Unprecedented Enhancement of Thermoelectric Power Factor Induced by Pressure in Small-Molecule Organic Semiconductors

Establishing the relationship between pressure and heat-electricity interconversion in van der Waals bonded small-molecule organic semiconductors is critical not only in designing flexible thermoelectric materials, but also in developing organic electronics. Here, based on first-principles calculations and using naphthalene as a case study, an unprecedented elevation of p-type thermoelectric power factor induced by pressure is demonstrated; and the power factor increases by 267% from 159.5 µW m^-1 K^-2 under ambient conditions to 585.8 µW m^-1 K^-2 at 2.1 GPa. The underlying mechanism is attributed to the dramatic inhibition of lattice-vibration-caused electronic scattering. Furthermore, it is revealed that both restraining low-frequency intermolecular vibrational modes and increasing intermolecular electronic coupling are two essential factors that effectively suppress the electron-phonon scattering. From the standpoint of molecular design, these two conditions can be achieved by extending the π-conjugated backbones, introducing long alkyl sidechains to the π-cores, and substituting heteroatoms in the π-cores.