Surface softening regulates size-dependent stiffness of diamond nanowires

Diamond nanowires (NWs) belong to an important class of nanoscale materials for their outstanding potential in mechanical, electrical, and thermal applications. However, their mechanical behavior under pristine and defective conditions remains less understood. This paper reveals a comprehensive understanding of the effective elastic behavior of diamond NWs, and it uncovers surface-softening as the dominant mechanism that regulates their effective behavior. We applied the force-based and energy-based approaches and constructed a comparative analysis to reveal the atomistic basis behind the diameter-dependent elastic properties of the nanowires. Our findings suggest the energy-based approach to produce physically meaningful results, whereas the widely used force-based scheme produces inconsistent size-dependent behavior. Results show that, with increasing diameter, the softening of the surface and the defective regimes decreases. As a direct consequence of the alteration in the softening state, the first-order elastic modulus increases with increasing diameter, whereas the second-order modulus decreases. Also, vacancy defects, even in very dilute concentrations, are found to substantially affect the elastic behavior of the nanowire. Furthermore, surface, core, and defective regimes exhibit very different roles in nanowires of different diameters: the surface regime acts as a softer regime and the core as stiffer, regardless of the diameter. Their cumulative effect is however dominated by the surface in smaller-diameter nanowire-but in wider diameter nanowires it is dominated by the core. As a result, the size-dependent behavior is strictly controlled by the softening state of the surface. The diameter-dependent elastic moduli show a power-law relation, which deviates substantially from the simple surface-to-volume ratio. These findings suggest surface-engineering as an important tool for modulating the effective behavior of brittle nanowires.