Inorganically Connecting Colloidal Nanocrystals Significantly Improves Mechanical Properties

Understanding and characterizing the mechanical behavior of colloidal nanocrystal (NC) assemblies are important for developing nanocrystalline materials with exceptional mechanical properties for robust electronic, thermoelectric, photovoltaic, and optoelectronic devices. However, the limited ranges of Young's modulus, hardness, and fracture toughness (≲1-10 GPa, ≲50-500 MPa, and ≲10-50 kPa m^1/2, respectively) in as-synthesized NC assemblies present challenges for their mechanical stability and therefore their practical applications. In this work, we demonstrate using a combination of nanoindentation measurements and coarse-grained modeling that the mechanical response of assemblies of as-synthesized NCs is governed by the van der Waals interactions of the organic surface ligands. More importantly, we report tremendous ∼60× enhancements in Young's modulus and hardness and an ∼80× enhancement in fracture toughness of CdSe NC assemblies through a simple inorganic Sn₂S₆^4- ligand exchange process. Moreover, our observation of softening in nanocrystalline materials with decreasing CdSe NC diameter is consistent with atomistic simulations.