Pressing solids directly into sheets of plasmonic nanojunctions enables solvent-free surface-enhanced Raman spectroscopy

Abstract Often chemical analysis of solid materials begins with dissolving the sample in a solvent but this is undesirable, particularly if the physical form is important. In principle surface-enhanced Raman spectroscopy (SERS) should allow detection of solid analytes and offers attomolar sensitivity combined with molecular specificity. SERS requires the target molecules to sit in plasmonic hot-spots, which are normally nanojunctions, just a few nm across. This means that solid samples normally need to be dissolved in a solvent so they can diffuse into the enhancing region. Here, we show that SERS spectra of picograms of solid analytes can be directly obtained by pressing them into a flexible SERS substrate with a dense field of exposed nanojunction hot-spots anchored on its surface. We demonstrate that this can be a powerful tool for straightforward and non-destructive forensic analysis of layered materials (crossing ink lines), solid explosives and illicit drugs as well as for studying previously intractable samples such as pharmaceutical co-crystals, whose important solid state structure is lost when they are dissolved.