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Luciano Colazzo

Publications and source records attributed to Luciano Colazzo.

13 recordsLinked to original sources
arXiv2025

Tailoring the Electronic Configurations of YPc$_2$ on Cu(111): Decoupling Strategies for Molecular Spin Qubits Platforms

Among the potential spin qubit candidates, yttrium phthalocyanine double-decker (YPc$_2$) features a diamagnetic metal ion core that stabilizes the molecular structure, while its magnetic properties arise primarily from an unpaired electron (S=1/2) delocalized over the two phthalocyanine (Pc) ligands. Understanding its properties in the proximity of metal electrodes is crucial to assess its potential use in molecular spin qubits architectures. Here, we investigated the morphology and electronic structure of this molecule adsorbed on Cu(111) surface using scanning tunneling microscopy (STM). On Cu(111), YPc$_2$ adsorbs flat, with isolated molecules showing a preferred orientation along the <111> crystal axes. Moreover, we observed two different types of self-assembly molecular packing when growing molecular patches. For YPc$_2$ in direct contact with Cu(111), STM revealed a widely separated highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO), suggesting the quenching of the unpaired spin. Conversely, when YPc$_2$ is separated from the metal substrate by a few-layer thick diamagnetic zinc phthalocyanine (ZnPc) layer, we found the HOMO to split into singly occupied and singly unoccupied molecular orbitals (SOMO/SUMO). We observed that more than 2 layers of ZnPc are needed to avoid intermixing between the two molecules and spin quenching in YPc2. Density functional theory (DFT) reveals the spin quenching is due to the hybridization between YPc$_2$ and Cu(111) states, confirming the importance of using suitable decoupling layers to preserve the unpaired molecular spin. Our results suggest the potential of YPc$_2$/ZnPc heterostructures as a stable and effective molecular spin qubit platform and validate the possibility of integrating this molecular spin qubit candidate in future quantum logic devices.

cond-mat.mes-hall↗
arXiv2023

A continuous-wave and pulsed X-band electron spin resonance spectrometer operating in ultra-high vacuum for the study of low dimensional spin ensembles

We report the development of a continuous-wave and pulsed X-band electron spin resonance (ESR) spectrometer for the study of spins on ordered surfaces down to cryogenic temperatures. The spectrometer operates in ultra-high vacuum and utilizes a half-wavelength microstrip line resonator realized using epitaxially grown copper films on single crystal Al$_2$O$_3$ substrates. The one-dimensional microstrip line resonator exhibits a quality factor of more than 200 at room temperature, close to the upper limit determined by radiation losses. The surface characterizations of the copper strip of the resonator by atomic force microscope, low-energy electron diffraction, and scanning tunneling microscope show that the surface is atomically clean, flat, and single crystalline. Measuring the ESR spectrum at 15 K from a few nm thick molecular film of YPc$_2$, we find a continuous-wave ESR sensitivity of $2.6 \cdot 10^{11}~\text{spins}/\text{G} \cdot \text{Hz}^{1/2}$ indicating that a signal-to-noise ratio of $3.9~\text{G} \cdot \text{Hz}^{1/2}$ is expected from a monolayer of YPc$_2$ molecules. Advanced pulsed ESR experimental capabilities including dynamical decoupling and electron-nuclear double resonance are demonstrated using free radicals diluted in a glassy matrix.

cond-mat.mes-hall↗
arXiv2023

Interpreting X-ray absorption spectra of Vanadyl Phthalocyanines Spin Qubit Candidates using a Machine Learning-Assisted Approach

The magnetic dilution of Vanadyl phthalocyanine (VOPc) within the isostructural diamagnetic Titanyl phthalocyanine (TiOPc) affords promising molecular spin qubit platforms for solid-state quantum computing. The development of quantitative methods for determining how the interactions with a supporting substrate impact the electronic structure of the system are fundamental to determine their potential integration in physical devices. In this work we propose a combined approach based on X-ray absorption spectroscopy (XAS), atomic multiplet calculations, and density functional theory (DFT) to investigate the 3d orbital level structure of VOPc on TiOPc/Ag(100). We characterize VOPc in different molecular environments realized by changing the thickness of TiOPc interlayer and adsorption configuration on Ag(100). Depending on the molecular film structure, we find characteristic XAS features that we analyze using atomic multiplet calculations. We use a Bayesian optimization algorithm to accelerate the parameter search process in the multiplet calculations and identify the ground state properties, such as the 3d orbital occupancy and splitting, as well as intra-atomic interactions. Our analysis indicates that VOPc retains its spin S = 1/2 character in all configurations. Conversely, the energy separation and sequence of the unoccupied V 3d orbitals sensitively depend on the interaction with the surface and TiOPc interlayer. We validate the atomic orbital picture obtained from the multiplet model by comparison with DFT, which further allows us to understand the VOPc electronic properties using a molecular orbital description.

cond-mat.mtrl-sci↗
arXiv2022

On-surface synthesis and evolution of self-assembled poly($p$-phenylene) chains on Ag(111): a joint experimental and theoretical study

The growth of controlled 1D carbon-based nanostructures on metal surfaces is a multistep process whose path, activation energies and intermediate metastable states strongly depend on the employed substrate. Whereas this process has been extensively studied on gold, less work has been dedicated to silver surfaces, which have a rather different catalytic activity. In this work, we present an experimental and theoretical investigation of the growth of poly-$p$-phenylene (PPP) chains and subsequent narrow graphene ribbons starting from 4,4''-dibromo-$p$-terphenyl molecular precursors deposited at the silver surface. By combing scanning tunneling microscopy (STM) imaging and density functional theory (DFT) simulations, we describe the molecular morphology and organization at different steps of the growth process and we discuss the stability and conversion of the encountered species on the basis of calculated thermodynamic quantities. Unlike the case of gold, at the debromination step we observe the appearance of organometallic molecules and chains, which can be explained by their negative formation energy in the presence of a silver adatom reservoir. At the dehydrogenation temperature the persistence of intercalated Br atoms hinders the formation of well-structured graphene ribbons, which are instead observed on gold, leading only to a partial lateral coupling of the PPP chains. We numerically derive very different activation energies for Br desorption from the Ag and Au surfaces, thereby confirming the importance of this process in defining the kinetics of the formation of molecular chains and graphene ribbons on different metal surfaces.

cond-mat.mtrl-sci↗
arXiv2020

Orbital-resolved single atom magnetism measured with X-ray absorption spectroscopy

Lanthanide atoms and molecules are promising candidates for atomic data storage and quantum logic due to the long magnetic lifetime of their electron quantum states. Accessing these states through electrical transport requires the engineering of their electronic configuration down to the level of individual atomic orbitals. Here, we address the magnetism of surface-supported lanthanide atoms, clusters, and films with orbital selectivity using X-ray absorption spectroscopy and magnetic circular dichroism. We exploit the selection rules of electric dipole transitions to reveal the occupation and magnetism of the valence electrons of Gd and Ho deposited on MgO/Ag(100). Comparing our results with multiplet calculations and density functional theory, we identify a charge transfer mechanism that leaves the lanthanide species in an unconventional singly ionized configuration. Our approach allows determining the role of valence electrons on the quantum level structure of lanthanide-based nanostructures.

cond-mat.mes-hall↗
arXiv2020

Keto-enol tautomerization drives the self-assembly of Leucoquinizarin on Au(111)

The self-assembly of Leucoquinizarin molecule on Au(111) surface is shown to be characterized by the molecules mostly in their keto-enolic tautomeric form, with evidences of their temporary switching to other tautomeric forms. This reveals a metastable chemistry of the assembled molecules, to be considered for their possible employment in the formation of more complex hetero-organic interfaces

cond-mat.mtrl-sci↗
arXiv2020

Electronic structure tunability by periodic meta-ligand spacing in one-dimensional organic semiconductors

Designing molecular organic semiconductors with distinct frontier orbitals is key for the development of devices with desirable properties. Generating defined organic nanostructures with atomic precision can be accomplished by on-surface synthesis. We use this dry chemistry to introduce topological variations in a conjugated poly-para-phenylene chain in the form of meta-junctions. As evidenced by STM and LEED, we produce a macroscopically ordered, monolayer thin zigzag chain film on a vicinal silver crystal. These cross-conjugated nanostructures are expected to display altered electronic properties, which are now unravelled by highly complementary experimental techniques (ARPES and STS) and theoretical calculations (DFT and EPWE). We find that meta-junctions dominate the weakly dispersive band structure, while the bandgap is tunable by altering the linear segment's length. These periodic topology effects induce significant loss of the electronic coupling between neighboring linear segments leading to partial electron confinement in the form of weakly coupled Quantum Dots. Such periodic quantum interference effects determine the overall semiconducting character and functionality of the chains.

cond-mat.mtrl-sci↗
arXiv2020

Steering alkyne homocoupling with on-surface synthesized catalysts

We report a multi-step on-surface synthesis strategy. The first step consists in the surface-supported synthesis of metal-organic complexes, which are subsequently used as catalysts to steer on-surface alkyne coupling reactions. In addition, we analyze and compare the electronic properties of the different coupling motifs obtained.

cond-mat.mtrl-sci↗
arXiv2020

Transferring Axial Molecular Chirality Through a Sequence of On-Surface Reactions

Fine management of chiral processes on solid surfaces has progressed over the years, yet still faces the need for the controlled and selective production of advanced chiral materials. Here, we report on the use of enantiomerically enriched molecular building blocks to demonstrate the transmission of their intrinsic chirality along a sequence of on-surface reactions. Triggered by thermal annealing, the on-surface reac-tions induced in this experiment involve firstly the coupling of the chiral reactants into chiral polymers and subsequently their transformation into planar prochiral graphene nanoribbons. Our study reveals that the axial chirality of the reactant is not only transferred to the polymers, but also to the planar chirality of the graphene nanoribbon end products. Such chirality transfer consequently allows, starting from ad-equate enantioenriched reactants, for the controlled production of chiral and prochiral organic nanoarchi-tectures with pre-defined handedness.

cond-mat.mtrl-sci↗
arXiv2020

Controlling the stereospecific bonding motif of Au-thiolate links

Organosulfur compounds at the interface to noble metals have proved over the last decades to be extremely versatile systems for both fundamental and applied research. However, the anchoring of thiols to gold remained an object of controversy for long times. The RS-Au-SR linkage, in particular, is a robust bonding configuration that displays interesting properties. It is generated spontaneously at room temperature and can be used for the production of extended molecular nanostructures. In this work we explore the behavior of 1,4-Bis(4-mercaptophenyl)benzene (BMB) on the Au(111) surface, which results in the formation of 2D crystalline metal-organic assemblies stabilized by this type of Au-thiolate bonds. We show how to control the thiolates stereospecific bonding motif and thereby choose whether to form ordered arrays of Au3BMB3 units with embedded triangular nanopores, or linearly stacked metal-organic chains. The former turn out to be the thermodynamically favored structures and display confinement of the underneath Au(111) surface state. The electronic properties of single molecules as well as of the 2D crystalline self-assemblies have been characterized both on the metal-organic backbone and inside the associated pores.

cond-mat.mtrl-sci↗
arXiv2020

Electronic Decoupling of Polyacenes from the Underlying Metal Substrate by sp3 Carbon Atoms

We report on the effect of sp3 hybridized carbon atoms in acene derivatives adsorbed on metal surfaces, namely decoupling the molecules from the supporting substrates. In particular, we have used a Ag(100) substrate and hydrogenated heptacene molecules, in which the longest conjugated segment determining its frontier molecular orbitals amounts to five consecutive rings. The non-planarity that the sp3 atoms impose on the carbon backbone results in electronically decoupled molecules, as demonstrated by the presence of charging resonances in dI/dV tunneling spectra and the associated double tunneling barriers, or in the Kondo peak that is due to a net spin S=1/2 of the molecule as its LUMO becomes singly charged. The spatially dependent appearance of the charging resonances as peaks or dips in the differential conductance spectra is further understood in terms of the tunneling barrier variation upon molecular charging, as well as of the different orbitals involved in the tunneling process.

cond-mat.mtrl-sci↗
arXiv2017

Width-Dependent Band Gap in Armchair Graphene Nanoribbons Reveals Fermi Level Pinning on Au(111)

We report on the energy level alignment evolution of valence and conduction bands of armchair-oriented graphene nanoribbons (aGNR) as their band gap shrinks with increasing width. We use 4,4-dibromo-para-terphenyl as molecular precursor on Au(111) to form extended poly-para-phenylene nanowires, which can be fused sideways to form atomically precise aGNRs of varying widths. We measure the frontier bands by means of scanning tunneling spectroscopy, corroborating that the nanoribbons band gap is inversely proportional to their width. Interestingly, valence bands are found to show Fermi level pinning as the band gap decreases below a threshold value around 1.7 eV. Such behavior is of critical importance to understand the properties of potential contacts in graphene nanoribbon-based devices. Our measurements further reveal a particularly interesting system for studying Fermi level pinning by modifying an adsorbates band gap while maintaining an almost unchanged interface chemistry defined by substrate and adsorbate.

cond-mat.mtrl-sci↗