arXiv subjects

Zengqing Zhuo

Publications and source records attributed to Zengqing Zhuo.

6 recordsLinked to original sources

arXiv2026

Interlayer Five-Spin Polaron in Superconducting Bilayer Nickelates

The discovery of high-$T_c$ superconductivity in Ruddlesden-Popper nickelates has sparked substantial effort towards understanding unconventional electronic states beyond a traditional cuprate-like $d^9$ configurational ground state. An understanding of the interplay between magnetic ground states and multi-orbital physics is key for establishing a microscopic mechanism for superconductivity. In the bilayer nickelates, spin density wave (SDW) order is a prominent feature in the non-superconducting regime, yet its relation to superconducting pairing remains an open question. Here, we use resonant x-ray scattering to examine the existence of SDW order in superconducting bilayer nickelate thin films La$_2$PrNi$_2$O$_7$ (LPNO). Comparing superconducting and oxygen-deficient LPNO thin films, we find that superconductivity occurs in SDW-free, oxygen-stoichiometric regions, whereas oxygen-deficiency promotes SDW order, indicating phase segregation of SDW and superconductivity. Furthermore, Ni-$L_3$ and O-$K$ edge spectroscopy reveals distinct electronic structures - particularly along the $c$-axis - between the two regions. Our results identify oxygen stoichiometry as a key parameter controlling interlayer coupling and thus the electronic structure of bilayer nickelates. In concert with theory, we propose that a ligand hole primarily resides at the inter-bilayer apical oxygen, forming a robust interlayer five-spin polaron state, which serves as the ground state for superconducting bilayer nickelates.

cond-mat.str-el↗

arXiv2025

Negative Charge Transfer: Ground State Precursor towards High Energy Batteries

Modern energy applications, especially electric vehicles, demand high energy batteries. However, despite decades of intensive efforts, the highest energy density and commercially viable batteries are still based on LiCoO2, the very first generation of cathode materials. The technical bottleneck is the stability of oxide-based cathodes at high operating voltages. The fundamental puzzle is that we actually never understood the redox mechanism of LiCoO2. Conventional wisdom generally defines redox to be centered on cations at low voltages, and on anions, i.e. oxygen, at high voltages by forming oxidized chemical states like O2 or peroxo-species. Here, through in-situ and ex-situ spectroscopy coupled with theoretical calculations, we show that high-energy layered cathodes, represented by LiCoO2 and LiNiO2, operate through enhancement of negative charge transfer (NCT) ground states upon charging throughout the whole voltage range - i.e., NCT evolution itself is the intrinsic redox mechanism regardless of voltage ranges. NCT inherently engages high covalency and oxygen holes, leading to optimized performance without conventional redox centers in LiCoO2. The level of NCT, i.e., number of ligand holes, naturally explains many seemingly controversial results. The redefinition of redox mechanism reveals the pathway toward viable high energy battery electrodes.

cond-mat.mtrl-sci↗

arXiv2025

Direct Observation of the Lindhard Continuum using Resonant Inelastic X-ray Scattering

Understanding the excitations of quantum materials is essential for unraveling how their microscopic constituents interact. Among these, particle-hole excitations form a particularly important class, as they govern fundamental processes such as screening, dissipation, and transport. In metals, the continuum of electron-hole excitations is described by the Lindhard function. Although central to the theory of Fermi liquids, the corresponding Lindhard continuum has remained experimentally elusive. Here, we report its direct observation in the weakly correlated metal MgB$_{2}$ using ultra-soft resonant inelastic X-ray scattering (RIXS). We resolve a linearly dispersing excitation with velocity comparable to the Fermi velocity and find quantitative agreement with simulations of the non-interacting charge susceptibility. A detailed analysis and decomposition of the simulations reveal the intra-band origin of this low-energy excitation, confirming it as the Lindhard continuum. Our results establish ultra-soft RIXS as a momentum-resolved probe of the fermiology in metals and call for deeper investigations of continuum features in RIXS and related spectroscopy of other materials beyond MgB$_{2}$.

cond-mat.str-el↗

arXiv2018

Fingerprint oxygen redox reactions in batteries through high-efficiency mapping of resonant inelastic X-ray scattering (mRIXS)

Realizing reversible reduction-oxidation (Redox) reactions of lattice oxygen in batteries is a promising way to improve the energy and power density. However, conventional oxygen absorption spectroscopy fails to distinguish the critical oxygen chemistry in oxide-based battery electrodes. Therefore, high-efficiency full-range mapping of resonant inelastic X-ray scattering (mRIXS) has been developed as a reliable probe of oxygen redox reactions. Here, based on mRIXS results collected from a series of Li1.17Ni0.21Co0.08Mn0.54O2 electrodes at different electrochemical states and its comparison with peroxides, we provide a comprehensive analysis of five components observed in the mRIXS results. While almost all the components change upon electrochemical cycling, comparison with peroxide species show that only two evolving features correspond to the critical oxidized oxygen states. One is a specific feature at 531.0eV excitation and 523.7eV emission energy, the other is a low-energy loss feature. We show that both features evolve with electrochemical cycling of Li1.17Ni0.21Co0.08Mn0.54O2 electrodes, and could be used for characterizing oxygen redox states in battery electrodes. This work is the first benchmark for a complete assignment of all the important mRIXS features collected from battery materials, which provides guidelines for future studies in characterization, analysis and theoretical calculation for probing and understanding oxygen redox reactions.

physics.chem-ph↗

arXiv2018

High Reversibility of Lattice Oxygen Redox in Na-ion and Li-ion Batteries Quantified by Direct Bulk Probes of both Anionic and Cationic Redox Reactions

The reversibility and cyclability of anionic redox in battery electrodes hold the key to its practical employments. Here, through mapping of resonant inelastic X-ray scattering (mRIXS), we have independently quantified the evolving redox states of both cations and anions in Na2/3Mg1/3Mn2/3O2. The bulk-Mn redox emerges from initial discharge and is quantified by inverse-partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn activities likely lead to the voltage fade. O-K super-partial fluorescence yield (sPFY) analysis of mRIXS shows 79% lattice oxygen-redox reversibility during initial cycle, with 87% capacity sustained after 100 cycles. In Li1.17Ni0.21Co0.08Mn0.54O2, lattice-oxygen redox is 76% initial-cycle reversible but with only 44% capacity retention after 500 cycles. These results unambiguously show the high reversibility of lattice-oxygen redox in both Li-ion and Na-ion systems. The contrast between Na2/3Mg1/3Mn2/3O2 and Li1.17Ni0.21Co0.08Mn0.54O2 systems suggests the importance of distinguishing lattice-oxygen redox from other oxygen activities for clarifying its intrinsic properties.

physics.chem-ph↗

arXiv2018

Spectroscopic Signature of Oxidized Oxygen States in Peroxides

Recent debates on the oxygen redox behaviors in battery electrodes have triggered a pressing demand for the reliable detection and understanding of non-divalent oxygen states beyond conventional absorption spectroscopy. Here, enabled by high-efficiency mapping of resonant inelastic X-ray scattering (mRIXS) coupled with first-principles calculations, we report distinct mRIXS features of the oxygen states in Li2O, Li2CO3, and especially, Li2O2, which are successfully reproduced and interpreted theoretically. mRIXS signals are dominated by valence-band decays in Li2O and Li2CO3. However, the oxidized oxygen in Li2O2 leads to partially unoccupied O-2p states that yield a specific intra-band excitonic feature in mRIXS. Such a feature displays a specific emission energy in mRIXS, which disentangles the oxidized oxygen states from the dominating transition-metal/oxygen hybridization features in absorption spectroscopy, thus providing critical hints for both detecting and understanding the oxygen redox reactions in transition-metal oxide based battery materials.

physics.chem-ph↗