The assembly of mixtures of nanoparticles with different properties into a binary nanoparticle superlattice (BNSL) provides a route to fabricate novel classes of materials with properties emerging from the choice of the building blocks. The common theoretical approach based on the hard-spheres model predicts crystallization of only a few metastable binary superstructures (NaCl, AlB 2 or the AB13). Recently [Shevchenko, E. V.; Talapin, D. V.; O'Brien, S.; Murray, C. B. Nature2006; 439, 55.)], it has been demonstrated that with the use of a combination of semiconducting, metallic, and magnetic nanoparticles, a variety of novel BNSL structures were formed, where at least 10 were low density structures that have not been previously reported. While some of the structures can be explained by the addition of electrostatic interactions, it is clear that at the nanometer scale one needs to consider other influences, such as van der Waals forces, steric effects, etc. Motivated by those experiments, we study, using Monte Carlo simulations, the phase behavior of binary mixtures of nanoparticles interacting via a combination of hard-core electrostatics and van der Waals forces. We include a tuning parameter that can be used to balance between electrostatic and dispersion interactions and study the phase behavior as a function of the different charges and size ratios of the nanoparticles. The results indicate that at the nanoscale, both electrostatic and dispersion interactions are necessary to explain the experimental observed BNSL structures.
- Monte Carlo simulations
- binary crystals
- dispersion and electrostatic interactions
- free energy