Conformational Relaxation Dynamics of Poly(3-hexylthiophene) Photoexcited in Solution as Studied by Femtosecond...

When a conjugated polymer is photoexcited in solution, its effective conjugation length in the singlet exciton state often increases through the conformational relaxation of the polymer main chain and/or hopping of the excitation. We measured femtosecond time-resolved near-IR stimulated Raman spectra of poly(3-hexylthiophene) (P3HT) photoexcited in four organic solvents for understanding the dynamics of the exciton elongation through the conformational relaxation separately from that through the exciton hopping. In the ring CC stretch frequency region, a band appears at around 1415 cm^-1 and decays, while a new band rises at around 1370 cm^-1. The average time constant of the change is estimated to be 8.7-19 ps and correlated almost linearly with the viscosity of the solvents. These results suggest that the main chain of P3HT in the singlet exciton state relaxes from a twisted form to a planar form in the 0-100 ps range when it surmounts an activation barrier of 5.8-7.8 kJ mol^-1, generated possibly by the steric effect of the hexyl side group. When the rise of the 1370 cm^-1 band is analyzed in detail, it is reproduced with two exponential rise functions with time constants of 0-3.3 and 16-22 ps. The two rise components suggest that a portion of P3HT forms a cluster in solution, while the other portion of P3HT is isolated.