In the formation of copper interconnects by CMP, barrier polishing is typically carried out using alkaline slurries containing copper corrosion inhibitors. Benzotriazole (BTA) has been the inhibitor of choice in such slurries. The effect of BTA on copper corrosion has been extensively studied in the past few decades, and there is general agreement that the adsorbed film formed in acidic solutions is a multilayer film with a chemisorbed first layer. However, simultaneous real time measurement of the amount of BTA adsorbed and characterization of nature of the adsorbed film (rigid/viscoelastic) has received very little attention. 

The objective of this work was to measure the extent of BTA adsorption onto PVD Cu films and characterize the nature of the adsorbed film in real time using a quartz crystal microbalance with dissipation monitoring (QCMD) capability.  Quartz crystals (fundamental frequency of 5 MHz) coated with ~300 nm PVD copper layer were used in the experiments. To mimic the conditions during barrier polishing, BTA dissolved in alkaline solutions was pumped through the flow cell containing the crystal, and the change in crystal oscillation frequency and dissipation data were collected at a time resolution of fraction of a second for several minutes. This was followed by rinsing with DI or solutions containing selected surfactants to determine extent of desorption of BTA.

As an example, adsorption of BTA from a solution of pH 10 is shown in figure 1. The measured frequency shift (Δf) and dissipation shift (ΔD) at different overtones (multiples) of crystal fundamental frequency are plotted as a function of time. At the time marked with t₁, a sharp decrease of frequency may be seen, which indicates rapid adsorption of BTA. The data points for all frequencies fall on one curve indicating that the adsorbed BTA film on copper is quite rigid in nature. This is confirmed by very little measured change in the ΔD values. At the end of adsorption marked with t₂, deionized water was introduced into the system, and the positive shift of frequency is indicative of BTA removal and/or etching of copper in DI water.

In the presentation, results of adsorption and desorption experiments carried out under different experimental conditions will be presented. The disruption of adsorbed BTA layer by selected chemicals will be addressed.