Publications
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Absence of Magnetic Proximity Effect at the Interface of Bi2Se3 and (Bi,Sb)2Te3 with EuS
Figueroa A.I., Bonell F., Cuxart M.G., Valvidares M., Gargiani P., Van Der Laan G., Mugarza A., Valenzuela S.O. Physical Review Letters; 125 (22, 226801) 2020. 10.1103/PhysRevLett.125.226801. IF: 8.385
We performed X-ray magnetic circular dichroism (XMCD) measurements on heterostructures comprising topological insulators (TIs) of the (Bi,Sb)2(Se,Te)3 family and the magnetic insulator EuS. XMCD measurements allow us to investigate element-selective magnetic proximity effects at the very TI/EuS interface. A systematic analysis reveals that there is neither significant induced magnetism within the TI nor an enhancement of the Eu magnetic moment at such interface. The induced magnetic moments in Bi, Sb, Te, and Se sites are lower than the estimated detection limit of the XMCD measurements of ∼10-3 μB/at. © 2020 American Physical Society.
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Band Depopulation of Graphene Nanoribbons Induced by Chemical Gating with Amino Groups
Li J., Brandimarte P., Vilas-Varela M., Merino-Díez N., Moreno C., Mugarza A., Mollejo J.S., Sánchez-Portal D., Garcia De Oteyza D., Corso M., Garcia-Lekue A., Peña D., Pascual J.I. ACS Nano; 14 (2): 1895 - 1901. 2020. 10.1021/acsnano.9b08162. IF: 14.588
The electronic properties of graphene nanoribbons (GNRs) can be precisely tuned by chemical doping. Here we demonstrate that amino (NH2) functional groups attached at the edges of chiral GNRs (chGNRs) can efficiently gate the chGNRs and lead to the valence band (VB) depopulation on a metallic surface. The NH2-doped chGNRs are grown by on-surface synthesis on Au(111) using functionalized bianthracene precursors. Scanning tunneling spectroscopy resolves that the NH2 groups significantly upshift the bands of chGNRs, causing the Fermi level crossing of the VB onset of chGNRs. Through density functional theory simulations we confirm that the hole-doping behavior is due to an upward shift of the bands induced by the edge NH2 groups. © 2020 American Chemical Society.
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Enhanced Magnetism through Oxygenation of FePc/Ag(110) Monolayer Phases
Bartolomé E., Bartolomé J., Sedona F., Lobo-Checa J., Forrer D., Herrero-Albillos J., Piantek M., Herrero-Martín J., Betto D., Velez-Fort E., García L.M., Panighel M., Mugarza A., Sambi M., Bartolomé F. Journal of Physical Chemistry C; 124 (25): 13993 - 14006. 2020. 10.1021/acs.jpcc.0c01988. IF: 4.189
Iron phthalocyanines (FePc) adsorbed onto a Ag(110) substrate self-assemble into different monolayer phases going from rectangular to different oblique phases, with increasing molecular density. We have investigated the oxygen uptake capability of the different phases and their associated magneto-structural changes. Our study combines scanning tunneling microscopy and spectroscopy (STM/STS), X-ray magnetic circular dichroism (XMCD), and density functional theory (DFT) calculations. STM measurements reveal that the oxygenation reaction of the FePc/Ag(110) generally involves a displacement and a rotation of the molecules, which affects the electronic state of the Fe centers. The oxygen intercalation between FePc and the substrate is greatly obstructed by the steric hindrance in the high-density phases, to the point that a fraction of oblique phase molecules cannot change their position after oxidizing. Depending on the oxidation state and adsoption geometry, the STS spectra show clear differences in the Fe local density of states, which are mirrored in the XAS and XMCD experiments. Particularly, XMCD spectra of the oxidized phases reflect the distribution of FePc species (nonoxygenated, oxygenated-rotated, and oxygenated-unrotated) in the different cases. Sum rule analysis yields the effective spin (mseff) and orbital (mL) magnetic moments of Fe in the different FePc species. Upon oxygenation, the magnetic moment of FePc molecules increases about an order of magnitude, reaching mTOT ∼2.2 μB per Fe atom. © 2020 American Chemical Society.
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Influence of 4f filling on electronic and magnetic properties of rare earth-Au surface compounds
Fernandez L., Blanco-Rey M., Castrillo-Bodero R., Ilyn M., Ali K., Turco E., Corso M., Ormaza M., Gargiani P., Valbuena M.A., Mugarza A., Moras P., Sheverdyaeva P.M., Kundu A.K., Jugovac M., Laubschat C., Ortega J.E., Schiller F. Nanoscale; 12 (43): 22258 - 22267. 2020. 10.1039/d0nr04964f. IF: 6.895
One-atom-thick rare-earth/noble metal (RE-NM) compounds are attractive materials to investigate two-dimensional magnetism, since they are easy to synthesize into a common RE-NM2 structure with high crystal perfection. Here we perform a comparative study of the GdAu2, HoAu2, and YbAu2 monolayer compounds grown on Au(111). We find the same atomic lattice quality and moiré superlattice periodicity in the three cases, but different electronic properties and magnetism. The YbAu2 monolayer reveals the characteristic electronic signatures of a mixed-valence configuration in the Yb atom. In contrast, GdAu2 and HoAu2 show the trivalent character of the rare-earth and ferromagnetic transitions below 22 K. Yet, the GdAu2 monolayer has an in-plane magnetic easy-axis, versus the out-of-plane one in HoAu2. The electronic bands of the two trivalent compounds are very similar, while the divalent YbAu2 monolayer exhibits different band features. In the latter, a strong 4f-5d hybridization is manifested in neatly resolved avoided crossings near the Fermi level. First principles theory points to a residual presence of empty 4f states, explaining the fluctuating valence of Yb in the YbAu2 monolayer. © The Royal Society of Chemistry.
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Molecular Approach for Engineering Interfacial Interactions in Magnetic/Topological Insulator Heterostructures
Cuxart M.G., Valbuena M.A., Robles R., Moreno C., Bonell F., Sauthier G., Imaz I., Xu H., Nistor C., Barla A., Gargiani P., Valvidares M., Maspoch D., Gambardella P., Valenzuela S.O., Mugarza A. ACS Nano; 14 (5): 6285 - 6294. 2020. 10.1021/acsnano.0c02498. IF: 14.588
Controlling interfacial interactions in magnetic/topological insulator heterostructures is a major challenge for the emergence of novel spin-dependent electronic phenomena. As for any rational design of heterostructures that rely on proximity effects, one should ideally retain the overall properties of each component while tuning interactions at the interface. However, in most inorganic interfaces, interactions are too strong, consequently perturbing, and even quenching, both the magnetic moment and the topological surface states at each side of the interface. Here, we show that these properties can be preserved using ligand chemistry to tune the interaction of magnetic ions with the surface states. By depositing Co-based porphyrin and phthalocyanine monolayers on the surface of Bi2Te3 thin films, robust interfaces are formed that preserve undoped topological surface states as well as the pristine magnetic moment of the divalent Co ions. The selected ligands allow us to tune the interfacial hybridization within this weak interaction regime. These results, which are in stark contrast with the observed suppression of the surface state at the first quintuple layer of Bi2Se3 induced by the interaction with Co phthalocyanines, demonstrate the capability of planar metal-organic molecules to span interactions from the strong to the weak limit. © 2020 American Chemical Society.
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Neutral Organic Radical Formation by Chemisorption on Metal Surfaces
Ajayakumar M.R., Moreno C., Alcón I., Illas F., Rovira C., Veciana J., Bromley S.T., Mugarza A., Mas-Torrent M. Journal of Physical Chemistry Letters; 11 (10): 3897 - 3904. 2020. 10.1021/acs.jpclett.0c00269. IF: 6.710
Organic radical monolayers (r-MLs) bonded to metal surfaces are potential materials for the development of molecular (spin)electronics. Typically, stable radicals bearing surface anchoring groups are used to generate r-MLs. Following a recent theoretical proposal based on a model system, we report the first experimental realization of a metal surface-induced r-ML, where a rationally chosen closed-shell precursor 3,5-dichloro-4-[bis(2,4,6-trichlorophenyl)methylen]cyclohexa-2,5-dien-1-one (1) transforms into a stable neutral open-shell species (1) via chemisorption on the Ag(111) surface. X-ray photoelectron spectroscopy reveals that the >C=O group of 1 reacts with the surface, forming a C-O-Ag linkage that induces an electronic rearrangement that transforms 1 to 1. We further show that surface reactivity is an important factor in this process whereby Au(111) is inert towards 1, whereas the Cu(111) surface leads to dehalogenation reactions. The radical nature of the Ag(111)-bound monolayer was further confirmed by angle-resolved photoelectron spectroscopy and electronic structure calculations, which provide evidence of the emergence of the singly occupied molecular orbital (SOMO) of 1. © 2020 American Chemical Society.
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Stabilizing Edge Fluorination in Graphene Nanoribbons
Panighel M., Quiroga S., Brandimarte P., Moreno C., Garcia-Lekue A., Vilas-Varela M., Rey D., Sauthier G., Ceballos G., Peña D., Mugarza A. ACS Nano; 14 (9): 11120 - 11129. 2020. 10.1021/acsnano.0c01837. IF: 14.588
The on-surface synthesis of edge-functionalized graphene nanoribbons (GNRs) is challenged by the stability of the functional groups throughout the thermal reaction steps of the synthetic pathway. Edge fluorination is a particularly critical case in which the interaction with the catalytic substrate and intermediate products can induce the complete cleavage of the otherwise strong C-F bonds before the formation of the GNR. Here, we demonstrate how a rational design of the precursor can stabilize the functional group, enabling the synthesis of edge-fluorinated GNRs. The survival of the functionalization is demonstrated by tracking the structural and chemical transformations occurring at each reaction step with complementary X-ray photoelectron spectroscopy and scanning tunneling microscopy measurements. In contrast to previous attempts, we find that the C-F bond survives the cyclodehydrogenation of the intermediate polymers, leaving a thermal window where GNRs withhold more than 80% of the fluorine atoms. We attribute this enhanced stability of the C-F bond to the particular structure of our precursor, which prevents the cleavage of the C-F bond by avoiding interaction with the residual hydrogen originated in the cyclodehydrogenation. This structural protection of the linking bond could be implemented in the synthesis of other sp2-functionalized GNRs. © 2020 American Chemical Society.
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Supergiant Barocaloric Effects in Acetoxy Silicone Rubber over a Wide Temperature Range: Great Potential for Solid-state Cooling
Imamura W., Usuda É.O., Paixão L.S., Bom N.M., Gomes A.M., Carvalho A.M.G. Chinese Journal of Polymer Science (English Edition); 38 (9): 999 - 1005. 2020. 10.1007/s10118-020-2423-9. IF: 3.154
Solid-state cooling based on caloric effects is considered a viable alternative to replace the conventional vapor-compression refrigeration systems. Regarding barocaloric materials, recent results show that elastomers are promising candidates for cooling applications around room-temperature. In the present paper, we report supergiant barocaloric effects observed in acetoxy silicone rubber—a very popular, low-cost and environmentally friendly elastomer. Huge values of adiabatic temperature change and reversible isothermal entropy change were obtained upon moderate applied pressures and relatively low strains. These huge barocaloric changes are associated both to the polymer chain rearrangements induced by confined compression and to the first-order structural transition. The results are comparable to the best barocaloric materials reported so far, opening encouraging prospects for the application of elastomers in near future solid-state cooling devices. © 2020, Chinese Chemical Society Institute of Chemistry, Chinese Academy of Sciences Springer-Verlag GmbH Germany, part of Springer Nature.
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Waste Tire Rubber-based Refrigerants for Solid-state Cooling Devices
Bom N.M., Usuda É.O., da Silva Gigliotti M., de Aguiar D.J.M., Imamura W., Paixão L.S., Carvalho A.M.G. Chinese Journal of Polymer Science (English Edition); 38 (7): 769 - 775. 2020. 10.1007/s10118-020-2385-y. IF: 3.154
Management of discarded tires is a compelling environmental issue worldwide. Although there are several approaches developed to recycle waste tire rubbers, their application in solid-state cooling is still unexplored. Considering the high barocaloric potential verified for elastomers, the use of waste tire rubber (WTR) as a refrigerant in solid-state cooling devices is very promising. Herein, we investigated the barocaloric effects in WTR and polymer blends made of vulcanized natural rubber (VNR) and WTR, to evaluate its feasibility for solid-state cooling technologies. The adiabatic temperature changes and the isothermal entropy changes reach giant values, as well as the performance parameters, being comparable or even better than most barocaloric materials in literature. Moreover, pure WTR and WTR-based samples also present a faster thermal exchange than VNR, consisting of an additional advantage of using these discarded materials. Thus, the present findings evidence the encouraging perspectives of employing waste rubbers in solid-state cooling based on barocaloric effects, contributing to both the recycling of polymers and the sustainable energy technology field. © 2020, Chinese Chemical Society Institute of Chemistry, Chinese Academy of Sciences Springer-Verlag GmbH Germany, part of Springer Nature.
