Nondestructive in Situ Characterization of Molecular Structures at the Surface and Buried Interface of Silicon-Supported Low‑<i>k</i> Dielectric Films

As low-<i>k</i> dielectric/copper interconnects continue to scale down in size, the interfaces of low-<i>k</i> dielectric materials will increasingly determine the structure and properties of the materials. We report an in situ nondestructive characterization method to characterize the molecular structure at the surface and buried interface of silicon-supported low-<i>k</i> dielectric thin films using interface sensitive infrared-visible sum frequency generation vibrational spectroscopy (SFG). Film thickness-dependent reflected SFG signals were observed, which were explained by multiple reflections of the input and SFG beams within the low-<i>k</i> film. The effect of multiple reflections on the SFG signal was determined by incorporating thin-film interference into the local field factors at the low-<i>k</i>/air and Si/low-<i>k</i> interfaces. Simulated thickness-dependent SFG spectra were then used to deduce the relative contributions of the low-<i>k</i>/air and low-<i>k</i>/Si interfaces to the detected SFG signal. The nonlinear susceptibilities at each interface, which are directly related to the interfacial molecular structure, were then deduced from the isolated interfacial contributions to the detected SFG signal. The method developed here is general and demonstrates that SFG measurements can be integrated into other modern analytical and microfabrication methods that utilize silicon-based substrates. Therefore, the molecular structure at the surface and buried interface of thin polymer or organic films deposited on silicon substrates can be measured in the same experimental geometry used to measure many optical, electrical, and mechanical properties