Diamond-coated ATR prism for infrared absorption spectroscopy of surface-modified diamond nanoparticles

► A novel tool for attenuated total reflectance (ATR) FTIR employing diamond-coated prism. ► Enhanced sensitivity, resolution and repeatability. ► IR absorption spectra characterizing surface moieties, in particular on plasma-oxidized and hydrogenated diamond nanoparticles. Linear antenna microwave chemical vapor deposition process was used to homogeneously coat a 7cm long silicon prism by 85nm thin nanocrystalline diamond (NCD) layer. To show the advantages of the NCD-coated prism for attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) of nanoparticles, we apply diamond nanoparticles (DNPs) of 5nm nominal size with various surface modifications by a drop-casting of their methanol dispersions. ATR-FTIR spectra of as-received, air-annealed, plasma-oxidized, and plasma-hydrogenated DNPs were measured in the 4000–1500cm−1 spectral range. The spectra show high spectral resolution, high sensitivity to specific DNP surface moieties, and repeatability. The NCD coating provides mechanical protection against scratching and chemical stability of the surface. Moreover, unlike on bare Si surface, NCD hydrophilic properties enable optically homogeneous coverage by DNPs with some aggregation on submicron scale as evidenced by scanning electron microscopy and atomic force microscopy. Compared to transmission FTIR regime with KBr pellets, direct and uniform deposition of DNPs on NCD-ATR prism significantly simplifies and speeds up the analysis (from days to minutes). We discuss prospects for in situ monitoring of surface modifications and molecular grafting.