Cu$_2$O has appealing properties as an electrode for photo-electrochemical water splitting, yet its practical performance is severely limited by inefficient charge extraction at the interface. Using hybrid DFT calculations, we investigate carrier capture processes by oxygen vacancies (V$_\mathrm{O}$) in the experimentally observed ($\sqrt{3} \times \sqrt{3}$)R30$^{\circ}$ reconstruction of the dominant (111) surface. Our results show that these V$_\mathrm{O}$ are doubly ionized and that associated defects states strongly suppress electron transport. In particular, the excited electronic state of a singly charged V$_\mathrm{O}$ plays a crucial role in the non-radiative electron capture process with a capture coefficient of about 10$^{-9}$~cm$^3$/s and a lifetime of 0.04~ps, explaining the experimentally observed ultrafast carrier relaxation. These results highlight that engineering the surface V$_\mathrm{O}$ chemistry will be a crucial step in optimizing Cu$_2$O for photoelectrode applications.

Chiara Ricca Lisa Grad Matthias Hengsberger Jürg Osterwalder Ulrich Aschauer

Understanding and control of spin degrees of freedom on the surfaces of topological materials are key to future applications as well as for realizing novel physics such as the axion electrodynamics associated with time-reversal (TR) symmetry breaking on the surface. We experimentally demonstrate magnetically induced spin reorientation phenomena simultaneous with a Dirac-metal to gapped-insulator transition on the surfaces of manganese-doped Bi2Se3 thin films. The resulting electronic groundstate exhibits unique hedgehog-like spin textures at low energies, which directly demonstrate the mechanics of TR symmetry breaking on the surface. We further show that an insulating gap induced by quantum tunnelling between surfaces exhibits spin texture modulation at low energies but respects TR invariance. These spin phenomena and the control of their Fermi surface geometrical phase first demonstrated in our experiments pave the way for the future realization of many predicted exotic magnetic phenomena of topological origin.

Su-Yang Xu Madhab Neupane Chang Liu Duming Zhang Anthony Richardella L. Andrew Wray Nasser Alidoust Mats Leandersson Thiagarajan Balasubramanian Jaime Sánchez-Barriga Oliver Rader Gabriel Landolt Bartosz Slomski Jan Hugo Dil Jürg Osterwalder Tay-Rong Chang Horng-Tay Jeng Hsin Lin Arun Bansil Nitin Samarth M. Zahid Hasan

We identify the multi-layered compound GeBi4Te7 to be a topological insulator with a freestanding Dirac point, slightly above the valence band maximum, using angle-resolved photoemission spectroscopy (ARPES) measurements. The spin polarization satisffies the time reversal symmetry of the surface states, visible in spin-resolved ARPES. For increasing Sb content in GeBi(4-x)SbxTe7 we observe a transition from n- to p-type in bulk sensitive Seebeck coefficient measurements at a doping of x = 0.6. In surface sensitive ARPES measurements a rigid band shift is observed with Sb doping, accompanied by a movement of the Dirac point towards the Fermi level. Between x = 0.8 and x = 1 the Fermi level crosses the band gap, changing the surface transport regime. This difference of the n- to p-type transition between the surface region and the bulk is caused by band bending effects which are also responsible for a non-coexistence of insulating phases in the bulk and in the near surface region.

Stefan Muff Fabian von Rohr Gabriel Landolt Bartosz Slomski Andreas Schilling Robert J. Cava Jürg Osterwalder J. Hugo Dil

We study the fate of the surface states of Bi$_2$Se$_3$ under disorder with strength larger than the bulk gap, caused by neon sputtering and nonmagnetic adsorbates. We find that neon sputtering introduces strong but dilute defects, which can be modeled by a unitary impurity distribution, whereas adsorbates, such as water vapor or carbon monoxide, are best described by Gaussian disorder. Remarkably, these two disorder types have a dramatically different effect on the surface states. Our soft x-ray ARPES measurements combined with numerical simulations show that unitary surface disorder pushes the Dirac state to inward quintuplet layers, burying it below an insulating surface layer. As a consequence, the surface spectral function becomes weaker, but retains its quasiparticle peak. This is in contrast to Gaussian disorder, which smears out the quasiparticle peak completely. At the surface of Bi$_2$Se$_3$, the effects of Gaussian disorder can be reduced by removing surface adsorbates using neon sputtering, which, however, introduces unitary scatterers. Since unitary disorder has a weaker effect than Gaussian disorder, the ARPES signal of the Dirac surface state becomes sharper upon sputtering.

Raquel Queiroz Gabriel Landolt Stefan Muff Bartosz Slomski Thorsten Schmitt Vladimir N. Strocov Jianli Mi Bo Brummerstedt Iversen Philip Hofmann Jürg Osterwalder Andreas P. Schnyder J. Hugo Dil

Irradiation of a sharp tungsten tip by a femtosecond laser and exposed to a strong DC electric field led to gradual and reproducible surface modifications. By a combination of field emission microscopy and scanning electron microscopy, we observed asymmetric surface faceting with sub-ten nanometer high steps. The presence of well pronounced faceted features mainly on the laser-exposed side implies that the surface modification was driven by a laser-induced transient temperature rise -- on a scale of a couple of picoseconds -- in the tungsten tip apex. Moreover, we identified the formation of a nano-tip a few nanometers high located at one of the corners of a faceted plateau. The results of simulations emulating the experimental conditions, are consistent with the experimental observations. The presented conditions can be used as a new method to fabricate nano-tips of few nm height, which can be used in coherent electron pulses generation. Besides the direct practical application, the results also provide insight into the microscopic mechanisms of light-matter interaction. The apparent growth mechanism of the features may also help to explain the origin of enhanced electron field emission, which leads to vacuum arcs, in high electric-field devices such as radio-frequency particle accelerators.

Hirofumi Yanagisawa Vahur Zadin Karsten Kunze Christian Hafner Alvo Aabloo Dong Eon Kim Matthias F. Kling Flyura Djurabekova Jürg Osterwalder Walter Wuensch

The adsorption of molecules on surfaces affects the surface dipole and thus changes in the work function may be expected. The effect in change of work function is particularly strong if charge between substrate and adsorbate is involved. Here we report the deposition of a strong electron acceptor molecule, tetrafluorotetracyanoquinodimethane C$_{12}$F$_4$N$_4$ (F$_{4}$TCNQ) on a monolayer of hexagonal boron nitride nanomesh ($h$-BN on Rh(111)). The work function of the F$_{4}$TCNQ/$h$-BN/Rh system increases upon increasing molecular coverage. The magnitude of the effect indicates electron transfer from the substrate to the F$_{4}$TCNQ molecules. Density functional theory calculations confirm the work function shift and predict doubly charged F$_{4}$TCNQ$^{2-}$ in the nanomesh pores, where the $h$-BN is closest to the Rh substrate, and to have the largest binding energy there. The preferred adsorption in the pores is conjectured from a series of ultraviolet photoelectron spectroscopy data, where the $\sigma$ bands in the pores are first attenuated. Scanning tunneling microscopy measurements indicate that F$_{4}$TCNQ molecules on the nanomesh are mobile at room temperature, as "hopping" between neighboring pores is observed.

Huanyao Cun Ari Paavo Seitsonen Silvan Roth Silvio Decurtins Shi-Xia Liu Jürg Osterwalder Thomas Greber

Orbital tomography has recently been established as a technique to reconstruct molecular orbitals directly from photoemission data using iterative phase retrieval algorithms. In this work, we present a detailed description of steps for processing of the photoemission data followed by an improved iterative phase retrieval procedure and the interpretation of reconstructed two-dimensional orbital distributions. We address the issue of background subtraction by suggesting a signal restoration routine based on the maximization of mutual information algorithm and solve the problem of finding the geometrical center in the reconstruction by using a tight-centered object support in a two-step phase retrieval procedure. The proposed image processing and improved phase retrieval procedures are used to reconstruct the highest occupied molecular orbital of pentacene on Ag(110), using photoemission data only. The results of the reconstruction agree well with the density functional theory simulation, modified to comply with the experimental conditions. By comparison with photoelectron holography, we show that the reconstructed two-dimensional orbital distribution can be interpreted as a superposition of the in-focus orbital distribution evaluated at the z = 0 plane and out-of-focus distributions evaluated at other z = const planes. Three-dimensional molecular orbital distributions could thus be reconstructed directly from two-dimensional photoemission data, provided the axial resolution of the imaging system is high enough.

Pavel Kliuiev Tatiana Latychevskaia Giovanni Zamborlini Matteo Jugovac Christian Metzger Manuel Grimm Achim Schöll Jürg Osterwalder Matthias Hengsberger Luca Castiglioni

Hydrogen as a fuel plays a crucial role in driving the transition to net zero greenhouse gas emissions. To realise its potential, obtaining a means of efficient storage is paramount. One solution is using metal hydrides, owing to their good thermodynamical absorption properties and effective hydrogen storage. Although metal hydrides appear simple compared to many other energy materials, understanding the electronic structure and chemical environment of hydrogen within them remains a key challenge. This work presents a new analytical pathway to explore these aspects in technologically relevant systems using Hard X-ray Photoelectron Spectroscopy (HAXPES) on thin films of two prototypical metal dihydrides: YH$_{2-\delta}$ and TiH$_{2-\delta}$. By taking advantage of the tunability of synchrotron radiation, a non-destructive depth profile of the chemical states is obtained using core level spectra. Combining experimental valence band spectra collected at varying photon energies with theoretical insights from density functional theory (DFT) calculations, a description of the bonding nature and the role of d versus sp contributions to states near the Fermi energy are provided. Moreover, a reliable determination of the enthalpy of formation is proposed by using experimental values of the energy position of metal s band features close to the Fermi energy in the HAXPES valence band spectra.

Curran Kalha Laura E. Ratcliff Giorgio Colombi Christoph Schlueter Bernard Dam Andrei Gloskovskii Tien-Lin Lee Pardeep K. Thakur Prajna Bhatt Yujiang Zhu Jürg Osterwalder Francesco Offi Giancarlo Panaccione Anna Regoutz

We present a spacetime diffeomorphism invariant formulation of the geodesic approximation to soliton dynamics.

Jürg Käppeli

The mathematical axiom systems for quantum field theory grew out of Hilbert's sixth problem, that of stating the problems of quantum theory in precise mathematical terms. There have been several competing mathematical systems of axioms, and here we shall deal with those of A.S. Wightman and of K. Osterwalder and R. Schrader, stated in historical order. They are centered around group symmetry, relative to unitary representations of Lie groups in Hilbert space. We also mention how the Osterwalder--Schrader axioms have influenced the theory of unitary representations of groups.

Palle E. T. Jorgensen Gestur Ólafsson