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Monolayers of chiral molecules can preferentially transmit electrons with a specific spin orientation, introducing chiral molecules as efficient spin filters. This phenomenon is established as chirality-induced spin selectivity (CISS) and was demonstrated directly for the first time in self-assembled monolayers (SAMs) of double-stranded DNA (dsDNA)1 . Here, we discuss SAMs of double-stranded peptide nucleic acid (dsPNA) as a system which allows for systematic investigations of the influence of various molecular properties on CISS. In photoemission studies, SAMs of chiral, γ-modified PNA show significant spin filtering of up to P = (24.4 ± 4.3)% spin polarization. The polarization values found in PNA lacking chiral monomers are considerably lower at about P = 12%. The results confirm that the preferred spin orientation is directly linked to the molecular handedness and indicate that the spin filtering capacity of the dsPNA helices might be enhanced by introduction of chiral centers in the constituting peptide monomers.

The development of materials that are non-magnetic in the bulk but exhibit two-dimensional (2D) magnetism at the surface is at the core of spintronics applications. Here, we present the valence-fluctuating material EuIrSi, where in contrast to its non-magnetic bulk, the Si-terminated surface reveals controllable 2D ferromagnetism. Close to the surface the Eu ions prefer a magnetic divalent configuration and their large 4f moments order below 48 K. The emerging exchange interaction modifies the spin polarization of the 2D surface electrons originally induced by the strong Rashba effect. The temperature-dependent mixed valence of the bulk allows to tune the energy and momentum size of the projected band gaps to which the 2D electrons are confined. This gives an additional degree of freedom to handle spin-polarized electrons at the surface. Our findings disclose valence-fluctuating rare-earth based materials as a very promising basis for the development of systems with controllable 2D magnetic properties which is of interest both for fundamental science and applications., This work was supported by the German Research Foundation (DFG) through Grants No. KR3831/5-1, No. LA655/20-1 and Fermi-NEst. Support was provided by the Spanish Ministry of Science, Innovation and Universities (Project No. FIS2016-76617-P and No. FIS2016-75862-P). We acknowledge financial support from the Spanish Ministry of Economy (MAT-2017-88374-P). The authors also acknowledge support by Saint Petersburg State University (Grant No. 15.61.202.2015) and Tomsk State University Academic D. I. Mendeleev Fund Program (Research Grant No. 8.1.01.2018). We acknowledge Diamond Light Source for access to beamline I05 (proposals no. SI18844-1 and SI17761-1) that contributed to the results presented here.

Semiconductors with strong spin–orbit interaction as the underlying mechanism for the generation of spin-polarized electrons are showing potential for applications in spintronic devices. Unveiling the full spin texture in momentum space for such materials and its relation to the microscopic structure of the electronic wave functions is experimentally challenging and yet essential for exploiting spin–orbit effects for spin manipulation. Here we employ a state-of-the-art photoelectron momentum microscope with a multichannel spin filter to directly image the spin texture of the layered polar semiconductor BiTeI within the full two-dimensional momentum plane. Our experimental results, supported by relativistic ab initio calculations, demonstrate that the valence and conduction band electrons in BiTeI have spin textures of opposite chirality and of pronounced orbital dependence beyond the standard Rashba model, the latter giving rise to strong optical selection-rule effects on the photoelectron spin polarization. These observations open avenues for spin-texture manipulation by atomic-layer and charge carrier control in polar semiconductors., This work was supported by DFG (through SFB 1170 ‘ToCoTronics’) and through FOR1162 (P3). We acknowledge the support by the Basque Departamento de Educacion, UPV/EHU (Grant Number IT-756-13), Spanish Ministerio de Economia y Competitividad (MINECO Grant Number FIS2013-48286-C2-2-P), Tomsk State University Academic D.I. Mendeleev Fund Program in 2015 (Research Grant Number 8.1.05.2015), the Russian Foundation for Basic Research (Grant Numbers 15-02-01797 and 15-02-589 02717). Partial support by the Saint Petersburg State University (Grant Number 15.61.202.2015) is also acknowledged.

Rozbíjení inverzní symetrie ve fereeleRashba efekt; Fotoemisse; DFTktrickém polovodiči způsobuje děleni stavů, tzv Rashba efekt. V tomto článku ukazujeme kompletně mapování spinové polarizace těchto Rashba stavů za pomoci spinovo rozlišené fotoemisse. The breaking of bulk inversion symmetry in ferroelectric semiconductors causes a Rashba-type spin splitting of electronic bulk bands. This is shown by a comprehensive mapping of the spin polarization of the electronic bands in ferroelectric α- GeTe(111) films using a time-of-flight momentum microscope equipped with an imaging spin filter that enables a simultaneous measurement of more than 10 000 data points. The experiment reveals an opposite spin helicity of the inner and outer Rashba bands with a different spin polarization in agreement with theoretical predictions, confirming a complex spin texture of bulk Rashba states. The outer band has about twice larger spin polarization than the inner one, giving evidence of a spin-orbit effect being related to the orbital composition of the band states. The switchable inner electric field of GeTe implies new functionalities for spintronic devices.

We report on a spectroscopic multitechnique approach to study the metal/radical spinterface formed by a perchlorinated trityl radical derivative and either gold or silver. The spectroscopic fingerprint of their paramagnetic properties could be determined by comparison with their diamagnetic precursor and by DFT calculations. Thanks to the presented approach, we could gain unprecedented insight into the radical–metal interaction and how this latter perturbs the spin polarization and consequently the magnetoelectronic properties of the radical adlayer. Knowledge of the factors influencing the spinterface is an essential tool toward the tailoring of the properties of spin-based electronic devices., We acknowledge the Helmholtz-Zentrum Berlin for provision of synchrotron radiation beamtime at SURICAT apparatus of BESSY II, receiving funding from the FP7/2007-2013 grant agreement no. 312284. The authors acknowledge financial support from the Instituto de Salud Carlos III, through “Acciones CIBER”. The Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBERBBN) is an initiative funded by the VI National R&D&I Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. The authors also appreciate the financial support through the projects BE-WELL (CTQ2013-40480-R), granted by DGI (Spain), and GenCat (2014-SGR-17), financed by DGR (Catalunya). This work is partially supported by the Italian Ministerio dell’Instruzione dell’ Universita’ e della Ricerca through the PRIN “GRAF” (Contract 20105ZZTSE) and Progetto Premiale ABNANOTECH.

Magnetite (Fe3O4) is a promising candidate for application in spintronic devices. This ferrimagnet with a high Curie temperature has been theoretically predicted to be a half-metal with a conductive minority-spin (↓) channel and a semiconductive majority-spin (↑) channel, resulting in 100 % spin polarization at the Fermi level. But up to now, any clear experimental evidence is lacking. This thesis presents spin- and angle-resolved photoemission studies on the magnetic and electronic structure of Fe3O4 (001) epitaxially grown on MgO (001). A band structure calculation using generalized gradient approximation plus U (GGA+U) to the density functional theory (DFT) is proposed to explain the experimental results. Although the PES intensity at Fermi level is very low because of the role played by polarons, a dispersion of the Fe 3d-t2g states is observed. The overall behaviour of these bands is in good agreement with the calculation of ground state electronic structure. In order to simulate the spectra, we used the free electron approximation for the final states, ignoring the matrix elements. Calculated ground state data are convoluted by Lorentzian and Gaussian functions to account for the lifetime and electron-phonon coupling effects, respectively. By integrating the spectral intensity over an energy interval of 100meV at Fermi level, we obtained the first experimental evidence of the Fermi surface plot. Determination of electron spin polarization is an ultimate test of both the band calculations and our model of Fe3O4 photoemission spectra. In our spin-resolved photoemission experiments 4.65 and 6.20 eV photons were used. The same sample was used as for spin-integrated ARPES, requiring its transfer through air to another chamber. It was not subject to any cleaning prior to the SRPES measurements that lead to a reduction of the spin polarization as a consequence of the presence of a dead layer on the surface. Nevertheless the spin polarization close to EF reaches - 50% and -72% for 6.20 and 4.65 eV photons respectively. We conclude that Fe3O4 can be described within a band model and in particular that it is half-metallic. We also used femtosecond laser pulses in pump-probe experiments to investigate ultrafast dynamics on atomic scale. Our results show that the lifetime of excited electrons in Fe3O4 is much longer than in an “ordinary” metal. From the spin analysis of excited electrons, we deduce that the demagnetization does not occur in the femtosecond range, which is compatible with half-metallic properties of magnetite., La magnétite (Fe3O4) est un candidat prometteur pour des applications dans des dispositifs en spintronique. Ce ferrimagnétique avec une température de Curie élevée a été théoriquement prévu pour être un demi-métal avec un canal conducteur pour les spins minoritaire et un semi-conducteur pour les spins majoritaires, résultant en 100% de polarisation en spin au niveau de Fermi. Cependant, jusqu'à présent, aucune preuve expérimentale claire sur ce sujet n'a été faite. Cette thèse présente des études en photoémission résolue en angle et en spin sur la structure électronique et magnétique de couches minces de Fe3O4 (001) épitaxiées sur MgO(001) . Un calcul de la structure de bande utilisant l'approximation du gradient généralisé (GGA + U) est proposé pour expliquer les résultats expérimentaux. Bien que l'intensité de photémission au niveau de Fermi soit très faible en raison du rôle joué par les polarons, une dispersion de la bande Fe 3d-t2g est observée. Le comportement global de cette bande est en bon accord avec le calcul de la structure état électronique représentant état fondamental. Pour simuler les spectres de photoémission, nous avons utilisé l'approximation de l'électron libre à l'état final, tout en ignorant les éléments de matrice de la transition électronique. Dans la simulation, les bandes calculées sont convoluées respectivement par la lorentzienne et la gaussien pour tenir compte de la durée de vie et des effets de couplage électron-phonon. En intégrant l'intensité spectrale sur un intervalle d'énergie de 100 MeV au niveau de Fermi, nous avons obtenu la première preuve expérimentale de la surface de Fermi. Détermination de la polarisation de spin des électrons est un test ultime des calculs de bandes et des spectres de photoémission modélisés. Dans nos expériences de photoémission résolue en spin, nous avons utilisé des photons de 4.65 et 6.20 eV. Le même échantillon comme pour la photoémission intégré en spin a été mesuré, nécessitant son transfert par l'air dans une autre chambre. L'échantillons n'a pas été soumis à un nettoyage avant les mesures résolues en spin ce a conduit à une réduction de la polarisation en spin à cause de la présence d'une couche polluée sur la surface. Néanmoins, une polarisation de spin de - 50% et -72 % a été mesurée au voisinage de EF respectivement pour les photons de 6.20 et de 4.65 eV. Nous en concluons que Fe3O4 peuvent être décrits par un modèle de bande et en particulier qu'il est demi-métallique. Nous avons également utilisé des impulsions femtoseconde laser dans une expérience pompe-sonde pour étudier la dynamique ultra-rapide à l'échelle atomique. Nos résultats montrent que la durée de vie des électrons excités dans Fe3O4 est beaucoup plus longue que dans un métal «ordinaire». L'analyse de la polarisation en spin des électrons excités montre que la désaimantation ne se produit pas dans le domaine de la femtoseconde, ce qui est compatible avec des propriétés demi-métalliques de la magnétite .

Several aspects of half-metallic magnetism at finite temperature are discussed. Since NiMnSb is the simplest half-metal and the longest known it will be used as an example. Also it is a half-metal with remarkable little on-site Coulomb repulsion. Consequently it is a half-metal that is not notably corrupted by non-quasiparticle states. There exists an anomaly at 90 K, described before, that will be shown to be unrelated to the position of the Fermi level in the bandgap. Several substitutions are investigated that could shed some light on the origin of the transition. The calculated phonon spectrum is compared with experimental neutron scattering data. Finally, the spin-polarization of interfaces of NiMnSb with the transition metal based non-magnetic semiconductors NiTiSn and CoTiSb is investigated and the electronic structure of an infinite two-dimensional array of NiMnSb quantum dots embedded in NiScSb is reported.

The low-energy electronic excitations in cobalt are studied by a theoretical method that includes many-body effects and a realistic description of the band structure. Angle-resolved photoemission spectra measured on a thick film of hexagonal close-packed Co on Cu(111) agree well with calculated spectral functions. Because of many-body effects no sharp quasiparticle peaks exist for binding energies larger than $2\mathrm{eV}$ and in this energy region the spectrum is essentially incoherent. The many-body corrections are much stronger in the majority-spin channel and drastically affect the spin polarization of the spectra.

The role of on-site correlation in the low-energy excitations of nickel is studied by comparing the results of high-angular and high-energy resolution photoemission spectroscopy with quasiparticle states calculated as a three-body scattering solution of a multiorbital Hubbard model. It is found that correlation effects modify the energy dispersion and spin polarization of electron states and are essential in order to get a quantitative agreement with experimental data.

The 2p3d and 2p4d x-ray emission spectral shapes have been calculated using a theoretical description of spin-polarized 2p photoemission and atomic multiplet calculations of the 2p3d and 2p4d radiative decay. Emphasis is given to the use of circular-polarized x rays for the excitation process. Good agreement with experiment is found and all visible experimental structures can be explained. It is shown that because of weak multiplet effects in the intermediate state, it is possible to use the incoherent, two-step model. The angle between the emitted x rays and the magnetization is able to affect the magnetic circular dichroism (MCD) spectral shape observed, while the angle between the incident x ray and the magnetization only affects the intensity of the MCD.

In the photoemission process electrons are emitted from a solid upon excitation with UV light. From the measurement of their energy and momentum, angle-resolved photoemission spectroscopy (ARPES) allows to reconstruct the electronic properties of the solid. In addition, in spin-resolved ARPES the spin polarization P of the electrons is measured while maintaining energy and momentum resolution of ARPES, required to probe a dispersive state of a solid. The spin information is related to the spin polarization of the state under investigation, but can be modified during the photoemission process. Indeed, even when the electrons originate from a spin-degenerate initial state, they can acquire a finite P. This effect, ultimately due to a symmetry breaking in the experiment, occurs when different channels in the matrix elements describing the transition coherently interfere. In particular, P is related to the phase shift between the complex matrix elements associated to the interfering channels. This phase shift is also closely related to another quantity: the Eisenbud-Wigner-Smith (EWS) time delay. Despite the fundamental difficulties to properly define the concept of time in quantum mechanics, the EWS time delay, introduced to describe the electron scattering process, can be adapted to study the chronoscopy of photoemission. Nowadays, thanks to advances in laser technology, time-resolved spectroscopic techniques that reach attosecond resolution allow to measure relative EWS time delays between photoelectrons from different states. In this Thesis, an alternative indirect way to probe the photoemission process in the attosecond domain without time-resolved laser techniques will be presented. The link between P from dispersive states of a solid and the EWS time delay will be introduced. An analytical model will be discussed, where the dependence of P with binding energy is related to the EWS time delay of photoemission as a scattering process and the EWS time delay between the interfering channels. The first experimental determination of EWS time delays from dispersive states by SARPES will be also presented. Synchrotron radiation-based SARPES is the main technique used in this Thesis. Results for a single crystal of Cu(111) give EWS time delays of about 26 as for the free-electron-like sp bulk-derived band. The P of the d bands and of the 3p core levels of copper is also investigated. On the other hand, experiments on the strongly correlated cuprate superconductor BSCCO2212 show EWS time delays that are at least 3 times larger than in Cu(111). A double polarization feature is observed for the dispersive states, likely related to self-energy corrections in the photoemission process. Recent results on BSCCO2212 performed with laser-based SARPES will be also discussed. The results presented in this Thesis pave the way for a qualitatively new kind of information accessible by the SARPES technique, which is complementary to attosecond-resolved spectroscopies. The model presented sheds light on the spin polarization that is obtained by one-step model photoemission calculations, where the time information becomes also available. This approach could help to advance in the understandings of the physics of materials of interests, in particular electronic correlations, but also to better interpret the spin information experimentally obtained in SARPES, as well as to describe the basics of the quantum mechanics of the photoemission process itself.