Fracture of crystalline silicon nanopillars during electrochemical lithium insertion.

From surface hardening of steels to doping of semiconductors, atom insertion in solids plays an important role in modifying chemical, physical, and electronic properties of materials for a variety of applications. High densities of atomic insertion in a solid can result in dramatic structural transformations and associated changes in mechanical behavior: This is particularly evident during electrochemical cycling of novel battery electrodes, such as alloying anodes, conversion oxides, and sulfur and oxygen cathodes. Silicon, which undergoes 400% volume expansion when alloying with lithium, is an extreme case and represents an excellent model system for study. Here, we show that fracture locations are highly anisotropic for lithiation of crystalline Si nanopillars and that fracture is strongly correlated with previously discovered anisotropic expansion. Contrary to earlier theoretical models based on diffusion-induced stresses where fracture is predicted to occur in the core of the pillars during lithiation, the observed cracks are present only in the amorphous lithiated shell. We also show that the critical fracture size is between about 240 and 360 nm and that it depends on the electrochemical reaction rate.