Anti-phase boundary accelerated exsolution of nanoparticles in non-stoichiometric perovskite thin films.
Anti-phase boundary accelerated exsolution of nanoparticles in non-stoichiometric perovskite thin films.
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DOI：
10.1038/s41467-022-34289-3
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发表时间：
2022-11-05
影响因子：
16.6
通讯作者：
Oh, Sang Ho
中科院分区：
文献类型：
--
作者：
Han, Hyeon;Xing, Yaolong;Park, Bumsu;Bazhanov, Dmitry, I;Jin, Yeongrok;Irvine, John T. S.;Lee, Jaekwang;Oh, Sang Ho
过量过渡金属阳离子从非化学计量的钙钛矿氧化物中的出溶作为在氧化物表面上形成稳定纳米颗粒的简便途径引起了人们的兴趣。然而，这种纳米颗粒形成的原子级机制在很大程度上仍然未知。原位扫描透射电子显微镜结合密度泛函理论计算表明，在< 011>非化学计量比的ABO 3钙钛矿氧化物中，以a/2型晶格位移为特征的反相边界（APBs）通过BO 6八面体的共边来容纳B位阳离子（Ni（La0.2Sr0.7Ni0.1Ti0.9O3-δ），并为通过出溶形成纳米颗粒提供快速扩散途径。此外，由于Ni在APB/表面相交处的偏析能较低，APB进一步促进了过量Ni向表面的向外扩散。纳米颗粒的形成通过两步结晶机制发生，即，无定形相的成核，随后结晶，以及通过氧化物载体上的反应性润湿，这促进了稳定的三重结和内聚界面的形成，导致纳米颗粒与氧化物载体的明显套接（socketing）。这项研究中揭示的原子尺度机制可以为高度稳定的纳米结构的设计提供见解。过渡金属阳离子从非化学计量的钙钛矿中的出溶提供了在表面上形成稳定的纳米颗粒的途径。在这里，作者提出了一个反相边界加速出溶和两步结晶的纳米粒子在非化学计量的钙钛矿薄膜。
Exsolution of excess transition metal cations from a non-stoichiometric perovskite oxide has sparked interest as a facile route for the formation of stable nanoparticles on the oxide surface. However, the atomic-scale mechanism of this nanoparticle formation remains largely unknown. The present in situ scanning transmission electron microscopy combined with density functional theory calculation revealed that the anti-phase boundaries (APBs) characterized by the a/2 < 011> type lattice displacement accommodate the excess B-site cation (Ni) through the edge-sharing of BO6 octahedra in a non-stoichiometric ABO3 perovskite oxide (La0.2Sr0.7Ni0.1Ti0.9O3-δ) and provide the fast diffusion pathways for nanoparticle formation by exsolution. Moreover, the APBs further promote the outward diffusion of the excess Ni toward the surface as the segregation energy of Ni is lower at the APB/surface intersection. The formation of nanoparticles occurs through the two-step crystallization mechanism, i.e., the nucleation of an amorphous phase followed by crystallization, and via reactive wetting on the oxide support, which facilitates the formation of a stable triple junction and coherent interface, leading to the distinct socketing of nanoparticles to the oxide support. The atomic-scale mechanism unveiled in this study can provide insights into the design of highly stable nanostructures. Exsolution of transition metal cations from non-stoichiometric perovskites offer a route for the formation of stable nanoparticles on the surface. Here authors present an anti-phase boundaries-accelerated exsolution and two-step crystallisation of nanoparticles in non-stoichiometric perovskite thin films.
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影响因子：
3.7
作者：
Kresse, G;Furthmuller, J
通讯作者：
Furthmuller, J
影响因子：
3.7
作者：
MONKHORST, HJ;PACK, JD
通讯作者：
PACK, JD
影响因子：
16.6
作者：
Neagu D;Papaioannou EI;Ramli WKW;Miller DN;Murdoch BJ;Ménard H;Umar A;Barlow AJ;Cumpson PJ;Irvine JTS;Metcalfe IS
通讯作者：
Metcalfe IS
DOI：
10.1111/j.1151-2916.1993.tb03964.x
发表时间：
1993-10-01
影响因子：
3.9
作者：
IKEDA, JAS;CHIANG, YM
通讯作者：
CHIANG, YM
影响因子：
19
作者：
Heisig, Thomas;Kler, Joe;Dittmann, Regina
通讯作者：
Dittmann, Regina