Controlling Crystal Texture in Programmable Atom Equivalent Thin Films

DNA is a powerful tool in the directed assembly of nanoparticle based superlattice materials, as the predictable nature of Watson Crick base pairing allows DNA-grafted particles to be programmably assembled into unit cells that arise from the complete control of nanoparticle coordination environment within the lattice. However, while the local environment around each nanoparticle within a superlattice can be precisely dictated, the same level of control over aspects of crystallite structure at the meso- or macroscale (e.g., lattice orientation) remains challenging. This study investigates the pathway through which DNA-functionalized nanoparticles bound to a DNA-functionalized substrate reorganize upon annealing to synthesize superlattice thin films with restricted orientation. Preferential alignment with the substrate occurs because of the energetic stabilization of specific lattice planes at the substrate interface, which drives the aligned grains to nucleate more readily and grow through absorption of surrounding grains. Crystal orientation during lattice reorganization is shown to be affected by film thickness, lattice symmetry, DNA sequence, and particle design. Importantly, judicious control over these factors allows for rational manipulation over crystalline texture in bulk films. Additionally, it is shown that this level of control enables a reduction in nanoscale symmetry of preferentially aligned crystallites bound to an interface through anisotropic thermal compression upon cooling. Ultimately, this investigation highlights the remarkable interplays between nanoscale building blocks and mesoscale orientation, and expands the structure-defining capabilities of DNA-grafted nanoparticles.