Electrochemical Quartz Crystal Microbalance apparatus.

The quartz crystal microbalance (QCM) is a variant of acoustic wave microsenseors that are capable of ultra sensitive mass measurements. Under favorable conditions, a typical QCM can measure a mass change of 0.1-1 ng/cm2. QCM oscillates in a mechanically resonant shear mode under the influence of a high frequency AC electric field which is applied across the thickness of the crystal. The next figure shows the type of the electrode shape we use:

The central portions of the top and bottom sides of the crystal are coated with thin films of Au deposited on these layers of Cr. The mass sensitivity of QCM originates from the relationship between the oscillation frequency on the total mass of the crystal and the adlayers of materials residing at the metal-coated crystals, the Sauerbrey equation, as shown below. f = -2f02 m / [A sqrt( )] where f0 is the resonant frequency of the fundamental mode of the crystal, A is the area of the gold disk coated onto the crystal, is the density of the crystal (= 2.684 g/cm3), and is the shear modulus of quartz (= 2.947 x 1011 g/cm.s2). Using a crystal with a 10-MHz fundamental frequency (as used in our measurements) as an example, a net change of 1 Hz corresponds to 1 ng of materials adsorbed or desorbed onto the crystal surface of an area of 0.2 cm2. As molecules adsorb onto the electrode, the oscillation frequency of the quartz crystal decreases and vise versa. Tracking the oscillation frequency as a function of time permits in situ monitoring of the kinetics of adsorption processes. QCM and the combination of QCM with electrochemistry (EQCM) have been widely employed for the determination of metals deposited onto the crystal, studies of ion-transport processes in polymer films, biosensor developments, and investigations of the kinetics of adsorption/desorption of adsorbate molecules.

In EQCM experiments, the measurements of the various electrochemical parameters, such as potential, current and charge at the working electrode, and the acquisition of the corresponding frequency change, are conducted simultaneously. Such simultaneous measurements were made possible by employing an experimental setup shown in the next figure.

The Elchema EQCN 701 series, which we use, contains a quartz crystal oscillator, a frequency counter, a fast digital function generator, a high-resolution and highspeed data acquisition circuitry, a potentiostat-galvanostat (Model 205). The subsequent measurement of the current, and the frequency counting were carried out with a potentiostat/frequency counter, which is, in turn, controlled by a computer. The QCM is integrated with potentiostat-galvanostat, making the EQCM study simple and convenient. Instead of measuring the frequency directly, the system uses time-resolved mode. The frequency signal of the QCM is subtracted from a standard reference frequency (10 Mhz crystal). The difference is then measured by reciprocal technique. This technique greatly reduces the time needed for sampling the QCM signal and gives much better time resolution for the QCM signal. The time-resolved mode allows QCM signal to be measured in milliseconds with much better resolution.

System setup diagram In our lab where usual research areas cover the interface of novel metal modified by organic layers, potential inhibitors of mono- or partial mono-layer on metal/water interfaces, the information of the mass increase/decrease is a complementary one to microscopic ones, i.e., SEM-EDS, EC-AFM, and the ECSTM.

Typical Results:

QCM results for 5-mercapto-1-phenyl-tetrazole (5-MPhTT):

EQCM for 5-MPhTT,

Mass change and Current Density vs. polarization Potential.