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Probing Nanoscale Ionic Dynamics in Functional Oxides Using FORC-IV Method

This highlight presents a novel scanning probe microscopy technique known as the FORC-IV (first-order reversal curve current-voltage) method, which allows for precise measurement of ionic dynamics at the nanoscale. This approach is applied to investigate Ca-doped BiFeO3, revealing insights into local ionic activity, conductivity contributions, and the dynamics of oxygen vacancies. The technique's relevance extends to energy applications, including batteries and fuel cells, where understanding ion flow is essential for performance optimization.

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Probing Nanoscale Ionic Dynamics in Functional Oxides Using FORC-IV Method

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  1. Probing NanoscaleIonic Dynamics in Functional Oxides CNMS Staff Science Highlight 1) 2) Schematic of FORC-IV method: current-voltage response is measured at individual locations on the sample’s surface. a) current-voltage curves displaying hysteretic behavior b) FORC-IV loop area map showing different distribution of electrochemical activity across the surface. E. Strelcov, Y. Kim, S. Jesse, Y. Cao, I. N. Ivanov, I. I. Kravchenko, C.-H. Wang, Y.-C. Teng, L.-Q. Chen, Y. H. Chu, S. V. Kalinin, Nano Lett. (2013) DOI:10.1021/nl400780d Work was performed at the Center for Nanophase Materials Sciences, ORNL Scientific Achievement A novel scanning probe microscopy technique for measuring electrochemical activity at the nanoscale was developed and employed to probe the ionic activity in Ca-doped BiFeO3. Significance and Impact FORC-IV (first-order reversal curve current-voltage) is a simple method for probing ionic dynamics at the nanoscale and will find application in studying batteries, memristors, and fuel cells, whose operation relies on nanoscale-size elements that control ion flow. Research Details • FORC-IV utilizes hysteresis in current-voltage curves measured locally to determine local ionic activity. • Application of FORC-IV to Ca-doped BiFeO3 distinguished electronic and ionic contributions to conductivity and demonstrated the link between oxygen vacancy dynamics and the metal-insulator transition. • Variable-temperature FORC-IV allowed local measurement of ion activation energies.

  2. Novel method for studying ion motion at the nanoscale CNMS Staff Science Highlight Above, drawing shows SPM tip in contact with the sample surface and irreversible current-voltage loops recorded at the junction. At left, modern batteries all rely on ion flows that can be studied by this approach. (photo source: Wikipedia) E. Strelcov, Y. Kim, S. Jesse, Y. Cao, I. N. Ivanov, I. I. Kravchenko, C.-H. Wang, Y.-C. Teng, L.-Q. Chen, Y. H. Chu, S. V. Kalinin, Nano Lett. (2013) DOI:10.1021/nl400780d Work was performed at the Center for Nanophase Materials Sciences, ORNL Scientific Achievement New simple and elegant technique for investigating electrochemical processes at the nanoscale was developed. Significance and Impact Energy applications such as batteries, fuel cells, electronic switches rely on flow of ions that happen on the nanoscale. This new technique probes ion motion locally at the length scales of the active elements of these devices. Research Details A scanning probe microscopy tip measures electronic current as voltage is swept in ever increasing pulses. The irreversibility of the current-voltage loop measures ion motion on the nanoscale.

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