Topochemical Fluorination of La$_2$NiO$_{4+δ}$ Single Crystals
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arXiv
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| Format: | Preprint |
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2026
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| _version_ | 1866918471738064896 |
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| author | Yilmaz, Hasan Isobe, Masahiko Clemens, Oliver Puphal, Pascal |
| author_facet | Yilmaz, Hasan Isobe, Masahiko Clemens, Oliver Puphal, Pascal |
| contents | Topochemical fluorination offers a low--temperature route for modifying the anion chemistry and electronic ground states of layered transition-metal oxides, providing access to metastable phases and functionalities that are not able to be achieved through conventional solid--state synthesis. Despite extensive work on polycrystalline samples and thin films, topochemical fluorination of bulk single crystals has not been studied, limiting insights into intrinsic structure property relationships. Here, we investigate the topochemical fluorination of optical float zone grown (OFZ) La$_2$NiO$_{4+δ}$ single crystals using polymer-based PTFE, PVDF and inorganic CuF$_{2}$ fluorination agents and compare it to our topochemical pathways of reduction of LaNiO$_{3-x}$. By systematically investigating direct and indirect contact reaction pathways, we can understand fluorination mechanisms, quantify the degree of fluorine incorporation, and evaluate the resulting structural and magnetic modifications in a detail that was not possible in powder and thin films. Powder and single--crystal X-ray diffraction reveal that fluorination proceeds without destroying the Ruddlesden--Popper framework, while inducing lattice parameter changes consistent with anion intercalation in the bulk and ion exchange on the surface. This even induces a clear superstructure, which was not reported before and extends the understanding of anion insertion reactions beyond what is known on stage ordering in nickelates. Energy-dispersive X--ray spectroscopy confirms strong fluorine incorporation on the surface and reduced homogeneity in the bulk. Magnetic susceptibility measurements demonstrate a change in antiferromagnetic ordering upon fluorination. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2604_25575 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Topochemical Fluorination of La$_2$NiO$_{4+δ}$ Single Crystals Yilmaz, Hasan Isobe, Masahiko Clemens, Oliver Puphal, Pascal Strongly Correlated Electrons Materials Science Superconductivity Topochemical fluorination offers a low--temperature route for modifying the anion chemistry and electronic ground states of layered transition-metal oxides, providing access to metastable phases and functionalities that are not able to be achieved through conventional solid--state synthesis. Despite extensive work on polycrystalline samples and thin films, topochemical fluorination of bulk single crystals has not been studied, limiting insights into intrinsic structure property relationships. Here, we investigate the topochemical fluorination of optical float zone grown (OFZ) La$_2$NiO$_{4+δ}$ single crystals using polymer-based PTFE, PVDF and inorganic CuF$_{2}$ fluorination agents and compare it to our topochemical pathways of reduction of LaNiO$_{3-x}$. By systematically investigating direct and indirect contact reaction pathways, we can understand fluorination mechanisms, quantify the degree of fluorine incorporation, and evaluate the resulting structural and magnetic modifications in a detail that was not possible in powder and thin films. Powder and single--crystal X-ray diffraction reveal that fluorination proceeds without destroying the Ruddlesden--Popper framework, while inducing lattice parameter changes consistent with anion intercalation in the bulk and ion exchange on the surface. This even induces a clear superstructure, which was not reported before and extends the understanding of anion insertion reactions beyond what is known on stage ordering in nickelates. Energy-dispersive X--ray spectroscopy confirms strong fluorine incorporation on the surface and reduced homogeneity in the bulk. Magnetic susceptibility measurements demonstrate a change in antiferromagnetic ordering upon fluorination. |
| title | Topochemical Fluorination of La$_2$NiO$_{4+δ}$ Single Crystals |
| topic | Strongly Correlated Electrons Materials Science Superconductivity |
| url | https://arxiv.org/abs/2604.25575 |