Hydrogen-based plasma etch of copper at low temperature

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Wu, Fangyu
Hess, Dennis W.
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Although copper (Cu) is the preferred interconnect material due to its lower resistivity than aluminum (Al), Cu subtractive etching processes have not been developed at temperatures less than 180 °C, primarily due to the inability to form volatile etch products at low temperature. The conventional damascene technology avoids the need for subtractive etching of Cu by electroplating Cu into previously etched dielectric trenches/vias, followed by a chemical/mechanical planarization (CMP) process. However, a critical "size effect" limitation has arisen for damascene technology as a result of the continuing efforts to adhere to "Moore's Law". The size effect relates to the fact that the resistivity of damascene-generated lines increases dramatically as the line width approaches the sub-100 nm regime, where feature size is similar to the mean free path of electrons in Cu (40 nm). As a result, an alternative Cu patterning process to that of damascene may offer advantages for device speed and thus operation. This thesis describes investigations into the development of novel, fully-plasma based etch processes for Cu at low temperatures (10 °C). Initially, the investigation of a two-step etch process has been studied. This etch approach was based on a previous thermodynamic analysis of the Cu-Cl-H system by investigators at the University of Florida. In the first step, Cu films are exposed to a Cl₂ plasma to preferentially form CuCl₂, which is believed to be volatilized as Cu₃Cl₃ by subsequent exposure to a hydrogen (H₂) plasma (second step). Patterning of Cu films masked with silicon dioxide (SiO₂) layers in an inductively coupled plasma (ICP) reactor indicates that the H₂ plasma step in the two-step process is the limiting step in the etch process. This discovery led to the investigation of a single step Cu etch process using a pure H₂ plasma. Etching of blanket Cu films and Cu film patterning at 10°C, display an etch rate ~ 13 nm/min; anisotropic etched features are also observed. Comparison of H₂ plasma etching to sputtering of Cu films in argon (Ar) plasmas, indicates that both a chemical component and a physical component are involved in the etching mechanism. Additional studies using helium plasmas and variation of power applied to the plasma and etching surface demonstrate that the etch rate is controlled by reactive hydrogen species, ion bombardment flux and likely photon flux. Optical Emission Spectroscopy (OES) of the H₂ plasma during the Cu etching process detects Cu emission lines, but is unable to identify specific Cu etch products that desorb from the etching surface. Variation of Cu etch rates as a function of temperature suggests a change in mechanism for the removal of Cu over the temperature of -150 °C to 150 °C. OES analyses also suggest that the Cl₂ plasma step in the two-step process can inhibit Cu etching, since the subsequent H₂ (second) plasma step shows a time delay in film removal. Preliminary results of the etching of the SiO₂ mask material in H₂ plasmas with various intentionally introduced contaminants demonstrate the robustness of the H₂ plasma Cu etch process.
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