Dynamical mean-field theory (DMFT) has been employed in conjunction with density functional theory (DFT+DMFT) to investigate the metal-insulator transition (MIT) of strongly correlated $3d$ electrons due to quantum confinement. We shed new light on t
he microscopic mechanism of the MIT and previously reported anomalous subband mass enhancement, both of which arise as a direct consequence of the quantization of V $xz(yz)$ states in the SrVO$_3$ layers. We therefore show that quantum confinement can sensitively tune the strength of electron correlations, leading the way to applying such approaches in other correlated materials.
Oxide heterostructures and superlattices have attracted a great deal of attention in recent years owing to the rich exotic properties encountered at their interfaces. We focus on the potential of tunable correlated oxides by investigating the spectra
l function of the prototypical correlated metal SrVO3, using soft x-ray absorption spectroscopy (XAS) and resonant inelastic soft x-ray scattering (RIXS) to access both unoccupied and occupied electronic states, respectively. We demonstrate a remarkable level of tunability in the spectral function of SrVO3 by varying its thickness within the SrVO3/SrTiO3 superlattice, showing that the effects of electron correlation can be tuned from dominating the energy spectrum in a strongly correlated Mott-Hubbard insulator, towards a correlated metal. We show that the effects of dimensionality on the correlated properties of SrVO3 are augmented by interlayer coupling, yielding a highly flexible correlated oxide that may be readily married with other oxide systems.
Emergent order at mesoscopic length scales in condensed matter can provide fundamental insight into the underlying competing interactions and their relationship with the order parameter. Using spectromicroscopy, we show that mesoscopic stripe order n
ear the metal-insulator transition (MIT) of strained VO2 represent periodic modulations in both crystal symmetry and V-V dimerization. Above the MIT, we unexpectedly find the long range order of V-V dimer strength and crystal symmetry become dissociated beyond ~ 200 nm, whereas the conductivity transition proceeds homogeneously in a narrow temperature range.
We report hard x-ray photoemission spectroscopy measurements of the electronic structure of the prototypical correlated oxide SrxCa1-xVO3. By comparing spectra recorded at different excitation energies, we show that 2.2 keV photoelectrons contain a s
ubstantial surface component, whereas 4.2 keV photoelectrons originate essentially from the bulk of the sample. Bulk-sensitive measurements of the O 2p valence band are found to be in good agreement with ab initio calculations of the electronic structure, with some modest adjustments to the orbital-dependent photoionization cross sections. The evolution of the O 2p electronic structure as a function of the Sr content is dominated by A-site hybridization. Near the Fermi level, the correlated V 3d Hubbard bands are found to evolve in both binding energy and spectral weight as a function of distance from the vacuum interface, revealing higher correlation at the surface than in the bulk.
The electronic structure of NdVO3, YVO3 has been investigated as a function of sample temperature using resonant inelastic soft x-ray scattering at the V L3-edge. Most of the observed spectral features are in good agreement with an atomic crystal-fie
ld multiplet model. However, a low energy feature is observed at ~0.4 eV that cannot be explained by crystal-field arguments. The resonant behaviour of this feature establishes it as due to excitations of the V t2g states. Moreover, this feature exhibits a strong sample temperature dependence, reaching maximum intensity in the orbitally-ordered phase of NdVO3, before becoming suppressed at low temperatures. This behaviour indicates that the origin of this feature is a collective orbital excitation, i.e. the bi-orbiton.
We report the simultaneous measurement of the structural and electronic components of the metal-insulator transition of VO$_2$ using electron and photoelectron spectroscopies and microscopies. We show that these evolve over different temperature scal
es, and are separated by an unusual monoclinic-like metallic phase. Our results provide conclusive evidence that the new monoclinic-like metallic phase, recently identified in high-pressure and nonequilibrium measurements, is accessible in the thermodynamic transition at ambient pressure, and we discuss the implications of these observations on the nature of the MIT in VO$_2$.
The evolution of electron correlation in Sr$_{x}$Ca$_{1-x}$VO$_3$ has been studied using a combination of bulk-sensitive resonant soft x-ray emission spectroscopy (RXES), surface-sensitive photoemission spectroscopy (PES), and ab initio band structur
e calculations. We show that the effect of electron correlation is enhanced at the surface. Strong incoherent Hubbard subbands are found to lie ~ 20% closer in energy to the coherent quasiparticle features in surface-sensitive PES measurements compared with those from bulk-sensitive RXES, and a ~ 10% narrowing of the overall bandwidth at the surface is also observed.
The connection between the Fermi surface and charge-density wave (CDW) order is revisited in 2H-TaSe2. Using angle-resolved photoemission spectroscopy, ab initio band structure calculations, and an accurate tight-binding model, we develop the empiric
al k-resolved susceptibility function, which we use to highlight states that contribute to the susceptibility for a particular q-vector. We show that although the Fermi surface is involved in the peaks in the susceptibility associated with CDW order, it is not through conventional Fermi surface nesting, but rather through finite energy transitions from states located far from the Fermi level. Comparison with monolayer TaSe2 illustrates the different mechanisms that are involved in the absence of bilayer splitting.
The electronic structure of the kagome staircase compounds, Ni3V2O8 and Co3V2O8, has been investigated using soft x-ray absorption, soft x-ray emission, and resonant inelastic x-ray scattering (RIXS). Comparison between the two compounds, and with fi
rst principles band structure calculations and crystal-field multiplet models, provide unique insight into the electronic structure of the two materials. Whereas the location of the narrow (Ni,Co) d bands is predicted to be close to EF, we experimentally find they lie deeper in the occupied O 2p and unoccupied V 3d manifolds, and determine their energy via measured charge-transfer excitations. Additionally, we find evidence for a dd excitation at 1.5 eV in Ni3V2O8, suggesting the V d states may be weakly occupied in this compound, contrary to Co3V2O8. Good agreement is found between the crystal-field dd excitations observed in the experiment and predicted by atomic multiplet theory.
We present a spectroscopic study that reveals that the metal-insulator transition of strained VO$_2$ thin films may be driven towards a purely electronic transition, which does not rely on the Peierls dimerization, by the application of mechanical st
rain. Comparison with a moderately strained system, which does involve the lattice, demonstrates the crossover from Peierls- to Mott-like transitions.
