Nanodiamonds (ND) exhibit unique properties due to their small size and high surface-to-volume ratio compared to bulk diamonds. A reduction in crystal size also affects ND Raman spectra. The confinement of optical phonons in nanocrystals $\left(<10\text{nm}\right)$ results in asymmetrically broadened Raman lines, which are shifted toward lower wavenumbers. The phonon confinement model (PCM) relates the observed changes in the Raman spectra to the crystal size and can be used for size characterization at the nanoscale. While the PCM was successfully applied to a variety of materials including Si and BN, results remained unsatisfactory in the case of ND. In order to improve the agreement between the predictions of the model and experimental Raman spectra of ND, effects such as crystal size distribution, lattice defects, and the energy dispersion of the phonon modes were taken into consideration and incorporated into the PCM. This work has shown that phonon wave vectors from small vibrational domains lead to a broad shoulder peak at $\sim 1250{\text{cm}}^{-1}$, that is often observed in the Raman spectrum of ND.

• Received 10 May 2009

DOI:https://doi.org/10.1103/PhysRevB.80.075419