I21-Resonant Inelastic X-ray Scattering (RIXS)
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Jiarui
Li
,
Daniel
Jost
,
Ta
Tang
,
Ruohan
Wang
,
Yong
Zhong
,
Zhuoyu
Chen
,
Mirian
Garcia-Fernandez
,
Jonathan
Pelliciari
,
Valentina
Bisogni
,
Brian
Moritz
,
Ke-Jin
Zhou
,
Yao
Wang
,
Thomas P.
Devereaux
,
Wei-Sheng
Lee
,
Zhi-Xun
Shen
Diamond Proposal Number(s):
[32900]
Abstract: Recent photoemission experiments on the quasi-one-dimensional Ba-based cuprates suggest that doped holes experience an attractive potential not captured using the simple Hubbard model. This observation has garnered significant attention due to its potential relevance to Cooper pair formation in high-𝑇𝑐 cuprate superconductors. To scrutinize this assertion, we examined signatures of such an attractive potential in doped 1D cuprates Ba2CuO3+𝛿 by measuring the dispersion of the 2-spinon excitations using Cu 𝐿3-edge resonant inelastic x-ray scattering (RIXS). Upon doping, the 2-spinon excitations appear to weaken, with a shift of the minimal position corresponding to the nesting vector of the Fermi points, 𝑞𝐹. Notably, we find that the energy scale of the 2-spinons near the Brillouin zone boundary is substantially softened compared to that predicted by the Hubbard model in one dimension. Such a discrepancy implies missing ingredients, which lends support for the presence of an additional attractive potential between holes.
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Apr 2025
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I21-Resonant Inelastic X-ray Scattering (RIXS)
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Sophia F. R.
Tenhuisen
,
Grace A.
Pan
,
Qi
Song
,
Denitsa R.
Baykusheva
,
Dan
Ferenc Segedin
,
Berit H.
Goodge
,
Hanjong
Paik
,
Jonathan
Pelliciari
,
Valentina
Bisogni
,
Yanhong
Gu
,
Stefano
Agrestini
,
Abhishek
Nag
,
Mirian
Garcia-Fernandez
,
Ke-Jin
Zhou
,
Lena F.
Kourkoutis
,
Charles M.
Brooks
,
Julia E. A.
Mundy
,
Mark P. M.
Dean
,
Matteo
Mitrano
Diamond Proposal Number(s):
[27484]
Abstract: Magnetic interactions are thought to play a key role in the properties of many unconventional superconductors, including cuprates, iron pnictides, and square-planar nickelates. Superconductivity was also recently observed in the bilayer and trilayer Ruddlesden-Popper nickelates, the electronic structure of which is expected to differ from that of cuprates and square-planar nickelates. Here we study how electronic structure and magnetic interactions evolve with the number of layers, 𝑛, in thin film Ruddlesden-Popper nickelates Nd𝑛+1Ni𝑛O3𝑛+1 with 𝑛=1,3, and 5 using resonant inelastic x-ray scattering (RIXS). The RIXS spectra are consistent with a high-spin |3𝑑8
𝐿
̲
⟩ electronic configuration, resembling that of La2−𝑥Sr𝑥NiO4 and the parent perovskite, NdNiO3. The magnetic excitations soften to lower energy in the structurally self-doped, higher-𝑛 films. Our observations confirm that structural tuning is an effective route for altering electronic properties, such as magnetic superexchange, in this prominent family of materials.
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Apr 2025
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I21-Resonant Inelastic X-ray Scattering (RIXS)
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Yanfang
Wang
,
Cheng
Li
,
Yingzhi
Li
,
Raquel
De Benito
,
Jacob
Williams
,
Joshua M.
Stratford
,
Zhiqiang
Li
,
Chun
Zeng
,
Ning
Qin
,
Hongzhi
Wang
,
Yulin
Cao
,
Dominic
Gardner
,
Wilgner
Lima Da Silva
,
Sahil
Tippireddy
,
Qingmeng
Gan
,
Fangchang
Zhang
,
Wen
Luo
,
Joshua W.
Makepeace
,
Ke-Jin
Zhou
,
Kaili
Zhang
,
Fucai
Zhang
,
Phoebe K.
Allan
,
Zhouguang
Lu
Diamond Proposal Number(s):
[35147]
Abstract: Simultaneously harnessing cation and anion redox activities in the cathode is crucial for the development of high energy-density lithium-ion batteries. However, achieving long-term stability for both mechanisms remains a significant challenge due to pronounced anisotropic volume changes at low lithium content, unfavorable cation migration, and oxygen loss. Here, we demonstrate exceptionally stable cation and anion redox behavior in a metastable, cobalt-free layered oxide, Li0.693[Li0.153Ni0.190Mn0.657]O2 (LLNMO). After 50 cycles at 50 mA/g (~0.2 C), the cathode retains 97.4% of its initial capacity (222.4 mAh/g) with negligible voltage decay. This remarkable stability is attributed to its metastable rhombohedral symmetry (R-3m) with unique local structures. The face-sharing connectivity between lithium layers and alternating transition metal (TM) layers effectively suppresses TM migration-induced voltage decay during anion redox. Additionally, the structure balances interlayer cation/cation and anion/anion repulsions, resulting in minimal expansion and contraction during de-/lithiation (< 2.3% along the c-axis) and excellent structural reversibility. These findings highlight that layered oxides with a metastable framework are promising cathode candidates for next-generation ultra-high-energy lithium-ion batteries.
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Feb 2025
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I21-Resonant Inelastic X-ray Scattering (RIXS)
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Zhengang
Dong
,
Marios
Hadjimichael
,
Bernat
Mundet
,
Jaewon
Choi
,
Charles C.
Tam
,
Mirian
Garcia-Fernandez
,
Stefano
Agrestini
,
Claribel
Domínguez
,
Regan
Bhatta
,
Yue
Yu
,
Yufeng
Liang
,
Zhenping
Wu
,
Jean-Marc
Triscone
,
Chunjing
Jia
,
Ke-Jin
Zhou
,
Danfeng
Li
Diamond Proposal Number(s):
[32305]
Abstract: Superconductivity in infinite-layer nickelates has stirred much research interest, to which questions regarding the nature of superconductivity remain elusive. A critical leap forward to address these intricate questions is through the growth of high-crystallinity infinite-layer nickelates, including the “parent” phase. Here, we report the synthesis of a high-quality thin-film nickelate, NdNiO2. This is achieved through the growth of a perovskite precursor phase (NdNiO3) of superior crystallinity on the NdGaO3 substrate by off-axis RF magnetron sputtering and a low-temperature topochemical reduction using NaH. We observe a nonlinear Hall effect at low temperatures in this “non-doped” phase. We further study the electronic properties using advanced X-ray scattering and first-principles calculations. We observe spectroscopic indications of the enhanced two-dimensionality and a reduced hybridization of Nd 5d and Ni 3d orbitals. These findings unlock new pathways for preparing high-quality infinite-layer nickelates and provide new insights into the intrinsic features of these compounds.
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Jan 2025
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I09-Surface and Interface Structural Analysis
I15-1-X-ray Pair Distribution Function (XPDF)
I21-Resonant Inelastic X-ray Scattering (RIXS)
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Liquan
Pi
,
Erik
Bjorklund
,
Gregory J.
Rees
,
Weixin
Song
,
Chen
Gong
,
John-Joseph
Marie
,
Xiangwen
Gao
,
Shengda D.
Pu
,
Mikkel
Juelsholt
,
Philip A.
Chater
,
Joohyuk
Park
,
Min Gyu
Kim
,
Jaewon
Choi
,
Stefano
Agrestini
,
Mirian
Garcia-Fernandez
,
Ke-Jin
Zhou
,
Alex W.
Robertson
,
Robert S.
Weatherup
,
Robert A.
House
,
Peter G.
Bruce
Diamond Proposal Number(s):
[27336, 29028, 25807]
Abstract: Disordered rocksalt cathodes deliver high energy densities, but they suffer from pronounced capacity and voltage fade on cycling. Here, we investigate fade using two disordered rocksalt lithium manganese oxyfluorides: Li3Mn2O3F2 (Li1.2Mn0.8O1.2F0.8), which stores charge by Mn2+/Mn4+ redox, and Li2MnO2F, where charge storage involves both Mn3+/Mn4+ and oxygen redox (O-redox). Li3Mn2O3F2 is reported for the first time. We identify the growth of an electronically resistive surface layer with cycling that is present in both Li2MnO2F and Li3Mn2O3F2 but more pronounced in the presence of O-redox. This resistive surface inhibits electronic contact between particles, leading to the observed voltage polarization and capacity loss. By increasing carbon loading in the composite cathode, it is possible to substantially improve the cycling performance. These results help to disentangle O-redox from other leading causes of capacity fading in Mn oxyfluorides and highlight the importance of maintaining electronic conductivity in improving capacity and voltage retention.
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Dec 2024
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I21-Resonant Inelastic X-ray Scattering (RIXS)
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Xiaoyang
Chen
,
Jaewon
Choi
,
Zhicheng
Jiang
,
Jiong
Mei
,
Kun
Jiang
,
Jie
Li
,
Stefano
Agrestini
,
Mirian
Garcia-Fernandez
,
Hualei
Sun
,
Xing
Huang
,
Dawei
Shen
,
Meng
Wang
,
Jiangping
Hu
,
Yi
Lu
,
Ke-Jin
Zhou
,
Donglai
Feng
Diamond Proposal Number(s):
[35805]
Open Access
Abstract: High-temperature superconductivity was discovered in the pressurized nickelate La3Ni2O7 which has a unique bilayer structure and mixed valence state of nickel. The properties at ambient pressure contain crucial information of the fundamental interactions and bosons mediating superconducting pairing. Here, using X-ray absorption spectroscopy and resonant inelastic X-ray scattering, we identified that Ni 3, Ni 3, and ligand oxygen 2p orbitals dominate the low-energy physics with a small charge-transfer energy. Well-defined optical-like magnetic excitations soften into quasi-static spin-density-wave ordering, evidencing the strong electronic correlation and rich magnetic properties. Based on an effective Heisenberg spin model, we extract a much stronger inter-layer effective magnetic superexchange than the intra-layer ones and propose two viable magnetic structures. Our findings emphasize that the Ni 3 orbital bonding within the bilayer induces novel electronic and magnetic excitations, setting the stage for further exploration of La3Ni2O7 superconductor.
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Nov 2024
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I21-Resonant Inelastic X-ray Scattering (RIXS)
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Gukhyun
Lim
,
Min Kyung
Cho
,
Jaewon
Choi
,
Ke-Jin
Zhou
,
Dongki
Shin
,
Seungyun
Jeon
,
Minhyung
Kwon
,
A-Re
Jeon
,
Jinkwan
Choi
,
Seok Su
Sohn
,
Minah
Lee
,
Jihyun
Hong
Abstract: Exploiting oxygen anion redox in Li-/Mn-rich layered oxides (LMR-NMCs) offers the highest capacity among cathode materials for Li-ion batteries (LIBs). However, its long-term utilization is challenging due to continuous voltage and capacity decay caused by irreversible phase transitions involving cation disordering and oxygen release. While extensive studies have revealed the thermodynamic origin of cation disordering, the mechanisms of oxygen loss and consequent lattice densification remain elusive. Moreover, mixed spinel-rocksalt nanodomains formed after cycling complicate the degradation mechanism. Herein, we reveal a strong correlation between phase transition pathways and oxygen stability at the particle surface in LMR-NMCs through a comparative study using electrolyte modification. By tailoring surface reconstruction pathways, we control the overall phase and electrochemistry evolution mechanisms. Removing polar ethylene carbonate from the electrolyte significantly suppresses irreversible oxygen loss at the cathode–electrolyte interface, preferentially promoting the in situ layered-to-spinel phase transition while avoiding typical rocksalt phase formation. The in situ formed spinel-stabilized surface enhances charge transfer kinetics through three-dimensional ion channels, maintaining reversible Ni, Mn, and O redox capability over 700 cycles, as revealed by electron microscopy, X-ray absorption spectroscopy, and resonant inelastic X-ray scattering. Deep delithiation and lithiation enabled by the surface spinel phase accelerate the bulk layered-to-spinel phase transition, inducing thermodynamic voltage fade without capacity loss. Conversely, conventional electrolytes induce layered-to-rocksalt surface reconstruction, impeding charge transfer reactions, which causes simultaneous capacity and (apparent) voltage fades. Our work decouples thermodynamic and kinetic aspects of voltage decay in LMR-NMCs, establishing the correlation between surface reconstruction, bulk phase transition, and the electrochemistry of high-capacity cathodes that exploit cation and anion redox couples. This study highlights the significance of electrochemical interface stabilization for advancing Mn-rich cathode chemistries in future LIBs.
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Nov 2024
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I21-Resonant Inelastic X-ray Scattering (RIXS)
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A.
Nag
,
L.
Zinni
,
J.
Choi
,
J.
Li
,
S.
Tu
,
A. C.
Walters
,
S.
Agrestini
,
S. M.
Hayden
,
Matías
Bejas
,
Z.
Lin
,
H.
Yamase
,
K.
Jin
,
M.
Garcia-Fernandez
,
J.
Fink
,
Andrés
Greco
,
Ke-Jin
Zhou
Diamond Proposal Number(s):
[27872]
Open Access
Abstract: Estimating many-body effects that deviate from an independent particle approach has long been a key research interest in condensed matter physics. Layered cuprates are prototypical systems, where electron-electron interactions are found to strongly affect the dynamics of single-particle excitations. It is, however, still unclear how the electron correlations influence charge excitations, such as plasmons, which have been variously treated with either weak or strong correlation models. In this work, we demonstrate the hybridized nature of collective valence charge fluctuations leading to dispersing acoustic-like plasmons in hole-doped La1.84Sr0.16CuO4 and electron-doped La1.84Ce0.16CuO4 using the two-particle probe, resonant inelastic x-ray scattering. We then describe the plasmon dispersions in both systems, within both the weak-coupling mean-field random phase approximation (RPA) and strong-coupling 𝑡−𝐽−𝑉 model in a large-𝑁 scheme. The 𝑡−𝐽−𝑉 model, which includes the correlation effects implicitly, accurately describes the plasmon dispersions as resonant excitations outside the single-particle intraband continuum. In comparison, a quantitative description of the plasmon dispersion in the RPA approach is obtained only upon explicit consideration of renormalized electronic band parameters. Our comparative analysis shows that electron correlations significantly impact the low-energy plasmon excitations across the cuprate doping phase diagram, even at long wavelengths. Thus, complementary information on the evolution of electron correlations, influenced by the rich electronic phases in condensed matter systems, can be extracted through the study of two-particle charge response.
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Nov 2024
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I21-Resonant Inelastic X-ray Scattering (RIXS)
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Changwei
Zou
,
Jaewon
Choi
,
Qizhi
Li
,
Shusen
Ye
,
Chaohui
Yin
,
Mirian
Garcia-Fernandez
,
Stefano
Agrestini
,
Qingzheng
Qiu
,
Xinqiang
Cai
,
Qian
Xiao
,
Xingjiang
Zhou
,
Ke-Jin
Zhou
,
Yayu
Wang
,
Yingying
Peng
Diamond Proposal Number(s):
[28855]
Open Access
Abstract: How Cooper pairs form and condense has been the main challenge in the physics of copper-oxide high-temperature superconductors. Great efforts have been made in the ‘underdoped’ region of the phase diagram, through doping a Mott insulator or cooling a strange metal. However, there is still no consensus on how superconductivity emerges when electron-electron correlations dominate and the Fermi surface is missing. To address this issue, here we carry out high-resolution resonant inelastic X-ray scattering and scanning tunneling microscopy studies on prototype cuprates Bi2Sr2Ca0.6Dy0.4Cu2O8+δ near the onset of superconductivity, combining bulk and surface, momentum- and real-space information. We show that an incipient charge order exists in the antiferromagnetic regime down to 0.04 holes per CuO2 unit, entangled with a particle-hole asymmetric pseudogap. The charge order induces an intensity anomaly in the bond-buckling phonon branch, which exhibits an abrupt increase once the system enters the superconducting dome. Our results suggest that the Cooper pairs grow out of a charge-ordered insulating state, and then condense accompanied by an enhanced interplay between charge excitations and electron-phonon coupling.
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Sep 2024
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I21-Resonant Inelastic X-ray Scattering (RIXS)
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Jan
Bosse
,
Jian
Gu
,
Jaewon
Choi
,
Vladimir
Roddatis
,
Yong-Bin
Zhuang
,
Nagaarjhuna A.
Kani
,
Anna
Hartl
,
Mirian
Garcia-Fernandez
,
Ke-Jin
Zhou
,
Alessandro
Nicolaou
,
Thomas
Lippert
,
Jun
Cheng
,
Andrew R.
Akbashev
Diamond Proposal Number(s):
[30053, 32904]
Abstract: Structural degradation of oxide electrodes during the electrocatalytic oxygen evolution reaction (OER) is a major challenge in water electrolysis. Although the OER is known to induce changes in the surface layer, little is known about its effect on the bulk of the electrocatalyst and its overall phase stability. Here, we show that under OER conditions, a highly active SrCoO3–x electrocatalyst develops bulk lattice instability, which results in the formation of molecular O2 dimers inside the bulk and nanoscale amorphization induced via chemo-mechanical coupling. Using high-resolution resonant inelastic X-ray scattering and first-principles calculations, we unveil the potential-dependent evolution of lattice oxygen inside the perovskite and demonstrate that O2 dimers are stable in a densely packed crystal lattice, thus challenging the assumption that O2 dimers require sufficient interatomic spacing. We also show that the energy cost of local atomic rearrangements in SrCoO3–x becomes very low under the OER conditions, leading to an unusual amorphization under intercalation-induced stress. As a result, we propose that the amorphization energy can be calculated from the first principles and can be used to assess the stability of electrocatalysts. Our study demonstrates that extreme oxidation of electrocatalysts under OER can intrinsically destabilize the lattice and result in bulk anion redox and disorder, suggesting why some oxide materials are unstable and develop a thick amorphous layer under water electrolysis conditions.
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Aug 2024
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