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Hard X-ray angle-resolved photoemission spectroscopy reveals significant alterations in the valence band states of EuPd$_2$Si$_2$ at a temperature $T_V$, where the Eu ions undergo a temperature-induced valence crossover from a magnetic Eu$^{2+}$ state to a low-temperature valence-fluctuating state. The introduction of small amounts of Au on Pd lattice sites and Ge on Si sites, respectively, results in a decrease in $T_V$ and the emergence of an antiferromagnetic state at low temperatures without valence fluctuations. It has been proposed that the boundary between AFM order and valence crossover represents a first-order phase transition associated with a specific type of second-order critical end point. In this scenario, strong coupling effects between fluctuating charge, spin, and lattice degrees of freedom are to be expected. In the case of EuPd$_2$(Si$_{1-x}$Ge$_x$)$_2$ with x=0.13, which is situated close to the critical end point, a splitting of conduction band states and the emergence of flat bands with one-dimensional character have been observed. A comparison with ab initio theory demonstrates a high degree of correlation with experimental findings, particularly in regard to the bands situated in proximity to the critical end point., Comment: 9 pages, 9 figures

We have experimentally demonstrated different operating modes for the front lenses of the momentum microscopes described in Part I. Measurements at energies from vacuum UV at a high-harmonic generation (HHG)-based source to the soft and hard X-ray range at a synchrotron facility validated the results of theoretical ray-tracing calculations. The key element is a ring electrode concentric with the extractor electrode, which can tailor the field in the gap. First, the gap-lens-assisted extractor mode reduces the field strength at the sample while mitigating image aberrations. This mode gave good results in all spectral ranges. Secondly, by compensating the field at the sample surface with a negative voltage at the ring electrode we can operate in zero-field mode, which is beneficial for operando experiments. Finally, higher negative voltages establish the repeller mode, which removes all slow electrons below a certain kinetic energy to eliminate the primary contribution to the space-charge interaction in pump-probe experiments. The switch from extractor to repeller mode is associated with a reduction in the k-field-of-view (10-20 % at hard-X-ray energies, increasing to ~50% at low energies). Real-space imaging also benefits from the new lens modes as confirmed by ToF-XPEEM imaging with 650 nm resolution., Comment: 22 pages, 9 figures, 56 references

A comprehensive study of the electronic and structural phase transition from 1T` to Td in the bulk Weyl semimetal Mo1-xWxTe2 at different doping concentrations has been carried out using time-of-flight momentum microscopy (including circular and linear dichroism), X-ray photoelectron spectroscopy (XPS), X-ray photoelectron diffraction (XPD), X-ray diffraction (XRD), angle-resolved Raman spectroscopy, transport measurements, density functional theory (DFT) and Kikuchi pattern calculations. High-resolution angle-resolved photoemission spectroscopy (ARPES) at 20 K reveals surface electronic states, which are indicative of topological Fermi arcs. Their dispersion agrees with the position of Weyl points predicted by DFT calculations based on the experimental crystal structure of our samples determined by XRD. Raman spectroscopy confirms the inversion symmetry breaking for the Td -phase, which is a necessary condition for the emergence of topological states. Transport measurements show that increasing the doping concentration from 2 to 9% leads to an increase in the temperature of the phase transition from 1T` to Td from 230 K to 270 K. Magnetoresistance and longitudinal elastoresistance show significantly increased values in the Td -phase due to stimulated inter-pocket electron backscattering. The results demonstrate the close relationship between electronic properties and elastic deformations in MoTe2., Comment: 22 pages, 10 figures

We present results of hard X-ray angle-resolved photoemission spectroscopy and photoemission diffraction measurements performed on high-quality single crystals of the valence transition compound EuPd$_2$Si$_2$ for temperatures 25~K $\leq$ T $\leq$ 300~K. At low temperatures we observe a Eu $4f$ valence $v=2.5$, % occupation number $n=6.5$, which decreases to $v=2.1$ for temperatures above the valence transition around $T_V \approx 160$~K. The experimental valence numbers resulting from an evaluation of the Eu(III)/Eu(II) $3d$ core levels, are used for calculating band structures using density functional theory. The valence transition significantly changes the band structure as determined by angle-resolved photoemission spectroscopy. In particular, the Eu $5d$ valence bands are shifted to lower binding energies with increasing Eu $4f$ occupancy. To a lesser extent, bands derived from the Si $3p$ and Pd $4d$ orbitals are also affected. This observation suggests a partial charge transfer between Eu and Pd/Si sites. Comparison with {\it ab-initio} theory shows a good agreement with experiment, in particular concerning the unequal band shift with increasing Eu $4f$ occupancy.

Hard X-ray angle-resolved photoemission spectroscopy reveals the momentum-resolved band structure in an epitaxial Mn2Au(001) film capped by a 2 nm thick ferromagnetic Permalloy layer. By magnetizing the Permalloy capping layer, the exceptionally strong exchange bias aligns the Neel vector in the Mn2Au(001) film accordingly. Uncompensated interface Mn magnetic moments in Mn2Au were identified as the origin of the exchange bias using X-ray magnetic circular dichroism in combination with photoelectron emission microscopy. Using time-of-flight momentum microscopy, we measure the asymmetry of the band structure in Mn2Au resulting from the homogeneous orientation of the Neel vector. Comparison with theory shows that the Neel vector, determined by the magnetic moment of the top Mn layer, is antiparallel to the Permalloy magnetization. The experimental results demonstrate that hard X-ray photoemission spectroscopy can measure the band structure of epitaxial layers beneath a metallic capping layer and corroborate the asymmetric band structure in Mn2Au that was previously inferred only indirectly., Comment: 7 pages, 4 figures

Altermagnets are an emerging third elementary class of magnets. Unlike ferromagnets, their distinct crystal symmetries inhibit magnetization while, unlike antiferromagnets, they promote strong spin polarization in the band structure. The corresponding unconventional mechanism of timereversal symmetry breaking without magnetization in the electronic spectra has been regarded as a primary signature of altermagnetism, but has not been experimentally visualized to date. We directly observe strong time-reversal symmetry breaking in the band structure of altermagnetic RuO$_2$ by detecting magnetic circular dichroism in angle-resolved photoemission spectra. Our experimental results, supported by ab initio calculations, establish the microscopic electronic-structure basis for a family of novel phenomena and functionalities in fields ranging from topological matter to spintronics, that are based on the unconventional time-reversal symmetry breaking in altermagnets.

Imaging energy filters in photoelectron microscopes and momentum microscopes employ spherical fields with deflection angles of 90{\deg}, 180{\deg} and even 2 x 180{\deg}. These instruments are optimized for high energy resolution, yet they come along with image aberrations when they are operated in high transmission mode with medium energy resolution. Here we present a new approach for bandpass-filtered imaging in real or reciprocal space, using an asymmetric electrostatic dodecapole. This multipole enables energy-dispersive beam deflection and correction of image aberrations up to the 3rd order. Owing to a deflection angle of only 4{\deg}, the total beam displacement in the filter is just ~10 mm. Hence, the entire instrument is compact and just requires a straight vacuum tube. The multipole is framed by transfer lenses in the entrance and exit branch. Two sets of 16 entrance and exit apertures with different sizes on piezomotor-driven holders allow selecting the desired resolution. The combination of apertures and dodecapole acts as a bandpass pre-selector in a high-energy time-of-flight momentum microscope at the hard X-ray beamline P22 at PETRA-III (DESY, Hamburg). At pass energies between 400 and 600 eV it transmits electrons with kinetic energies in the range of 20-40 eV and thus effectively eliminates unwanted intensity from higher-energy electrons in the ToF analyzer. At low pass energies, the instrument allows energy-filtered imaging without subsequent ToF analysis. In a laboratory experiment the 4{\deg} prototype reached < 500 meV resolution, which is sufficient for fast survey studies in the X-ray range., Comment: 16 pages, 6 figures, 26 references

The small time gap of synchrotron radiation in conventional multi-bunch mode (100-500MHz) is prohibitive for time-of-flight (ToF) based electron spectroscopy. Even the new generation of delay-line detectors with improved time resolution (<100ps) yields only 20-100 resolved time slices within a 2-10ns gap. Here we present two techniques of implementing efficient ToF recording at sources with high repetition rate. A fast electron-optical beam blanking unit with GHz bandwidth, integrated in a photoelectron momentum microscope, allows chopping the photon-pulse train to any desired repetition period. Aberration-free momentum distributions have been recorded at chopped pulse periods of 5MHz (at MAX II) and 1.25MHz (at BESSY II). The approach is benchmarked against the alternative way of implementing a dispersive element, e.g. a hemispherical analyzer, in the electron optics. Both approaches, chopping in the time domain as well as bandpass pre-selection in the energy domain, can enable efficient ToF spectroscopy, spectroscopic real-space imaging and momentum microscopy with few-meV resolution using 100-500MHz Synchrotron radiation, highly-repetitive lasers or cavity-enhanced high-harmonic sources. For comparison, we show results recorded at BESSY II with a parasitic 4-bunch island-orbit pulse train, coexisting with the 500MHz filling pattern on the main orbit., Comment: 21 pages, 6 figures Best regards, Gerd Schoenhense

Recent advances in the brilliance of hard-X-ray beamlines and photoelectron momentum microscopy facilitate bulk valence-band mapping and core-level-resolved hard-X-ray photoelectron diffraction (hXPD) for structural analysis in the same setup. High-quality MBE-grown (In,Ga,Mn)As films represent an ideal testing ground, because of the non-centrosymmetric GaAs crystal structure itself and In and Mn doping concentrations of few percent. Here we present results of k-mapping and hXPD for the title compound with 3% In and 2.5 or 5.6% Mn using hard X-ray photons (3 to 5 keV) at beamline P22 at PETRA III (DESY, Hamburg). Numerical processing (difference or ratio images) emphasizes subtle differences of hXPD patterns like the fingerprint-like hXPD-signatures of As and Ga sites. XPD calculations using the Bloch-wave method show a one-to-one correspondence with the measurements. The hXPD results reveal a predominant Ga substitutional site for Mn. Valence band mapping shows that the Fermi energy lies within the valence band and decreases as the Mn concentration increases. The results support the p-d Zener model of ferromagnetism in the title compound. In addition to the shift of the Fermi energy, the band splitting increases with increasing Mn content, which we attribute to an increase of many-body correlations with increasing metallicity of the sample.

Photoelectron momentum microscopy is an emerging powerful method for angle-resolved photoelectron spectroscopy (ARPES), especially in combination with imaging spin filters. These instruments record kx-ky images, typically exceeding a full Brillouin zone. As energy filters double-hemispherical or time-of-flight (ToF) devices are in use. Here we present a new approach for momentum mapping of the full half-space, based on a single hemispherical analyzer (path radius 225 mm). Excitation by an unfocused He lamp yielded an energy resolution of 7.7 meV. The performance is demonstrated by k-imaging of quantum-well states in Au and Xe multilayers. The alpha-square-aberration term (alpha: entrance angle in the dispersive plane) and the transit-time spread of the electrons in the spherical field are studied in a large pass-energy (6 to 660 eV) and angular range (alpha up to about 7{\deg}). It is discussed how the method circumvents the preconditions of previous theoretical work on the resolution limitation due to the alpha-square-term and the transit-time spread, being detrimental for time-resolved experiments. Thanks to k-resolved detection, both effects can be corrected numerically. We introduce a dispersive-plus-ToF hybrid mode of operation, with an imaging ToF analyzer behind the exit slit of the hemisphere. This instrument captures 3D data arrays I(EB,kx,ky), yielding a gain up to N^2 in recording efficiency (N being the number of resolved time slices). A key application will be ARPES at sources with high pulse rates like Synchrotrons with 500 MHz time structure.

Spin-filtered time-of-flight photoelectron momentum microscopy reveals a systematic variation of the band structure within a series of highly spin-polarized ferromagnetic Heusler compounds with increasing number of valence electrons (Co2MnGa, Co2MnSi and Co2Fe0.4Mn0.6Si). The positions of the Fermi energy for minority and majority electrons deviate strongly from a simple band-filling model. Photoexcitation at h$\nu$=6.05 eV (4th harmonic of a Ti:sapphire laser) gives access to the spin-polarization texture P(EB,kx,ky) of the bulk bands in a (kx,ky)-range with diameter 1.4{\AA}$^{-1}$ and energies from the Fermi energy EF to a binding energy of EB=2 eV. The minority bands of Co2MnGa cross the Fermi level, inhibiting half-metallicity; the crossing points allow a precise adjustment of experimental and theoretical majority and minority bands, requiring shifts in opposite directions. The top of the minority band lies only 0.15 eV above EF, i.e. Co2MnGa is much closer to being half-metallic than predicted by calculations. For half-metallic Co2MnSi and Co2Fe0.4Mn0.6Si clear minority band gaps are visible, the topmost occupied minority bands lie 0.5 and 0.35 eV below EF, in reasonable agreement with theory; the exchange splitting is significantly smaller than in theory. The comparison of all three compounds uncovers the surprising fact that with increasing number of valence electrons the frontier majority bands (close to EF) exhibit an increasing deficiency in filling, in comparison with the prediction of a DFT calculation. The same trend is visible in comparison with a DMFT calculation. For s-polarized excitation both half-metallic compounds exhibit nearly complete positive spin polarization close to EF, consistent with previous work in literature., Comment: 27 pages, 6 figures

The newly developed method of time-of-flight (ToF) momentum microscopy was used to analyse the cold electron emission from a Cs 3D magneto-optical trap (MOT). Three-step resonant photoionization was implemented via two intermediate states (6P3/2 pumped with 852 nm laser and 7S1/2 with 1470 nm) and a tuneable femtosecond Ti:sapphire laser for the final ionization step. The magnetic field of the MOT is switched off during the photoionization step. The natural bandwidth of the fs-laser is reduced to 4 meV using optical spectral filters. Precise tuning of the photon energy makes it possible to observe the transition regime between direct photoemission into the open continuum and field induced ionization of highly-excited Rydberg states. The paths can be identified by their characteristic dependency on the extraction field and on the Ti:sapphire polarization. ToF analysis allowed us to disentangle the ionization paths and the dependence of the spatio-temporal distribution of the cold electrons on the polarization of the ionizing laser., Comment: 7 pages, 5 figures

Surface alloys are highly flexible materials for tailoring the spin-dependent properties of surfaces. Here, we study the spin-dependent band structure of a DyAg$_2$ surface alloy formed on an Ag(111) crystal. We find a significant exchange spin-splitting of the localized Dy 4f states pointing to a ferromagnetic coupling between the localized Dy moments at $40\,$K. The magnetic coupling between these moments is mediated by an indirect, RKKY-like exchange coupling via the spin-polarized electrons of the hole-like Dy-Ag hybrid surface state.

We established a new approach to hard-X-ray photoelectron spectroscopy (HAXPES). The instrumental key feature is an increase of the dimensionality of the recording scheme from 2D to 3D. A high-energy momentum microscope can detect electrons with initial kinetic energies more than 6 keV with high angular resolution < 0.1{\deg}. The large k-space acceptance of the special objective lens allows for simultaneous full-field imaging of many Brillouin zones. Combined with time-of-flight parallel energy recording, this method yields maximum parallelization of data acquisition. In a pilot experiment at the new beamline P22 at PETRA III, Hamburg, count rates of more than $10^{6}$ counts per second in the d-band complex of transition metals established an unprecedented HAXPES recording speed. It was found that the concept of tomographic k-space mapping previously demonstrated in the soft X-ray regime works equally well in the hard X-ray range. Sharp valence band k-patterns of Re collected at an excitation energy of 6 keV correspond to direct transitions to the 28th repeated Brillouin zone. Given the high X-ray brilliance (1.1x$10^{13}$ hv/s in a spot of less than 20x15 $mu^{2}$), the 3D bulk Brillouin zone can be mapped in a few hours. X-ray photoelectron diffraction (XPD) patterns with < 0.1{\deg} resolution are recorded within minutes. Previously unobserved fine details in the diffractograms reflect the large number of scatterers, several $10^{4}$ to $10^{6}$, depending on energy. The short photoelectron wavelength (an order of magnitude smaller than the interatomic distance) amplifies phase differences and makes hard X-ray XPD with high resolution a very sensitive structural tool. The high count rates pave the way towards spin-resolved HAXPES using an imaging spin filter.

Owing to strongly enhanced bulk sensitivity, angle- or momentum-resolved photoemission using X-rays is an emergent powerful tool for electronic structure mapping. A novel full-field k-imaging method with time-of-flight energy detection allowed rapid recording of 4D (EB,k) data arrays (EB binding energy; k final-state electron momentum) in the photon-energy range of 400-1700eV. Arrays for the d-band complex of several transition metals (Mo, W, Re, Ir) reveal numerous spots of strong local intensity enhancement up to a factor of 5. The enhancement is confined to small (EB,k)-regions (dk down to 0.01 A-1; dEB down to 200 meV) and is a fingerprint of valence-band photoelectron diffraction. Regions of constructive interference in the (EB,k)-scheme can be predicted in a manner resembling the Ewald construction. A key factor is the transfer of photon momentum to the electron, which breaks the symmetry and causes a rigid shift of the final-state energy isosphere. Working rigorously in k-space, our model does not need to assume a localization in real space, but works for itinerant band states without any assumptions or restrictions. The role of momentum conservation in Fermi's Golden Rule at X-ray energies is revealed in a graphical, intuitive way. The results are relevant for the emerging field of time-resolved photoelectron diffraction and can be combined with standing-wave excitation to gain element sensitivity., Comment: 24 pages, 7 figures

Co/BaTiO$_3$(001) is one of the most interesting multiferroic heterostructures as it combines different ferroic phases, setting this way the fundamentals for innovative technical applications. Various theoretical approaches have been applied to investigate the electronic and magnetic properties of Co/BaTiO$_3$(001). Here we determine the magnetic properties of 3 ML Co/BaTiO$_3$ by calculating spin-polarized electron diffraction as well as angle-resolved photoemission spectra, with both methods being well established as surface sensitive techniques. Furthermore, we discuss the impact of altering the BaTiO$_3$ polarization on the spectra and ascribe the observed changes to characteristic details of the electronic structure.

The magnitude of the spin polarization at the Fermi level of ferromagnetic materials at room temperature is a key property for spintronics. Investigating the Heusler compound Co$_2$MnSi a value of 93$\%$ for the spin polarization has been observed at room temperature, where the high spin polarization is related to a stable surface resonance in the majority band extending deep into the bulk. In particular, we identified in our spectroscopical analysis that this surface resonance is embedded in the bulk continuum with a strong coupling to the majority bulk states. The resonance behaves very bulk-like, as it extends over the first six atomic layers of the corresponding (001)-surface. Our study includes experimental investigations, where the bulk electronic structure as well as surface-related features have been investigated using spin-resolved photoelectron spectroscopy (SR-UPS) and for a larger probing depth spin-integrated high energy x-ray photoemission spectroscopy (HAXPES). The results are interpreted in comparison with first-principles band structure and photoemission calculations which consider all relativistic, surface and high-energy effects properly., Comment: 9 pages, 8 figures, Heusler alloy, electronic structure and photoemission

Changes of the electronic structure accompanied by charge localization and a transition to an antiferromagnetic ground state were observed in the (DOEO)$_4$[HgBr$_4$]TCE organic semiconductor. Localization starts in the region of about 150 K and the antiferromagnetic state occurs below 60 K. The magnetic moment of the crystal contains contributions of antiferromagnetic inclusions (droplets), individual paramagnetic centers formed by localized holes and free charge carriers at 2 K. Two types of inclusions of 100-400 nm and 2-5 nm sizes were revealed by transmission electron microscopy. Studying the symmetry of the antiferromagnetic droplets (100-400 nm inclusions) and individual localized holes by electron spin resonance (ESR) revealed fingerprints of the antiferromagnetic resonance spectra of the spin correlated droplets as well as paramagnetic resonance spectra of the individual localized charge carriers. Photoelectron spectroscopy in the VUV, soft and hard X-ray range shows temperature-dependent effects upon crossing the critical temperature. The substantially different probing depths of soft and hard X-ray photoelectron spectroscopy yield information on the surface termination. The combined investigation using soft and hard X-ray photons to study the same sample results in details of electronic structure including structural aspects at the surface., Comment: 22 pages, 9 figures. arXiv admin note: text overlap with arXiv:0710.5586 by other authors

It is demonstrated that the near-edge X-ray absorption fine structure (NEXAFS) provides a powerful local probe of functional groups in novel charge transfer (CT) compounds. Microcrystals of tetra- and hexamethoxypyrene as donors with the strong acceptor tetracyanoquinodimethane (TMPx/HMPx - TCNQy) were grown from solution via vapour diffusion in different stoichiometries x:y = 1:1, 1:2 and 2:1. Owing to the element specificity of NEXAFS, the oxygen and nitrogen K-edge spectra are direct spectroscopic fingerprints of the donating and accepting moieties. The orbital selectivity of the NEXAFS resonances allows to precisely elucidate the participation of specific orbitals in the charge-transfer process. In the present case charge is transferred from methoxy-orbitals 2e (PI*) and 6a1 (SIGMA*) to the cyano-orbitals b3g and au (PI*) and - to a weaker extent - to b1g and b2u (SIGMA*). The occupation of 2e reflects the anionic character of the methoxy groups. Surprisingly, the charge transfer increases with increasing HMP content of the complex. As additional indirect signature, all spectral features of the donor and acceptor are shifted to higher and lower photon energies, respectively. Providing quantitative access to the relative occupation of specific orbitals, the approach constitutes the most direct probe of the charge-transfer mechanism in organic salts found so far. Although demonstrated for the specific example of pyrene-derived donors with the classical acceptor TCNQ, the method is very versatile and can serve as routine probe for novel CT-complexes on the basis of functionalized polycyclic aromatic hydrocarbons., Comment: 13 pages, 5 figures

UHV-deposited films of the mixed phase of tetramethoxypyrene and tetracyanoquinodimethane (TMP1-TCNQ1) on gold have been studied using ultraviolet photoelectron spectroscopy (UPS), X-ray-diffraction (XRD), infrared (IR) spectroscopy and scanning tunnelling spectroscopy (STS). The formation of an intermolecular charge-transfer (CT) compound is evident from the appearance of new reflexes in XRD (d1= 0.894 nm, d2= 0.677 nm). A softening of the CN stretching vibration (red-shift by 7 cm-1) of TCNQ is visible in the IR spectra, being indicative of a CT of the order of 0.3e from TMP to TCNQ in the complex. Characteristic shifts of the electronic level positions occur in UPS and STS that are in reasonable agreement with the prediction of from DFT calculations (Gaussian03 with hybrid functional B3LYP). STS reveals a HOMO-LUMO gap of the CT complex of about 1.25 eV being much smaller than the gaps (>3.0 eV) of the pure moieties. The electron-injection and hole-injection barriers are 0.3 eV and 0.5 eV, respectively. Systematic differences in the positions of the HOMOs determined by UPS and STS are discussed in terms of the different information content of the two methods., Comment: 20 pages, 6 figures

The influence of 30 keV He$^+$ ion irradiation on structural, electronic and magnetic properties of Co$_2$MnSi thin films with B2 order was investigated. It was found, that irradiation with light ions can improve the local chemical order. This provokes changes of the electronic structure and element-specific magnetization towards the bulk properties of the well-ordered Co$_2$MnSi Heusler compound with L2$_1$ structure., Comment: 4 pages, 4 figures

A concept is presented serving to guide in the search for new materials with high spin polarization. It is shown that the magnetic moment of half-metallic ferromagnets can be calculated from the generalized Slater-Pauling rule. Further, it was found empirically that the Curie temperature of Co$_2$ based Heusler compounds can be estimated from a seemingly linear dependence on the magnetic moment. As a successful application of these simple rules, it was found that Co$_2$FeSi is, actually, the half-metallic ferromagnet exhibiting the highest magnetic moment and the highest Curie temperature measured for a Heusler compound.

Photoemission electron microscopy was used to image the electrons photoemitted from specially tailored Ag nanoparticles deposited on a Si substrate (with its native oxide SiO$_{x}$). Photoemission was induced by illumination with a Hg UV-lamp (photon energy cutoff $\hbar\omega_{UV}=5.0$ eV, wavelength $\lambda_{UV}=250$ nm) and with a Ti:Sapphire femtosecond laser ($\hbar\omega_{l}=3.1$ eV, $\lambda_{l}=400$ nm, pulse width below 200 fs), respectively. While homogeneous photoelectron emission from the metal is observed upon illumination at energies above the silver plasmon frequency, at lower photon energies the emission is localized at tips of the structure. This is interpreted as a signature of the local electrical field therefore providing a tool to map the optical near field with the resolution of emission electron microscopy., Comment: 10 pages, 4 figures; submitted to Physical Review Letters