Ultrafast Time-resolved Photoluminescence Spectroscopy Research Articles

Effect of Multiple Adduct Fullerenes on Microstructure and Phase Behavior of P3HT:Fullerene Blend Films for Organic Solar Cells

The bis and tris adducts of [6,6]phenyl-C(61)-butyric acid methyl ester (PCBM) offer lower reduction potentials than PCBM and are therefore expected to offer larger open-circuit voltages and more efficient energy conversion when blended with conjugated polymers in photovoltaic devices in place of PCBM. However, poor photovoltaic device performances are commonly observed when PCBM is replaced with higher-adduct fullerenes. In this work, we use transmission electron microscopy (TEM), steady-state and ultrafast time-resolved photoluminescence spectroscopy (PL), and differential scanning calorimetry (DSC) to probe the microstructural properties of blend films of poly(3-hexylthiophene-2,5-diyl) (P3HT) with the bis and tris adducts of PCBM. TEM and PL indicate that, in as-spun blend films, fullerenes become less soluble in P3HT as the number of adducts increases. PL indicates that upon annealing crystallization leads to phase separation in P3HT:PCBM samples only. DSC studies indicate that the interactions between P3HT and the fullerene become weaker with higher-adduct fullerenes and that all systems exhibit eutectic phase behavior with a eutectic composition being shifted to higher molar fullerene content for higher-adduct fullerenes. We propose two different mechanisms of microstructure development for PCBM and higher-adduct fullerenes. P3HT:PCBM blends, phase segregation is the result of crystallization of either one or both components and is facilitated by thermal treatments. In contrast, for blends containing higher adducts, the phase separation is due to a partial demixing of the amorphous phases. We rationalize the lower photocurrent generation by the higher-adduct fullerene blends in terms of film microstructure.

Effects of reabsorption and spatial trap distributions on the radiative quantum efficiencies of ZnO

Ultrafast time-resolved photoluminescence spectroscopy following one- and two-photon excitation of ZnO powder is used to gain unprecedented insight into the surprisingly high external quantum efficiency of its "green" defect emission band. The role of exciton diffusion, the effects of reabsorption, and the spatial distributions of radiative and nonradiative traps are comparatively elucidated for the ultraviolet excitonic and "green" defect emission bands in both unannealed, nanometer-sized ZnO powders and annealed, micrometer-sized ZnO:Zn powders. We find that the primary mechanism limiting quantum efficiency is surface recombination because of the high density of nonradiative surface traps in these powders. It is found that unannealed ZnO has a high density of bulk nonradiative traps as well, but the annealing process reduces the density of these bulk traps while simultaneously creating a high density of green-emitting defects near the particle surface. The data are discussed in the context of a simple rate equation model that accounts for the quantum efficiencies of both emission bands. The results indicate how defect engineering could improve the efficiency of ultraviolet-excited ZnO:Zn-based white light phosphors.

Femtosecond spectroscopy of carrier-spin relaxation in GaAs-AlxGa1-xAs quantum wells.

We investigate the spin relaxation of optically excited charge carriers in a variety of GaAs-${\mathrm{Al}}_{\mathit{x}}$${\mathrm{Ga}}_{1\mathrm{\ensuremath{-}}\mathit{x}}$As quantum wells and superlattices at low temperatures by ultrafast time-resolved photoluminescence spectroscopy. Structures with uniform static optical properties show a markedly varied spin scattering in the time domain, thereby requiring a series of studies with systematically modified epitaxial growth conditions. A multiexponential spin relaxation is seen in quantum wells with a fast initial component of less than 1 ps and a subsequent relaxation within \ensuremath{\sim}150 ps. For the same growth conditions, the polarization decay time in superlattices approaches bulk values, indicating a dimensionality dependence of the spin scattering.