Cobalt Monolayer Research Articles

Functional Monolayers on a Superatomic Pegboard.

We advance the chemistry of apical chlorine substitution in the 2D superatomic semiconductor Re6Se8Cl2 to build functional and atomically precise monolayers on the surface of the 2D superatomic Re6Se8 substrate. We create a functional monolayer by installing surface (2,2'-bipyridine)-4-sulfide (Sbpy) groups that chelate to catalytically active metal complexes. Through this reaction chemistry, we can create monolayers where we can control the distribution of catalytic sites. As a demonstration, we create highly active electrocatalysts for the oxygen evolution reaction using monolayers of cobalt(acetylacetonate)2bipyridine. We can further produce a series of catalysts by incorporating organic spacers in the functional monolayers. The structure and flexibility of the surface linkers can affect the catalytic performance, possibly by tuning the coupling between the functional monolayer and the superatomic substrate. These studies establish that the Re6Se8 sheet behaves as a chemical pegboard: a surface amenable to geometrically and chemically well-defined modification to yield functional monolayers, in this case catalytically active, that are atomically precise. This is an effective method to generate diverse families of functional nanomaterials.

Strong effect of crystal structure on the proximity effect between a superconductor and monolayer of cobalt

We present an unexpectedly strong influence of the proximity effect between the bulk Ru(0001) superconductor and atomically thin layers of Co on the crystal structure of the latter. The Co monolayer grows in two different modifications, such as hcp stacking and a reconstructed ε-like phase. While hcp islands show a weak proximity effect on Co and a little suppression of superconductivity in the substrate next to it, the more complex ε-like stacking becomes almost fully superconducting. We explain the weak proximity effect between Ru and hcp Co and the rather abrupt jump of the superconducting order parameter by a low transparency of the interface. In contrast, the strong proximity effect without a jump of the order parameter in the ε-like phase indicates a highly transparent interface. This work highlights that the proximity effect between a superconductor and a normal metal strongly depends on the crystal structure of the interface, which allows to engineer the proximity effect in hybrid structures.

Tuning the length/width aspect ratio of epitaxial unidirectional silicide nanowires on Si(110)-16 × 2 surfaces

The reactive deposition epitaxy growth of self-organized cobalt silicide nanowires (NWs) on clean Si(110) surfaces has been investigated by in situ scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) as well as by scanning electron microscopy (SEM). Half a monolayer of cobalt was deposited on the Si(110) surfaces at ∼600 °C substrate temperature. Following cobalt deposition, the substrates have been annealed for different durations. Cobalt forms aligned cobalt disilicide nanowires upon reaction with the silicon substrate, following the twofold substrate symmetry. With increasing duration of annealing, the NWs have been found to grow with larger aspect ratio (length/width), eventually producing narrower NWs. These self-organized unidirectional NWs of sub-hundred nanometer width and ∼4–7 nm height produce a Schottky barrier with the silicon substrate and are expected to find applications in nanoelectronic devices.

Molybdenum and Phosphorous Dual Doping in Cobalt Monolayer Interfacial Assembled Cobalt Nanowires for Efficient Overall Water Splitting

AbstractThe necessity for better water splitting requires speedy development of efficient catalysts with high activity, long‐term stability, and cost effectiveness. In this work, a bifunctional catalyst originating from the interfacial assembly of a thin Mo,P‐codoped Co layer (≈50 nm) shelled Co nanowire (Co‐Mo‐P/CoNWs) network is fabricated via a facile approach. The catalyst exhibits low overpotentials of 0.08 and 0.27 V to reach a current response of 20 mA cm−2 for the hydrogen evolution reaction and oxygen evolution reaction, respectively, together with long‐term stability in 1.0 m KOH medium. The outstanding performance is further demonstrated by a Co‐Mo‐P/CoNWs‐based electrolyzer, which enables a cell voltage of only 1.495 V to reach 10 mA cm−2, superior to one derived from commercial (Pt/C + RuO2/C) as well as to various reports recently published elsewhere. It is recognized that the formation of multiactive centers together with the increased active site number caused by Mo and P dual doping synergistically promote both hydrogen and oxygen evolution performance. Such a hybrid material opens a new approach for developing efficient and cost‐effective catalysts for water splitting application.

Effects of strain on electronic and magnetic properties of Co/WS2 nanolayer: A density functional and Monte Carlo study

In this work, density functional computations and Monte Carlo simulations are performed to investigate structural, electronic, magnetic, and thermodynamic properties of Co/WS$_2$ junction, a semiconductor WS$_2$ monolayer covered by a ferromagnetic cobalt monolayer. In addition to a conventional semilocal exchange-correlation functional, three nonlocal functional, including the novel ACBN0 scheme, are applied to obtain reliable electronic and magnetic properties. It is argued that the ACBN0 scheme, is very efficient for first principles description of the Co/WS$_2$ junction. The obtained electronic structures evidence a trustworthy half-metallic gap in the majority spin channel of the lowest energy configuration of the junction, promising for spintronic applications. The obtained magnetic thermodynamics properties from Monte Carlo simulations predict a Curie temperature of about 110\,K, which is far small for device applications of this junction. The electronic and magnetic properties of the system are calculated under various compressive and tensile strains and it is shown that a tensile strain of about 4\% may effectively improve thermal stability of half-metallic ferromagnetism in the Co/WS$_2$ junction.

Nanoparticle Linker‐Controlled Molecular Wire Devices Based on Double Molecular Monolayers

Highly conductive molecular wires are an important component for realizing molecular electronic devices and have to be explored in terms of interactions between molecules and electrodes in their molecular junctions. Here, new molecular wire junctions are reported to enhance charge transport through gold nanoparticle (AuNP)-linked double self-assembled monolayers (SAMs) of cobalt (II) bis-terpyridine molecules (e.g., Co(II)(tpyphS)2 ). Electrical characteristics of the double-SAM devices are explored in terms of the existence of AuNP. The AuNP linker in the Co(II)(tpyphS)2 -AuNP-Co(II)(tpyphS)2 junction acts as an electronic contact that is transparent to electrons. The weak temperature dependency of the AuNP-linked molecular junctions strongly indicates sequential tunneling conduction through the highest occupied molecular orbitals (HOMOs) of Co(II)(tpyphS)2 molecules. The electrochemical characteristics of the AuNP-Co(II)(tpyphS)2 SAMs reveal fast electron transfer through molecules linked by AuNP. Density functional theory calculations reveal that the molecular HOMO levels are dominantly affected by the formation of junctions. The intermolecular charge transport, controlled by the AuNP linker, can provide a rational design for molecular connection that achieves a reliable electrical connectivity of molecular electronic components for construction of molecular electronic circuits.

Intercalating cobalt between graphene and iridium (111): Spatially dependent kinetics from the edges

Using low-energy electron microscopy, we image in real time the intercalation of a cobalt monolayer between graphene and the (111) surface of iridium. Our measurements reveal that the edges of a graphene flake represent an energy barrier to intercalation. Based on a simple description of the growth kinetics, we estimate this energy barrier and find small, but substantial, local variations. These local variations suggest a possible influence of the graphene orientation with respect to its substrate and of the graphene edge termination on the energy value of the barrier height. Besides, our measurements show that intercalated cobalt is energetically more favorable than cobalt on bare iridium, indicating a surfactant role of graphene.

Unconventional magnetisation texture in graphene/cobalt hybrids.

Magnetic domain structure and spin-dependent reflectivity measurements on cobalt thin films intercalated at the graphene/Ir(111) interface are investigated using spin-polarised low-energy electron microscopy. We find that graphene-covered cobalt films have surprising magnetic properties. Vectorial imaging of magnetic domains reveals an unusually gradual thickness-dependent spin reorientation transition, in which magnetisation rotates from out-of-the-film plane to the in-plane direction by less than 10° per cobalt monolayer. During this transition, cobalt films have a meandering spin texture, characterised by a complex, three-dimensional, wavy magnetisation pattern. In addition, spectroscopy measurements suggest that the electronic band structure of the unoccupied states is essentially spin-independent already a few electron-Volts above the vacuum level. These properties strikingly differ from those of pristine cobalt films and could open new prospects in surface magnetism.

Water Oxidation Using a Cobalt Monolayer Prepared by Underpotential Deposition

Development of electrocatalysts for the conversion of water to dioxygen is important in a variety of chemical applications. Despite much research in this field, there are still several fundamental issues about the electrocatalysts that need to be resolved. Two such problems are that the catalyst mass loading on the electrode is subject to large uncertainties and the wetted surface area of the catalyst is often unknown and difficult to determine. To address these topics, a cobalt monolayer was prepared on a gold electrode by underpotential deposition and used to probe its efficiency for the oxidation of water. This electrocatalyst was characterized by atomic force microscopy, grazing-incidence X-ray diffraction, and X-ray photoelectron spectroscopy at various potentials to determine if changes occur on the surface during catalysis. An enhancement of current was observed upon addition of PO4(3-) ions, suggesting an effect from surface-bound ligands on the efficiency of water oxidation. At 500 mV overpotential, current densities of 0.20, 0.74, and 2.4 mA/cm(2) for gold, cobalt, and cobalt in PO4(3-) were observed. This approach thus provided electrocatalysts whose surface areas and activity can be accurately determined.

Tuning the Kondo effect in thin Au films by depositing a thin layer of Au on molecular spin-dopants

We report on the tuning of the Kondo effect in thin Au films containing a monolayer of cobalt(II) terpyridine complexes by altering the ligand structure around the Co2+ ions by depositing a thin Au capping layer on top of the monolayer on Au by magnetron sputtering (more energetic) and e-beam evaporation (softer). We show that the Kondo effect is slightly enhanced with respect to that of the uncapped film when the cap is deposited by evaporation, and significantly enhanced when magnetron sputtering is used. The Kondo temperature (TK) increases from 3 to 4.2/6.2 K for the evaporated/sputtered caps. X-ray absorption spectroscopy and surface-enhanced Raman spectroscopy investigation showed that the organic ligands remain intact upon Au e-beam evaporation; however, sputtering inflicts significant change in the Co2+ electronic environment. The location of the monolayer—on the surface or embedded in the film—has a small effect. However, the damage of Co–N bonds induced by sputtering has a drastic effect on the increase of the impurity–electron interaction. This opens up the way for tuning of the magnetic impurity states, e.g. spin quantum number, binding energy with respect to the host Fermi energy, and overlap via the ligand structure around the ions.

Concentration Phase Transition and Hysteresis Phenomena in Co-Nanofilms. Computer Data Processing and Simulation

The critical phenomena on cobalt monolayer films were studied by means of computersimulation. Proposed approach on the base of data of scanning tunneling microscopy gives possibilityestimate of critical concentration needed for concentration transition into ferromagnetic state. Assumptionabout presence of critical switching field allowed simulated hysteresis loops for given 1.5,2.0, 2.5 and 3.0 ML cobalt samples in frame of Ising model, which ones have qualitative agreementwith magnetometric data.

Interstratified hybrids of α-hydroxides of nickel and cobalt as supercapacitor electrode materials

Zwitterionic p-aminobenzoate ion intercalated α-hydroxides of nickel and cobalt exfoliate in water. The hydroxide monolayers of nickel and cobalt could be co-stacked from a mixture of their colloidal dispersions by the addition of excess of nitrate ions resulting in hybrids in which the layers of the two hydroxides were randomly co-stacked. The α-hydroxide hybrids were explored for their potential as supercapacitor electrode materials. The specific capacitance of hybrids vary with [Ni]/[Co] ratio and a maximum capacitance of 990Fg−1 (at a current density of 1Ag−1) with good cycling stability was obtained for the hybrid with [Ni]/[Co]=4.

Critical Temperatures of Random Iron–Cobalt Overlayers on the fcc-Cu(001) Substrate

We have theoretically investigated thermodynamic properties of random iron–cobalt monolayer deposited on the fcc(001) face of copper. The effective two-dimensional Heisenberg Hamiltonian was constructed from first principles and used to estimate the Curie temperature. The random-phase approximation as well as Monte Carlo approach are used and critically compared. Calculations indicate a weak maximum of the Curie temperature for Fe-rich composition of the overlayer.

Giant coercivity in perpendicularly magnetized cobalt monolayer

We report giant coercivity (HC) up to 35 kOe at 4 K, measured by the anomalous Hall effect, in perpendicularly magnetized Co (∼0.3 nm) films, where Co is approximately one monolayer. The HC is dramatically reduced with huge applied current, due to Joule heating rather than Rashba effect. It is also sensitive to temperatures, producing almost zero HC at 200 K. The Curie temperature of the Co monolayer is ∼275 K, far lower than that of bulk Co. The giant HC could be explained by the strong interaction at Co/Pd interface, providing a promising paradise: one monolayer, one permanent magnet.

Cobalt induced nanocrystals on Ge(001)

The deposition of several monolayers of cobalt on germanium (001) substrates results in the formation of two types of clusters: flat-topped and peaked nanocrystals. Scanning tunneling spectroscopy and helium ion microscopy measurements reveal that these nanocrystals contain cobalt. The shape evolution of the flat-topped and peaked nanocrystals as a function of their size is investigated with scanning tunneling microscopy. For small sizes the nanocrystals are compact. Beyond a critical size, however, the peaked nanocrystals exhibit an elongated shape, whilst the flat-topped nanocrystals remain compact. The shape transition of the peaked nanocrystals is driven by a competition between boundary and strain energies. For small sizes the boundary energy is the dominant term leading to a minimization of the peaked nanocrystal's perimeter, whereas at larger sizes the strain energy wins resulting in a maximization of the perimeter. On the top facet of the flat-topped nanocrystals one-dimensional structures are observed that are comprised of small square shaped units of about 1nm2. Time-resolved scanning tunneling microscopy measurements reveal that these square shaped units are dynamic at room temperature.

Cobalt Monolayer Islands on Ag(111) for ORR Catalysis

The design of a catalyst for one of the most important electrocatalytic reactions, the oxygen reduction reaction (ORR), was done following the most recent guidelines of theoretical studies on this topic. Aim of this work was to achieve a synergic effect of two different metals acting on different steps of the ORR. The catalytic activity of Ag, already known and characterized, was enhanced by the presence of a monolayer of cobalt subdivided into nanosized islands. To obtain such a controlled nanostructure, a novel method utilizing self-assembled monolayers (SAMs) as templates was employed. In a recent study, we were able to perform a confined electrodeposition of cobalt onto Ag(111) in a template formed by selectively desorbing a short-chain thiol (3-mercaptopropionic acid, MPA) from binary SAMs using 1-dodecanthiols (DDT). This method allows for an excellent control of the morphology of the deposit by varying the molar ratio of the two thiols. Because cobalt does not deposit on silver at an underpotential, the alternative approach of surface limited redox replacement (SLRR) was used. This method, recently developed by Adžić et al., consists of the use of a monolayer of a third metal, which can be deposited at an underpotential, as a template for the spontaneous deposition of a more noble metal. Herein, we choose zinc as template for the deposition of cobalt. Ag(111) crystals were covered by monolayer islands consisting of cobalt, with the surface atomic ratios ranging from 12 to 39% for cobalt. The catalytic activity of such samples towards ORR was evaluated and the best improvement in activity was found to be that of the sample with a cobalt percentage of approximately 30% with respect to the bare silver, which is in good agreement with theoretical hypotheses.

Thermally Activated Processes at the Co/ZnO Interface Elucidated Using High Energy X-rays

A detailed picture of the thermally activated processes occurring at the Co/ZnO interface is obtained by a combination of high energy X-ray based techniques: X-ray photoelectron and absorption spectroscopies and the kinematical X-ray standing wave method. At room temperature, the growth of a few monolayers of cobalt proceeds by the nucleation of nanometer-sized clusters on the polar oxygen-terminated (0001) surface of a ZnO single crystal. Progressive annealing from 600 to 970 K allows separating the various interfacial reactions. At the lowest annealing temperature, Co clusters coalesce while keeping their metallic character. Above 700 K Co0 is gradually oxidized to Co2+ and a thin Co rich (Zn,Co)O layer is formed. It is observed that rock salt CoO phases may form at the surface when the initial Co thickness exceeds 1 nm. At the highest annealing temperature (970 K), Co diffuses deeper into ZnO and Zn vacancies are created at subsurface sites that were previously occupied by Co.

Structural elements in the oxidation process of a single cobalt layer on Ir(100)-(1×1)

The ordered phases developing in sequence by oxidation of a single monolayer of cobalt deposited on Ir(100)-$(1\ifmmode\times\else\texttimes\fi{}1)$ were investigated by low-energy electron diffraction (LEED), scanning tunneling microscopy, and thermal desorption spectroscopy. It turns out that the structural elements of the different phases observed for increasing oxygen content and analyzed by quantitative LEED are pyramids based on squares or triangles made up by cobalt species and oxygen on top. The Co-O bond lengths are smaller than in the bulk of cobalt oxide owing to the reduced coordination of oxygen. For O:Co ratios of $r=1/4$, 1/2, and 5/8, the bonding of the oxide to the iridium substrate is merely by the cobalt species, and at $r=1$ it is via both Co and O.

Ab initio study of the fcc-WC(1 0 0) surface and its interaction with cobalt monolayers

The WC(100) surface has been studied by using ab initio methods of the density functional theory and pseudopotentials. Calculations have shown that surface and undersurface atoms move from their bulk positions. Namely, carbon atoms moved outward, while tungsten atoms moved inward. Five geometric cases for Co/WC(100) system were compared: (A) Co atoms are above C atoms; (B) Co atoms are above W atoms; (C) Co atoms are in the four-fold sites above WC pairs; (D and E) Co atoms are above the W–W–C and C–C–W three-fold sites, respectively – and the (A) case has been found to be energetically preferable. In all cases, Co layers have been found to be ferromagnetic. The densities of states for the bulk fcc-WC, the WC(100) surface, and the WC/Co system were compared.

Tuneable perpendicular magnetic anisotropy in single crystal [Co/Ni](111) superlattices

This paper is dedicated to the preparation of thin film with a strong perpendicular to the film plane magnetic anisotropy, behaviour of great interest for spintronics. Single-crystalline [Co/Ni] (111) superlattices have been grown by molecular beam epitaxy. The epitaxial growth of Co and Ni was controlled by using reflection high energy diffraction (RHEED), allowing us to get an accurate control of the thicknesses . The superlattices magnetic properties were studied using magnetometry. All of them exhibit strong perpendicular to the plane magnetic anisotropy. The maximum of magneto-crystalline anisotropy is obtained for one cobalt mo nolayer. A simple model which takes into account surface and volume anisotropy explains the evolution of perpendicular anisotropy in these layers.