High energy photoelectron spectroscopy of correlated electron systems and recoil effects in photoelectron emission

The bulk sensitivity of the high energy photoelectron spectroscopy (PES) in the soft and hard X-ray regions is gradually recognized to be essential for studying the electronic structures of strongly correlated electron systems with different surface and bulk electronic structures. With increasing hν, the kinetic energy (E_K) of photoelectrons is increased with realizing longer inelastic mean free path. Studies of three-dimensional genuine bulk band dispersions and bulk Fermiology are only possible by the soft X-ray angle resolved PES (ARPES). Examples are given for Nd_{2 - x}Ce_xCuO₄ and CeRu₂X₂(X: Si, Ge). The temperature dependence of the Yb 4f spectra provides useful information on valence fluctuation and Kondo resonance. The applicability of the single impurity Anderson model (SIAM) and its limit is discussed in the examples of Yb_{1 - x}Lu_xAl₃ and YbAl₃. The importance of the bulk sensitivity is also demonstrated by the soft and hard X-ray PES for SmOs₄Sb₁₂. When E_K becomes very large, the nucleus (ion) recoil effects become observable on the core photoelectron emission from light elements. The example is shown for Yb_7/8Lu_1/8B₁₂ and the influence of the recoil effects for the future high energy ARPES is briefly discussed.     

Studies on the electronic structures of three-dimensional topological insulators by angle resolved photoemission spectroscopy

Three-dimensional (3D) topological insulators represent a new state of quantum matter with a bulk gap and odd number of relativistic Dirac fermions on the surface. The unusual surface states of topological insulators rise from the nontrivial topology of their electronic structures as a result of strong spin-orbital coupling. In this review, we will briefly introduce the concept of topological insulators and the experimental method that can directly probe their unique electronic structure: angle resolved photoemission spectroscopy (ARPES). A few examples are then presented to demonstrate the unique band structures of different families of topological insulators and the unusual properties of the topological surface states. Finally, we will briefly discuss the future development of topological quantum materials.     

Special features in photoemission from the s-p bands of copper

Angle-resolved photoemission (ARPES) studies of the (100) face of clean copper using He I radiation reveal two distinct peaks with binding energies between 0 and 2 eV. These peaks have the opposite dispersion with emission angle and have very different widths, one peak in particular being unusually sharp. We show that both of these peaks are associated with the upper part of the s-p band and that their behaviour can be qualitatively explained by an examination of the bulk band structure for finite values of k_∥ away from the Δ-symmetry direction. We also show that rather good quantitative agreement with the experimental spectra can be obtained by performing realistic photocurrent calculations which include a proper treatment of the surface electronic structure, matrix elements and lifetime effects. Finally, the significance of a sharp peak arising from the s-p band for ARPES studies of random alloys and chemisorption systems is briefly discussed.     

Electronic structure of single crystal UPd3, UGe2, and USb2 from hard X-ray and angle-resolved photoelectron spectroscopy

Electronic structure of single crystal UPd₃, UGe₂, and USb₂ has been measured from hard X-ray photoelectron spectroscopy (HAXPES) with 7.6 keV photons at the European Synchrotron Radiation Facility (ESRF). Lower photon energy angle-resolved photoelectron spectroscopy (ARPES) was also performed at the Synchrotron Radiation Center (SRC). Herein the following results are presented: (i) ARPES results demonstrate hybridization between the U 5f and Pd 4d electrons within UPd₃. (ii) The greatly reduced surface sensitivity of HAXPES enabled observation of the bulk core levels in spite of surface oxidation. Photoelectron mean-free-path versus oxide layer thickness considerations were used to model the effectiveness of HAXPES for probing bulk features of in-air cleaved samples. (iii) Two distinct features separated by 800 meV were observed for the Sb 3d core level. These two features are attributed to manifestations of two distinct Sb sites within the USb₂ single crystal as supported by consideration of interatomic distances and enthalpy-of-formation. (iv) Doniach–Sunjic line shape analysis of core level spectral features revealed correlations between asymmetry coefficients and 5f localization.     

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 SrVO₃ (SVO) bulk single crystals and La_{1? x} Sr _x FeO₃ (LSFO) and La_{1? x} Sr _x MnO₃ (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 APRES results of three-dimensional materials.     

Electronic structure of La (0001) thin films on W (110) studied by photoemission spectroscopy and first principle calculations

Surface states that have a dz2 symmetry around the center of the surface Brillouin zone(BZ)have been regarded common in closely-packed surfaces of rare-earth metals.In this work,we report the electronic structure of dhcp La(0001)thin films by ultrahigh energy resolution angle-resolved photoemission spectroscopy(ARPES)and first principle calculations.Our first principle analysis is based on the many-body approach,therefore,density function theory(DFT)combined with dynamic mean-field theory(DMFT).The experimentally observed Fermi surface topology and band structure close to the Fermi energy qualitatively agree with first principle calculations when using a renormalization factor of between 2 and 3 for the DFT bands.Photon energy dependent ARPES measurements revealed clear kZ dependence for the hole-like band around the BZ center,previously regarded as a surface state.The obtained ARPES results and theoretical calculations suggest that the major bands of dhcp La(0001)near the Fermi level originate from the bulk La 5d orbits as opposed to originating from the surface states.     

Dopant-induced nanoscale electronic inhomogeneities in Ca(2-x)Sr(x)RuO4

Ca(2-x)Sr(x)RuO4 single crystals with 0.1 < or = x < or = 2.0 have been studied systematically using scanning tunneling microscopy (STM) and spectroscopy, low-energy electron diffraction, and angle resolved photoelectron spectroscopy (ARPES). In contrast with the well-ordered lattice structure, the local density of states at the surface clearly shows a strong doping dependent nanoscale electronic inhomogeneity, regardless of the fact of isovalent substitution. Remarkably, the surface electronic roughness measured by STM and the inverse spectral weight of quasiparticle states determined by ARPES are found to vary with x in the same manner as the bulk in-plane residual resistivity, following the Nordheim rule. For the first time, the surface measurements--especially those with STM--are shown to be in good agreement with the bulk transport results, all clearly indicating a doping-induced electronic disorder in the system.     

Bulk vs. surface effects in ARPES experiment from La2/3Sr1/3MnO3 thin films

Experiments directly probing the electronic states using angle-resolved photoemission (ARPES) were carried out on La_2/3Sr_1/3MnO₃ in order to elucidate its electronic properties. ARPES is a surface sensitive technique where bulk and surface states are usually both present. We present high-resolution ARPES studies in the (1 0 0) and (1 1 0) mirror planes and compare them with simulated ARPES based on GGA + U band structure calculations. In the (1 1 0) mirror plane we identify surface umklapps accounted by surface reconstruction which couple to bulk electronic states. As predicted by the simulated spectra there is additional spectral intensity at the Fermi level detected in ARPES data due to k_⊥-broadening effects in the photoemission final states. We demonstrate that this additional spectral intensity is a convenient spectral marker for determination of the k_F Fermi momenta.     

Determination of the surface states from the ultrafast electronic states in a thermoelectric material

We reveal the electronic structure in Yb Cd₂Sb₂,a thermoelectric material,by angle-resolved photoemission spectroscopy(ARPES)and time-resolved ARPES(tr ARPES).Specifically,three bulk bands at the vicinity of the Fermi level are evidenced near the Brillouin zone center,consistent with the density functional theory(DFT)calculation.It is interesting that the spin-unpolarized bulk bands respond unexpectedly to right-and left-handed circularly polarized probe.In addition,a hole band of surface states,which is not sensitive to the polarization of the probe beam and is not expected from the DFT calculation,is identified.We find that the non-equilibrium quasiparticle recovery rate is much smaller in the surface states than that of the bulk states.Our results demonstrate that the surface states can be distinguished from the bulk ones from a view of time scale in the nonequilibrium physics.     

High resolution hard X-ray photoemission using synchrotron radiation as an essential tool for characterization of thin solid films

Recently, we have shown that hard X-ray photoemission spectroscopy using undulator X-rays at SPring-8 is quite feasible with both high resolution and high throughput. Here we report an application of hard X-ray photoemission spectroscopy to the characterization of electronic and chemical states of thin solid films, for which conventional PES is not applicable. As a typical example, we focus on the problem of the scatter in the reported band-gap values for InN. We show that oxygen incorporation into the InN film strongly modifies the valence and plays a crucial role in the band gap problem. The present results demonstrate the powerful applicability of high resolution photoemission spectroscopy with hard X-rays from a synchrotron source.     

Angle-resolved photoemission spectroscopy study of the (101) surface of the Kondo insulator CeNiSn

The electronic structure of CeNiSn, which is considered a possible topological Kondo insulator, has been investigated by employing synchrotron radiation excited angle-resolved photoemission spectroscopy (ARPES). We have found that the easy cleavage plane in CeNiSn is (101), for which we have investigated the Fermi surface (FS) and band structures. The measured FS and ARPES for the (101) plane are described well by the calculated FS and band structures, obtained from the DFT calculations. The measured ARPES bands and photon energy map show that the metallic states crossing the Fermi level have the 3D nature, casting a negative suspicion for the existence of the topological surface states of the 2D character in CeNiSn. The Ce 4f Kondo resonance peak is observed in Ce 4d → 4f resonant photoemission spectroscopy, suggesting the importance of the Ce 4f electrons in determining the temperature-dependent topological electronic structure of CeNiSn.     

Measurement of the bulk and surface bands in Dirac line-node semimetal ZrSiS

Dirac semimetals are materials in which the conduction and the valence bands have robust crossing points protected by topology or symmetry. Recently, a new type of Dirac semimetals, so called the Dirac line-node semimetals(DLNSs), have attracted a lot of attention, as they host robust Dirac points along the one-dimensional(1D) lines in the Brillouin zone(BZ).In this work, using angle-resolved photoemission spectroscopy(ARPES) and first-principles calculations, we systematically investigated the electronic structures of non-symmorphic ZrSiS crystal where we clearly distinguished the surface states from the bulk states. The photon-energy-dependent measurements further prove the existence of Dirac line node along the X-R direction. Remarkably, by in situ surface potassium doping, we clearly observed the different evolutions of the bulk and surface electronic states while proving the robustness of the Dirac line node. Our studies not only reveal the complete electronic structures of ZrSiS, but also demonstrate the method manipulating the electronic structure of the compound.     

Surface-induced orbital-selective band reconstruction in kagome superconductor CsV3Sb5

The two-dimensional (2D) kagome superconductor CsV₃Sb₅ has attracted much recent attention due to the coexistence of superconductivity, charge orders, topology and kagome physics, which manifest themselves as distinct electronic structures in both bulk and surface states of the material. An interesting next step is to manipulate the electronic states in this system. Here, we report angle-resolved photoemission spectroscopy (ARPES) evidence for a surface-induced orbital-selective band reconstruction in CsV₃Sb₅. A significant energy shift of the electron-like band around Γ and a moderate energy shift of the hole-like band around M are observed as a function of time. This evolution is reproduced in a much shorter time scale by in-situ annealing of the CsV₃Sb₅ sample. Orbital-resolved density functional theory (DFT) calculations reveal that the momentum-dependent band reconstruction is associated with different orbitals for the bands around Γ and M, and the time-dependent evolution points to the change of sample surface that is likely caused by the formation of Cs vacancies on the surface. Our results indicate the possibility of orbital-selective control of the band structure via surface modification, which may open a new avenue for manipulating exotic phenomena in this material system, including superconductivity.     

Nature of the well screened state in hard X-ray Mn 2p core-level photoemission measurements of La1-xSrxMnO3 films

Using hard x-ray (HX; hnu=5.95 keV) synchrotron photoemission spectroscopy (PES), we study the intrinsic electronic structure of La(1-x)Sr(x)MnO(3) (LSMO) thin films. Comparison of Mn 2p core-levels with soft x-ray (SX; hnu approximately 1000 eV) PES shows a clear additional well-screened feature only in HX PES. Takeoff-angle dependent data indicate its bulk (> or =20 A) character. The doping and temperature dependence track the ferromagnetism and metallicity of the LSMO series. Cluster model calculations including charge transfer from doping-induced states show good agreement, confirming this picture of bulk properties reflected in Mn 2p core-levels using HX PES.     

Existence, character, and origin of surface-related bands in the high temperature iron pnictide superconductor BaFe(2-x)Co(x)As2

Low energy electron diffraction (LEED) experiments, LEED simulations, and finite slab density functional calculations are combined to study the cleavage surface of Co doped BaFe(2-x)Co(x)As2 (x = 0.1,0.17). We demonstrate that the energy dependence of the LEED data can only be understood from a terminating 1/2 Ba layer accompanied by distortions of the underlying As-Fe2-As block. As a result, surface-related Fe 3d states are present in the electronic structure, which we identify in angle resolved photoemission spectroscopy (ARPES) experiments. The close proximity of the surface-related states to the bulk bands inevitably leads to broadening of the ARPES signals, which excludes the use of the BaFe(2-x)Co(x)As2 system for accurate determination of self-energies using ARPES.     

Hard X-ray photoemission spectroscopy: Variable depth analysis of bulk,surface and interface electronic properties

The electronic properties of surfaces and buried interfaces can vary considerably in comparison to the bulk. In turn, analyzing bulk properties, without including those of the surface, is understandably challenging. Hard X-ray photoelectron spectroscopy (HAXPES) allows the well known ability of photoemission to interrogate the electronic structure of material systems with bulk volume sensitivity. This is achieved by tuning the kinetic energy range of the analyzed photoelectrons in the multi-keV regime. This unique ability to probe truly bulk properties strongly compliments normal photoemission, which generally probes surface electronic structure that is different than the bulk selected examples of HAXPES and possible implications towards the study of complex oxide-based interfaces and highly correlated systems are discussed.     

Correlation of conductivity and angle integrated valence band photoemission characteristics in single crystal iron perovskites for 300 K < T < 800 K: Comparison of surface and bulk sensitive methods

A single crystal monolith of La_0.9Sr_0.1FeO₃ and thin pulsed laser deposited film of La_0.8Sr_0.2Fe_0.8Ni_0.2O₃ were subject to angle integrated valence band photoemission spectroscopy in ultra high vacuum and conductivity experiments in ambient air at temperatures from 300 K to 800 K. Except for several sputtering and annealing cycles, the specimens were not prepared in situ. Peculiar changes in the temperature dependent, bulk representative conductivity profile as a result of reversible phase transitions, and irreversible chemical changes are semi-quantitatively reflected by the intensity variation in the more surface representative valence band spectra near the Fermi energy. X-ray photoelectron diffraction images reflect the symmetry as expected from bulk iron perovskites. The correlation of spectral details in the valence band photoemission spectra (VB PES) and details of the conductivity during temperature variation suggest that valuable information on electronic structure and transport properties of complex materials may be obtained without in situ preparation.     

Structural and electronic properties of thin Ni layers on Cu(1 1 1) as investigated by ARPES, STM and GIXD

The growth and the crystalline and electronic structure of Ni deposited on single crystalline Cu(1 1 1) were studied by scanning tunnelling microscopy (STM), grazing incidence X-ray diffraction (GIXD) and angle-resolved photoemission spectroscopy (ARPES). In the early stages of growth monoatomic-high flat Ni islands, partially covered by Cu migrating from the surface, are observed. Starting from a pseudomorphic epitaxial relationship the in-plane lattice parameter progressively relaxes with increasing coverage. For a 20 monolayer (ML) thick deposit the in-plane lattice parameter is still found halfway between the bulk Ni and Cu lattice parameters. ARPES data also rule out the layer-by-layer growth and provide the values of the Ni exchange splitting.     

Fabrication of multi-scale structures with multiple X-ray masks and synchrotron hard X-ray irradiations

Synchrotron hard X-ray irradiation can be utilized in lithography processes to manufacture precise structures. Due to the difficulty of precise X-ray mask fabrication in hard X-ray lithography, this X-ray process has been used mainly to fabricate precise microstructures. In this study, a technology is proposed for fabricating novel multi-scale patterns that include submicron-scale structures using hard X-rays. The required X-ray masks for submicron-sized patterning are fabricated by a simple UV lithography process and sidewall metal deposition. Above all, thanks to the high penetration capability of hard X-rays with sub-nanometer wavelengths, it is possible to employ multiple masks to fabricate a variety of patterns. By combining each sub-micron X-ray mask with typical micro-sized X-ray masks, a unique X-ray lithography is performed, and various multi-scale structures are fabricated. The usefulness of the proposed technology is demonstrated by the realization of these structures.     

Hard X-ray PhotoEmission Spectroscopy of strongly correlated systems

Hard X-ray PhotoEmission Spectroscopy (HAXPES) is a new tool for the study of bulk electronic properties of solids using synchrotron radiation. We review recent achievements of HAXPES, with particular reference to the VOLPE project, showing that high energy resolution and bulk sensitivity can be obtained at kinetic energies of 6–8 keV. We present also the results of recent studies on strongly correlated materials, such as vanadium sesquioxide and bilayered manganites, revealing the presence of different screening properties in the bulk with respect to the surface. We discuss the relevant experimental features of the metal–insulator transition in these materials. To cite this article: G. Panaccione et al., C. R. Physique 9 (2008).