Baure G, Kasse R M, Rudawski N G, Nino J C
Department of Materials Science and Engineering, University of Florida, Gainesville, Florida 32611, USA.
Phys Chem Chem Phys. 2015 May 14;17(18):12259-64. doi: 10.1039/c5cp00668f.
A methodology to limit interfacial effects in thin films is proposed and explained. The strategy is to reduce the impact of the electrode interfaces and eliminate cross grain boundaries that impede ionic motion. To this end, highly oriented Nd0.1Ce0.9O2-δ (NDC) nanocrystalline thin films were grown using pulsed laser deposition (PLD) on platinized single crystal a-plane sapphire substrates. High resolution cross-sectional transmission electron microscopy (HR-XTEM), scanning electron microscopy (SEM) and X-ray diffraction (XRD) verified the films were textured with columnar grains. The average widths of the columns were approximately 40 nm and not significantly changed by film thickness between 100 and 300 nm. HR-XTEM and XRD determined the {111} planes of NDC were grown preferentially on top of the {111} planes of platinum despite the large lattice mismatch between the two planes. From the XRD patterns, the out of plane strains on the platinum and NDC layers were less than 1%. This can be explained by the coincident site lattice (CSL) theory. Rotating the {111} ceria planes 19.11° with respect to the {111} platinum planes forms a Σ7 boundary where 1 in 7 cerium lattice sites are coincident with the platinum lattice sites. This orientation lowers interfacial energy promoting the preferential alignment of those two planes. The across plane ionic conductivity was measured at low temperatures (<350 °C) for the various film thicknesses. It is here shown that columnar grain growth of ceria can be induced on platinized substrates allowing pathways that are clear of blocking grain boundaries that cause conductivities to diminish as film thickness decreases.
本文提出并解释了一种限制薄膜界面效应的方法。该策略是减少电极界面的影响,并消除阻碍离子运动的交叉晶界。为此,采用脉冲激光沉积(PLD)在镀铂的单晶a面蓝宝石衬底上生长了高度取向的Nd0.1Ce0.9O2-δ(NDC)纳米晶薄膜。高分辨率横截面透射电子显微镜(HR-XTEM)、扫描电子显微镜(SEM)和X射线衍射(XRD)证实,这些薄膜具有柱状晶粒织构。柱体的平均宽度约为40nm,在100至300nm的膜厚范围内,膜厚对其影响不显著。HR-XTEM和XRD确定,尽管两个平面之间存在较大的晶格失配,但NDC的{111}面优先生长在铂的{111}面上。从XRD图谱可知,铂层和NDC层的面外应变小于1%。这可以用重合点阵(CSL)理论来解释。将二氧化铈的{111}面相对于铂的{111}面旋转19.11°,形成一个Σ7边界,其中每7个铈晶格位点中有1个与铂晶格位点重合。这种取向降低了界面能,促进了这两个平面的优先排列。在低温(<350°C)下测量了不同膜厚的面内离子电导率。结果表明,在镀铂衬底上可以诱导二氧化铈的柱状晶粒生长,从而形成无阻碍晶界的通道,避免了随着膜厚减小电导率降低的情况。