Formation of a defect-free π-electron system in single ß-phase polyfluorene chains.

Single-molecule spectroscopy can help to uncover the underlying heterogeneity of conjugated polymers used in organic electronics, revealing the most effective molecules in an ensemble in terms of the transport of charge and excitation energy. We demonstrate that ß-phase polyfluorene chains can form a near-perfect π-electron system, whereas conventional polymers exhibit chromophoric localization due to perturbation of the conjugation. Broad-band excitation spectroscopy demonstrates that only one absorbing and emitting unit is present on the polymer chain with an average length of ∼500 repeat units, illustrating that the material effectively behaves as a molecular quantum wire with strong electronic coupling throughout the entire system.

The role of particle morphology in interfacial energy transfer in CdSe/CdS heterostructure nanocrystals.

Nanoscale semiconductor heterostructures such as tetrapods can be used to mimic light-harvesting processes. We used single-particle light-harvesting action spectroscopy to probe the impact of particle morphology on energy transfer and carrier relaxation across a heterojunction. The generic form of an action spectrum [in our experiments, photoluminescence excitation (PLE) under absorption in CdS and emission from CdSe in nanocrystal tetrapods, rods, and spheres] was controlled by the physical shape and resulting morphological variation in the quantum confinement parameters of the nanoparticle. A correlation between single-particle PLE and physical shape as determined by scanning electron microscopy was demonstrated. Such an analysis links local structural non-uniformities such as CdS bulbs forming around the CdSe core in CdSe/CdS nanorods to a lower probability of manifesting excitation energy-dependent emission spectra, which in turn is probably related to band alignment and electron delocalization at the heterojunction interface.

Unraveling the inhomogeneously broadened absorption spectrum of conjugated polymers by single-molecule light-harvesting action spectroscopy.

The distribution of chromophores in single polymer chains is revealed by photoluminescence excitation spectroscopy under excitation of the backbone and detection of emission from an end cap. Spectral broadening in excitation exceeds that in emission. An increase in vibronic coupling for shorter (higher energy) chromophores is resolved, leading to intrinsic spectral broadening and making higher energy units more effective donors. The results suggest routes to increasing absorption breadth while minimizing disorder as required for efficient photovoltaics.

Toward subdiffraction transmission microscopy of diffuse materials with silver nanoparticle white-light beacons.

We demonstrate high resolution transmission microscopy in a conventional two-photon wide-field fluorescence microscope by exploiting nonlinear white light generation from clusters of silver nanoparticles placed beneath the specimen. Surface-enhanced two-photon luminescence occurs at nanoparticle hot spots in the form of spectrally broad, spatially confined light which can be exploited to determine the transmission properties of a sample placed on the silver nanoparticles. We demonstrate the versatility of the technique by revealing individual crystalline domains formed in the diffuse biological photonic crystals of the scales of a beetle. We can identify submicron changes between photonic crystal facets as well as the occurrence of stacked domains invisible to surface-sensitive methods. Control over wavelength, polarization, and pulse shape promises selective addressing of hot spots in nanoparticle assemblies for motionless spatial scanning of the transmission properties with subdiffraction resolution.

Spatial anticorrelation between nonlinear white-light generation and single molecule surface-enhanced Raman scattering.

We investigate the correlation between plasmon-enhanced nonlinear white-light emission and single-molecule surface-enhanced Raman scattering (SERS) on fractal silver films using a conjugated polymer as a versatile analyte. Single molecule resonance SERS is preferentially observed from sample positions which do not exhibit nonlinear light emission under infrared excitation. The results suggest that the broad emission background often associated with single molecule SERS may not be intrinsic to the huge optical field amplifications characteristic of SERS. The two-photon imaging technique promises to offer a facile approach to prescreen substrates for their single molecule SERS capability.

Light-harvesting action spectroscopy of single conjugated polymer nanowires.

We study exciton migration in single molecular nanowires, dye-endcapped multichromophoric conjugated polymers, as a function of excitation energy. This approach reveals the actual molecular absorption properties, uncovering the molecules within an ensemble and the chromophores within a molecule which contribute to absorption at a given wavelength. As the excitation energy is raised, an increasing number of polymers exhibit energy transfer suggesting that, in contrast to the emission spectrum, the absorption of a single chain under energy transfer conditions can be very broad even at 5 K. At the same time, the polarization anisotropy in excitation decreases due to an increase in the number of noncolinear chromophores involved in absorption. Power and wavelength-dependent measurements clearly discern the exciton blockade effect that gives rise to strong fluctuations of energy transfer. Although the polymer and endcap constitute nominally discrete spectroscopic entities, we are able to identify a subtle influence of the primary backbone exciton energy on the ultimate endcap emission. This demonstration of interchromophoric cooperativity provides a direct realization of how nonradiative energy dissipation in one nanoscale unit influences the spectroscopy of another.

Simultaneous Raman and fluorescence spectroscopy of single conjugated polymer chains.

Simultaneous surface enhanced Raman scattering (SERS) and fluorescence is demonstrated from single conjugated polymer chains. As resonance enhancement of SERS depends on the spectral overlap of the polymer's absorption and the incident laser, resonance Raman and fluorescence effectively probe the absorbing and emitting part of the polymer, respectively. The optical phonon energies change along the polymer chain, providing a window to spatially track excited state relaxation. Whereas a mean spatial redistribution of the excitation is witnessed by a change in vibronic fingerprint following interchromophoric energy transfer, intrachromophoric exciton self-trapping leaves the vibrations unchanged.

Spin-conserving carrier recombination in conjugated polymers.

The ultimate efficiency of polymer light-emitting diodes is limited by the fraction of charges recombining in the molecular singlet manifold. We address the question of whether this fraction can principally exceed the fundamental limit set down by spin statistics, which requires the possibility of spin changes during exciton formation. Sensitized phosphorescence at 4-300 K enables a direct quantification of spin conversion in coulombically bound electron-hole pairs, the precursors to exciton formation. These are stabilized in external electric fields over times relevant to carrier transport, capture and recombination in devices. No interconversion of exciton intermediates between singlet and triplet configurations is observed. Static magnetic fields are equally unable to induce spin mixing in electroluminescence. Our observations imply substantial exchange splitting at all times during carrier capture. Prior statements regarding increased singlet yields above 25% merely on the basis of higher singlet than triplet formation rates should therefore be re-examined.