Valence-Ordered Thin-Film Nickelate with Tri-component Nickel Coordination Prepared by Topochemical Reduction

Aravind Raji; Zhengang Dong; Victor Porée; Alaska Subedi; Xiaoyan Li; Bernat Mundet; Lucia Varbaro; Claribel Domínguez; Marios Hadjimichael; Bohan Feng; Alessandro Nicolaou; Jean-Pascal Rueff; Danfeng Li; Alexandre Gloter

doi:10.1021/acsnano.3c07614

Valence-Ordered Thin-Film Nickelate with Tri-component Nickel Coordination Prepared by Topochemical Reduction

Aravind Raji, Zhengang Dong, Victor Porée, Alaska Subedi, Xiaoyan Li, Bernat Mundet, Lucia Varbaro, Claribel Domínguez, Marios Hadjimichael, Bohan Feng, Alessandro Nicolaou, Jean-Pascal Rueff, Danfeng Li^*, Alexandre Gloter^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

7 Citations (Scopus)

Abstract

The metal-hydride-based “topochemical reduction” process has produced several thermodynamically unstable phases across various transition metal oxide series with unusual crystal structures and nontrivial ground states. Here, by such an oxygen (de-)intercalation method we synthesis a samarium nickelate with ordered nickel valences associated with tri-component coordination configurations. This structure, with a formula of Sm₉Ni₉O₂₂ as revealed by four-dimensional scanning transmission electron microscopy (4D-STEM), emerges from the intricate planes of {303}_pc ordered apical oxygen vacancies. X-ray spectroscopy measurements and ab initio calculations show the coexistence of square planar, pyramidal, and octahedral Ni sites with mono-, bi-, and tri-valences. It leads to an intense orbital polarization, charge-ordering, and a ground state with a strong electron localization marked by the disappearance of ligand-hole configuration at low temperature. This nickelate compound provides another example of previously inaccessible materials enabled by topotactic transformations and presents an interesting platform where mixed Ni valence can give rise to exotic phenomena. © 2024 American Chemical Society.

Original language	English
Pages (from-to)	4077-4088
Journal	ACS Nano
Volume	18
Issue number	5
Online published	25 Jan 2024
DOIs	https://doi.org/10.1021/acsnano.3c07614
Publication status	Published - 6 Feb 2024

Funding

A.G., A.N., and J.-P.R. acknowledge financing from EU-H2020 IMPRESS under Grant Agreement No. 101094299. A.R. acknowledges financing from LABEX NanoSaclay and EU-H2020 ESTEEM-3 under Grant Agreement No. 823717 for doctoral funding. A.G. and X.L. also acknowledge financing from EU-H2020 ESTEEM-3 under Grant Agreement No. 823717. Nion UltraSTEM at LPS Orsay and the FIB at C2N, University of Paris-Saclay were accessed in the TEMPOS project framework (ANR 10-EQPX-0050). Z.D., B.F., and D.L. acknowledge the funding support from the Natural Science Foundation of China (No. 12174325) and Guang Dong Basic and Applied Basic Research Foundation (2023A1515011352). The work performed in Hong Kong is supported by the Research Grants Council of Hong Kong through the Early Career Scheme (CityU 21301221) and the General Research Fund (CityU 11309622, CityU 11300923). The work benefits from the framework of the joint ANR-RGC ImagingQM project (RGC, A-CityU102/23; ANR, ANR-23-CE42-0027). L.V., C.D., and M.H. acknowledge support by the Swiss National Science Foundation─division II (Grant Nos. 200020_179155 and 200020_207338) and by the European Research Council under the European Union Seventh Framework Programme (FP7/2007–2013)/ERC Grant Agreement No. 319286 (Q-MAC). A.S. acknowledges GENCI-TGCC for computing time under Grant A0130913028. We acknowledge SOLEIL Synchrotron for provision of beamtime under the proposals 20220630 and 20221574. We thank Daniele Preziosi, Alberto Zobelli, Zhizhong Li, Nicolas Jaouen, and Jean-Marc Triscone for fruitful discussions.

Research Keywords

4D-STEM
Carrier localization
Charge order
Nickelates
Oxygen vacancies
RIXS
Topotactic transitions

Access Output

10.1021/acsnano.3c07614

Other Access Options

Check CityUHK Library

Permanent Link

Right click to copy link

Cite this

@article{20972212339446bdbfce19c75552192c,

title = "Valence-Ordered Thin-Film Nickelate with Tri-component Nickel Coordination Prepared by Topochemical Reduction",

abstract = "The metal-hydride-based “topochemical reduction” process has produced several thermodynamically unstable phases across various transition metal oxide series with unusual crystal structures and nontrivial ground states. Here, by such an oxygen (de-)intercalation method we synthesis a samarium nickelate with ordered nickel valences associated with tri-component coordination configurations. This structure, with a formula of Sm9Ni9O22 as revealed by four-dimensional scanning transmission electron microscopy (4D-STEM), emerges from the intricate planes of {303}pc ordered apical oxygen vacancies. X-ray spectroscopy measurements and ab initio calculations show the coexistence of square planar, pyramidal, and octahedral Ni sites with mono-, bi-, and tri-valences. It leads to an intense orbital polarization, charge-ordering, and a ground state with a strong electron localization marked by the disappearance of ligand-hole configuration at low temperature. This nickelate compound provides another example of previously inaccessible materials enabled by topotactic transformations and presents an interesting platform where mixed Ni valence can give rise to exotic phenomena. {\textcopyright} 2024 American Chemical Society.",

keywords = "4D-STEM, Carrier localization, Charge order, Nickelates, Oxygen vacancies, RIXS, Topotactic transitions",

author = "Aravind Raji and Zhengang Dong and Victor Por{\'e}e and Alaska Subedi and Xiaoyan Li and Bernat Mundet and Lucia Varbaro and Claribel Dom{\'i}nguez and Marios Hadjimichael and Bohan Feng and Alessandro Nicolaou and Jean-Pascal Rueff and Danfeng Li and Alexandre Gloter",

year = "2024",

month = feb,

day = "6",

doi = "10.1021/acsnano.3c07614",

language = "English",

volume = "18",

pages = "4077--4088",

journal = "ACS Nano",

issn = "1936-0851",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - Valence-Ordered Thin-Film Nickelate with Tri-component Nickel Coordination Prepared by Topochemical Reduction

AU - Raji, Aravind

AU - Dong, Zhengang

AU - Porée, Victor

AU - Subedi, Alaska

AU - Li, Xiaoyan

AU - Mundet, Bernat

AU - Varbaro, Lucia

AU - Domínguez, Claribel

AU - Hadjimichael, Marios

AU - Feng, Bohan

AU - Nicolaou, Alessandro

AU - Rueff, Jean-Pascal

AU - Li, Danfeng

AU - Gloter, Alexandre

PY - 2024/2/6

Y1 - 2024/2/6

N2 - The metal-hydride-based “topochemical reduction” process has produced several thermodynamically unstable phases across various transition metal oxide series with unusual crystal structures and nontrivial ground states. Here, by such an oxygen (de-)intercalation method we synthesis a samarium nickelate with ordered nickel valences associated with tri-component coordination configurations. This structure, with a formula of Sm9Ni9O22 as revealed by four-dimensional scanning transmission electron microscopy (4D-STEM), emerges from the intricate planes of {303}pc ordered apical oxygen vacancies. X-ray spectroscopy measurements and ab initio calculations show the coexistence of square planar, pyramidal, and octahedral Ni sites with mono-, bi-, and tri-valences. It leads to an intense orbital polarization, charge-ordering, and a ground state with a strong electron localization marked by the disappearance of ligand-hole configuration at low temperature. This nickelate compound provides another example of previously inaccessible materials enabled by topotactic transformations and presents an interesting platform where mixed Ni valence can give rise to exotic phenomena. © 2024 American Chemical Society.

AB - The metal-hydride-based “topochemical reduction” process has produced several thermodynamically unstable phases across various transition metal oxide series with unusual crystal structures and nontrivial ground states. Here, by such an oxygen (de-)intercalation method we synthesis a samarium nickelate with ordered nickel valences associated with tri-component coordination configurations. This structure, with a formula of Sm9Ni9O22 as revealed by four-dimensional scanning transmission electron microscopy (4D-STEM), emerges from the intricate planes of {303}pc ordered apical oxygen vacancies. X-ray spectroscopy measurements and ab initio calculations show the coexistence of square planar, pyramidal, and octahedral Ni sites with mono-, bi-, and tri-valences. It leads to an intense orbital polarization, charge-ordering, and a ground state with a strong electron localization marked by the disappearance of ligand-hole configuration at low temperature. This nickelate compound provides another example of previously inaccessible materials enabled by topotactic transformations and presents an interesting platform where mixed Ni valence can give rise to exotic phenomena. © 2024 American Chemical Society.

KW - 4D-STEM

KW - Carrier localization

KW - Charge order

KW - Nickelates

KW - Oxygen vacancies

KW - RIXS

KW - Topotactic transitions

UR - http://www.scopus.com/inward/record.url?scp=85184292977&partnerID=8YFLogxK

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85184292977&origin=recordpage

U2 - 10.1021/acsnano.3c07614

DO - 10.1021/acsnano.3c07614

M3 - RGC 21 - Publication in refereed journal

C2 - 38271616

SN - 1936-0851

VL - 18

SP - 4077

EP - 4088

JO - ACS Nano

JF - ACS Nano

IS - 5

ER -

Valence-Ordered Thin-Film Nickelate with Tri-component Nickel Coordination Prepared by Topochemical Reduction

Abstract

Funding

Research Keywords

Access Output

Other Access Options

Permanent Link

Other Files and Links

Fingerprint

ANR: An atomic-level platform for probing intertwined orders in correlated quantum materials (ImagingQM)

GRF: Phase-Sensitive Measurements in Mesoscopic Nickelate Superconducting Junction Devices

GRF: Flexible Nano-mechanical Approaches to Unravelling the Intertwined Orders in Paradigm Oxide Superconductors

Cite this

Valence-Ordered Thin-Film Nickelate with Tri-component Nickel Coordination Prepared by Topochemical Reduction

Abstract

Funding

Research Keywords

Access Output

Other Access Options

Permanent Link

Other Files and Links

Fingerprint

Projects

ANR: An atomic-level platform for probing intertwined orders in correlated quantum materials (ImagingQM)

GRF: Phase-Sensitive Measurements in Mesoscopic Nickelate Superconducting Junction Devices

GRF: Flexible Nano-mechanical Approaches to Unravelling the Intertwined Orders in Paradigm Oxide Superconductors

Cite this