Structural characterization of sputtered hydrogenated amorphous carbon films by solid state nuclear magnetic resonance

Abstract

Solid state nuclear magnetic resonance (NMR) methods have been used to investigate the effect of H content on the structure of sputtered hydrogenated amorphous carbon a-C:H films. Carbon-13 NMR spectra of a-C:H consist of two broad peaks at 135 and 40 ppm, which correspond to the sp2 and sp3 carbons, respectively. Surprisingly, the sp2 /sp 3 carbon ratio (2.0±0.3) is relatively independent of the H content in the range of 13%-35%. Hence, all a-C:H films contain approximately 66% graphitelike sp2 carbon. Cross polarization and spectral editing experiments reveal that the nonprotonated (quaternary) sp3 carbon fraction reaches as high as 30% at low H concentrations of 13%-23%. As the H content exceeds 23%, however, quaternary carbon bonds are terminated by H atoms to form protonated sp3 carbons, such as methylene (CH2) and methine (CH). Our results show that the hardness of a-C:H correlates with the quaternary carbon fraction rather than the sp2/sp3 ratio, as commonly believed. We also report the first extensive studies of both H1 and 13C spin-lattice relaxation for sputtered a-C:H. Relaxation data for hydrogen and carbon indicate that the unpaired electrons are probably equally distributed among sp2 and sp3 carbons. Moreover, the number of unpaired electrons in the a-C:H samples is relatively independent of H content, as revealed by spin counting experiments. 13C and H1 magnetization recovery curves for samples with H content up to 28% can be fitted with a single exponential, which is in contrast to the biexponential behavior reported for plasma-enhanced chemical vapor deposition (PECVD) a-C:H films. Hence, our results for sputtered a-C:H films do not support the model of proton-rich and proton-deficient regions proposed for PECVD carbon. © 2008 American Institute of Physics.