Evolution of Highly Anisotropic Magnetism in the Titanium-Based Kagome Metals LnTi3Bi4 (Ln: La···Gd3+, Eu2+, Yb2+)

Ortiz, Brenden R.; Miao, Hu; Parker, David S.; Yang, Fazhi; Samolyuk, German D.; Clements, Eleanor M.; Rajapitamahuni, Anil; Yilmaz, Turgut; Vescovo, Elio; Yan, Jiaqiang; May, Andrew F.; McGuire, Michael A.

doi:10.1021/acs.chemmater.3c02289

Title: Evolution of Highly Anisotropic Magnetism in the Titanium-Based Kagome Metals LnTi₃Bi₄ (Ln: La···Gd³⁺, Eu²⁺, Yb²⁺)

Journal Article · 15 November 2023 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.3c02289 · OSTI ID:2281120

^[1];

^[1]; Yang, Fazhi ^[1];

^[1]; Clements, Eleanor M. ^[1]; Rajapitamahuni, Anil ^[2]; Yilmaz, Turgut ^[2]; Vescovo, Elio ^[2];

^[1];

^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Here, we present a family of titanium-based kagome metals of the form LnTi₃Bi₄ (Ln: La···Gd³⁺, Eu²⁺, Yb²⁺). Four previously unreported compounds are presented: YbTi₃Bi₄, GdTi₃Bi₄, NdTi₃Bi₄, and PrTi₃Bi₄. Single-crystal growth methods are provided alongside detailed magnetic and thermodynamic measurements across the entire series. The LnTi₃Bi₄ family of compounds are orthorhombic (Fmmm), layered compounds that exhibit slightly distorted titanium-based kagome nets interwoven with zigzag lanthanide-based (Ln) chains. Crystals are easily exfoliated parallel to the kagome sheets, and angular resolved photoemission (ARPES) measurements highlight the intricacy of the electronic structure in these compounds. Density functional theory (DFT) and ARPES studies find Dirac points near the Fermi level, consistent with the kagome-derived band structure. The magnetic properties and the associated anisotropy emerge from the quasi-1D zigzag chains of Ln and impart a wide array of magnetic ground states ranging from anisotropic ferromagnetism to complex antiferromagnetism with a cascade of metamagnetic transitions. In conclusion, the combination of the kagome-based electronic structure and highly anisotropic Ln-based magnetism on an exfoliatable platform cements the LnTi₃Bi₄ family as an interesting addition to the ever-expanding suite of kagome metals.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725; SC0012704

OSTI ID:: 2281120

Alternate ID(s):: OSTI ID: 2319170

Report Number(s):: BNL-225358-2024-JAAM

Journal Information:: Chemistry of Materials, Vol. 35, Issue 22; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (54)

Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
EuCo 2 P 2 : A model molecular-field helical Heisenberg antiferromagnet Sangeetha, N. S.; Cuervo-Reyes, Eduardo; Pandey, Abhishek Physical Review B, Vol. 94, Issue 1 https://doi.org/10.1103/PhysRevB.94.014422	journal	July 2016
Cs V 3 Sb 5 : A Z 2 Topological Kagome Metal with a Superconducting Ground State Ortiz, Brenden R.; Teicher, Samuel M. L.; Hu, Yong Physical Review Letters, Vol. 125, Issue 24 https://doi.org/10.1103/PhysRevLett.125.247002	journal	December 2020
Use of frit-disc crucibles for routine and exploratory solution growth of single crystalline samples Canfield, Paul C.; Kong, Tai; Kaluarachchi, Udhara S. Philosophical Magazine, Vol. 96, Issue 1 https://doi.org/10.1080/14786435.2015.1122248	journal	December 2015
Realizing Kagome Band Structure in Two-Dimensional Kagome Surface States of RV6Sn6 ( R=Gd , Ho) Peng, Shuting; Han, Yulei; Pokharel, Ganesh Physical Review Letters, Vol. 127, Issue 26 https://doi.org/10.1103/PhysRevLett.127.266401	journal	December 2021
Strongly correlated fermions on a kagome lattice O’Brien, A.; Pollmann, F.; Fulde, P. Physical Review B, Vol. 81, Issue 23 https://doi.org/10.1103/PhysRevB.81.235115	journal	June 2010
Superconductivity and Normal-State Properties of Kagome Metal RbV ₃ Sb ₅ Single Crystals Yin, Qiangwei; Tu, Zhijun; Gong, Chunsheng Chinese Physics Letters, Vol. 38, Issue 3 https://doi.org/10.1088/0256-307X/38/3/037403	journal	March 2021
High-field depinned phase and planar Hall effect in the skyrmion host Gd 2 PdSi 3 Hirschberger, Max; Nakajima, Taro; Kriener, Markus Physical Review B, Vol. 101, Issue 22 https://doi.org/10.1103/PhysRevB.101.220401	journal	June 2020
Flat bands in the CoSn-type compounds Meier, William R.; Du, Mao-Hua; Okamoto, Satoshi Physical Review B, Vol. 102, Issue 7 https://doi.org/10.1103/PhysRevB.102.075148	journal	August 2020
Unconventional chiral charge order in kagome superconductor KV3Sb5 Jiang, Yu-Xiao; Yin, Jia-Xin; Denner, M. Michael Nature Materials https://doi.org/10.1038/s41563-021-01034-y	journal	June 2021
Crystal field effects on the saturation magnetic moment of Sm3+ ion in ferronagnetic samarium compounds Malik, S. K.; Vijayaraghavan, R. Pramana, Vol. 3, Issue 2 https://doi.org/10.1007/BF02847119	journal	August 1974
Highly anisotropic magnetism in the vanadium-based kagome metal TbV6Sn6 Pokharel, Ganesh; Ortiz, Brenden; Chamorro, Juan Physical Review Materials, Vol. 6, Issue 10 https://doi.org/10.1103/PhysRevMaterials.6.104202	journal	October 2022
Interplay of thermal and quantum spin fluctuations in the kagome lattice compound herbertsmithite Wulferding, Dirk; Lemmens, Peter; Scheib, Patric Physical Review B, Vol. 82, Issue 14 https://doi.org/10.1103/PhysRevB.82.144412	journal	October 2010
Fractionally charged topological point defects on the kagome lattice Rüegg, Andreas; Fiete, Gregory A. Physical Review B, Vol. 83, Issue 16 https://doi.org/10.1103/PhysRevB.83.165118	journal	April 2011
Electronic properties of the topological kagome metals YV6Sn6 and GdV6Sn6 Pokharel, Ganesh; Teicher, Samuel M. L.; Ortiz, Brenden R. Physical Review B, Vol. 104, Issue 23 https://doi.org/10.1103/PhysRevB.104.235139	journal	December 2021
Competing electronic orders on kagome lattices at van Hove filling Wang, Wan-Sheng; Li, Zheng-Zhao; Xiang, Yuan-Yuan Physical Review B, Vol. 87, Issue 11 https://doi.org/10.1103/PhysRevB.87.115135	journal	March 2013
Effect of Eu magnetism on the electronic properties of the candidate Dirac material EuMnBi 2 May, Andrew F.; McGuire, Michael A.; Sales, Brian C. Physical Review B, Vol. 90, Issue 7 https://doi.org/10.1103/PhysRevB.90.075109	journal	August 2014
Competing magnetic phases and fluctuation-driven scalar spin chirality in the kagome metal YMn ₆ Sn ₆ Ghimire, Nirmal J.; Dally, Rebecca L.; Poudel, L. Science Advances, Vol. 6, Issue 51 https://doi.org/10.1126/sciadv.abe2680	journal	December 2020
Skyrmion phase and competing magnetic orders on a breathing kagomé lattice Hirschberger, Max; Nakajima, Taro; Gao, Shang Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-13675-4	journal	December 2019
Evidence for a gapped spin-liquid ground state in a kagome Heisenberg antiferromagnet Fu, M.; Imai, T.; Han, T. -H. Science, Vol. 350, Issue 6261 https://doi.org/10.1126/science.aab2120	journal	November 2015
Crystal structure of Ti₈Bi₉O_0.25 containing interstitial oxygen atoms Yamane, Hisanori; Hiraka, Keita Acta Crystallographica Section E Crystallographic Communications, Vol. 74, Issue 9 https://doi.org/10.1107/S205698901801188X	journal	August 2018
New kagome prototype materials: discovery of KV 3 Sb 5 , RbV 3 Sb 5 , and CsV 3 Sb 5 Ortiz, Brenden R.; Gomes, Lídia C.; Morey, Jennifer R. Physical Review Materials, Vol. 3, Issue 9 https://doi.org/10.1103/PhysRevMaterials.3.094407	journal	September 2019
NMR determination of an incommensurate helical antiferromagnetic structure in EuCo 2 As 2 Ding, Q. -P.; Higa, N.; Sangeetha, N. S. Physical Review B, Vol. 95, Issue 18 https://doi.org/10.1103/PhysRevB.95.184404	journal	May 2017
Sign of Knight Shift in Samarium Intermetallic Compounds White, J. A.; Van Vleck, J. H. Physical Review Letters, Vol. 6, Issue 8 https://doi.org/10.1103/PhysRevLett.6.412	journal	April 1961
Topological insulator on the kagome lattice Guo, H. -M.; Franz, M. Physical Review B, Vol. 80, Issue 11 https://doi.org/10.1103/PhysRevB.80.113102	journal	September 2009
Unconventional Fermi Surface Instabilities in the Kagome Hubbard Model Kiesel, Maximilian L.; Platt, Christian; Thomale, Ronny Physical Review Letters, Vol. 110, Issue 12 https://doi.org/10.1103/PhysRevLett.110.126405	journal	March 2013
Hard-Core Bosons on the Kagome Lattice: Valence-Bond Solids and Their Quantum Melting Isakov, S. V.; Wessel, S.; Melko, R. G. Physical Review Letters, Vol. 97, Issue 14 https://doi.org/10.1103/PhysRevLett.97.147202	journal	October 2006
Structure, magnetic properties and giant magnetoresistance of YMn ₆ Sn _{6- x} Ga _x ( x = 0-0.6) compounds Shao-ying, Zhang; Peng, Zhao; Run-wei, Li Chinese Physics, Vol. 10, Issue 4 https://doi.org/10.1088/1009-1963/10/4/318	journal	April 2001
Chapter 227 Bismuthides Mar, Arthur Handbook on the Physics and Chemistry of Rare Earths https://doi.org/10.1016/S0168-1273(06)36001-1	book	November 2006
Covalent organic framework atropisomers with multiple gas-triggered structural flexibilities Kang, Chengjun; Zhang, Zhaoqiang; Kusaka, Shinpei Nature Materials, Vol. 22, Issue 5 https://doi.org/10.1038/s41563-023-01523-2	journal	April 2023
Spin liquids in frustrated magnets Balents, Leon Nature, Vol. 464, Issue 7286 https://doi.org/10.1038/nature08917	journal	March 2010
Anisotropic magnetic property of single crystals RV6Sn6 (R=Y, Gd−Tm, Lu) Lee, Jeonghun; Mun, Eundeok Physical Review Materials, Vol. 6, Issue 8 https://doi.org/10.1103/PhysRevMaterials.6.083401	journal	August 2022
Chiral superconducting phase and chiral spin-density-wave phase in a Hubbard model on the kagome lattice Yu, Shun-Li; Li, Jian-Xin Physical Review B, Vol. 85, Issue 14 https://doi.org/10.1103/PhysRevB.85.144402	journal	April 2012
Electronic and magnetic properties of intermetallic kagome magnets RV6Sn6(R=Tb−Tm) Zhang, Xiaoxiao; Liu, Ziyi; Cui, Qi Physical Review Materials, Vol. 6, Issue 10 https://doi.org/10.1103/PhysRevMaterials.6.105001	journal	October 2022
Quantum-limit Chern topological magnetism in TbMn6Sn6 Yin, Jia-Xin; Ma, Wenlong; Cochran, Tyler A. Nature, Vol. 583, Issue 7817 https://doi.org/10.1038/s41586-020-2482-7	journal	July 2020
Charge Density Wave in Kagome Lattice Intermetallic ScV6Sn6 Arachchige, Hasitha W. Suriya; Meier, William R.; Marshall, Madalynn Physical Review Letters, Vol. 129, Issue 21 https://doi.org/10.1103/PhysRevLett.129.216402	journal	November 2022
YbV3Sb4 and EuV3Sb4 vanadium-based kagome metals with Yb2+ and Eu2+ zigzag chains Ortiz, Brenden R.; Pokharel, Ganesh; Gundayao, Malia Physical Review Materials, Vol. 7, Issue 6 https://doi.org/10.1103/PhysRevMaterials.7.064201	journal	June 2023
Imaging the coupling between itinerant electrons and localised moments in the centrosymmetric skyrmion magnet GdRu2Si2 Yasui, Yuuki; Butler, Christopher J.; Khanh, Nguyen Duy Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-19751-4	journal	November 2020
Cascade of correlated electron states in the kagome superconductor CsV3Sb5 Zhao, He; Li, Hong; Ortiz, Brenden R. Nature, Vol. 599, Issue 7884 https://doi.org/10.1038/s41586-021-03946-w	journal	September 2021
Coexistence of trihexagonal and star-of-David pattern in the charge density wave of the kagome superconductor AV3Sb5 Hu, Yong; Wu, Xianxin; Ortiz, Brenden R. Physical Review B, Vol. 106, Issue 24 https://doi.org/10.1103/PhysRevB.106.L241106	journal	December 2022
Electronic instabilities of kagome metals: Saddle points and Landau theory Park, Takamori; Ye, Mengxing; Balents, Leon Physical Review B, Vol. 104, Issue 3 https://doi.org/10.1103/PhysRevB.104.035142	journal	July 2021
Magnetic properties of new antiferromagnetic heavy-fermion compounds, Ce3TiBi5 and CeTi3Bi4 Motoyama, Gaku; Sezaki, Masumi; Gouchi, Jun Physica B: Condensed Matter, Vol. 536 https://doi.org/10.1016/j.physb.2017.10.005	journal	May 2018
Skyrmion lattice with a giant topological Hall effect in a frustrated triangular-lattice magnet Kurumaji, Takashi; Nakajima, Taro; Hirschberger, Max Science, Vol. 365, Issue 6456 https://doi.org/10.1126/science.aau0968	journal	August 2019
Field-induced topological Hall effect and double-fan spin structure with a c -axis component in the metallic kagome antiferromagnetic compound Y Mn 6 Sn 6 Wang, Qi; Neubauer, Kelly J.; Duan, Chunruo Physical Review B, Vol. 103, Issue 1 https://doi.org/10.1103/PhysRevB.103.014416	journal	January 2021
Superconductivity in the Z 2 kagome metal KV 3 Sb 5 Ortiz, Brenden R.; Sarte, Paul M.; Kenney, Eric M. Physical Review Materials, Vol. 5, Issue 3 https://doi.org/10.1103/PhysRevMaterials.5.034801	journal	March 2021
Evolution of anisotropic magnetic properties through helix-to-fan transition in helical antiferromagnetic EuCo2As2 Kim, Jong Hyuk; Kim, Mi Kyung; Hong, Jae Min Communications Physics, Vol. 6, Issue 1 https://doi.org/10.1038/s42005-023-01134-y	journal	January 2023
Fractionalized excitations in the spin-liquid state of a kagome-lattice antiferromagnet Han, Tian-Heng; Helton, Joel S.; Chu, Shaoyan Nature, Vol. 492, Issue 7429 https://doi.org/10.1038/nature11659	journal	December 2012
Uniaxial ferromagnetism in the kagome metal TbV6Sn6 Rosenberg, Elliott; DeStefano, Jonathan M.; Guo, Yucheng Physical Review B, Vol. 106, Issue 11 https://doi.org/10.1103/PhysRevB.106.115139	journal	September 2022
Doped kagome system as exotic superconductor Ko, Wing-Ho; Lee, Patrick A.; Wen, Xiao-Gang Physical Review B, Vol. 79, Issue 21 https://doi.org/10.1103/PhysRevB.79.214502	journal	June 2009
Bismuth as a Reactive Solvent in the Synthesis of Multicomponent Transition-Metal-Bearing Bismuthides Ovchinnikov, Alexander; Bobev, Svilen Inorganic Chemistry https://doi.org/10.1021/acs.inorgchem.9b02881	journal	December 2019
Site Specific X-ray Anomalous Dispersion of the Geometrically Frustrated Kagomé Magnet, Herbertsmithite, ZnCu ₃ (OH) ₆ Cl ₂ Freedman, Danna E.; Han, Tianheng H.; Prodi, Andrea Journal of the American Chemical Society, Vol. 132, Issue 45 https://doi.org/10.1021/ja1070398	journal	November 2010
Rare Earth Engineering in R Mn 6 Sn 6 ( R = Gd − Tm , Lu) Topological Kagome Magnets Ma, Wenlong; Xu, Xitong; Yin, Jia-Xin Physical Review Letters, Vol. 126, Issue 24 https://doi.org/10.1103/PhysRevLett.126.246602	journal	June 2021
Synthesis, Crystal and Electronic Structure of the Titanium Bismuthides Sr ₅ Ti ₁₂ Bi _{19+ x} , Ba ₅ Ti ₁₂ Bi _{19+ x} , and Sr _5- _δ Eu _δ Ti ₁₂ Bi _{19+ x} ( x ≈ 0.5-1.0; δ ≈ 2.4, 4.0) : Synthesis, Crystal and Electronic Structure of the Titanium Bismuthides Sr5Ti12Bi19+x, Ba5Ti12Bi19+x, and Sr5-δEuδTi12Bi19+x (x ≈ 0.5-1.0; δ ≈ 2.4, 4. Ovchinnikov, Alexander; Bobev, Svilen European Journal of Inorganic Chemistry, Vol. 2018, Issue 11 https://doi.org/10.1002/ejic.201701426	journal	March 2018
Fermi Surface Mapping and the Nature of Charge-Density-Wave Order in the Kagome Superconductor CsV 3 Sb 5 Ortiz, Brenden R.; Teicher, Samuel M. L.; Kautzsch, Linus Physical Review X, Vol. 11, Issue 4 https://doi.org/10.1103/PhysRevX.11.041030	journal	November 2021

Similar Records

Intricate Magnetic Landscape in Antiferromagnetic Kagome Metal TbTi₃Bi₄ and Interplay with Ln_2–xTi_6+xBi₉ (Ln: Tb···Lu) Shurikagome Metals

Journal Article · 2024 · Chemistry of Materials · OSTI ID:2438874

Ortiz, Brenden R.; Zhang, Heda; Górnicka, Karolina; +8 more

Diverse electronic landscape of the kagome metal YbTi₃Bi₄

Journal Article · 2024 · Communications Materials · OSTI ID:2478327

Sakhya, Anup Pradhan; Ortiz, Brenden R.; Ghosh, Barun; +8 more

Ternary rare-earth titanium antimonides: Phase equilibria in the RE-Ti-Sb (RE=La, Er) systems and crystal structures of RE{sub 2}Ti{sub 7}Sb{sub 12} (RE=La, Ce, Pr, Nd) and RETi{sub 3}(Sn{sub x}Sb{sub 1-x}){sub 4} (RE=Nd, Sm)

Journal Article · 2007 · Journal of Solid State Chemistry · OSTI ID:21043797

Haiying, Bie; Devon Moore, S H; Piercey, Davin G; +3 more

Related Subjects

36 MATERIALS SCIENCE
Crystal structure
Crystals
Electronic structure
Magnetic properties
Order

Title: Evolution of Highly Anisotropic Magnetism in the Titanium-Based Kagome Metals LnTi3Bi4 (Ln: La···Gd3+, Eu2+, Yb2+)

Citation Formats

References (54)

Similar Records

Related Subjects

Title: Evolution of Highly Anisotropic Magnetism in the Titanium-Based Kagome Metals LnTi₃Bi₄ (Ln: La···Gd³⁺, Eu²⁺, Yb²⁺)