Size-Specific Magnetic Configurations in Electrodeposited Epitaxial Iron Nanocuboids: From Landau Pattern to Vortex and Single Domain States.

As the size of magnetic devices continuously decreases, the creation of three-dimensional nanomagnets and the understanding of their magnetic configurations become increasingly important for modern applications. Here, by progressive nucleation during epitaxial nanoelectrodeposition, we synthesize single-crystal iron nanocuboids with sizes ranging 10 to 200 nm on one sample. The size-dependent magnetic configurations of these nanocuboids are studied by quantitative magnetic force microscopy and electron holography. In conjunction, a "magnetic configuration versus size" phase diagram is established via micromagnetic simulations. Both experiment and theory reveal a sequential transition from Landau pattern to vortex and finally single domain when decreasing the sizes of the nanocuboids. The combinatorial-like approach leads to a quantitative understanding of the magnetic configurations of the nanomagnets in a broad size range. It can be transferred to other materials and shapes and thereby presents an advanced route to enrich the material library for future nanodevice design.

Single-Crystalline Body Centered FeCo Nano-Octopods: From One-Pot Chemical Growth to a Complex 3D Magnetic Configuration.

Single crystalline magnetic FeCo nanostars were prepared using an organometallic approach under mild conditions. The fine-tuning of the experimental conditions allowed the direct synthesis of these nano-octopods with body-centered cubic (bcc) structure through a one-pot reaction, contrarily to the seed-mediated growth classically used. The FeCo nanostars consist of 8 tetrahedrons exposing {311} facets, as revealed by high resolution transmission electron microscopy (HRTEM) imaging and electron tomography (ET), and exhibit a high magnetization comparable with the bulk one (Ms = 235 A·m2·kg-1). Complex 3D spin configurations resulting from the competition between dipolar and exchange interactions are revealed by electron holography. This spin structures are stabilized by the high aspect ratio tetrahedral branches of the nanostars, as confirmed by micromagnetic simulations. This illustrates how magnetic properties can be significantly tuned by nanoscale shape control.

Tuning Magnetic Properties of a Carbon Nanotube-Lanthanide Hybrid Molecular Complex through Controlled Functionalization.

Molecular magnets attached to carbon nanotubes (CNT) are being studied as potential candidates for developing spintronic and quantum technologies. However, the functionalization routes used to develop these hybrid systems can drastically affect their respective physiochemical properties. Due to the complexity of this systems, little work has been directed at establishing the correlation between the degree of functionalization and the magnetic character. Here, we demonstrate the chemical functionalization degree associated with molecular magnet loading can be utilized for controlled tuning the magnetic properties of a CNT-lanthanide hybrid complex. CNT functionalization degree was evaluated by interpreting minor Raman phonon modes in relation to the controlled reaction conditions. These findings were exploited in attaching a rare-earth-based molecular magnet (Gd-DTPA) to the CNTs. Inductively coupled plasma mass spectrometry, time-of-flight secondary ion mass spectrometry and super conducting quantum interference device (SQUID) measurements were used to elucidate the variation of magnetic character across the samples. This controlled Gd-DTPA loading on the CNT surface has led to a significant change in the nanotube intrinsic diamagnetism, showing antiferromagnetic coupling with increase in the Weiss temperature with respect to increased loading. This indicates that synthesis of a highly correlated spin system for developing novel spintronic technologies can be realized through a carbon-based hybrid material.

Concerted Growth and Ordering of Cobalt Nanorod Arrays as Revealed by Tandem in Situ SAXS-XAS Studies.

The molecular and ensemble dynamics for the growth of hierarchical supercrystals of cobalt nanorods have been studied by in situ tandem X-ray absorption spectroscopy-small-angle X-ray scattering (XAS-SAXS). The supercrystals were obtained by reducing a Co(II) precursor under H2 in the presence of a long-chain amine and a long-chain carboxylic acid. Complementary time-dependent ex situ TEM studies were also performed. The experimental data provide critical insights into the nanorod growth mechanism and unequivocal evidence for a concerted growth-organization process. Nanorod formation involves cobalt nucleation, a fast atom-by-atom anisotropic growth, and a slower oriented attachment process that continues well after cobalt reduction is complete. Smectic-like ordering of the nanorods appears very early in the process, as soon as nanoparticle elongation appears, and nanorod growth takes place inside organized superlattices, which can be regarded as mesocrystals.

Size-Specific Spin Configurations in Single Iron Nanomagnet: From Flower to Exotic Vortices.

The different spin configurations in the vicinity of the single-domain/vortex transition are reported in isolated magnetic nanoparticles. By combining chemical synthesis, electron holography in a dedicated transmission electron microscope and micromagnetic simulations, we establish the "magnetic configurations vs size" phase diagram of Fe single-crystalline nanocubes. Room temperature high resolution magnetic maps reveal the transition between single-domain and vortex states for Fe nanocubes from 25 to 27 nm, respectively. An intermediate spin configuration consisting of an ⟨111⟩ vortex is for the first time evidenced.

Co-Fe nanodumbbells: synthesis, structure, and magnetic properties.

We report the solution phase synthesis, the structural analysis, and the magnetic properties of hybrid nanostructures combining two magnetic metals. These nano-objects are characterized by a remarkable shape, combining Fe nanocubes on Co nanorods. The topological composition, the orientation relationship, and the growth steps have been studied by advanced electron microscopy techniques, such as HRTEM, electron tomography, and state-of-the-art 3-dimensional elemental mapping by EDX tomography. The soft iron nanocubes behave as easy nucleation centers that induce the magnetization reversal of the entire nanohybrid, leading to a drastic modification of the overall effective magnetic anisotropy.

Solution epitaxial growth of cobalt nanowires on crystalline substrates for data storage densities beyond 1 Tbit/in2.

The implementation of nano-objects in numerous emerging applications often demands their integration in macroscopic devices. Here we present the bottom-up epitaxial solution growth of high-density arrays of vertical 5 nm diameter single-crystalline metallic cobalt nanowires on wafer-scale crystalline metal surfaces. The nanowires form regular hexagonal arrays on unpatterned metallic films. These hybrid heterostructures present an important perpendicular magnetic anisotropy and pave the way to a high density magnetic recording device, with capacities above 10 Terabits/in(2). This method bypasses the need of assembling and orientating free colloidal nanocrystals on surfaces. Its generalization to other materials opens new perspectives toward many applications.

Stabilizing vortices in interacting nano-objects: a chemical approach.

We report a chemical method to prepare metallic Fe porous nanocubes. The presence of pores embedded inside the cubes was attested by electron tomography. Thanks to electronic holography and micromagnetic simulations, we show that the presence of these defects stabilizes the vortices in assembly of interacting cubes. These results open new perspectives toward magnetic vortex stabilization at relatively low cost for various applications (microelectronics, magnetic recording, or biological applications).

Room-temperature tunnel magnetoresistance in self-assembled chemically synthesized metallic iron nanoparticles.

We report on room temperature magnetoresistance in networks of chemically synthesized metallic Fe nanoparticles surrounded by two types of organic barriers. Electrical properties, featuring Coulomb blockade, and magnetotransport measurements show that this magnetoresistance arises from spin-dependent tunnelling, so the organic ligands stabilizing the nanoparticles are efficient spin-conservative tunnel barrier. These results demonstrate the feasibility of an all-chemistry approach for room temperature spintronics.

Growth and analysis of the tetragonal (ST12) germanium nanowires.

New semiconducting materials, such as state-of-the-art alloys, engineered composites and allotropes of well-established materials can demonstrate unique physical properties and generate wide possibilities for a vast range of applications. Here we demonstrate, for the first time, the fabrication of a metastable allotrope of Ge, tetragonal germanium (ST12-Ge), in nanowire form. Nanowires were grown in a solvothermal-like single-pot method using supercritical toluene as a solvent, at moderate temperatures (290-330 °C) and a pressure of ∼48 bar. One-dimensional (1D) nanostructures of ST12-Ge were achieved via a self-seeded vapour-liquid-solid (VLS)-like paradigm, with the aid of an in situ formed amorphous carbonaceous layer. The ST12 phase of Ge nanowires is governed by the formation of this carbonaceous structure on the surface of the nanowires and the creation of Ge-C bonds. The crystalline phase and structure of the ST12-Ge nanowires were confirmed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. The nanowires produced displayed a high aspect ratio, with a very narrow mean diameter of 9.0 ± 1.4 nm, and lengths beyond 4 µm. The ST12-Ge nanowire allotrope was found to have a profound effect on the intensity of the light emission and the directness of the bandgap, as confirmed by a temperature-dependent photoluminescence study.

Polarizability is a key parameter for molecular electronics.

Identifying descriptors that govern charge transport in molecular electronics is of prime importance for the elaboration of devices. The effects of molecule characteristics, such as size, bulkiness or charge, have been widely reported. Herein, we show that the molecule polarizability can be a crucial parameter to consider. To this end, platinum nanoparticle self-assemblies (PtNP SAs) are synthesized in solution, including a series of polyoxometalates (POMs). The charge of the POM unit can be modified according to the nature of the central heteroatom while keeping its size constant. POM hybrids that display remote terminal thiol functions strongly anchor the PtNP surface to form robust SAs. IV curves, recorded by conductive AFM, show a decrease in Coulomb blockade as the dielectric constant of the POMs increases. In this system, charge transport across molecular junctions can be interpreted as variations in polarizability, which is directly related to the dielectric constant.

Magnetophoresis-Assisted Capillary Assembly: A Versatile Approach for Fabricating Tailored 3D Magnetic Supercrystals.

The fabrication and integration of sub-millimeter magnetic materials into predefined circuits is of major importance for the realization of portable devices designed for telecommunications, automotive, biomedical, and space applications but remains highly challenging. We report here a versatile approach for the fabrication and direct integration of nanostructured magnetic materials of controlled shaped at specific locations onto silicon substrates. The magnetophoresis-assisted capillary assembly of magnetic nanoparticles, either spherical or anisotropic, leads to the fabrication of high-performance Co-based permanent magnets and Fe-based supercrystals. Integrated sub-millimeter magnets as well as millimeter self-standing magnets exhibiting magnetic properties competing with NdFeB-based composites were obtained through this cost- and time-efficient process. The proof-of-concept of electromagnetic actuation of a micro-electromechanical system cantilever by means of these supercrystals highlights their potentiality as efficient integrated magnetic materials within nomadic devices.

Shape selection through epitaxy of supported platinum nanocrystals.

Supported nanocrystals of original shapes are highly desirable for the development of optimized catalysts; however, conventional methods for the preparation of supported catalysts do not allow shape control. In this work, we have synthesized concave platinum nanocubes exposing {110} crystallographic facets at 20 °C. In the presence of a crystallographically oriented Pt(111) support in the reaction medium, the concave nanocubes grow epitaxially on the support, producing macroscopic nanostructured surfaces. Higher reaction temperature produces a mixture of different nanostructures in solution; however, only the nanostructures growing along the 111 direction are obtained on the Pt(111) support. Therefore, the oriented surface acts as a template for a selective immobilization of specific nanostructures out of a mixture, which can be regarded as an "epitaxial resolution" of an inhomogeneous mixture of nanocrystals. Thus, a judicious choice of the support crystallographic orientation may allow the isolation of original nanostructures that cannot be obtained in a pure form.

Platinum tripods as nanometric frequency multiplexing devices.

Electrical and structural characterization studies of nano-particles are very important steps to determine their potential applications in microelectronics. In this paper, we address the crystallographic and electric transport properties of soft-chemistry-grown nanometric Pt tribranches. We report that Pt nanostars grown from the reduction of H2PtCl6 salt in pure oleylamine present a remarkable crystalline structure and deeply metallic character despite being grown under mild conditions. We demonstrate that such devices are able to operate at current densities surpassing 200 MA cm-2, actuating as highly compact frequency multiplexers in the non-ohmic regime.

Oriented Metallic Nano-Objects on Crystalline Surfaces by Solution Epitaxial Growth.

Chemical methods offer the possibility to synthesize a large panel of nanostructures of various materials with promising properties. One of the main limitations to a mass market development of nanostructure based devices is the integration at a moderate cost of nano-objects into smart architectures. Here we develop a general approach by adapting the seed-mediated solution phase synthesis of nanocrystals in order to directly grow them on crystalline thin films. Using a Co precursor, single-crystalline Co nanowires are directly grown on metallic films and present different spatial orientations depending on the crystalline symmetry of the film used as a 2D seed for Co nucleation. Using films exposing 6-fold symmetry surfaces such as Pt(111), Au(111), and Co(0001), the Co heterogeneous nucleation and epitaxial growth leads to vertical nanowires self-organized in dense and large scale arrays. On the other hand, using films presenting 4-fold symmetry surfaces such as Pt(001) and Cu(001), the Co growth leads to slanted wires in discrete directions. The generality of the concept is demonstrated with the use of a Fe precursor which results in Fe nanostructures on metallic films with different growth orientations which depend on the 6-fold/4-fold symmetry of the film. This approach of solution epitaxial growth combines the advantages of chemistry in solution in producing shape-controlled and monodisperse metallic nanocrystals, and of seeded growth on an ad hoc metallic film that efficiently controls orientation through epitaxy. It opens attractive opportunities for the integration of nanocrystals in planar devices.