscopic descriptions of the different mechanisms involved in the energy transfer can contribute to enlighten the basis of the highly efficient light harvesting observed in this kind of materials. Herein, the nature of intramolecular energy transfer in a dye-end-capped conjugated polymer is explored by using atomistic nonadiabatic excited-state molecular dynamics. Linear perylene end-capped (PEC) polyindenofluorenes (PIF), consisting of n (n = 2, 4, and 6) repeat units, i.e., PEC-PIFn oligomers, are considered as model systems. After photoexcitation at the oligomer absorption maximum, an initial exciton becomes self-trapped on one of the monomer units (donors). Thereafter, an efficient ultrafast through-space energy transfer from this unit to the perylene acceptor takes place. We observe that this energy transfer occurs equally well from any monomer unit on the chain. Effective specific vibronic couplings between each monomer and the acceptor are identified. These oligomer → end-cap energy transfer steps do not match with the rates predicted by Förster-type energy transfer. The through-space and through-bond mechanisms are two distinct channels of energy transfer. The former dominates the overall process, whereas the through-bond energy transfer between indenofluorene monomer units along the oligomer backbone only makes a minor contribution.

Floquet spin states in OLEDs.

Electron and hole spins in organic light-emitting diodes constitute prototypical two-level systems for the exploration of the ultrastrong-drive regime of light-matter interactions. Floquet solutions to the time-dependent Hamiltonian of pairs of electron and hole spins reveal that, under non-perturbative resonant drive, when spin-Rabi frequencies become comparable to the Larmor frequencies, hybrid light-matter states emerge that enable dipole-forbidden multi-quantum transitions at integer and fractional g-factors. To probe these phenomena experimentally, we develop an electrically detected magnetic-resonance experiment supporting oscillating driving fields comparable in amplitude to the static field defining the Zeeman splitting; and an organic semiconductor characterized by minimal local hyperfine fields allowing the non-perturbative light-matter interactions to be resolved. The experimental confirmation of the predicted Floquet states under strong-drive conditions demonstrates the presence of hybrid light-matter spin excitations at room temperature. These dressed states are insensitive to power broadening, display Bloch-Siegert-like shifts, and are suggestive of long spin coherence times, implying potential applicability for quantum sensing.

Ultrafast Single-Molecule Fluorescence Measured by Femtosecond Double-Pulse Excitation Photon Antibunching.

Most measurements of fluorescence lifetimes on the single-molecule level are carried out using avalanche photon diodes (APDs). These single-photon counters are inherently slow, and their response shows a strong dependence on photon energy, which can make reconvolution of the instrument response function (IRF) challenging. An ultrafast time resolution in single-molecule fluorescence is crucial, e.g., in determining donor lifetimes in donor-acceptor couples which undergo energy transfer, or in plasmonic antenna structures, where the radiative rate and non-radiative rates are enhanced. We introduce a femtosecond double-excitation (FeDEx) photon correlation technique, which measures the degree of photon antibunching as a function of time delay between two excitation pulses. In this boxcar integration, the time resolution of fluorescence transients is limited solely by the laser pulse length and is independent of the detector IRF. The versatility of the technique is demonstrated with a custom-made donor-acceptor complex with one donor and two acceptors and with single dye molecules positioned accurately between two gold nanoparticles using DNA origami. The latter structures show ∼75-fold radiative-rate enhancement and fluorescence lifetimes down to 19 ps, which is measured without the need for any reconvolution. With the potential of measuring subpicosecond fluorescence lifetimes, plasmonic antenna structures can now be optimized further.

Ultrafast transition between exciton phases in van der Waals heterostructures.

Heterostructures of atomically thin van der Waals bonded monolayers have opened a unique platform to engineer Coulomb correlations, shaping excitonic1-3, Mott insulating4 or superconducting phases5,6. In transition metal dichalcogenide heterostructures7, electrons and holes residing in different monolayers can bind into spatially indirect excitons1,3,8-11 with a strong potential for optoelectronics11,12, valleytronics1,3,13, Bose condensation14, superfluidity14,15 and moiré-induced nanodot lattices16. Yet these ideas require a microscopic understanding of the formation, dissociation and thermalization dynamics of correlations including ultrafast phase transitions. Here we introduce a direct ultrafast access to Coulomb correlations between monolayers, where phase-locked mid-infrared pulses allow us to measure the binding energy of interlayer excitons in WSe2/WS2 hetero-bilayers by revealing a novel 1s-2p resonance, explained by a fully quantum mechanical model. Furthermore, we trace, with subcycle time resolution, the transformation of an exciton gas photogenerated in the WSe2 layer directly into interlayer excitons. Depending on the stacking angle, intra- and interlayer species coexist on picosecond scales and the 1s-2p resonance becomes renormalized. Our work provides a direct measurement of the binding energy of interlayer excitons and opens the possibility to trace and control correlations in novel artificial materials.

Anomalous Linear Dichroism in Bent Chromophores of π-conjugated Polymers: Departure from the Franck-Condon Principle.

We examine the influence of bending of π-conjugated chromophores on photoluminescence (PL) by spectrally resolving the depolarization of fluorescence on the single-molecule level. The effect of excited-state mixing mediated by molecular vibrations is manifested in the departure from the usual achromatic linear dichroism of fluorescence, with the polarization anisotropy decreasing in the vibronic progression. Bent chromophores reveal an overall increase in vibronic PL intensity with polarization orthogonal to the molecular long axis. This manifestation of the Renner-Herzberg-Teller (RHT) effect illustrates the breakdown of the Franck-Condon principle in macromolecules used in organic electronics, providing information on the orientation of transition-dipole moments and the origin of spectral broadening. While some of the spectral signatures of the RHT effect appear similar to those of H aggregation in molecular dimers, discrimination between the two phenomena is straightforward since H aggregation does not induce anomalous linear dichroism.

Interactions between π-conjugated chromophores in a giant molecular spoked wheel.

We discuss the intriguing photophysics of a giant molecular spoked wheel of π-conjugated arylene-alkynylene chromophores on the single-molecule level. This "molecular mesoscopic" structure, C1878H2682, shows fast switching between the 12 identical chromophores since the fluorescence is unpolarised but only one chromophore emits at a time.

Organic electronics. Room-temperature coupling between electrical current and nuclear spins in OLEDs.

The effects of external magnetic fields on the electrical conductivity of organic semiconductors have been attributed to hyperfine coupling of the spins of the charge carriers and hydrogen nuclei. We studied this coupling directly by implementation of pulsed electrically detected nuclear magnetic resonance spectroscopy in organic light-emitting diodes (OLEDs). The data revealed a fingerprint of the isotope (protium or deuterium) involved in the coherent spin precession observed in spin-echo envelope modulation. Furthermore, resonant control of the electric current by nuclear spin orientation was achieved with radiofrequency pulses in a double-resonance scheme, implying current control on energy scales one-millionth the magnitude of the thermal energy.

Slow hopping and spin dephasing of Coulombically bound polaron pairs in an organic semiconductor at room temperature.

Polaron pairs are intermediate electronic states that are integral to the optoelectronic conversion process in organic semiconductors. Here, we report on electrically detected spin echoes arising from direct quantum control of polaron pair spins in an organic light-emitting diode at room temperature. This approach reveals phase coherence on a microsecond time scale, and offers a direct way to probe charge recombination and dissociation processes in organic devices, revealing temperature-independent intermolecular carrier hopping on slow time scales. In addition, the long spin phase coherence time at room temperature is of potential interest for developing quantum-enhanced sensors and information processing systems which operate at room temperature.

Robust absolute magnetometry with organic thin-film devices.

Magnetic field sensors based on organic thin-film materials have attracted considerable interest in recent years as they can be manufactured at very low cost and on flexible substrates. However, the technological relevance of such magnetoresistive sensors is limited owing to their narrow magnetic field ranges (∼30 mT) and the continuous calibration required to compensate temperature fluctuations and material degradation. Conversely, magnetic resonance (MR)-based sensors, which utilize fundamental physical relationships for extremely precise measurements of fields, are usually large and expensive. Here we demonstrate an organic magnetic resonance-based magnetometer, employing spin-dependent electronic transitions in an organic diode, which combines the low-cost thin-film fabrication and integration properties of organic electronics with the precision of a MR-based sensor. We show that the device never requires calibration, operates over large temperature and magnetic field ranges, is robust against materials degradation and allows for absolute sensitivities of <50 nT Hz(-1/2).

Hyperfine-field-mediated spin beating in electrostatically bound charge carrier pairs.

Organic semiconductors offer a unique environment to probe the hyperfine coupling of electronic spins to a nuclear spin bath. We explore the interaction of spins in electron-hole pairs in the presence of inhomogeneous hyperfine fields by monitoring the modulation of the current through an organic light emitting diode under coherent spin-resonant excitation. At weak driving fields, only one of the two spins in the pair precesses. As the driving field exceeds the difference in local hyperfine field experienced by electron and hole, both spins precess, leading to pronounced spin beating in the transient Rabi flopping of the current. We use this effect to measure the magnitude and spatial variation in hyperfine field on the scale of single carrier pairs, as required for evaluating models of organic magnetoresistance, improving organic spintronics devices, and illuminating spin decoherence mechanisms.

Spin Rabi flopping in the photocurrent of a polymer light-emitting diode.

Electron spin is fundamental in electrical and optical properties of organic electronic devices. Despite recent interest in spin mixing and spin transport in organic semiconductors, the actual spin coherence times in these materials have remained elusive. Measurements of spin coherence provide impartial insight into spin relaxation mechanisms, which is significant in view of recent models of spin-dependent transport and recombination involving high levels of spin mixing. We demonstrate coherent manipulation of spins in an organic light-emitting diode (OLED), using nanosecond pulsed electrically detected electron spin resonance to drive singlet-triplet spin Rabi oscillations. By measuring the change in photovoltaic response due to spin-dependent recombination, we demonstrate spin control of electronic transport and thus directly observe spin coherence over 0.5 s. This surprisingly slow spin dephasing underlines that spin mixing is not responsible for magnetoresistance in OLEDs. The long coherence times and the spin manipulation demonstrated are crucially important for expanding the impact of organic spintronics.

How chromophore shape determines the spectroscopy of phenylene-vinylenes: origin of spectral broadening in the absence of aggregation.

Single oligo(phenylene-vinylene) molecules constitute model systems of chromophores in disordered conjugated polymers and can elucidate how the actual conformation of an individual chromophore, rather than that of an overall polymer chain, controls its photophysics. Single oligomers and polymer chains display the same range of spectral properties. Even heptamers support pi-electron conjugation across approximately 80 degrees curvature, as revealed by the polarization anisotropy in excitation and supported by quantum chemical calculations. As the chain becomes more deformed, the spectral linewidth at low temperatures, often interpreted as a sign of aggregation, increases up to 30-fold due to a reduction in photophysical stability of the molecule and an increase in random spectral fluctuations. The conclusions aid the interpretation of results from single-chain Stark spectroscopy in which large static dipoles were only observed in the case of narrow transition lines. These narrow transitions originate from extended chromophores in which the dipoles induced by backbone substituents do not cancel out. Chromophores in conjugated polymers are often thought of as individual linear transition dipoles, the sum of which make up the polymer's optical properties. Our results demonstrate that, at least for phenylene-vinylenes, it is the actual shape of the individual chromophore rather than the overall chromophoric arrangement and form of the polymer chain that dominates the spectroscopic properties.

Phenylene-ethynylene macrocycles as model systems of interchromophoric interactions in pi-conjugated macromolecules.

Unraveling the complex photophysics of macromolecular pi-conjugated systems requires both the development of suitable model systems to access a particular subset of a material's parameter space and the choice of matching spectroscopic techniques. We address the question of the strength of interchromophoric interactions in macromolecular systems by studying the fluorescence depolarization kinetics of a family of prototypical conjugated macrocycles. Shrinking the size of the molecular system decelerates fluorescence depolarization even though the radius of gyration decreases. Although the smaller macrocycles show faster rotational diffusion, the larger compounds exhibit an additional initial depolarization mechanism, attributed to intramolecular interchromophoric energy transfer. Comparison with fragments of the molecule illustrates that the larger macrocycles can be interpreted as bichromophoric systems, whereas the effectively parallel chromophoric elements of the smaller ring are indistinguishable in terms of polarization. The potential role of strong interchromophoric interaction is discussed. The results illustrate a subtle link between interchromophoric arrangement and ultrafast fluorescence depolarization, phenomena, which are often considered in the context of conjugated polymers: chromophoric alignment can potentially counteract the effect of polarization memory loss through energy transfer.

Picosecond time resolved photoluminescence spectroscopy of a tetracene film on highly oriented pyrolytic graphite: dynamical relaxation, trap emission, and superradiance.

A detailed time resolved investigation of the photoluminescence of a thin tetracene film deposited on highly oriented pyrolytic graphite is presented. In agreement with Lim et al. [Phys. Rev. Lett. 92, 107402 (2004)], we find strong evidence for superradiance: an increase of the relative intensity of the pure electronic transition with respect to the vibronic sideband and a concomitant decrease of the radiative lifetime from 10 to 1.83 ns upon cooling from 300 to 4 K. For lower temperatures, a redshift (approximately 200 cm(-1)) of the free exciton is observed. Previously, this shift was attributed to a structural phase transition. Our time resolved spectra reveal that the spectral shift is related to a dynamical relaxation process which occurs within the first 50 ps.

Room-temperature exciton storage in elongated semiconductor nanocrystals.

The excited state of colloidal nanoheterostructures consisting of a spherical CdSe nanocrystal with an epitaxially attached CdS rod can be perturbed effectively by electric fields. Field-induced fluorescence quenching coincides with a conversion of the excited state species from the bright exciton to a metastable trapped state (dark exciton) characterized by a power-law luminescence decay. The conversion is reversible so that up to 10% of quenched excitons recombine radiatively post turn-off of a 1 micro s field pulse, increasing the delayed luminescence by a factor of 80. Excitons can be stored for up to 10(5) times the natural lifetime, opening up applications in optical memory elements.

Wave function engineering in elongated semiconductor nanocrystals with heterogeneous carrier confinement.

We explore two routes to wave function engineering in elongated colloidal CdSe/CdS quantum dots, providing deep insight into the intrinsic physics of these low-dimensional heterostructures. Varying the aspect ratio of the nanoparticle allows control over the electron-hole overlap (radiative rate), and external electric fields manipulate the interaction between the delocalized electron and the localized hole. In agreement with theory, this leads to an exceptional size dependent quantum confined Stark effect with field induced intensity modulations, opening applications as electrically switchable single photon sources.

Monitoring surface charge movement in single elongated semiconductor nanocrystals.

We demonstrate a universal correlation between the spectral linewidth and position of the excitonic transition in the spectral jitter observed from single elongated colloidal quantum dots. Breaking the symmetry of electron and hole confinement as well as of the spatial directions for surface charge diffusion enables us to microscopically track meandering surface charges, providing a novel probe of the particle's nanoenvironment. Spectral diffusion exhibits only a weak temperature dependence, which allows us to uncover the single particle homogeneous linewidth of 50 meV at room temperature.

Experimental evidence for exciton scaling effects in self-assembled molecular wires.

Resonant Rayleigh scattering from self-assembled one-dimensional molecular J-aggregate wires reveals a distinct dependence of the exciton energy on the width of lateral extension. For the J aggregates used in this study, strong in-line dipole coupling leads to a delocalization of the exciton wave function over several molecular units. Polarization dependent measurements of resonantly scattered light from the wires show that the exciton dipole moment is oriented perpendicular to the long axis. The experimental observations can be described by applying a quantization condition to the center of mass motion of the J-band exciton in the wires.

Linewidth-limited energy transfer in single conjugated polymer molecules.

Using low temperature single molecule spectroscopy on rigid-rod conjugated polymers we are able to identify homogeneously broadened, strongly polarized emission from individual chromophore units on a single chain. Gated fluorescence spectroscopy allows real time imaging of intramolecular energy transfer as the chain behaves as a series of weakly interacting chromophores. Energy transfer is controlled by the chromophoric spectral linewidth, which depends on temperature. Linewidths exceeding intramolecular disorder lead to incoherent chromophore coupling and collective fluorescence phenomena.

Intrinsic room-temperature electrophosphorescence from a pi-conjugated polymer.

Electrically induced phosphorescence from a poly(para-phenylene) ladder-type polymer is observed for the first time and characterized using time resolved spectroscopy. Short-lived phosphorescence is also observed in gated fluorescence spectra and is found to be quenched reversibly by oxygen. Thermally activated triplet diffusion to covalently bound palladium sites, which are formed at a concentration of about 80 ppm in a side reaction during polymer synthesis, is believed to be the cause of this novel effect, which suggests a new approach to the design of efficient electroluminescent materials.