Surface enhanced raman spectroscopy for ultra-sensitive detection of energetic materials

Abstract

The prospect of ultra-sensitive detection of molecular species, particularly those of energetic materials, has prompted the present research initiative. The combination of metal surface nano-technology and Raman spectroscopy has given rise to ‘Surface Enhanced Raman Spectroscopy’ (SERS). This is a very sensitive technique and has proved to be capable of detecting a single molecule. SERS was demonstrated by recording Raman spectra of the sample molecules adsorbed on various specially prepared SER-active surfaces both in the form of a colloidal suspension and on the solid roughened surfaces. Using a gold colloidal suspension, pyridine has been detected down to 10-11 molar (M) concentration. A silver slab was roughened to a dimension of a nano-scale by etching in nitric acid solution to make SER-active surface. Pentaerythritol Tetranitrate (PETN) explosive was detected using this surface after its 10-2 M solution was dropped, dried and washed (of any residue) from the surface. Lithographically engineered silver structures in the form of nanoarrays having a number of silver structures of approximately 106 in a region of 0.1 mm2 have been used for SERS. The major noise contribution to the scattering from impurities in an ordinary glass substrate has been eliminated by replacing glasses as substrates with pure quartz discs. The headspace vapours from peroxide explosives, Triacetone Triperoxide (TATP) and Hexamethylene Triperoxide Diamine (HMTD), were detected at approximately 70 parts per million (ppm) and 0.3 ppm concentrations respectively using a portable commercial Raman Spectrometer. PETN was also detected from its headspace vapour at about 18 parts per trillion (ppt) in spite of it having a much lower vapour pressure. The possibility of desorption of adsorbed molecules from a nano-structured surface by laser irradiation has been demonstrated experimentally with the aim of reusability of SER-active surfaces. Also demonstrated was the enhancement in Raman intensity through resonance Raman effect spectroscopy for the future use in surface enhanced resonance Raman spectroscopy (SERRS).