Methyl depletion and subsequent moisture uptake have been found to be the primary plasma damages leading to dielectric loss in porous organosilicate (OSG) low-k dielectrics. A vacuum vapor silylation process was developed for dielectric recovery of plasma damaged OSG low-k dielectrics. The methyl or phenyl containing silylation agents were used to convert the hydrophilic -OH groups to hydrophobic groups. Compared with Trimethylchlorosilane (TMCS) and Phenyltrimethoxysilane (PTMOS), Dimethyldichlorosilane (DMDCS) was found to be more effective in recovering surface carbon concentration and surface hydrophobicity. But the carbon recovery effect was limited to the surface region.

Alternatively, UV radiation with thermal activation was applied for dielectric recovery of plasma damaged OSG low-k dielectrics. The combined UV/thermal process was found to be efficient in reducing −OH, physisorbed water, and C=O bonds. The dielectric constant was recovered within 5% of the pristine sample and the leakage current was also much reduced. Aging test in air showed that no moisture retake was observed, indicating the repaired film was stable.

During an O2 plasma ashing process, carbon depletion and subsequent moisture uptake caused increase of keff and the leakage current in an organosilicate (OSG) low-k dielectric. For dielectric restoration, additional CH4 plasma treatment on the O2 plasma ashed OSG low-k dielectric was investigated using angle resolved x-ray photoelectron spectroscopy (ARXPS), XPS depth profiling, x-ray reflectivity (XRR), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and contact angle goniometer. After CH4 plasma treatment on the O2 plasma ashed OSG, the surface carbon concentration and surface hydrophobicity were partially recovered. A dense surface layer containing C=C bonds was found to have formed on the top of the damaged OSG. The C-V hysteresis and the leakage current were reduced as a result of the CH4 plasma treatment. XPS depth profiling revealed that the recovery effect was limited to the surface region.

Atomic layer deposition (ALD) of ultra-thin barrier layers is a key process for implementation of Cu/low k interconnects. Low k dielectric surfaces are generally characterized by weak surface bonds which have to be properly activated for barrier formation. In this study, we investigated the surface activation of low k dielectrics by atomic hydrogen, nitrogen and ammonia beams for ALD of Ta/TaN barrier layers. In-situ x-ray photoemiision spectroscopy (XPS) together with differential FTIR were used to examine the beam modification of the surface and the subsequent growth on the low k surface. The evolution of the low k surface chemistry revealed an initial transient growth region controlled mainly by the substrate surface chemistry. The initial chemisorption was found to be through formation of Ta-O bonds on organosilicates (OSG) and charge transfer complexes on aromatic SiLK. This led to a significant slower initial nucleation on the OSG low k surface without beam activation. The atomic beams, particularly the nitrogen and amine radials, were found to serve as effective reducing agents in initiating and enhancing the precursor chemisorption. This led to an improvement of the barrier film quality and an increase of the deposition rate at a temperature compatible with low k dielectrics (< 400C). In the subsequent linear growth region, atomic hydrogen species was able to reduce the chlorine content under appropriate temperature and with sufficient purge. The effect of porosity in low k dielectrics on barrier formation will be discussed.

Beams of nitrogen and hydrogen radicals were investigated as surfacepre-treatment and process enhancement techniques for atomic layer deposition(ALD) of tantalum nitride barrier layer on a dense organosilicate (OSG) lowk film. In-situ x-ray photoelectron spectroscopy (XPS)studies of the evolution of the low k surface chemistry revealed an initialtransient growth region controlled mainly by the substrate surfacechemistry. Pre-treatment of the low k surface with radical beams,particularly with nitrogen radicals, was found to enhance significantly thechemisorption of the TaCl5 precursor on the OSG surfaces. Theenhancement was attributed to the dissociation of the weakly bonded methylgroups from the low k surface followed by nitridation with the nitrogenradicals. In the subsequent linear growth region, atomic hydrogen specieswas able to reduce the chlorine content under appropriate temperature andwith sufficient purge. The role of the atomic hydrogen in this processenhancement is discussed.