The quest for a spin-polarized organic light-emitting diode (spin-OLED) is a common goal in the emerging fields of molecular electronics and spintronics. In this device, two ferromagnetic (FM) electrodes are used to enhance the electroluminescence intensity of the OLED through a magnetic control of the spin polarization of the injected carriers. The major difficulty is that the driving voltage of an OLED device exceeds a few volts, while spin injection in organic materials is only efficient at low voltages. The fabrication of a spin-OLED that uses a conjugated polymer as bipolar spin collector layer and ferromagnetic electrodes is reported here. Through a careful engineering of the organic/inorganic interfaces, it is succeeded in obtaining a light-emitting device showing spin-valve effects at high voltages (up to 14 V). This allows the detection of a magneto-electroluminescence (MEL) enhancement on the order of a 2.4% at 9 V for the antiparallel (AP) configuration of the magnetic electrodes. This observation provides evidence for the long-standing fundamental issue of injecting spins from magnetic electrodes into the frontier levels of a molecular semiconductor. The finding opens the way for the design of multifunctional devices coupling the light and the spin degrees of freedom.

The understanding of magnetoresistance (MR) in organic spin valves (OSVs) based on molecular semiconductors is still incomplete after its demonstration more than a decade ago. Although carrier concentration may play an essential role in spin transport in these devices, direct experimental evidence of its importance is lacking. We probed the role of the charge carrier concentration by studying the interplay between MR and multilevel resistive switching in OSVs. The present work demonstrates that all salient features of these devices, particularly the intimate correlation between MR and resistance, can be accounted for by the impurity band model, based on oxygen migration. Finally, we highlight the critical importance of the carrier concentration in determining spin transport and MR in OSVs and the role of interface-mediated oxygen migration in controlling the OSV response.

Magnetic Fe3O4 (magnetite) nanoparticles are synthesized via a chemical precipitation route in different alkaline environments (NH3 or NaOH) and subsequently functionalized with a (propynylcarbamate)triethoxysilane moiety, with the aim of promoting the nucleation and subsequent stabilization of gold nanoparticles. The propynylcarbamate group is able to capture the gold precursor (HAuCl4), spontaneously reduce it, and stabilize the resulting Au nanoaggregates. The obtained results show that though the dimensions of the starting magnetite substrate depend on the base used in the preparation, they remain unaltered upon the subsequent modification. Conversely, the average Au nanoparticle dimensions can be conveniently tailored as a function of the base used in Fe3O4 preparation and the presence/absence of the organic functionalization. The smallest dimensions (15 nm) are obtained for AuNP supported on propynylcarbamate-functionalized Fe3O4 prepared in the presence of ammonia. Magnetization measurements highlight that all the Au/Fe3O4 nanocomposites display a superparamagnetic behavior and those obtained using ammonia showed consistently smaller Hc and Mr values (av. values of 7.4 Oe and 0.8 emu/g) than those prepared with sodium hydroxide (av. values of 28 Oe and 2.8 emu/g).

One promising route toward encoding information is to utilize the two stable electronic states of a spin crossover molecule. Although this property is clearly manifested in transport across single molecule junctions, evidence linking charge transport across a solid-state device to the molecular film's spin state has thus far remained indirect. To establish this link, we deploy materials-centric and device-centric operando experiments involving X-ray absorption spectroscopy. We find a correlation between the temperature dependencies of the junction resistance and the Fe spin state within the device's [Fe(H2B(pz)2)2(NH2-phen)] molecular film. We also factually observe that the Fe molecular site mediates charge transport. Our dual operando studies reveal that transport involves a subset of molecules within an electronically heterogeneous spin crossover film. Our work confers an insight that substantially improves the state-of-the-art regarding spin crossover-based devices, thanks to a methodology that can benefit device studies of other next-generation molecular compounds.

The understanding of spin injection and transport in organic spintronic devices is still incomplete, with some experiments showing magnetoresistance and others not detecting it. We have investigated the transport properties of a large number of tris-(8-hydroxyquinoline)aluminum-based organic spintronic devices with an electrical resistance greater than 5 M? that did not show magnetoresistance. Their transport properties could be described satisfactorily by known models for organic semiconductors. At high voltages (>2 V), the results followed the model of space charge limited current with a Poole-Frenkel mobility. At low voltages (~0.1 V), that are those at which the spin valve behavior is usually observed, the charge transport was modelled by nearest neighbor hopping in intra-gap impurity levels, with a charge carrier density of n0 = (1.44 ± 0.21) × 1015 cm-3 at room temperature. Such a low carrier density can explain why no magnetoresistance was observed.

Vertical crossbar devices based on manganite and cobalt injecting electrodes and a metal-quinoline molecular transport layer are known to manifest both magnetoresistance (MR) and electrical bistability. The two effects are strongly interwoven, inspiring new device applications such as electrical control of the MR and magnetic modulation of bistability. To explain the device functionality, we identify the mechanism responsible for electrical switching by associating the electrical conductivity and the impedance behavior with the chemical states of buried layers obtained by in operando photoelectron spectroscopy. These measurements revealed that a significant fraction of oxygen ions migrate under voltage application, resulting in a modification of the electronic properties of the organic material and of the oxidation state of the interfacial layer with the ferromagnetic contacts. Variable oxygen doping of the organic molecules represents the key element for correlating bistability and MR, and our measurements provide the first experimental evidence in favor of the impurity-driven model describing the spin transport in organic semiconductors in similar devices.

We introduce a Faraday magnetometer based on an analytical balance in which we were able to apply magnetic fields up to 0.14 T. We calibrated it with a 1mm Ni sphere previously characterized in a superconducting quantum interference device (SQUID) magnetometer. The proposed magnetometer reached a theoretical sensitivity of 3 x 10(-8) A m(2). We demonstrated its operation on magnetic composite scaffolds made of poly(epsilon-caprolactone)/ iron-doped hydroxyapatite. To confirm the validity of the method, we measured the same scaffold properties in a SQUID magnetometer. The agreement between the two measurements was within 5% at 0.127 T and 12% at 24mT. With the addition, for a small cost, of a permanent magnet and computer controlled linear translators, we were thus able to assemble a Faraday magnetometer based on an analytical balance, which is a virtually ubiquitous instrument. This will make simple but effective magnetometry easily accessible to most laboratories, in particular, to life sciences ones, which are increasingly interested in magnetic materials. Published by AIP Publishing.

Pb-Co nanowires were electrodeposited in 100 nm nominal pore diameter polycarbonate membranes. Above the T-C of Pb we modelled the behaviour of the wires with a Langevin function, obtaining a Co volume of (1.06 +/- 0.01) x 10(-7) cm(3) divided into clusters of approximate to 10 atoms in size. The magnetic response of the wires in the 3-10 K interval, which comprises T-C, was modelled by adding spherical superconducting Pb grains to the Co clusters; the Pb grains were found to be (87 +/- 6) nm in diameter. The Co clusters were not interacting and were not magnetically screened by the superconducting Pb.

Magnetic nanoparticles (MNPs) are widely utilized in magnetic-field-assisted bio-separation, bio- interaction, imaging and drug delivery, due to their large surface area and easy manipulation by an external magnetic force. Nanomagnets constituted by polymers, dendrimers and cyclodextrins functionalizing magnetite have been widely developed for therapy and diagnosis.1-2 Amphiphilic cyclodextrin (aCD) are largely employed to deliver different types of therapeutic and diagnostic molecules.3-4 Here we propose novel nanomagnets based on non ionic amphiphilic cyclodextrin heptakis (2-oligo(ethyleneoxide)-6-hexadecylthio-)-?-CD (SC16OH) -capping Fe3O4 NPs and decorated with Adamantanil-(PEG)4-KLVFF, (Ada-Pep), as nanoconstructs based on the self-recognizing sequence of the Amyloid-? (A?) peptides. Fe3O4@SC16OH was prepared by mixing Fe3O4 NPs with an aqueous dispersion of SC16OH and then isolated by settling down with a magnet. Fe3O4@SC16OH/Ada-Pep was prepared by hydration of an organic film of Ada-Pep, and isolated by centrifugation. In order to assess the recognition properties of the KLVFF active peptide, a magnetic cyclodextrin decorated with the scrambled units adamantanil-(PEG)4VFLKF (Ada-PepSCR) was fabricated. Peptide-tailored nanomagnets were characterized at solid state by TGA, STEM, AFM, X-Ray Diffraction, XPS and magnetization mass measurements. In aqueous physiological solutions, DLS and Z-potential measurements, point out a size of @200 nm and a negative surface potential ( -30 mV) dependently by the co-presence of aCD olygoethylenglycol chains and peptide units on the external fringe. The ability of these novel nanomagnets to target the A? peptides was studied either in A? containing aqueous samples by means of Maldi-Tof-Ms or in the medium of cultured cells over-expressing the A? peptides, by using an ELISA based assay. Our results indicate that in both the experimental conditions the nanomagnets can perform an unbiased A?-targeted fishing, thereby suggesting their potential use as efficient diagnostic agents.

The possible influence of internal barrier dynamics on spin, charge transport and their fluctuations in organic spintronics remains poorly understood. Here we present investigation of the electron transport and low frequency noise at temperatures down to 0.3K in magnetic tunnel junctions with an organic PTCDA barriers with thickness up to 5 nm in the tunneling regime and with 200 nm thick Alq3 barrier in the hopping regime. We observed high tunneling magneto-resistance at low temperatures (15-40%) and spin dependent super-poissonian shot noise in organic magnetic tunnel junctions (OMTJs) with PTCDA. The Fano factor exceeds 1.5-2 values which could be caused by interfacial states controlled by spin dependent bunching in the tunneling events through the molecules.1 The bias dependence of the low frequency noise in OMTJs with PTCDA barriers which includes both 1/f and random telegraph noise activated at specific biases will also be discussed. On the other hand, the organic junctions with ferromagnetic electrodes and thick Alq3 barriers present sub-poissonian shot noise which depends on the temperature, indicative of variable range hopping. © (2016) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

We introduce an innovative approach to the simultaneous control of growth mode and magnetotransport properties of manganite thin films, based on an easy-to-implement film/substrate interface engineering. The deposition of a manganite seed layer and the optimization of the substrate temperature allows a persistent bi-dimensional epitaxy and robust ferromagnetic properties at the same time. Structural measurements confirm that in such interface-engineered films, the optimal properties are related to improved epitaxy. A new growth scenario is envisaged, compatible with a shift from heteroepitaxy towards pseudo-homoepitaxy. Relevant growth parameters such as formation energy, roughening temperature, strain profile and chemical states are derived. (C) 2016 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

A versatile approach for the design and fabrication of multilayer magnetic scaffolds with tunable magnetic gradients is described. Multilayer magnetic gelatin membrane scaffolds with intrinsic magnetic gradients were designed to encapsulate magnetized bioagents under an externally applied magnetic field for use in magnetic-field-assisted tissue engineering. The temperature of the individual membranes increased up to 43.7 degrees C under an applied oscillating magnetic field for 70 s by magnetic hyperthermia, enabling the possibility of inducing a thermal gradient inside the final 3D multilayer magnetic scaffolds. On the basis of finite element method simulations, magnetic gelatin membranes with different concentrations of magnetic nanoparticles were assembled into 3D multilayered scaffolds. A magnetic-gradient-controlled distribution of magnetically labeled stem cells was demonstrated in vitro. This magnetic biomaterial-magnetic cell strategy can be expanded to a number of different magnetic biomaterials for various tissue engineering applications.

The outgrowth formation in inorganic thin films is a dramatic problem that has limited the technological impact of many techniques and materials. Outgrowths are often themselves part of the films, but are detrimental for vertical junctions since they cause short-circuits or work as defects, compromising the reproducibility and in some cases the operation of the corresponding devices. The problem of outgrowth is particularly relevant in ablation-based methods and in some complex oxides, but is present in a large variety of systems and techniques. Here we propose an efficient local electrochemical method to selectively decompose the outgrowths of conductive oxide thin films by electrochemical decomposition, without altering the properties of the background film. The process is carried out using the same set-up as for local oxidation nanolithography, except for the sign of the voltage bias and it works at the nanoscale both as serial method using a scanning probe and as parallel method using conductive stamps. We demonstrated our process using La0.7Sr0.3MnO3 perovskite as a representative material but in principle it can be extended to many other conductive systems.

In this article we present the morphological and magnetic characterization of ferrofluid-impregnated biomimetic scaffolds made of hydroxyapatite and collagen used for bone reconstruction. We describe an innovative and simple impregnation process by which the ferrofluid is firmly adsorbed onto the hydroxyapatite/collagen scaffolds. The process confers sufficient magnetization to attract potential magnetic carriers, which may be used to transport bioactive agents that favour bone regeneration. The crystalline structure of the magnetite contained in the ferrofluid is preserved and its quantity, estimated from the weight gain due to the impregnation process, is consistent with that obtained from energy dispersive X-ray spectroscopy. The magnetization, measured with a superconducting quantum interference device, is uniform throughout the scaffolds, demonstrating the efficiency of the impregnation process. The field emission gun scanning electron microscopy characterization demonstrates that the process does not alter the morphology of the hydroxyapatite/collagen scaffolds, which is essential for the preservation of their bioactivity and consequently for their effectiveness in promoting bone formation.

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We propose a model for the consistent interpretation of the transport behavior of manganese perovskites in both the metallic and insulating regimes. The concept of polarons as charge carriers in the metallic ferromagnetic phase of manganites also solves the conflict between transport models, which usually neglects polaron effects in the metallic phase, and, on the other hand, optical conductivity, angle-resolved spectroscopy, and neutron scattering measurements, which identify polarons in the metallic phase of manganites down to 6 K. Transport characterizations of epitaxial La0.7Sr0.3MnO3 thin films in the thickness range of 5-40 nm and temperature interval of 25-410 K have been accurately collected. We show that taking into account polaron effects allows us to achieve an excellent fit of the transport curves in the whole temperature range. The current carriers density collapse picture accurately accounts for the properties variation across the metal-insulator transitions. The electron-phonon coupling parameter ? estimations are in a good agreement with theoretical predictions. The results promote a clear and straightforward quantitative description of the manganite films involved in charge transport device applications and promises to describe other oxide systems involving a metal-insulator transition. © 2014 American Physical Society.

Nanocrystalline freestanding Pb nanowires similar to 200 nm in diameter were fabricated by electrodeposition into track etched polycarbonate membranes in order to study their superconducting properties. Their superconducting critical temperature, as determined by measuring the Meissner effect, was the same as for bulk Pb, but their critical field was greatly enhanced up to similar to 3000 Oe. By assuming the wires consisted of spherical superconducting grains, an estimated grain size r = 60 +/- 25 nm was obtained from the magnetization measured as a function of the applied magnetic field at a fixed temperature. An independent estimate for r = 47 +/- 12 nm, in good agreement with the previous one, was obtained from the magnetization measured as a function of temperature at a fixed applied magnetic field. Transmission electron microscopy was used to characterize grain size at the wire edges, where a grain size in agreement with the magnetic studies was observed. (C) 2014 AIP Publishing LLC.

Thermo switchable magnetic hydrogels undoubtedly have a great potential for medical applications since they can behave as smart carriers able to transport bioactive molecules to a chosen part of the body and release them on demand via magneto-thermal activation. We report on the ability to modify the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide) (PNIPAM) on demand from 32 °C to LCST >=37 °C. This was achieved by the absorption of controlled amounts of magnetite nanoparticles on the polymer chains. We show, through the effect on cell viability, that the resulting magnetic PNIPAM is able to trap and to release bio-active molecules, such as cell growth factors. The activities of the released bio molecule are tested on human umbilical vein endothelial cells culture. We demonstrate that the LCST of the magnetic PNIPAM can be reached remotely via inductive heating with an alternating magnetic field. This approach on magnetic PNIPAM clearly supports appealing applications in safe biomedicine. © 2014 Springer Science+Business Media New York.