Unusual Raman Enhancement Effect of Ultrathin Copper Sulfide

Abstract In surface‐enhanced Raman spectroscopy (SERS), 2D materials are explored as substrates owing to their chemical stability and reproducibility. However, they exhibit lower enhancement factors (EFs) compared to noble metal‐based SERS substrates. This study demonstrates the application of ultrathin covellite copper sulfide (CuS) as a cost‐effective SERS substrate with a high EF value of 7.2 × 10 4 . The CuS substrate is readily synthesized by sulfurizing a Cu thin film at room temperature, exhibiting a Raman signal enhancement comparable to that of an Au noble metal substrate of similar thickness. Furthermore, computational simulations using the density functional theory are employed and time‐resolved photoluminescence measurements are performed to investigate the enhancement mechanisms. The results indicate that polar covalent bonds (Cu─S) and strong interlayer interactions in the ultrathin CuS substrate increase the probability of charge transfer between the analyte molecules and the CuS surface, thereby producing enhanced SERS signals. The CuS SERS substrate demonstrates the selective detection of various dye molecules, including rhodamine 6G, methylene blue, and safranine O. Furthermore, the simplicity of CuS synthesis facilitates large‐scale production of SERS substrates with high spatial uniformity, exhibiting a signal variation of less than 5% on a 4‐inch wafer.