Charge carrier generation in a conjugated polymer studied via ultrafast pump-push-probe experiments

Conjugated polymers find rapidly growing application in electroluminescent displays and are extensively studied for use in photovoltaics and laser diodes. For a wide range of conjugated materials ultrafast pump-probe experiments have revealed the excited state dynamics of singlet and triplet excitons as well as positively and negatively charged polarons. Charge carriers play a key role in all the above mentioned applications. However, there is yet no clear picture of the mechanisms which lead to their generation. Photocurrent excitation cross-correlation measurement on methyl-substituted ladder-type poly(para)phenyl (m-LPPP), a prototypical conjugated polymer with very appealing properties for the above mentioned applications, have suggested that charge carrier generation occurs preferentially from higher lying states during energy migration. Our approach to examining this mechanism consists of an innovative modification of the ultrafast time-resolved pump-probe technique

Tuning Intermolecular Interactions: A Study of the Structural and Vibrational Properties of p-Hexaphenyl under Pressure

Hydrostatic pressure is used to modulate the intermolecular interactions in the conjugated oligophenyl, parahexaphenyl. These interactions affect the structural properties and also cause changes in the molecular geometry that directly alter the electronic properties. We use Raman spectroscopy to investigate the nature of the structural changes. Our Raman studies in the temperature range of 12 K to 300 K, under pressures up to 70 kbar, indicate that the potential energy of two neighboring phenyl rings as a function of the torsional angle is W -shaped. The libration of the phenyl rings between the two minima of the W -shaped potential can be modulated by either promoting the molecule to a higher energy state (activation energy of 0.045 eV) by raising the temperature or by decreasing the intermolecular separation, which makes the potential more U -shaped. Both these situations make the molecule seem more planar. We infer the shape of the potential from the relative intensity of the inter-ring C-C stretch Raman mode at 1280 cm-1 to the C-H bending mode at 1220 cm-1 (I1280/I1220). These results are interpreted within the framework of ab initio electronic and vibrational spectra calculations of a biphenyl molecule. We have also conducted X-ray studies to check the sample purity