Potential-modulated, attenuated total reflectance spectroscopy of poly(3,4-ethylenedioxythiophene) and poly(3,4-ethylenedioxythiophene methanol) copolymer films on indium-tin oxide

The Journal of Physical Chemistry. B
Walter J DohertyS Scott Saavedra

Abstract

We report the first application of a potential-modulated spectroelectrochemical ATR (PM-ATR) instrument utilizing multiple internal reflections at an optically transparent electrode to study the charge-transfer kinetics and electrochromic response of adsorbed films. A sinusoidally modulated potential waveform was applied to an indium-tin oxide (ITO) electrode while simultaneously monitoring the optical reflectivity of thin (2-6 equivalent monolayers) copolymer films of poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedioxythiophene methanol) (PEDTM), previously characterized in our laboratory. At high modulation frequencies the measured response of the polymer film is selective toward the fastest electrochromic processes in the film, presumably those occurring within the first adsorbed monolayer. Quantitative determination of the electrochromic switching rate, derived from the frequency response of the attenuated reflectivity, shows a linear decrease in the rate, from 11 x 10(3) s(-1) to 3 x 10(3) s(-1), with increasing proportions of PEDTM in the copolymer, suggesting that interactions between the methanol substituent on EDTM and the ITO surface slow the switching process by limiting the rate of conformational cha...Continue Reading

Citations

Apr 11, 2017·Analytical Sciences : the International Journal of the Japan Society for Analytical Chemistry·Yilong Zheng, S Scott Saavedra
Jan 15, 2010·Chemical Reviews·Pierre M Beaujuge, John R Reynolds
Dec 9, 2009·Langmuir : the ACS Journal of Surfaces and Colloids·Bo Yun KimJeffrey Pyun
Aug 11, 2017·ACS Applied Materials & Interfaces·Ramanan EhamparamS Scott Saavedra
Dec 15, 2016·ACS Applied Materials & Interfaces·Yilong ZhengS Scott Saavedra
Jan 16, 2008·Journal of the American Chemical Society·Zeynep Ozkan AraciS Scott Saavedra
Jan 24, 2007·Langmuir : the ACS Journal of Surfaces and Colloids·F Saneeha MarrikarNeal R Armstrong
Apr 27, 2021·Analytical Sciences : the International Journal of the Japan Society for Analytical Chemistry·Jafar H GhithanSergio B Mendes

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