Abstract
A thermodynamic framework has been provided for the interpretation of combined cyclic voltammetry and surface stress measurements, the latter being obtained from wafer curvature or beam deflection measurements of a solid electrode as a function of applied potential (so-called voltstressograms). Firstly, the derivation of electrocapillarity equations for solid electrodes has been critically reviewed by starting from the Gibbs adsorption equation appropriate for solid–electrolyte interfaces. This allowed us to demonstrate the critical importance of elastic surface strain in the thermodynamic boundary conditions of the partial derivatives intervening in the interpretation of voltstressograms. From these considerations, it was shown for the first time that the electrocapillarity equations for solid electrodes are not appropriate for describing the variation of surface stress with potential obtained from wafer curvature measurements, because such measurements are intrinsically incompatible with the constant strain condition implied in the electrocapillarity equations. An alternative explanation is provided for the experimentally observed proportionality between the current density, measured in cyclic voltammograms, and the first derivative of surface stress with respect to potential, obtained from voltstressograms.
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Haiss W, Sass JK (1996) Langmuir 12:4311
Heusler KE, Pietrucha J (1992) J Electroanal Chem 329:339
Ibach H, Bach CE, Giesen M, Grossmann A (1997) Surface Sci 375:107
Jin-Hua C, Shi-Hui S, Li-Hua N, Shou-Zhuo Y (1997) Electrochim Acta 42:689
Heusler KE, Lang G (1997) Electrochim Acta 42:747
Haiss W (2001) Rep Prog Phys 64:591
Novotny L, Navratil T, Sander S, Basova P (2003) Electroanalysis 15:1687
Bard AJ, Faulkner LR (1980) Electrochemical methods. Wiley, New York, pp 494
Grahame DC (1947) Chem Rev 41:441
Cammarata RC, Sieradzki K, Spaepen F (2000) J Appl Phys 87:1227
Trasatti S, Parsons R (1986) J Electroanal Chem 205:359
Jaeckel L, Lang G, Heusler KE (1994) Electrochim Acta 39:1031
Haiss W, Sass JK (1996) J Electroanal Chem 410:119
Lipkowski J, Schmickler W, Kolb DM, Parsons R (1998) J Electroanal Chem 452:193
Grafov BM, Paasch G, Plieth W, Bund A (2003) Electrochim Acta 48:581
Haiss W, Nichols RJ, Sass JK, Charle KP (1998) J Electroanal Chem 452:199
Habib MA, Bockris JOM (1980) Comprehensive treatise in electrochemistry, vol. 1. Plenum, New York, p 135
Shuttleworth R (1950) Proc R Soc A 63:445
Couchman PR, Davidson CR (1977) J Electroanal Chem 85:407
Guidelli R (1998) J Electroanal Chem 453:69
Valincius G (1999) J Electroanal Chem 478:40
Gokhshtein A (1975) Russ Chem Rev 44:921
Ibach H (1994) J Vacuum Sci Technol A12:2240
Sander D (2003) Curr Opin Solid State Mater Sci 7:51
Schmickler W, Leiva E (1998) J Electroanal Chem 453:61
Valincius G, Reipa V (2000) J Electrochem Soc 147:1459
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Proost, J. Thermodynamic issues associated with combined cyclic voltammetry and wafer curvature measurements in electrolytes. J Solid State Electrochem 9, 660–664 (2005). https://doi.org/10.1007/s10008-004-0631-9
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DOI: https://doi.org/10.1007/s10008-004-0631-9