Side chain dynamics in semiconducting polymer MEH-PPV

The characteristic nanoscale dynamics of the alkyl side groups in the light-emitting polymer poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] have been investigated using quasi-elastic neutron scattering (QENS). The measurements were taken below the polymer's glass transition (T ≤ T_g ≃ 353 K), where the main backbone is in a rigid state and does not contribute to the broadening of the QENS signal. An analytical diffusion model consisting of a static term and two dynamical components, characterizing the flexible side groups, provide an excellent fit to the experimental data. The two observed dynamical processes are all localized in character, with no meaningful dependence on temperature. The faster process, with characteristic timescale of ∼18 ps at room temperature (RT), can be linked to the average mobility of the terminal protons of the alkyl chain, while the slower process, with characteristic timescale of ∼170 ps at RT, to those protons at the other end of the alkyl chain, closest to the backbone. While the fraction of mobile protons contributing to the QENS signal increases with increasing temperature, the characteristic timescale and confining volume within which the protons are able to move locally depend chiefly on the polymer conformational state.