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This paper describes film characterization of Ultra Low-k (ULK) dielectrics modified by UV curing with different wavelength bands. We have demonstrated UV hardening of ULK-SiOC (k=2.65) with two types of UV bulbs (UV-X and UV-Y) and the UV modifications of ULK-SiOC film properties are characterized by using FT-IR spectroscopy, 29Si Solid-state NMR spectroscopy and Raman spectroscopy. FT-IR and NMR analyses reveal that UV-Y curing is preferable for UV curing modification of ULK-SiOC. UV-Y curing increases Q mode peak in NMR, resulting in the enhanced Si-O crosslinking, while UV-X curing increases TH mode and TOR mode peaks. Spin lattice relaxation time T1 for 29Si is decreased with UV curing. This result indicates that UV curing enhances molecular motion in Si-O network. Raman analysis shows that UV curing increases amorphous carbon groups, which corresponds to the enhanced molecular motion in Si-O network.
This paper describes process optimization of UV curing for ultra Low-k SiOC (ULK-SiOC, k=2.65) and High stress silicon nitride (HS-SiN) liner. We have investigated the impact of UV curing using different UV bulbs (UV-X and UV-Y) on BEOL process damages to the ULK-SiOC. The k-value variations of ULK-SiOC modified with UV-X with higher photon energy than UV-Y are greater than those of the pristine ULK-SiOC and the ULK-SiOC modified with UV-Y. These results are consistent with the previously reported FT-IR and NMR analyses that the UV-X generates 3-fold Si-O ring defects and Si-H bonds in the ULK-SiOC. In order to discuss the pore structure in UV-modified ULK-SiOC, the solvent diffusion of toluene and ethanol in ULK-SiOC were measured. The solvent diffusion of the UV-modified ULK-SiOC with UV-X is faster than that of the UV-modified ULK-SiOC with UV-Y. This result indicates that the pore size of UV-modified ULK-SiOC with UV-X is larger than that of UV- modified ULK-SiOC with UV-Y. The dependence of the stress increase in HS-SiN liner on different UV bulbs (UV-X and UV-Y) has been investigated by using stress measurement and FT-IR. The UV-modified HS-SiN liner with UV-Y achieves higher tensile stress, compared to the UV-X. FT-IR results have revealed that UV-Y is more effective for the dehydrogenation and SiN crosslinking, resulting in the greater increase in the tensile stress. In conclusion, UV-Y bulb with medium photon energy yields the desired UV modifications for ULK-SiOC and HS-SiN applications.
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