Molecular bilayers made up of a donor-acceptor blend in contact with the metal and capped with a single-component layer show a tunable energy level alignment at both metal-organic and organic-organic interfaces. To ensure sharp heteromolecular interfaces, a contact layer is formed by a stable blend of pentacene (PEN) and perfluorinated copper phthalocyanine (FCuPc) on Au(111) and Ag(111) and of perfluoropentacene (PFP) and copper phthalocyanine (CuPc) on Ag(111). Core-level and valence band photoemission reveal that, upon capping with pure FCuPc, CuPc, and PEN, the electronic states of both contact and capping layers >realign> with respect to the monolayer and the multilayer references. The sign of the shift depends clearly on whether the capping layer is donor-like (PEN, CuPc) or acceptor-like (FCuPc). As revealed by NEXAFS, the shift in electronic levels of the contact layer upon capping leads to a spectral density variation across the Fermi edge (E); i.e., it induces molecule/metal charge transfer. ; This work was supported by Spanish Grant No. MAT2013-46593-C6-4-P, the Basque Government grant IT-621-13 and the MIUR of Italy through PRIN project DESCARTES (no. 2010BNZ3F2). We acknowledge funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under Grant No. 226716 and under grant agreement No. 312284. ; Peer Reviewed
The properties of water at the nanoscale are crucial in many areas of biology, but the confinement of water molecules in sub-nanometre channels in biological systems has received relatively little attention. Advances in nanotechnology make it possible to explore the role played by water molecules in living systems, potentially leading to the development of ultrasensitive biosensors. Here we show that the adsorption of water by a self-assembled monolayer of single-stranded DNA on a silicon microcantilever can be detected by measuring how the tension in the monolayer changes as a result of hydration. Our approach relies on the microcantilever bending by an amount that depends on the tension in the monolayer. In particular, we find that the tension changes dramatically when the monolayer interacts with either complementary or single mismatched single-stranded DNA targets. Our results suggest that the tension is mainly governed by hydration forces in the channels between the DNA molecules and could lead to the development of a label-free DNA biosensor that can detect single mutations. The technique provides sensitivity in the femtomolar range that is at least two orders of magnitude better than that obtained previously with label-free nanomechanical biosensors and with label-dependent microarrays. ; D.R. acknowledges the fellowship funded by the Autonomic Community of Madrid (CAM). J.T, M.C, J.M and D.R acknowledge financial support by Spanish Ministry of Science (MEC) under grant No. TEC2006-10316 and CAM under grant No. 200550M056. C.B. acknowledges funding provided by MEC under grant No. BIO2007-67523. Work at Centro de Astrobiología was supported by European Union (EU), Instituto Nacional de Técnica Aeroespacial (INTA), MEC and CAM. All the authors acknowledge A. Cebollada, J.M. García-Martín, J. García, J.L. Costa-Kramer, M. Arroyo-Hernández and J.V. Anguita for their assistance in the gold deposition on the cantilevers. ; Peer reviewed
et al. ; A vicinal rutile TiO(110) crystal with a smooth variation of atomic steps parallel to the [1-10] direction was analyzed locally with STM and ARPES. The step edge morphology changes across the samples, from [1-11] zigzag faceting to straight [1-10] steps. A step-bunching phase is attributed to an optimal (110) terrace width, where all bridge-bonded O atom vacancies (O vacs) vanish. The [1-10] steps terminate with a pair of 2-fold coordinated O atoms, which give rise to bright, triangular protrusions (S) in STM. The intensity of the Ti 3d-derived gap state correlates with the sum of O vacs plus S protrusions at steps, suggesting that both O vacs and steps contribute a similar effective charge to sample doping. The binding energy of the gap state shifts when going from the flat (110) surface toward densely stepped planes, pointing to differences in the Ti polaron near steps and at terraces. ; We acknowledge financial support from the Spanish Ministry of Economy (Grants MAT2013-46593-C6-4-P and MAT2013-46593-C6-2-P) and the Basque Government (Grant IT621-13 and IT756-13). M.S. and U.D. acknowledge support from the ERC Advanced Grant "OxideSurfaces". D.S.P. and M.M. acknowledge support from the Marie Curie ITN "THINFACE" and financial support by the Deutsche Forschungsgemeinschaft. through SFB 1083 "Structure and Dynamics of Internal Interfaces". ; Peer Reviewed
The electronic character of a π-conjugated molecular overlayer on a metal surface can change from semiconducting to metallic, depending on how molecular orbitals arrange with respect to the electrodes Fermi level. Molecular level alignment is thus a key property that strongly influences the performance of organic-based devices. In this work, we report how the electronic level alignment of copper phthalocyanines on metal surfaces can be tailored by controlling the substrate work function. We even show the way to finely tune it for one fixed phthalocyanine-metal combination without the need to intercalate substrate-functionalizing buffer layers. Instead, the work function is trimmed by appropriate design of the phthalocyanines supramolecular environment, such that charge transfer into empty molecular levels can be triggered across the metal-organic interface. These intriguing observations are the outcome of a powerful combination of surface-sensitive electron spectroscopies, which further reveal a number of characteristic spectroscopic fingerprints of a lifted LUMO degeneracy associated with the partial phthalocyanine charging. ; This work was supported by the Spanish Grant Nos. MAT2010-21156-C03-01, PIB2010US-00652, and the Basque Government Grant No. IT-621-13. We acknowledge funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under Grant No. 226716. ; Peer Reviewed
A combined scanning tunneling microscopy, x-ray photoelectron spectroscopy, angle-resolved photoemission spectroscopy, and density functional theory study of graphene on a Fe-Ir(111) alloy with variable Ir concentration is presented. Starting from an intercalated Fe layer between the graphene and Ir(111) surface we find that graphene-substrate interaction can be fine-tuned by Fe-Ir alloying at the interface. When a critical Ir-concentration close to 0.25 is reached in the Fe layer, the Dirac cone of graphene is largely restored and can thereafter be tuned across the Fermi level by further increasing the Ir content. Indeed, our study reveals an abrupt transition between a chemisorbed phase at small Ir concentrations and a physisorbed phase above the critical concentration. The latter phase is highly reminiscent of the graphene on the clean Ir(111) surface. Furthermore, the transition is accompanied by an inversion of the graphene's induced magnetization due to the coupling with the Fe atoms from antiferromagnetic when chemisorbed to weakly ferromagnetic in the physisorption regime, with spin polarizations whose magnitude may be tuned with the amount of Fe content. ; This work has been funded by the Spanish MINECO under contract Nos. FIS2013-48286-C2-1-P, MAT2013-47878-C2-R, MAT2015-66888-C3-1R, and MAT2013-46593-C6-4-P as well as the Basque Government Grants IT621-13 and IT756-13. ; Peer Reviewed
Surface-confined dehalogenation reactions are versatile bottom-up approaches for the synthesis of carbonbased nanostructures with predefined chemical properties. However, for devices generally requiring low-conductivity substrates, potential applications are so far severely hampered by the necessity of a metallic surface to catalyze the reactions. In this work we report the synthesis of ordered arrays of poly(p-phenylene) chains on the surface of semiconducting TiO(110) via a dehalogenative homocoupling of 4,4″- dibromoterphenyl precursors. The supramolecular phase is clearly distinguished from the polymeric one using low-energy electron diffraction and scanning tunneling microscopy as the substrate temperature used for deposition is varied. X-ray photoelectron spectroscopy of C 1s and Br 3d core levels traces the temperature of the onset of dehalogenation to around 475 K. Moreover, angle-resolved photoemission spectroscopy and tightbinding calculations identify a highly dispersive band characteristic of a substantial overlap between the precursor's π states along the polymer, considered as the fingerprint of a successful polymerization. Thus, these results establish the first spectroscopic evidence that atomically precise carbon-based nanostructures can readily be synthesized on top of a transition-metal oxide surface, opening the prospect for the bottom-up production of novel molecule-semiconductor devices. ; This work was supported by the Spanish Ministry of Economy (Grant No. MAT2013-46593-C6-4-P), the Basque Government (Grant No. IT-621-13), and the European Research Council under the EU Horizon 2020 research and innovation program (Grant Agreement No. 635919). We also acknowledge support from the Basque Department of Education, UPV/EHU (Grant No. IT-756-13), the Spanish Ministry of Science and Innovation (Grant No. MAT2013-46593-C6-2-P), and the European Union FP7-ICT Integrated Project PAMS (Contract No. 610446). ; Peer Reviewed
Under the terms of the Creative Commons Attribution License 3.0 (CC-BY). ; We report measurements of a new type of magnetoresistance in Pt and Ta thin films. The spin accumulation created at the surfaces of the film by the spin Hall effect decreases in a magnetic field because of the Hanle effect, resulting in an increase of the electrical resistance as predicted by Dyakonov [Phys. Rev. Lett. 99, 126601 (2007)]. The angular dependence of this magnetoresistance resembles the recently discovered spin Hall magnetoresistance in Pt/Y3Fe5O12 bilayers, although the presence of a ferromagnetic insulator is not required. We show that this Hanle magnetoresistance is an alternative simple way to quantitatively study the coupling between charge and spin currents in metals with strong spin-orbit coupling. ; This work was supported by the European Union 7th Framework Programme under NMP Project No. 263104-HINTS and the European Research Council (Project No. 257654-SPINTROS), by the Spanish Ministry of Economy and Competitiveness under Projects No. MAT2012-37638, No. FIS2011-28851-C02-02, No. FIS2014-55987-P, and No. MAT2013-46593-C6-4-P, and by the Basque Government under UPV/EHU Projects No. IT-756-13 and No. IT-621-13. M. I. and E. S. thank the Basque Government and the Spanish Ministry of Education, Culture and Sport, respectively, for a Ph.D. fellowship (Grants No. BFI-2011-106 and No. FPU14/03102). ; Peer Reviewed
Trabajo presentado al Symposium on Surface Science (3S), celebrado en St. Christoph am Arlberg (Austria) del 21 al 27 de febrero de 2016. ; We acknowledge financial support from the Spanish Ministry of Economy (grant MAT2013-46593-C6-4-P and MAT2013-46593-C6-2-P) and the Basque Government (grant IT621-13 and IT756-13), the ERC Advanced Grant "OxideSurfaces"., and the Marie Curie ITN "THINFACE". ; Peer reviewed
Ferromagnetic insulators (FI) can induce a strong exchange field in an adjacent superconductor (S) via the magnetic proximity effect. This manifests as spin splitting of the BCS density of states of the superconductor, an important ingredient for numerous superconducting spintronics applications and the realization of Majorana fermions. A crucial parameter that determines the magnitude of the induced spin splitting in FI/S bilayers is the thickness of the S layer d: In very thin samples, the superconductivity is suppressed by the strong magnetism. By contrast, in very thick samples, the spin splitting is absent at distances away from the interface. In this work, we calculate the density of states and critical exchange field of FI/S bilayers of arbitrary thickness. From here, we determine the range of parameters of interest for applications, where the exchange field and superconductivity coexist. We show that for d>3.0ξs, the paramagnetic phase transition is always of the second order, in contrast to the first-order transition in thinner samples at low temperatures. Here ξs is the superconducting coherence length. Finally, we compare our theory with the tunneling spectroscopy measurements in several EuS/Al/AlOx/Al samples. If the Al film in contact with the EuS is thinner than a certain critical value, we do not observe superconductivity, whereas, in thicker samples, we find evidence of a first-order phase transition induced by an external field. The complete transition is preceded by a regime in which normal and superconducting regions coexist. We attribute this mixed phase to inhomogeneities of the Al film thickness and the presence of superparamagnetic grains at the EuS/Al interface with different switching fields. The steplike evolution of the tunnel-barrier magnetoresistance supports this assumption. Our results demonstrate on the one hand, the important role of the S layer thickness, which is particularly relevant for the fabrication of high-quality samples suitable for applications. On the other hand, the agreement between theory and experiment demonstrates the accuracy of our theory, which, originally developed for homogeneous situations, is generalized to highly inhomogeneous systems. ; F.S.B. acknowledges funding by the Spanish Ministerio de Ciencia, Innovación y Universidades (MICINN) (Project FIS2017-82804-P). T.T.H. acknowledges funding from the Academy of Finland (Project number 317118). A.H. acknowledges funding by the Department of Education of the Basque Government (Ikasiker grant). C.G.-O. acknowledges funding of the Ph.D. fellowship from MPC foundation. S.K. acknowledges for the fellowship of the ICTP Program for Training and Research in Italian laboratories, Trieste, Italy. C.R. acknowledges support from Gobierno Vasco (Grant No. IT 1255-19). F.G. acknowledges the European Research Council under the EU's Horizon 2020 Grant Agreement No. 899315-TERASEC for partial financial support. We acknowledge funding from EU's Horizon 2020 research and innovation program under Grant Agreement No. 800923 (SUPERTED). ; Peer reviewed
Contributing to the need for new graphene nanoribbon (GNR) structures that can be synthesized with atomic precision, we have designed a reactant that renders chiral (3,1)-GNRs after a multistep reaction including Ullmann coupling and cyclodehydrogenation. The nanoribbon synthesis has been successfully proven on different coinage metals, and the formation process, together with the fingerprints associated with each reaction step, has been studied by combining scanning tunneling microscopy, core-level spectroscopy, and density functional calculations. In addition to the GNR's chiral edge structure, the substantial GNR lengths achieved and the low processing temperature required to complete the reaction grant this reactant extremely interesting properties for potential applications. ; The project leading to this publication has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (Grant Agreement No. 635919), from ICT-FET EU integrated project PAMS (Agreement No. 610446), from the Spanish Ministry of Science and Competitiveness (MINECO, Grant Nos. MAT2013-46593-C6-01, MAT2013-46593-C6-2-P, MAT2013-46593-C6-4-P, MAT2013-46593-C6-6-P), FEDER, from the Basque Government (Grant Nos. IT-621-13, IT-756-13, and PI2015-042), from the World Premier International Center (WPI) for Materials Nanoarchitectonics (MANA) of the National Institute for Materials Science (NIMS), Tsukuba, Japan, and from JSPS Bilateral Open Partnership Joint Research Project. ; Peer reviewed
Metal halides are a class of layered materials with promising electronic and magnetic properties persisting down to the two-dimensional limit. While most recent studies focused on the trihalide components of this family, the rather unexplored metal dihalides are also van der Waals layered systems with distinctive magnetic properties. Here we show that the dihalide NiBr2 grows epitaxially on a Au(111) substrate and exhibits semiconducting and magnetic behavior starting from a single layer. Through a combination of a low-temperature scanning-tunneling microscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy, and photoemission electron microscopy, we identify two competing layer structures of NiBr2 coexisting at the interface and a stoichiometrically pure layer-by-layer growth beyond. Interestingly, X-ray absorption spectroscopy measurements revealed a magnetically ordered state below 27 K with in-plane magnetic anisotropy and zero-remanence in the single layer of NiBr2/Au(111), which we attribute to a noncollinear magnetic structure. The combination of such two-dimensional magnetic order with the semiconducting behavior down to the 2D limit offers the attractive perspective of using these films as ultrathin crystalline barriers in tunneling junctions and low-dimensional devices. ; D.B. acknowledges funding from the Austrian Science Fund (FWF) under the Erwin Schrödinger fellowship agreement (project number: J4395-N). C.G.-O. and M.P.-D. acknowledge funding of the Ph.D. fellowship from the MPC Foundation. We gratefully acknowledge financial support from Spanish AEI (Grant Nos. PID2019-107338RB-C6, RTI-2018-095303-C53, and the Maria de Maeztu Units of Excellence Programme MDM-2016-0618) and from the European Union (EU) through Horizon 2020 (SUPERTED Grant No. 800923), from Interred POCTEFA V-A Spain/France/Andorra Program (EFA 194/16/TNSI), the Basque Government (GV/EJ) under grants IT-1255-19, and the European Regional Development Fund. P.G. acknowledges funding from MINECO Grant No. FIS2016-78591-C3-2-R and FLAG-ERA Grant No. PCI2019-111908-2. ; Peer reviewed
The NEXT collaboration: et al. ; The Neutrino Experiment with a Xenon TPC (NEXT) searches for the neutrinoless double-beta (0νββ) decay of 136Xe using high-pressure xenon gas TPCs with electroluminescent amplification. A scaled-up version of this technology with about 1 tonne of enriched xenon could reach in less than 5 years of operation a sensitivity to the half-life of 0νββ decay better than 1027 years, improving the current limits by at least one order of magnitude. This prediction is based on a well-understood background model dominated by radiogenic sources. The detector concept presented here represents a first step on a compelling path towards sensitivity to the parameter space defined by the inverted ordering of neutrino masses, and beyond. ; The NEXT Collaboration acknowledges support from the following agencies and institutions: the European Research Council (ERC) under the Advanced Grant 339787-NEXT; the European Union's Framework Programme for Research and Innovation Horizon 2020 (2014–2020) under the Grant Agreements No. 674896, 690575 and 740055; the Ministerio de Economía y Competitividad and the Ministerio de Ciencia, Innovación y Universidades of Spain under grants FIS2014-53371-C04, RTI2018-095979, the Severo Ochoa Program grants SEV-2014-0398 and CEX2018-000867-S, and the María de Maeztu Program MDM2016-0692; the Generalitat Valenciana of Spain under grants PROMETEO/2016/120 and SEJI/2017/011; the Portuguese FCT under project PTDC/FIS-NUC/2525/2014 and under projects UID/FIS/04559/2020 to fund the activities of LIBPhys-UC; the Pazy Foundation (Israel) under grants 877040 and 877041; the US Department of Energy under contracts number DE-AC02-06CH11357 (Argonne National Laboratory), DE-AC02-07CH11359 (Fermi National Accelerator Laboratory), DE-FG02-13ER42020 (Texas A&M) and DE-SC0019223 / DE-SC0019054 (University of Texas at Arlington); and the University of Texas at Arlington. DGD acknowledges support from the Ramón y Cajal program (Spain) under contract number RYC-2015-18820. JM-A acknowledges support from Fundación Bancaria la Caixa (ID 100010434), grant code LCF/BQ/PI19/11690012, and from the Plan GenT program of the Generalitat Valenciana, grant code CIDEGENT/2019/049. ; Peer reviewed
