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1.
Nanotechnology ; 31(36): 365603, 2020 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-32442980

RESUMO

Porphyrins are a versatile class of molecules, which have attracted attention over the years due to their electronic, optical and biological properties. Self-assembled monolayers of porphyrins were widely studied on metal surfaces in order to understand the supramolecular organization of these molecules, which is a crucial step towards the development of devices starting from the bottom-up approach. This perspective could lead to tailor the interfacial properties of the surface, depending on the specific interaction between the molecular assembly and the metal surface. In this study, we revisit the investigation of the assembly of zinc-tetraphenylporphyrins on Au(111) in order to explore the adsorption of the molecular network on the noble metal substrate. The combined analysis of scanning tunneling microscopy (STM) imaging and core levels photoemission spectroscopy measurements support a peculiar arrangement of the ZnTPP molecular network, with Zn atoms occupying the bridge sites of the Au surface atoms. Furthermore, we prove that, at few-layers coverage, the interaction between the deposited layers allows a relevant molecular mobility of the adlayer, as observed by STM and supported by core levels photoemission analysis.

2.
J Phys Chem Lett ; 9(10): 2510-2517, 2018 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-29688007

RESUMO

The challenge of synthesizing graphene nanoribbons (GNRs) with atomic precision is currently being pursued along a one-way road, based on the synthesis of adequate molecular precursors that react in predefined ways through self-assembly processes. The synthetic options for GNR generation would multiply by adding a new direction to this readily successful approach, especially if both of them can be combined. We show here how GNR synthesis can be guided by an adequately nanotemplated substrate instead of by the traditionally designed reactants. The structural atomic precision, unachievable to date through top-down methods, is preserved by the self-assembly process. This new strategy's proof-of-concept compares experiments using 4,4''-dibromo-para-terphenyl as a molecular precursor on flat Au(111) and stepped Au(322) substrates. As opposed to the former, the periodic steps of the latter drive the selective synthesis of 6 atom-wide armchair GNRs, whose electronic properties have been further characterized in detail by scanning tunneling spectroscopy, angle resolved photoemission, and density functional theory calculations.

3.
Small ; 14(14): e1704321, 2018 04.
Artigo em Inglês | MEDLINE | ID: mdl-29405570

RESUMO

Carbon nanomaterials exhibit extraordinary mechanical and electronic properties desirable for future technologies. Beyond the popular sp2 -scaffolds, there is growing interest in their graphdiyne-related counterparts incorporating both sp2 and sp bonding in a regular scheme. Herein, we introduce carbonitrile-functionalized graphdiyne nanowires, as a novel conjugated, one-dimensional (1D) carbon nanomaterial systematically combining the virtues of covalent coupling and supramolecular concepts that are fabricated by on-surface synthesis. Specifically, a terphenylene backbone is extended with reactive terminal alkyne and polar carbonitrile (CN) moieties providing the required functionalities. It is demonstrated that the CN functionalization enables highly selective alkyne homocoupling forming polymer strands and gives rise to mutual lateral attraction entailing room-temperature stable double-stranded assemblies. By exploiting the templating effect of the vicinal Ag(455) surface, 40 nm long semiconducting nanowires are obtained and the first experimental assessment of their electronic band structure is achieved by angle-resolved photoemission spectroscopy indicating an effective mass below 0.1m0 for the top of the highest occupied band. Via molecular manipulation it is showcased that the novel oligomer exhibits extreme mechanical flexibility and opens unexplored ways of information encoding in clearly distinguishable CN-phenyl trans-cis species. Thus, conformational data storage with density of 0.36 bit nm-2 and temperature stability beyond 150 K comes in reach.

4.
Nano Lett ; 18(5): 2751-2758, 2018 05 09.
Artigo em Inglês | MEDLINE | ID: mdl-29380606

RESUMO

The electric and nonvolatile control of the spin texture in semiconductors would represent a fundamental step toward novel electronic devices combining memory and computing functionalities. Recently, GeTe has been theoretically proposed as the father compound of a new class of materials, namely ferroelectric Rashba semiconductors. They display bulk bands with giant Rashba-like splitting due to the inversion symmetry breaking arising from the ferroelectric polarization, thus allowing for the ferroelectric control of the spin. Here, we provide the experimental demonstration of the correlation between ferroelectricity and spin texture. A surface-engineering strategy is used to set two opposite predefined uniform ferroelectric polarizations, inward and outward, as monitored by piezoresponse force microscopy. Spin and angular resolved photoemission experiments show that these GeTe(111) surfaces display opposite sense of circulation of spin in bulk Rashba bands. Furthermore, we demonstrate the crafting of nonvolatile ferroelectric patterns in GeTe films at the nanoscale by using the conductive tip of an atomic force microscope. Based on the intimate link between ferroelectric polarization and spin in GeTe, ferroelectric patterning paves the way to the investigation of devices with engineered spin configurations.

5.
J Synchrotron Radiat ; 24(Pt 4): 750-756, 2017 07 01.
Artigo em Inglês | MEDLINE | ID: mdl-28664881

RESUMO

Complete photoemission experiments, enabling measurement of the full quantum set of the photoelectron final state, are in high demand for studying materials and nanostructures whose properties are determined by strong electron and spin correlations. Here the implementation of the new spin polarimeter VESPA (Very Efficient Spin Polarization Analysis) at the APE-NFFA beamline at Elettra is reported, which is based on the exchange coupling between the photoelectron spin and a ferromagnetic surface in a reflectometry setup. The system was designed to be integrated with a dedicated Scienta-Omicron DA30 electron energy analyzer allowing for two simultaneous reflectometry measurements, along perpendicular axes, that, after magnetization switching of the two targets, allow the three-dimensional vectorial reconstruction of the spin polarization to be performed while operating the DA30 in high-resolution mode. VESPA represents the very first installation for spin-resolved ARPES (SPARPES) at the Elettra synchrotron in Trieste, and is being heavily exploited by SPARPES users since autumn 2015.

6.
Sci Rep ; 7(1): 6609, 2017 07 26.
Artigo em Inglês | MEDLINE | ID: mdl-28747687

RESUMO

Carbon (C) surface segregation from bulk stabilizes the Fe(0 18 1) vicinal surface by forming a c(3[Formula: see text] × [Formula: see text] reconstruction with C zig-zag chains oriented at 45° with respect to the iron surface steps. The iron surface electronic states as measured by high resolution ARPES at normal emission with polarized synchrotron radiation split in two peaks that follow distinct energy dispersion curves. One peak follows the dispersion of the carbon superstructure and is photoexcited only when the polarization vector is parallel to the steps, the second peak disperses similarly to the pristine Fe(0 0 1) surface. Such surface electronic structure is robust as it persists even after coating with an Ag overlayer. The robustness of this surface electronic structure and its similarity with that of the clean Fe(0 0 1) surface make this system of interest for magnetic and spintronic properties such as magneto tunnel junctions based on Fe/MgO interface.

7.
ACS Appl Mater Interfaces ; 9(27): 23099-23106, 2017 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-28613812

RESUMO

We report the study of anatase TiO2(001)-oriented thin films grown by pulsed laser deposition on LaAlO3(001). A combination of in situ and ex situ methods has been used to address both the origin of the Ti3+-localized states and their relationship with the structural and electronic properties on the surface and the subsurface. Localized in-gap states are analyzed using resonant X-ray photoelectron spectroscopy and are related to the Ti3+ electronic configuration, homogeneously distributed over the entire film thickness. We find that an increase in the oxygen pressure corresponds to an increase in Ti3+ only in a well-defined range of deposition pressure; outside this range, Ti3+ and the strength of the in-gap states are reduced.

8.
Sci Rep ; 7(1): 4120, 2017 06 23.
Artigo em Inglês | MEDLINE | ID: mdl-28646153

RESUMO

Rashba spin-orbit splitting in the magnetic materials opens up a new perspective in the field of spintronics. Here, we report a giant Rashba spin-orbit splitting on the PrGe [010] surface in the paramagnetic phase with Rashba coefficient α R = 5 eVÅ. We find that α R can be tuned in this system as a function of temperature at different magnetic phases. Rashba type spin polarized surface states originates due to the strong hybridization between Pr 4f states with the conduction electrons. Significant changes observed in the spin polarized surface states across the magnetic transitions are due to the competition between Dzyaloshinsky-Moriya interaction and exchange interaction present in this system. Presence of Dzyaloshinsky-Moriya interaction on the topological surface give rise to Saddle point singularity which leads to electron-like and hole-like Rashba spin split bands in the [Formula: see text] and [Formula: see text] directions, respectively. Supporting evidences of Dzyaloshinsky-Moriya interaction have been obtained as anisotropic magnetoresistance with respect to field direction and first-order type hysteresis in the X-ray diffraction measurements. A giant negative magnetoresistance of 43% in the antiferromagnetic phase and tunable Rashba parameter with temperature makes this material a suitable candidate for application in the antiferromagnetic spintronic devices.

9.
Sci Rep ; 7: 44400, 2017 03 10.
Artigo em Inglês | MEDLINE | ID: mdl-28281666

RESUMO

The remarkable properties of graphene stem from its two-dimensional (2D) structure, with a linear dispersion of the electronic states at the corners of the Brillouin zone (BZ) forming a Dirac cone. Since then, other 2D materials have been suggested based on boron, silicon, germanium, phosphorus, tin, and metal di-chalcogenides. Here, we present an experimental investigation of a single silicon layer on Au(111) using low energy electron diffraction (LEED), high resolution angle-resolved photoemission spectroscopy (HR-ARPES), and scanning tunneling microscopy (STM). The HR-ARPES data show compelling evidence that the silicon based 2D overlayer is responsible for the observed linear dispersed feature in the valence band, with a Fermi velocity of comparable to that of graphene. The STM images show extended and homogeneous domains, offering a viable route to the fabrication of silicene-based opto-electronic devices.

10.
Nano Lett ; 16(6): 3409-14, 2016 06 08.
Artigo em Inglês | MEDLINE | ID: mdl-27010705

RESUMO

Topological insulators are a promising class of materials for applications in the field of spintronics. New perspectives in this field can arise from interfacing metal-organic molecules with the topological insulator spin-momentum locked surface states, which can be perturbed enhancing or suppressing spintronics-relevant properties such as spin coherence. Here we show results from an angle-resolved photemission spectroscopy (ARPES) and scanning tunnelling microscopy (STM) study of the prototypical cobalt phthalocyanine (CoPc)/Bi2Se3 interface. We demonstrate that that the hybrid interface can act on the topological protection of the surface and bury the Dirac cone below the first quintuple layer.

11.
ACS Nano ; 10(3): 3518-24, 2016 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-26895427

RESUMO

By means of angle-resolved photoemission spectroscopy (ARPES) measurements, we unveil the electronic band structure of three-dimensional PbBi6Te10 topological insulator. ARPES investigations evidence multiple coexisting Dirac surface states at the zone-center of the reciprocal space, displaying distinct electronic band dispersion, different constant energy contours, and Dirac point energies. We also provide evidence of Rashba-like split states close to the Fermi level, and deeper M- and V-shaped bands coexisting with the topological surface states. The experimental findings are in agreement with scanning tunneling microscopy measurements revealing different surface terminations according to the crystal structure of PbBi6Te10. Our experimental results are supported by density functional theory calculations predicting multiple topological surface states according to different surface cleavage planes.

12.
Adv Mater ; 28(3): 560-5, 2016 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-26599640

RESUMO

Photoelectron spectroscopy in combination with piezoforce microscopy reveals that the helicity of Rashba bands is coupled to the nonvolatile ferroelectric polarization of GeTe(111). A novel surface Rashba band is found and fingerprints of a bulk Rashba band are identified by comparison with density functional theory calculations.

13.
ACS Nano ; 10(1): 1132-8, 2016 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-26653134

RESUMO

We investigated the structural, magnetic, and electronic properties of Bi2Se3 epilayers containing Fe grown on GaAs(111) by molecular beam epitaxy. It is shown that, in the window of growth parameters leading to Bi2Se3 epilayers with optimized quality, Fe atom clustering leads to the formation of FexSey inclusions. These objects have platelet shape and are embedded within Bi2Se3. Monoclinic Fe3Se4 is identified as the main secondary phase through detailed structural measurements. Due to the presence of the hard ferrimagnetic Fe3Se4 inclusions, the system exhibits a very large coercive field at low temperature and room temperature magnetic ordering. Despite this composite structure and the proximity of a magnetic phase, the surface electronic structure of Bi2Se3 is preserved, as shown by the persistence of a gapless Dirac cone at Γ.

14.
ACS Nano ; 8(4): 3947-54, 2014 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-24617647

RESUMO

Metal tungstates (with general formula MWO4) are functional materials with a high potential for a diverse set of applications ranging from low-dimensional magnetism to chemical sensing and photoelectrocatalytic water oxidation. For high level applications, nanoscale control of film growth is necessary, as well as a deeper understanding and characterization of materials properties at reduced dimensionality. We succeeded in fabricating and characterizing a two-dimensional (2-D) copper tungstate (CuWO4). For the first time, the atomic structure of an ultrathin ternary oxide is fully unveiled. It corresponds to a CuWO4 monolayer arranged in three sublayers with stacking O-W-O/Cu from the interface. The resulting bidimensional structure forms a robust framework with localized regions of anisotropic flexibility. Electronically it displays a reduced band gap and increased density of states close to the Fermi level with respect to the bulk compound. These unique features open a way for new applications in the field of photo- and electrocatalysis, while the proposed synthesis method represents a radically new and general approach toward the fabrication of 2-D ternary oxides.

15.
ACS Nano ; 6(10): 9299-304, 2012 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-23020302

RESUMO

By combining angle-resolved photoemission spectroscopy and scanning tunneling microscopy we reveal the structural and electronic properties of multilayer graphene on Ru(0001). We prove that large ethylene exposure allows the synthesis of two distinct phases of bilayer graphene with different properties. The first phase has Bernal AB stacking with respect to the first graphene layer and displays weak vertical interaction and electron doping. The long-range ordered moiré pattern modulates the crystal potential and induces replicas of the Dirac cone and minigaps. The second phase has an AA stacking sequence with respect to the first layer and displays weak structural and electronic modulation and p-doping. The linearly dispersing Dirac state reveals the nearly freestanding character of this novel second-layer phase.


Assuntos
Cristalização/métodos , Grafite/química , Membranas Artificiais , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Rubídio/química , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Transição de Fase , Propriedades de Superfície
16.
Nano Lett ; 11(10): 4079-82, 2011 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-21861485

RESUMO

Spin-based electronics in topological insulators (TIs) is favored by the long spin coherence(1,2) and consequently fault-tolerant information storage. Magnetically doped TIs are ferromagnetic up to 13 K,(3) well below any practical operating condition. Here we demonstrate that the long-range ferromagnetism at ambient temperature can be induced in Bi(2-x)Mn(x)Te(3) by the magnetic proximity effect through deposited Fe overlayer. This result opens a new path to interface-controlled ferromagnetism in TI-based spintronic devices.

17.
Nano Lett ; 10(3): 992-5, 2010 Mar 10.
Artigo em Inglês | MEDLINE | ID: mdl-20141155

RESUMO

The outstanding properties of graphene, a single graphite layer, render it a top candidate for substituting silicon in future electronic devices. The so far exploited synthesis approaches, however, require conditions typically achieved in specialized laboratories and result in graphene sheets whose electronic properties are often altered by interactions with substrate materials. The development of graphene-based technologies requires an economical fabrication method compatible with mass production. Here we demonstrate for the fist time the feasibility of graphene synthesis on commercially available cubic SiC/Si substrates of >300 mm in diameter, which result in graphene flakes electronically decoupled from the substrate. After optimization of the preparation procedure, the proposed synthesis method can represent a further big step toward graphene-based electronic technologies.


Assuntos
Compostos Inorgânicos de Carbono/química , Cristalização/métodos , Eletrônica/instrumentação , Grafite/química , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Compostos de Silício/química , Silício/química , Condutividade Elétrica , Desenho de Equipamento , Análise de Falha de Equipamento , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Nanotecnologia/métodos , Tamanho da Partícula , Propriedades de Superfície
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