Preparation of Ordered Nanoporous Indium Tin Oxides with Large Crystallites and Individual Control over Their Thermal and Electrical Conductivities

Metal oxides are considered suitable candidates for thermoelectric materials owing to their high chemical stabilities. The formation of ordered nanopores within these materials, which decreases thermal conductivity (kappa), has attracted significant interest. However, the electrical conductivity (sigma) of reported nanoporous metal oxides is low, owing to electron scattering at the thin pore walls and many grain boundaries formed by small crystallites. Therefore, a novel synthesis method that can control pore walls while forming relatively large crystallites to reduce kappa and retain sigma is required. In this study, we used indium tin oxide (ITO), which is a typical example among metal oxides with high sigma. Nanoporous ITOs with large crystallite sizes of several hundred nanometers and larger were successfully prepared using indium chloride as a source of indium. The pore sizes were varied using colloidal silica nanoparticles with different particle sizes as templates. The crystal phase and nanoporous structure of ITO were preserved after spark plasma sintering at 723 K and 80 MPa. The kappa was significantly lower than that reported for bulk ITO due to the phonon scattering caused by the nanoporous structure and thin pore walls. There was a limited decrease in sigma even with high porosity. These findings show that kappa and sigma are independently controllable through the precise control of the structure. The control of the thickness of the pore walls at tens of nanometers was effective for the selective scattering of phonons, while almost retaining electron mobility. The remarkable preservation of sigma was attributed to the large crystallites that maintained paths for electron conduction and decreased electron scattering at the grain boundaries.

Automated summary

Metal oxides, particularly indium tin oxide (ITO), are promising candidates for thermoelectric materials due to their high chemical stabilities. In this study, nanoporous ITOs with large crystallite sizes were successfully prepared using indium chloride as a source of indium and colloidal silica nanoparticles as templates. The controlled pore structure significantly reduced thermal conductivity while maintaining electrical conductivity, showing the potential for independent control of these properties in thermoelectric materials.