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Thermodynamic Analysis of Multiply Twinned Particles: Surface Stress Effects
In nanoparticle technologies, such
as SERS, fuel cell catalysis
and data storage, icosahedral and decahedral nanoparticles, owing
to their defect structure, provide higher functionality than their
single-crystal Wulff counterparts. However, precise control on the
yield of multiply twinned structures during solution synthesis has
been challenging. In particular, it is difficult to synthesize icosahedral
structures due to the high volumetric strain energy associated with
the disclination defects and the transition to decahedral morphologies.
In this Letter, we elucidate the role of surface stresses in influencing
the thermodynamic stability of multiply twinned particles. Increasing
the surface stresses inhibits the formation of decahedral structures
and increases the likelihood of synthesizing metastable icosahedral
particles. Analogously, large decahedral particles may be stabilized
by decreasing the surface stresses. Therefore, by tailoring the solution
chemistry to influence the surface stresses, greater control over
the synthesis of multiply twinned structures can be achieved