The moisture barrier properties of large-grain single-layer graphene (SLG) deposited on a Cu(111)/sapphire substrate are demonstrated by comparing with the bare Cu(111) surface under an accelerated degradation test (ADT) at 85 °C and 85% relative humidity (RH) for various durations. The change in surface color and the formation of Cu oxide are investigated by optical microscopy (OM) and X-ray photoelectron spectroscopy (XPS), respectively. First-principle simulation is performed to understand the mechanisms underlying the barrier properties of SLG against O diffusion. The correlation between Cu oxide thickness and SLG quality are also analyzed by spectroscopic ellipsometry (SE) measured on a non-uniform SLG film. SLG with large grains shows high performance in preventing the Cu oxidation due to moisture during ADT.

The moisture barrier properties of stacked graphene layers on Cu surfaces were investigated with the goal of improving the moisture barrier efficiency of single-layer graphene (SLG) for Cu metallization. SLG with large grain size were stacked on Cu surfaces coated with CVD-SLG to cover the grain-boundaries and defective areas of the underneath SLG film, which was confirmed to be oxidized by Raman spectroscopy measurements. To evaluate the humidity resistance of the graphene-coated Cu surfaces, temperature humidity storage (THS) testing was conducted under accelerated oxidation conditions (85 °C and 85% relative humidity) for 100 h. The color changes of the Cu surfaces during THS testing were observed by optical microscopy, while the oxidized Cu into Cu 2 O and CuO was detected by X-ray photoelectron spectroscopy (XPS). The experimental results were accord with the results of first-principle simulation for the energetic barrier against water diffusion through the stacked graphene layers with different overlap. The results demonstrate the efficiency of SLG stacking approach against moisture for Cu metallization.

To enhance the humidity reliability of copper (Cu) metallization used in memory LSIs, nitrogen (N)-doped amorphous-carbon (a-C:N) deposited by sputtering on the Cu surface is proposed. Since the preparation of a-C:N film can be achieved at room temperature, the process temperature is compatible with LSIs fabrication. After the high-temperature/humidity storage test, the a-C:N layer was found to be an excellent barrier to protect the Cu surface from oxidation and avoid the increase of Cu sheet resistance. Depth profiles imply no oxidation occurs on the underlying Cu surface. An appropriate concentration of N-doping is considered to prevent the penetration of moisture with the effects of the repulsive force between both N and O atoms. The proposed method is promising as a practical method to improve the reliability of Cu metallization for long-term storage.

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To establish the lifetime prediction model for Cu-based metallization against moisture, temperature humidity storage test under the various accelerated conditions is performed. The increase of Cu sheet resistance induced by Cu-oxidation is measured by a four-point probe method. X-ray photoelectron spectroscopy analysis is carried out to investigate the variation of oxidized Cu. The activation energy and the humidity acceleration factor for Cu-based metallization have been derived by the statistical analysis to predict the lifetime against moisture for the first time. The results indicate that Cu-based metallization is comparatively more sensitive to the temperature than humidity at around the practical use condition.