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Electrochemical Strain Microscopy of Silica Glasses

Piezoresponse Force Microscopy (PFM) and Electrochemical Strain Microscopy (ESM) are two related techniques that have had considerable success in nano-scale probing of functional material properties. Both measure the strain of the sample in response to a localized electric field beneath a sharp conductive tip. In this work, a collection of commercially available glass samples were measured with a variety of Si cantilevers coated with different conductive metals. In some cases, these glasses showed significant hysteresis loops, similar in appearance to those measured on ferroelectric materials with spontaneous permanent electric dipoles. The magnitude of the electrochemical strain and hysteresis correlated well with the molar percentage of sodium in the glass material, with high sodium (soda-lime) glass showing large hysteresis and fused silica (pure SiO2) showing essentially no hysteresis. The elephant-ear shape of the hysteresis loops correlated well with it originating from relaxation behavior, an interpretation verified by observing the temperature dependent relaxation of the ESM response. Cation mobility in a disordered glass should have a low diffusion constant. To evaluate this diffusion constant, the temperature of the glass was varied between room temperature and 200C. Vanishing hysteresis as the temperature increased was associated with a decrease in the relaxation time of the electrochemical response. The hysteretic behavior changed drastically in this temperature range, consistent with bound surface water playing a large role in the relaxation. This demonstrates the ability of ESM to differentiate cationic concentrations in a range of silica glasses. In addition, since glass is a common sample substrate for, this provides some clear guidance for avoiding unwanted substrate crosstalk effects in piezoresponse and electrochemical strain response measurements.