This paper presents an in-depth overview of the present status and novel developments in the field of plasma processing of low dielectric constant (low-k) materials developed for advanced interconnects in ULSI technology. The paper summarizes the major achievements accomplished during the last 10 years. It includes analysis of advanced experimental techniques that have been used, which are most appropriate for low-k patterning and resist strip, selection of chemistries, patterning strategies, masking materials, analytical techniques, and challenges appearing during the integration. Detailed discussions are devoted to the etch mechanisms of low-k materials and their degradation during the plasma processing. The problem of k-value degradation (plasma damage) is a key issue for the integration, and it is becoming more difficult and challenging as the dielectric constant of low-k materials scales down. Results obtained with new experimental methods, like the small gap technique and multi-beams systems with separated sources of ions, vacuum ultraviolet light, and radicals, are discussed in detail. The methods allowing reduction of plasma damage and restoration of dielectric properties of damaged low-k materials are also discussed.

Abstract. Plasma damage to low k dielectric materials was investigated from a mechanistic point of view. Low k dielectric films were treated by plasma Ar, O2, N2/H2, N2 and H2 in a standard RIE chamber and the damage was characterized by Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS), X-Ray Reflectivity (XRR), Fourier Transform Infrared Spectroscopy (FTIR) and Contact Angle measurements. Both carbon depletion and surface densification were observed on the top surface of damaged low k materials while the bulk remained largely unaffected. Plasma damage was found to be a complicated phenomenon involving both chemical and physical effects, depending on chemical reactivity and the energy and mass of the plasma species. A downstream hybrid plasma source with separate ions and atomic radicals was employed to study their respective roles in the plasma damage process. Ions were found to play a more important role in the plasma damage process. The dielectric constant of low k materials can increase up to 20% due to plasma damage and we attributed this to the removal of the methyl group making the low k surface hydrophilic. Annealing was generally effective in mitigating moisture uptake to restore the k value but the recovery was less complete for higher energy plasmas. Quantum chemistry calculation confirmed that physisorbed water in low k materials induces the largest increase of dipole moments in comparison with changes of surface bonding configurations, and is primarily responsible for the dielectric constant increase.

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The damage induced by CO2 and O2 plasmas to an ultra low-k (ULK) dielectric film with a dielectric constant (κ) of 2.2 was investigated. The dielectric constant was observed to increase due to methyl depletion, moisture uptake, and surface densification. A gap structure was used to delineate the role of ions, photons and radicals in inducing the damage, where the experimental variables included an optical mask (MgF2, fused silica, and Si), a gap height, an inductively coupled plasma power source, a bias power on the bottom electrode, variable chamber pressure, and variable substrate temperature. The plasma radical density distribution inside the gap between the optical mask and the ULK film was simulated. The simulation was based on radical diffusion, reaction, and recombination inside the gap. The experimental results and the numerical simulation showed that the oxygen radicals played an important role in plasma induced damage which was found to be proportional to the oxygen radical density and enhanced byvacuum ultraviolet (VUV) photon radiation. Under certain experimental conditions, ion bombardment can induce surface densification and suppress radical diffusion. The role of UV and VUV photons in induced damage was investigated with Ar plasma using the gap structure and it was found that the photons can induce surface damage directly.

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