Polar Ruddlesden–Popper Rare-Earth Aluminum Oxynitrides with Partial Anion Order
- 1Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Carrer dels Til.lers, 08193 Cerdanyola del Vallès, Spain
- 2Institut Laue-Langevin, 71 Av. de Martyrs, BP 156, F-38042 Grenoble Cedex 9, France
- 3ICFO-Institut de Ciències Fotòniques, The Barcelona Institute of Science and Technology, 08860 Castelldefels, Spain
Abstract
Anion order in heteroanionic compounds may induce electrical dipoles and the formation of noncentrosymmetric polar structures. The majority of perovskite oxynitrides are centrosymmetric, but some of them show high dielectric permittivities and ferroelectric response resulting from local anion order. Here, we report a study of polar, partially anion-ordered Nd2AlO3N and Sm2AlO3N n = 1 Ruddlesden–Popper oxynitrides, prepared by solid-state reaction in flowing N2 at 1500 °C. They crystallize in the noncentrosymmetric I4mm space group with parameters a = 3.703314(3) and c = 12.545382(14) Å for Nd2AlO3N and a = 3.674477(5) and c = 12.40414(3) Å for Sm2AlO3N. Neutron powder diffraction data of Nd2AlO3N indicate that oxygen occupies the equatorial sites 4b of the AlO5N octahedra, whereas both anions occupy two crystallographically independent 2a axial X2 and X3 sites, with different O/N populations (68/32 for X2 and 32/68 for X3) and a larger bond distance to the Al atom for the oxygen rich site. Dielectric permittivities of 260 and 150 are measured for Nd2AlO3N and Sm2AlO3N, respectively, and second-harmonic generation spectroscopy and scanning transmission electron microscopy furnish complementary evidence of the polar nature of both compounds. These results represent the first experimental demonstration of acentric functionalities in a Ruddlesden–Popper oxynitride.
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BibTeX
@article{orosole2026polar,
title = {{Polar Ruddlesden–Popper Rare-Earth Aluminum Oxynitrides with Partial Anion Order}},
author = {Judith Oró-Solé and Jhonatan R. Guarín and Ignasi Fina and Carlos Frontera and Jaume Gàzquez and Saul Estandia and Mehrdad Ghiasabadi Farahani and Clemens Ritter and Pablo Loza-Alvarez and Gustavo Castro-Olvera and Josep Fontcuberta and Amparo Fuertes},
journal = {Inorganic Chemistry},
year = {2026},
month = oct,
doi = {10.1021/acs.inorgchem.6c03989},
url = {https://doi.org/10.1021/acs.inorgchem.6c03989},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Polar Ruddlesden–Popper Rare-Earth Aluminum Oxynitrides with Partial Anion Order
AU - Judith Oró-Solé
AU - Jhonatan R. Guarín
AU - Ignasi Fina
AU - Carlos Frontera
AU - Jaume Gàzquez
AU - Saul Estandia
AU - Mehrdad Ghiasabadi Farahani
AU - Clemens Ritter
AU - Pablo Loza-Alvarez
AU - Gustavo Castro-Olvera
AU - Josep Fontcuberta
AU - Amparo Fuertes
PY - 2026
DA - 2026/10/13
JO - Inorganic Chemistry
DO - 10.1021/acs.inorgchem.6c03989
UR - https://doi.org/10.1021/acs.inorgchem.6c03989
AB - Anion order in heteroanionic compounds may induce electrical dipoles and the formation of noncentrosymmetric polar structures. The majority of perovskite oxynitrides are centrosymmetric, but some of them show high dielectric permittivities and ferroelectric response resulting from local anion order. Here, we report a study of polar, partially anion-ordered Nd2AlO3N and Sm2AlO3N n = 1 Ruddlesden–Popper oxynitrides, prepared by solid-state reaction in flowing N2 at 1500 °C. They crystallize in the noncentrosymmetric I4mm space group with parameters a = 3.703314(3) and c = 12.545382(14) Å for Nd2AlO3N and a = 3.674477(5) and c = 12.40414(3) Å for Sm2AlO3N. Neutron powder diffraction data of Nd2AlO3N indicate that oxygen occupies the equatorial sites 4b of the AlO5N octahedra, whereas both anions occupy two crystallographically independent 2a axial X2 and X3 sites, with different O/N populations (68/32 for X2 and 32/68 for X3) and a larger bond distance to the Al atom for the oxygen rich site. Dielectric permittivities of 260 and 150 are measured for Nd2AlO3N and Sm2AlO3N, respectively, and second-harmonic generation spectroscopy and scanning transmission electron microscopy furnish complementary evidence of the polar nature of both compounds. These results represent the first experimental demonstration of acentric functionalities in a Ruddlesden–Popper oxynitride.
SN - 0020-1669
SN - 1520-510X
ER -