How single conjugated polymer molecules respond to electric fields

Conjugated polymers find applications in a range of devices such as light-emitting diodes, field-effect transistors and solar cells. The elementary electronic response of these semiconductors to electric fields is understood in terms of nanoscale perturbations of charge density. We demonstrate a general breaking of spatial charge symmetry by considering the linear Stark effect in the emission of single chromophores on individual chains. Spectral shifts of several nanometres occur due to effective dipoles exceeding 10 D. Although the electric field does not ionize the exciton, some molecules exhibit field-induced intensity modulations. This quenching illustrates the equivalence of charge symmetry breaking and polaron-pair or charge-transfer-state formation, and provides a microscopic picture of permanent charging, which leads to doping and exciton dissociation in actual devices. In addition to using this tuneable emission in single-photon electro-optic modulators, hysteresis in the Stark shift suggests a route to designing nanoscale memory elements such as molecular switches.