Comparison of Electronic-Excitation-Induced Structural Modification of Carbon-Based Nanomaterials with that of Semiconductor Surfaces

Abstract

Modification by electronic excitation of semiconductor surfaces and carbon-related quasi-two-dimensional (2D) nanostructured materials, namely graphene, carbon nanotubes is reviewed. Defect creation in these materials takes place not by low-intensity photoirradiation, but by laser or electron irradiation. The defect creation processes are different from ordinary photochemical processes in molecules or in some solids like alkali halides, which can be modified by a localized exciton. It is pointed out that there are common features in defect creation by electronic excitation in semiconductor surfaces and carbon-related quasi-2D nanomaterials: the yield-intensity relation shows strong superlinearity for laser irradiation near the bandgap energies and linearity or weak superlinearity for higher energy electron or photon irradiation. These results are explained in terms of multi-hole localization, in which bonds are weakened more strongly and more energy is available upon recombination with trapped electrons in comparison with excitons. The multi-hole localized state is considered to be realized by the creation of dense excitons or by cascade excitation for laser irradiation and by multiple excitations or multiple exciton generation by single impacts for electron irradiation. The review includes also polymerization of C[Formula: see text] films by electronic excitation, which is induced by low-intensity photoirradiation as well as by laser or electron irradiation. The experimental observation that laser or electron irradiation polymerize C[Formula: see text] films differently from low-intensity photoirradiation is explained in terms of multi-hole localization similar to the defect formation mechanism. Although fragmentation of C[Formula: see text] is due to electronic excitation of the molecule, it is included in the review because its yield is strongly superlinear for laser irradiation near bandgap energies and weakly superlinear for high-energy electron or photon irradiation as for other cases.