Low-threshold polymeric distributed feedback lasers with metallic contacts

Journal ArticleOptical losses in waveguides comprising metallic contacts are thought to be a major hurdle to the realization of organic laser diodes. We demonstrate here that careful tuning of the waveguide mode in flexible distributed feedback lasers can allow lasing action to occur in organic thin films in the presence of contacting electrodes with virtually no difference when compared to metal free devices. A metallic electrode is most suited as the bottom contact between the polymer and the substrate as it reduces mode leakage into the substrate and enhances modal gain. In contrast, a thin transparent electrode such as a metal oxide is preferable for the top electrode, where confinement is not a problem

Stimulated emission depletion of triplet excitons in a phosphorescent organic laser

Journal ArticleTriplet formation is investigated in an optically pumped polymer laser by detecting the phosphorescence emission after excitation. A clear correlation is observed between the onset of lasing and a saturation of phosphorescence intensity due to stimulated emission depletion of the singlet state and the resulting reduction in intersystem crossing. The results are consistent with intersystem crossing constituting the dominant triplet formation pathway in conjugated polymers. Excitation at different wavelengths has no effect on the triplet saturation behavior, which allows the authors to exclude singlet fission or breaking as the origin of triplet formation. The method constitutes an implementation of a highly nondegenerate excitonic switch

Evidence for temperature-independent triplet diffusion in a ladder-type conjugated polymer

Journal ArticleWe study the temperature dependence of triplet formation and decay by considering the phosphorescence dynamics in a prototypical conjugated polymer matrix. The dynamics of triplet formation as a function of temperature are unraveled by applying an electric field during optical singlet generation and recording the phosphorescence quenching. The diffusivity of triplet excitons in conjugated polymers is shown to be independent of temperature up to 200 K. We propose a diffusion model that describes the relaxation dynamics of triplet excitons at all times through triplet-triplet annihilation and spin orbit coupling at static heavy atom sites

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

Journal ArticleA 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 (~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

Journal ArticleThe 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 us field pulse, increasing the delayed luminescence by a factor of 80. Excitons can be stored for up to 105 times the natural lifetime, opening up applications in optical memory elements

Exciton storage in CdSe/CdS tetrapod semiconductor nanocrystals: Electric field effects on exciton and multiexciton states

CdSe/CdS nanocrystal tetrapods are interesting building blocks for excitonic circuits, where the flow of excitation energy is gated by an external stimulus. The physical morphology of the nanoparticle, along with the electronic structure, which favors electron delocalization between the two semiconductors, suggests that all orientations of a particle relative to an external electric field will allow for excitons to be dissociated, stored, and released at a later time. While this approach, in principle, works, and fluorescence quenching of over 95% can be achieved electrically, we find that discrete trap states within the CdS are required to dissociate and store the exciton. These states are rapidly filled up with increasing excitation density, leading to a dramatic reduction in quenching efficiency. Charge separation is not instantaneous on the CdS excitonic antennae in which light absorption occurs, but arises from the relaxed exciton following hole localization in the core. Consequently, whereas strong electromodulation of the core exciton is observed, the core multiexciton and the CdS arm exciton are not affected by an external electric field

On-chain defect emission in electroluminescent polyfluorenes

Journal ArticleWe present time-resolved photoluminescence measurements on a range of poly- and oligofluorenes with different molecular weights in both dilute solution and thin films. The commonly observed parasitic broad green emission band, which has previously been attributed to an excimer, is identified in all solution and film samples and assigned to an on-chain emissive defect. By comparison of the luminescence decay in the solid state at different temperatures it is shown that, at room temperature, intramolecular relaxation is faster in these polyphenylenes than intermolecular exciton diffusion

Direct Detection of Singlet-Triplet Interconversion in OLED Magnetoelectroluminescence with a Metal-Free Fluorescence-Phosphorescence Dual Emitter

We demonstrate that a simple phenazine derivative can serve as a dual emitter for organic light-emitting diodes, showing simultaneous luminescence from the singlet and triplet excited states at room temperature without the need of heavy-atom substituents. Although devices made with this emitter achieve only low quantum efficiencies of < 0.2%, changes in fluorescence and phosphorescence intensity on the subpercent scale caused by an external magnetic field of up to 30 mT are clearly resolved with an ultra-low-noise optical imaging technique. The results demonstrate the concept of using simple reporter molecules, available commercially, to optically detect the spin of excited states formed in an organic light-emitting diode and thereby probe the underlying spin statistics of recombining electron-hole pairs. A clear anticorrelation of the magnetic-field dependence of singlet and triplet emission shows that it is the spin interconversion between singlet and triplet which dominates the magnetoluminescence response: the phosphorescence intensity decreases by the same amount as the fluorescence intensity increases. The concurrent detection of singlet and triplet emission as well as device resistance at cryogenic and room temperature constitute a useful tool to disentangle the effects of spin-dependent recombination from spin-dependent transport mechanisms

Impact of charge carrier injection on single-chain photophysics of conjugated polymers

Charges in conjugated polymer materials have a strong impact on the photophysics and their interaction with the primary excited state species has to be taken into account in understanding device properties. Here, we employ single-molecule spectroscopy to unravel the influence of charges on several photoluminescence (PL) observables. The charges are injected either stochastically by a photochemical process, or deterministically in a hole-injection sandwich device configuration. We find that upon charge injection, besides a blue-shift of the PL emission and a shortening of the PL lifetime due to quenching and blocking of the lowest-energy chromophores, the non-classical photon arrival time distribution of the multichromophoric chain is modified towards a more classical distribution. Surprisingly, the fidelity of photon antibunching deteriorates upon charging, whereas one would actually expect the number of chromophores to be reduced. A qualitative model is presented to explain the observed PL changes. The results are of interest to developing a microscopic understanding of the intrinsic charge-exciton quenching interaction in devices