Manfred J. Walter

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

An Upside of Asymmetry Advances in synthetic techniques have enabled the preparation of nanometer-scale semiconductors in a wide range of precise shapes and sizes, including core-shell morphologies that layer several different materials in the same particle. Such two-in-one motifs are promising for light-harvesting applications because they allow optically induced charge separation across the internal interface. Borys et al. (p. 1371) studied a series of rod-shaped cadmium sulfide–cadmium selenide hybrid particles using single-particle–resolved optical spectroscopy and found that smooth versus bulbous geometries produced distinct emission spectra. Further analysis of more complex, tetrapodal particles (with four arms aligned tetrahedrally) suggested that nonuniform geometries facilitate interfacial charge transfer by reducing the likelihood of electronic band misalignment. Single-particle spectroscopy suggests that non-uniform geometries favor efficient charge separation for light harvesting. 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.

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.

Formation of a defect-free π-electron system in single β-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 β-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.

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.

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.