The present study investigates the complex relationship between nanostructures and microscale thermal transport in nanoporous thin films for energy applications. It experimentally and numerically demonstrates that the effective thermal conductivity of nanoporous materials can be tuned by controlling their nanoscale architectures including porosity, pore diameter, wall thickness, nanocrystal size, and crystallinity as well as surface passivation.
This study reports measurements of the cross-plane thermal conductivity of nanoporous thin films with various architectures between 25 and 315 K. Physics-based models combining phonon transport theory and effective medium approximations were developed to interpret the experimental data. Ordered mesoporous titania and silicon thin films were prepared based on evaporation-induced self-assembly method. Pure silica zeolite films were produced by either in-situ growth or by spin coating a zeolite nanoparticle suspension followed by crystal growth upon heating. These synthesized thin films were systematically and fully characterized. They featured ordered nanopores with porosity, pore diameter, and film thickness ranging from 30% to 59%, 0.5 to 25 nm, and 120 to 370 nm, respectively. Their dense matrix was amorphous, polycrystalline, or consisted of an aggregate of nanocrystals. The thermal conductivity of all synthesized nanoporous films increased monotonically with temperature within the temperature range considered. At low temperatures, the nanoporous films behaved like amorphous or strongly disordered materials and their thermal conductivity was proportional to Tn with n varied between 1 and 2.3. At high temperatures, the thermal conductivity increased slowly with temperature or reached a plateau due to strong phonon Umklapp scattering and the saturation of phonon modes. The presence of pores in amorphous mesoporous thin films had a purely geometrical effect by reducing the cross-sectional area through which heat can diffuse. By contrast, in crystalline mesoporous thin films the presence of pores also increased phonon scattering. In addition, the film thickness generally did not affect the measured thermal conductivity. Indeed, phonon scattering by pores and by nanocrystal grain boundary dominated over boundary scattering and were identified as the dominant scattering mechanisms for nanoscale energy transport in the synthesized nanoporous films.
This study further establishes that the effective thermal conductivity keff of crystalline nanoporous silicon was strongly affected not only by the porosity fv and the system's length Lz but also by the pore interfacial area concentration Ai. A modified effective medium approximation combining kinetic theory and the coherent potential approximation suggested that keff was proportional to (1–1.5 fv) and inversely proportional to the sum (A i/4+1/Lz). This scaling law was in excellent agreement with the thermal conductivity of nanoporous silicon predicted by molecular dynamics simulations for spherical pores as well as for cylindrical pores and vacancy defects.
Finally, this study demonstrated, using equilibrium molecular dynamics simulations, that surface passivation added another parameter for reducing the thermal conductivity of nanostructured materials. To do so, there should be strong acoustic vibrational modes coupling between surface and passivation atoms. For example, oxygen passivation reduced the thermal conductivity of nanoporous crystalline silicon. In addition, the effect of passivation reduced with temperature because of increasing contribution of Umklapp scattering.
These results could help establish new strategies to control the thermal conductivity of nanoporous materials for a wide range of applications including thermoelectric devices, supercapacitors, dye-sensitized solar cells, and hydrogen storage devices.