Guiding the self-assembly of colloidal diamond

TL;DR

This study uses molecular dynamics simulations to identify optimal conditions for the self-assembly of colloidal cubic diamond structures, focusing on depletion and DNA-mediated interactions to guide crystal formation.

Contribution

It reveals how the balance of depletion interaction strength and range influences the nucleation and stability of colloidal cubic diamond, providing a pathway for targeted self-assembly.

Findings

Optimal depletion conditions promote stable cubic diamond nucleation.

Strong short-range depletion leads to gel or network formation.

Internal structure varies with arrest, affecting fractal dimension and ring strain.

Abstract

The assembly of colloidal cubic diamond is a challenging process since the shape and interaction parameters and the thermodynamic conditions where this structure is stable are elusive. The simultaneous use of shape-anisotropic particles and strong directional interactions has proven to be a successful path to exclusively nucleate this structure. Here, using molecular dynamics simulations, we explore in detail the conditions where nucleation of cubic diamond from tetrahedral building blocks is favored. In particular, we focus on the effect of depletion and DNA-mediated interactions to form and stabilize this cubic diamond crystal. We find that a particular balance between the strength and range of the depletion interactions enhances the self-assembly of stable cubic diamond, leading to a narrow region where this structure is nucleated. Moreover, we determine that stronger short-range depletion attractions may arrest the system leading to the formation of percolating diamond networks or fully disordered gel structures. Accordingly, the internal arrangements of these structures exhibit a distinct variation in terms of fractal dimension and the presence of six-membered rings that increasingly acquire internal strain as the arrest gets more pronounced. With these results we provide a clear route for the self-assembly of cubic colloidal diamond, towards the realization of crystals with superior photonic properties.