Chemically-induced structural deformation of layered perovskite oxides

2016 IEEE 16th International Conference on Nanotechnology (IEEE-NANO) Pub Date : 2016-08-01 DOI:10.1109/NANO.2016.7751481

Takashi Nakamura, K. Amezawa

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引用次数: 1

Abstract

In order to understand the behavior of the crystal lattice deformation induced by the interstitial oxygen formation in La₂(Ni_0.9M_0.1)O_4+δ (M = Fe, Co, Cu), thermogravimetry, coulometric titration, and high temperature X-ray diffraction measurements were carried out in the temperature range between 873 to 1173 K and the P(O₂) range between 10^-24 to 1 bar. Oxygen content variation under wide range of P(O₂) could be successfully evaluated by combining thermogravimetry and coulometric titration techniques. Compared with non-doped La₂NiO_4+δ, La₂(Ni_0.9Fe_0.1)O_4+δ and La₂(Ni_0.9Co_0.1)O_4+δ have more interstitial oxygen while La₂(Ni_0.9Cu_0.1)O_4+δ have less. Crystal structure at high temperatures was analyzed assuming the tetragonal symmetry, I4/mmm, for all compositions. With increasing interstitial oxygen concentration, the lattice parameter perpendicular to the perovskite layer increased and that parallel to the perovskite layer decreased. Consequently, the change of the cell volume by the interstitial oxygen formation was small, meaning macroscopic chemical expansion is small.

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层状钙钛矿氧化物的化学诱导结构变形

为了了解La2(Ni0.9M0.1)O4+δ (M = Fe, Co, Cu)中间隙氧形成引起的晶格变形行为，在873 ~ 1173 K的温度范围和10 ~ 24 ~ 1 bar的P(O2)范围内进行了热重、库仑滴定和高温x射线衍射测量。热重法与库仑滴定法相结合，可以成功地评价大范围P(O2)下氧含量的变化。与未掺杂的La2NiO4+δ相比，La2(Ni0.9Fe0.1)O4+δ和La2(Ni0.9Co0.1)O4+δ间氧含量较高，而La2(Ni0.9Cu0.1)O4+δ间氧含量较低。在高温条件下，假设所有成分的晶体结构为I4/mmm的四方对称，分析了它们的晶体结构。随着空隙氧浓度的增加，垂直于钙钛矿层的晶格参数增大，平行于钙钛矿层的晶格参数减小。因此，间质氧形成对细胞体积的改变很小，即宏观化学膨胀很小。

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2016 IEEE 16th International Conference on Nanotechnology (IEEE-NANO)

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