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Since the first observation of the metal-to-insulator transition (MIT), VO2 has attracted substantial attention in terms of whether this transition is impelled by electron–phonon interaction (Peierls transition) or electron–electron interaction. Regarding Peierls transition, it has been theoretically predicted that the Fermi surface (FS) cross-section exhibits certain nesting features for a metallic phase of VO2. Various experimental studies related to the nesting feature have been reported. Nevertheless, there is no experimental result on FS topology. In this work, we determine the FS topology of the metallic phase of VO2 through studies of VO2 epitaxial thin films on TiO2(001) substrates, using synchrotron radiation angle-resolved photoemission spectroscopy (ARPES). Three electron pockets around Γ are observed in band structures along the Γ–X direction. These three bands form electron surfaces around Γ in the ΓXRZ plane. Furthermore, the lowest energy band FS exhibits the nesting feature corresponding to a nesting vector $$\overrightarrow{q}$$ q → = ΓR, as predicted by the calculation. Our results strongly indicate the formation of the charge-density wave with $$\overrightarrow{q}$$ q → = ΓR and thus, the importance of Peierls transition for the mechanism of the MIT in VO2.

We have performed soft x-ray spectroscopy in order to study the photoirradiation time dependence of the valence band structure and chemical states of layered transition metal nitride chloride TiNCl. Under the soft x-ray irradiation, the intensities of the states near the Fermi level (E F) and the Ti3+ component increased, while the Cl 2p intensity decreased. Ti 2p–3d resonance photoemission spectroscopy confirmed a distinctive Fermi edge with Ti 3d character. These results indicate the photo-induced metallization originates from deintercalation due to Cl desorption, and thus provide a new carrier doping method that controls the conducting properties of TiNCl.

Recently CeOBiS2 system without any fluorine doping is found to show superconductivity posing question on its origin. Using space resolved ARPES we have found a metallic phase embedded in the morphological defects and at the sample edges of stoichiometric CeOBiS2. While bulk of the sample is semiconducting, the embedded metallic phase is characterized by the usual electron pocket at X point, similar to the Fermi surface of doped BiS2-based superconductors. Typical size of the observed metallic domain is larger than the superconducting correlation length of the system suggesting that the observed superconductivity in undoped CeOBiS2 might be due to this embedded metallic phase at the defects. The results also suggest a possible way to develop new systems by manipulation of the defects in these chalcogenides with structural instability.

Stoichiometric ${\mathrm{EuFBiS}}_{2}$ with mixed valent Eu shows self-doped superconductivity at low temperatures due to the Eu-to-Bi charge transfer. The metallic/nonmetallic bistability of the ${\mathrm{BiS}}_{2}$ layer can couple with the valence fluctuation of Eu and provide a highly susceptible electronic state. Here, we report space-resolved photoemission measurements on ${\mathrm{EuFBiS}}_{2}$ revealing an inhomogeneous charge distribution with the coexistence of metallic and nonmetallic phases at mesoscopic length scales. Angle-resolved photoemission measurements using a submicron beam size have confirmed a clear Fermi surface around the zone boundaries in the metallic region, typically observed in a doped system, while it can be hardly seen in the nonmetallic region. Density functional theory calculations suggest that the out-of-plane S atom position in the structure is one of the important factors for the self-doping in this material.

NaSn(2)As(2 )is mechanically exfoliable layered van der Waals (vdW) Zintl phase that is getting interesting due to its low thermal conductivity and recently observed superconductivity. Here, we have investigated the temperature dependent local structure of NaSn2As2 by a combined analysis of As K-edge and Sn K-edge extended x-ray absorption fine structure measurements. The system is intrinsically disordered with the interatomic distances largely consistent to those estimated by average structure measurements. The stretching force constants of different bond distances have been determined using temperature dependent mean square relative displacements. The Sn-As distance is the strongest bond in this system, having covalent nature, unlike the weaker interlayer distances which are characterized by vdW type bonding. Among them, As-Na distance is slightly weaker than Sn-Sn(i) below similar to 200 K and tends to get stronger above this temperature. The anomalous behavior of As-Na bond suggests that the mechanical exfoliation in this system is likely to be temperature dependent. The anomaly in the interlayer atomic correlations may be due to a charge density wave-like instability around this temperature, indicated by earlier experiments. The local structure and disorder are discussed in relation to the physical properties of NaSn2As2.

The local structure of correlated spin-orbit insulator Sr$_{2-x}$M$_x$IrO$_4$ (M = K, La) has been investigated by Ir L$_3$-edge extended x-ray absorption fine structure measurements. The measurements were performed as a function of temperature for different dopings induced by substitution of Sr with La or K. It is found that Ir-O bonds have strong covalency and they hardly show any change across the N\'eel temperature. In the studied doping range, neither Ir-O bonds nor their dynamics, measured by their mean square relative displacements, show any appreciable change upon carrier doping, indicating possibility of a nanoscale phase separation in the doped system. On the other hand, there is a large increase of the static disorder in Ir-Sr correlation, larger for K doping than La doping. Similarities and differences with respect to the local lattice displacements in cuprates are briefly discussed., Comment: Main text: 6 pages, 4 figures, Supplemental information: 2 pages, 2 figures

We have studied the local structure of layered Nax(NH3)yMoSe2 system by Mo K-edge extended X-ray absorption fine structure (EXAFS) measurements performed as a function of temperature. We find that molecular intercalation in MoSe2 largely affects the Mo-Se network while Mo-Mo seems to sustain small changes. The Einstein temperature ( Θ E ) of Mo-Mo distance hardly changes ( ∼ 264 K) indicating that bond strength of this distance remains unaffected by intercalation. On the other hand, Mo-Se distance suffers a softening, revealed by the decrease of Θ E from ∼ 364 K to ∼ 350 K. The results indicate that Na+ ion transported by NH3 molecules may enter between the two MoSe-layers resulting reduced Se-Se coupling. Therefore, increased hybridization between Se 4p and Mo 4d orbitals due to inter-layer disorder is the likely reason of metallicity in intercalated MoSe2 and superconductivity at low temperature.

We report syntheses of new superconducting metal-doped MoSe2 materials (MxMoSe2). The superconducting MxMoSe2 samples were prepared using a liquid NH3 technique and can be represented as ‘(NH3)yMxMoSe2’. The Tcs of these materials were approximately 5.0 K, independent of x and the specific metal atom. X-ray diffraction patterns of (NH3)yNaxMoSe2 were recorded using polycrystalline powders. An increase in lattice constant c showed that the Na atom was intercalated between MoSe2 layers. The x-independence of c was observed in (NH3)yNaxMoSe2, indicating the formation of a stoichiometric compound in the entire x range, which is consistent with the x-independence of Tc. A metallic edge of the Fermi level was observed in the photoemission spectrum at 30 K, demonstrating its metallic character in the normal state. Doping of MoSe2 with Li and K also yielded superconductivity. Thus, MoSe2 is a promising material for designing new superconductors, as are other transition metal dichalcogenides.

We have observed zero resistivity above 10 K and an onset of resistivity reduction at 25.2 K in a heavily B-doped diamond film. However, the effective carrier concentration is similar to that of superconducting diamond with a lower Tc. We found that the carrier has a longer mean free path and lifetime than in the previous report, indicating that this highest Tc diamond has better crystallinity compared to that of other superconducting diamond films. In addition, the susceptibility shows a small transition above 20 K in the high quality diamond, suggesting a signature of superconductivity above 20 K. These results strongly suggest that heavier carrier doped defect-free crystalline diamond could give rise to high Tc diamond.

We present the results of angle-resolved photoemission spectroscopy (ARPES) measurements of metallic VO2 thin films. The VO2 thin films have been grown on TiO2 (0 0 1) single crystal substrates using pulsed laser deposition. The films exhibit a first-order metal–insulator transition (MIT) at 305 K. In the ARPES spectra of the metallic phase for the films, the O 2p band shows highly dispersive feature in the binding energy range of 3–8 eV along the Г–Z direction. The periodicity of the dispersive band is found to be 2.2 Å-1 which is almost identical with the periodicity expected from the c-axis length of the VO2 thin films. The overall feature of the experimental band structure is similar to the band structure calculations, supporting that we have succeeded in observing the dispersive band of the O 2p state in the metallic VO2 thin film. The present work indicates that the ARPES measurements using epitaxial thin films are promising for determining the band structure of VO2.

URu2Si2 is a uranium compound that exhibits a so-called ‘hidden-order’ transition at ~17.5 K. However, the order parameter of this second-order transition as well as many of its microscopic properties remain unclarified despite considerable research. One of the key questions in this regard concerns the type of spontaneous symmetry breaking occurring at the transition; although rotational symmetry breaking has been detected, it is not clear whether another type of symmetry breaking also occurs. Another key question concerns the property of Fermi-surface gapping in the momentum space. Here we address these key questions by a momentum-dependent observation of electronic states at the transition employing ultrahigh-resolution three-dimensional angle-resolved photoemission spectroscopy. Our results provide compelling evidence of the spontaneous breaking of the lattice's translational symmetry and particle-hole asymmetric gapping of a heavy quasiparticle pocket at the transition.

Particle-hole (p-h) mixing is a fundamental consequence of the existence of a pair condensate. We present direct experimental evidence for p-h mixing in the angle-resolved photoemission (ARPES) spectra in the superconducting state of Bi_2Sr_2CaCu_2O_{8+\delta}. In addition to its pedagogical importance, this establishes unambiguously that the gap observed in ARPES is associated with superconductivity., Comment: 3 pages, revtex, 4 postscript figures

We use photoemission spectroscopy to study electronic structures of pristine and K-doped solid picene. The valence band spectrum of pristine picene consists of three main features with no state at the Fermi level (EF), while that of K-doped picene has three structures similar to those of pristine picene with new states near EF, consistent with the semiconductor-metal transition. The K-induced change cannot be explained with a simple rigid-band model of pristine picene, but can be interpreted by molecular orbital calculations considering electron-intramolecular-vibration interaction. Excellent agreement of the K-doped spectrum with the calculations points to importance of electron-intramolecular-vibration interaction in K-doped picene., This article is accepted by Physical Review B

We have performed x-ray photoemission spectroscopy on the system of noncentrosymmetric superconductor, Li$_2$(Pd$_x$Pt$_{1-x}$3)B. For Li$_2$Pt$_3$B, we found 2 major peaks with 2 other weak components, and the band calculations were in agreement with the observation. The assignment of valence band features using the calculated partial density of states determined that Pt 5d and B 2p contribute to the density of states at the Fermi level. The effect of antisymmetric spin-orbit coupling on the band structure might have been probed, and the analysis on the effect of Pt incorporation into the system indicates the smooth evolution of electronic structures. We presented the measurements of core levels (Pd 3d, Pt 4f, and B 1s) and discussed the chemical bonding states and electronic structures from them., 14 pages, 5 figures

In this work, we have performed resonant photoemission studies of Ca-intercalated graphite superconductor CaC6. Using photon energy of the Ca 2p-3d threshold, the photoemission intensity of the peak at Fermi energy (E-F) is resonantly enhanced. This result provides spectroscopic evidence for the existence of Ca 3d states at E-F, and strongly supports that Ca 3d state plays a crucial role for the superconductivity of this material with relatively high T-c.

In this paper, we review some of our ARPES results on the superconducting and pseudo gaps in Bi2Sr2CaCu2O8+x. We find that optimally and overdoped samples exhibit a d-wave gap, which closes at the same temperature, Tc, for all k points. In underdoped samples, a leading edge gap is found up to a temperature T* > Tc. We find that T* scales with the maximum low temperature gap, increasing as the doping is reduced. The momentum dependence of the pseudogap is similar to that of the superconducting gap; however, the pseudogap closes at different temperatures for different k points., 7 pages, revtex, 7 postscript figures, SNS97 proceedings

The Fermi surface is a central concept in the theory of metals. Even though the optimally doped high temperature superconductors exhibit an anomalous normal state, angle resolved photoemission spectroscopy (ARPES) has revealed a large Fermi surface despite the absence of well-defined quasiparticles and the necessity of working at finite temperatures. However, the even more unusual behavior in the underdoped high temperature superconductors, which show a pseudogap above Tc, requires us to carefully re-examine this concept. Here, we present the first results on how the Fermi surface is destroyed as a function of temperature in underdoped Bi2212 using ARPES. We find the remarkable effect that different k points become gapped at different temperatures. This leads to a break up of the Fermi surface at a temperature T* into disconnected Fermi arcs which shrink with decreasing T, eventually collapsing to the point nodes of the dx2-y2 superconducting ground state below Tc. This novel behavior, where the Fermi surface does not form a continuous contour in momentum space, is unprecedented in that it occurs in the absence of long range order. Moreover, although the d-wave superconducting gap below Tc smoothly evolves into the pseudogap above Tc, the gaps at different k points are not related to one another above Tc the same way as they are below, implying an intimate, but non-trivial relation, between the two., 4 pages, revtex, 5 eps figures, minor changes (note, a and c should be interchanged in upper right panel of old Fig. 2), accepted for Nature

We have performed high-resolution core level photoemission spectroscopy on a heavily phosphorus (P)-doped diamond film in order to elucidate the chemical sites of doped-phosphorus atoms in diamond. P 2p core level study shows two bulk components, providing spectroscopic evidence for multiple chemical sites of doped-phosphorus atoms. This indicates that only a part of doped-phosphorus atoms contribute to the formation of carriers. From a comparison with band calculations, possible origins for the chemical sites are discussed.

We have prepared VO2 thin films epitaxially grown on TiO2(001) substrates with thickness systematically varied from 2.5 to 13 nm using a pulsed laser deposition method, and studied the transport property and electronic states of the films by means of resistivity and in situ synchrotron photoemission spectroscopy (SRPES). In resistivity measurements, the 13-nm-thick film exhibits a metal-insulator transition at around 290 K on cooling with change of three orders of magnitudes in resistivity. As the film thickness decreases, the metal-insulator transition broadens and the transition temperature increases. Below 4 nm, the films do not show the transition and become insulators. In situ SRPES measurements of near the Fermi level valence band find that the electronic state of the 2.5-nm-thick film is different than that of the temperature-induced insulator phase of VO2 itself although these two states are insulating. Ti 2p core-level photoemission measurements reveal that Ti ions exist near the interface between the films and TiO2 substrates, with a chemical state similar to that in (V,Ti)O-2 solid solution. These results indicate that insulating (V,Ti)O-2 solid solution is formed in the thinner films. We propose a simple growth model of a VO2 thin film on a TiO2(001) substrate. Near the interface, insulating (V,Ti) O-2 solid solution is formed due to the diffusion of Ti ions from the TiO2 substrate into the VO2 film. The concentration of Ti in (V,Ti) O-2 is relatively high near the interface and decreases toward the surface of the film. Beyond a certain film thickness (about 7 nm in the case of the present 13-nm-thick film), the VO2 thin film without any Ti ions starts to grow. Our work suggests that developing a technique for preparing the sharp interface between the VO2 thin films and TiO2 substrates is a key issue to study the physical property of an ultrathin film of "pure" VO2, especially to examine the presence of the novel electronic state called a semi-Dirac point phase predicted by calculations.

We have performed soft x-ray photoemission spectroscopy (SXPES) and resonant photoemission spectroscopy (RPES) of the filled skutterudite superconductor PrPt4Ge12 in order to study the electronic structure of valence band and the character of Pr 4f. SXPES of PrPt4Ge12 measured with 1200 eV photon energy, where spectral contribution of Pr 4f is negligible, was found nearly identical with that of LaPt4Ge12, indicating similarity of Pt–Ge derived electronic states of the two compounds. Good correspondence with band calculations allows us to ascribe the dominant Ge 4p character of the density of states at the Fermi level (EF). Pr 3d → 4f RPES shows that, although Pr 4f electrons in PrPt4Ge12 are not as strongly hybridized with conduction electrons near EF as in PrFe4P12, there are finite Pr 4f contribution to the states near EF in PrPt4Ge12. These PES results give the information of fundamental electronic structure for understanding the physical properties of the novel filled skutterudite superconductor PrPt4Ge12.

Magnetic domain formation in thin films of La1−xSrxMnO3 (LSMO) with x=0.2 and 0.4 epitaxially grown on stepped SrTiO3 (001) substrates has been investigated by photoelectron emission microscopy. The magnetic domains show a stripe structure elongated along the step directions, indicating uniaxial magnetic anisotropy induced by step structures. We have also found that the magnetization of the magnetic domains is slightly meandering at domain boundaries. The existence of the additional structures suggests that the magnetic domains in LSMO films are also influenced by biaxial magnetocrystalline anisotropy. The direct observation of the magnetic domain structures suggests that the competition between the two magnetic anisotropies may play an important role in magnetic properties in LSMO films.

With a strong help of high-resolution photoemission spectroscopy we demonstrate in this paper that the large thermoelectric power observed in the layered cobalt oxides, such as Ca_3Co_4O_9, Na_0.6CoO_2, and Bi_2Sr_2Co_2O_9, can be well accounted for with the Boltzmann-type metallic electrical conduction. An intense peak with 1.5–2 eV in width was observed in the photoemission spectra with its center at 1.0 eV below the Fermi level E_F in these compounds. The density of states at E_F is finite but negligibly small at room temperature, because E_F is located near the high-energy edge of this narrow band. We calculated thermoelectric power S using the Boltzmann transport equation with the electronic structure near E_F determined by the photoemission measurement. The calculated S shows fairly good consistency with the measured value both in its magnitude and the temperature dependence.