Staff directory
Marcos Paradinas Aranjuelo
Laboratory Engineer
marcos.paradinas(ELIMINAR)@icn2.cat
Atomic Manipulation and Spectroscopy
- ORCID: 0000-0003-1006-9506
Publications
2021
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Tuning the Magnetic Anisotropy of Lanthanides on a Metal Substrate by Metal–Organic Coordination
Parreiras S.O., Moreno D., Cirera B., Valbuena M.A., Urgel J.I., Paradinas M., Panighel M., Ajejas F., Niño M.A., Gallego J.M., Valvidares M., Gargiani P., Kuch W., Martínez J.I., Mugarza A., Camarero J., Miranda R., Perna P., Écija D. Small; 17 (35, 2102753) 2021. 10.1002/smll.202102753. IF: 13.281
Taming the magnetic anisotropy of lanthanides through coordination environments is crucial to take advantage of the lanthanides properties in thermally robust nanomaterials. In this work, the electronic and magnetic properties of Dy-carboxylate metal–organic networks on Cu(111) based on an eightfold coordination between Dy and ditopic linkers are inspected. This surface science study based on scanning probe microscopy and X-ray magnetic circular dichroism, complemented with density functional theory and multiplet calculations, reveals that the magnetic anisotropy landscape of the system is complex. Surface-supported metal–organic coordination is able to induce a change in the orientation of the easy magnetization axis of the Dy coordinative centers as compared to isolated Dy atoms and Dy clusters, and significantly increases the magnetic anisotropy. Surprisingly, Dy atoms coordinated in the metallosupramolecular networks display a nearly in-plane easy magnetization axis despite the out-of-plane symmetry axis of the coordinative molecular lattice. Multiplet calculations highlight the decisive role of the metal–organic coordination, revealing that the tilted orientation is the result of a very delicate balance between the interaction of Dy with O atoms and the precise geometry of the crystal field. This study opens new avenues to tailor the magnetic anisotropy and magnetic moments of lanthanide elements on surfaces. © 2021 The Authors. Small published by Wiley-VCH GmbH
2019
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Effect of the Molecular Polarizability of SAMs on the Work Function Modification of Gold: Closed- versus Open-Shell Donor–Acceptor SAMs
Diez-Cabanes V., Morales D.C., Souto M., Paradinas M., Delchiaro F., Painelli A., Ocal C., Cornil D., Cornil J., Veciana J., Ratera I. Advanced Materials Technologies; 4 (5, 1800152) 2019. 10.1002/admt.201800152. IF: 5.395
Charge injection barriers at metal/organic interfaces can be tuned by modifying the work function of metallic electrodes using self-assembled monolayers (SAMs) of polar molecules. An interesting example of polar molecules is offered by donor–acceptor (D–A) dyads based on ferrocene (Fc) as electron-donor unit and either a polychlorotriphenylmethyl radical or a polychlorotriphenylmethane as electron-acceptor units, connected by a π-conjugated vinylene bridge. The D–A radical exhibits high chemical and thermal stability and presents different electronic, optical, and magnetic properties with respect to the closed-shell form. The magnitude of the shift in the charge injection barriers for these two D–A systems is estimated by means of surface potential measurements performed by Kelvin probe force microscopy. The experimental data are compared with density functional theory calculations, which evidence the importance of the molecular dipole moments and polarizabilities to understand the experimental values. In order to achieve high work function shifts of metals upon SAM formation, the molecules forming the SAM have to exhibit both a high permanent dipole moment and a low polarizability along the direction normal to the substrate. In presence of polarizable molecules, the work function shifts can be enhanced by reducing the intermolecular interactions; by using mixed SAMs with active molecules embedded into a passive matrix. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2018
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Bottom-up synthesis of multifunctional nanoporous graphene
Moreno C., Vilas-Varela M., Kretz B., Garcia-Lekue A., Costache M.V., Paradinas M., Panighel M., Ceballos G., Valenzuela S.O., Peña D., Mugarza A. Science; 360 (6385): 199 - 203. 2018. 10.1126/science.aar2009. IF: 41.058
Nanosize pores can turn semimetallic graphene into a semiconductor and, from being impermeable, into the most efficient molecular-sieve membrane. However, scaling the pores down to the nanometer, while fulfilling the tight structural constraints imposed by applications, represents an enormous challenge for present top-down strategies. Here we report a bottom-up method to synthesize nanoporous graphene comprising an ordered array of pores separated by ribbons, which can be tuned down to the 1-nanometer range. The size, density, morphology, and chemical composition of the pores are defined with atomic precision by the design of the molecular precursors. Our electronic characterization further reveals a highly anisotropic electronic structure, where orthogonal one-dimensional electronic bands with an energy gap of ∼1 electron volt coexist with confined pore states, making the nanoporous graphene a highly versatile semiconductor for simultaneous sieving and electrical sensing of molecular species. 2017 © The Authors
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In-Situ Scrutiny of the Relationship between Polymorphic Phases and Properties of Self-Assembled Monolayers of a Biphenyl Based Thiol
Paradinas M., Munuera C., Buck M., Ocal C. Journal of Physical Chemistry B; 122 (2): 657 - 665. 2018. 10.1021/acs.jpcb.7b05958. IF: 3.146
Two polymorphic phases of ω-(4′-methylbiphenyl-4-yl) butane-1-thiol (BP4) molecules formed on Au(111) were investigated by multidimensional atomic force microscopy, combining conductivity measurements, electrostatic characterization, friction force mapping, and normal force spectroscopy. Based on the same molecular structure but differing in molecular order, packing density, and molecular tilt, the two phases serve as a test bench to establish the structure-property relationships in self-assembled monolayers (SAMs). From a detailed analysis of the charge transport and electrostatics, the contributions of geometrical and electronic effects to the tunneling are discussed. © 2017 American Chemical Society.
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On-surface synthesis of superlattice arrays of ultra-long graphene nanoribbons
Moreno C., Paradinas M., Vilas-Varela M., Panighel M., Ceballos G., Peña D., Mugarza A. Chemical Communications; 54 (68): 9402 - 9405. 2018. 10.1039/c8cc04830d. IF: 6.290
We report the on-surface synthesis of graphene nanoribbon superlattice arrays directed by the herringbone reconstruction of the Au(111) surface. The uniaxial anisotropy of the zigzag pattern of the reconstruction defines a one dimensional grid for directing the Ullmann polymerization and inducing periodic arrays of parallel ultra-long nanoribbons (>100 nm), where the periodicity is varied with coverage at discrete values following a hierarchical templating behavior. © 2018 The Royal Society of Chemistry.
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Real Space Demonstration of Induced Crystalline 3D Nanostructuration of Organic Layers
Paradinas M., Pérez-Rodríguez A., Barrena E., Ocal C. Journal of Physical Chemistry B; 122 (2): 633 - 639. 2018. 10.1021/acs.jpcb.7b05342. IF: 3.146
The controlled 3D nanostructuration of molecular layers of the semiconducting molecules C22H14 (pentacene) and N,N′-dioctyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C8) is addressed. A tip-assisted method using atomic force microscopy (AFM) is developed for removing part of the organic material and relocating it in up to six layer thick nanostructures. Moreover, unconventional molecular scale imaging combining diverse friction force microscopy modes reveals the stacking sequence of the piled layers. In particular, we unambiguously achieve epitaxial growth, an issue of fundamental importance in thin film strategies for the nanostructuration of more efficient organic nanodevices. © 2017 American Chemical Society.
2017
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Electronic Structure of Titanylphthalocyanine Layers on Ag(111)
Lerch A., Fernandez L., Ilyn M., Gastaldo M., Paradinas M., Valbuena M.A., Mugarza A., Ibrahim A.B.M., Sundermeyer J., Höfer U., Schiller F. Journal of Physical Chemistry C; 121 (45): 25353 - 25363. 2017. 10.1021/acs.jpcc.7b09147. IF: 4.536
We have investigated the electronic structures of axially oxo functionalized titanylphthalocyanine (TiOPc) on Ag(111) by X-ray and ultraviolet photoelectron spectroscopies, two-photon photoemission, X-ray absorption spectroscopy, and X-ray magnetic circular dichroism. Furthermore, we use complementary data of TiOPc on graphite and planar copper phthalocyanine (CuPc) on Ag(111) for a comparative analysis. Both molecules adsorb on Ag(111) in a parallel orientation to the surface, for TiOPc with an oxygen-up configuration. The interaction of nitrogen and carbon atoms with the substrate is similar for both molecules, while the bonding of the titanium atom to Ag(111) in the monolayer is found to be slightly more pronounced than in the CuPc case. Ultraviolet photoemission spectroscopy reveals an occupation of the lowest unoccupied molecular orbital (LUMO) level in monolayer thick TiOPc on Ag(111) related to the interaction of the molecules and the silver substrate. This molecule-metal interaction also causes an upward shift of the Ag(111) Shockley state that is transformed into an unoccupied interface state with energies of 0.23 and 0.33 eV for the TiOPc monolayer and bilayer, respectively, at the Brillouin zone center. © 2017 American Chemical Society.
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Inductively coupled remote plasma-enhanced chemical vapor deposition (rPE-CVD) as a versatile route for the deposition of graphene micro- and nanostructures
Cuxart M.G., Šics I., Goñi A.R., Pach E., Sauthier G., Paradinas M., Foerster M., Aballe L., Fernandez H.M., Carlino V., Pellegrin E. Carbon; 117: 331 - 342. 2017. 10.1016/j.carbon.2017.02.067. IF: 6.337
Multiple layers of graphene thin films with micro-crystalline orientation and vertical graphene nano-sheets were grown on different substrates (i.e., polycrystalline nickel foil, Ni(111), highly oriented pyrolytic graphite) using a single-step process based on low-pressure remote Plasma-Enhanced Chemical Vapor Deposition (rPE-CVD). In contrast to previous studies, a novel basic approach to this technique including a new remote inductively coupled RF plasma source has been used to (i) minimize the orientational effect of the plasma electrical fields during the catalyst-free growth of graphene nano-sheets, (ii) warrant for a low graphene defect density via low plasma kinetics, (iii) decouple the dissociation process of the gas from the growth process of graphene on the substrate, (iv) tune the feedstock gas chemistry in view of improving the graphene growth, and (v) reduce the growth temperature as compared to conventional chemical vapor deposition (CVD). In order to study the various aspects of the rPE-CVD graphene growth modes and to assess the characteristics of the resulting graphene layers, Raman spectroscopy, XPS, SEM, and STM were used. The results give evidence for the successful performance of this new rPE-CVD plasma deposition source, that can be combined with in situ UHV-based processess for the production of, e. g., hybrid metal ferromagnet/graphene systems. © 2017 Elsevier Ltd
2016
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Film Quality and Electronic Properties of a Surface-Anchored Metal-Organic Framework Revealed by using a Multi-technique Approach
Liu J., Paradinas M., Heinke L., Buck M., Ocal C., Mugnaini V., Wöll C. ChemElectroChem; 3 (5): 713 - 718. 2016. 10.1002/celc.201500486. IF: 3.506
The virtually unlimited versatility and unparalleled level of control in the design of metal-organic frameworks (MOFs) has recently been shown to also entail a potential for applications based on the electrical and electronic properties of this rich class of materials. At present, methods to provide reliable and reproducible contacts to MOF materials are scarce; therefore, we have carried out a detailed, multi-technique investigation of an empty and loaded prototype MOF, HKUST-1. Epitaxial thin films of this material grown on a substrate by using liquid-phase epitaxy have been studied by cyclic voltammetry, atomic force microscopy, and quartz crystal microbalance and their quality assessed. By using an ionic liquid as the electrolyte, it is shown that redox-active molecules like ferrocene can be embedded in the pores, enabling a change in the overall conductivity of the framework and the study of the redox chemistry of guest molecules inside the MOF. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Microfluidic pneumatic cages: A novel approach for in-chip crystal trapping, manipulation and controlled chemical treatment
Abrishamkar A., Paradinas M., Bailo E., Rodriguez-Trujillo R., Pfattner R., Rossi R.M., Ocal C., Demello A.J., Amabilino D.B., Puigmartí-Luis J. Journal of Visualized Experiments; 2016 (113, e54193) 2016. 10.3791/54193. IF: 1.113
The precise localization and controlled chemical treatment of structures on a surface are significant challenges for common laboratory technologies. Herein, we introduce a microfluidic-based technology, employing a double-layer microfluidic device, which can trap and localize in situ and ex situ synthesized structures on microfluidic channel surfaces. Crucially, we show how such a device can be used to conduct controlled chemical reactions onto on-chip trapped structures and we demonstrate how the synthetic pathway of a crystalline molecular material and its positioning inside a microfluidic channel can be precisely modified with this technology. This approach provides new opportunities for the controlled assembly of structures on surface and for their subsequent treatment. © 2016 Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License.
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Misfit Dislocation Guided Topographic and Conduction Patterning in Complex Oxide Epitaxial Thin Films
Sandiumenge F., Bagués N., Santiso J., Paradinas M., Pomar A., Konstantinovic Z., Ocal C., Balcells L., Casanove M.-J., Martínez B. Advanced Materials Interfaces; 3 (14, 1600106) 2016. 10.1002/admi.201600106. IF: 3.365
Interfacial dissimilarity has emerged in recent years as the cornerstone of emergent interfacial phenomena, while enabling the control of electrical transport and magnetic behavior of complex oxide epitaxial films. As a step further toward the lateral miniaturization of functional nanostructures, this work uncovers the role of misfit dislocations in creating periodic surface strain patterns that can be efficiently used to control the spatial modulation of mass transport phenomena and bandwidth-dependent properties on a ≈20 nm length scale. The spontaneous formation of surface strain-relief patterns in La0.7Sr0.3MnO3/LaAlO3 films results in lateral periodic modulations of the surface chemical potential and tetragonal distortion, controlling the spatial distribution of preferential nucleation sites and the bandwidth of the epilayer, respectively. These results provide insights into the spontaneous formation of strain-driven ordered surface patterns, topographic and functional, during the growth of complex oxide heterostructures on lengths scales far below the limits achievable through top-down approaches. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2015
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Enhanced conduction and ferromagnetic order at (100)-type twin walls in L a0.7 S r0.3Mn O3 thin films
Balcells L., Paradinas M., Baguès N., Domingo N., Moreno R., Galceran R., Walls M., Santiso J., Konstantinovic Z., Pomar A., Casanove M.-J., Ocal C., Martínez B., Sandiumenge F. Physical Review B - Condensed Matter and Materials Physics; 92 (7, 075111) 2015. 10.1103/PhysRevB.92.075111. IF: 3.736
There is increasing evidence supporting the strong potential of twin walls in ferroic materials as distinct, spatially tunable, functional elements in future electronic devices. Here, we report an increase of about one order of magnitude in conductivity and more robust magnetic interactions at (100)-type twin walls in La0.7Sr0.3MnO3 thin films. The nature and microscopic origin of such distinctive behavior is investigated by combining conductive, magnetic, and force modulation scanning force microscopies with transmission electron microscopy techniques. Our analyses indicate that the observed behavior is due to a severe compressive strained state within an ∼1nm slab of material centered at the twin walls, promoting stronger Mn 3d-O2p orbital overlapping leading to a broader bandwidth and enhanced magnetic interactions. © 2015 American Physical Society.
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Giant reversible nanoscale piezoresistance at room temperature in Sr2IrO4 thin films
Domingo N., López-Mir L., Paradinas M., Holy V., Železný J., Yi D., Suresha S.J., Liu J., Rayan Serrao C., Ramesh R., Ocal C., Martí X., Catalan G. Nanoscale; 7 (8): 3453 - 3459. 2015. 10.1039/c4nr06954d. IF: 7.394
Layered iridates have been the subject of intense scrutiny on account of their unusually strong spin-orbit coupling, which opens up a narrow bandgap in a material that would otherwise be a metal. This insulating state is very sensitive to external perturbations. Here, we show that vertical compression at the nanoscale, delivered using the tip of a standard scanning probe microscope, is capable of inducing a five orders of magnitude change in the room temperature resistivity of Sr2IrO4. The extreme sensitivity of the electronic structure to anisotropic deformations opens up a new angle of interest on this material, with the giant and fully reversible perpendicular piezoresistance rendering iridates as promising materials for room temperature piezotronic devices. This journal is © The Royal Society of Chemistry.
2014
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Influence of the relative molecular orientation on interfacial charge-transfer Excitons at donor/acceptor Nanoscale heterojunctions
Aghamohammadi, M.; Fernández, A.; Schmidt, M.; Pérez-Rodríguez, A.; Goñi, A.R.; Fraxedas, J.; Sauthier, G.; Paradinas, M.; Ocal, C.; Barrena, E. Journal of Physical Chemistry C; 118 (27): 14833 - 14839. 2014. 10.1021/jp5041579. IF: 4.835