Improved synthesis of concave cubic gold nanoparticles and their applications for Raman analysis of surfaces

In this contribution, we present a modification of the procedure for producing concave cubic gold (cc-Au) nanoparticles; this modification significantly increases the homogeneity of the product obtained. The synthesis of cc-Au is carried out by the slow growth of seed nanostructures in a solution containing chloroauric acid, silver nitrate, ascorbic acid and hexadecyltrimethylammonium chloride. We show that, when nanoparticles synthesized in a solution containing both chloroauric acid and copper chloride (with the molar ratio equal to ca. 10 : 1) are used as seeds (instead of seeds formed without the addition of copper), one can observe a significant increase in the homogeneity of the cc-Au nanostructures formed. The resulting cc-Au, and cc-Au@Ag nanoparticles (cc-Au covered by a nanometric layer of silver) as well, have been used as plasmonic cores in nanoresonators dedicated for shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). To our knowledge, the SHINERS nanoresonators produced in this work display a homogeneity that is significantly better than that of any anisotropic SHINERS nanostructures previously synthesized without the subsequent complex process of purifying the nanoparticles. Concave cubic nanoparticles were about 5 times more efficient as electromagnetic nanoresonators than spherical nanostructures of a similar size formed from the same material.