Study on Chemical Interaction Analysis of Reactive Fullerenol Molecules in Cu-CMP Using High-Sensitive Raman Spectroscopy

Abstract

Surface with nanometer accuracy is required to manufacturing process of integrated circuit (IC) devices. One of the most promising techniques for surface planarization is chemical mechanical polishing (CMP). CMP is a high efficiency process, both due to the varied chemical and physical properties of the surface materials. Conventional CMP uses the slurry, which is composed of abrasive particles suspended in a chemical solution. The abrasive particle is effective for surface planarization by a chemical mechanism with little mechanical abrasion. So chemical reactivity appears to be an essential factor of CMP process. In our conventional study, fullerenols have been proposed as suitable abrasives for copper CMP. The chemical reactivity of fullerenol is suggested by the fact that high removal rate (150 nm/min) and surface flatness (0.6 nm RMS) have been confirmed using fullerenol slurry. In this study, we analyzed the chemical reactivity between fullerenol molecule and copper surface, which is important to understand the material removal mechanism. Using the intrinsic Raman spectroscopic signal of interaction between fullerenol and copper with surface plasmon resonance (SPR), the chemical reactivity over a period of the reaction process was analyzed. Raman spectroscopy is commonly used in chemical analysis, since vibrational information is specific to the chemical bonds and symmetry of molecules. Therefore, it provides a fingerprint by which the molecule can be identified. However, spontaneous Raman spectroscopic signal is typically very weak, and as a result the main difficulty of Raman spectroscopy is separating the weak inelastically scattered light from the intense Rayleigh scattered laser light. Then Raman spectroscopic signal in this study is further enhanced by the SPR, also known as surface enhanced Raman scattering (SERS). The increase in intensity of the Raman spectroscopic signal for adsorbates on copper surface occurs because of an enhancement in the electric field provided by the surface. This technique enables high-sensitive analysis in the near-surface region. The signature of copper-oxygen bond was measured by Raman spectroscopy for fullerenol/copper system by in-process SERS analysis. It is thought to be caused by the hydroxyls of fullerenol molecule adsorbed on the copper surface. This result suggests that fullerenol molecules absorbing onto the copper surface affect the high efficient material removal.