arXiv subjects

Giovanni Onida

Publications and source records attributed to Giovanni Onida.

At least 19 recordsLinked to original sources

arXiv2024

Unravelling the Band Structure and Orbital Character of a $\pi$-Conjugated 2D Graphdiyne-Based Organometallic Network

Graphdiyne-based carbon systems generate intriguing layered sp-sp$^2$ organometallic lattices, characterized by flexible acetylenic groups connecting planar carbon units through metal centers. At their thinnest limit, they can result in two-dimensional (2D) organometallic networks exhibiting unique quantum properties and even confining the surface states of the substrate, which is of great importance for fundamental studies. In this work, we present the on-surface synthesis of a highly crystalline 2D organometallic network grown on Ag(111). The electronic structure of this mixed honeycomb-kagome arrangement - investigated by angle-resolved photoemission spectroscopy and scanning tunneling spectroscopy - reveals a strong electronic conjugation within the network, leading to the formation of two intense electronic band-manifolds. In comparison to theoretical density functional theory calculations, we observe that these bands exhibit a well-defined orbital character that can be associated with distinct regions of the sp-sp$^2$ monomers. Moreover, we find that the halogen by-products resulting from the network formation locally affect the pore-confined states, causing a significant energy shift. This work contributes to the understanding of the growth and electronic structure of graphdiyne-like 2D networks, providing insights into the development of novel carbon materials beyond graphene with tailored properties.

cond-mat.mes-hall↗

arXiv2022

Steric hindrance in the on-surface synthesis of diethynyl-linked anthracene polymers

Hybrid sp-sp2 structures can be efficiently obtained on metal substrates via on-surface synthesis. The choice of both the precursor and of the substrate impacts on the effectiveness of the process and the stability of the formed structures. Here we demonstrate that using anthracene-based molecules as precursor, the formation on Au(111) of polymers hosting sp carbon chains is affected by the steric hindrance between aromatic groups. In particular, by scanning tunneling microscopy and density functional theory calculations we show that the de-metalation of organometallic structures induces a lateral separation of adjacent polymers preventing the formation of ordered domains.

cond-mat.mtrl-sci↗

arXiv2021

Graphdiynes interacting with metal surfaces: first-principles electronic and vibrational properties

Graphdiynes (GDYs) represent a class of 2D carbon materials based on sp-sp$^2$ hybridization with appealing properties and potential applications. Recent advances have demonstrated the experimental self-assembly of GDYs on metal substrates. Here we focus on $α$- and $β$-GDYs on Au(111) and Pt(111), and investigate how their electronic and vibrational properties are affected by the interaction with a metal substrate. We adopt hydrogenated GDY, previously characterized experimentally, as a benchmark for density functional theory simulations, that we apply to show that Au and Pt substrates impose a different degree of distortion on both $α$- and $β$-GDY. By comparing the adsorbed and the freestanding structures, we evaluate the effect of the surface interaction on the bandstructure and the simulated Raman spectra. Different charge transfers result in different energy shift of the Dirac cone in semi-metallic $α$-GDY and changes from semiconducting to metallic behavior for $β$-GDY. These changes in electronic properties are accompanied by characteristic frequency shifts and modifications of Raman active modes. Our results contribute in the understanding of the metal-interaction effects on GDYs and can open a route to the design of novel 2D materials with tailored properties.

cond-mat.mtrl-sci↗

arXiv2021

Position-controlled functionalization of vacancies in silicon by single-ion implanted germanium atoms

Special point defects in semiconductors have been envisioned as suitable components for quantum-information technology. The identification of new deep centers in silicon that can be easily activated and controlled is a main target of the research in the field. Vacancy-related complexes are suitable to provide deep electronic levels but they are hard to control spatially. With the spirit of investigating solid state devices with intentional vacancy-related defects at controlled position, here we report on the functionalization of silicon vacancies by implanting Ge atoms through single-ion implantation, producing Ge-vacancy (GeV) complexes. We investigate the quantum transport through an array of GeV complexes in a silicon-based transistor. By exploiting a model based on an extended Hubbard Hamiltonian derived from ab-initio results we find anomalous activation energy values of the thermally activated conductance of both quasi-localized and delocalized many-body states, compared to conventional dopants. We identify such states, forming the upper Hubbard band, as responsible of the experimental sub-threshold transport across the transistor. The combination of our model with the single-ion implantation method enables future research for the engineering of GeV complexes towards the creation of spatially controllable individual defects in silicon for applications in quantum information technologies.

cond-mat.mtrl-sci↗

arXiv2020

Structural, Electronic, and Vibrational Properties of 2D Graphdiyne-Like Carbon Nanonetwork Synthesized on Au(111): Implications for the Engineering of sp-sp2 Carbon Nanostructures

Graphdiyne, atomically-thin 2D carbon nanostructure based on sp-sp2 hybridization, is an appealing system potentially showing outstanding mechanical and optoelectronic properties. Surface-catalyzed coupling of halogenated sp-carbon-based molecular precursors represents a promising bottom-up strategy to fabricate extended 2D carbon systems with engineered structure on metallic substrates. Here, we investigate the atomic-scale structure and electronic and vibrational properties of an extended graphdiyne-like sp-sp2 carbon nanonetwork grown on Au(111) by means of on-surface synthesis. The formation of such 2D nanonetwork at its different stages as a function of the annealing temperature after the deposition is monitored by scanning tunneling microscopy (STM), Raman spectroscopy and combined with density functional theory (DFT) calculations. High-resolution STM imaging and the high sensitivity of Raman spectroscopy to the bond nature provide a unique strategy to unravel the atomic-scale properties of sp-sp2 carbon nanostructures. We show that hybridization between the 2D carbon nanonetwork and the underlying substrate states strongly affects its electronic and vibrational properties, modifying substantially the density of states and the Raman spectrum compared to the free standing system. This opens the way to the modulation of the electronic properties with significant prospects in future applications as active nanomaterials for catalysis, photoconversion and carbon-based nanoelectronics.

cond-mat.mtrl-sci↗

arXiv2019

GeVn complexes for silicon-based room-temperature single-atom nanoelectronics

We characterize germanium-vacancy GeVn complexes in silicon using first-principles Density Functional Theory calculations with screening-dependent hybrid functionals. We report on the local geometry and electronic excited states of these defects, including charge transition levels corresponding to the addition of one or more electrons to the defect. Our main theoretical result concerns the GeV complex, which we show to give rise to two excited states deep in the gap, at -0.51 and -0.35 eV from the conduction band, consistently with the available spectroscopic data. The adopted theoretical scheme, suitable to compute a reliable estimate of the wavefunction decay, leads us to predict that such states are associated to an electron localization over a length of about 0.45 nm. By combining the electronic properties of the bare silicon vacancy, carrying deep states in the band gap, with the spatial controllability arising from single Ge ion implantation techniques, the GeVn complex emerges as a suitable ingredient for silicon-based room-temperature single-atom devices.

physics.comp-ph↗

arXiv2016

Anisotropic Effects of Oxygen Vacancies on Electrochromic Properties and Conductivity of $γ$-Monoclinic WO$_3$

Tungsten trioxide (WO$_3$) is a paradigmatic electrochromic material, whose peculiar optical properties in the presence of oxygen vacancies or intercalated alkali atoms have been observed and investigated for a long time. In this paper we propose a rationalization of experiments based on first-principles calculations of optical and electrical properties of oxygen deficient (reduced) WO$_3$. Our approach is based on a parameter-free dielectric-dependent hybrid density functional methodology, used in combination with the charge transition levels formalism, for studying excitation mechanisms in the presence of defects. Our results indicate that oxygen vacancies lead to a different physics in $γ$-monoclinic WO$_3$, depending on the orientation of the W-O-W chain where the vacancy is created, thus evidencing strong anisotropic effects rooted in the peculiar structural properties of the original nondefective monoclinic cell. Different types of oxygen vacancies can hence be classified on the basis of the calculated ground state properties, electronic structure, and excitation/emission energies, giving a satisfactory explanation to a range of experimental observations made on oxygen deficient WO$_3$.

cond-mat.mtrl-sci↗

arXiv2015

Communication: Hole localization in Al-doped quartz SiO2 within ab initio hybrid-functional DFT

We investigate the long-standing problem of the hole localization at the Al impurity in quartz SiO$_2$, using a relatively recent DFT hybrid-functional method in which the exchange fraction is obtained \emph{ab initio}, based on an analogy with the static many-body COHSEX approximation to the electron self-energy. As the amount of the admixed exact exchange in hybrid functionals has been shown to be determinant for properly capturing the hole localization, this problem constitutes a prototypical benchmark for the accuracy of the method, allowing one to assess to what extent self-interaction effects are avoided. We obtain good results in terms of description of the charge localization and structural distortion around the Al center, improving with respect to the more popular B3LYP hybrid-functional approach. We also discuss the accuracy of computed hyperfine parameters, by comparison with previous calculations based on other self-interaction-free methods, as well as experimental values. We discuss and rationalize the limitations of our approach in computing defect-related excitation energies in low-dielectric-constant insulators.

cond-mat.mtrl-sci↗

arXiv2015

Defect calculations in semiconductors through a dielectric-dependent hybrid DFT functional: the case of oxygen vacancies in metal oxides

We investigate the behavior of oxygen vacancies in three different metal-oxide semiconductors (rutile and anatase TiO2, monoclinic WO3, and tetragonal ZrO2) using a recently proposed hybrid density-functional method in which the fraction of exact exchange is material-dependent but obtained ab initio in a self-consistent scheme. In particular, we calculate charge-transition levels relative to the oxygen-vacancy defect and compare computed optical and thermal excitation/emission energies with the available experimental results, shedding light on the underlying excitation mechanisms and related materials properties. We find that this novel approach is able to reproduce not only ground-state properties and band structures of perfect bulk oxide materials, but also provides results consistent with the optical and electrical behavior observed in the corresponding substoichiometric defective systems.

cond-mat.mtrl-sci↗

arXiv2015

Electronic structure and phase stability of oxide semiconductors: Performance of dielectric-dependent hybrid functional DFT, benchmarked against $GW$ band structure calculations and experiments

We investigate band gaps, equilibrium structures, and phase stabilities of several bulk polymorphs of wide-gap oxide semiconductors ZnO, TiO2,ZrO2, and WO3. We are particularly concerned with assessing the performance of hybrid functionals built with the fraction of Hartree-Fock exact exchange obtained from the computed electronic dielectric constant of the material. We provide comparison with more standard density-functional theory and GW methods. We finally analyze the chemical reduction of TiO2 into Ti2O3, involving a change in oxide stoichiometry. We show that the dielectric-dependent hybrid functional is generally good at reproducing both ground-state (lattice constants, phase stability sequences, and reaction energies) and excited-state (photoemission gaps) properties within a single, fully ab initio framework.

cond-mat.mtrl-sci↗

arXiv2015

$Ab$-$initio$ electronic structure, optical and magneto-optical properties of $MnGaAs$ digital ferromagnetic heterostructures

We report on a theoretical study of the electronic, optical and magneto-optical properties of digital ferromagnetic hetero-structures based on $Mn$ $δ$--doped $GaAs$. We consider different structures corresponding to $Mn$ contents within the range 12-50\% and we study how the system changes as a function of the doping concentration. Our first--principles approach includes the spin-orbit interaction in a fully relativistic pseudopotential scheme and the local fields effect in the description of the optical absorption. We show that $Mn$ $δ$-doped $GaAs$ shares many properties with the uniformly doped $Ga_{1-x}Mn_xAs$ system, i.e. half-metallicity, similar absorption spectra, and moderate Kerr rotation angles in the visible spectral region.

cond-mat.mtrl-sci↗

arXiv2011

Vibrational characterization of dinaphthylpolyynes: A model system for the study of end-capped sp carbon chains

We perform a systematic investigation of the resonance and vibrational properties of naphthyl-terminated sp carbon chains (dinaphthylpolyynes) by combined multi-wavelength resonant Raman (MWRR) spectroscopy, ultraviolet-visible spectroscopy, and Fourier-transform infrared (FT-IR) spectroscopy, plus ab initio density functional theory (DFT) calculations. We show that the MWWR and FT-IR spectroscopies are particularly suited to identify chains of different lengths and different terminations, respectively. By DFT calculations, we further extend those findings to sp carbon chains end-capped by other organic structures. The present analysis shows that combined MWRR and FT-IR provide a powerful tool to draw a complete picture of chemically stabilized sp carbon chains.

physics.chem-ph↗

arXiv2011

Carbon sp chains in graphene nanoholes

Nowadays sp carbon chains terminated by graphene or graphitic-like carbon are synthesized routinely in several nanotech labs. We propose an ab-initio study of such carbon-only materials, by computing their structure and stability, as well as their electronic, vibrational and magnetic properties. We adopt a fair compromise of microscopic realism with a certain level of idealization in the model configurations, and predict a number of properties susceptible to comparison with experiment.

cond-mat.mes-hall↗

arXiv2010

Synthesis, Characterization, and Modeling of Naphthyl-Terminated sp Carbon Chains: Dinaphthylpolyynes

We report a combined study on the synthesis, spectroscopic characterization and theoretical modelling of a series of α,ω-dinaphthylpolyynes. We synthesized this family of naphtyl-terminated sp carbon chains by reacting diiodoacetylene and 1-ethynylnaphthalene under the Cadiot-Chodkiewicz reaction conditions. By means of liquid chromatography (HPLC), we separated the products and recorded their electronic absorption spectra, which enabled us to identify the complete series of dinaphthylpolyynes Ar-C2n-Ar (with Ar = naphthyl group and n = number of acetilenic units) with n ranging from 2 to 6. The longest wavelength transition (LWT) in the electronic spectra of the dinaphthylpolyynes red shifts linearly with n away from the LWT of the bare termination. This result is also supported by DFT-LDA simulations. Finally, we probed the stability of the dinaphthylpolyynes in a solid-state precipitate by Fourier-transform infrared spectroscopy and by differential scanning calorimetry (DSC).

physics.chem-ph↗

arXiv2010

Vibrational properties of sp carbon atomic wires in cluster-assembled carbon films

Linear chains made by a single row of sp-hybridized carbon are predicted to display fascinating mechano-electronic properties connected with their termination and stabilization inside realistic carbon structures. The present work describes how the computed vibrational properties of cumulenic and polyynic carbon chains allow one to interpret the carbynic features observed in Raman spectra of cluster-assembled sp-sp2 films. The overall picture is consistent with the measured decay of the sp components induced by air or oxygen exposure.

cond-mat.mes-hall↗

arXiv2010

Comment to "Imaging the atomic orbitals of carbon atomic chains with field-emission electron microscopy"

The observation of a stable doublet pattern in the field-emission electron microscopy of a linear atomic chain requires a stable mechanism breaking the axial symmetry, which is not identified correctly by Mikhailovskij et al. [Phys. Rev. B 80, 165404 (2009)]. Using microscopic calculations, we attribute the observed pattern to the symmetry breaking produced by the ligand where the chain is attached, plus carbon pi-bonding alternation.

cond-mat.mes-hall↗

arXiv2009

Effects of axial torsion on sp carbon atomic nanowires

Ab-initio calculations within Density Functional Theory combined with experimental Raman spectra on cluster-beam deposited pure carbon films provide a consistent picture of sp-carbon chains stabilized by sp^3 or sp^2 terminations, the latter being sensitive to torsional strain. This unexplored effect promises many exciting applications since it allows one to modify the conductive states near the Fermi level and to switch on and off the on-chain pi-electron magnetism.

cond-mat.mtrl-sci↗

arXiv2009

Structure and stability of the Si(331)-(12x1) surface reconstruction

We recently proposed a new structural model for the Si(331)-(12x1) surface reconstruction containing silicon pentamers as elementary structural building blocks. Using first-principles density-functional theory we here investigate the stability of a variety of adatom configurations and determine the lowest energy configuration. We also present a detailed comparison of the energetics between our model for Si(331)-(12x1) and the adatom-tetramer-interstitial model for Si(110)-(16x2), which shares the same structural building blocks.

cond-mat.mtrl-sci↗