Size-Dependent Thermal Stability and Optical Properties of Ultra-Small Nanodiamonds Synthesized under High Pressure

Diamond properties down to the quantum-size region are still poorly understood. High-pressure high-temperature (HPHT) synthesis from chloroadamantane molecules allows precise control of nanodiamond size. Thermal stability and optical properties of nanodiamonds with sizes spanning range from < 1 to 8 nm are investigated. It is shown that the existing hypothesis about enhanced thermal stability of nanodiamonds smaller than 2 nm is incorrect. The most striking feature in IR absorption of these samples is the appearance of an enhanced transmission band near the diamond Raman mode (1332 cm-1). Following the previously proposed explanation, we attribute this phenomenon to the Fano effect caused by resonance of the diamond Raman mode with continuum of conductive surface states. We assume that these surface states may be formed by reconstruction of broken bonds on the nanodiamond surfaces. This effect is also responsible for the observed asymmetry of Raman scattering peak. The mechanism of nanodiamond formation in HPHT synthesis is proposed, explaining peculiarities of their structure and properties.

Automated summary

Properties of nanodiamonds in the quantum-size region, particularly their thermal stability and optical properties, are investigated. It is found that the existing hypothesis about enhanced thermal stability of nanodiamonds smaller than 2 nm is incorrect. The appearance of an enhanced transmission band and the asymmetry of the Raman scattering peak can be explained by the resonance of the diamond Raman mode with the continuum of conductive surface states, known as the Fano effect.