Resolved Photoelectron Spectroscopy Research Articles

Cooperative interactions govern the fermiology of the polar metal Ca3Ru2O7

The antiferromagnetic Ruddlesden-Popper ruthenate Ca$_3$Ru$_2$O$_7$ is a model polar metal, combining inversion symmetry breaking with metallic conductivity; however, its low temperature ($T < 48$ K) crystal structure and Fermi surface topology remain ambiguous despite numerous measurements and theoretical studies. Here we perform both first principles calculations with static correlations and angle resolved photoelectron spectroscopy experiments to construct a complete model of Ca$_3$Ru$_2$O$_7$, reconciling inconsistencies among interpretations of electrical transport, thermopower measurements, and momentum- and energy-resolved band dispersions. The solution relies on treating the interplay among Coulomb repulsion, magnetic ordering, spin-orbit interactions, and the RuO$_6$ octahedral degrees-of-freedom on equal footing. For temperatures $30<T < 48$ K, we propose weak electron-electron interactions produce a symmetry-preserving metal-semimetal transition with Weyl nodes in proximity to the Fermi level, whereas a new orthorhombic $Pn2_1a$ structure emerges for $T<30$ K, exhibiting charge and spin density waves from enhanced Coulombic interactions.

High harmonic generation-2ω attosecond stereo-photoionization interferometry in N2

We have investigated photoionization delays in N2 by combining an extreme ultraviolet (XUV) attosecond pulse train generated by high harmonic generation (HHG) and a second harmonic femtosecond pulse with angularly resolved photoelectron spectroscopy. While photoionization delay measurements are usually performed by using a standard XUV-infrared scheme, here we show that the present approach allows us to separate electronic states that otherwise would overlap, thus avoiding the spectral congestion found in most molecules. We have found a relative delay between the X and A ionic molecular states as a function of the photon energy of up to 40 attoseconds, which is due to the presence of a shape resonance in the X channel. This approach can be applied to other small quantum systems with few active electronic states.

Distinct behavior of localized and delocalized carriers in anatase TiO2 (001) during reaction with O2

Two-dimensional (2D) metallic states induced by oxygen vacancies (${V}_{O}\mathrm{s}$) at oxide surfaces and interfaces provide opportunities for the development of advanced applications, but the ability to control the behavior of these states is still limited. We used angle resolved photoelectron spectroscopy combined with density-functional theory (DFT) to study the reactivity of ${V}_{O}$-induced states at the (001) surface of anatase ${\mathrm{TiO}}_{2}$, where both 2D metallic and deeper lying in-gap states (IGs) are observed. The 2D and IG states exhibit remarkably different evolutions when the surface is exposed to molecular ${\mathrm{O}}_{2}$: while IGs are almost completely quenched, the metallic states are only weakly affected. DFT calculations indeed show that the IGs originate from surface ${V}_{O}\mathrm{s}$ and remain localized at the surface, where they can promptly react with ${\mathrm{O}}_{2}$. In contrast, the metallic states originate from subsurface vacancies whose migration to the surface for recombination with ${\mathrm{O}}_{2}$ is kinetically hindered on anatase ${\mathrm{TiO}}_{2}$ (001), thus making them much less sensitive to oxygen dosing.

Vibrationally resolved photoelectron spectroscopy of oligothiophene radical anions.

Vibrationally resolved photoelectron spectroscopy of terthiophene, quaterthiophene, and quinquethiophene radical anions is presented. The increased spectral resolution afforded by the combination of slow photoelectron velocity-map imaging and ion cooling in a cryogenic ion trap allows the characterization of vibronic structures within the S0 and T1 states. Analysis of the spectra, aided by electronic structure calculations and Franck-Condon simulations, revealed evidence for significant contributions from kinetically trapped higher energy conformers in the anion-to-triplet transitions. Unlike the lowest energy structures, where all the thiophene linkers are in the trans configuration, these higher energy conformers contain at least one cis linker. We also found that the adiabatic Franck-Condon simulations drastically underestimated the intensities of some vibronic features in the singlet ground state spectra due to large geometry changes upon photodetachment and anharmonic couplings in the singlet state.

Excited state dynamics of CH2I2 and CH2BrI studied with UV pump VUV probe photoelectron spectroscopy.

We compare the excited state dynamics of diiodomethane (CH2I2) and bromoiodomethane (CH2BrI) using time resolved photoelectron spectroscopy. A 4.65 eV UV pump pulse launches a dissociative wave packet on excited states of both molecules and the ensuing dynamics are probed via photoionization using a 7.75 eV probe pulse. The resulting photoelectrons are measured with the velocity map imaging technique for each pump-probe delay. Our measurements highlight differences in the dynamics for the two molecules, which are interpreted with high-level ab initio molecular dynamics (trajectory surface hopping) calculations. Our analysis allows us to associate features in the photoelectron spectrum with different portions of the excited state wave packet represented by different trajectories. The excited state dynamics in bromoiodomethane are simple and can be described in terms of direct dissociation along the C-I coordinate, whereas the dynamics in diiodomethane involve internal conversion and motion along multiple dimensions.

Van der Waals integration of silicene and hexagonal boron nitride

Silicene, the silicon analogue of graphene, consists of an atomically buckled honeycomb lattice of silicon atoms. Theory predicts exceptional electronic properties, including Dirac fermions and a topological spin Hall insulator phase. An important obstacle impeding exploration of such properties in electronic devices is the chemical sensitivity of silicene, hampering its incorporation in layer stacks. Here we show experimentally that epitaxial silicene and hexagonal boron nitride (h-BN) can be stacked without perturbing the electronic properties of silicene. Intercalated silicene underneath epitaxial h-BN on ZrB2(0 0 0 1) substrate films is obtained by depositing Si atoms at room temperature. Using (angle resolved) photoelectron spectroscopy (ARPES, PES) and scanning tunneling microscopy (STM) we find that the intercalated silicene exhibits the same electronic properties as epitaxial silicene on ZrB2, while it resists oxidation in air up to several hours. This is an essential step towards the development of layer stacks that allow for fabrication of devices.

Signatures of Quantum Transport Steps in Bi2Se3 Single Crystal

We report signatures of quantum magneto transport steps in a Bi2Se3 single crystal. The Bi2Se3 crystal is grown by self-flux method through solid-state reaction. Details of its structural analysis along with physical properties in terms of low temperature and high field transport, thermal (heat capacity), Raman, X-ray photo electron and angle resolved photo electron spectroscopy were reported earlier (J. Sup. Novel. Mag. 30, 2031 2017). In a present short letter, we show the details of its 2 K and up to 14 Tesla magneto transport, exhibiting quantum transport (QT) like steps above say 11 Tesla field. The possible QT steps cannot be modelled with the SdH (Shubnikov-de Haas) or other possible quantum oscillations. The observed QT like steps are possibly the result of the mixed out-of-plane Rxy(H) and in-plane Rxx(H) contributions from the misaligned [00l] planes of the studied crystal and this may happen with other studied topological insulator (TI) crystals as well. Our careful assessment of crystal XRD data shows the same.

Angle resolved photoelectron spectroscopy as applied to X-ray mirrors: an in depth study of Mo/Si multilayer systems.

We present an approach adapted to study the interface (composition and extension) of X-ray multilayer mirrors using angle resolved photoelectron spectroscopy (ARXPS). In the approach we rely on the concept of the average effective attenuation length (EAL) of the photoelectron and not on the inelastic mean free path (IMPF), which allows us to take into account the contribution of elastically scattered electrons and to increase the accuracy of the determined thickness of the layers. We apply the developed approach to study the formation of interfaces in a multilayer periodic Mo/Si mirror. The chemical composition and significance of the interfaces depending on the number of periods were investigated by means of the ARXPS spectra decomposition technique. Formation of a molybdenum silicide MoSi2 at the interfaces was revealed. It was shown that molybdenum silicide with different thicknesses is formed at the interfaces depending on the film order. In addition, it was established that increasing the period number of the [Mo/Si] system leads to a decrease of the interface extension.

Delicate interactions of PTCDI molecules on Ag/Si(111)-3×3

PTCDI molecules were evaporated onto a Ag/Si(111) surface and studied using scanning tunneling microscopy (STM) and angular resolved ultraviolet photoelectron spectroscopy (ARUPS). High resolution STM images are used to identify the delicate molecule/molecule and molecule/substrate interactions and the shapes of the molecular orbitals. The results show that the substrate/molecule interaction strongly modifies the electronic configuration of the molecules as their orbital shapes are quite different at 1 and 2 monolayer (ML) coverage. Simple models of molecular HOMO/LUMO levels and intermolecular hydrogen-bondings have been made for 1 and 2 ML PTCDI coverages to explain the STM images. Changes due to the interaction with the substrate are also found in ARUPS as extra states above the regular HOMO level at 1 ML PTCDI coverage. The ARUPS data also show that the electronic structure of the substrate remains unchanged after the deposition of molecules as the dispersion of the substrate related bands is unchanged. The changes in electronic structure of the molecules are discussed based on a HOMO/LUMO split.

Temperature dependent percolation mechanism for conductivity in TiO3 revealed by a microstructure study

We have performed optical microscopy, micro-photoelectron spectroscopy, and micro-Raman scattering measurements on TiO3 single crystals in order to clarify the interplay between the microstructure and the temperature dependent electronic transport mechanisms in this material. Optical microscopy observations reveal dark and bright domain patterns on the surface with length scales of the order of several to a hundred micrometers showing a pronounced temperature dependent evolution. Spatially resolved photoelectron spectroscopy measurements show the different electronic character of these domains. Using micro-Raman spectroscopy, we observe a distinct temperature dependence of the crystal structure of these domains. On the basis of these findings the different domains are assigned to insulating and metallic volume fractions, respectively. By decreasing the temperature, the volume fraction of the conducting domains increases, hence allowing the electrons to percolate through the sample at temperatures lower than ∼150 K.

Rigid valence band shift due to molecular surface counter-doping of MoS2

Adsorption of the acceptor material tetracyanoquinodimethane can control optoelectronic properties of MoS2 by accepting defect generated excess negative charge from the surface that would otherwise interfere with radiative decay processes. Angle Resolved Photoelectron Spectroscopy measurements show that the MoS2 band structure near the Γ point shifts rigidly upward by ∼0.2 eV for a complete surface coverage of acceptor species as expected for an upward Fermi level shift due to charge transfer to the TCNQ. The molecular adsorbate orbitals visible in photoemission are indicative of an anionic species, consistent with interfacial charge transfer but without evidence for hybrid states arising from covalent adsorbate-surface interactions. Thus, our interface studies support the notion that molecular adsorbates are a useful tool for controlling optoelectronic functionality in 2D materials without fundamentally modifying their favorable band structures.

Fundamentally fastest optical processes at the surface of a topological insulator

We predict that a single oscillation of a strong optical pulse can significantly populate the surface conduction band of a three-dimensional topological insulator, Bi2Se3. Both linearly- and circularly-polarized pulses generate chiral textures of interference fringes of population in the surface Brillouin zone. These fringes constitute a self-referenced electron hologram carrying information on the topology of the surface Bloch bands, in particular, on the effect of the warping term of the low-energy Hamiltonian. These electron-interference phenomena are in a sharp contrast to graphene where there are no chiral textures for a linearly-polarized pulse and no interference fringes for circularly-polarized pulse. These predicted reciprocal space electron-population textures can be measured experimentally by time resolved angle resolved photoelectron spectroscopy (TR-ARPES) to gain direct access to non-Abelian Berry curvature at topological insulator surfaces.

Anion photoelectron spectroscopy and chemical bonding of ThO2- and ThO3.

We conducted a study of electronic structures and chemical bonding of gaseous ThO2- and ThO3- using velocity-map imaging and ab initio calculations. The electron affinity of neutral ThO2 molecule is reported for the first time with the value of 1.21(5) eV. We obtained a vibrationally resolved photoelectron spectroscopy of ThO2- and observed the symmetric stretching frequency of 824(40) cm-1 for neutral molecules. One hot band transition is observed in the spectrum of ThO2-, which allows the measurement of symmetric stretching mode for ThO2-. The ground state of ThO2- is 2A1 with C2v symmetry: the detachment of an electron from the singly occupied molecular orbital (SOMO) results in the ground state of ThO2. Kohn-Sham molecular orbital analyses reveal an σ and two weak π bonds for Th-O multiple bonds in ThO2. Global minimum search methodology combined with quantum chemical calculations are used to find the minima of ThO3 and ThO3-, and the adiabatic detachment energy of ThO3- is calculated to be 3.26 eV at the coupled cluster with singles and doubles plus perturbative triples level. Our theoretical calculations suggest that the ground state of ThO3 is 1A' with a symmetry of Cs, while the most stable ThO3- is 2A1 with C2v symmetry; thus, the transition from ThO3- to ThO3 undergoes a significant geometry reorganization. Molecular orbital analyses suggest that the SOMO of ThO3- is mainly participated by O 2p and O to Th back donation was found in HOMO-2 molecular orbital. This investigation will shed some light on the understanding of covalent bonding in Th-contained molecules.

Spatially Resolved Photoelectron Spectroscopy from Ultra-high Vacuum to Near Ambient Pressure Sample Environments

Modern scanning photoemission microscopes use zone plates to de-magnify the X-ray beam to nanometer size allowing spatially resolved XPS analysis of materials relevant in nanotechnology. So far these microscopes have been designed to operate in the ultra-high or high vacuum environments as all XPS systems; but at the beginning of this century the dream of K. Siegbahn, the inventor of XPS, to use it in the near ambient or ambient pressure regimes became a reality. Despite the fast development and spread of these setups designed for not spatially resolved experiments, now available both as synchrotron and laboratory facilities, it took more than a decade before a similar result could be extended to photoemission microscopy. The scanning photoemission microscope at Elettra is the first instrument where near ambient pressure conditions for in operando analysis can be fulfilled. This paper shows some recent results obtained at this microscope at different sample environment conditions.

The adsorption geometry and molecular self-assembly of graphene for 1,3,5-triphenylbenzene on Cu(111)

Electronic structures and adsorption geometry of 1,3,5-triphenylbenzene (TPB) on the Cu(111) surface, and followed by formation of graphene nano flakes (GNFs) upon annealing the sample were investigated by using angle resolved ultraviolet photoelectron spectroscopy (ARUPS) and density functional theory (DFT) calculations. The emission features d, e and f originated from TPB molecule at a coverage of 1.3 monolayer (ML) in UPS spectra are located at 4.65 eV, 6.76 eV and 8.57 eV below Fermi level, and the decrease of the work function upon increasing of TPB coverage on Cu(111) is attributed to the interfacial dipole formed between the adsorbate and the substrate. Formation of GNFs upon annealing of TPB overlayer on Cu(111) is approved by appearance of new features g, h, i, j and k originating from GNFs, and located at 1.09, 4.97, 6.64, 9.23 and 11.23 eV below Fermi level. The ARUPS measurements and DFT calculations indicate that both TPB molecules and GNFs planes are nearly parallel to the Cu(111) substrate in the monolayer regime. Most importantly, the results show that, with decreasing of the coverage of TPB as precursor, the formation of GNFs, or graphitization temperature can be decreased down to 350 °C, indicating the crucial influence of intermolecular interaction on the dehydrogenation process.

Probing band parity inversion in the topological insulator GeBi2Te4 by linear dichroism in ARPES

Here we report on experiments performed by linear-dichroism angle resolved photoelectron spectroscopy (LD-ARPES) on septuple layers (SL) topological insulator GeBi2Te4. The linear dichroic signals, both for the valence band states and in the topologically protected surface state are interpreted as a probe of the symmetry of the states. The observation of a change in the LD-ARPES spectrum at the top of VB is attributed to the band parity inversion which is predicted by theory for all materials entering the topologically protected phase. Finally, the opening of a gap in the surface state dispersion along the non-high symmetry direction is reported. This is proposed to originated from the interaction between the surface state and the VB, leading to the formation of surface resonances.

Massless Dirac Fermions in ZrTe2 Semimetal Grown on InAs(111) by van der Waals Epitaxy.

Single and few layers of the two-dimensional (2D) semimetal ZrTe2 are grown by molecular beam epitaxy on InAs(111)/Si(111) substrates. Excellent rotational commensurability, van der Waals gap at the interface and moiré pattern are observed indicating good registry between the ZrTe2 epilayer and the substrate through weak van der Waals forces. The electronic band structure imaged by angle resolved photoelectron spectroscopy shows that valence and conduction bands cross at the Fermi level exhibiting abrupt linear dispersions. The latter indicates massless Dirac Fermions which are maintained down to the 2D limit suggesting that single-layer ZrTe2 could be considered as the electronic analogue of graphene.

Investigation of the atomic and electronic structures of highly ordered two-dimensional germanium on Au(111)

Low energy electron diffraction (LEED), scanning tunneling microscopy (STM), and photoelectron spectroscopy have been used to study an ordered structure formed by Ge atoms deposited onto the Au(111) surface. Based on a careful analysis of STM images and LEED patterns, we propose a new unit cell for the atomic structure of the Ge layer. Core level data indicate that some Ge atoms diffuse into the Au(111) crystal during annealing after deposition at room temperature. This is further corroborated by angle resolved photoelectron spectroscopy measured for different amounts of Ge remaining after sputtering and annealing. The results of the ARPES study clearly exclude the interpretation, in the literature, of a parabolic band as part of a Dirac cone of germanene.

Enhanced ultrafast relaxation rate in the Weyl semimetal phase of MoTe2 measured by time- and angle-resolved photoelectron spectroscopy

$\mathrm{MoTe_2}$ has recently been shown to realize in its low-temperature phase the type-II Weyl semimetal (WSM). We investigated by time- and angle- resolved photoelectron spectroscopy (tr-ARPES) the possible influence of the Weyl points in the electron dynamics above the Fermi level $\mathrm{E_F}$, by comparing the ultrafast response of $\mathrm{MoTe_2}$ in the trivial and topological phases. In the low-temperature WSM phase, we report an enhanced relaxation rate of electrons optically excited to the conduction band, which we interpret as a fingerprint of the local gap closure when Weyl points form. By contrast, we find that the electron dynamics of the related compound $\mathrm{WTe_2}$ is slower and temperature-independent, consistent with a topologically trivial nature of this material. Our results shows that tr-ARPES is sensitive to the small modifications of the unoccupied band structure accompanying the structural and topological phase transition of $\mathrm{MoTe_2}$.

Amorphous carbon nanocomposite films doped by titanium: Surface and sub-surface composition and bonding

Hydrogen free Ti-doped amorphous carbon layers were prepared by dual beam pulsed laser deposition using two excimer lasers. The air-exposed surfaces were analyzed by high-energy resolved and angular-resolved core-level photoelectron spectroscopy, and were then step-by-step sputtered with an argon gas cluster ion beam (ArGCIB), which is known to be a very gentle technique with respect to changes in surface chemistry. The results show that the top surface of the sample and its sub-surface region differ in composition and in bonding. The top surface is enriched by oxygen-bearing species. Carbon-bearing species located on the surface are mostly in sp3 hybridization. Titanium carbide clusters, TiC, are not directly exposed at the surface. They are embedded in a carbon network with dominating C sp2 hybridization. Their interface is formed by a distinct carbon-rich titanium carbide with stoichiometry close to TiC3. The surface damage induced by ArGCIB was found to be minimal, verifiably affecting carbon atoms in the carbon network.