A ProboStat™ thin film setup for for the electrical characterization of thin films for both across-plane and in-plane comes in two variants, one for low temperatures (upto 200ºC) and one for high temperatures, under controlled atmosphere.
For across-plane measurements the film should be deposited on a conductive substrate and equipped with single or multiple Pt (or other) electrodes and for in-plane measurements the film should be deposited on non-conducting substrate with parallel line electrodes. Smallest recommended electrode resolution 1mm, largest recommended substrate dimensions 20 x 26mm. (For low temperature measurements in ambient atmosphere sample dimensions can be larger.)
The bottom electrode is a brass plate (gold plated for the high temperature setup). For across-plane measurements it acts normally as an electrode, and for in-plane measurements it is grounded to remove capacitance.
The two top electrodes are gold wire wrapped around a thin alumina bar, which is gently springloaded. The user can lift and place the top electrode(s) on any painted electrode dot or stripe.
The thin film measurement setup is compatible with standard ProboStat.
These articles refer to ProboStat or other NORECS products, filtered with keywords: 'thin film'The Role of Strain in Proton Conduction in Multi-Oriented BaZr0.9Y0.1O3−δ Thin Film
Authors |
Muhammad Shahrukh Saleem, Qianli Chen, Nick A. Shepelin, Simone Dolabella, Marta D. Rossell, Xuhai Zhang, Coleman X. Kronawitter, Fabio La Mattina, and Artur Braun
|
Source |
ACS Appl. Mater. Interfaces
Volume: 14,
Issue: 50,
Pages: 55915–55924 Time of Publication: 2022 |
Abstract | Within the emerging field of proton-conducting fuel cells, BaZr0.9Y0.1O3−δ (BZY10) is an attractive material due to its high conductivity and stability. The fundamentals of conduction in sintered pellets and thin films heterostructures have been explored in several studies; however, the role of crystallographic orientation, grains, and grain boundaries is poorly understood for proton conduction. This article reports proton conduction in a self-assembled multi-oriented BZY10 thin film grown on top of a (110) NdGaO3 substrate. The multiple orientations are composed of different lattices, which provide a platform to study the lattice-dependent conductivity through different orientations in the vicinity of grain boundary between them and the substrate. The crystalline stacking of each orientation is confirmed by X-ray diffraction analysis and scanning transmission electron microscopy. The transport measurements are carried out under different gas atmospheres. The highest conductivity of 3.08 × 10–3 S cm–1 at 400 °C is found under a wet H2 environment together with an increased lattice parameter of 4.208 Å, while under O2 and Ar environments, the film shows lower conductivity and lattice parameter. Our findings not only demonstrate the role of crystal lattice for conduction properties but also illustrate the importance of self-assembled strategies to achieve high proton conduction in BZY10 thin films. |
Keywords | BaZrO3 thin film; BaZr0.9Y0.1O3−δ strained structure; proton conduction; crystallographic orientation |
Remark |
https://doi.org/10.1021/acsami.2c12657 Link |
Ni-doped A-site excess SrTiO3 thin films modified with Au nanoparticles by a thermodynamically-driven restructuring for plasmonic activity
Authors |
Kevin G. Both, Vilde M. Reinertsen, Thomas M. Aarholt, Ingvild J.T. Jensen, Dragos Neagu, Øystein Prytz, Truls Norby, Athanasios Chatzitakis
|
Source |
Catalysis Today
Time of Publication: 2023
|
Abstract | Plasmonically active nanoparticles offer a promising pathway to extend the absorption range of photocatalysts. While not necessarily catalytically active themselves, these particles allow the absorption of lower energy photons in wide band gap photocatalysts. Here, we present A-site excess SrTiO3 thin films, doped with Ni, where through a subsequent exsolution process we created well-socketed Ni nanoparticles in the surface of SrTiO3. These were galvanically replaced by Au, resulting in well-socketed Au nanoparticles with variable size on the surface, depending on the galvanic replacement time. Photoelectrochemical measurements and electron energy loss spectroscopy revealed the improved photoresponse of the thin films by plasmonic activity of the nanoparticles. The energy of the plasmon peak suggests that the main improvement results from the injection of hot charge carriers. Our study opens new avenues for the design and synthesis of the next generation of photocatalytic materials. |
Remark |
In press, https://doi.org/10.1016/j.cattod.2022.11.011 Link |
Structural, Optical, and Sensing Properties of Nb-Doped ITO Thin Films Deposited by the Sol–Gel Method
Authors |
Madalina Nicolescu, Daiana Mitrea, Cristian Hornoiu, Silviu Preda, Hermine Stroescu, Mihai Anastasescu, Jose Maria Calderon-Moreno, Luminita Predoana, Valentin Serban Teodorescu, Valentin-Adrian Maraloiu, Maria Zaharescu and Mariuca Gartner
|
Source |
Gels
Volume: 8,
Issue: 11,
Pages: 717 Time of Publication: 2022 |
Abstract | The aim of the present study was the development of Nb-doped ITO thin films for carbon monoxide (CO) sensing applications. The detection of CO is imperious because of its high toxicity, with long-term exposure having a negative impact on human health. Using a feasible sol–gel method, the doped ITO thin films were prepared at room temperature and deposited onto various substrates (Si, SiO2/glass, and glass). The structural, morphological, and optical characterization was performed by the following techniques: X-ray diffractometry (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV/Vis/NIR spectroscopic ellipsometry (SE). The analysis revealed a crystalline structure and a low surface roughness of the doped ITO-based thin films. XTEM analysis (cross-sectional transmission electron microscopy)showed that the film has crystallites of the order of 5–10 nm and relatively large pores (around 3–5 nm in diameter). A transmittance value of 80% in the visible region and an optical band-gap energy of around 3.7 eV were found for dip-coated ITO/Nb films on SiO2/glass and glass supports. The EDX measurements proved the presence of Nb in the ITO film in a molar ratio of 3.7%, close to the intended one (4%). Gas testing measurements were carried out on the ITO undoped and doped thin films deposited on glass substrate. The presence of Nb in the ITO matrix increases the electrical signal and the sensitivity to CO detection, leading to the highest response for 2000 ppm CO concentration at working temperature of 300 â—¦C. |
Remark |
https://doi.org/10.3390/gels8110717 Link |
Magnetron sputtered LSC-GDC composite cathode interlayer for intermediate-temperature solid oxide fuel cells
Authors |
A.A. Solovyev, A.V. Shipilova, S.V. Rabotkin, E.A. Smolyanskiy, A.N. Shmakov
|
Source |
International Journal of Hydrogen Energy
Volume: 47,
Issue: 89,
Pages: 37967-37977 Time of Publication: 2022 |
Abstract | The paper investigates the influence of the La0.6Sr0.4CoO3-δ-Gd0.1Ce0.9O1.95 (LSC-GDC) composite cathode interlayer on the operation of solid oxide fuel cells (SOFCs). Thin composite layers with the different GDC content are obtained by the reactive magnetron sputtering. The impact of the high-temperature annealing on the LSC-GDC phase composition is studied by the X-ray diffraction instrument using additionally a synchrotron radiation. The NiO-YSZ anodes with the YSZ electrolyte thin film and GDC barrier layer are used for the SOFC fabrication. The current-voltage curves and impedance spectra of SOFCs are obtained in the temperature range of 700–800°Ð¡. It is shown that not annealed composite layers with ∼50 vol% GDC content possess the most efficient electrochemical activity. The maximum power density of the SOFC with the LSC-GDC interlayer is 1322, 1041 and 796 mW/cm2 at 800, 750 and 700 °C, respectively, which is 20–35% higher than that of the cell without cathode interlayer. |
Remark |
https://doi.org/10.1016/j.ijhydene.2022.08.281 Link |
Nanostructured La0.75Sr0.25Cr0.5Mn0.5O3–Ce0.8Sm0.2O2 Heterointerfaces as All-Ceramic Functional Layers for Solid Oxide Fuel Cell Applications
Authors |
Juan de Dios Sirvent, Albert Carmona, Laetitia Rapenne, Francesco Chiabrera, Alex Morata, Mónica Burriel, Federico Baiutti, and Albert Tarancon
|
Source |
ACS Appl. Mater. Interfaces
Volume: 14,
Issue: 37,
Pages: 42178–42187 Time of Publication: 2022 |
Abstract | The use of nanostructured interfaces and advanced functional materials opens up a new playground in the field of solid oxide fuel cells. In this work, we present two all-ceramic thin-film heterostructures based on samarium-doped ceria and lanthanum strontium chromite manganite as promising functional layers for electrode application. The films were fabricated by pulsed laser deposition as bilayers or self-assembled intermixed nanocomposites. The microstructural characterization confirmed the formation of dense, well-differentiated, phases and highlighted the presence of strong cation intermixing in the case of the nanocomposite. The electrochemical properties─solid/gas reactivity and in-plane conductivity─are strongly improved for both heterostructures with respect to the single-phase constituents under anodic conditions (up to fivefold decrease of area-specific resistance and 3 orders of magnitude increase of in-plane conductivity with respect to reference single-phase materials). A remarkable electrochemical activity was also observed for the nanocomposite under an oxidizing atmosphere, with no significant decrease in performance after 400 h of thermal aging. This work shows how the implementation of nanostructuring strategies not only can be used to tune the properties of functional films but also results in a synergistic enhancement of the electrochemical performance, surpassing the parent materials and opening the field for the fabrication of high-performance nanostructured functional layers for application in solid oxide fuel cells and symmetric systems. |
Keywords | thin films, hydrogen oxidation reaction, symmetric functional layers, solid oxide cells, nanocomposites |
Remark |
https://doi.org/10.1021/acsami.2c14044 Link |
Protonic Transport Properties of Perovskite Heterostructures A Thin Film Study
Author |
Erik E. P. Alsgaard
|
Source |
Time of Publication: 2021
|
Remark |
Master Thesis Materials Science for Energy and Nanotechnology Link |
Anode-supported solid oxide fuel cells with multilayer LSC/CGO/LSC cathode
Authors |
A.A. Solovyev, K.A. Kuterbekov, S.A. Nurkenov, A.S. Nygymanova, A.V. Shipilova, E.A. Smolyanskiy, S.V. Rabotkin., I.V. Ionov
|
Source |
Fuel Cells
Volume: 21,
Issue: 4,
Pages: 408-412 Time of Publication: 2021 |
Abstract | The multilayer La0.6Sr0.4CoO3/Ce0.9Gd0.1O2/La0.6Sr0.4CoO3 (LSC/CGO/LSC) thin film cathode of the solid oxide fuel cell (SOFC) with the different thickness of the LSC and CGO layers are obtained by magnetron sputtering. Cathodes are deposited onto the NiO/8YSZ anode-supported 8YSZ/CGO bilayer electrolyte. The influence of the deposited multilayer cathode on the SOFC performance is investigated in the temperature range between 800 and 600°C. It is shown that the thin-film multilayer cathode allows increasing the SOFC efficiency, and the obtained optimum thickness of the LSC and CGO layers provides the maximum power density for SOFCs. The maximum power density of 2430, 1170, and 290 mW cm–2 is obtained respectively at 800, 700, and 600°C for the SOFCs with the LSC/CGO/LSC layer 50/50/50 nm thick. The polarization resistance measured at 800 and 750°C on the symmetric SOFC with the CGO electrolyte and LSC/CGO/LSC cathode is 0.17 and 0.3 Ω cm2, respectively. |
Remark | Link |
Metal Supported Proton Conducting Ceramic Cell with Thin Film Electrolyte for Electrolysis Application
Authors |
Haoyu Zheng, Feng Han, Noriko Sata, Matthias Riegraf, Amir Masoud Dayaghi, Truls Norby and Rémi Costa
|
Source |
ECS Transactions
Volume: 103,
Issue: 1,
Pages: 693 Time of Publication: 2021 |
Abstract | Manufacturing of metal supported proton conducting ceramic cells is investigated in the present study. A low temperature fabrication route was chosen to avoid metal corrosion during the fabrication process, in which pulsed laser deposition (PLD) was employed to apply the thin-film BaZr0.7Ce0.2Y0.1O3-δ electrolyte layer. The surface condition of the support layer is a critical aspect to produce a dense and gas-tight electrolyte layer by PLD. In order to decrease the average size of the 10-30 µm large pores in metal substrate down to the nano-scale, different powders with different particles size were successfully fabricated and integrated into a pore-size graded structure to form a homogeneous porous surface whose size distribution meets the requirements for making a dense PLD coating layer. An electrolyte layer with the intended phase is achieved with a thickness of around 1 µm. Initial electrochemical investigation with a Pt oxygen electrode showed a total resistance of 4.92 Ω cm2 at 600°C at OCV. |
Remark | Link |
The Electrochemical Society, find out more The Electrochemical Society, find out more Metal Supported Proton Conducting Ceramic Cell with Thin Film Electrolyte for Electrolysis Application
Authors |
Haoyu Zheng, Feng Han, Noriko Sata, Matthias Riegraf, Amir Masoud Dayaghi, Truls Norby and Rémi Costa
|
Source |
ECS Transactions
Volume: 103,
Pages: 693 Time of Publication: 2021 |
Abstract | Manufacturing of metal supported proton conducting ceramic cells is investigated in the present study. A low temperature fabrication route was chosen to avoid metal corrosion during the fabrication process, in which pulsed laser deposition (PLD) was employed to apply the thin-film BaZr0.7Ce0.2Y0.1O3-δ electrolyte layer. The surface condition of the support layer is a critical aspect to produce a dense and gas-tight electrolyte layer by PLD. In order to decrease the average size of the 10-30 µm large pores in metal substrate down to the nano-scale, different powders with different particles size were successfully fabricated and integrated into a pore-size graded structure to form a homogeneous porous surface whose size distribution meets the requirements for making a dense PLD coating layer. An electrolyte layer with the intended phase is achieved with a thickness of around 1 µm. Initial electrochemical investigation with a Pt oxygen electrode showed a total resistance of 4.92 Ω cm2 at 600°C at OCV. |
Remark | Link |
Structural and Electrochemical Properties of Scandia Alumina Stabilized Zirconia Thin Films
Authors |
Mantas Sriubas, Darius Virbukas, Nursultan Kainbayev, Kristina Bockute and Giedrius Laukaitis
|
Source |
Coatings
Volume: 11,
Issue: 7,
Pages: 800 Time of Publication: 2021 |
Abstract | This work presents a systematic investigation of scandia alumina stabilized zirconia (ScAlSZ, composition: ZrO2:Sc2O3:Al2O3 93:6:1 wt.%) thin films (~2 μm). Thin films were formed by the e-beam evaporation method on 450 °C substrates. The influence of Al concentration on thin film microstructure, structure, and electrochemical properties was characterized by EDS, XRD, Raman, and EIS methods. It was found that the aluminum concentration in the deposited thin films decreased with an increase in the deposition rate. The concentration of Al changed from 15.9 to 3.8 at.% when the deposition rates were 0.2 and 1.6 nm/s, respectively. The crystallinity of the thin films depended strongly on the concentration of Al, resulting in an amorphous phase when Al concentration was 22.2 at.% and a crystalline phase when Al concentration was lower. ScAlSZ thin films containing 15.9 at.% of Al had monoclinic and tetragonal phases, while thin films with 1.6 and 3.8 at.% of Al had a mixture of cubic, tetragonal, and monoclinic phases. The phase transition was observed during the thermal annealing process. Cubic and rhombohedral phases formed in addition to monoclinic and tetragonal phases appeared after annealing ScAlSZ thin films containing 15.9 and 22.2 at.% of aluminum. The highest total ionic conductivity (σbulk = 2.89 Sm−1 at 800 °C) was achieved for ScAlSZ thin films containing 3.8 at.% of Al. However, thin films containing a higher concentration of aluminum had more than 10 times lower total conductivity and demonstrated changes in activation energy at high temperatures (>560 °C). Activation energies changed from ~1.10 to ~1.85 eV. |
Keywords | electron beam deposition; scandia alumina stabilized zirconia (ScAlSZ); solid oxide fuel cells (SOFC); ionic conductivity |
Remark |
https://doi.org/10.3390/coatings11070800 Link |
Amorphous ZnO modified anatase TiO2 thin films templated by tripropylamine and their electrical properties
Authors |
Izabella Dascalu, Jose Maria Calderon-Moreno, Petre Osiceanu, Veronica Bratan, Cristian Hornoiu, Simona Somacescu
|
Source |
Thin Solid Films
Volume: 729,
Pages: 138697 Time of Publication: 2021 |
Abstract | In the present study we report on a low cost synthesis of amorphous ZnO modified anatase TiO2 (40 and 20 mol% ZnO) thin films deposited via sol-gel spin coating technique on glass substrate. The effects of the composition on the structural, morphological and surface chemistry properties were discussed and correlated with the electrical behavior. Thus, by X-ray diffraction and Raman spectroscopy only TiO2 indexed in the anatase crystalline structure was identified without any ZnO characteristic crystalline phase. The surface chemistry assessed by X-ray Photoelectron spectroscopy highlighted the presence of Ti4+ in TiO2 as well as the presence of Zn2+ coordinated in the amorphous ZnO proved by the Auger ZnLMM transition shifted toward lower binding energies. The films are continuous, homogeneous with grain size below 20 nm and exhibit an intergranular porosity, as it was displayed by Scanning Electron Microscopy. The sensor signal towards CO exposure is strongly related to the amount of the ZnO amorphous phase formation. Thus, we found that a higher content of the ZnO amorphous phase leads to a lower sensitivity. The electrical and sensing measurements were performed in the temperature range (room temperature 400 °C), over the range of CO concentrations (0-2000 ppm). The sensor containing 20 mol.% amorphous ZnO exhibits a good sensitivity at ~300 °C for a low CO concentration . |
Keywords | Amorphous zinc oxide; Titanium dioxide; Mixed oxides; Sol-gel spin coating technique; Electrical conductivity; Carbon monoxide detection |
Remark | Link |
The performance of intermediate temperature solid oxide fuel cells with sputter deposited La1-xSrxCoO3 interlayer
Authors |
A. A. Solovyev, A. V. Shipilova, I. V. Ionov, E. A. Smolyanskiy, A. V. Nikonov & N. B. Pavzderin
|
Source |
Journal of Electroceramics
Volume: 45,
Pages: 156–163 Time of Publication: 2020 |
Abstract | The paper studies the performance of the intermediate temperature solid oxide fuel cells with the sputter deposited La1-xSrxCoO3 (LSC) interlayer between the cathode and electrolyte. The sputter deposition of the LSC thin films is carried out in argon gas and in a mixture of argon and oxygen gases and then are annealed at 600, 800 and 1000 °C in air for 2 h. The structure and composition of the sputter deposited LSC films are investigated by the X-ray diffraction analysis, scanning and transmission electron microscopies, and energy-dispersive X-ray spectroscopy. The polarization resistance of the sputter deposited LSC films (600 nm thick) on the symmetric cells is 0.13, 0.45 and 2.48 Ohm·cm2 measured at 800, 700 and 600 °C, respectively. Measurements are performed by electrochemical impedance spectroscopy. The maximum power density of the anode-supported solid oxide fuel cells with the yttria-stabilized zirconia/gadolinia-doped ceria bilayer electrolyte, LSC interlayer, and LSC cathode is 2.27, 1.58 and 0.68 W/cm2 measured at 800, 700 and 600 °C, respectively. These values of the power density are respectively 1.4, 1.6 and 2.3 times higher than that of the reference cell without the LSC interlayer. |
Remark | Link |
Properties of Barium Cerate Thin Films Formed Using E-Beam Deposition
Authors |
Monica Susana Campos Covarrubias, Mantas Sriubas, Kristina Bockute, Piotr Winiarz, Tadeusz Miruszewski, Wojciech Skubida, Daniel Jaworski, Michał Bartmanski, Marek Szkodo, Maria Gazda and Giedrius Laukaitis
|
Source |
Crystals
Volume: 10,
Pages: 1152 Time of Publication: 2020 |
Abstract | This article focuses on the properties of the BaCeO3 thin films formed by electron-beam vapor deposition and investigates the formation of barium cerates on supports with different thermal expansion coefficients (Stainless Steel, Invar, Glass Sealing, and Inconel substrates) and the influence of the technological parameters on the properties of the formed thin films with an emphasis on the stability of the films. Morphology and phase composition and mechanical and electrical properties were investigated. It was found that the main factors influencing the phase composition and morphology of the films are the temperature of the support and the deposition rate. However, the mechanical properties of the films are mostly influenced by strains introduced to thin films by using different supports. Two interesting features of the electrical properties of the studied strained films were noticed: the film with the highest in-plane tensile strain showed the lowest activation energy of total conductivity, whereas the film with the lowest strain showed the highest value of total conductivity. |
Remark | Link |
Ionic conductivity in LixTaOy thin films grown by atomic layer deposition
Authors |
Yang Hu, Ville Miikkulainen, Kenichiro Mizohata, Truls Norby, Ola Nilsen, Helmer Fjellvåg
|
Source |
Electrochimica Acta
Volume: 361,
Pages: 137019 Time of Publication: 2020 |
Abstract | The material system Li-Ta-O is a promising candidate for thin-film solid-state electrolytes in Li-ion batteries. In the present study, we have varied the Li content x in LixTaOy thin films grown by atomic layer deposition (ALD) with the aim of improving the Li-ion conductivity. The amorphous films were grown at 225 °C on insulating sapphire and on conductive Ti substrates using tantalum ethoxide (Ta(OEt)5), lithium tert-butoxide (LiOtBu) and water as reactants. The film composition was determined by time-of-flight elastic recoil detection analysis (TOF-ERDA), displaying an almost linear relationship between the pulsed and deposited Li content. The ionic conductivities were determined by in-plane and cross-plane AC measurements, exhibiting an Arrhenius-type behaviour and comparatively weak thickness-dependence. Increasing Li content x from 0.32 to 0.98 increases the film conductivity by two orders of magnitude while higher Li content x = 1.73 results in decreased conductivity. A room-temperature conductivity σRT of ~10−8 S cm−1 is obtained for a 169 nm thick Li0.98TaOy film. The evolution of conductivity and activation energy suggests a competing effect between the concentration and the mobility of mobile Li ions when more Li are incorporated. The compositional dependence of Li transport mechanism is discussed. |
Keywords | Atomic layer deposition; LixTaOy thin films; Solid-state electrolytes; TOF-ERDA; Ionic conductivity |
Remark | Link |
AlTiN based thin films for degradation protection of tetrahedrite thermoelectric material
Authors |
S. Battiston, F. Montagner, S. Fiameni, A. Famengo, S. Boldrini, A. Ferrario, C. Fanciulli, F. Agresti, M. Fabrizio
|
Source |
Journal of Alloys and Compounds
Volume: 792,
Pages: 953-959 Time of Publication: 2019 |
Abstract | Efficient protection against degradation process of tetrahedrite-based thermoelectric materials was obtained employing AlTiN based thin films. The coatings were deposited via reactive direct current physical vapour deposition magnetron sputtering. The composition, thermal and electrical behaviour of thin films were investigated by X-ray diffraction, energy dispersive spectroscopy associated to field emission scanning electron microscopy, thermogravimetric analyses and electrical conductivity measurements. The barrier features for oxygen protection during thermal treatment in air at 500 °C were qualitatively evaluated, studying the coating behaviour over the higher operating temperature of tetrahedrite based thermoelectric devices. |
Remark |
https://doi.org/10.1016/j.jallcom.2019.04.116 Link |
Unraveling bulk and grain boundary electrical properties in La0.8Sr0.2Mn1−yO3±δ thin films
Authors | |
Source |
APL Materials Volume: 7, Pages: 013205 Time of Publication: 2019 |
Abstract | Grain boundaries in Sr-doped LaMnO3±δthin films have been shown to strongly influence the electronic and oxygen mass trans-port properties, being able to profoundly modify the nature of the material. The unique behavior of the grain boundaries canbe correlated with substantial modifications of the cation concentration at the interfaces, which can be tuned by changing theoverall cationic ratio in the films. In this work, we study the electronic properties of La0.8Sr0.2Mn1−yO3±δthin films with variableMn content. The influence of the cationic composition on the grain boundary and grain bulk electronic properties is elucidatedby studying the manganese valence state evolution using spectroscopy techniques and by confronting the electronic propertiesof epitaxial and polycrystalline films. Substantial differences in the electronic conduction mechanism are found in the presenceof grain boundaries and depending on the manganese content. Moreover, the unique defect chemistry of the nanomaterial is elu-cidated by measuring the electrical resistance of the thin films as a function of oxygen partial pressure, disclosing the importanceof the cationic local non-stoichiometry on the thin film behavior. |
Remark | Link |
Effect of magnetron sputtered anode functional layer on the anode-supported solid oxide fuel cell performance
Authors |
A.A. Solovyeva, A.M. Lebedynskiy, A.V. Shipilova, I.V. Ionov, E.A. Smolyanskiy, A.L. Lauk, G.E. Remnev
|
Source |
International Journal of Hydrogen Energy
Time of Publication: 2018
|
Abstract | Nickel oxide-yttria stabilized zirconia (NiO-YSZ) thin films were reactively sputter-deposited by pulsed direct current magnetron sputtering from the Ni and ZrY targets onto heated commercial NiO-YSZ substrates. The microstructure and composition of the deposited films were investigated with regard to application as thin anode functional layers (AFLs) for solid oxide fuel cells (SOFCs). The pore size, microstructure and phase composition of both as-deposited and annealed at 1200 °C for 2 h AFLs were studied by scanning electron microscopy and X-ray diffractometry and controlled by changing the deposition process parameters. The results show that annealing in air at 1200 °C is required to improve structural homogeneity of the films. NiO-YSZ films have pores and grains of several hundred nanometers in size after reduction in hydrogen. Adhesion of deposited films was evaluated by scratch test. Anode-supported solid oxide fuel cells with the magnetron sputtered anode functional layer, YSZ electrolyte and La0.6Sr0.4Co0.2Fe0.8O3/Ce0.9Gd0.1O2 (LSCF/CGO) cathode were fabricated and tested. Influence of thin anode functional layer on performance of anode-supported SOFCs was studied. It was shown that electrochemical properties of the single fuel cells depend on the NiO volume content in the NiO-YSZ anode functional layer. Microstructural changes of NiO-YSZ layers after nickel reduction-oxidation (redox) cycling were studied. After nine redox cycles at 750 °C in partial oxidation conditions, the cell with the anode NiO-YSZ layer showed stable open circuit voltage values with the power density decrease by 11% only. |
Remark |
In Press, https://doi.org/10.1016/j.ijhydene.2018.11.193 Link |
Engineering Transport in Manganites by Tuning Local Nonstoichiometry in Grain Boundaries
Authors | |
Source |
Advanced Materials
Volume: 31,
Issue: 4,
Pages: 1805360 Time of Publication: 2019 |
Abstract | Interface‐dominated materials such as nanocrystalline thin films have emerged as an enthralling class of materials able to engineer functional properties of transition metal oxides widely used in energy and information technologies. In particular, it has been proven that strain‐induced defects in grain boundaries of manganites deeply impact their functional properties by boosting their oxygen mass transport while abating their electronic and magnetic order. In this work, the origin of these dramatic changes is correlated for the first time with strong modifications of the anionic and cationic composition in the vicinity of strained grain boundary regions. We are also able to alter the grain boundary composition by tuning the overall cationic content in the films, which represents a new and powerful tool, beyond the classical space charge layer effect, for engineering electronic and mass transport properties of metal oxide thin films useful for a collection of relevant solid‐state devices. |
Remark | Link |
Influence of the Initial Powder’s Specific Surface Area on the Properties of Sm-Doped Ceria Thin Films
Authors |
Mantas Sriubas, Kristina Bockute, Nursultan Kainbayev and Giedrius Laukaitis
|
Source |
Crystals
Time of Publication: 2018
|
Remark | Link |
Influence of texture and grain misorientation on the ionic conduction in multilayered solid electrolytes – interface strain effects in competition with blocking grain boundaries
Authors |
J. Keppner, J. Schubert, M. Ziegner, B. Mogwitz, J. Janek and C. Korte
|
Source |
Physical Chemistry Chemical Physics
Issue: 14
Time of Publication: 2018
|
Abstract | Interface strain and its influence on the ionic transport along hetero-interfaces has gained a lot of attention over the last decade and is controversially discussed. We investigate the relaxation of mismatch induced interfacial strain as a function of the degree of orientation/texture of the columnar crystallites and assess the impact on the oxygen ion conductivity in Er2O3/YSZ multilayer systems. Results from X-ray diffraction clearly show, that the width of the strained hetero-interface region increases with an increasing degree of orientation of the crystallites. The combined impact of film texture and strain at the hetero-interfaces of the film on the ionic conductivity however is not easily deduced from these measurements. The samples with the highest degree of orientation, i.e. with only one azimuthal variant, show strong anisotropic electrical properties. In samples with a lower degree of orientation, i.e. samples with a fiber texture, anisotropic properties cannot be detected, possibly due to a geometrical averaging of the electrical properties. The expected strain induced monotonic increase of the ionic conductivity with decreasing layer thickness and thus increasing interfacial influence could only be detected for samples with a fiber texture and a considerable degree of crystallite misorientation. This leads to the important conclusion that the texture and therefore the nature of the grain boundaries and their network influence the ionic conductivity of the multilayer thin films in the same order of magnitude as the misfit induced interface strain. Thus, the potential design of strain-controlled ionic conductors requires additionally the control of the microstructure in terms of grain orientation. |
Remark | Link |
Deposition of nickel oxide-yttria stabilized zirconia thin films by reactive magnetron sputtering
Authors |
A.A .Solovyev, A.M. Lebedynskiy, A.V. Shipilova, I.V.Ionov, E.A. Smolyanskiy, A.L. Lauk, G.E. Remnev
|
Source |
International Journal of Hydrogen Energy
Time of Publication: 2018
|
Abstract | Nickel oxide-yttria stabilized zirconia (NiO-YSZ) thin films were reactively sputter-deposited by pulsed direct current magnetron sputtering from the Ni and Zr-Y targets onto heated commercial NiO-YSZ substrates. The microstructure and composition of the deposited films were investigated with regard to application as thin anode functional layers (AFLs) for solid oxide fuel cells (SOFCs). The porosity and microstructure of both as-deposited and annealed at 1200 °C for 2 h AFLs were studied by scanning electron microscopy and X-ray diffractometry and controlled by changing the deposition process parameters. The results show that annealing in air at 1200 °C is required to improve film crystallinity and structural homogeneity. NiO-YSZ films have pores and grains of several hundred nanometers in size after reduction in hydrogen. Adhesion of deposited films was evaluated by scratch test. Anode-supported solid oxide fuel cells with the magnetron sputtered anode functional layer, YSZ electrolyte and La0.6Sr0.4Co0.2Fe0.8O3/Ce0.9Gd0.1O2 (LSCF/CGO) cathode were fabricated and tested. Influence of thin anode functional layer on performance of anode-supported SOFCs was studied. It was shown that electrochemical properties of the single fuel cells depend on the NiO volume content in the NiO-YSZ anode functional layer. Microstructural changes of NiO-YSZ layers after nickel reduction-oxidation (redox) cycling were studied. After nine redox cycles at 750 °C in partial oxidation conditions, the cell with the anode NiO-YSZ layer showed stable open circuit voltage values with the power density decrease by 11% only. |
Keywords | Solid oxide fuel cells, Magnetron sputtering, Thin-film anode, Microstructure, Redox cycling |
Remark |
Available online 7 February 2018, https://doi.org/10.1016/j.ijhydene.2018.01.076 Link |
Optimisation of growth parameters to obtain epitaxial Y-doped BaZrO3 proton conducting thin films
Authors | |
Source |
Volume: 314,
Pages: 9–16 Time of Publication: 2018 |
Abstract | We hereby report developments on the fabrication and characterization of epitaxial thin films of proton conducting Y-doped BaZrO3 (BZY) by pulsed laser deposition (PLD) on different single crystal substrates (MgO, GdScO3, SrTiO3, NdGaO3, LaAlO3 and sapphire) using Ni-free and 1% Ni-containing targets. Pure, high crystal quality epitaxial films of BZY are obtained on MgO and on perovskite-type substrates, despite the large lattice mismatch. The deposition conditions influence the morphology, cell parameters and chemical composition of the film, the oxygen partial pressure during film growth being the most determining. Film characterization was carried out using X-ray diffraction, transmission electron and atomic force microscopies, wavelength dispersive X-ray spectroscopy and angle-resolved X-ray photoelectron spectroscopy. All films show a slight tetragonal distortion that is not directly related to the substrate-induced strain. The proton conductivity of the films depends on deposition conditions and film thickness, and for the optimised conditions its total conductivity is slightly higher than the bulk conductivity of the target material (3 mS/cm at 600 °C, in wet 5% H2/Ar). The conductivities are, however, more than one order of magnitude lower than the highest reported in literature and possible reasoning is elucidated in terms of local and extended defects in the films. |
Keywords | BaZrO3; Thin film; Electrolyte; Proton conductivity; SOFC; PC-SOFC |
Remark |
https://doi.org/10.1016/j.ssi.2017.11.002 Link |
Microstructural engineering and use of efficient poison resistant Au-doped Ni-GDC ultrathin anodes in methane-fed solid oxide fuel cells
Authors | |
Source |
International Journal of Hydrogen Energy
Volume: 43,
Issue: 2,
Pages: 885–893 Time of Publication: 2018 |
Abstract | Ultrathin porous solid oxide fuel cell (SOFC) anodes consisting of nickel-gadolinia-doped-ceria (Ni-GDC) cermets with a unique porous micro-columnar architecture with intimate contact between the GDC and the Ni phases were made by magnetron sputtering at an oblique deposition angle and characterised in detail by a variety of methods prior to use in hydrogen or methane-fuelled SOFCs. These Ni-GDC anodes exhibited excellent transport properties, were robust under thermal cycling and resistant to delamination from the underlying yttria-stabilised zirconia electrolyte. Similarly prepared Au-doped Ni-GDC anodes exhibited the same morphology, porosity and durability. The gold associated exclusively with the Ni component in which it was present as a surface alloy. Strikingly, whatever their treatment, a substantial amount of Ce3+ persisted in the anodes, even after operation at 800 °C under fuel cell conditions. With hydrogen as fuel, the un-doped and Au-doped Ni-GDC anodes exhibited identical electrochemical performances, comparable to that of much thicker commercial state-of-the-art Ni-GDC anodes. However, under steam reforming conditions with CH4/H2O mixtures the behaviour of the Au-doped Ni-GDC anodes were far superior, exhibiting retention of good power density and dramatically improved resistance to deactivation by carbon deposition. Thus two distinct beneficial effects contributed to overall performance: persistence of Ce3+ in the working anodes could induce a strong metal-support interaction with Ni that enhanced the catalytic oxidation of methane, while formation of a Nisingle bondAu surface alloy that inhibited carbonisation and poisoning of the active nickel surface. |
Keywords | SOFC; Ultrathin film anodes; Magnetron sputtering; Gadolinia doped ceria; Carbon-tolerant; Gold doping |
Remark |
https://doi.org/10.1016/j.ijhydene.2017.11.020 Link |
High performance novel gadolinium doped ceria/yttria stabilized zirconia/nickel layered and hybrid thin film anodes for application in solid oxide fuel cells
Authors | |
Source |
Journal of Power Sources
Volume: 363,
Pages: 251-259 Time of Publication: 2017 |
Abstract | Magnetron sputtering under oblique angle deposition was used to produce Ni-containing ultra thin film anodes comprising alternating layers of gadolinium doped ceria (GDC) and yttria stabilized zirconia (YSZ) of either 200 nm or 1000 nm thickness. The evolution of film structure from initial deposition, through calcination and final reduction was examined by XRD, SEM, TEM and TOF-SIMS. After subsequent fuel cell usage, the porous columnar architecture of the two-component layered thin film anodes was maintained and their resistance to delamination from the underlying YSZ electrolyte was superior to that of corresponding single component Ni-YSZ and Ni-GDC thin films. Moreover, the fuel cell performance of the 200 nm layered anodes compared favorably with conventional commercially available thick anodes. The observed dependence of fuel cell performance on individual layer thicknesses prompted study of equivalent but more easily fabricated hybrid anodes consisting of simultaneously deposited Ni-GDC and Ni-YSZ, which procedure resulted in exceptionally intimate mixing and interaction of the components. The hybrids exhibited very unusual and favorable IV characteristics, along with exceptionally high power densities at high currents. Their discovery is the principal contribution of the present work. |
Keywords | Magnetron sputtering, Oblique angle deposition, Thin film anodes, Layered and hybrid structures, SOFC |
Remark |
https://doi.org/10.1016/j.jpowsour.2017.07.085 Link |
Development of novel metal-supported proton ceramic electrolyser cell with thin film BZY15–Ni electrode and BZY15 electrolyte
Authors | |
Source |
International Journal of Hydrogen Energy
Volume: 42,
Issue: 19,
Pages: 13454–13462 Time of Publication: 2017 |
Abstract | Metal supports for planar MS-PCEC were manufactured using tape-casting of low-cost ferritic stainless steel. A coating protecting the metal support against oxidation was applied by vacuum infiltration and a buffer layer of La0.5Sr0.5Ti0.75Ni0.25O3–δ (LSTN) was further deposited to smoothen the surface. The BaZr0.85Y0.15O3–δ–NiO (BZY15–NiO) cathode and the BaZr0.85Y0.15O3–δ (BZY15) electrolyte were applied by pulsed laser deposition (PLD) at elevated substrate temperatures (at 700 °C and 600 °C, respectively). The main challenges are related to the restrictions in sintering temperature and atmosphere induced by the metal support, as well as strict demands on the roughness of substrates used for PLD. Reduction treatment of the half cells confirmed that NiO in the BZY15–NiO layer was reduced to Ni, resulting in increased porosity of the BZY15–Ni cathode, while keeping the columnar and dense microstructure of the BZY15 electrolyte. Initial electrochemical testing with a Pt anode showed a total resistance of 40 Ω·cm2 at 600 °C. Through this work important advances in using metal supports and thin films in planar PCEC assemblies have been made. |
Keywords | Proton ceramic electrolyser cell (PCEC); Tape casting; Thin film deposition; Metal supports |
Remark |
https://doi.org/10.1016/j.ijhydene.2017.03.028 Link |
Magnetron-sputtered La0.6Sr0.4Co0.2Fe0.8O3 nanocomposite interlayer for solid oxide fuel cells
Authors |
A. A. Solovyev, I. V. Ionov, A. V. Shipilova, A. N. Kovalchuk, M. S. Syrtanov
|
Source |
Journal of Nanoparticle Research
Time of Publication: 2017
|
Abstract | A thin layer of a La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) is deposited between the electrolyte and the La0.6Sr0.4Co0.2Fe0.8O3/Ce0.9Gd0.1O2 (LSCF/CGO) cathode layer of a solid oxide fuel cell (SOFC) by pulsed magnetron sputtering using an oxide target of LSCF. The films were completely dense and well adherent to the substrate. The effects of annealing in temperature range from 200 to 1000 °C on the crystalline structure of the LSCF films have been studied. The films of nominal thickness, 250–500 nm, are crystalline when annealed at temperatures above 600 °C. The crystalline structure, surface topology, and morphology of the films were determined using X-ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM), respectively. To study the electrochemical characteristics of the deposited-film, solid oxide fuel cells using 325-nm LSCF films as interlayer between the electrolyte and the cathode have been fabricated. The LSCF interlayer improves the overall performance of the SOFC by increasing the interfacial area between the electrolyte and cathode. The electrolyte-supported cells with the interlayer have 30% greater, overall power output compared to that achieved with the cells without interlayer. The LSCF interlayer could also act as a transition layer that improves adhesion and relieves both thermal stress and lattice strain between the cathode and the electrolyte. Our results demonstrate that pulsed magnetron sputtering provides a low-temperature synthesis route for realizing ultrathin nanocrystalline LSCF film layers for intermediate- or low-temperature solid oxide fuel cells. |
Keywords | (La,Sr)(Co,Fe)O3 Magnetron sputtering Nanocomposite Interlayer Solid oxide fuel cells Nanostructured thin films Energy conversion |
Remark |
DOI: 10.1007/s11051-017-3791-0 Link |
The structural and electrical properties of samarium doped ceria films formed by e-beam deposition technique
Authors |
Darius Virbukas, Giedrius Laukaitis
|
Source |
Solid State Ionics
Time of Publication: 2016
|
Abstract | Sm2O3-doped CeO2 (Sm0.15Ce0.85O1.925, SDC) thin films were formed by e-beam evaporation method. Thin films were formed evaporating micro powders (particle size varied from 0.3 to 0.5 μm). The influence of deposition rate on formed thin film structures and surface morphology were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersion spectrometry (EDS), and atomic force microscopy (AFM). The deposition rate of formed SDC thin films was changed from 2 to 16 Å/s. The electrical properties were investigated as a function of frequency (0.1–106 Hz) at different temperatures (473–873 K). The formed SDC thin ceramic films repeat the crystallographic orientation of the initial powders using different substrates and different deposition rate. It was determined that crystallites size and samarium concentration are decreasing by increasing the deposition rate. The crystallites size decreased from 17.0 nm to 10.4 nm when SDC thin films were deposited on Alloy 600 (Fe-Ni-Cr), and decreased from 13.7 nm to 8.9 nm when were used optical quartz substrate. The best ionic conductivity σtot = 1.66 Sm− 1 at 873 K temperature, activation energy ΔEa = 0.87 eV (σg = 1.66 Sm− 1, σgb = 1.66 Sm− 1) was achieved when 2 Å/s deposition rate was used. The grain size (in the formed SDC thin films) was ~ 83 nm in this case. |
Keywords | Electron beam deposition; Samarium doped ceria oxide (SDC); Solid oxide fuel cells (SOFC); Ionic conductivity |
Remark |
http://dx.doi.org/10.1016/j.ssi.2016.12.003 Link |
Oxygen ion conductivity in samarium and gadolinium stabilized cerium oxide heterostructures
Authors |
Marius Zienius, Kristina Bockute, Darius Virbukas, Giedrius Laukaitis
|
Source |
Solid State Ionics
Time of Publication: 2016
|
Abstract | Gadolinium (GDC) and samarium (SDC) doped ceria were investigated in terms of multilayer systems, evaporated by e-beam technique on optical quartz, Alloy600 and sapphire substrate. GDC-SDC heterostructures of 1.3 μm thicknesses, composed of 1, 2, 3, 5 and 7 layers and they were investigated by structural and ionic conductivity techniques. Bragg peaks show nanocrystalline state of Gd and Sm doped ceria thin films. XRD patterns show fluorite type structure with space group Fm3m. The XRD analysis of thin films, deposited on quartz substrate, reveals the increase of (220) peak with increasing number of layers. The decrease of (111) peak is slightly notable, also. Thin film heterostructures have a face-centered cubic cell with the following lattice parameters, such as 5.4180 nm for GDC of and of 5.4245 nm for SDC. The scanning electron microscopy cross sectional analysis of three-layered structure clearly indicates the interfaces of different material. There are no visually distinct discontinuities in higher layer structures (5–7 layers). Total conductivity increases linearly with increasing of temperature, but decreases with the increase of number of layers. The highest total ionic conductivity at 1214 K temperature for SDC and GDC thin monolayers was 1.62 S/m and 1.02 S/m, respectively. The activation energy increases with the increase of number of layer as well. |
Keywords | Multilayer electrolyte; SDC; GDC; e-Beam deposition |
Remark |
http://dx.doi.org/10.1016/j.ssi.2016.11.025 Link |
AgI thin films prepared by laser ablation
Authors |
Svetlana V. Fokina, Eugene N. Borisov, Vladimir V. Tomaev, Ilya I. Tumkin, Yuri S. Tveryanovich
|
Source |
Solid State Ionics
Volume: 297,
Pages: 64–67 Time of Publication: 2016 |
Abstract | High quality and uniform morphology AgI films consisting of crystal grains about 30 nm in size were obtained by the laser (XeCl) ablation method. The designed silver iodide films have crystalline structure, optical and electrical properties corresponding to stoichiometric compound films. We have demonstrated that the laser ablation method commonly used for the preparation of thin films and nanolayered structures with the defined thickness can be successfully used for the deposition of AgI superionic conductor layers as well. The films were studied by XRD, EDA, optical absorption, photoluminescence, and impedance spectroscopies. |
Keywords | Thin films; Laser ablation; Conductivity; Optical band gap; Luminescence; Morphology; Excitons; XRD; Electron microscopy |
Remark |
http://dx.doi.org/10.1016/j.ssi.2016.10.004 Link |
Insights into the enhancement of oxygen mass transport properties of strontium-doped lanthanum manganite interface-dominated thin films
Authors | |
Source |
Solid State Ionics
Time of Publication: 2016
|
Abstract | Strontium-doped lanthanum manganite thin films were deposited by pulsed laser deposition on yttria-stabilized zirconia single crystals for a comprehensive electrochemical characterization of the material acting as a cathode. A physically-meaningful electrical model was employed to fit the electrochemical impedance spectroscopy results in order to extract the main oxygen mass transport parameters as a function of the temperature and oxygen partial pressure. The oxygen diffusion and surface exchange coefficients extracted from the analysis showed several orders of magnitude of enhancement with respect to the bulk values reported in the literature and an unexpectedly low dependence with the oxygen partial pressure. Different observations were combined to propose a mechanism for the enhanced incorporation of oxygen in interface-dominated thin films mainly based on the high concentration of oxygen vacancies expected in the grain boundaries. |
Remark |
http://dx.doi.org/10.1016/j.ssi.2016.08.009 Link |
Synthesis, characterization and performance of robust poison-resistant ultrathin film yttria stabilized zirconia – nickel anodes for application in solid electrolyte fuel cells
Authors | |
Source |
Journal of Power Sources
Volume: 324,
Pages: 679–686 Time of Publication: 2016 |
Abstract | We report on the synthesis of undoped ∼5 μm YSZ-Ni porous thin films prepared by reactive pulsed DC magnetron sputtering at an oblique angle of incidence. Pre-calcination of the amorphous unmodified precursor layers followed by reduction produces a film consisting of uniformly distributed tilted columnar aggregates having extensive three-phase boundaries and favorable gas diffusion characteristics. Similarly prepared films doped with 1.2 at.% Au are also porous and contain highly dispersed gold present as Ni-Au alloy particles whose surfaces are strongly enriched with Au. With hydrogen as fuel, the performance of the undoped thin film anodes is comparable to that of 10–20 times thicker typical commercial anodes. With a 1:1 steam/carbon feed, the un-doped anode cell current rapidly falls to zero after 60 h. In striking contrast, the initial performance of the Au-doped anode is much higher and remains unaffected after 170 h. Under deliberately harsh conditions the performance of the Au-doped anodes decreases progressively, almost certainly due to carbon deposition. Even so, the cell maintains some activity after 3 days operation in dramatic contrast with the un-doped anode, which stops working after only three hours of use. The implications and possible practical application of these findings are discussed. |
Keywords | Magnetron sputtering; Oblique angle deposition; Thin film anodes; Carbon-tolerant; SOFC |
Remark |
doi:10.1016/j.jpowsour.2016.05.124 Link |
Electrical characterization of amorphous LiAlO2 thin films deposited by atomic layer deposition
Authors | |
Source |
RSC Advances
Volume: 6,
Issue: 65,
Pages: 60479-60486 Time of Publication: 2016 |
Abstract | LiAlO2 thin films deposited by atomic layer deposition (ALD) have a potential application as an electrolyte in three-dimensional (3D) all-solid-state microbatteries. In this study, Li-ion conductivity of such films is investigated by both in-plane and cross-plane methods. LiAlO2 thin films with a Li composition of [Li]/([Li] + [Al]) = 0.46 and an amorphous structure were grown by ALD with thicknesses of 90, 160 and 235 nm on different substrates. The electrical characterization was conducted by impedance spectroscopy using inert electrodes over a temperature range of 25–200 °C in an inert atmosphere. In-plane conductivities were obtained from films on insulating sapphire substrates, whereas cross-plane conductivities were measured from films on conducting titanium substrates. For the first time, comparison of the in-plane and cross-plane conductivities in these ALD LiAlO2 films has been achieved. More comparable results are obtained using a cross-plane method, whereas in-plane conductivity measurements demonstrate a considerable thickness-dependence with thinner film thickness. The room-temperature conductivity of the LiAlO2 films has been determined to be in the order of 10−10 S cm−1 with an activation energy of ca. 0.8 eV. |
Remark |
DOI: 10.1039/C6RA03137D Link |
Thin film YSZ-based limiting current-type oxygen and humidity sensor on thermally oxidized silicon substrates
Author |
Shunsuke Akasaka
|
Source |
Sensors and Actuators B: Chemical
Volume: 236,
Pages: 499–505 Time of Publication: 2016 |
Abstract | In this paper, we propose a thin film yttria-stabilized-zirconia (YSZ)-based limiting current-type oxygen and humidity sensor. These sensors were fabricated from layers of thin films on thermally oxidized silicon substrates, with the intention of installing such sensors onto microheaters. Sputtered porous Pt cathode are situated beneath the YSZ films, and are designed to provide a gas diffusion layer as well as function as electrodes. The porous Pt layer exhibits good performance as a gas diffusion layer because of its small pore size. Optimized YSZ sputtering growth conditions result in in-plane densification without the presence of cracks. The temperature dependence of the oxygen sensor’s level of limiting current was T −0.5. This result was attributed to the shrinkage of the extremely small pores in the gas diffusion layer. Between 450 and 550 °C, following the application of a voltage of 1.1 V, the time response measurements show a rapid response of a few seconds. The oxygen concentration and water vapor pressure correspond to the level of the limiting current at 1.1 V and 1.8 V, respectively. |
Keywords | Yttria-stabilized-zirconia; Limiting current; Oxygen sensor; Humidity sensor; Thin film; Silicon substrate |
Remark |
doi:10.1016/j.snb.2016.06.025 Link |
Magnetron-Sputtered YSZ and CGO Electrolytes for SOFC
Authors |
A. A. Solovyev , A. V. Shipilova, I. V. Ionov, A. N. Kovalchuk, S. V. Rabotkin, V. O. Oskirko
|
Source |
Journal of Electronic Materials
Time of Publication: 2016
|
Abstract | Reactive magnetron sputtering has been used for deposition of yttria-stabilized ZrO2 (YSZ) and gadolinium-doped CeO2 (CGO) layers on NiO-YSZ commercial anodes for solid oxide fuel cells. To increase the deposition rate and improve the quality of the sputtered thin oxide films, asymmetric bipolar pulse magnetron sputtering was applied. Three types of anode-supported cells, with single-layer YSZ or CGO and YSZ/CGO bilayer electrolyte, were prepared and investigated. Optimal thickness of oxide layers was determined experimentally. Based on the electrochemical characteristics of the cells, it is shown that, at lower operating temperatures of 650°C to 700°C, the cells with single-layer CGO electrolyte are most effective. The power density of these fuel cells exceeds that of the cell based on YSZ single-layer electrolyte at the same temperature. Power densities of 650 mW cm−2 and 500 mW cm−2 at 700°C were demonstrated by cells with single-layer YSZ and CGO electrolyte, respectively. Significantly enhanced maximum power density was achieved in a bilayer-electrolyte single cell, as compared with cells with a single electrolyte layer. Maximum power density of 1.25 W cm−2 at 800°C and 1 W cm−2 at 750°C under voltage of 0.7 V were achieved for the YSZ/CGO bilayer electrolyte cell with YSZ and CGO thickness of about 4 μm and 1.5 μm, respectively. This signifies that the YSZ thin film serves as a blocking layer to prevent electrical current leakage in the CGO layer, leading to the overall enhanced performance. This performance is comparable to the state of the art for cells based on YSZ/CGO bilayer electrolyte. |
Keywords | Solid oxide fuel cell CGO YSZ bilayer electrolyte magnetron sputtering pulse electron-beam treatment |
Remark | Link |
Structural and electrical study of samarium doped cerium oxide thin films prepared by e-beam evaporation
Authors |
Darius Virbukas, Mantas Sriubas, Giedrius Laukaitis
|
Source |
Solid State Ionics
Time of Publication: 2014
|
Abstract | Samarium doped cerium oxide (Sm0.15Ce0.85O1.925, SDC) thin films were grown on the Alloy 600 (Fe–Ni–Cr) and optical quartz (SiO2) substrates using e-beam deposition technique. Formed SDC thin films were characterized using different X-ray diffraction (XRD) techniques, scanning electron microscope (SEM), energy-dispersive spectrometry (EDS) and impedance spectroscopy. The deposition rate of formed SDC thin films was changed from 2 Å/s to 16 Å/s. XRD analysis shows that all thin films have a cubic (FCC) structure and repeat the crystallographic orientation of the initial powders evaporated with different deposition rate and on different substrates. The crystallite size increases from 7.7 nm to 10.3 nm and from 7.2 nm to 9.2 nm on Alloy 600 substrate and optical quartz (SiO2) substrate respectively as the thin film deposition rate increases. SEM images indicate a dense and homogeneous structure of all formed SDC thin films. The ionic conductivity depends on thin films density and blocking factor. The best ionic conductivity (σg = 1.34 Sm− 1 and σgb = 2.29 Sm −1 at 873 K temperature, activation energy ΔEg = 0.91 eV and ΔEgb = 0.99 eV) was achieved for SDC thin films formed at 4 Å/s deposition rate. It was found that the highest density (5.25 g/cm3) and the lowest relaxation time in grain (τg = 9.83 × 10− 7 s), and the lowest blocking factor (0.39) is in SDC thin films formed at 4 Å/s deposition rate. The deposition rate influences the stoichiometry of the formed SDC thin ceramic films. |
Keywords | Electron beam deposition; Samarium doped ceria oxide (SDC); Solid oxide fuel cells (SOFC); Ionic conductivity |
Remark |
DOI: 10.1016/j.ssi.2014.09.036 Link |
Application of PVD methods to solid oxide fuel cells
Authors |
A.A. Solovyeva, N.S. Sochugov, S.V. Rabotkin, A.V. Shipilova, I.V. Ionov, A.N. Kovalchuk, A.O. Borduleva
|
Source |
Applied Surface Science
Time of Publication: 2014
|
Abstract | In this paper, attention is paid to the application of such a method of vacuum physical vapor deposition (PVD) as magnetron sputtering for fabrication of a solid oxide fuel cell (SOFC) materials and structures. It is shown that the YSZ (yttria-stabilized zirconia) electrolyte and Ni–YSZ anode layers with required thickness, structure and composition can be effectively formed by PVD methods. The influence of parameters of pulsed power magnetron discharge on the deposition rate and the microstructure of the obtained YSZ electrolyte films were investigated. It is shown that the deposition rate of the oxide layers by magnetron sputtering can be significantly increased by using asymmetric bipolar power magnetrons, which creates serious prerequisites for applying this method on the industrial scale. Porous Ni–YSZ anode films were obtained by reactive co-sputtering of Ni and Zr–Y targets and subsequent reduction in the H2 atmosphere at a temperature of 800 °C. The Ni–YSZ films comprised small grains and pores of tens of nanometers. |
Keywords | Solid oxide fuel cell; Metal support; Magnetron sputtering; Thin film; YSZ electrolyte; NiO/YSZ anode |
Remark |
http://dx.doi.org/10.1016/j.apsusc.2014.03.163 Link |
Porous La 0.6 Sr 0.4 CoO 3-δ thin film cathodes for large area micro solid oxide fuel cell MEMS power generators
Authors | |
Source |
Journal of Power Sources
Time of Publication: 2013
|
Abstract | Porous La0.6Sr0.4CoO3-δ thin films were fabricated by pulsed laser deposition for being used as a cathode for micro solid oxide fuel cell applications as MEMS power generators. Symmetrical La0.6Sr0.4CoO3-δ/yttria-stabilized zirconia/La0.6Sr0.4CoO3-δ free-standing membranes were fabricated using silicon as a substrate. A novel large-area membrane design based on grids of doped-silicon slabs. Thermo-mechanical stability of the tri-layer membranes was ensured in the intermediate range of temperatures up to 700°C. In-plane conductivity of ca. 300 S/cm was measured for the cathode within the whole range of application temperatures. Finally, area specific resistance values below 0.3 Ω·cm2 were measured for the cathode/electrolyte bi-layer at 700°C in the exact final micro solid oxide fuel cell device configuration, thus presenting La0.6Sr0.4CoO3-δ as a good alternative for fabricating reliable micro solid oxide fuel cells for intermediate temperature applications. |
Keywords | Micro Solid Oxide Fuel Cell, thin film cathode, self-supported electrolyte |
Remark |
DOI: 10.1016/j.jpowsour.2013.10.038 |
Porous La0.6Sr0.4CoO3-δ thin film cathodes for large area micro solid oxide fuel cell MEMS power generators
Authors | |
Source |
Journal of Power Sources
Time of Publication: 2013
|
Abstract | Porous La0.6Sr0.4CoO3-δ thin films were fabricated by pulsed laser deposition for being used as a cathode for micro solid oxide fuel cell applications as MEMS power generators. Symmetrical La0.6Sr0.4CoO3-δ/yttria-stabilized zirconia/La0.6Sr0.4CoO3-δ free-standing membranes were fabricated using silicon as a substrate. A novel large-area membrane design based on grids of doped-silicon slabs. Thermo-mechanical stability of the tri-layer membranes was ensured in the intermediate range of temperatures up to 700°C. In-plane conductivity of ca. 300 S/cm was measured for the cathode within the whole range of application temperatures. Finally, area specific resistance values below 0.3 Ω·cm2 were measured for the cathode/electrolyte bi-layer at 700°C in the exact final micro solid oxide fuel cell device configuration, thus presenting La0.6Sr0.4CoO3-δ as a good alternative for fabricating reliable micro solid oxide fuel cells for intermediate temperature applications. |
Remark |
Available online 18 October 2013 Link |
The Investigation of E-beam Deposited Titanium Dioxide and Calcium Titanate Thin Films
Authors |
Kristina BOČKUTĖ, Giedrius LAUKAITIS, Darius VIRBUKAS, Darius MILČIUS
|
Source |
Volume: 19,
Issue: 3,
Pages: 245-249 Time of Publication: 2013 |
Abstract | Thin titanium dioxide and calcium titanate films were deposited using electron beam evaporation technique. The substrate temperature during the deposition was changed from room temperature to 600 °C to test its influence on TiO2 film formation and optical properties. The properties of CaTiO3 were investigated also. For the evaluation of the structural properties the formed thin ceramic films were studied by X-ray diffraction (XRD), energy dispersive spectrometry (EDS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Optical properties of thin TiO2 ceramics were investigated using optical spectroscope and the experimental data were collected in the ultraviolet-visible and near-infrared ranges with a step width of 1 nm. Electrical properties were investigated by impedance spectroscopy.It was found that substrate temperature has influence on the formed thin films density. The density increased when the substrate temperature increased. Substrate temperature had influence on the crystallographic, structural and optical properties also. |
Keywords | electron beam evaporation; titanium oxide; calcium titanate; optical properties |
Remark |
DOI: http://dx.doi.org/10.5755/j01.ms.19.3.1805 Link |
Multilayered thin films for oxidation protection of Mg2Si thermoelectric material at middle–high temperatures
Authors |
S. Battiston, S. Boldrini, S. Fiameni, A. Famengo, M. Fabrizio, S. Barison
|
Source |
Thin Solid Films
Volume: 526,
Pages: 150–154 Time of Publication: 2012-12 |
Abstract | Multilayered molybdenum silicide-based thin films were deposited via radio frequency magnetron sputtering in order to obtain efficient barrier against oxidation process which affected Mg2Si thermoelectric materials at middle–high temperatures. X ray diffraction, energy dispersive spectroscopy, secondary ion mass spectroscopy, field emission scanning electron microscopy (FE-SEM) and electrical measurements at high temperature were carried out in order to obtain, respectively, the structural, compositional, morphological and electrical characterization of coatings. Furthermore, the mechanical behavior of the thin film/Mg2Si-pellet system was observed in situ as a function of temperature by FE-SEM employing a heating module. Moreover, the barrier properties for oxygen protection after thermal treatment in air at high temperature were qualitatively evaluated. |
Keywords | Thin film; Thermoelectric material; Magnesium silicide; Molybdenum silicide; Middle–high temperature |
Remark | Link |
Thin films of SnO2-CeO2 binary oxides obtained by pulsed laser deposition for sensing application
Authors |
Simona Somacescua, Rares Scurtu, George Epurescu, Rovena Pascu, Bogdana Mitu, Petre Osiceanu, Maria Dinescu
|
Source |
Applied Surface Science
Time of Publication: 2012-11
|
Abstract | Binary tin oxide – cerium oxide thin films with ceria concentrations in the range 10- 30% have been obtained by pulsed laser deposition technique, with or without additional oxygen RF plasma beam assistance. A good preservation of the Ce/Sn atomic concentration and Ce3+ content on the film surface of about 30% was obtained for almost all the investigated conditions of substrate temperature and RF powers. The sharp decrease of the electrical resistance in hydrogen environment at temperatures above 300 °C indicates a direct interaction between hydrogen and metal oxides surfaces leading to OH groups formation, as evidenced by XPS measurements. The highest sensitivity (∼40) was attained for the sample with 10% ceria and RF assistance, while the lowest operating temperature (∼250-320 °C) was encountered for that with 30% ceria deposited in the presence of RF discharge. |
Keywords | RF assisted pulsed laser deposition; SnO2-CeO2 binary oxides; Ce3+ and Ce4+ concentration; sensitivity in H2 atmosphere |
Remark |
Available online Link |
Nd-doped Ba(Ce,Zr)O3 − δ proton conductors for application in conversion of CO2 into liquid fuels
Authors |
Wojciech Zając , Emil Hanc, Agnieszka Gorzkowska-Sobas, Konrad Świerczek, Janina Molenda
|
Source |
Solid State Ionics
Volume: 225,
Pages: 297–303 Time of Publication: 2012-10 |
Abstract | The paper presents crystal structure, transport properties, chemical stability in CO2 atmosphere and thin film membrane preparation for materials from the Ba(Ce1 − xZrx)0.9Nd0.1O2.95 (x = 0, 0.25, 0.5, 0.75, 1) group of perovskite-type structure oxides. Transformation of crystal structure from orthorhombic Pnma to orthorhombic Imma and cubic with increasing xZr was observed along with linear decrease of pseudo-cubic unit cell volume and free lattice volume. Electrical conductivity of bulk and grain boundary was determined in dry air, as well as in air humidified with H2O or D2O. The highest proton conductivity was observed for material with xZr = 0.25. Further increase of Zr content led to decrease of conductivity as high as 2 orders of magnitude. This effect was coupled with bell-shape dependence of activation energy and pre-exponential term. Such behavior was explained as superimposed effects of high proton mobility for zirconium-rich materials due to cubic symmetry and cerium-rich materials due to softness of oxygen–oxygen separation distance, along with high proton concentration for cerium-rich perovskites. The deteriorating effect of grain boundaries on total electrical conductivity was far more pronounced for Zr-rich materials than in the case of Ce-rich ones. Declining grain boundary conductivity was attributed to both increase of number of grain boundaries and decrease of inherent grain boundary conductivity for Zr-rich samples. The highest chemical stability in CO2 atmosphere was achieved for high-Zr content materials, on the contrary, for BaCe0.9Nd0.1O2.95 in CO2 atmosphere, the decomposition onset temperature was below 500 °C. 2 μm thin film membrane of Ba(Ce0.75Zr0.25)0.9Nd0.1O2.95 was successfully prepared on c-plane sapphire and fused silica substrates. Film's crystal structure matched that of the bulk material. The electrical conductivity of thermally treated film obtained on c-plane sapphire in wet air was 3.7 × 10− 4 S cm− 1 at 600 °C. |
Keywords | Proton conductors; BaCeO3–BaZrO3 solid solutions; Isotope effect; Grain boundary effect; Thin films |
Remark | Link |
Solid oxide fuel cells with Sm0.2Ce0.8O2−δ electrolyte film deposited by novel aerosol deposition method
Authors |
Sea-Fue Wang, Yung-Fu Hsu, Chih-Hao Wang and Chin-Ting Yeh
|
Source |
Journal of Power Sources
Volume: 196,
Issue: 11,
Pages: 5064-5069 Time of Publication: 2011-06 |
Abstract | In this study, dense electrolyte ceramic Sm0.2Ce0.8O2−δ (SDC) thin films are successfully deposited on NiO-SDC anode substrate by aerosol deposition (AD) with oxygen as the carrier gas at the substrate temperature ranging from room temperature to 300 °C. To remove the effect of humidity on the starting powders, this study found that, in depositing SDC films, having the starting powders preheat-treated at 200 °C helped generate a smooth and dense layer, though a lower deposition rate was achieved. At a deposition time of 22 min, SDC films with a uniform thickness of 1.5 μm and grain sizes of ≈67 nm are obtained. SOFC single cells are then built by screen printing a LSCF cathode on the anode-supported substrates with SDC electrolyte. The cross-sectional SEM micrographs exhibit highly dense, granular, and crack-free microstructures. The open circuit voltages (OCV) of the single cells decrease with the rise in temperature, dropping from 0.81 V at 500 °C to 0.59 V at 700 °C. Maximum power densities (MPD) decline with decreasing operating temperature from 0.34 to 0.01 W cm−2 due to the increase of the R0 and RP of the single cells. The electrochemical results testify to the fine quality of SDC films as well as illustrate the electrolyte thickness effect and the effect of mixed ionic and electronic conduction of the SDC electrolyte in the reducing atmosphere. |
Keywords |
Fabrication and Characterization of Anode-Supported BaIn0.3Ti0.7O2.85 Thin Electrolyte for Solid Oxide Fuel Cell
Authors |
M. Rieu, P. K. Patro, T. Delahaye*, E. Bouyer
|
Source |
International Journal of Applied Ceramic Technology
Article first published online: 28 MAR 2011 Time of Publication: 2011-03 |
Abstract | BaIn0.3Ti0.7O2.85 (BIT07) is a promising electrolyte for solid oxide fuel cells, due to its chemical compatibility with most of the cathode electrode material such as LSM and Ln2NiO4. The present work is aimed on the fabrication of anode-supported half cells with thin BIT07 electrolyte. For this, Ni-8YSZ cermet was chosen due to its excellent mechanical and electrochemical properties, in addition to its low cost. The NiO–8YSZ anode support was prepared by tape casting, and for this, an organic slurry formulation was optimized. The BIT07 electrolyte thin film was deposited through screen printing on the green anode. The formulation of the ink was optimized, and sintering at 1350°C for 3 h led to a dense electrolyte with controlled thickness varying from 2 to 12 μm. Further, the cermet electrode still had a homogeneous microstructure with well-defined anode/electrolyte interface. The electrode ASR was about 0.5 Ω cm2 and was stable over 500 h at 800°C under H2–3% H2O. The fabrications of half cells were successfully scaled up to 100 mm × 100 mm retaining the dimensional control and without any surface defects. |
Yttria-stabilized zirconia thin film electrolyte produced by RF sputtering for solid oxide fuel cell applications
Authors |
Federico Smeacetto, Milena Salvo, Lakshmi Chandru Ajitdoss, Sergio Perero, Tomasz Moskalewicz, Stefano Boldrini, Lioudmila Doubova and Monica Ferraris
|
Source |
Materials Letters
Volume: 64,
Issue: 22,
Pages: 2450-2453 Time of Publication: 2010-11 |
Abstract | Thin film (40–600 nm) yttria-stabilized zirconia (YSZ) electrolytes for solid oxide fuel cells (SOFC) were deposited on NiO-YSZ anodes and fused silica substrates by RF sputtering, using low applied power without the use of post deposition annealing heat treatment. YSZ film showed a nanocrystalline structure and consisted of the Zr.85Y.15O1.93 (fcc) phase. The film was dense and the YSZ/anode interface was continuous and crack free. According to preliminary in-plane conductivity measurements (temperature range 550–750 °C) on the YSZ film, the activation energy for ionic conduction was found to be 1.18 ± 0.01 eV. |
Keywords | Thin films; Ceramics; Microstructure; Nanomaterials |
Scandium stabilized zirconium thin films formation by e-beam technique
Authors |
Darius Virbukas, Giedrius Laukaitis, Julius Dudonis, Oresta Katkauskė and Darius Milčius
|
Source |
Solid State Ionics
Volume: 184,
Issue: 1,
Pages: 10–13 Time of Publication: 2011-03 |
Abstract | Scandiumstabilizedzirconium (10ScSZ) thin ceramic films were deposited by e-beam evaporation of (ZrO2)0.90(Sc2O3)0.10 micro powder (particle size 0.5 ÷ 0.7 μm). The influence of deposition rate on formed thinfilms microstructure and electrical properties was studied. 10ScSZ thinfilms were deposited on two types of different substrates: optical quartz (SiO2) and Alloy-600 (Fe–Ni–Cr) substrates. Deposition rate was changed from 2 to 16 Å/s to test its influence on thinfilmformation and its properties. The microstructure of formed 10ScSZ thin ceramic films was studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Electrical parameters of formed thin ceramics were investigated in the frequency range from 0.1 Hz to 1.0 MHz (in temperature range from 473 to 873 K). The ionic conductivity of the deposited electrolyte 10ScSZ thinfilms was determined by impedance spectroscopy. It was determined that the deposition rate (in range from 2 to 16 Å/s) has influence on crystallite size. It increases by increasing the deposition rate from 18.4 to 26.9 nm. The XRD measurements show that the formed 10ScSZ thinfilms do not repeat the crystallographic phase of the initial evaporated powder material—it is changes from rhombohedra (initial powder) to cubic (the formed thinfilms). |
Keywords | Scandium stabilized zirconium (ScSZ); Ionic conductivity; Electron beam deposition; Solid oxide fuel cells (SOFC) |
Remark | Link |
The properties of scandium and cerium stabilized zirconium thin films formed by e-beam technique
Authors |
Darius Virbukas, Giedrius Laukaitis, Julius Dudonis and Darius Milčius
|
Source |
Solid State Ionics
Volume: 188,
Issue: 1,
Pages: 46–49 Time of Publication: 2011-04 |
Abstract | Scandium and ceriumstabilizedzirconium (10Sc1CeSZ) thin ceramic films were formed evaporating (ZrO2)0.89(CeO2)0.01(Sc2O3)0.10 micro powder using e-beam evaporation technique. The influence of deposition rate on formedthinfilms electrical properties and microstructure was studied. 10Sc1CeSZ thinfilms were deposited on two types of different substrates: optical quartz (SiO2) and Alloy 600 (Fe–Ni–Cr). Deposition rate was changed from 2 to 16 Å/s to understand its influence on thinfilm formation and other properties. The formed 10Sc1CeSZ thinfilms keep the cubic crystal structure as the initial evaporated powder material but change the main crystallographic peak from (111) to (200) for both types of substrate and used deposition rates. It was determined that the crystallites size increases from 19.0 to 24.9 nm and from 15.6 to 19.9 nm on optical quartz and Alloy 600 respectively by increasing the deposition rate (in range from 2 to 16 Å/s). The thinfilm density decreases by increasing the deposition rate. The ionic conductivity of 10Sc1CeSZ thinfilms was determined by impedance spectroscopy in the frequency range from 0.1 Hz to 1.0 MHz in temperature range from 473 K to 873 K. The best ionic conductivity σtot = 4.91 · 10− 2 Sm− 1 at 873 K temperature and the lowest value of activation energy ΔEa = 0.88 eV were found for 10Sc1CeSZ thinfilmsformed at 4 Å/s deposition rate. |
Keywords | Scandium and cerium stabilized zirconium (10Sc1CeSZ); Electron beam deposition; Solid oxide fuel cells (SOFC); Ionic conductivity |
Remark | Link |
Thin film chemical sensors based on p-CuO/n-ZnO heterocontacts
Authors |
C.S. Dandeneau, Y.H. Jeon, C.T. Shelton, T.K. Plant, D.P. Cann and B.J. Gibbons
|
Source |
Thin Solid Films
Volume: 517,
Issue: 15,
Pages: 4448-4454 Time of Publication: 2009 |