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SrFeMn(O,F) 氧化物(δ = 0 和 0.5)及氟氧化物钙钛矿薄膜的合成与表征

Synthesis and Characterization of SrFeMn(O,F) Oxide (δ = 0 and 0.5) and Oxyfluoride Perovskite Films.

作者信息

Wang Jiayi, Lefler Benjamin M, May Steven J

机构信息

Department of Materials Science and Engineering, Drexel University, Philadelphia, Pennsylvania 19104, United States.

出版信息

Inorg Chem. 2020 Jul 20;59(14):9990-9997. doi: 10.1021/acs.inorgchem.0c01148. Epub 2020 Jul 6.

DOI:10.1021/acs.inorgchem.0c01148
PMID:32628463
Abstract

We report the synthesis and characterization of as-grown SrFeMnO epitaxial films, which were also subjected to postgrowth oxidation and topotactic fluorination to obtain SrFeMnO and SrFeMnOF films. We show how both the B-site cation and anion composition influence the structural, electronic, and optical properties of this family of perovskite materials. The Fe substitution of Mn in SrMnO gradually expands the -axis parameter, as indicated by X-ray diffraction. With increasing , the F content incorporated under identical fluorination conditions increases, reaching its maximum in SrFeOF. In the compounds with mixed B-site occupation, the Fe 2p photoemission peaks are shifted upon fluorination, while the Mn 2p peaks are not, suggesting inductive effects lead to asymmetric responses in how F alters the Mn and Fe bonds. Electronic transport measurements reveal all compounds are insulators, with the exception of SrFeO, and demonstrate that fluorination increases resistivity for all values of . Optical absorption spectra in the SrFeMnO and SrFeMnO films evolve systematically as a function of , consistent with a physical scenario in which optical changes with Fe substitution arise from a linear combination of Mn and Fe 3d bands within the electronic structure. In contrast, the F incorporation induces nonlinear changes to the optical response, suggesting a more complex impact on the electronic structure in materials with concurrent B-site and anion site substitution.

摘要

我们报道了生长态的SrFeMnO外延薄膜的合成与表征,这些薄膜还经过了生长后氧化和拓扑氟化处理,以获得SrFeMnO和SrFeMnOF薄膜。我们展示了B位阳离子和阴离子组成如何影响这一系列钙钛矿材料的结构、电子和光学性质。如X射线衍射所示,SrMnO中Mn被Fe取代会逐渐扩大c轴参数。随着x增加,在相同氟化条件下掺入的F含量增加,在SrFeOF中达到最大值。在具有混合B位占据的化合物中,Fe 2p光电子能谱峰在氟化时发生位移,而Mn 2p峰未发生位移,这表明诱导效应导致F改变Mn和Fe键的方式存在不对称响应。电子输运测量表明,除了SrFeO外,所有化合物都是绝缘体,并表明氟化会使所有x值下的电阻率增加。SrFeMnO和SrFeMnO薄膜的光吸收光谱随x系统地演变,这与一种物理情景一致,即随着Fe取代的光学变化源于电子结构中Mn和Fe 3d能带的线性组合。相比之下,F的掺入对光学响应产生非线性变化,这表明在同时存在B位和阴离子位取代的材料中,对电子结构有更复杂的影响。

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