Hierarchical Laser-Patterned Silver/Graphene Oxide Hybrid SERS Sensor for Explosive Detection

We demonstrate an ultrafast laser-ablated hierarchically patterned silver nanoparticle/graphene oxide (AgNP/GO) hybrid surface-enhanced Raman scattering (SERS) substrate for highly sensitive and reproducible detection of an explosive marker 2,4-dinitrotoluene (2,4-DNT). A hierarchical laser-patterned silver sheet (Ag–S) is achieved by ultrafast laser ablation in air with pulse energies of 25, 50, and 100 μJ. Multiple laser pulses at a wavelength of 800 nm and a pulse repetition rate of 50 fs at 1 kHz are directly focused on Ag–S to produce and deposit AgNPs onto Ag–S. The surface morphology of ablated Ag–S was evaluated using atomic force microscopy, optical profilometry, and field emission scanning electron microscopy (FESEM). A rapid increase in the ablation rate with increasing laser energy was observed. Selected area Raman mapping is performed to understand the intensity and size distribution of AgNPs on Ag–S. Further, GO was spin-coated onto the AgNPs produced by ultrafast ablation on Ag–S. The hierarchical laser-patterned AgNP/GO hybrid structure was characterized using FESEM, high-resolution transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. Further, hierarchical laser-patterned AgNP/GO hybrid structures have been utilized as SERS-active substrates for the selective detection of 2,4-DNT, an explosive marker. The developed SERS-active sensor shows good stability and high sensitivity up to picomolar (pM) concentration range with a Raman intensity enhancement of ∼10¹⁰ for 2,4-DNT. The realized enhancement of SERS intensity is due to the cumulative effect of GO coated on Ag–S as a proactive layer and AgNPs produced by ultrafast ablation.