Atomic Layer Deposition of TiO2 on Surface Modified Nanoporous Low‑k Films

This paper explores the effects of different plasma treatments on low dielectric constant (low-k) materials and the consequences for the growth behavior of atomic layer deposition (ALD) on these modified substrates. An O2 and a He/H2 plasma treatment were performed on SiCOH low-k films to modify their chemical surface groups. Transmission FTIR and water contact angle (WCA) analysis showed that the O2 plasma changed the hydrophobic surface completely into a hydrophilic surface, while the He/H2 plasma changed it only partially. In a next step, in situ X-ray fluorescence (XRF), ellipsometric porosimetry (EP), and Rutherford backscattering spectroscopy (RBS) were used to characterize ALD growth of TiO2 on these substrates. The initial growth of TiO2 was found to be inhibited in the original low-k film containing only Si-CH3 surface groups, while immediate growth was observed in the hydrophilic O2 plasma treated film. The latter film was uniformly filled with TiO2 after 8 ALD cycles, while pore filling was delayed to 17 ALD cycles in the hydrophobic film. For the He/H2 plasma treated film, containing both Si-OH and Si-CH3 groups, the in situ XRF data showed that TiO2 could no longer be deposited in the He/H2 plasma treated film after 8 ALD cycles, while EP measurements revealed a remaining porosity. This can be explained by the faster deposition of TiO2 in the hydrophilic top part of the film than in the hydrophobic bulk which leaves the bulk porous, as confirmed by RBS depth profiling. The outcome of this research is not only of interest for the development of advanced interconnects in ULSI technology, but also demonstrates that ALD combined with RBS analysis is a handy approach to analyze the modifications induced by a plasma treatment on a nanoporous thin film.