Photoexcitations in polythiophene at high pressure

We report optical-absorption, photoluminescence (PL), and picosecond photoinduced absorption (PA) decay in films of poly-3-hexyl-thiophene at pressures up to 80 kbar. The spectral bands redshift nonlinearly with pressure and the PL intensity decreases markedly. Thermochromic transitions are completely inhibited at pressures as low as 14 kbar. The picosecond recovery of the PA decay at high pressure is similar to that of unpressed polythiophene, but has a power-law exponent consistent with more ordered chains at high pressure. These effects suggest changes with pressure in the chain conformation and in the electronic polarizability; no changes in the interchain transfer integral are observed.