Quantum paramagnetism in a non-Kramers rare-earth oxide: Monoclinic Pr2Ti2O7

Man, Huiyuan; Ghasemi, Alireza; Adnani, Moein; Siegler, Maxime A.; Anber, Elaf A.; Li, Yufan; Chien, Chia-Ling; Taheri, Mitra L.; Chu, Ching-Wu; Broholm, Collin L.; Koohpayeh, Seyed M.

doi:10.1103/physrevmaterials.7.063401

Quantum paramagnetism in a non-Kramers rare-earth oxide: Monoclinic Pr2 Ti2 O7

Journal Article · Fri Jun 16 00:00:00 EDT 2023 · Physical Review Materials

DOI:https://doi.org/10.1103/physrevmaterials.7.063401· OSTI ID:2008106

^[1]; ^[1]; ^[2]; ^[1]; Anber, Elaf A. ^[1]; Li, Yufan ^[1]; Chien, Chia-Ling ^[3]; Taheri, Mitra L. ^[1]; ^[4]; ^[1]; ^[1]

Johns Hopkins University, Baltimore, MD (United States)
University of Houston, TX (United States)
Johns Hopkins University, Baltimore, MD (United States); Academia Sinica, Taipei (Taiwan); National Taiwan University, Taipei (Taiwan)
University of Houston, TX (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Little is so far known about the magnetism of the A₂B₂O₇ monoclinic layered perovskites that replace the spin-ice supporting pyrochlore structure for r_A/r_B > 1.78. We show that high quality monoclinic Pr₂Ti₂O₇ single crystals with a three-dimensional network of non-Kramers Pr³⁺ ions that interact through edge-sharing superexchange interactions, form a singlet ground-state quantum paramagnet that does not undergo any magnetic phase transitions down to, at least, 1.8 K. The chemical phase stability, structure, and magnetic properties of the layered perovskite Pr₂Ti₂O₇ were investigated using x-ray diffraction, transmission electron microscopy, and magnetization measurements. Synthesis of polycrystalline samples with the nominal compositions of Pr₂Ti_2+xO₇ (–0.16 ≤ x ≤ 0.16 ) showed that deviations from the Pr₂Ti₂O₇ stoichiometry lead to secondary phases of related structures including the perovskite phase Pr_2/3 TiO₃ and the orthorhombic phases Pr₄Ti₉O₂₄ and Pr₂TiO₅. No indications of site disordering (stuffing and antistuffing) or vacancy defects were observed in the Pr₂Ti₂O₇ majority phase. A procedure for growth of high-structural-quality stoichiometric single crystals of Pr₂Ti₂O₇ by the traveling solvent floating zone method is reported. Thermomagnetic measurements of single-crystalline Pr₂Ti₂O₇ reveal an isolated singlet ground state that we associate with the low-symmetry crystal electric-field environments that split the (2J + 1 = 9)-fold degenerate spin-orbital multiplets of the four differently coordinated Pr³⁺ ions into 36 isolated singlets resulting in an anisotropic temperature-independent van Vleck susceptibility at low T. Here, a small isotropic Curie term is associated with 0.96(2)% noninteracting Pr⁴⁺ impurities.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Gordon and Betty Moore Foundation; Office of Naval Research Multidisciplinary University Research Initiative (MURI)

Grant/Contract Number:: SC0019331; SC0009390; SC0020314; AC02-05CH11231

OSTI ID:: 2008106

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 6 Vol. 7; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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