“Atomic Force Masking” Induced Formation of Effective Hot Spots along Grain Boundaries of Metal Thin Films

We present an interesting phenomenon, "atomic force masking", which is the deposition of a few-nanometer-thick gold film on ultrathin low-molecular-weight (LMW) polydimethylsiloxane (PDMS) engineered on a polycrystalline gold thin film, and demonstrated the formation of hot spot based on SERS. The essential principle of this atomic force masking phenomenon is that an LMW PDMS layer on a single crystalline grain of gold thin film would repel gold atoms approaching this region during a second cycle of evaporation, whereas new nucleation and growth of gold atoms would occur on LMW PDMS deposited on grain boundary regions. The nanostructure formed by the atomic force masking, denoted here as "hot spots on grain boundaries" (HOGs), which is consistent with finite-difference time-domain (FDTD) simulation, and the mechanism of atomic force masking were investigated by carrying out systematic experiments, and density functional theory (DFT) calculations were made to carefully explain the related fundamental physics. Also, to highlight the manufacturing advantages of the proposed method, we demonstrated the simple synthesis of a flexible HOG SERS, and we used this substrate in a swabbing test to detect a common pesticide placed on the surface of an apple.