Ultrafast intramolecular exciton splitting dynamics in isolated low-band-gap polymers and their implications in photovoltaic materials design

Record-setting organic photovoltaic cells with PTB polymers have recently achieved ~8% power conversion efficiencies (PCE). A subset of these polymers, the PTBF series, has a common conjugated backbone with alternating thieno[3,4-b]thiophene and benzodithiophene moieties but differs by the number and position of pendant fluorine atoms attached to the backbone. These electron-withdrawing pendant fluorine atoms fine tune the energetics of the polymers and result in device PCE variations of 2-8%. Using near-IR, ultrafast optical transient absorption (TA) spectroscopy combined with steady-state electrochemical methods we were able to obtain TA signatures not only for the exciton and charge-separated states but also for an intramolecular ("pseudo") charge-transfer state in isolated PTBF polymers in solution, in the absence of the acceptor phenyl-C(61)-butyric acid methyl ester (PCBM) molecules. This led to the discovery of branched pathways for intramolecular, ultrafast exciton splitting to populate (a) the charge-separated states or (b) the intramolecular charge-transfer states on the subpicosecond time scale. Depending on the number and position of the fluorine pendant atoms, the charge-separation/transfer kinetics and their branching ratios vary according to the trend for the electron density distribution in favor of the local charge-separation direction. More importantly, a linear correlation is found between the branching ratio of intramolecular charge transfer and the charge separation of hole-electron pairs in isolated polymers versus the device fill factor and PCE. The origin of this correlation and its implications in materials design and device performance are discussed.     

Ultrafast wavelength-dependent lasing-time dynamics in single ZnO nanotetrapod and nanowire lasers

The ultrafast lasing dynamics of single zinc oxide nanotetrapods and nanowires are investigated by two-color femtosecond excitation/optical injection spectroscopy. The transient spectral gain induced by time-delayed optical injection pulses (400 nm) is used to investigate the spectrally and temporally resolved lasing properties in a single tetrapod or nanowire laser excited by 267-nm pulses. The lasing output pulse exhibits a faster lasing decay time than the carrier decays due to the superlinear dependence of the lasing on the carrier density. Lasing at the low-energy side of the gain bandwidth (392 nm) has a full width at half maximum (fwhm) for stimulated emission of 1.7 ps. Lasing at 390 nm, the high-energy side of the gain bandwidth, has a fwhm of 2.1 ps for a single example nanowire. The change in lasing dynamics as a function of wavelength is affected by band gap renormalization, since lasing in the electron-hole plasma regime depends not only on the carrier density but also on the band gap shift with carrier density.