Surface charged species and electrochemistry of ferroelectric thin films

Neus Domingo; Iaroslav Gaponenko; Kumara Cordero-Edwards; Nicolas Stucki; Virginia Pérez-Dieste; Carlos Escudero; Elzbieta Pach; Albert Verdaguer; Patrycja Paruch

doi:10.1039/c9nr05526f

Surface charged species and electrochemistry of ferroelectric thin films

Neus Domingo, Iaroslav Gaponenko, Kumara Cordero-Edwards, Nicolas Stucki, Virginia Pérez-Dieste, Carlos Escudero, Elzbieta Pach, Albert Verdaguer, Patrycja Paruch

Research output: Contribution to journal › Article › peer-review

48 Scopus citations

Abstract

The combination of scanning probe microscopy and ambient pressure X-ray photoelectron spectroscopy opens up new perspectives for the study of combined surface chemical, electrochemical and electromechanical properties at the nanoscale, providing both nanoscale resolution of physical information and the chemical sensitivity required to identify surface species and bulk ionic composition. In this work, we determine the nature and evolution over time of surface chemical species obtained after water-mediated redox reactions on Pb(Zr_0.2,Ti_0.8)O₃ thin films with opposite as-grown polarization states. Starting with intrinsically different surface chemical composition on the oppositely polarized films (as a result of their ferroelectric-dominated interaction with environmental water), we identify the reversible and irreversible electrochemical reactions under an external electric field, distinguishing switching and charging events. We find that while reversible ionic displacements upon polarization switching dominate screening in the bulk of the sample, polarization dependent irreversible redox reactions determine surface chemical composition, which reveals itself as a characteristic fingerprint of the ferroelectric polarization switching history.

Original language	English
Pages (from-to)	17920-17930
Number of pages	11
Journal	Nanoscale
Volume	11
Issue number	38
DOIs	https://doi.org/10.1039/c9nr05526f
State	Published - Oct 14 2019
Externally published	Yes

Funding

Financial support was obtained under projects from the Spanish Ministerio de Economía y Competitividad (MINECO) under projects FIS2015-73932-JIN and MAT2016-77852-C2-1-R (AEI/FEDER, UE), and by Division II of the Swiss National Science Foundation under project 200021_178782. ICN2 is supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706), and ICMAB acknowledges support from the Severo Ochoa Program (MINECO, Grant No. SEV-2015-0496). This work was partially funded by 2017-SGR-579 and 2017-SGR-668 projects from the Generalitat de Catalunya. The authors thank the support of ALBA staff for the successful performance of the measurements at CIRCE beamline from the ALBA Synchrotron Light Source. Financial support was obtained under projects from the Spanish Ministerio de Econo?a y Competitividad (MINECO) under projects FIS2015-73932-JIN and MAT2016-77852-C2-1-R (AEI/FEDER, UE), and by Division II of the Swiss National Science Foundation under project 200021-178782. ICN2 is supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706), and ICMAB acknowledges support from the Severo Ochoa Program (MINECO, Grant No. SEV-2015-0496). This work was partially funded by 2017-SGR-579 and 2017-SGR-668 projects from the Generalitat de Catalunya. The authors thank the support of ALBA staff for the successful performance of the measurements at CIRCE beamline from the ALBA Synchrotron Light Source.

Funders	Funder number
AEI/FEDER
Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung	2017-SGR-668, SEV-2015-0496, SEV-2017-0706, 200021_178782, 2017-SGR-579
Generalitat de Catalunya
Federación Española de Enfermedades Raras
Ministerio de Economía y Competitividad	FIS2015-73932-JIN, MAT2016-77852-C2-1-R
Agencia Estatal de Investigación

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abstract = "The combination of scanning probe microscopy and ambient pressure X-ray photoelectron spectroscopy opens up new perspectives for the study of combined surface chemical, electrochemical and electromechanical properties at the nanoscale, providing both nanoscale resolution of physical information and the chemical sensitivity required to identify surface species and bulk ionic composition. In this work, we determine the nature and evolution over time of surface chemical species obtained after water-mediated redox reactions on Pb(Zr0.2,Ti0.8)O3 thin films with opposite as-grown polarization states. Starting with intrinsically different surface chemical composition on the oppositely polarized films (as a result of their ferroelectric-dominated interaction with environmental water), we identify the reversible and irreversible electrochemical reactions under an external electric field, distinguishing switching and charging events. We find that while reversible ionic displacements upon polarization switching dominate screening in the bulk of the sample, polarization dependent irreversible redox reactions determine surface chemical composition, which reveals itself as a characteristic fingerprint of the ferroelectric polarization switching history.",

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AU - Gaponenko, Iaroslav

AU - Cordero-Edwards, Kumara

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AU - Pérez-Dieste, Virginia

AU - Escudero, Carlos

AU - Pach, Elzbieta

AU - Verdaguer, Albert

AU - Paruch, Patrycja

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AB - The combination of scanning probe microscopy and ambient pressure X-ray photoelectron spectroscopy opens up new perspectives for the study of combined surface chemical, electrochemical and electromechanical properties at the nanoscale, providing both nanoscale resolution of physical information and the chemical sensitivity required to identify surface species and bulk ionic composition. In this work, we determine the nature and evolution over time of surface chemical species obtained after water-mediated redox reactions on Pb(Zr0.2,Ti0.8)O3 thin films with opposite as-grown polarization states. Starting with intrinsically different surface chemical composition on the oppositely polarized films (as a result of their ferroelectric-dominated interaction with environmental water), we identify the reversible and irreversible electrochemical reactions under an external electric field, distinguishing switching and charging events. We find that while reversible ionic displacements upon polarization switching dominate screening in the bulk of the sample, polarization dependent irreversible redox reactions determine surface chemical composition, which reveals itself as a characteristic fingerprint of the ferroelectric polarization switching history.

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Surface charged species and electrochemistry of ferroelectric thin films

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