The Intercoupling of Thermal Transport and Mechanical Properties in Colloidal Nanocrystal Assemblies

Colloidal nanocrystals (NCs) are promising candidates for a wide range of applications (electronics, optoelectronics, photovoltaics, thermoelectrics, etc.). Mechanical and thermal transport property play very important roles in all of these applications. On one hand, mechanical robustness and high thermal conductivity are desired in electronics, optoelectronics, and photovoltaics. This improves thermomechanical stability and minimizes the temperature rise during the device operation. On the other hand, low thermal conductivity is desired for higher thermoelectric figure of merit (ZT). This dissertation demonstrates that ligand structure and nanocrystal ordering are the primary determining factors for thermal transport and mechanical properties in colloidal nanocrystal assemblies. To eliminate the mechanics and thermal transport barrier, I first propose a ligand crosslinking method to improve the thermal transport across the ligand-ligand interface and thus increasing the overall thermal conductivity of NC assemblies. Young’s modulus of nanocrystal solids also increases simultaneously upon ligand crosslinking. My thermal transport measurements show that the thermal conductivity of the iron oxide NC solids increases by a factor of 2-3 upon ligand crosslinking. Further, I demonstrate that, though with same composition, long-range ordered nanocrystal superlattices possess higher mechanical and thermal transport properties than disordered nanocrystal thin films. Experimental measurements along with theoretical modeling indicate that stronger ligand-ligand interaction in NC superlattice accounts for the improved mechanics and thermal transport. This suggests that NC/ligand arranging order also plays important roles in determining mechanics and thermal transport properties of NC assemblies. Lastly, I show that inorganic ligand functionalization could lead to tremendous mechanical enhancement (a factor of ~60) in NC solids. After ligand exchange and drying, the short inorganic Sn2S64- ligands dissociate into a few atomic layers of amorphous SnS2 at room temperature and interconnects the neighboring NCs. I observe a reverse Hall-Petch relation as the size of NC decreases. Both atomistic simulations and analytical phase mixture modeling identify the grain boundaries and their activities as the mechanic bottleneck.