Macroscopic Superlattice Membranes Self‐Assembled from Gold Nanobipyramids with Precisely Tunable Tip Arrangements for SERS

A persistent challenge in utilizing Au nanocrystals for surface‐enhanced Raman spectroscopy (SERS) lies in achieving controllable superstructures that maximize SERS performance. Here, a novel strategy is proposed to enhance the SERS performance by precisely adjusting the tip arrangements of Au nanobipyramids (BPs) in two‐dimensional (2D) superlattices (SLs). This is achieved through ligand‐exchange of Au BPs, followed by liquid‐air interfacial assembly, resulting in large‐area, transferrable SL membranes. The key to controlling the arrangement of Au BPs in the SLs is the regulation of the amount of free ligands added during self‐assembly, which allows for the precise formation of various configurations such as tilted SLs, tip‐on‐tip SLs, and tip‐to‐tip SLs. Among these configurations, tip‐on‐tip SLs exhibit the highest enhancement factor for SERS, reaching an impressive value of 1.95×108, with uniform and consistent SERS signals across a large area. The experimental findings are further corroborated by simulations using the finite element method. This study establishes an efficient method for engineering the microstructure of 2D SLs composed of Au BPs, highlighting the importance of fine‐tuning the tip arrangements of Au BPs to regulate SERS performance. A simple and efficient strategy is proposed to fabricate macroscopic two‐dimensional superlattice (SL) membranes composed of Au nanobipyramids, the microstructure and tip arrangements of which can be precisely tailored by adjusting the amount of free ligands added during self‐assembly. Among various SLs, the tip‐on‐tip SLs exhibit the highest enhancement factor for surface‐enhanced Raman spectroscopy (SERS), reaching an impressive value of 1.95×108, with uniform and consistent SERS signals across a large area.