Exploring seebeck-coefficient fluctuations in endohedral-fullerene, single-molecule junctions

For the purpose of creating single-molecule junctions, which can convert a temperature difference ΔT into a voltage ΔV via the Seebeck effect, it is of interest to screen molecules for their potential to deliver high values of the Seebeck coefficient S = -ΔV/ΔT. Here we demonstrate that insight into molecular-scale thermoelectricity can be obtained by examining the widths and extreme values of Seebeck histograms. Using a combination of experimental scanning-tunnelling-microscopy-based transport measurements and density-functional-theory-based transport calculations, we study the electrical conductance and Seebeck coefficient of three endohedral metallofullerenes (EMFs) Sc₃N@C₈₀, Sc₃C₂@C₈₀, and Er₃N@C₈₀, which based on their structures, are selected to exhibit different degrees of charge inhomogeneity and geometrical disorder within a junction. We demonstrate that standard deviations in the Seebeck coefficient σ_S of EMF-based junctions are correlated with the geometric standard deviation σ and the charge inhomogeneity σ. We benchmark these molecules against C₆₀ and demonstrate that both σ, σ are the largest for Sc₃C₂@C₈₀, both are the smallest for C₆₀ and for the other EMFs, they follow the order Sc₃C₂@C₈₀ > Sc₃N@C₈₀ > Er₃N@C₈₀ > C₆₀. A large value of σ is a sign that a molecule can exhibit a wide range of Seebeck coefficients, which means that if orientations corresponding to high values can be selected and controlled, then the molecule has the potential to exhibit high-performance thermoelectricity. For the EMFs studied here, large values of σ are associated with distributions of Seebeck coefficients containing both positive and negative signs, which reveals that all these EMFs are bi-thermoelectric materials.