As circuitry approaches single nanometer length scales, it is important to predict the stability of metals at these scales. The behavior of metals at larger scales can be predicted based on the behavior of dislocations, but it is unclear if dislocations can form and be sustained at single nanometer dimensions. Here, we report the formation of dislocations within individual 3.9 nm Au nanocrystals under nonhydrostatic pressure in a diamond anvil cell. We used a combination of x-2 ray diffraction, optical absorbance spectroscopy, and molecular dynamics simulation to characterize the defects that are formed, which were found to be surface-nucleated partial dislocations. These results indicate that dislocations are still active at single nanometer length scales and can lead to permanent plasticity. Main text:
Pseudoelasticity in metal nanocrystals allows for shape recovery from strains much larger than their bulk counterparts. This fascinating property could be used to engineer self-healing or reconfigurable materials, but to take full advantage of its possibilities, a deeper understanding of its mechanism and limitations is needed. For instance, it is unknown whether room-temperature pseudoelasticity can occur in all metal nanocrystals without the introduction of plastic damage. Here we report the use of nonhydrostatic compression of gold nanocrystals in a diamond anvil cell to a range of maximum pressures, up to 11.4 GPa. Optical absorbance spectroscopy of the localized surface plasmon resonance is used to noninvasively monitor changes in particle shape and crystallinity, as indicated by the plasmon resonance peak position and intensity, respectively. We find that while complete shape recovery occurs following compression to all pressures tested, irreversible crystalline defects are only introduced above a threshold of ∼2.5 GPa. In this way, we establish the capacity of gold nanocrystals to undergo complete pseudoelastic shape recovery following compression under moderate loads as well as the onset of limited pseudoelastic behavior at higher loads. This work lays a foundation for future investigations of the limits of pseudoelastic deformation in a wide variety of metal nanocrystals.
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