It is generally accepted that chemically synthesized nanoparticles lose their ferroelectricity (spontaneous polarization) as the particles become smaller. In contrast, ball-milled ferroelectric nanoparticles have an enhanced ferroelectric response at remarkably small sizes (≤10 nm). Although prior theory suggests that surface stress influences ferroelectricity, the source of such a stress and how it physically influences ferroelectricity in zero-dimensional nanoparticles has remained a mystery. In this paper, we demonstrate that the top-down approach of wet ball-milling not only results in fragmented materials on the nanoscale, but it also is responsible for a mechanochemical synthesis of metal carboxylates forming at the nanoparticles' surface. We prove that the presence of such a compound with a particular type of binding mode chemisorbed at the nanoparticles' surface is responsible for producing surface stress. This surface stress results in a stabilization and dramatic enhancement of the spontaneous polarization, which is 5 times greater than that of the bulk material and 650 times greater than what is measured in materials fabricated using standard chemical synthesis techniques. The results of this study have further led to the development of a new process that produces ferroelectric nanoparticles (≤10 nm) with uniform shape and size using a combination of wet chemistry and mechanochemical synthesis.
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