Hole doping in a negative charge transfer insulator

Patel, Ranjan Kumar; Patra, Krishnendu; Ojha, Shashank Kumar; Kumar, Siddharth; Sarkar, Sagar; Saha, Akash; Bhattacharya, Nandana; Freeland, John W.; Kim, Jong-Woo; Ryan, Philip J.; Mahadevan, Priya; Middey, Srimanta

doi:10.1038/s42005-022-00993-1

Title: Hole doping in a negative charge transfer insulator

Journal Article · 27 August 2022 · Communications Physics

DOI: https://doi.org/10.1038/s42005-022-00993-1 · OSTI ID:1909633

^[1]; Patra, Krishnendu ^[2];

^[1];

^[3]; Saha, Akash ^[1]; Bhattacharya, Nandana ^[1];

^[4];

^[4]; Ryan, Philip J. ^[4];

^[2];

^[1]

Indian Institute of Science (India)
S.N. Bose National Centre for Basic Sciences (India)
S.N. Bose National Centre for Basic Sciences (India); Asia Pacific Center for Theoretical Physics (Korea)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

RENiO₃ is a negative charge transfer energy system and exhibits a temperature-driven metal-insulator transition (MIT), which is also accompanied by a bond disproportionation (BD) transition. In order to explore how hole doping affects the BD transition, we have investigated the electronic structure of single-crystalline thin films of Nd_1-xCa_xNiO₃ by synchrotron based experiments and ab-initio calculations. Here we show that for a small value of x, the doped holes are localized on one or more Ni sites around the dopant Ca²⁺ ions, while the BD state for the rest of the lattice remains intact. The effective charge transfer energy (Δ) increases with Ca concentration and the formation of BD phase is not favored above a critical x, suppressing the insulating phase. Our present study firmly demonstrates that the appearance of BD mode is essential for the MIT of the RENiO₃ series.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: India Department of Science and Technology (DST); India Science and Engineering Research Board (SERB) Early Career Research (ECR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1909633

Journal Information:: Communications Physics, Journal Name: Communications Physics Journal Issue: 1 Vol. 5; ISSN 2399-3650

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (75)

Hole‐Trapping‐Induced Stabilization of Ni ^4 + in SrNiO ₃ /LaFeO ₃ Superlattices Wang, Le; Yang, Zhenzhong; Bowden, Mark E. Advanced Materials, Vol. 32, Issue 45 https://doi.org/10.1002/adma.202005003	journal	October 2020
Tuning the Electronic Structure of LaNiO ₃ through Alloying with Strontium to Enhance Oxygen Evolution Activity Liu, Jishan; Jia, Endong; Wang, Le Advanced Science, Vol. 6, Issue 19 https://doi.org/10.1002/advs.201901073	journal	August 2019
Electron-hole doping of the metal-insulator transition compound RENiO3 Cheong, S-W.; Hwang, H. Y.; Batlogg, B. Physica B: Condensed Matter, Vol. 194-196 https://doi.org/10.1016/0921-4526(94)90873-7	journal	February 1994
Evolution of electronic structure across the rare-earth RNiO3 series Freeland, John W.; van Veenendaal, Michel; Chakhalian, Jak Journal of Electron Spectroscopy and Related Phenomena, Vol. 208 https://doi.org/10.1016/j.elspec.2015.07.006	journal	April 2016
Oxygen nonstoichiometry of NdNiO3−δ and SmNiO3−δ Nikulin, I. V.; Novojilov, M. A.; Kaul, A. R. Materials Research Bulletin, Vol. 39, Issue 6 https://doi.org/10.1016/j.materresbull.2004.02.005	journal	May 2004
Ground-state oxygen holes and the metal–insulator transition in the negative charge-transfer rare-earth nickelates Bisogni, Valentina; Catalano, Sara; Green, Robert J. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13017	journal	October 2016
Heterointerface engineered electronic and magnetic phases of NdNiO3 thin films Liu, Jian; Kargarian, Mehdi; Kareev, Mikhail Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3714	journal	November 2013
Structurally triggered metal-insulator transition in rare-earth nickelates Mercy, Alain; Bieder, Jordan; Íñiguez, Jorge Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01811-x	journal	November 2017
Energetics of the coupled electronic–structural transition in the rare-earth nickelates Hampel, Alexander; Liu, Peitao; Franchini, Cesare npj Quantum Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41535-019-0145-4	journal	February 2019
Electronic structure of the parent compound of superconducting infinite-layer nickelates Hepting, M.; Li, D.; Jia, C. J. Nature Materials, Vol. 19, Issue 4 https://doi.org/10.1038/s41563-019-0585-z	journal	January 2020
Superconductivity in an infinite-layer nickelate Li, Danfeng; Lee, Kyuho; Wang, Bai Yang Nature, Vol. 572, Issue 7771 https://doi.org/10.1038/s41586-019-1496-5	journal	August 2019
Mott Transition and Magnetism in Rare Earth Nickelates and its Fingerprint on the X-ray Scattering Haule, Kristjan; Pascut, Gheorghe L. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-10374-2	journal	September 2017
Quantifying the role of the lattice in metal–insulator phase transitions Georgescu, Alexandru B.; Millis, Andrew J. Communications Physics, Vol. 5, Issue 1 https://doi.org/10.1038/s42005-022-00909-z	journal	May 2022
On the lack of monoclinic distortion in the insulating regime of EuNiO₃ and GdNiO₃ perovskites by high-angular resolution synchrotron X-ray diffraction: a comparison with YNiO₃ Serrano-Sánchez, Federico; Martínez, José Luis; Fauth, François Dalton Transactions, Vol. 50, Issue 20 https://doi.org/10.1039/D1DT00646K	journal	January 2021
Room temperature Mott metal-insulator transition and its systematic control in Sm1−xCaxNiO3 thin films Xiang, P. -H.; Asanuma, S.; Yamada, H. Applied Physics Letters, Vol. 97, Issue 3 https://doi.org/10.1063/1.3467199	journal	July 2010
Phase engineering of rare earth nickelates by digital synthesis Middey, S.; Meyers, D.; Kumar Patel, Ranjan Applied Physics Letters, Vol. 113, Issue 8 https://doi.org/10.1063/1.5045756	journal	August 2018
Epitaxial stabilization of ultra thin films of high entropy perovskite Patel, Ranjan Kumar; Ojha, Shashank Kumar; Kumar, Siddharth Applied Physics Letters, Vol. 116, Issue 7 https://doi.org/10.1063/1.5133710	journal	February 2020
Emergent behavior of LaNiO₃ in short-periodic nickelate superlattices Patel, Ranjan Kumar; Meyers, D.; Liu, Xiaoran APL Materials, Vol. 8, Issue 4 https://doi.org/10.1063/5.0004530	journal	April 2020
Disentangling lattice and electronic contributions to the metal–insulator transition from bulk vs. layer confined RNiO ₃ Georgescu, Alexandru B.; Peil, Oleg E.; Disa, Ankit S. Proceedings of the National Academy of Sciences, Vol. 116, Issue 29 https://doi.org/10.1073/pnas.1818728116	journal	July 2019
Doping evolution of the Mott–Hubbard landscape in infinite-layer nickelates Goodge, Berit H.; Li, Danfeng; Lee, Kyuho Proceedings of the National Academy of Sciences, Vol. 118, Issue 2 https://doi.org/10.1073/pnas.2007683118	journal	January 2021
Progress in perovskite nickelate research Catalan, G. Phase Transitions, Vol. 81, Issue 7-8 https://doi.org/10.1080/01411590801992463	journal	July 2008
Rare-earth nickelates R NiO ₃ : thin films and heterostructures Catalano, S.; Gibert, M.; Fowlie, J. Reports on Progress in Physics, Vol. 81, Issue 4 https://doi.org/10.1088/1361-6633/aaa37a	journal	February 2018
First-principles study of electron and hole doping effects in perovskite nickelates Iglesias, Lucia; Bibes, Manuel; Varignon, Julien Physical Review B, Vol. 104, Issue 3 https://doi.org/10.1103/PhysRevB.104.035123	journal	July 2021
Orbital and spin character of doped carriers in infinite-layer nickelates Rossi, M.; Lu, H.; Nag, A. Physical Review B, Vol. 104, Issue 22 https://doi.org/10.1103/PhysRevB.104.L220505	journal	December 2021
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Electron-spectroscopy study of the semiconductor-metal transition in La 1 − x Sr x CoO 3 Chainani, A.; Mathew, M.; Sarma, D. D. Physical Review B, Vol. 46, Issue 16 https://doi.org/10.1103/PhysRevB.46.9976	journal	October 1992
Nature of hole doping in Nd 2 NiO 4 and La 2 NiO 4 : Comparison with La 2 CuO 4 Tan, Zhengquan; Heald, S. M.; Cheong, S-W. Physical Review B, Vol. 47, Issue 18 https://doi.org/10.1103/PhysRevB.47.12365	journal	May 1993
Electron spectroscopic investigation of the semiconductor-metal transition in La 1 − x Sr x MnO 3 Chainani, A.; Mathew, M.; Sarma, D. D. Physical Review B, Vol. 47, Issue 23 https://doi.org/10.1103/PhysRevB.47.15397	journal	June 1993
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Mean-field results of the multiple-band extended Hubbard model for the square-planar CuO 2 lattice Nimkar, Seva; Sarma, D. D.; Krishnamurthy, H. R. Physical Review B, Vol. 48, Issue 10 https://doi.org/10.1103/PhysRevB.48.7355	journal	September 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Covalency-driven unusual metal-insulator transition in nickelates Barman, S. R.; Chainani, A.; Sarma, D. D. Physical Review B, Vol. 49, Issue 12 https://doi.org/10.1103/PhysRevB.49.8475	journal	March 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Influence of carrier injection on the metal-insulator transition in electron- and hole-doped R 1 − x A x NiO 3 perovskites García-Muñoz, J. L.; Suaaidi, M.; Martínez-Lope, M. J. Physical Review B, Vol. 52, Issue 18 https://doi.org/10.1103/PhysRevB.52.13563	journal	November 1995
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Transport and magnetic properties of a Mott-Hubbard system whose bandwidth and band filling are both controllable: R 1 − x Ca x TiO 3 + y / 2 Katsufuji, T.; Taguchi, Y.; Tokura, Y. Physical Review B, Vol. 56, Issue 16 https://doi.org/10.1103/PhysRevB.56.10145	journal	October 1997
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Electronic structure of one-dimensional cuprates Maiti, K.; Sarma, D. D.; Mizokawa, T. Physical Review B, Vol. 57, Issue 3 https://doi.org/10.1103/PhysRevB.57.1572	journal	January 1998
Spin and charge ordering in self-doped Mott insulators Mizokawa, T.; Khomskii, D. I.; Sawatzky, G. A. Physical Review B, Vol. 61, Issue 17 https://doi.org/10.1103/PhysRevB.61.11263	journal	May 2000
Different routes to charge disproportionation in perovskite-type Fe oxides Matsuno, J.; Mizokawa, T.; Fujimori, A. Physical Review B, Vol. 66, Issue 19 https://doi.org/10.1103/PhysRevB.66.193103	journal	November 2002
Resonant x-ray scattering experiments on electronic orderings in NdNiO 3 single crystals Lorenzo, J. E.; Hodeau, J. L.; Paolasini, L. Physical Review B, Vol. 71, Issue 4 https://doi.org/10.1103/PhysRevB.71.045128	journal	January 2005
Charge disproportionation and search for orbital ordering in Nd Ni O 3 by use of resonant x-ray diffraction Scagnoli, V.; Staub, U.; Janousch, M. Physical Review B, Vol. 72, Issue 15 https://doi.org/10.1103/PhysRevB.72.155111	journal	October 2005
Role of magnetic and orbital ordering at the metal-insulator transition in NdNiO 3 Scagnoli, V.; Staub, U.; Mulders, A. M. Physical Review B, Vol. 73, Issue 10 https://doi.org/10.1103/PhysRevB.73.100409	journal	March 2006
Manifestation of screening effects and A − O covalency in the core level spectra of A site elements in the A B O 3 structure of Ca 1 − x Sr x Ru O 3 Singh, Ravi Shankar; Maiti, Kalobaran Physical Review B, Vol. 76, Issue 8 https://doi.org/10.1103/PhysRevB.76.085102	journal	August 2007
Structure and charge order in the antiferromagnetic band-insulating phase of NdNiO 3 García-Muñoz, J. L.; Aranda, M. A. G.; Alonso, J. A. Physical Review B, Vol. 79, Issue 13 https://doi.org/10.1103/PhysRevB.79.134432	journal	April 2009
Quantum confinement of Mott electrons in ultrathin LaNiO 3 /LaAlO 3 superlattices Liu, Jian; Okamoto, S.; van Veenendaal, M. Physical Review B, Vol. 83, Issue 16 https://doi.org/10.1103/PhysRevB.83.161102	journal	April 2011
Lattice normal modes and electronic properties of the correlated metal LaNiO 3 Gou, Gaoyang; Grinberg, Ilya; Rappe, Andrew M. Physical Review B, Vol. 84, Issue 14 https://doi.org/10.1103/PhysRevB.84.144101	journal	October 2011
Strain-modulated Mott transition in EuNiO 3 ultrathin films Meyers, D.; Middey, S.; Kareev, M. Physical Review B, Vol. 88, Issue 7 https://doi.org/10.1103/PhysRevB.88.075116	journal	August 2013
Charge order and antiferromagnetism in epitaxial ultrathin films of EuNiO 3 Meyers, D.; Middey, S.; Kareev, M. Physical Review B, Vol. 92, Issue 23 https://doi.org/10.1103/PhysRevB.92.235126	journal	December 2015
Quantitative determination of bond order and lattice distortions in nickel oxide heterostructures by resonant x-ray scattering Lu, Y.; Frano, A.; Bluschke, M. Physical Review B, Vol. 93, Issue 16 https://doi.org/10.1103/PhysRevB.93.165121	journal	April 2016
Bond disproportionation and dynamical charge fluctuations in the perovskite rare-earth nickelates Green, R. J.; Haverkort, M. W.; Sawatzky, G. A. Physical Review B, Vol. 94, Issue 19 https://doi.org/10.1103/PhysRevB.94.195127	journal	November 2016
Phase coexistence and dynamical behavior in NdNiO 3 ultrathin films Alsaqqa, Ali M.; Singh, Sujay; Middey, S. Physical Review B, Vol. 95, Issue 12 https://doi.org/10.1103/PhysRevB.95.125132	journal	March 2017
Interplay between breathing mode distortion and magnetic order in rare-earth nickelates R NiO 3 within DFT + U Hampel, Alexander; Ederer, Claude Physical Review B, Vol. 96, Issue 16 https://doi.org/10.1103/PhysRevB.96.165130	journal	October 2017
Anomalous electron transport in epitaxial NdNiO 3 films Ojha, Shashank Kumar; Ray, Sujay; Das, Tanmoy Physical Review B, Vol. 99, Issue 23 https://doi.org/10.1103/PhysRevB.99.235153	journal	June 2019
Mechanism and control parameters of the coupled structural and metal-insulator transition in nickelates Peil, Oleg E.; Hampel, Alexander; Ederer, Claude Physical Review B, Vol. 99, Issue 24 https://doi.org/10.1103/PhysRevB.99.245127	journal	June 2019
Mott Physics near the Insulator-To-Metal Transition in NdNiO 3 Stewart, M. K.; Liu, Jian; Kareev, M. Physical Review Letters, Vol. 107, Issue 17 https://doi.org/10.1103/PhysRevLett.107.176401	journal	October 2011
Site-Selective Mott Transition in Rare-Earth-Element Nickelates Park, Hyowon; Millis, Andrew J.; Marianetti, Chris A. Physical Review Letters, Vol. 109, Issue 15 https://doi.org/10.1103/PhysRevLett.109.156402	journal	October 2012
Charge Disproportionation without Charge Transfer in the Rare-Earth-Element Nickelates as a Possible Mechanism for the Metal-Insulator Transition Johnston, Steve; Mukherjee, Anamitra; Elfimov, Ilya Physical Review Letters, Vol. 112, Issue 10 https://doi.org/10.1103/PhysRevLett.112.106404	journal	March 2014
Tunable Charge and Spin Order in PrNiO 3 Thin Films and Superlattices Hepting, M.; Minola, M.; Frano, A. Physical Review Letters, Vol. 113, Issue 22 https://doi.org/10.1103/PhysRevLett.113.227206	journal	November 2014
Disentangled Cooperative Orderings in Artificial Rare-Earth Nickelates Middey, S.; Meyers, D.; Kareev, M. Physical Review Letters, Vol. 120, Issue 15 https://doi.org/10.1103/PhysRevLett.120.156801	journal	April 2018
Direct Evidence of the Competing Nature between Electronic and Lattice Breathing Order in Rare-Earth Nickelates Kim, Jong-Woo; Choi, Yongseong; Middey, S. Physical Review Letters, Vol. 124, Issue 12 https://doi.org/10.1103/PhysRevLett.124.127601	journal	March 2020
Critical Nature of the Ni Spin State in Doped NdNiO 2 Jiang, Mi; Berciu, Mona; Sawatzky, George A. Physical Review Letters, Vol. 124, Issue 20 https://doi.org/10.1103/PhysRevLett.124.207004	journal	May 2020
Band gaps and electronic structure of transition-metal compounds Zaanen, J.; Sawatzky, G. A.; Allen, J. W. Physical Review Letters, Vol. 55, Issue 4 https://doi.org/10.1103/PhysRevLett.55.418	journal	July 1985
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
Spin, Charge, and Orbital Ordering in La 0.5 Sr 1.5 MnO 4 Mahadevan, Priya; Terakura, K.; Sarma, D. D. Physical Review Letters, Vol. 87, Issue 6 https://doi.org/10.1103/PhysRevLett.87.066404	journal	July 2001
Direct Observation of Charge Order in an Epitaxial NdNiO 3 Film Staub, U.; Meijer, G. I.; Fauth, F. Physical Review Letters, Vol. 88, Issue 12 https://doi.org/10.1103/PhysRevLett.88.126402	journal	March 2002
Metal-insulator transitions Imada, Masatoshi; Fujimori, Atsushi; Tokura, Yoshinori Reviews of Modern Physics, Vol. 70, Issue 4, p. 1039-1263 https://doi.org/10.1103/RevModPhys.70.1039	journal	October 1998
Tuning bad metal and non-Fermi liquid behavior in a Mott material: Rare-earth nickelate thin films Mikheev, Evgeny; Hauser, Adam J.; Himmetoglu, Burak Science Advances, Vol. 1, Issue 10 https://doi.org/10.1126/sciadv.1500797	journal	November 2015
Electric Conduction in Phosphorus Doped Silicon at Low Temperatures Yamanouchi, Chikako; Mizuguchi, Kanji; Sasaki, Wataru Journal of the Physical Society of Japan, Vol. 22, Issue 3 https://doi.org/10.1143/JPSJ.22.859	journal	March 1967
Physics of Ultrathin Films and Heterostructures of Rare-Earth Nickelates Middey, S.; Chakhalian, J.; Mahadevan, P. Annual Review of Materials Research, Vol. 46, Issue 1 https://doi.org/10.1146/annurev-matsci-070115-032057	journal	July 2016
Perspective—Emergent Phases in Rare Earth Nickelate Heterostructure Chakhalian, J.; Middey, S. ECS Journal of Solid State Science and Technology, Vol. 11, Issue 5 https://doi.org/10.1149/2162-8777/ac64c3	journal	May 2022
Energetics of the coupled electronic–structural transition in the rare-earth nickelates Alexander, Hampel,; Claude, Ederer,; Peitao, Liu, Materials Cloud https://doi.org/10.24435/materialscloud:2019.0009/v1	dataset	January 2019
Mechanism and control parameters of the coupled structural and metal-insulator transition in nickelates Peil, Oleg E.; Hampel, Alexander; Ederer, Claude Materials Cloud https://doi.org/10.24435/materialscloud:2019.0061/v1	dataset	January 2019
The driving force for charge ordering in rare earth nickelates Mandal, Basudeb; Sarkar, Sagar; Pandey, Shishir Kumar arXiv https://doi.org/10.48550/arXiv.1701.06819	preprint	January 2017
Magnetic Order Driven Ultrafast Phase Transition in NdNiO$_3$ Stoica, V.; Puggioni, D.; Zhang, J. arXiv https://doi.org/10.48550/arXiv.2004.03694	preprint	January 2020

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Title: Hole doping in a negative charge transfer insulator

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