Formation of yttria-stabilized zirconia nanotubes by atomic layer deposition toward efficient solid electrolytes
© The Author(s) 2017
Received: 26 October 2017
Accepted: 6 November 2017
Published: 5 December 2017
We describe a fabrication strategy for preparing yttria-stabilized zirconia nanotube (YSZ-NT) arrays embedded in porous alumina membranes by means of template-directed atomic layer deposition (ALD) technique. The individual YSZ-NTs have a high aspect-ratio of well over 120, about ~ 110 nm in diameter, and ~ 14 µm in length. Interfacing the tube arrays with porous Pt was also introduced on the basis of partial etching technique in order to construct Pt/YSZ-NTs/Pt membrane electrode assembly (MEA) structures. The resulting YSZ-NTs MEAs show a 7 mm in diameter with a roughness factor of ~ 2. Area specific resistance was measured up to 1.84 Ω cm2 at 400 °C using H2 as fuel.
Owing to high diffusivity for oxygen ions , exceptional resistance against mechanical and thermal stress , electrical insulation  and high biocompatibility , zirconia-based materials have many industrial applications. Notable examples are solid oxide fuel cells [5–7], catalysts , thermal barrier coatings , jet engines , alternative gate-oxides in microelectronics [11, 12], and implantable biomaterials for a hip joint . Bulk ZrO2 has three well-known polymorphisms at normal atmospheric pressure . The monoclinic baddeleyite structure (m-ZrO2) is thermodynamically stable under ambient conditions, where Zr atoms are in a distorted sevenfold coordination, and O atoms have four- or three-fold coordination. m-ZrO2 transforms reversibly to the tetragonally distorted fluorite structure (t-ZrO2) above ~ 1175 °C, with Zr in an eightfold coordination. This phase transformation is known to be accompanied by a substantial volume change of ~ 5 vol.%. Cubic fluorite structured ZrO2 (c-ZrO2) is the most stable one and is stabilized upon ~ 2370 °C. Stabilization of t-ZrO2 and c-ZrO2, which is required to be technologically viable over m-ZrO2, is of significant importance in many applications. In order to stabilize the cubic structure even down to room temperatures, adding aliovalent oxides such as CaO, Y2O3 and Gd2O3 has been suggested .
In principle, formation of the oxygen vacancies plays a major role in applications using zirconia-based ceramics. The vacancy diffusivity depends not only on the phase itself , but also on the strain , space-charge [17, 18], and defect localization  effects. Therefore, microstructures such as grain boundaries and defect densities are essential in determining the materials properties . For example, thin film/layer electrolytes of doped-ZrO2 exhibited enhanced performance at lower operation temperatures in application for solid oxide fuel cells (SOFCs) [21, 22]. Currently, YSZ is the most common solid-electrolyte materials for SOFCs.
To accomplish adequate ionic conductivity in conventional ZrO2-based electrolytes, SOFCs generally require an operating temperature above 850 °C. Such high operating temperatures require severe demands on the materials used to satisfy chemical as well as thermal stability . Quite long start-up and shutdown time is also limited to many applications, such as portable power and transportations . There are considerable interests in bringing the operating temperature down to intermediate range (600–800 °C) and even to lower (< 500 °C) temperature. At even lower temperature, system costs can significantly reduce due to wider range of materials used for components. On the other hand, low operating temperature could cause reducing significantly the ionic conductivity of the solid electrolyte and thus leads to higher ohmic losses. Ohmic loss is governed by the ionic conductivity and the layer thickness of electrolytes. The first approach is to introduce novel electrolytes with higher ionic conductivity at lower temperatures such as La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) , and Sm0.075Nd0.075Ce0.85O2-δ (SNDC) . These have generally shown lower chemical stability than that observed in YSZ electrolytes. The second approach is to extremely reduce the layer thickness of electrolyte less than 100 nm, i.e. to decrease the diffusion path of oxygen ions . Typical MEA structure for thin-film SOFCs is a planar thin-film membrane with two porous electrodes separated by a thin and at the same time dense, air-tight, oxygen-ion conducting electrolyte. Micrometer-thick MEAs have been fabricated using micro-electro-mechanical systems (MEMS) processing based on silicon wafers using chemical etching as mechanical support for free-standing ultrathin MEA [27–32]. Several substrates have been used as alternate support materials for MEA, including nickel foil , porous nickel cermet , glass-ceramic , and AAO substrates [36–39]. Moreover, three-dimensional (3D) nanostructured MEAs also increased the cell performance due to the increased active surface area. Chao et al. reported a corrugated MEA by nanosphere lithography which active membrane area was enhanced to 1.6–twofold [40, 41]. Su et al. also reported a cup-shape MEA at micrometer scale which roughness factor of active surface area was increased to ~ 5 . In order to achieve extremely large roughness factors, a natural occurrence is to employ the nanotubular geometry with high aspect ratio. However, the resulting power density was rather disappointed down to only 1 μW cm−2 , calling for the emergent design using zirconia-based nanotubes with high aspect ratio as solid electrolytes.
To fabricate the 3D nanostructured MEAs, ALD is one of the most ideal deposition technique of choice. ALD is a gas phase thin film deposition based on alternate, self-limiting surface reaction of precursors . ALD allows for fabricating high aspect-ratio and complex surface structures employing templates such as AAO [45–48], Opals , and aerogel structures . And also, nanoscale laminated films can be grown by alternative depositions at each atomic layer with desired ratio of the number of deposition cycles . In this paper, we studied on the formation of YSZ NTs by template-directed ALD. By controlling the atomic layer depositing ratio of ZrO2 and Y2O3, we were able to achieve the cubic phase YSZ-NTs with high aspect-ratio up to ~ 110. To expose the large active surface area of YSZ-NTs, partial etching procedures were developed. The resulting free-standing YSZ-NT-based MEA was prepared having porous Pt electrodes at the both sides with an active area of 7 mm in diameter. The preliminary results exhibit promising resistance values under H2 ambient at 400 °C.
AAO templates were fabricated by a two-step anodization method base on aluminum (99.999%, Goodfellow, UK) [52–54]. The aluminum foils were electropolished with a mixture of HClO4/EtOH (1:3 vol.%) at 18 V for 4 min. The first anodization was performed in 1 wt.% H3PO4 solution at 0.5 °C under applied DC voltage of 195 V for 16 h. Then, the alumina layers were removed wet-chemically in a mixture of 6 wt.% H2CrO4 and 1.8 wt.% H3PO4 at 45 °C for 24 h. The second anodization was done under the identical conditions to the first one for a desired time. Approximately, 11 μm-thick templates were prepared upon ~ 4 h. The pore widening was proceeded in 10 wt.% H3PO4 solutions at 45 °C for 30 min, when increased for pore diameter up to ~ 200 nm. Separation of AAO template from the aluminum foil could be accomplished by wet-chemically etching aluminum with a mixture of 3.4 wt.% CuCl2 in water and 37% HCl solution.
ZrO2 and YSZ were grown on the AAO templates using a commercial ALD reactor (TFS-200, Beneq, Finland) at 200 °C. Tetrakis(ethylmethylamino)zirconium [TEMAZr] (UP Chem., Korea) and Tris(methylcyclopentadienyl)yttrium [(MeCp)3Y] (Strem Chem., USA) were used as metal containing reactants preheated at 80 and 130 °C, respectively. Deionized water was used as oxygen source and delivered at room temperature. Dried N2 was used as purge/carrier gas. Both ZrO2 and YSZ thin films depositions were used in expose-mode protocol, where a full ALD cycle is consisting of 10 s pulse, 50 s waiting, and 60 s purging. For the deposition of cubic phase YSZ films, 7 ALD cycles of ZrO2 layer and 1 ALD cycle of Y2O3 layer were repeatedly deposited for desired thickness . Porous Pt thin films were deposited on both cathode and anode by DC sputtering (Cressington 308R, Cressington, UK) at room temperature in 10 Pa Ar ambient.
Physical dimensions of the resulting tubes and MEAs were inspected by field-emission scanning electron microscopy (FE-SEM, JEOL JSM-7000F, Japan & Carl Zeiss AG SIGMA, Germany). The structures of as-grown and post-annealed nanotubes were investigated by X-ray diffraction (XRD, Rigaku Ultima IV, Japan) and high-resolution transmission electron microscopy (HRTEM, JEOL JEM-4010, Japan). And also, specific crystal structure of nanotubes was obtained using a synchrotron radiation source at beam line 5A with the wavelength 0.7653 Å at Pohang Light Source using Mar 345-image plate. For converting image to the 2D diffraction pattern, FIT2D program was used . The 2θ of XRD pattern was recalculated to the corresponding angles of λ = 1.54 Å (Cu-Kα radiation). The electrochemical impedance spectroscopy was measured to determine the polarization resistance of the cells using potentiostat and frequency analyser (1252, Solartron, UK) in the frequency range of 100 kHz–0.1 Hz with AC amplitude of 20 mV.
3 Results and discussion
Figure 1a shows a mosaic of TEM images of YSZ-NTs by the template-directed ALD method and subsequent wet-chemical etching of the templates. The resulting YSZ-NTs have no-cracks and pinhole-free with a high aspect ratio over 120, ~ 110 nm in diameter, and ~ 14 μm in length. Since YSZ-NTs function as electrolyte for the oxygen transport as well as anti-fuel-crossover layers, even the small pinholes and cracks could result in severe damage to the performance and failure of cells. HR-TEM image and selected electron area diffraction (SAED) patterns confirmed that YSZ-NTs were polycrystalline with the grain size of sub 10 nm in the cubic polymorphism (Fig. 1b, c). Figure 1d shows the energy-dispersive X-ray spectroscopy (EDS) elemental line profile taken from the YSZ-NT. The green line indicated for yttrium which confirmed the presence of Y2O3 as dopant in the ZrO2 matrix (to be 6–8 mol%).
In summary, we studied on the formation of YSZ-NTs with high aspect ratio up to ~ 110 by template-directed ALD method. The crystal structures of tetragonal phase ZrO-2 NTs and cubic Phase YSZ NTs were demonstrated using both conventional XRD and high-resolution synchrotron radiation diffraction, complementarily. And also, the YSZ NTs based MEAs with AAO template as mechanical support structures were introduced by wet chemical etching technique. Using this fabrication process, the total area of the free-standing MEA and the roughness factor have achieved up to 7 mm in diameter and approximately ~ 2 times, respectively. The present study will open a new venue for realizing the micro-SOFCs with ultra-high efficiency and low-temperature operation capability.
All authors have contributed to the writing of the manuscript. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
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Funding and acknowledgements
This research was supported by the National Research Foundation of Korea (NRF) grant funded by the Ministry of Science, ICT Future Planning (MSIP) of Korea under contracts NRF-2017R1A4A1015770 (Basic Research Laboratory Program), NRF-2016M3D1A1027664 (Future Materials Discovery Program), NRF-2014M3A7B4052201 (Basic Science Research Program). We would like to express sincere thanks for the support.
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