Ground state oxygen holes and the metal-insulator transition in the negative charge transfer rare-earth nickelates

Abstract

The metal-insulator transitions and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here, taking a NdNiO3 thin film as a representative example, we utilize a combination of x-ray absorption and resonant inelastic x-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of the rare-earth nickelates. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for the abundance of oxygen 2p holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that these distinct spectral signatures arise from a Ni 3d8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy, in line with recent models interpreting the metal to insulator transition in terms of bond disproportionation.

27 pages, 6 figures

References in corpus (6)

• Orbital order and possible superconductivity in LaNiO3/LaMO3 superlattices
• Role of magnetic and orbital ordering at the metal-insulator transition in NdNiO3
• Low-energy description of the metal-insulator transition in the rare-earth nickelates
• Electronic Transitions in Strained SmNiO_3 Thin Films
• Tailoring the electronic transitions of NdNiO_3 films through (111)_pc oriented interfaces
• Tuning the metal-insulator transition in NdNiO3 heterostructures via Fermi surface instability and spin-fluctuations

Cited by in corpus (64)

• Visualization of Oxygen Vacancies and Self-doped Ligand Holes in La3Ni2O7-δ
• Electronic correlations and superconducting instability in La${}_3$Ni${}_2$O${}_7$ under high pressure
• Interlayer Coupling Driven High-Temperature Superconductivity in La${}_3$Ni${}_2$O${}_7$ Under Pressure
• Bond disproportionation and dynamical charge fluctuations in the perovskite rare earth nickelates
• Electronic and magnetic excitations in La${}_3$Ni${}_2$O${}_7$
• Orbital and Spin Character of Doped Carriers in Infinite-Layer Nickelates
• Observation of perfect diamagnetism and interfacial effect on the electronic structures in Nd0.8Sr0.2NiO2 superconducting infinite layers
• Quantum anomalous Hall effect from inverted charge transfer gap
• Absence of $3a_0$ Charge Density Wave Order in the Infinite Layer Nickelates
• Complex magnetic order in nickelate slabs
• Electronic structure of superconducting nickelates probed by resonant photoemission spectroscopy
• Reproducibility and off-stoichiometry issues in nickelate thin films grown by pulsed laser deposition
• Exploring Quantum Materials with Resonant Inelastic X-Ray Scattering
• Renormalization of effective interactions in a negative charge-transfer insulator
• Crossover from Collective to Incoherent Spin Excitations in Superconducting Cuprates Probed by Detuned Resonant Inelastic X-ray Scattering
• LiNiO${}_2$ as a high-entropy charge- and bond-disproportionated glass
• Soft X-ray Spectroscopy of Low-Valence Nickelates
• Synthesis and electronic properties of Nd${}_{n+1}$Ni${}_n$O${}_{3n+1}$ Ruddlesden-Popper nickelate thin films
• Sudden collapse of magnetic order in oxygen deficient nickelate films
• Tuning spin excitations in magnetic films by confinement
• Superconductivity in PrNiO2 infinite-layer nickelates
• Epitaxial engineering of flat silver fluorides cuprate analogs
• Anomalous electron transport in epitaxial NdNiO${}_3$ films
• X-ray spectroscopy of rare-earth nickelate LuNiO${}_3$: LDA+DMFT study
• First-principles study of electron and hole doping in perovskite nickelates
• A fundamental correlative spectroscopic study on LixNiO2 and NaNiO2
• Spectroscopic comprehension of Mott-Hubbard insulator to negative charge transfer metal transition in LaNi_{x}V_{1-x}O_{3} thin films
• High pO2 Floating Zone Crystal Growth of the Perovskite Nickelate PrNiO3
• Resolving the nature of electronic excitations in resonant inelastic x-ray scattering
• Superconductivity in a layered cobalt oxychalcogenide Na${}_2$CoSe${}_2$O with a triangular lattice
• Hybridization driving distortions and multiferroicity in rare-earth nickelates
• Control of the metal-insulator transition in NdNiO${}_3$ thin films through the interplay between structural and electronic properties
• Anisotropic magnetic excitations and incipient Néel order in Ba(Fe${}_{1-x}$Mn${}_x$)${}_2$As${}_2$
• Resonant inelastic x-ray scattering study of bond order and spin excitations in nickelate thin-film structures
• Assessing the correlated electronic structure of lanthanum nickelates
• Negative charge transfer energy in correlated compounds
• Metal-insulator transition and local-moment collapse in negative charge-transfer CaFeO${}_3$ under pressure
• Spin and charge excitations in the correlated multiband metal Ca3Ru2O7
• FeS2 monolayer: a high valence and high-$T_{\mathrm{C}}$ Ising ferromagnet
• Intertwined charge and spin instability of La${}_3$Ni${}_2$O${}_7$
• Emergent electronic landscapes in a novel valence-ordered nickelate with tri-component nickel coordination
• Spin waves and orbital contribution to ferromagnetism in a topological metal
• Dispersionless orbital excitations in (Li,Fe)OHFeSe superconductors
• PERSPECTIVE: Emergent phases in rare earth nickelate heterostructures
• Interplay between electron correlations, magnetic state, and structural confinement in LaNiO3 ultrathin films
• Unusual coexistence of negative/positive charge-transfer in mixed-valence Na${}_x$Ca${}_{1-x}$Cr${}_2$O${}_4$
• Effects of reduced dimensionality, crystal field, electron-lattice coupling, and strain on the ground-state of a rare-earth nickelates monolayer
• Ferromagnetic Negative Charge-Transfer Insulator: from Theoretical Proposal to Material Realization
• Magnetic excitations in Nd${}_{n+1}$Ni${}_n$O${}_{3n+1}$ Ruddlesden-Popper nickelates observed via resonant inelastic x-ray scattering
• Persistence of small polarons into the superconducting phase of Ba${}_{1-x}$K${}_x$BiO${}_3$
• Temperature-Dependent Dynamic Disproportionation in LiNiO${}_2$
• High-resolution valence band RIXS at the actinide M${}_{4,5}$-edges
• Time-resolved photoemission and RIXS study of a site-selective Mott insulator
• Valence Transition Theory of the Pressure-Induced Dimensionality Crossover in Superconducting Sr${}_{14-x}$Ca${}_x$Cu${}_{24}$O${}_{41}$
• Signatures of polarized chiral spin disproportionation in rare earth nickelates
• Emergence of interfacial magnetism in strongly-correlated nickelate-titanate superlattices
• Emergence and tunability of Fermi-pocket and electronic instabilities in layered Nickelates
• Weak electronic correlations in the cobalt oxychalcogenide superconductor Na2CoSe2O
• Grotthuss-type oxygen hole polaron transport in desodiated Na${}_2$Mn${}_3$O${}_7$
• Enhanced Itinerant Ferromagnetism in Hole-doped Transition Metal Oxides: Beyond the Canonical Double Exchange Mechanism
• Revisiting the metal-to-metal transition in $2H$-AgNiO${}_2$
• Probing electronic and magnetic transitions of short periodic nickelate superlattices using synchrotron x-ray
• Valency, charge-transfer, and orbital-dependent correlation in bilayer nickelates Nd3Ni2O7
• High resolution resonant inelastic EUV scattering from orbital excitations in a Heisenberg antiferromagnet