The influence of nanostructuring and quantum confinement on the thermoelectric properties of materials has been extensively studied. While this has made possible multiple breakthroughs in the achievable figure of merit, classical confinement, and its effect on the local Seebeck coefficient has mostly been neglected, as has the Peltier effect in general due to the complexity of measuring small temperature gradients locally. Here we report that reducing the width of a graphene channel to 100 nm changes the Seebeck coefficient by orders of magnitude. Using a scanning thermal microscope allows us to probe the local temperature of electrically contacted graphene two-terminal devices or to locally heat the sample. We show that constrictions in mono- and bilayer graphene facilitate a spatially correlated gradient in the Seebeck and Peltier coefficient, as evidenced by the pronounced thermovoltage V_th and heating/cooling response T_Peltier, respectively. This geometry dependent effect, which has not been reported previously in 2D materials, has important implications for measurements of patterned nanostructures in graphene and points to novel solutions for effective thermal management in electronic graphene devices or concepts for single material thermocouples.

Although it was demonstrated that discrete molecular levels determine the sign and magnitude of the thermoelectric effect in single-molecule junctions, full electrostatic control of these levels has not been achieved to date. Here, we show that graphene nanogaps combined with gold microheaters serve as a testbed for studying single-molecule thermoelectricity. Reduced screening of the gate electric field compared to conventional metal electrodes allows control of the position of the dominant transport orbital by hundreds of meV. We find that the power factor of graphene-fullerene junctions can be tuned over several orders of magnitude to a value close to the theoretical limit of an isolated Breit-Wigner resonance. Furthermore, our data suggest that the power factor of an isolated level is only given by the tunnel coupling to the leads and temperature. These results open up new avenues for exploring thermoelectricity and charge transport in individual molecules and highlight the importance of level alignment and coupling to the electrodes for optimum energy conversion in organic thermoelectric materials.