Online Monitoring of Copper Damascene Electroplating Bath by Voltammetry: Selection of Variables for Multiblock and Hierarchical Chemometric Analysis of Voltammetric Data

The Real Time Analyzer (RTA) utilizing DC- and AC-voltammetric techniques is an in situ, online monitoring system that provides a complete chemical analysis of different electrochemical deposition solutions. The RTA employs multivariate calibration when predicting concentration parameters from a multivariate data set. Although the hierarchical and multiblock Principal Component Regression- (PCR-) and Partial Least Squares- (PLS-) based methods can handle data sets even when the number of variables significantly exceeds the number of samples, it can be advantageous to reduce the number of variables to obtain improvement of the model predictions and better interpretation. This presentation focuses on the introduction of a multistep, rigorous method of data-selection-based Least Squares Regression, Simple Modeling of Class Analogy modeling power, and, as a novel application in electroanalysis, Uninformative Variable Elimination by PLS and by PCR, Variable Importance in the Projection coupled with PLS, Interval PLS, Interval PCR, and Moving Window PLS. Selection criteria of the optimum decomposition technique for the specific data are also demonstrated. The chief goal of this paper is to introduce to the community of electroanalytical chemists numerous variable selection methods which are well established in spectroscopy and can be successfully applied to voltammetric data analysis.