Seebeck effects in n-type and p-type polymers driven simultaneously by surface polarization and entropy differences based on conductor/polymer/conductor thin-film devices

This paper reports Seebeck effects driven by both surface polarization difference and entropy difference by using photoinduced intramolecular charge-transfer states in n-type and p-type conjugated polymers, namely IIDT and IIDDT, respectively, based on vertical conductor/polymer/conductor thin-film devices. We obtain large Seebeck coefficients of -898 μV/K from n-type IIDT and 1300 μV/K from p-type IIDDT when the charge-transfer states are generated by a white light illumination of 100 mW/cm², compared with the values of 380 and 470 μV/K in dark condition, respectively. Simultaneously, the electrical conductivities are increased from almost insulating state in dark condition to conducting state under photoexcitation in both n-type IIDT and p-type IIDDT based devices. The large Seebeck effects can be attributed to the following two mechanisms. First, the intramolecular charge-transfer states exhibit strong electron-phonon coupling, which leads to a polarization difference between high and low temperature surfaces. This polarization difference essentially forms a temperature-dependent electric field, functioning as a new driving force additional to entropy difference, to drive the energetic carriers for the development of Seebeck effects under a temperature difference. Second, the intramolecular charge-transfer states generate negative or positive majority carriers (electrons or holes) in the n-type IIDT or p-type IIDDT, ready to be driven between high and low temperature surfaces for developing Seebeck effects. On the basis of coexisted polarization difference and entropy difference, the intramolecular charge-transfer states can largely enhance the Seebeck effects in both n-type IIDT and p-type IIDDT devices. Furthermore, we find that changing electrical conductivity can switch the Seebeck effects between polarization and entropy regimes when the charge-transfer states are generated upon applying photoexcitation. Therefore, using intramolecular charge-transfer states presents an approach to develop thermoelectric effects in organic materials-based vertical conductor/polymer/conductor thin-film devices.