Bimetallic Ag–Cu Alloy Microflowers as SERS Substrates with Single-Molecule Detection Limit

Bimetallic Ag–Cu alloy microflowers with tunable surface compositions were fabricated as surface-enhanced Raman spectroscopy (SERS) substrates with a limit of detection in the zeptomolar range for the analyte molecule rhodamine 6G (R6G). The substrates were prepared on a glass coverslip through a bottom-up strategy by simple thermolysis of metal-alkyl ammonium halide precursors. The reaction temperature and composition of the alloy were varied sequentially to find out the maximum SERS efficiency from the substrates. While UV–vis spectroscopy was employed to characterize the optical properties of the substrates, the bulk and surface compositions of the microflowers were determined using energy-dispersive X-ray fluorescence (ED-XRF) and X-ray photoelectron spectroscopy (XPS) techniques, respectively. Also, the structural and morphological characterizations of the substrates were performed by X-ray diffraction and scanning electron microscope (SEM), respectively. For alloys, the ED-XRF studies confirmed that the bulk compositions matched with the feed ratio, while the surface compositions were found to be rich in copper in the form of both elementary copper and copper oxide, as revealed by XPS studies. From the efficiency studies for different compositions prepared, it was found that 10% Ag–Cu alloy microflowers produced the maximum SERS intensity for resonant R6G molecules as probes. In fact, R6G evidences a 50-fold enhancement in SERS spectra with 10% alloy microflowers as against pure Ag microflowers. Using 1, 2, 3-benzotriazole as a nonresonant Raman probe, uniform enhancement factors on the order of ≈108 were achieved from different parts of the 10% Ag–Cu alloy microflower. The same substrate showed excellent Raman response for detecting R6G at very low concentrations such as 10 zM, leading to detection and analysis of SERS spectra from a single R6G molecule.