Constructing and Investigating a Ceria-Based Electro-Chemo-Resistivity Switch
Authors: Freidzon Daniel , Cohen Hagai , Kossoy Anna , Brontvein Olga , Wachtel Ellen , Ehre David , Lubomirsky Igor 
Published: August 2024

Coupling between an electrochemical reaction and a functional material property has been termed electro-chemo-X, or EC-X, where X can refer to mechanical, optical, magnetic, or thermal properties. Recently, our group has demonstrated a two-terminal electro-chemo-mechanical (ECM) membrane actuator operating under ambient conditions and containing a Ce0.8Gd0.2O1.9 (20GDC) solid electrolyte (SE) layer sandwiched between two Ti oxide/Ce0.8Gd0.2O1.9 (Ti-GDC) nanocomposite thin films. Reducing one nanocomposite film while oxidizing the other was observed to produce reversible volume change thereby driving actuator operation. Here, we use the same electrolyte and nanocomposite layers to further explore the EC-X effect: we present, as proof-of-concept, a functioning, three-terminal, thin film based EC-electrical switching device operating at room temperature.
The stacked lamellar structure which comprises the device (Figure 1) was fabricated by first depositing, using magnetron sputtering, a ~200nm thick layer of Ti metal on a sapphire substrate. This was followed by patterning with photolithography and etching, using a commercial, buffered oxide etch solution, thereby creating a 1mm wide channel. The resulting bottom electrode pair ("source" and "drain"), which could be temporarily shorted together when necessary, were subsequently covered by the WB/SE/RV stack, where the same co-sputtered, ~200nm thick Ti-GDC nanocomposite (<40nm grain size; 39at% Ti) was used for both the working body (lower: WB) and the reservoir (upper: RV) layers; a ~400nm thick 20GDC layer served as the SE. Upon WB deposition, the 1mm channel between the source and drain electrodes was filled with the nanocomposite material. The upper electrical contact, a ~200nm Ti layer, covered the RV, and using the same photolithography and etching process already described, the top "gate" electrode was defined. To avoid oxidation of the ion reservoir (RV) surface by atmospheric oxygen during device operation, a ~500 nm thick Ta-oxide layer was deposited by reactive magnetron sputtering and patterned by lift-off techniques.
We find that following two hours application of -/+ 6V bias between the "gate" and (temporarily shorted) "source" / "drain" electrodes under ambient conditions, the average change in ohmic resistance of the WB in the 1mm channel upon reversal of electrode bias was determined, by cyclic voltammetry between the source and drain electrodes, to be 6.5 ±1.8Gohm with statistical uncertainty based on at least 3 cycles, 5 samples. Negative "gate" bias produced the lower resistance values. The low resistance state decayed during approx. 24 hours, as monitored by cyclic voltammetry. Raising the temperature above ambient (333K) further reduced resistance. We interpret these observations as follows: Negative bias voltage application to the "gate" produces a gradient of the chemical potential of diffusing oxygen ions at the SE-WB interface. This gradient leads to the injection of ions into the WB, thereby promoting an electrochemical oxidation reaction. The nanocomposite in the 1mm channel decays from the more highly conductive state during approximately twenty-four hours. Reversing the bias polarity extracts ions from the WB, with the opposite results. To complement the findings of the E-field promoted oxidation, we performed annealing at 633K for 23 hours in air of a device which lacked the SE/RV/"gate" electrode/Ta-oxide layers, i.e. the WB was uncovered. We observed an increase of two orders of magnitude in the conductivity of the nanocomposite in the 1mm channel, which then relaxes with time. As a control, the same thermal treatment was conducted under vacuum. In this case no change was observed in channel conductivity.
A possible explanation for how oxidation increases the Ti-GDC nanocomposite conductivity may be found in a suitable variant of the space charge model [1, 2]. We note that nanocrystallinity introduces such a high density of interfaces/grain boundaries that total conductivity may become interfacially controlled. Grain boundaries in doped ceria lack long range order and are relatively rich in oxygen vacancies (VO) and Ce3+, which, along with a space charge zone which forms for charge neutrality, produce a blocking effect for ion conduction. Oxidation of Ce3+ => Ce4+ leads to a lowering of total real charge, causing the spatial extent of the space charge zone to shrink as well. Finally, this succeeds in lowering the potential barrier for ion diffusion across the grain boundary, which increases the overall conductivity. Reduction of the Ti-GDC nanocomposite produces the opposite effect.
[1] S. K. Kim, S. Khodorov, I. Lubomirsky, S. Kim, Phys Chem Chem Phys 2014, 16, 14961, https://doi.org/10.1039/c4cp01254b
[2] S. Kim, J. Maier, J. Elecrochem. Soc. 2002, 149, J73, https://doi.org/10.1149/1.1507597

Figure 1