Probing space charge and resolving overlimiting current mechanisms at the microchannel-nanochannel interface.

We present results demonstrating the space charge-mediated transition between classical, diffusion-limited current and surface-conduction dominant over-limiting current in a shallow microchannel-nanochannel device. The extended space charge layer develops at the depleted microchannel-nanochannel entrance at high current and is correlated with a distinctive maximum in the dc resistance. Experimental results for a shallow surface-conduction dominated system are compared with theoretical models, allowing estimates of the effective surface charge at high voltage to be obtained. In comparison to an equilibrium estimate of the surface charge obtained from electrochemical impedance spectroscopy, it is further observed that the effective surface charge appears to change under applied voltage.