arXiv subjects

T. Mizokawa

Publications and source records attributed to T. Mizokawa.

At least 55 records · Page 3Linked to original sources

arXiv2012

Probing the role of Co substitution in the electronic structure of iron-pnictides

The role of Co substitution in the low-energy electronic structure of Ca(Fe$_{0.944}$Co$_{0.056}$)$_2$As$_2$ is investigated by resonant photoemission spectroscopy and density functional theory. The Co 3d-state center-of-mass is observed at 250 meV higher binding energy than Fe's, indicating that Co posses one extra valence electron, and that Fe and Co are in the same 2+ oxidation state. Yet, significant Co character is detected for the Bloch wavefunctions at the chemical potential, revealing that the Co 3d electrons are part of the Fermi sea determining the Fermi surface. This establishes the complex role of Co substitution in CaFe2As2, and the inadequacy of a rigid-band shift description.

cond-mat.supr-con↗

arXiv2012

Utility of the inverse partial fluorescence for electronic structure studies of battery materials

X-ray absorption spectroscopy (XAS) is one of the most widely used experimental techniques to study the electronic and spatial structure of materials. Fluorescence yield mode is bulk-sensitive, but has several serious problems coming from saturation effects. In this study, we show the usefulness of partial fluorescence yields in addressing these problems. We discuss the different behaviors of La2NiMnO6 and LiMnO2 at the Mn 2p absorption edges. The total fluorescence yield produces misleading spectra for LiMnO2 due to the absence of high-Z (Z: atomic number) elements. We conclude that the measurement of the inverse partial fluorescence yield is essential in studies of LiMnO2, which is a hotly debated Li-ion battery material.

cond-mat.mtrl-sci↗

arXiv2011

Magnetic Frustration in a Mn Honeycomb Lattice Induced by Mn-O-O-Mn Pathways

We investigated the electronic structure of layered Mn oxide Bi3Mn4O12(NO3) with a Mn honeycomb lattice by x-ray absorption spectroscopy. The valence of Mn was determined to be 4+ with a small charge-transfer energy. We estimated the values of superexchange interactions up to the fourth nearest neighbors (J1, J2, J3, and J4) by unrestricted Hartree-Fock calculations and a perturbation method. We found that the absolute values of J1 through J4 are similar with positive (antiferromagnetic) J1 and J4, and negative (ferromagnetic) J2 and J3, due to Mn-O-O-Mn pathways activated by the smallness of charge-transfer energy. The negative J3 provides magnetic frustration in the honeycomb lattice to prevent long-range ordering.

cond-mat.str-el↗

arXiv2010

A study of electronic structure of FeSe$_{1-x}$Te$_{x}$ chalcogenides by Fe and Se K-edge x-ray absorption near edge structure measurements

Fe K-edge and Se K-edge x-ray absorption near edge structure (XANES) measurements are used to study FeSe$_{1-x}$Te$_{x}$ electronic structure of chalcogenides. An intense Fe K-edge pre-edge peak due to Fe 1s$\to$3d (and admixed Se/Te $p$ states) is observed, showing substantial change with the Te substitution and X-ray polarization. The main white line peak in the Se K-edge XANES due to Se 1s $\to$ 4p transition appear similar to the one expected for Se$^{2-}$ systems and changes with the Te substitution. Polarization dependence reveals that unoccupied Se orbitals near the Fermi level have predominant $p_{x,y}$ character. The results provide key information on the hybridization of Fe $3d$ and chalcogen $p$ states in the Fe-based chalcogenide superconductors.

cond-mat.supr-con↗

arXiv2010

Valence evaluation of LiMnO2 and related battery materials by x-ray absorption spectroscopy

We present an x-ray absorption study of the oxidation states of transition-metal-ions of LiMnO2 and its related materials, widely used as cathodes in Li-ion batteries. The comparison between the obtained spectrum and the configuration-interaction cluster-model calculations showed that the Mn3+ in LiMnO2 is a mixture of the high-spin and low-spin states. We found that Li deficiencies occur in the case of Cr substitution, whereas there are no Li deficiencies in the case of Ni substitution. We conclude that the substitution of charge-transfer-type Ni or Cu is effective for LiMnO2 battery materials.

cond-mat.mtrl-sci↗

arXiv2009

Madelung potentials and covalency effect in strained La$_{1-x}$Sr$_x$MnO$_3$ thin films studied by core-level photoemission spectroscopy

We have investigated the shifts of the core-level photoemission spectra of La$_{0.6}$Sr$_{0.4}$MnO$_3$ thin films grown on three kinds of substrates, SrTiO$_3$, (LaAlO$_3$)$_{0.3}$-(SrAl$_{0.5}$Ta$_{0.5}$O$_3$)$_{0.7}$, and LaAlO$_3$. The experimental shifts of the La 4d and Sr 3d core levels are almost the same as the calculation, which we attribute to the absence of covalency effects on the Madelung potentials at these atomic sites due to the nearly ionic character of these atoms. On the other hand, the experimental shifts of the O $1s$ and Mn $2p$ core levels are negligibly small, in disagreement with the calculation. We consider that this is due to the strong covalent character of the Mn-O bonds.

cond-mat.str-el↗

arXiv2008

Systematic tight-binding analysis of ARPES spectra of transition-metal oxides

We have performed systematic tight-binding (TB) analyses of the angle-resolved photoemission spectroscopy (ARPES) spectra of transition-metal (TM) oxides A$M$O$_3$ ($M=$ Ti, V, Mn, and Fe) with the perovskite-type structure and compared the obtained parameters with those obtained from configuration-interaction (CI) cluster-model analyses of photoemission spectra. The values of $ε_d-ε_p$ from ARPES are found to be similar to the charge-transfer energy $Δ$ from O $2p$ orbitals to empty TM 3d orbitals and much larger than $Δ-U/2$ ($U$: on-site Coulomb energy) expected for Mott-Hubbard-type compounds including SrVO$_3$. $ε_d-ε_p$ values from {\it ab initio} band-structure calculations show similar behaviors to those from ARPES. The values of the $p-d$ transfer integrals to describe the global electronic structure are found to be similar in all the estimates, whereas additional narrowing beyond the TB description occurs in the ARPES spectra of the $d$ band.

cond-mat.str-el↗

arXiv2008

In-gap state and effect of light illumination in CuIr$_2$S$_4$ probed by photoemission spectroscopy

We have studied disorder-induced in-gap states and effect of light illumination in the insulating phase of spinel-type CuIr$_2$S$_4$ using ultra-violet photoemission spectroscopy (UPS). The Ir$^{3+}$/Ir$^{4+}$ charge-ordered gap appears below the metal-insulator transition temperature. However, in the insulating phase, in-gap spectral features with $softgap$ are observed in UPS just below the Fermi level ($E_F$), corresponding to the variable range hopping transport observed in resistivity. The spectral weight at $E_F$ is not increased by light illumination, indicating that the Ir$^{4+}$-Ir$^{4+}$ dimer is very robust although the long-range octamer order would be destructed by the photo-excitation. Present results suggest that the Ir$^{4+}$-Ir$^{4+}$ bipolaronic hopping and disorder effects are responsible for the conductivity of CuIr$_2$S$_4$.

cond-mat.str-el↗

arXiv2007

Unusual superexchange pathways in a Ni triangular lattice of NiGa$_2$S$_4$ with negative charge-transfer energy

We have studied the electronic structure of the Ni triangular lattice in NiGa$_2$S$_4$ using photoemission spectroscopy and subsequent model calculations. The cluster-model analysis of the Ni 2$p$ core-level spectrum shows that the S 3$p$ to Ni 3$d$ charge-transfer energy is $\sim$ -1 eV and the ground state is dominated by the $d^9L$ configuration ($L$ is a S 3$p$ hole). Cell perturbation analysis for the NiS$_2$ triangular lattice indicates that the strong S 3$p$ hole character of the ground state provides the enhanced superexchange interaction between the third nearest neighbor sites.

cond-mat.str-el↗

arXiv2007

Observation of photoinduced phase transition in phase-separated Pr$_{0.55}$(Ca$_{1-y}$Sr$_{y}$)$_{0.45}$MnO$_3$ thin films via x-ray photoemission spectroscopy

Perovskite manganite thin films, $Pr_{0.55}(Ca_{1-y}Sr_y)_{0.45}MnO_3$, have been studied using x-ray photoemission spectroscopy in order to clarify the consequence of the competition between ferromagnetic metal (FM) and charge-orbital ordered insulator (COOI). Films with $y$ = 0.40 undergo uniform paramagnetic insulator to FM transition. On the other hand, in films with $y$ = 0.25, the composition near the bicritical point, phase separation of COOI and FM domains is indicated by the spectral change below 125 K. Interestingly, between 50 K and 70 K, the visible laser illumination transfers the COOI-like spectra obtained in cooling process to the FM-like spectra obtained in warming process. This indicates that the photoinduced IMT is governed by the increase of the FM volume fraction and is deeply related to the phase separation between the FM and COOI states.

cond-mat.str-el↗

arXiv2006

Angle-resolved photoemission spectroscopy of perovskite-type transition-metal oxides and their analyses using tight-binding band structure

Nowadays it has become feasible to perform angle-resolved photoemission spectroscopy (ARPES) measurements of transition-metal oxides with three-dimensional perovskite structures owing to the availability of high-quality single crystals of bulk and epitaxial thin films. In this article, we review recent experimental results and interpretation of ARPES data using empirical tight-binding band-structure calculations. Results are presented for SrVO$_3$ (SVO) bulk single crystals, and La$_{1-x}$Sr$_x$FeO$_3$ (LSFO) and La$_{1-x}$Sr$_x$MnO$_3$ (LSMO) thin films. In the case of SVO, from comparison of the experimental results with calculated surface electronic structure, we concluded that the obtained band dispersions reflect the bulk electronic structure. The experimental band structures of LSFO and LSMO were analyzed assuming the G-type antiferromagnetic state and the ferromagnetic state, respectively. We also demonstrated that the intrinsic uncertainty of the electron momentum perpendicular to the crystal surface is important for the interpretation of the ARPES results of three-dimensional materials.

cond-mat.str-el↗

arXiv2006

Effect of strong localization of doped holes in angle-resolved photoemission spectra of La$_{1-x}$Sr$_x$FeO$_3$

We have performed an angle-resolved photoemission spectroscopy study of La$_{0.6}$Sr$_{0.4}$FeO$_3$ using {\it in situ} prepared thin films and determined its band structure. The experimental band dispersions could be well explained by an empirical band structure assuming the G-type antiferromagnetic state. However, the Fe 3d bands were found to be shifted downward relative to the Fermi level ($E_F$) by $\sim 1$ eV compared with the calculation and to form a (pseudo)gap of $\sim 1$ eV at $E_F$. We attribute this observation to a strong localization effect of doped holes due to polaron formation.

cond-mat.str-el↗

arXiv2006

Signature of Carrier-Induced Ferromagnetism in Ti_{1-x}Co_{x}O_{2-delta}: Exchange Interaction Between High-Spin Co 2+ and the Ti 3d Conduction Band

X-ray photoemission spectroscopy measurements were performed on thin-film samples of rutile Ti_{1-x}Co_{x}O_{2-delta} to reveal the electronic structure. The Co 2p core level spectra indicate that the Co ions take the high-spin Co 2+ configuration, consistent with substitution on the Ti site. The high spin state and the shift due to the exchange splitting of the conduction band suggest strong hybridization between carriers in the Ti 3d t2g band and the t2g states of the high-spin Co 2+. These observations support the argument that room temperature ferromagnetism in Ti_{1-x}Co_{x}O_{2-delta} is intrinsic.

cond-mat.str-el↗

arXiv2005

Orbital ordering in La$_{0.5}$Sr$_{1.5}$MnO$_4$ studied by model Hartree-Fock calculation

We have investigated orbital ordering in the half-doped manganite La$_{0.5}$Sr$_{1.5}$MnO$_4$, which displays spin, charge and orbital ordering, by means of unrestricted Hartree-Fock calculations on the multiband $p$-$d$ model. From recent experiment, it has become clear that La$_{0.5}$Sr$_{1.5}$MnO$_4$ exhibits a cross-type $(z^2-x^2/y^2-z^2)$ orbital ordering rather than the widely believed rod-type $(3x^2-r^2/3y^2-r^2)$ orbital ordering. The calculation reveals that cross-type $(z^2-x^2/y^2-z^2)$ orbital ordering results from an effect of in-plane distortion as well as from the relatively long out-of-plane Mn-O distance. For the "Mn$^{4+}$" site, it is shown that the elongation along the c-axis of the MnO$_6$ octahedra leads to an anisotropic charge distribution rather than the isotropic one.

cond-mat.str-el↗

arXiv2005

Valence changes associated with the metal-insulator transition in Bi$_{1-x}$La$_x$NiO$_3$

Perovskite-type BiNiO$_3$ is an insulating antiferromagnet in which a charge disproportionation occurs at the Bi site. La substitution for Bi suppresses the charge disproportionation and makes the system metallic. We have measured the photoemission and x-ray absorption (XAS) spectra of Bi$_{1-x}$La$_{x}$NiO$_{3}$ to investigate how the electronic structure changes with La doping. From Ni $2p$ XAS, we observed an increase of the valence of Ni from 2+ toward 3+. Combined with the core-level photoemission study, it was found that the average valence of Bi remains $\sim 4+$ and that the Ni valence behaves as $\sim (2+x)+$, that is, La substitution results in hole doping at the Ni sites. In the valence-band photoemission spectra, we observed a Fermi cutoff for $x>0$, consistent with the metallic behavior of the La-doped compounds. The Ni $2p$ XAS, Ni $2p$ core-level photoemission, and valence-band photoemission spectra were analyzed by configuration-interaction cluster-model calculation, and the spectral line shapes were found to be consistent with the gradual Ni$^{2+} \to$ Ni$^{3+}$ valence change.

cond-mat.str-el↗

arXiv2005

Characterization of Magnetic Components in the Diluted Magnetic Semiconductor Zn$_{1-x}$Co$_x$O by X-ray Magnetic Circular Dichroism

We report on the results of x-ray absorption (XAS), x-ray magnetic circular dichroism (XMCD), and photoemission experiments on {\it n}-type Zn$_{1-x}$Co$_x$O ($x=0.05$) thin film, which shows ferromagnetism at room temperature. The XMCD spectra show a multiplet structure, characteristic of the Co$^{2+}$ ion tetrahedrally coordinated by oxygen, suggesting that the ferromagnetism comes from Co ions substituting the Zn site in ZnO. The magnetic field and temperature dependences of the XMCD spectra imply that the non-ferromagnetic Co ions are strongly coupled antiferromagnetically with each other.

cond-mat.mtrl-sci↗

arXiv2005

High-energy spectroscopic study of the III-V nitride-based diluted magnetic semiconductor Ga$_{1-x}$Mn$_{x}$N

We have studied the electronic structure of the diluted magnetic semiconductor Ga$_{1-x}$Mn$_{x}$N ($x$ = 0.0, 0.02 and 0.042) grown on Sn-doped $n$-type GaN using photoemission and soft x-ray absorption spectroscopy. Mn $L$-edge x-ray absorption have indicated that the Mn ions are in the tetrahedral crystal field and that their valence is divalent. Upon Mn doping into GaN, new state were found to form within the band gap of GaN, and the Fermi level was shifted downward. Satellite structures in the Mn 2$p$ core level and the Mn 3$d$ partial density of states were analyzed using configuration-interaction calculation on a MnN$_{4}$ cluster model. The deduced electronic structure parameters reveal that the $p$-$d$ exchange coupling in Ga$_{1-x}$Mn$_{x}$N is stronger than that in Ga$_{1-x}$Mn$_{x}$As.

cond-mat.mtrl-sci↗

arXiv2004

Determination of the orbital moment and crystal field splitting in LaTiO$_{3}$

Utilizing a sum-rule in a spin-resolved photoelectron spectroscopic experiment with circularly polarized light, we show that the orbital moment in LaTiO$_3$ is strongly reduced both below and above the Néel temperature. Using Ti $L_{2,3}$ x-ray absorption spectroscopy as a local probe, we found that the crystal field splitting in the $t_{2g}$ subshell is about 0.12-0.30 eV. This large splitting does not facilitate the formation of an orbital liquid.

cond-mat.str-el↗