Broadband Spectroelectrochemical Interrogation of Molecular Thin Films by Single-Mode Electro-Active Integrated Optical Waveguides

  • Sergio B. MendesEmail author
  • S. Scott Saavedra
  • Neal R. Armstrong
Part of the Springer Series on Chemical Sensors and Biosensors book series (SSSENSORS, volume 7)


Electron transfer processes to/from monolayers or submonolayers of surface-confined molecules are at the core of several established or emerging sensor technologies. Spectroelectrochemical techniques to monitor these redox processes combine spectroscopic information with the normally monitored electrochemical parameters, such as changes in current or voltage, and can be much more sensitive to changes in optical properties coupled with electron transfer than electrochemical techniques alone. Spectroelectrochemical techniques based on absorbance measurements typically suffer from low sensitivity owing to the low concentrations of redox active species on the surface, and their low absorptivities. Electro-active, single-mode waveguide technologies, developed over the last decade, have provided more than adequate sensitivity to characterize electron transfer to surface-confined molecules where the coverage can be as low as a few percent of a monolayer. In this chapter, we review the major developments in combining electrochemical analysis with optical platforms that maximize optical sensitivity, through the development of electro-active integrated planar waveguides operating in the single-mode optical regime. We provide here a general overview of the theoretical formalisms associated with light propagation and absorbance measurements in integrated optical waveguides, and their electro-active counterparts. We also describe the major implementations of the technology, including the extension of the single-mode configuration into a broadband spectroscopic tool to facilitate the interrogation of the entire visible wavelength region during the redox event, and review some specific applications of these techniques, which demonstrate its sensitivity and broad utility.


Spectroelectrochemistry Integrated optical waveguides Electrochemistry Optical absorbance 



Amplified spontaneous emission


Attenuated total reflectance


Charge coupled device


Cyclic voltamogramm

Cyt c

Cytochrome c




Integrated optical waveguide


Indium tin oxide


Methylene blue


Numerical aperture




Transverse electric


Transverse magnetic



The preparation of this manuscript was supported by grants from the National Science Foundation (DBI-0352449, CHE-0518702) and the National Institutes of Health (RR022864, EB007047). Any opinions, findings, and conclusions, or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation or the National Institutes of Health. The authors express their gratitude to Mrs. Ina S. Nakao for the preparation of several drawings included in this chapter.


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Copyright information

© Springer-Verlag Berlin Heidelberg 2010

Authors and Affiliations

  • Sergio B. Mendes
    • 1
    Email author
  • S. Scott Saavedra
    • 2
  • Neal R. Armstrong
    • 2
  1. 1.Department of Physics and AstronomyUniversity of LouisvilleLouisvilleUSA
  2. 2.Department of ChemistryUniversity of ArizonaTucsonUSA

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