Size Effects on Surface Chemistry and Raman Spectra of Sub‑5 nm Oxidized High-Pressure High-Temperature and Detonation Nanodiamonds

Understanding materials with dimensions down to a few nanometers is of major importance for fundamental science as well as prospective applications. Structural transformation and phonon-confinement effects in the nanodiamonds (NDs) have been theoretically predicted below 3 nm in size. Here, we investigate the effect of size on the surface chemistry, microscopic structure, and Raman scattering of high-pressure high-temperature (HPHT) and detonation nanodiamonds (DNDs) down to 2–3 nm. The surface and size of NDs are controlled by annealing in air and ultracentrifugation resulting in three ND fractions. Particle size distribution (PSD) of the fractions is analyzed by combining dynamic light scattering, analytical ultracentrifugation, small-angle X-ray scattering, X-ray diffraction, and transmission electron microscopy as complementary techniques. Based on the obtained PSD, we identify size-dependent and synthesis-dependent differences of ND properties. In particular, interpretation of Raman scattering on NDs is revisited. Comprehensive comparison of detonation and pure monocrystalline HPHT NDs reveals effects of diamond core size and defects, chemical and temperature (in)­stability, and limitations of current phonon confinement models. In addition, low-frequency Raman scattering in the 20–200 cm^–1 range is experimentally observed. The size dependence of this signal for both HPHT NDs and DNDs suggests that it may correspond to confined acoustic vibrational, “breathing-like” modes of NDs.