Ultrafast holography and transient-absorption spectroscopy in charge-transfer polymers

Charge-transfer polymers are a new class of nonlinear optical materials which can be used for generating femtosecond holographic gratings. Using semiconducting polymers sensitized with varying concentrations of C{sub 60}, holographic gratings were recorded by individual ultrafast laser pulses; the diffraction efficiency and time decay of the gratings were measured using non-degenerate four-wave mixing. Using a figure of merit for dynamic data processing, the temporal diffraction efficiency, this new class of materials exhibits between two and 12 orders of magnitude higher response than previous reports. The charge transfer range at polymer/C{sub 60} interfaces was further studied using transient absorption spectroscopy. The fact that charge-transfer occurs in the picosecond-time scale in bilayer structures (thickness 200 {angstrom}) implies that diffusion of localized excitations to the interface is not the dominant mechanism; the charge transfer range is a significant fraction of the film thickness. From analysis of the excited state decay curves, we estimate the charge transfer range to be 80 {angstrom} and interpret that range as resulting from quantum delocalization of the photoexcitations

Exciton bimolecular annihilation dynamics in supramolecular nanostructures of conjugated oligomers

We present femtosecond transient absorption measurements on $\pi$-conjugated supramolecular assemblies in a high pump fluence regime. Oligo(\emph{p}-phenylenevinylene) monofunctionalized with ureido-\emph{s}-triazine (MOPV) self-assembles into chiral stacks in dodecane solution below 75$^{\circ}$C at a concentration of $4\times 10^{-4}$ M. We observe exciton bimolecular annihilation in MOPV stacks at high excitation fluence, indicated by the fluence-dependent decay of $1^1$B$_{u}$-exciton spectral signatures, and by the sub-linear fluence dependence of time- and wavelength-integrated photoluminescence (PL) intensity. These two characteristics are much less pronounced in MOPV solution where the phase equilibrium is shifted significantly away from supramolecular assembly, slightly below the transition temperature. A mesoscopic rate-equation model is applied to extract the bimolecular annihilation rate constant from the excitation fluence dependence of transient absorption and PL signals. The results demonstrate that the bimolecular annihilation rate is very high with a square-root dependence in time. The exciton annihilation results from a combination of fast exciton diffusion and resonance energy transfer. The supramolecular nanostructures studied here have electronic properties that are intermediate between molecular aggregates and polymeric semiconductors

Efficiency of radiative emission from thin films of a light-emitting conjugated polymer

J. A. E. Wasey, A. Safonov, I. D. W. Samuel, and William L. Barnes, Physical Review B, Vol. 64, article 205201 (2001). "Copyright © 2001 by the American Physical Society."We examine the efficiency of radiative emission from thin layers of light-emitting conjugated polymers. We compare our experimental results for photoluminescence of the conjugated polymer poly(2-methoxy, 5-(2′-ethyl-hexyloxy) 1,4 phenylenevinylene) (MEH-PPV) with those of a theoretical model, finding good agreement between the two. The specially developed model takes into account several factors including absorption in the emissive layer, a spread of emitter sites within the layer, and the broad emission spectrum of the polymer. We find that the photoluminescence quantum efficiency for radiative emission of a bare MEH-PPV film on a glass substrate is ∼25%. We then apply our model to study electroluminescent devices. We show that for these structures the efficiency of radiative emission is ∼10%. There is thus potential for considerable improvement in efficiency for both systems through recovery of some of the wasted waveguided light. Finally we use our model to reexamine some controversial results that indicate the probability of singlet exciton formation to be 0.4±0.05, and thus greater than the 0.25 expected from spin statistics. Our reanalysis supports a probability >0.25. We conclude by discussing the limitations of present models, including our own, in predicting the performance of realistic light-emitting diodes

Nonlinear optical microscopy for imaging thin films and surfaces

We have used the inherent surface sensitivity of second harmonic generation to develop an instrument for nonlinear optical microscopy of surfaces and interfaces. We have demonstrated the use of several nonlinear optical responses for imaging thin films. The second harmonic response of a thin film of C{sub 60} has been used to image patterned films. Two photon absorption light induced fluorescence has been used to image patterned thin films of Rhodamine 6G. Applications of nonlinear optical microscopy include the imaging of charge injection and photoinduced charge transfer between layers in semiconductor heterojunction devices as well as across membranes in biological systems

Nature of the Primary Photoexcitations in Poly(Arylene-Vinylenes)

We present an overview of the optical properties and related experimental results obtained from poly(para-phenylene vinylene), PPV, and its soluble derivatives, and we critically examine the interpretation of these data in the context of both the band model and the exciton model of the electronic structure of these semiconducting and luminescent polymers. Results obtained from highly oriented and structurally ordered PPVs demonstrate that the observed disparities between the physical properties of PPV and the polydiacetylenes (PDAs) are not due to disorder; these differences are intrinsic and arise from the fundamental difference in the nature of the low energy photoexcited states: excitons in the PDAs and free carriers in the PPVs