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Operando X-Ray Photoelectron spectroscopy (o-XPS) has been used to record the binding energy shifts in C1s peak of a pristine poly-ethylene glycol (PEG) liquid drop in an electrowetting on dielectric (EWOD) geometry, and after exposing it to several high-voltage breakdown processes. This was achieved by recording XPS data while the samples were subjected to 10 V DC and AC (square-wave modulation) actuations to extract electrical information related with the liquid and its interface with the dielectric. Through analysis of the XPS data under AC actuation a critical frequency of 170 Hz is extracted for the pristine PEG, which is translated to a resistance value of 14 MOhm for the liquid and a capacitance value of 60 pF for the dielectric, by help of simulations using an equivalent circuit model, and also by XPS analyses of a mimicking device, under similar conditions. The same measurements yield an increased value of 23 MOhm for the resistance of the liquid after the breakdown, by assuming the capacitance of the dielectric stays constant. In addition, an asymmetry in polarity dependence is observed with respect to both the onset of the breakdown voltage, and also the leakage behavior of the deteriorated (PEG + dielectric) system, such that deviations are more pronounced at positive voltages. Both DC and AC behaviors of the post-breakdown system can also be simulated, but only by introducing an additional element, a diode or a polarity and magnitude dependent voltage source (VCVS), which might be attributed to negative charge accumulation at the interface. Measurements for a liquid mixture of PEG with 8 % ionic liquid, yields almost two orders of magnitude smaller resistance for the drop, due to the enhanced conductivity by the ions. Coupled with modelling, XPS measurements under DC and AC modulations enable probing unique electrochemical properties of liquid/solid interfaces.
This article was published in the following journal.
Name: Langmuir : the ACS journal of surfaces and colloids
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