Work

Pathway-Directed Symmetry of Binary Superlattices Crystallized from Polymer-Tethered Inorganic Nanoparticles

Year: 2026

Type: article

Abstract: Crystallization of two distinct colloidal building blocks into binary nanoparticle superlattices (BNSLs) offers an innovative strategy for preparing advanced functional materials with integrated and remarkable properties, enabling various applications in optoelectronics, catalysis and sensing. The symmetries and architectures of binary superlattices critically govern their intrinsic properties and primarily are dictated by thermodynamically stable and favorable structures. However, the construction of kinetically trapped metastable superlattices in non-equilibrium phases remains a formidable challenge. Here, we demonstrate a pathway-directed preparation of BNSLs crystallized from polymer-tethered gold nanoparticles at the two-dimensional interface, where internal symmetries and architectures are readily modulated through thermodynamic and kinetic control. Unlike conventional hexagonal packing in the lowest-energy state, the specific tic-tac-toe checkerboard and AB-type square lattices are achieved by precise kinetic control of the formation process. Moreover, the entropy-related parameter is proposed to quantitatively evaluate the influence of effective size of each component on the final symmetry of the BNSLs, providing guiding and significant phase diagrams of the acquired architectures. This pathway-controlled design of BNSLs transcends fundamental constraints in symmetry tunability inherent to thermodynamic crystallization, thereby establishing a new versatile paradigm for engineering functional BNSLs.

Source: Langmuir

DOI: 10.1021/acs.langmuir.5c05791