Modifying the Cu(111) Shockley surface state by Au alloying

The deposition of submonolayer amounts of Au onto Cu(111) results in a Au-Cu surface alloy with temperature- and thickness-dependent stoichiometry. Upon alloying, the characteristic Shockley state of Cu(111) is modified, shifting to 0.53 eV binding energy for a particular surface Au2Cu concentration, which is a very high binding energy for a noble-metal surface. Based on a phase accumulation model analysis, we discuss how this unusually large shift is likely reflecting an effective increase in the topmost layer thickness of the order of, but smaller than, the value expected from the moiré undulation. © 2012 American Physical Society.This work was supported in part by the Spanish MINECO (Grants No. MAT2010-21156-C03-01 and No. MAT2010-21156-C03-03), and the Basque Government (Grant No. IT-257-07). The SRC is funded by the National Science Foundation (Award No. DMR-0084402).Peer Reviewe

Magnetism and morphology of Co nanocluster superlattices on GdAu2 /Au(111)- (13×13)

Under the terms of the Creative Commons Attribution License 3.0 (CC-BY).-- et al.We present a comprehensive study of the magnetism and morphology of an ultrahigh density array of Co nanoclusters self-assembled on the single atomic layer GdAu2 on Au(111) template surface. Combining scanning tunneling microscopy, x-ray magnetic circular dichroism, and magneto-optical Kerr effect measurements, we reveal a significant enhancement of the perpendicular magnetic anisotropy energy for noncoalesced single atomic layer nanoclusters compared to Co/Au(111). For coverages well beyond the onset of coalescence, we observe room-temperature in-plane magnetic remanence.We acknowledge funding from the Swiss National Science Foundation, from the Sino-Swiss Science and Technology Cooperation Project No. IZLCZ2 123892, from the Spanish Ministerio de Ciencia e Innovacion (MAT2010-21156-C03-03), from the Gipuzkoako Foru Aldundia, from the European Social Fund within the program JAE-Doc, the Basque Government (IT-621-13 and IT-627-13) and SAIOTEK (S-PE12UN095), as well as from the EU Calipso program for synchrotron access funding. The MBE chamber on DEIMOS was funded by the Agence National de la Recherche with Grant No. ANR-05-NANO-073.Peer Reviewe

On-Surface Engineering of a Magnetic Organometallic Nanowire

The manipulation of the molecular spin state by atom doping is an attractive strategy to confer desirable magnetic properties to molecules. Here, we present the formation of novel magnetic metallocenes by following this approach. In particular, two different on-surface procedures to build isolated and layer-integrated Co-ferrocene (CoFc) molecules on a metallic substrate via atomic manipulation and atom deposition are shown. The structure as well as the electronic properties of the so-formed molecule are investigated combining scanning tunneling microscopy and spectroscopy with density functional theory calculations. It is found that unlike single ferrocene a CoFc molecule possesses a magnetic moment as revealed by the Kondo effect. These results correspond to the first controlled procedure toward the development of tailored metallocene-based nanowires with a desired chemical composition, which are predicted to be promising materials for molecular spintronics

Tuning the magnetic properties of NiPS3through organic-ion intercalation

Atomically thin van der Waals magnetic crystals are characterized by tunable magnetic properties related to their low dimensionality. While electrostatic gating has been used to tailor their magnetic response, chemical approaches like intercalation remain largely unexplored. Here, we demonstrate the manipulation of the magnetism in the van der Waals antiferromagnet NiPS3 through the intercalation of different organic cations, inserted using an engineered two-step process. First, the electrochemical intercalation of tetrabutylammonium cations (TBA+) results in a ferrimagnetic hybrid compound displaying a transition temperature of 78 K, and characterized by a hysteretic behavior with finite remanence and coercivity. Then, TBA+ cations are replaced by cobaltocenium via an ion-exchange process, yielding a ferrimagnetic phase with higher transition temperature (98 K) and higher remanent magnetization. Importantly, we demonstrate that the intercalation and cation exchange processes can be carried out in bulk crystals and few-layer flakes, opening the way to the integration of intercalated magnetic materials in devices.The authors acknowledge R. Llopis and A. Eleta for technical support. This work is supported by “la Caixa” Foundation (ID 100010434), under the agreement LCF/BQ/PI19/11690017, by the Spanish MICINN under Project PID2019-108153GA-I00, RTI2018-094861-B-100 and under the María de Maeztu Units of Excellence Program (MDM-2016-0618). B. M.-G. thanks Gipuzkoa Council (Spain) in the frame of Gipuzkoa Fellows Program.Peer reviewe

Influence of 4f filling on electronic and magnetic properties of rare earth-Au surface compounds

Altres ajuts: This work was supported in part by the Basque Government Project IT-1255-19, and University of the Basque Country (UPV/EHU) grant GIU18/138 and the European Regional Development Fund (ERDF) under the program Interreg V-A España-Francia-Andorra (Contract No. EFA 194/16 TNSI).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

Rare earth/Noble metal surface alloys

A thesis submitted for the degree of Doctor of Philosophy in Physics.Peer reviewe

Assembly of ferrocene molecules on metal surfaces revisited

Metallocene (MCp2) wires have recently attracted considerable interest in relation to molecular spintronics due to predictions concerning their half-metallic nature. This exciting prospect is however hampered by the little and often-contradictory knowledge we have concerning the metallocene self-assembly and interaction with a metal. Here, we elucidate these aspects by focusing on the adsorption of ferrocene on Cu(111) and Cu(100). Combining low-temperature scanning tunneling microscopy and density functional theory calculations, we demonstrate that the two-dimensional molecular arrangement consists of vertical- and horizontal-lying molecules. The noncovalent T-shaped interactions between Cp rings of vertical and horizontal molecules are essential for the stability of the physisorbed molecular layer. These results provide a fresh insight into ferrocene adsorption on surfaces and may serve as an archetypal reference for future work with this important variety of organometallic molecules. (Figure Presented).This work has been supported by the Agence Nationale de la Recherche (Grant No. ANR-13-BS10-0016). L.L. acknowledges also financial support from the Agence Nationale de la Recherche through projects LabEx NIE and LabEx CSC. R.R. and N.L. acknowledge financial support from Spanish MINECO (Grant No. MAT2012-38318- C03-02 with joint financing by FEDER Funds from the European Union). P.A. acknowledges financial support from CONICET. ICN2 acknowledges support from the Severo Ochoa Program (MINECO, Grant SEV-2013-0295).Peer Reviewe

Engineering Magnetism and Superconductivity in van der Waals Materials via Organic‐Ion Intercalation

Abstract Intercalation is the insertion of guest species between the planes of a host van der Waals layered crystal. The process is accompanied by a significant change of the charge carrier density and by the expansion of the interlayer distance, overall leading to a modification of the electronic band structure of the layered material. This perspective focuses on the possibilities offered by the intercalation of organic ions toward finely tuning the physical properties of van der Waals materials, in particular their magnetism and superconductivity. How the intercalation of organic ions offers several advantages over conventional guest species such as alkali metals is highlighted, since a careful choice of the molecular intercalant opens the possibility to tailor the interlayer distance and the charge carrier density. Moreover, specific properties of the molecular guest can be transferred to the host material, as recently demonstrated by the intercalation of thermo‐responsive and chiral molecules. It is anticipated that other functional organic ions can be incorporated in van der Waals materials to provide additional optical and magnetic capabilities, with the potential to enable an optical control of magnetism and superconductivity

On-Surface Engineering of a Magnetic Organometallic Nanowire

The manipulation of the molecular spin state by atom doping is an attractive strategy to confer desirable magnetic properties to molecules. Here, we present the formation of novel magnetic metallocenes by following this approach. In particular, two different on-surface procedures to build isolated and layer-integrated Co-ferrocene (CoFc) molecules on a metallic substrate via atomic manipulation and atom deposition are shown. The structure as well as the electronic properties of the so-formed molecule are investigated combining scanning tunneling microscopy and spectroscopy with density functional theory calculations. It is found that unlike single ferrocene a CoFc molecule possesses a magnetic moment as revealed by the Kondo effect. These results correspond to the first controlled procedure toward the development of tailored metallocene-based nanowires with a desired chemical composition, which are predicted to be promising materials for molecular spintronics

The Kondo Effect of a Molecular Tip As a Magnetic Sensor

A single molecule offers to tailor and control the probing capability of a scanning tunneling microscope when placed on the tip. With the help of first-principles calculations, we show that on-tip spin sensitivity is possible through the Kondo ground state of a spin S = 1/2 cobaltocene molecule. When attached to the tip apex, we observe a reproducible Kondo resonance, which splits apart upon tuning the exchange coupling of cobaltocene to an iron atom on the surface. The spin-split Kondo resonance provides quantitative information on the exchange field and on the spin polarization of the iron atom. We also demonstrate that molecular vibrations cause the emergence of Kondo side peaks, which, unlike the Kondo resonance, are sensitive to cobaltocene adsorption.Fil: Garnier, Léo. Centre National de la Recherche Scientifique; Francia. Université de Strasbourg; FranciaFil: Verlhac, Benjamin. Université de Strasbourg; Francia. Centre National de la Recherche Scientifique; FranciaFil: Abufager, Paula Natalia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Física de Rosario. Universidad Nacional de Rosario. Instituto de Física de Rosario; ArgentinaFil: Lorente, Nicolás. Consejo Superior de Investigaciones Científicas; España. Universidad del País Vasco; España. Donostia International Physics Center; EspañaFil: Ormaza, Maider. Université de Strasbourg; Francia. Centre National de la Recherche Scientifique; FranciaFil: Limot, Laurent. Université de Strasbourg; Francia. Centre National de la Recherche Scientifique; Franci