M. Respaud

Simple models for dynamic hysteresis loop calculations of magnetic single-domain nanoparticles: Application to magnetic hyperthermia optimization

To optimize the heating properties of magnetic nanoparticles (MNPs) in magnetic hyperthermia applications, it is necessary to calculate the area of their hysteresis loops in an alternating magnetic field. The separation between “relaxation losses” and “hysteresis losses” presented in several articles is artificial and criticized here. The three types of theories suitable for describing hysteresis loops of MNPs are presented and compared to numerical simulations: equilibrium functions, Stoner–Wohlfarth model based theories (SWMBTs), and a linear response theory (LRT) using the Neel–Brown relaxation time. The configuration where the easy axis of the MNPs is aligned with respect to the magnetic field and the configuration of a random orientation of the easy axis are both studied. Suitable formulas to calculate the hysteresis areas of major cycles are deduced from SWMBTs and from numerical simulations; the domain of validity of the analytical formula is explicitly studied. In the case of minor cycles, the hysteresis area calculations are based on the LRT. A perfect agreement between the LRT and numerical simulations of hysteresis loops is obtained. The domain of validity of the LRT is explicitly studied. Formulas are proposed to calculate the hysteresis area at low field that are valid for any anisotropy of the MNP. The magnetic field dependence of the area is studied using numerical simulations: it follows power laws with a large range of exponents. Then analytical expressions derived from the LRT and SWMBTs are used in their domains of validity for a theoretical study of magnetic hyperthermia. It is shown that LRT is only pertinent for MNPs with strong anisotropy and that SWMBTs should be used for weakly anisotropic MNPs. The optimum volume of MNPs for magnetic hyperthermia is derived as a function of material and experimental parameters. Formulas are proposed to allow to the calculation of the optimum volume for any anisotropy. The maximum achievable specific absorption rate (SAR) is calculated as a function of the MNP anisotropy. It is shown that an optimum anisotropy increases the SAR and reduces the detrimental effects of the size distribution of the MNPs. The optimum anisotropy is simple to calculate; it depends only on the magnetic field used in the hyperthermia experiments and the MNP magnetization. The theoretical optimum parameters are compared to those of several magnetic materials. A brief review of experimental results as well as a method to analyze them is proposed. This study helps in the determination of suitable and unsuitable materials for magnetic hyperthermia and provides accurate formulas to analyze experimental data. It is also aimed at providing a better understanding of magnetic hyperthermia to researchers working on this subject.To optimize the heating properties of magnetic nanoparticles (MNPs) in magnetic hyperthermia applications, it is necessary to calculate the area of their hysteresis loops in an alternating magnetic field. The three types of theories suitable for describing the hysteresis loops of MNPs are presented and compared to numerical simulations: equilibrium functions, Stoner-Wohlfarth model based theories (SWMBTs) and linear response theory (LRT). Suitable formulas to calculate the hysteresis area of major cycles are deduced from SWMBTs and from numerical simulations; the domain of validity of the analytical formula is explicitly studied. In the case of minor cycles, the hysteresis area calculations are based on the LRT. A perfect agreement between LRT and numerical simulations of hysteresis loops is obtained. The domain of validity of the LRT is explicitly studied. Formulas to calculate the hysteresis area at low field valid for any anisotropy of the MNP are proposed. Numerical simulations of the magnetic field dependence of the area show it follows power-laws with a large range of exponents. Then, analytical expressions derived from LRT and SWMBTs are used for a theoretical study of magnetic hyperthermia. It is shown that LRT is only pertinent for MNPs with strong anisotropy and that SWMBTs should be used for weak anisotropy MNPs. The optimum volume of MNPs for magnetic hyperthermia as function of material and experimental parameters is derived. The maximum specific absorption rate (SAR) achievable is calculated versus the MNP anisotropy. It is shown that an optimum anisotropy increases the SAR and reduces the detrimental effects of size distribution. The optimum anisotropy is simple to calculate and depends on the magnetic field used in the hyperthermia experiments and on the MNP magnetization only. The theoretical optimum parameters are compared to the one of several magnetic materials.

On-chip and freestanding elastic carbon films for micro-supercapacitors

Flexible power for flexible electronics A challenge for flexible electronics is to couple devices with power sources that are also flexible. Ideally, they could also be processed in a way that is compatible with current microfabrication technologies. Huang et al. deposited a relatively thick layer of TiC on top of an oxide-coated Si film. After chlorination, most, but importantly not all, of the TiC was converted into a porous carbon film that could be turned into an electrochemical capacitor. The carbon films were highly flexible, and the residual TiC acted as a stress buffer with the underlying Si film. The films could be separated from the Si to form free-floating films, with the TiC providing a support layer. Science, this issue p. 691 Porous carbon-based supercapacitors are directly fabricated onto silicon substrates. Integration of electrochemical capacitors with silicon-based electronics is a major challenge, limiting energy storage on a chip. We describe a wafer-scale process for manufacturing strongly adhering carbide-derived carbon films and interdigitated micro-supercapacitors with embedded titanium carbide current collectors, fully compatible with current microfabrication and silicon-based device technology. Capacitance of those films reaches 410 farads per cubic centimeter/200 millifarads per square centimeter in aqueous electrolyte and 170 farads per cubic centimeter/85 millifarads per square centimeter in organic electrolyte. We also demonstrate preparation of self-supported, mechanically stable, micrometer-thick porous carbon films with a Young’s modulus of 14.5 gigapascals, with the possibility of further transfer onto flexible substrates. These materials are interesting for applications in structural energy storage, tribology, and gas separation.

A Simple Chemical Route toward Monodisperse Iron Carbide Nanoparticles Displaying Tunable Magnetic and Unprecedented Hyperthermia Properties

We report a tunable organometallic synthesis of monodisperse iron carbide and core/shell iron/iron carbide nanoparticles displaying a high magnetization and good air-stability. This process based on the decomposition of Fe(CO)(5) on Fe(0) seeds allows the control of the amount of carbon diffused and therefore the tuning of nanoparticles magnetic anisotropy. This results in unprecedented hyperthermia properties at moderate magnetic fields, in the range of medical treatments.

Iron Nanoparticle Growth in Organic Superstructures

A tunable synthesis of iron nanoparticles (NPs) based on the decomposition of {Fe[N(SiMe(3))(2)](2)}(2) in the presence of organic superstructures composed of palmitic acid and hexadecylamine is reported. Control of the size (from 1.5 to 27 nm) and shape (spheres, cubes, or stars) of the NPs has been achieved. An environment-dependent growth model is proposed on the basis of results obtained for the NP morphology under various conditions and a complete Mossbauer study of the colloid composition at different reacting stages. It involves (i) an anisotropic growth process inside organic superstructures, leading to monocrystalline cubic NPs, and (ii) isotropic growth outside these superstructures, yielding polycrystalline spherical NPs.

Magnetic configurations of 30 nm iron nanocubes studied by electron holography.

Ferromagnetic nanomaterials exhibit unique magnetic properties common to materials with dimensions approaching the atomic scale and have potential applications in magnetic data storage. Technological applications, however, require that the detailed magnetic behaviors and configurations of individual and interacting magnetic nano-objects be clarified. We determined the magnetic remnant configurations in single crystalline 30 nm Fe nanocubes and groups of nanocubes using off-axis electron holography in a transmission electron microscope. Our measurements on an isolated cube reveal a vortex state whose core size has been determined. Two neighboring nanocubes with adjacent {100} surfaces exhibit a ferromagnetic dipolar coupling, while similar magnetic interactions between four cubes in a square arrangement induce a bending of the magnetic induction, i.e., a magnetic flux closure state. The various configurations were successfully simulated by micromagnetic calculations.

Magnetic hyperthermia in single-domain monodisperse FeCo nanoparticles: Evidences for Stoner–Wohlfarth behavior and large losses

We report on hyperthermia measurements on a colloidal solution of 14.2±1.5 nm monodisperse FeCo nanoparticles (NPs). Losses as a function of the magnetic field display a sharp increase followed by a plateau, which is what is expected for losses of ferromagnetic single-domain NPs. The frequency dependence of the coercive field is deduced from hyperthermia measurement and is in quantitative agreement with a simple model of noninteracting NPs. The measured losses (1.5 mJ/g) compare to the highest of the literature, although the saturation magnetization of the NPs is well below the bulk one.

Increase of magnetic hyperthermia efficiency due to dipolar interactions in low-anisotropy magnetic nanoparticles: Theoretical and experimental results

When magnetic nanoparticles (MNPs) are single-domain and magnetically independent, their magnetic properties and the conditions to optimize their efficiency in magnetic hyperthermia applications are now well-understood. However, the influence of magnetic interactions on magnetic hyperthermia properties is still unclear. Here, we report hyperthermia and high-frequency hysteresis loop measurements on a model system consisting of MNPs with the same size but a varying anisotropy, which is an interesting way to tune the relative strength of magnetic interactions. A clear correlation between the MNP anisotropy and the squareness of their hysteresis loop in colloidal solution is observed : the larger the anisotropy, the smaller the squareness. Since low anisotropy MNPs display a squareness higher than the one of magnetically independent nanoparticles, magnetic interactions enhance their heating power in this case. Hysteresis loop calculations of independent and coupled MNPs are compared to experimental results. It is shown that the observed features are a natural consequence of the formation of chains and columns of MNPs during hyperthermia experiments: in these structures, when the MNP magnetocristalline anisotropy is small enough to be dominated by magnetic interactions, the hysteresis loop shape tends to be rectangular, which enhance their efficiency. On the contrary, when MNPs do not form chains and columns, magnetic interactions reduces the hysteresis loop squareness and the efficiency of MNPs compared to independent ones. The present work should improve the understanding and interpretation of magnetic hyperthermia experiments.

Nano-electromanipulation of Spin Crossover Nanorods: Towards Switchable Nanoelectronic Devices

The nanoscale manipulation and charge transport properties of the [Fe(Htrz)2(trz)](BF4) spin-crossover compound is demonstrated. Such 1D spin-crossover nanostructures are attractive building blocks for nanoelectronic switching and memory devices.

Cobalt Growth on the Tips of CdSe Nanorods

Best of both worlds: Reduction of an organometallic Co precursor on preformed CdSe nanorods yields two distinct semiconducting-magnetic heterostructures (see picture). The selective growth of Co on the tips of CdSe first gives nanosphere-nanorod dimers, which evolve into nanorod-nanorod structures. In the hybrid objects the magnetic properties of Co remain intact, while the luminescence properties of CdSe are affected but not completely quenched.

Chemisorption on nickel nanoparticles of various shapes: Influence on magnetism

Nanoparticles of nickel have been obtained in solution through reaction of an organometallic precursor, Ni(COD)2 (COD=cycloocta-1,5-diene), with dihydrogen, in the presence of various stabilizing agents. X-ray diffraction studies evidence a face-centered-cubic structure for all samples. Spherical isolated superparamagnetic nanoparticles (d∼4.5 nm) are produced in the presence of poly(N-vinylpyrrolid-2-one). They display a magnetization value comparable to that of bulk nickel, as determined from superconducting quantum iinterference device (SQUID) measurements. Exposure of the surface of the nanoparticles to CO, leading to CO coordination as monitored by infrared spectroscopy, or to methanol, strongly reduces their magnetization. This reduction corresponds respectively to one or two magnetically inactive layers of nickel atoms at the nanoparticles surface. The production of elongated nanoparticles was favored when either trioctylphosphineoxide or hexadecylamine (HDA) were used as stabilizing agents. In this case, SQUID measurements show that only HDA preserves the magnetization of the surface. This stabilizing agent was selected for the production of nickel nanorods. The influence of ligands on the effective anisotropy is discussed.Nanoparticles of nickel have been obtained in solution through reaction of an organometallic precursor, Ni(COD)2 (COD=cycloocta-1,5-diene), with dihydrogen, in the presence of various stabilizing agents. X-ray diffraction studies evidence a face-centered-cubic structure for all samples. Spherical isolated superparamagnetic nanoparticles (d∼4.5 nm) are produced in the presence of poly(N-vinylpyrrolid-2-one). They display a magnetization value comparable to that of bulk nickel, as determined from superconducting quantum iinterference device (SQUID) measurements. Exposure of the surface of the nanoparticles to CO, leading to CO coordination as monitored by infrared spectroscopy, or to methanol, strongly reduces their magnetization. This reduction corresponds respectively to one or two magnetically inactive layers of nickel atoms at the nanoparticles surface. The production of elongated nanoparticles was favored when either trioctylphosphineoxide or hexadecylamine (HDA) were used as stabilizing agents. In thi...