An instrument for simultaneous EQCM impedance and SECM measurements.

A novel combination of an electrochemical quartz crystal microbalance (EQCM) and a scanning electrochemical microscope (SECM) has been built. Unlike conventional EQCMs, the instrument described here allows rapid in situ measurement of the modulus of the quartz crystal's transfer function. Data analysis in the complex plane for the Butterworth-Van Dyke (BVD) equivalent circuit yields the real and the imaginary components R (damping resistance) and XL (reactive inductance) of the crystal's electroacoustic impedance around its resonant frequency of 10 MHz. The influence of different tip shapes of an approaching microelectrode on the electroacoustic impedance of the quartz crystal was studied and found to be minimal for certain geometries. The capability of the EQCM/SECM instrument was tested in cyclic voltammetric plating/stripping experiments using a copper(I) chloride solution of high concentration in 1 M HCl. Four parameters, XL, R, the substrate, and the tip current, can be recorded simultaneously. Depletion layer effects were observed and could be corrected for to yield accurate current efficiencies for potentiodynamic and potentiostatic copper plating. The amperometric response of the SECM tip positioned closely to the substrate reflects the concentration changes of electroactive ions in the diffusion layer of the substrate electrode.