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Single crystalline films of ion conductors

Applicant Lippert Thomas
Number 126783
Funding scheme Project funding (Div. I-III)
Research institution Paul Scherrer Institut
Institution of higher education Paul Scherrer Institute - PSI
Main discipline Physical Chemistry
Start/End 01.11.2009 - 30.06.2013
Approved amount 407'909.00
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All Disciplines (2)

Discipline
Physical Chemistry
Material Sciences

Keywords (2)

pulsed laser deposition (PLD); solid oxide fuel cell (SOFC)

Lay Summary (English)

Lead
Lay summary
Background:Sub-µm thin films of oxygen-ion conductive materials are of interest as solid electrolyte in miniaturized high temperature electrochemical devices such as micro solid oxide fuel cells (SOFCs), solid oxide electrolysis cells (SOECs) and gas sensors. Due to a significant reduction of the ohmic resistance, the use of thin film technologies promises lower operational temperatures, an enhanced performance as well as an increased lifetime and wider eligible material range compared to traditional processing techniques. The fabrication as well as the analysis of the oxygen ion conduction in thin films of the ion conductors is challenging as cross-plane measurements are strongly influenced by holes, cracks, or voids in the films. Cross plane measurements are most important for the characterization, as they closely resemble the geometry of an operational SOFC. This would allow in principle to apply polycrystalline films, which are relatively easy to prepare with many methods, for the cross-plane measurements. This is unfortunately also not really possible, as grain boundaries, which serve as segregation centers for impurities, and short circuits created by metal migration along the grain boundaries, strongly influence the measurements. In addition, the influence of microstrain and varying degree of crystallinity from amorphous to nanocrystalline or mixed phases on the ionic conduction in these fluorite related structures is unclear.Goal:The thin film electrolyte in a micro-SOFC is a key component for the operation of the fuel cell. It is therefore necessary to measure the true ion conductivity of material without any influences of the film preparation and crystallinity.Approach:The best approach to measure the true ion conductivity of a material is the application of the single crystalline material, and one possibility is the preparation in the form of thin films by pulsed laser deposition. In literature different approaches are described for the deposition of single crystalline ion conducting materials, and we will adopt these approaches for the deposition of relevant materials. The second important aspect in addition to the single crystalline film preparation is the analysis of the cross plane ion conductivity.We will apply an approach, named ion exchange depth profiling, where the diffusion of isotopic oxygen (18O) in the material is analyzed by secondary ion mass spectrometry and by standard cross plane conductivity measurements with and without blocking electrodes.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Tracing the origin of oxygen for La0.6Sr0.4MnO3 thin film growth by pulsed laser deposition
Chen Jichun, Doebeli Max, Lee Michael, Conder Kazimierz, Schneider Christof W., Wokaun Alexander, Lippert Thomas (2016), Tracing the origin of oxygen for La0.6Sr0.4MnO3 thin film growth by pulsed laser deposition, in J. Phys. D: Appl. Phys. , 49, 045201.
Crystallization of zirconia based thin films
Stender Dieter, Frison R, Conder K., Rupp Jennifer L. M., Scherrer Barbara, Martynczuk J. M., Gauckler L. J., Schneider Christof W., Lippert Thomas, Wokaun Alexander (2015), Crystallization of zirconia based thin films, in Phys. Chem. Chem. Phys , 17, 18613.
Dense zig-zag microstructures in YSZ thin films by pulsed laser deposition
Stender Dieter, Schäuble Nina, Weidenkaff Anke, Montagne Alex, Ghisleni Rudy, Michler Johann, Schneider Christof W, Wokaun Alexander, Lippert Thomas (2015), Dense zig-zag microstructures in YSZ thin films by pulsed laser deposition, in APL Materials , 3, 016104.
Low-Temperature Micro-Solid Oxide Fuel Cells with Partially Amorphous La0.6Sr0.4CoO3-δ Cathodes
Evans Anna, Martynczuk Julia, Stender Dieter, Schneider Christof W, Lippert Thomas, Prestat Michel (2015), Low-Temperature Micro-Solid Oxide Fuel Cells with Partially Amorphous La0.6Sr0.4CoO3-δ Cathodes, in Adv. Energy Mater., 5, 1400747.
Tracing the plasma interactions for pulsed reactive crossed-beam laser ablation
Chen Jikun, Stender Dieter, Pichler Markus, Doebeli Max, Pergolesi Daniele, Schneider Christof, Wokaun Alexander, Lippert Thomas (2015), Tracing the plasma interactions for pulsed reactive crossed-beam laser ablation, in J. Appl. Phys. , 118, 165306.
Langmuir probe measurements and mass spectrometry of plasma plumes generated by laser ablation of La0.4Ca0.6MnO3
Chen Jikun, Lunney J. G., Lippert Thomas, Ojeda-G-P Alejandro, Stender Dieter, Schneider Christof W, Wokaun Alexander (2014), Langmuir probe measurements and mass spectrometry of plasma plumes generated by laser ablation of La0.4Ca0.6MnO3, in J. Appl. Phys. , 116, 073303.
Laser deposition and direct-writing of thermoelectric misfit cobaltite thin films
Chen Jikun, Palla-Papavlu Alexandra, Li Yi, Chen L., Chi X., Doebeli Max, Stender Dieter, Populoh S., Xie W., Weidenkaff Anke, Schneider Christof W, Wokaun Alexander, Lippert Thomas (2014), Laser deposition and direct-writing of thermoelectric misfit cobaltite thin films, in Appl. Phys. Lett., 104, 231907.
Plasma interactions determine the composition in pulsed laser deposited thin films
Chen Jikun, Doebeli Max, Stender Dieter, Conder Kazimir, Wokaun Alexander, Schneider Christof W, Lippert Thomas (2014), Plasma interactions determine the composition in pulsed laser deposited thin films, in Appl. Phys. Lett. , 105, 114104.
A comparison between micro-Raman spectroscopy and SIMS of beveled surfaces for isotope depth profiling
Stender Dieter, Heiroth Sebastian, Lippert Thomas, Wokaun Alexander (2013), A comparison between micro-Raman spectroscopy and SIMS of beveled surfaces for isotope depth profiling, in Solid State Ionics , 253 , 185.
Influence of an O2 background gas on the composition and kinetic energies of species in laser induced La0.4Ca0.6MnO3 plasmas
Chen Jikun, Stender Dieter, Bator Matthias, Schneider Christof w, Lippert Thomas, Wokuan Alexander (2013), Influence of an O2 background gas on the composition and kinetic energies of species in laser induced La0.4Ca0.6MnO3 plasmas, in Applied Surface Science , 278 , 317.
Lattice distortion and strain relaxation in epitaxial thin films of multiferroic TbMnO3 probed by X-ray diffractometry and micro-Raman spectroscopy
Hu Y, Stender Dieter, Medarde M, Lippert Thomas, Wokaun Alexander, Schneider Christof W (2013), Lattice distortion and strain relaxation in epitaxial thin films of multiferroic TbMnO3 probed by X-ray diffractometry and micro-Raman spectroscopy, in Applied Surface Science , 278 , 92.
On Proton Conductivity in Porous and Dense Yttria Stabilized Zirconia at Low Temperature
Scherrer Barbara, Schlupp Meike V.F., Stender Dieter, Martynczuk Julia, Grolig Jan G., Ma Huan, Kocher Peter, Lippert Thomas, Prestat Michel, Gauckler Ludwig J. (2013), On Proton Conductivity in Porous and Dense Yttria Stabilized Zirconia at Low Temperature, in Adv. Funct. Mater., 23, 1957.
SIMS of thin films grown by pulsed laser deposition on isotopically labeled substrates
Stender Dieter, Cook Stuart, Kilner John A, Doebeli Max, Conder Kazimierz, Lippert Thomas, Wokaun Alexander (2013), SIMS of thin films grown by pulsed laser deposition on isotopically labeled substrates, in Solid State Ionics , 249, 56.
Relevance and formation mechanisms of negative ions upon ablation of Al2O3
Peláez R. J., Afonso C. N., Chen J., Esposito M., Lippert Thomas, Stender Dieter, Wokaun Alexander (2012), Relevance and formation mechanisms of negative ions upon ablation of Al2O3, in J. Phys. D. Appl. Phys., 45, 285402.
Spatially resolved strain-imprinted magnetic states in an artificial multiferroic
Chopdekar R. V., Malik V. K., Fraile Rodriguez A., Le Guyader L., Takamura Y., Scholl A., Stender D., Schneider C. W., Bernhard C., Nolting F., Heyderman L. J. (2012), Spatially resolved strain-imprinted magnetic states in an artificial multiferroic, in Phys. Rev. B , 86, 014408.

Collaboration

Group / person Country
Types of collaboration
Empa Dübendorf Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Empa Thun Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Imperial College, London Great Britain and Northern Ireland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Electroceramics XIII Talk given at a conference Zigzag-structured yttria stabilized zirconia thin films grown by pulsed laser deposition 24.06.2012 Enschede , Netherlands Stender Dieter; Lippert Thomas;
Solid State Ionics Talk given at a conference SIMS characterization of thin films grown on isotopically labelled substrates 03.07.2011 Warsaw , Poland Lippert Thomas; Stender Dieter;
ICCPS-11 Poster Crystallization behavior of 3 mol% yttria doped zirconia 29.08.2010 Zürich , Switzerland Stender Dieter; Lippert Thomas;


Associated projects

Number Title Start Funding scheme
147190 Influence of Strain and Interfaces on the Properties of Ion Conducting Thin Films for micro-Solid-Oxide-Fuel-Cells 01.05.2013 Project funding (Div. I-III)
117642 Thin oxide films by PLD: "Tracing" the oxygen and understanding its role 01.01.2008 Project funding (Div. I-III)
136211 Dynamics of Plasma Species as Generated by Laser Ablation of Al2O3 01.03.2011 International short research visits
142176 Small band-gap nanostructured perovskite materials for photovoltaic and photocatalytic hydrogen generation applications 01.01.2013 Romanian-Swiss Research Programme (RSRP)
133793 Pulsed laser deposition chamber for an advanced in situ growth control of oxide thin films and multilayers for materials research 01.12.2010 R'EQUIP

Abstract

Sub-µm thin films of oxygen-ion conductive materials are of interest as solid electrolyte in miniaturized high temperature electrochemical devices such as micro solid oxide fuel cells (SOFCs), solid oxide electrolysis cells (SOECs) and gas sensors. Due to a significant reduction of the ohmic resistance, the use of thin film technologies promises lower operational temperatures, an enhanced performance as well as an increased lifetime and wider eligible material range compared to traditional processing techniques. The fabrication as well as the analysis of the oxygen ion conduction in thin films of the ion conductors is challenging as cross-plane measurements are strongly influenced by holes, cracks, or voids in the films, grain boundaries, which serve as segregation centers for impurities, and short circuits created by metal migration especially along the grain boundaries. In addition, the influence of microstrain and varying degree of crystallinity from amorphous to nanocrystalline or mixed phases on the ionic conduction in these fluorite related structures is unclear. The application of single crystalline, i.e. perfect dense films, on conducting substrates is the most promising pathway to overcome these limitations. One intriguing approach is the deposition of single crystalline yttria stabilized zirconia (YSZ) on biaxially textured Ni substrates (with an intermediate CeO2 layer), which has been used for the deposition of superconducting YBCO tapes (RABiTS approach= rolling-assisted-biaxially-textured substrates). This highly developed system will be the starting point for the deposition of ion conduction films such as YSZ on conducting substrates. The ion conductivity will be determined by cross-plane conductivity measurements, with and without blocking electrodes and by ion exchange depth profiling (IEDP), where the isotopic oxygen exchange (18O2) and secondary ion mass spectrometry (SIMS) are used as methods. The application of depth profiling SIMS allows also to determine whether metal migration takes place and whether the formation of impurity segregations is present and how this influences the material properties. The metal migration will be tested by using intermediate layers with various thicknesses, while the role and importance of the impurities can be analyzed by using PLD targets with well-defined impurity contents. This requires also a certain control over the microstructure in the thin films, i.e. not only in the form of single crystalline films, which can be achieved by varying the deposition conditions, such as target temperature and deposition angle. As final step various ion-conducting materials will be deposited. This will allow to determine the “true” properties of the material that will be prepared without any influence of microstructures (voids etc.), impurity segregation sites, or metal migration pathways. In addition, the alternating deposition of YSZ layers with different size of unit cells, made by different Y content dopings, will create microstrain at the heteroepitaxial interfaces. Ionic conductivity measurements parallel to these strained interfaces would allow capturing the influence of microstain on ionic conductance for the first time
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