Evidence of hydrogen termination at grain boundaries in ultrananocrystalline diamond/hydrogenated amorphous carbon composite thin films synthesized via coaxial arc plasma

TL;DR

This study provides spectroscopic evidence that hydrogen atoms preferentially terminate grain boundary dangling bonds in ultrananocrystalline diamond/hydrogenated amorphous carbon films, potentially improving their electronic and optical properties for device applications.

Contribution

It demonstrates hydrogen incorporation at grain boundaries and its role in bond termination using multiple spectroscopic techniques, revealing chemical and structural changes.

Findings

Hydrogen preferentially incorporates at grain boundaries.

Hydrogenation transforms sp^2 to sp^3 carbon bonds.

Hydrogenation enhances optical and electrical properties.

Abstract

Ultranonocrystalline diamond/hydrogenated amorphous carbon composite thin films consist of three different components; ultrananocrystalline diamond crystallites, hydrogenated amorphous carbon, and grain boundaries between them. Since grain boundaries contain a lot of dangling bonds and unsaturated bonds, they would be a cause of carrier trap center degrading device performance in possible applications such as UV photo-detectors. We experimentally demonstrate hydrogen atoms preferentially incorporate at grain boundaries and terminate dangling bonds by means of several spectroscopic techniques. XPS measurements cannot detect quantitative transitions of sp^2- and sp^3-hybridized carbons in the films, resulting in 55-59 % of sp^3 contents. On the other hand, FT-IR and NEXAFS exhibit some variations of the amounts of certain carbon hybridization for sure. The former confirms the transformation from sp^2 to sp^3 hydrocarbons by ~10 % by additional hydrogenation, and the latter represents chemical configuration changes from {\pi}* C{\equiv}C and {\pi}* C=C to {\sigma}* C-H. These results can be an evidence of localized hydrogen at grain boundaries, which plays a part in terminating dangling bonds and unsaturated bonds, and they are correlated with the optical and electrical properties of the films investigated in some previous research. Our spectroscopic studies on the hydrogenation effects combined with the discussion on the optical and electrical characteristics confirm that the hydrogenation can be an effective tool of an enhancement of photovoltaic performance in the above sensing applications.