Supramolecular control of the magnetic anisotropy in two-dimensional high-spin Fe arrays at a metal interface

Magnetic atoms at surfaces are a rich model system for solid-state magnetic bits exhibiting either classical(1,2) or quantum(3,4) behaviour. Individual atoms, however, are difficult to arrange in regular patterns(1-5). Moreover, their magnetic properties are dominated by interaction with the substrate, which, as in the case of Kondo systems, often leads to a decrease or quench of their local magnetic moment(6,7). Here, we show that the supramolecular assembly of Fe and 1,4-benzenedicarboxylic acid molecules on a Cu surface results in ordered arrays of high-spin mononuclear Fe centres on a 1.5nm square grid. Lateral coordination with the molecular ligands yields unsaturated yet stable coordination bonds, which enable chemical modification of the electronic and magnetic properties of the Fe atoms independently from the substrate. The easy magnetization direction of the Fe centres can be switched by oxygen adsorption, thus opening a way to control the magnetic anisotropy in supramolecular layers akin to that used in metallic thin films.

Ring-Opening-Induced Toughening of a Low-Permittivity Polymer-Metal Interface

Integrating low dielectric permittivity (low-k) polymers to metals is an exacting fundamental challenge because poor bonding between low-polarizability moieties and metals precludes good interfacial adhesion. Conventional adhesion-enhancing methods such as using intermediary layers are unsuitable for engineering polymer/metal interfaces for many applications because of the collateral increase in dielectric permittivity. Here, we demonstrate a completely new approach without surface treatments or intermediary layers to obtain an excellent interfacial fracture toughness of > 13 J/m(2) in a model system comprising copper. and a cross-linked polycarbosilane with k similar to 2.7 obtained by curing a cyclolinear polycarbosilane in air.Our results suggest that interfacial oxygen catalyzed molecularring-opening and anchoring of the opened ring moieties of the polymer to copper is the main toughening mechanism. This novel approach of realizing adherent low-k polymer/metal structures without intermediary layers by activating metal-anchoring polymer moieties at the interface could be adapted for applications such as device wiring and packaging, and laminates and composites.

Large negative magnetoresistance and metal-insulator transition observed in MnO/C composite coatings grown on ceramic alumina by metalorganic chemical vapor deposition

MnO/C composite coatings were grown by the metalorganic chemical vapor deposition process on ceramic alumina in argon ambient. Characterization by various techniques confirms that these coatings are homogeneous composites comprising nanometer-sized MnO particles embedded in a matrix of nanometer-sized graphite. Components of the MnO/C composite coating crystalline disordered, but are electrically quite conductive. Resistance vs. temperature measurements show that coating resistance increases exponentially from a few hundred ohms at room temperature to a few megaohms at 30 K. Logarithmic plots of reduced activation energy vs. temperature show that the coating material undergoes a metal-insulator transition. The reduced activation energy exponent for the film under zero magnetic field was 2.1, which is unusually high, implying that conduction is suppressed at much faster rate than the Mott or the Efros-Shklovskii hopping mechanism. Magnetoconductance us. magnetic field plots obtained at various temperatures show a high magnetoconductance (similar to 28.8%) at 100 K, which is unusually large for a disordered system, wherein magnetoresistance is attributed typically to weak localization. A plausible explanation for the unusual behavior observed in the carbonaceous disordered composite material is proposed. (C) 2010 Elsevier Ltd. All rights reserved.

Mechanism of enhanced corrosion of alumina graphite refractories near slag/metal interface

All refractories show enhanced corrosion near the slag/metal interface due to Marangoni and convective flows. However, in the case of oxide refractories containing graphite flakes, corrosion is severe due to periodic oscillations in the contact angle at the slag/metal interface, resulting in cyclic dissolution of oxide and graphite into the slag and metal, respectively. Alumina--graphite (AG) refractories should be used only where they are not in simultaneous contact with slag (flux) and low carbon steel.

Early osseointegration of a strontium containing glass ceramic in a rabbit model

The most important property of a bone cement or a bone substitute in load bearing orthopaedic implants is good integration with host bone with reduced bone resorption and increased bone regeneration at the implant interface. Long term implantation of metal-based joint replacements often results in corrosion and particle release, initiating chronic inflammation leading onto osteoporosis of host bone. An alternative solution is the coating of metal implants with hydroxyapatite (HA) or bioglass or the use of bulk bioglass or HA-based composites. In the above perspective, the present study reports the in vivo biocompatibility and bone healing of the strontium (Sr)-stabilized bulk glass ceramics with the nominal composition of 4.5SiO(2)-3Al(2)O(3)-1.5P(2)O(5)-3SrO-2SrF(2) during short term implantation of up to 12 weeks in rabbit animal model. The progression of healing and bone regeneration was qualitatively and quantitatively assessed using fluorescence microscopy, histological analysis and micro-computed tomography. The overall assessment of the present study establishes that the investigated glass ceramic is biocompatible in vivo with regards to local effects after short term implantation in rabbit animal model. Excellent healing was observed, which is comparable to that seen in response to a commercially available implant of HA-based bioglass alone. (C) 2013 Elsevier Ltd. All rights reserved.

Prospects of zero Schottky barrier height in a graphene-inserted MoS2-metal interface

A low Schottky barrier height (SBH) at source/drain contact is essential for achieving high drive current in atomic layer MoS(2-)channel-based field effect transistors. Approaches such as choosing metals with appropriate work functions and chemical doping are employed previously to improve the carrier injection from the contact electrodes to the channel and to mitigate the SBH between the MoS2 and metal. Recent experiments demonstrate significant SBH reduction when graphene layer is inserted between metal slab (Ti and Ni) and MoS2. However, the physical or chemical origin of this phenomenon is not yet clearly understood. In this work, density functional theory simulations are performed, employing pseudopotentials with very high basis sets to get insights of the charge transfer between metal and monolayer MoS2 through the inserted graphene layer. Our atomistic simulations on 16 different interfaces involving five different metals (Ti, Ag, Ru, Au, and Pt) reveal that (i) such a decrease in SBH is not consistent among various metals, rather an increase in SBH is observed in case of Au and Pt; (ii) unlike MoS2-metal interface, the projected dispersion of MoS2 remains preserved in any MoS2-graphene- metal system with shift in the bands on the energy axis. (iii) A proper choice of metal (e.g., Ru) may exhibit ohmic nature in a graphene-inserted MoS2-metal contact. These understandings would provide a direction in developing high-performance transistors involving heteroatomic layers as contact electrodes. (c) 2016 AIP Publishing LLC.

Density functional theory based study of chlorine doped WS2-metal interface

Investigation of a transition metal dichalcogenide (TMD)-metal interface is essential for the effective functioning of monolayer TMD based field effect transistors. In this work, we employ the Density Functional Theory calculations to analyze the modulation of the electronic structure of monolayer WS2 with chlorine doping and the relative changes in the contact properties when interfaced with gold and palladium. We initially examine the atomic and electronic structures of pure and doped monolayer WS2 supercell and explore the formation of midgap states with band splitting near the conduction band edge. Further, we analyze the contact nature of the pure supercell with Au and Pd. We find that while Au is physiosorbed and forms n-type contact, Pd is chemisorped and forms p-type contact with a higher valence electron density. Next, we study the interface formed between the Cl-doped supercell and metals and observe a reduction in the Schottky barrier height (SBH) in comparison to the pure supercell. This reduction found is higher for Pd in comparison to Au, which is further validated by examining the charge transfer occurring at the interface. Our study confirms that Cl doping is an efficient mechanism to reduce the n-SBH for both Au and Pd, which form different types of contact with WS2. (C) 2016 AIP Publishing LLC.

The fracture energy of metal fibre reinforced ceramic composites (MFCs)

A model is presented for prediction of the fracture energy of ceramic-matrix composites containing dispersed metallic fibres. It is assumed that the work of fracture comes entirely from pull-out and/or plastic deformation of fibres bridging the crack plane. Comparisons are presented between these predictions and experimental measurements made on a commercially-available composite material of this type, containing stainless steel (304) fibres in a matrix predominantly comprising alumina and alumino-silicate phases. Good agreement is observed, and it's noted that there is scope for the fracture energy levels to be high (~20kJm-2). Higher toughness levels are both predicted and observed for coarser fibres, up to a practical limit for the fibre diameter of the order of 0.5mm. Other deductions are also made concerning strategies for optimisation of the toughness of this type of material. © 2010 Elsevier Ltd.

Interface Fracture Property Of Peo Ceramic Coatings On Aluminum Alloy

This paper combines the four-point bending test, SEM and finite element method to study the interface fracture property of PEO coatings on aluminum alloy. The interface failure mode of the coating on the compression side is revealed. The ceramic coating crack firstly along the 45 degrees to the interface, then the micro crack in the coating deduces the interface crack. The plastic deformation observed by SEM shows excellent adhesion property between the coating and substrate. The plastic deformation in the substrate is due to the interfacial crack extension, so the interface crack mode of PEO coatings is ductile crack. The results of FEM show that the compression strength is about 600 MPa. (C) 2008 Elsevier B.V. All rights reserved.

Peeling Experiments Of Ductile Thin Films Along Ceramic Substrates - Critical Assessment Of Analytical Models

Two types of peeling experiments are performed in the present research. One is for the Al film/Al2O3 substrate system with an adhesive layer between the film and the substrate. The other one is for the Cu film/Al2O3 substrate system without adhesive layer between the film and the substrate, and the Cu films are electroplated onto the Al2O3 substrates. For the case with adhesive layer, two kinds of adhesives are selected, which are all the mixtures of epoxy and polyimide with mass ratios 1:1.5 and 1:1, respectively. The relationships between energy release rate, the film thickness and the adhesive layer thickness are measured during the steady-state peeling process. The effects of the adhesive layer on the energy release rate are analyzed. Using the experimental results, several analytical criteria for the steady-state peeling based on the bending model and on the two-dimensional finite element analysis model are critically assessed. Through assessment of analytical models, we find that the cohesive zone criterion based on the beam bend model is suitable for a weak interface strength case and it describes a macroscale fracture process zone case, while the two-dimensional finite element model is effective to both the strong interface and weak interface, and it describes a small-scale fracture process zone case. (C) 2007 Elsevier Ltd. All rights reserved.

Interface Fracture Behavior Of Electroplated Coating On Metal Substrate Under Compressive Strain

The inducement of interface fracture is crucial to the analysis of interfacial adhesion between coating and substrate. For electroplated coating/metal substrate adhering materials with strong adhesion, interface cracking and coating spalling are difficult to be induced by conventional methods. In this paper an improved bending test named as T-bend test was conducted on a model coating system, i.e. electroplated chromium on a steel substrate. After the test, cross-sections of the coated materials were prepared to compare the failure behaviors under tensile strain and compressive strain induced by T-bend test. And the observation results show that coating cracking, interface cracking and partial spalling appear step by step. Based on experimental results, a new method may be proposed to rank the coated materials with strong inter-facial adhesion. (C) 2008 Elsevier B.V. All rights reserved.

Role of interface dipole in metal gate/high-k effective work function modulation by aluminum incorporation

The interface dipole and its role in the effective work function (EWF) modulation by Al incorporation are investigated. Our study shows that the interface dipole located at the high-k/SiO2 interface causes an electrostatic potential difference across the metal/high-k interface, which significantly shifts the band alignment between the metal and high-k, consequently modulating the EWF. The electrochemical potential equalization and electrostatic potential methods are used to evaluate the interface dipole and its contribution. The calculated EWF modulation agrees with experimental data and can provide insight to the control of EWF in future pMOS technology.