Morphology-Driven SERS Activation in TMDCs: A Dual-Mode Platform for Sensorics and Theranostics

The development of reproducible and stable plasmon-free substrates for surface-enhanced Raman scattering (SERS) is critical for practical applications in analytical chemistry. Transition metal dichalcogenides (TMDCs) have emerged as promising candidates due to their unique electronic properties, yet their performance is often constrained by the chemical inertness of their pristine basal planes. This work presents a systematic comparison of crystalline flakes and nanoparticles of tungsten diselenide (WSe₂) and tungsten ditelluride (WTe₂), prepared via liquid-phase ultrasonic exfoliation and non-equilibrium femtosecond pulsed laser ablation in liquid (PLAL), respectively. The results demonstrate that nanoparticle-based substrates consistently outperform their flake-based counterparts, achieving enhancement factors in the range of 104. The superior performance of the nanoparticles is hypothesized to originate from the synthesis-induced defects and high-curvature regions in the nanoparticles shell which facilitates efficient, defect-mediated charge transfer between the substrate and the analyte. At the same time, the inner polycrystalline volume conserves the important characteristics of the bulk counterparts like excitons in semiconducting WSe₂ and broadband absorption in semimetallic WTe₂, which unblocks the tunable photothermal colloidal response. The study establishes morphology engineering through non-equilibrium synthesis as a powerful and generalizable strategy for designing high-performance, dual-function colloidal platforms, offering a pathway toward robust and reproducible analytical systems.