In this study, we report the development of an electrically active solid−liquid interface for the evanescent-wave cavity-ring-down spectroscopic (EW-CRDS) technique to enable spectroelectrochemical investigations of redox events. Because of a high-quality transparent conductive electrode film of indium tin oxide (ITO) coated on the interface of total internal reflection of the EW-CRDS platform, a cavity ring-down time of about 900 ns was obtained allowing spectroelectrochemical studies at solid− liquid interfaces. As a proof-of-concept on the capabilities of the developed platform, measurements were performed to address the effects of an applied electric potential to the adsorption behavior of the redox protein cytochrome c (Cyt-C) onto different interfaces, namely, bare-ITO, 3-aminopropyl triethoxysilane (APTES), and Cyt-C antibody. For each interface, the adsorption and desorption constants, the surface equilibrium constant, the Gibbs free energy of adsorption, and the surface coverage were optically measured by our electrically active EW-CRDS tool. Optical measurements at a set of constant discrete values of the applied electric potential were acquired for kinetic adsorption analysis. Cyclic voltammetry (CV) scans under synchronous optical readout were performed to study the effects of each molecular interface on the redox process of surface-adsorbed protein species. Overall, the experimental results demonstrate the ability of the electro-active EW-CRDS platform to unambiguously measure electrode-driven redox events of surface-confined molecular species at low submonolayer coverages and at a single diffraction-limited spot. Such capability is expected to open several opportunities for the EW-CRDS technique to investigate a variety of electrochemical phenomena at solid−liquid interfaces.

In this work, an ultra-sensitive optical absorption technique based on Cavity Ring-Down Spectroscopy (CRDS) was employed to study the effects of UV treatment on the optical properties of ultra-thin indium tin oxide (ITO) films. The ITO films were submitted to UV treatment either after the deposition process or in-situ during the thin-film growth process. Different flow rates of oxygen in the vacuum chamber during film growth were also investigated. An ITO-coated glass substrate inserted in the CRDS cavity at a Brewster’s angle provided a ring-down time of about 1.6 µs, which enabled measurements of optical absorption loss as small as 3 × 10−6. To compare the effects of the UV film treatment, the CRDS technique was employed to measure the extinction coefficient for samples coated with and without the UV treatment. While the optical absorption data was being collected, the electrical resistivity was also simultaneously monitored. The post-deposition UV treatment was found to improve the optical transparency and the electrical performance of ITO film; the optical extinction coefficient of the ultra-thin ITO film is shown to decrease by about 24%. The in-situ UV treatment during growth is also shown to consistently increase the optical transparency of the ultra-thin ITO films and providing outstanding optical performance especially for high flow rates of oxygen during film growth. The electrical resistivity for oxygen flow rates in the range 0.6 - 1.4 sccm is also improved by the in-situ UV treatment, however it shows a sharp increase for oxygen flow rates beyond 1.4 sccm. The CRDS platform is demonstrated here to provide a highly accurate and sensitive methodology for measurement of minute optical absorption losses in ultra-thin films that typically cannot be precisely measured using other conventional spectrophotometric techniques.

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