arXiv subjects

Giovanni Zamborlini

Publications and source records attributed to Giovanni Zamborlini.

13 recordsLinked to original sources

arXiv2026

Circular dichroism in the photoelectron angular distribution of achiral molecules

Circular dichroism in the angular distribution (CDAD) is the effect that the angular intensity distribution of photoemitted electrons depends on the handedness of the incident circularly polarized light. A CDAD may arise from intrinsic material properties like chirality, spin-orbit interaction, or quantum-geometrical effects on the electronic structure. In addition, CDAD has also been reported for achiral organic molecules at the interface to metallic substrates. For this latter case, we investigate two prototypical $π$-conjugated molecules, namely tetracene and pentacene, whose frontier orbitals have a similar shape but exhibit distinctly different symmetries. By comparing experimental CDAD momentum maps with simulations within time-dependent density functional theory, we show how the final state of the photoelectron must be regarded as the source of the CDAD in such otherwise achiral systems. We gain additional insight into the mechanism by employing a simple scattering model for the final state, which allows us to decompose the CDAD signal into partial wave contributions.

cond-mat.mtrl-sci↗

arXiv2026

Bottom-up realization of a type-II organic-TMD heterointerface: Pentacene on monolayer WS2

Stacked van der Waals heterostructures based on transition metal dichalcogenides (TMDs) exhibit a rich variety of exotic interfacial phenomena. Substituting one component with an organic semiconductor (OSC) enables the design of hybrid heterostructures with tunable functionalities for optoelectronic, photovoltaic, and spintronic applications. In this work, exploiting scanning tunneling spectroscopy (STS), photoemission orbital tomography (POT) and G0W0 electronic structure calculations, we experimentally and theoretically demonstrate the self-assembly of an ordered single layer of pentacene (5A) above monolayer WS2, exhibiting a type-II (staggered) band alignment in the hybrid 5A/WS2 interface. Central to this result is the synthesis of extended, atomically flat WS2 - an essential prerequisite for a highly ordered and electronically homogeneous OSC/TMD interface - which can only be reliably achieved via bottom-up growth, most notably molecular beam epitaxy (MBE). We realize this by leveraging Au(111) as an atomically clean and conductive sample for epitaxial growth - a necessary requirement for reliable and comparable STS/POT characterizations. The high quality of the synthesized heterostructure, together with its type-II band alignment, establishes pentacene/WS2 as a model system for orbital-resolved studies of charge transfer, energy-level renormalization, and non-equilibrium interfacial processes in hybrid organic-inorganic-2D heterostructures.

cond-mat.mtrl-sci↗

arXiv2024

Giant Rashba-Splitting of One-Dimensional Metallic States in Bi Dimer Lines on InAs(100)

Bismuth produces different types of ordered superstructures on the InAs(100) surface, depending on the growth procedure and coverage. The (2x1) phase forms at completion of a Bi monolayer and consists of a uniformly oriented array of parallel lines of Bi dimers. Scanning tunneling and core level spectroscopies demonstrate its metallic character, in contrast with the semiconducting properties expected on the basis of the electron counting principle. The weak electronic coupling among neighboring lines gives rise to quasi one-dimensional Bi-derived bands with open contours at the Fermi level. Spin- and angle-resolved photoelectron spectroscopy reveals a giant Rashba splitting of these bands, in good agreement with ab-initio electronic structure calculations. The very high density of the dimer lines, the metallic and quasi one-dimensional band dispersion and the Rashba-like spin texture make the Bi/InAs(100)-(2x1) phase an intriguing system, where novel transport regimes can be studied.

cond-mat.mtrl-sci↗

arXiv2024

Tracing d-d transitions in FePS$_{3}$ on ultrafast time scales

Excitations between localized 3d states of transition metal ions within crystalline solids, commonly known as d-d transitions, play a pivotal role in diverse phenomena across solid state physics, materials science, and chemistry. These transitions contribute to the coloration in transition metal oxides, catalytic processes on oxide surfaces, and high-temperature superconductivity. They also couple optical excitation to quantized collective phenomena such as phonons and magnons in magnetic systems. Until now, an experimental method to unravel the complex quasiparticle dynamics associated with d-d transitions has remained elusive. We bridge this gap by demonstrating that d-d transitions can be distinctly traced in momentum space and time using time- and angle-resolved photoelectron spectroscopy (trARPES). Through this approach, we can assign specific momentum-dependent characteristics and elucidate the decay mechanisms of specific d-d transitions in FePS$_{3}$, a two-dimensional van der Waals antiferromagnet with a rich array of quantum phenomena stemming from d-d transitions. This study pioneers the use of ARPES in probing the dynamics of d-d transitions across a wide spectrum of solid-state systems.

cond-mat.mtrl-sci↗

arXiv2023

Metalloporphyrins on Oxygen-Passivated Iron: Conformation and Order Beyond the First Layer

On-surface metal porphyrins can undergo electronic and conformational changes that play a crucial role in determining the chemical reactivity of the molecular layer. Therefore, understanding those properties is pivotal for the design and implementation of organic-based devices. Here, by means of photoemission orbital tomography supported by density functional theory calculations, we investigate the electronic and geometrical structure of two metallated tetraphenyl porphyrins (MTPPs), namely ZnTPP and NiTPP, adsorbed on the oxygen-passivated Fe(100)-p(1x1)O surface. Both molecules weakly interact with the surface as no charge transfer is observed. In the case of ZnTPP our data correspond to those of moderately distorted molecules, while NiTPP exhibits a severe saddle-shape deformation. From additional experiments on NiTPP multilayer films, we conclude that this distortion is a consequence of the interaction with the substrate, as the NiTPP macrocycle of the second layer turns out to be flat. We further find that distortions in the MTPP macrocycle are accompanied by an increasing energy gap between the highest occupied molecular orbitals (HOMO and HOMO-1). Our results demonstrate that photoemission orbital tomography can simultaneously probe the energy level alignment, the azimuthal orientation, and the adsorption geometry of complex aromatic molecules even in the multilayer regime.

cond-mat.mtrl-sci↗

arXiv2022

Dirac bands in the topological insulator Bi2Se3 mapped by time-resolved momentum microscopy

We have studied the energy dispersion of the Dirac bands of the topological insulator Bi2Se3 at large parallel momenta using a setup for laser-based time-resolved momentum microscopy with 6 eV probe-photons. Using this setup, we can probe the manifold of unoccupied states up to higher intermediate-state energies in a wide momentum window. We observe a strongly momentum-dependent evolution of the topologically protected Dirac states into a conduction band resonance, highlighting the anisotropy dictated by the surface symmetry. Our results are in remarkable agreement with the theoretical surface spectrum obtained from a GW-corrected tight-binding model, suggesting the validity of the approach in the prediction of the quasiparticle excitation spectrum of large systems with non-trivial topology. After photoexcitation with 0.97 eV photons, assigned to a bulk valence band-conduction band transition, the out-of-equilibrium population of the surface state evolves on a multi-picosecond time scale, in agreement with a simple thermodynamical model with a fixed number of particles, suggesting a significant decoupling between bulk and surface states.

cond-mat.mtrl-sci↗

arXiv2022

Link between Weyl-fermion chirality and spin texture

Topological semimetals have recently attracted great attention due to prospective applications governed by their peculiar Fermi surfaces. Weyl semimetals host chiral fermions that manifest as pairs of non-degenerate massless Weyl points in their electronic structure, giving rise to novel macroscopic quantum phenomena such as the chiral anomaly, an unusual magnetoresistance, and various kinds of Hall effects These properties enable the engineering of non-local electric transport devices, magnetic sensors and memories, and spintronics devices. Nevertheless, little is known about the underlying spin- and orbital-degrees of freedom of the electron wave functions in Weyl semimetals, that govern the electric transport. Here, we give evidence that the chirality of the Weyl points in the Type-II Weyl semimetal MoTe$_2$ is directly linked to the spin texture and orbital angular momentum of the electron wave functions. By means of state-of-the-art spin- and momentum-resolved photoemission spectroscopy the spin- and orbital texture in the Fermi surface is directly resolved. Supported by first-principles calculations, we examined the relationship between the topological chiral charge and spin texture, which significantly contributes to the understanding of the electronic structure in topological quantum materials.

cond-mat.mtrl-sci↗

arXiv2020

Evaluation of molecular orbital symmetry via oxygen-induced charge transfer quenching at a metal-organic interface

Thin molecular films under model conditions are often exploited as benchmarks and case studies to investigate the electronic and structural changes occurring on the surface of metallic electrodes. Here we show that the modification of a metallic surface induced by oxygen adsorption allows the preservation of the geometry of a molecular adlayer, giving access to the determination of molecular orbital symmetries by means of near-edge x-ray absorption fine structure spectroscopy, NEXAFS. As a prototypical example, we exploited Nickel Tetraphenyl Porphyrin molecules deposited on a bare and on an oxygen pre-covered Cu(100) surface. We find that adsorbed atomic oxygen quenches the charge transfer at the metal-organic interface but, in contrast to a thin film sample, maintains the ordered adsorption geometry of the organic molecules. In this way, it is possible to disentangle π* and σ* symmetry orbitals, hence estimating the relative oscillator strength of core level transitions directly from the experimental data, as well as to evaluate and localize the degree of charge transfer in a coupled system. In particular, we neatly single out the σ* contribution associated with the N 1s transition to the mixed N 2px,y-Ni 3dx2-y2 orbital, which falls close to the leading π*-symmetry LUMO resonance.

cond-mat.mtrl-sci↗

arXiv2020

Molecular anchoring stabilizes low valence Ni(I)TPP on copper against thermally induced chemical changes

Many applications of molecular layers deposited on metal surfaces, ranging from single-atom catalysis to on-surface magnetochemistry and biosensing, rely on the use of thermal cycles to regenerate the pristine properties of the system. Thus, understanding the microscopic origin behind the thermal stability of organic/metal interfaces is fundamental for engineering reliable organic-based devices. Here, we study nickel porphyrin molecules on a copper surface as an archetypal system containing a metal center whose oxidation state can be controlled through the interaction with the metal substrate. We demonstrate that the strong molecule-surface interaction, followed by charge transfer at the interface, plays a fundamental role in the thermal stability of the layer by rigidly anchoring the porphyrin to the substrate. Upon thermal treatment, the molecules undergo an irreversible transition at 420 K, which is associated with an increase of the charge transfer from the substrate, mostly localized on the phenyl substituents, and a downward tilting of the latters without any chemical modification

cond-mat.mtrl-sci↗

arXiv2020

Signatures of an Atomic Crystal in the Band Structure of a Molecular Thin Film

Transport phenomena in molecular materials are intrinsically linked to the orbital character and the degree of localization of the valence states. Here, we combine angle-resolved photoemission with photoemission tomography to determine the spatial distribution of all molecular states of the valence band structure of a C$_{60}$ thin film. While the two most frontier valence states exhibit a strong band dispersion, the states at larger binding energies are characterized by distinct emission patterns in energy and momentum space. Our findings demonstrate the formation of an atomic crystal-like band structure in a molecular solid with delocalized $π$-like valence states and strongly localized $σ$-states at larger binding energies.

cond-mat.mes-hall↗

arXiv2018

Algorithms and image formation in orbital tomography

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.

physics.chem-ph↗

arXiv2018

Localized segregation of gold in ultra-thin Fe films on Au(001)

The growth of up to 10 monolayer-thick Fe films on a Au(001) surface was investigated during deposition at room temperature and during annealing using low-energy electron diffraction and x-ray photoemission spectroscopy as well as locally with low-energy electron microscopy and photoemission electron microscopy. The growth proceeds with a submonolayer of Au segregating to the surface of Fe, which is in agreement with previous studies. Annealing was found to be critical for the presence of Au on the Fe surface. Our findings show that Au segregation proceeds by the formation of cracks in the Fe film, starting at the annealing temperature of 190 °C, through which Au diffuses towards the surface. We explain the localized Au segregation with a shadowing effect due to the oblique deposition geometry. As a result, an Fe film with significantly improved roughness, but covered with a Au overlayer, is obtained. This study shows the necessity to employ spatially-resolved techniques to fully understand the growth modes of the layered epitaxial systems.

cond-mat.mtrl-sci↗

arXiv2017

Direct observation of the band gap transition in atomically thin ReS$_2$

ReS$_2$ is considered as a promising candidate for novel electronic and sensor applications. The low crystal symmetry of the van der Waals compound ReS$_2$ leads to a highly anisotropic optical, vibrational, and transport behavior. However, the details of the electronic band structure of this fascinating material are still largely unexplored. We present a momentum-resolved study of the electronic structure of monolayer, bilayer, and bulk ReS$_2$ using k-space photoemission microscopy in combination with first-principles calculations. We demonstrate that the valence electrons in bulk ReS$_2$ are - contrary to assumptions in recent literature - significantly delocalized across the van der Waals gap. Furthermore, we directly observe the evolution of the valence band dispersion as a function of the number of layers, revealing a significantly increased effective electron mass in single-layer crystals. We also find that only bilayer ReS$_2$ has a direct band gap. Our results establish bilayer ReS$_2$ as a advantageous building block for two-dimensional devices and van der Waals heterostructures.

cond-mat.mtrl-sci↗