Upper Hubbard Band Research Articles

Mott Gap Filling by Doping Electrons through Depositing One Sub-Monolayer Thin Film of Rb on Ca2CuO2Cl2

Understanding the doping evolution from a Mott insulator to a superconductor probably holds the key to resolve the mystery of unconventional superconductivity in copper oxides. To elucidate the evolution of the electronic state starting from the Mott insulator, we dose the surface of the parent phase Ca2CuO2Cl2 by depositing Rb atoms, which are supposed to donate electrons to the CuO2 planes underneath. We successfully achieved the Rb sub-monolayer thin films in forming the square lattice. The scanning tunneling microscopy or spectroscopy measurements on the surface show that the Fermi energy is pinned within the Mott gap but close to the edge of the charge transfer band. In addition, an in-gap state appears at the bottom of the upper Hubbard band (UHB), and the Mott gap will be significantly diminished. Combined with the Cl defect and the Rb adatom/cluster results, the electron doping is likely to increase the spectra weight of the UHB for the double occupancy. Our results provide information to understand the electron doping to the parent compound of cuprates.

Alternative Structure Model of Correlated Charge Density Wave in Monolayer 1T-Nb(Ta)Se2.

The putative Mott charge density wave (CDW) phases of monolayer 1T-NbSe2 and 1T-TaSe2 have attracted a lot of recent interest due to the unexpected orbital texture of their Mott-Hubbard states and the superstructure related to an exotic possibility of a quantum spin liquid with a spinon Fermi surface. The origins of the orbital texture and the superstructure have been, however, elusive. We find by using density functional theory calculations that these CDW phases can have an alternative metastable structure, an anion (Se) centered cluster, in contrast to the prevailing model of a cation (Nb or Ta) centered David star cluster. This structure can be stabilized by the charge transfer from the bilayer graphene/SiC substrate used commonly in the experiments. The anion-centered structure has a similar electronic band structure of a charge transfer insulator to that of DS clusters but naturally explains the orbital texture of the upper Hubbard band from simply its atomic structure. Moreover, this band structure exhibits a Fermi surface nesting to possibly break the symmetry spontaneously into a -R30° superstructure observed experimentally. The resulting ground state of the superstructure is shown to be a trivial band insulator, in contrast to exotic proposals. This result emphasizes the huge structural flexibility of these heteroexpitaxial monolayers, for which careful studies on atomic structures and interactions with substrates are highly requested.

Behavior under magnetic field of resonance at the edge of the upper Hubbard band in 1T−TaS2

Recent theoretical investigations of quantum spin liquids have described phenomenology amenable to experimental observation using scanning tunneling microscopy. This includes characteristic resonances found at the edge of the upper Hubbard band of the host Mott insulator, that under certain conditions shift into the Mott gap under external magnetic field [W.-Y. He and P. A. Lee, arXiv:2212.08767]. In light of this we report scanning tunneling microscopy observations, in samples of the quantum spin liquid candidate 1T-TaS2, of a conductance peak at the upper Hubbard band edge and its magnetic field dependent behavior. These observations potentially represent evidence for the existence of a quantum spin liquid in 1T TaS2. We also observe samples in which such field dependence is absent, but with no observed correlate for the presence or absence of field dependence. This suggests one or more material properties controlling electronic behavior that are yet to be understood, and should help to motivate renewed investigation of the microscopic degrees of freedom in play in 1T-TaS2, as well as the possible realization of a quantum spin liquid phase.

Exploring the Charge Density Wave Phase of 1T-TaSe_{2}: Mott or Charge-Transfer Gap?

1T-TaSe_{2} is widely believed to host a Mott metal-insulator transition in the charge density wave (CDW) phase according to the spectroscopic observation of a band gap that extends across all momentum space. Previous investigations inferred that the occurrence of the Mott phase is limited to the surface only of bulk specimens, but recent analysis on thin samples revealed that the Mott-like behavior, observed in the monolayer, is rapidly suppressed with increasing thickness. Here, we report combined time- and angle-resolved photoemission spectroscopy and theoretical investigations of the electronic structure of 1T-TaSe_{2}. Our experimental results confirm the existence of a state above E_{F}, previously ascribed to the upper Hubbard band, and an overall band gap of ∼0.7 eV at Γ[over ¯]. However, supported by density functional theory calculations, we demonstrate that the origin of this state and the gap rests on band structure modifications induced by the CDW phase alone, without the need for Mott correlation effects.

Numerical study of resonant inelastic x-ray scattering at the oxygen K edge in insulating cuprates

We investigate resonant inelastic X-ray scattering (RIXS) at the O $K$-edge in insulating cuprates by means of three methods: cluster perturbation theory (CPT), Hartree--Fock approximation (HFA) and exact diagonalization (ED) method. We consider the three-band Hubbard model and show the overall momentum-dependence of the Zhang--Rice singlet (ZRS) excitation and charge-transfer excitation by the CPT combining with the perturbation scheme. A comparison of the RIXS spectra calculated using CPT and HFA reveals different momentum-dependencies through the changes in the properties of the upper Hubbard band and the ZRS band. These findings are supported by analyses using the ED method on the RIXS spectra and dynamical charge structure factor.

Nanoscale chemical and structural investigation of solid solution polyelemental transition metal oxide nanoparticles

Although it has been shown that configurational entropy can improve the structural stability in transition metal oxides (TMOs), little is known about the oxidation state of transition metals under random mixing of alloys. Such information is essential in understanding the chemical reactivity and properties of TMOs stabilized by configurational entropy. Herein, utilizing electron energy loss spectroscopy (EELS) technique in an aberration-corrected scanning transmission electron microscope (STEM), we systematically studied the oxidation state of binary (Mn,Fe)3O4, ternary (Mn, Fe, Ni)3O4, and quinary (Mn, Fe, Ni, Cu, Zn)3O4 solid solution polyelemental transition metal oxides (SSP-TMOs) nanoparticles. Our findings show that the random mixing of multiple elements in the form of solid solution phase not only promotes the entropy stabilization but also results in stable oxidation state in transition metals spanning from binary to quinary transition metal oxide nanoparticles.

Magnetic anisotropy energies and metal-insulator transitions in monolayers of α−RuCl3 and OsCl3 on graphene

Transition metal thriclorides, with $4d$ or $5d$ electrons, are materials at the forefront of recent studies about the interplay of spin-orbit coupling and strong Coulomb interactions. Within our first-principles calculations (DFT+$U$+SOC) we study the effects of graphene on the electronic and magnetic properties of the monolayers of $\alpha$-RuCl$_3$ and OsCl$_3$. Despite the spatially inhomogeneous $n$-type doping induced by graphene, we show that the occupancy of the upper Hubbard bands of MLs of \rucl and OsCl$_3$ can be tuned through external electric fields, and allows the control of (i) metal-insulator transitions, and (ii) the magnetic easy-axis and anisotropy energies. Our findings point towards the tunning of electronic and magnetic properties of transition metal thriclorides monolayers by using graphene and external electronic fields.

Moment functional based spectral density functional theory

We describe a density-functional method which aims at computing the ground state electron density and the spectral function at the same time. One basic ingredient of our method is the construction of the spectral function from the first four spectral moment matrices. The second basic ingredient is the construction of the spectral moment matrices from density functionals. We call our method moment-functional based spectral density-functional theory (MFbSDFT), because it is based on density-functionals for the spectral moments and because it allows us to compute the spectral function. If it is implemented in second variation our method consumes only a fraction more computer time than a standard DFT calculation with the PBE functional. We show that MFbSDFT captures correlation effects such as the valence-band satellite in Ni and the formation of lower and upper Hubbard bands in SrVO$_3$. For the purpose of constructing the spectral function from the first four $N\times N$ spectral moment matrices we describe an efficient algorithm based on the diagonalization of one hermitean $2N\times 2N$ matrix.

Correlated Mott insulators in strong electric fields: Role of phonons in heat dissipation

We study the spectral and transport properties of a Mott insulator driven by a static electric field into a non-equilibrium steady state. For the dissipation, we consider two mechanisms: Wide-band fermion reservoirs and phonons included within the Migdal approximation. The electron correlations are treated via non-equilibrium dynamical mean field theory with an impurity solver suitable for strong correlations. We find that dissipation via phonons is limited to restricted ranges of field values around Wannier-Stark resonances. To cover the full range of field strengths, we allow for a small coupling with fermionic baths, which stabilizes the solution. When considering both dissipation mechanisms, we find that phonons enhance the current for field strengths close to half of the gap while lowering it at the gap resonance as compared to the purely electronic dissipation used by Murakami and Werner [arXiv:1804.08257]. Once phonons are the only dissipation mechanism, the current in the metallic phase is almost one order of magnitude smaller than the typical values obtained by coupling to a fermionic bath. In this case, the transport regime is characterized by an accumulation of charge in the upper Hubbard band described by two effective chemical potentials.

Anomalous Ferromagnetism of quasiparticle doped holes in cuprate heterostructures revealed using resonant soft X-ray magnetic scattering

We report strong ferromagnetism of quasiparticle doped holes both within the ab-plane and along the c-axis of Cu-O planes in low-dimensional Au/d-La1.8Ba0.2CuO4/LaAlO3(001) heterostructures (d = 4, 8 and 12 unit-cells) using resonant soft X-ray and magnetic scattering together with X-ray magnetic circular dichroism. Interestingly, ferromagnetism is stronger at a hole doped peak and at an upper Hubbard band of O with spin-polarization degree as high as 40%, revealing strong ferromagnetism of Mottness. For in-ab-plane spin-polarizations, the spin of doped holes in O2p–Cu3d–O2p is a triplet state yielding strong ferromagnetism. For out-of-ab-plane spin-polarization, while the spins of doped holes in both O2p–O2p and Cu3d–Cu3d are triplet states, the spin of doped holes in Cu3d–O2p is a singlet state yielding ferrimagnetism. A ferromagnetic-(002) Bragg-peak of the doped holes is observed and enhanced as a function of d revealing strong ferromagnetism coupling between Cu-O layers along the c-axis.

Estimation of the on-site Coulomb potential and covalent state in La2CuO4 by muon spin rotation and density functional theory calculations

The on-site Coulomb potential, U, and the covalent state of electronic orbitals play key roles for the Cooper pair symmetry and exotic electromagnetic properties of high-Tc superconducting cuprates. In this paper, we demonstrate a way to determine the value of U and present the whole picture of the covalent state of Cu spins in the mother system of the La-based high-Tc superconducting cuprate, La2CuO4, by combining the muon spin rotation ({\mu}SR) and the density functional theory (DFT) calculation. We reveal local deformations of the CuO6 octahedron followed by changes in Cu-spin distributions caused by the injected muon. Adjusting the DFT and muSR results, U and the minimum charge-transfer energy between the upper Hubbard band and the O 2p band were optimized to be 4.87(4) and 1.24(1) eV, respectively.

Magnetic impurity as a local probe of the U (1) quantum spin liquid with spinon Fermi surface

We solve the problem of a magnetic impurity coupled to a $U(1)$ quantum spin liquid with a spinon Fermi surface, and we compute the impurity spectral function. Using the slave rotor mean-field approach combined with gauge field fluctuations, we find that a peak located at the top of the lower Hubbard band and one at the bottom of the upper Hubbard band can emerge in the impurity spectral function. The peaks at the Hubbard band edges arise from the gauge field fluctuation-induced spinon-chargon binding inside the spinon Kondo screening cloud of the magnetic impurity. For a magnetic impurity embedded in a Mott insulator, our findings suggest that the emergence of a pair of peaks at the Hubbard band edges in the impurity density of states spectra provides strong evidence that the host Mott insulator is a $U(1)$ quantum spin liquid with a spinon Fermi surface.

Effect of Impurity on the Doping-Induced in-Gap States in a Mott Insulator

Motivated by the recent measurements of the spatial distribution of single particle excitation states in a hole-doped Mott insulator, we study the effects of impurity on the in-gap states, induced by the doped holes, in the Hubbard model on the square lattice by the cluster perturbation theory. We find that a repulsive impurity potential can move the in-gap state from the lower Hubbard band towards the upper Hubbard band, providing a good account for the experimental observation. The distribution of the spectral function in the momentum space can be used to discriminate the in-gap state induced by doped holes and that by the impurity. The spatial characters of the in-gap states in the presence of two impurities are also discussed and compared to the experiment.

Rational Design of 3d Transition-Metal Compounds for Thermoelectric Properties by Using Periodic Trends in Electron-Correlation Modulation.

The electronic structures in solid-state transition-metal compounds can be represented by two parameters: the charge-transfer energy (Δ), which is the energy difference between the p-band of an anion and an upper Hubbard band contributed by transition-metal d-orbitals, and the onsite Coulomb repulsion energy (U), which represents the energy difference between lower and upper Hubbard bands composed of split d-orbitals in transition metals. These parameters can facilitate the classification of various types of electronic structures. In this study, the dependences of anion species (N3-, P3-, As3-, O2-, S2-, Se2-, Te2-, F-, Cl-, Br-, and I-) on Δ and U of 566 different binary and ternary 3d transition-metal compounds were investigated using ionic-model calculations. We were able to identify the systematic chemical trends in the variations in Δ and U values with the anion species of 11 different families of 3d transition-metal compounds in a comprehensive manner. The effective use of Δ-U diagrams given here, to facilitate the discovery and development of functional compounds, was demonstrated on thermoelectric compounds by classifying the thermoelectric properties of 3d transition-metal compounds and by predicting unrealized high-performance thermoelectric compounds.

Ultrafast Renormalization of the On-Site Coulomb Repulsion in a Cuprate Superconductor

Ultrafast lasers are an increasingly important tool to control and stabilize emergent phases in quantum materials. Among a variety of possible excitation protocols, a particularly intriguing route is the direct light-engineering of microscopic electronic parameters, such as the electron hopping and the local Coulomb repulsion (Hubbard $U$). In this work, we use time-resolved x-ray absorption spectroscopy to demonstrate the light-induced renormalization of the Hubbard $U$ in a cuprate superconductor, La$_{1.905}$Ba$_{0.095}$CuO$_4$. We show that intense femtosecond laser pulses induce a substantial redshift of the upper Hubbard band, while leaving the Zhang-Rice singlet energy unaffected. By comparing the experimental data to time-dependent spectra of single- and three-band Hubbard models, we assign this effect to a $\sim140$ meV reduction of the onsite Coulomb repulsion on the copper sites. Our demonstration of a dynamical Hubbard $U$ renormalization in a copper oxide paves the way to a novel strategy for the manipulation of superconductivity, magnetism, as well as to the realization of other long-range-ordered phases in light-driven quantum materials.

The Role of On-site Coulumb Interaction on Electronic Structure of FeO

We report our density functional theory (DFT) calculation on FeO in order to describe its electronic properties. FeO exhibits an antiferromagnetic at the ground state with cubic structure and Neel temperature T N = 198 K. The DFT calculation is as powerful tool to describe electronic properties but known to be failed to describe the electronic properties of system with strong on-site Coulomb interaction such as FeO. Here, we introduce the Hubbard correction, U , in order to take into account the on-site Coulomb interaction of d-electron at Fe ion. Hybridization of 3 d -electron of Fe and 2 p -electron of O splits the energy level to become upper Hubbard band (UHB) and low Hubbard band (LHB). Based on the DFT+U calculation, the band structure of FeO shows an insulator feature with the band gap of 1.65 eV, and its density of state (DOS) implies that this gap arises from splitting 3 d -electron of Fe.

Temperature Dependence of the Electronic Structure of Ca3Cu2O4Cl2 Mott Insulator

We use scanning tunneling microscopy to study the temperature evolution of electronic structure in Ca3Cu2O4Cl2 parent Mott insulator of cuprates. It is found that the upper Hubbard band moves towards the Fermi energy with increasing temperature, while the charge transfer band remains basically unchanged. This leads to a reduction of the charge transfer gap size at high temperatures, and the rate of reduction is much faster than that of conventional semiconductors. Across the Neel temperature for antiferromagnetic order, there is no sudden change in the electronic structure. These results shed new light on the theoretical models about the parent Mott insulator of cuprates.

In-gap band in the one-dimensional two-orbital Kanamori-Hubbard model with interorbital Coulomb interaction

We study the electronic spectral properties at zero temperature of the one-dimensional (1D) version of the degenerate two-orbital Kanamori Hubbard model (KHM), one of the well established frameworks to study transition metal compounds, using state-of-the-art numerical techniques based on the Density Matrix Renormalization Group. While the system is Mott insulating for the half-filled case, as expected for an interacting 1D system, we find interesting and rich structures in the single-particle density of states (DOS) for the hole-doped system. In particular, we find the existence of in-gap states which are pulled down to lower energies from the upper Hubbard band (UHB) with increasing the inter-orbital Coulomb interaction $V$. We analyze the composition of the DOS by projecting it onto different local excitations and we observe that for large dopings these in-gap excitations are formed mainly by inter-orbital holon-doublon (HD) states and their energies follow approximately the HD states in the atomic limit. We observe that the Hund interaction $J$ increases the width of the in-gap band, as expected from the two-particle fluctuations in the Hamiltonian. The observation of a finite density of states within the gap between the Hubbard bands for this extended 1D model indicates that these systems present a rich excitation spectra which could help us understand the microscopic physics behind multi-orbital compounds.

Monolayer 1T-NbSe2 as a 2D-correlated magnetic insulator.

Monolayer group V transition metal dichalcogenides in their 1T phase have recently emerged as a platform to investigate rich phases of matter, such as spin liquid and ferromagnetism, resulting from strong electron correlations. Newly emerging 1T-NbSe2 has inspired theoretical investigations predicting collective phenomena such as charge transfer gap and ferromagnetism in two dimensions; however, the experimental evidence is still lacking. Here, by controlling the molecular beam epitaxy growth parameters, we demonstrate the successful growth of high-quality single-phase 1T-NbSe2. By combining scanning tunneling microscopy/spectroscopy and ab initio calculations, we show that this system is a charge transfer insulator with the upper Hubbard band located above the valence band maximum. To demonstrate the electron correlation resulted magnetic property, we create a vertical 1T/2H NbSe2 heterostructure, and we find unambiguous evidence of exchange interactions between the localized magnetic moments in 1T phase and the metallic/superconducting phase exemplified by Kondo resonances and Yu-Shiba-Rusinov–like bound states.

Visualizing Spatial Evolution of Electron-Correlated Interface in Two-Dimensional Heterostructures.

Microscopically visualizing the evolution of electronic structures at the interface between two electron-correlated domains shows fundamental importance in both material science and physics. Here, we report scanning tunneling microscopy and spectroscopy studies of the interfacial electronic structures evolution in a phase-engineered monolayer NbSe2 heterostructure. The H-NbSe2 metallic state penetrates the Mott insulating T-NbSe2 at the H/T phase interface, with a prominent 2D charge density wave (CDW) proximity effect. Moreover, an insulating Mott gap collapse with the disappearance of the upper Hubbard band is detected at the electronic phase transition region. Theoretical calculations reveal that such insulating Mott gap collapse can be attributed to the electron doping effect induced by the interface. Our findings promote a microscopical understanding of the interactions between different electron-correlated systems and provide an effective method for controlling the Mott insulating states with phase engineering.