Silver was deposited onto surfaces of GaN that were differently
nanostructured (by formation of individual nanopillars, bunches of
nanopillars, or hexagonal etch micropits). The different levels of
surface-enhanced Raman scattering (SERS) activity of the nanomaterials
obtained were compared by using them for the SERS detection of penicillin
G in milk. The lowest limit of detection (LOD) of penicillin G was
achieved for silver-covered GaN surfaces nanostructured with bunches
of nanopillars (LOD = 1.1 × 10–9 M). The penicillin
G LODs of other silver-covered GaN surfaces were higher, equal to
4.1 × 10–9 M for individual nanopillars, 7.3
× 10–8 M for hexagonal etch micropits, and
1.0 × 10–7 M for a flat GaN surface. SERS measurements
carried out for analytes having significantly different sizes of molecules
showed that the ratio of intensities of the SERS spectra measured
on a layer of silver clusters deposited on a highly developed GaN
surface or on a smooth GaN surface depends on the size of the analyte
molecule and on the metal-analyte affinity. The larger the molecule,
the smaller this ratio (for example, it was 9.5 for pyridine, 3.5
for penicillin G, and 1.5 for hemoglobin). These results show that
some “SERS hot spots” cannot be reached by large molecules.