This chapter provides an introduction to the fundamental physical ideas and models relevant to the phenomenon of magnetic hysteresis in nanoparticle assemblies. The concepts of single-domain particles and superparamagnetism are discussed. The mechanisms of magnetization by coherent rotation and the role of temperature in the gradual decay of magnetization are analyzed in the framework of simple analytical models. Modern numerical techniques (Monte Carlo simulations, Magnetization Dynamics) used to study dense nanoparticle assemblies are presented. An overview of the most common experimental techniques used to measure the magnetic hysteresis effect in nanoparticle assemblies are presented and the underlying principles are exposed.
Recent work [1] demonstrated high coercivity and magnetic moment in cobalt carbide nanoparticle assemblies and explained the high coercivity from first principles in terms of the high magnetocrystalline anisotropy of the cobalt carbide nanoparticles. In this work, we comprehensively model the interaction between the nanoparticles comprising the assembly and systematically understand the effect of particle size, distribution of the orientations of the nanoparticles' magnetocrystalline anisotropy axis with respect to the applied magnetic field, and dipole coupling between nanoparticles on the te…
Thermal Rectification from Size-Dependent Phonon Confinement in Nanoparticle Assemblies
Università degli Studi di Milano（米兰大学）；Interdisciplinary Centre for Nanostructured Materials and Interfaces (CIMaINa)（纳米材料与界面跨学科中心）；German Aerospace Centre (DLR), Institute of Space Research（德国航空航天中心空间研究所）；Physikalisch-Technische Bundesanstalt (PTB) Berlin（德国联邦物理技术研究院）
Applications based on aggregates of magnetic nanoparticles are becoming increasingly widespread, ranging from hyperthermia to magnetic recording. However, although some uses require a collective behavior, other need a more individual-like response, the conditions leading to either of these behaviors are still poorly understood. Here we use nanoscale-uniform binary random dense mixtures with different proportions of oxide magnetic nanoparticles with low$/$high anisotropy as a valuable tool to explore the crossover from individual to collective behavior. Two different anisotropy scenarios have b…
Design of nanoscale structures with desired nanophotonic properties are key tasks for nanooptics and nanophotonics. Here, the correlative relationship between local nanoparticle geometries and their plasmonic responses is established using encoder-decoder neural networks. In the im2spec network, the correlative relationship between local particle geometries and local spectra is established via encoding the observed geometries to a small number of latent variables and subsequently decoding into plasmonic spectra; in the spec2im network, the relationship is reversed. Surprisingly, these reduced …
We report the precise control of tunneling magnetoresistance (TMR) in devices of self-assembled core/shell Fe$_3$O$_4$/Co$_{1-x}$Zn$_x$Fe$_2$O$_4$ nanoparticles ($0\leq x\leq 1$). Adjusting the magnetic anisotropy through the content of Co$^{2+}$ in the shell, provides an accurate tool to control the switching field between the bistable states of the TMR. In this way, different combinations of soft/hard and hard/soft core/shell configurations can be envisaged for optimizing devices with the required magnetotransport response.
Strong light-matter interactions facilitate not only emerging applications in quantum and non-linear optics but also modifications of materials properties. In particular the latter possibility has spurred the development of advanced theoretical techniques that can accurately capture both quantum optical and quantum chemical degrees of freedom. These methods are, however, computationally very demanding, which limits their application range. Here, we demonstrate that the optical spectra of nanoparticle-molecule assemblies, including strong coupling effects, can be predicted with good accuracy us…
: Understanding the correlations between magnetic nanoparticles is important for nanotechnologies, such as high-density magnetic recording and biomedical applications, where functionalized magnetic particles are used as contrast agents and for drug delivery. The ability to control the magnetic state of individual particles depends on the good knowledge of magnetic correlations between particles when assembled. Inaccessible via standard magnetometry techniques, nanoscale magnetic ordering in self-assemblies of Fe3O4 nanoparticles is here unveiled via x-ray resonant magnetic scattering (XRMS). M…
The distance-dependent interaction of an emitter with a plasmonic nanoparticle or surface forms the basis of the field of plexitonics. Semiconductor quantum dots (QDs) are robust emitters due to their photostability, and offer the possibility of understanding the fundamental photophysics between one emitter and one metal nanoparticle. A key enabling challenge is the formation of systems containing both QDs and plasmonic nanoparticles in high purity. We present the translation of DNA-based self-assembly techniques to assemble metal and semiconductor nanocrystals into discrete hybrid structures,…
Spatially Uniform and Defect-Tolerant Plasmonic Responses in 3D printed Gold Nanoparticle Assemblies
Paderborn University（帕德博恩大学）；Kumoh National Institute of Technology（龟尾国立科学技术院）；Gumi Electronics & Information Technology Research Institute（龟尾电子信息技术研究院）；Hallym University（韩国基督教大学）
In this contribution, we will present a review of our works on the time dependence of magnetization in nanoparticle systems starting from non-interacting systems, presenting a general theoretical framework for the analysis of relaxation curves which is based on the so-called $\svar$ scaling method. We will detail the basics and explain its range of validity, showing also its application in experimental measurements of magnetic relaxation. We will also discuss how it can be applied to determine the energy barrier distributions responsible for the relaxation. Next, we will show how the proposed …
Charge transport within Coulomb blockade regime in two-dimensional nanoparticle arrays exhibits nonlinear I-V characteristics, where the level of nonlinearity strongly associates with the array's architecture. Here, we use different mathematical approaches to quantify collective behavior in the charge transport inside the sample and its relationship to the structural characteristics of the assembly and the presence of charge disorder. In particular, we simulate single-electron tunneling conduction in several assemblies with controlled variation of the structural components (branching, extended…
In this communication we study the transport properties of two-dimensional assemblies of [Fe(Htrz)2(trz)](BF4) spin-crossover nanoparticles (NPs) with two different morphologies. The NPs have been synthesized made in a similar manner than in our previous study in which single NPs were measured. We prepared free-standing self-assembled monolayer sheets of both SCO NPs formed at the air/liquid interface on holey carbon TEM grids to extract their global arrangement and NP size distributions by STEM-HAADF technique. The SCO NP systems present a rod-like shape and possess two different volumes, cor…
The properties and applications of metallic nanoparticles are inseparably connected not only to their detailed morphology and composition, but also to their structural configuration and mutual interactions. As a result, the assemblies often have superior properties as compared to individual nanoparticles. Although it has been reported that nanoparticles can form highly symmetric clusters, if the configuration can be predicted as a function of the synthesis parameters, more targeted and accurate synthesis will be possible. We present here a theoretical model that accurately predicts the structu…
Zero Field Cooling (ZFC) and Field Cooling (FC) protocols are commonly used to investigate the properties of magnetic nanoparticle systems. For non-interacting conditions the particle properties are fairly well correlated with the shape of the ZFC/FC curves. However, that is not the case when significant dipolar interparticle interactions (DII) are present, what frequently occurs in experimental samples (e.g. aggregates in biological systems; or the dried powder often used for the ZFC/FC measurements). The purpose of this work is to show how the influence of the DII on the ZFC/FC curves, compu…
Assemblies of magnetic nanoparticles show a great potential for application in biomedicine, in particular, in magnetic hyperthermia. However, to achieve desired therapeutic effect in magnetic hyperthermia the assembly of nanoparticles should have a sufficiently high specific absorption rate in alternating magnetic field of moderate amplitude and frequency.
We introduce TERMS, an open-source Fortran program to simulate near-field and far-field optical properties of clusters of particles. The program solves rigorously the Maxwell equations via the superposition T-matrix method, where incident and scattered fields are decomposed into series of vector spherical waves. TERMS implements several algorithms to solve the coupled system of multiple scattering equations that describes the electromagnetic interaction between neighbouring scatterers. From this formal solution, the program can compute a number of physically-relevant optical properties, such a…
We realise an antibacterial nanomaterial based on the self-limited assembly of patchy plasmonic colloids, obtained by adsorption of lysozyme to gold nanoparticles. The possibility of selecting the size of the assemblies within several hundred nanometres allows for tuning their optical response in a wide range of frequencies from visible to near infrared. We also demonstrate an aggregation-dependent modulation of the catalytic activity, which results in an enhancement of the antibacterial performances for assemblies of the proper size. The gained overall control on structure, optical properties…
It has recently been possible to synthesize ordered assemblies composed of magnetic superatomic clusters Ni9Te6(PEt3)8 separated by C60 and study their magnetic behavior. We have carried out theoretical studies on model systems consisting of magnetic superatoms separated by non-magnetic species to examine the evolution in magnetic response as the nature of the magnetic superatom (directions of spin quantization), the strength of isotropic and anisotropic interactions, the magnetic anisotropy energy, and the size of the assembly are varied. We have examined square planar configurations consisti…
Elevated-temperature polyol-based colloidal-chemistry approach allows for the development of size-tunable (50 and 86 nm) assemblies of maghemite iso-oriented nanocrystals, with enhanced magnetization. 1H-Nuclear Magnetic Resonance (NMR) relaxometric experiments show that the ferrimagnetic cluster-like colloidal entities exhibit a remarkable enhancement (4 to 5 times) in the transverse relaxivity, if compared to that of the superparamagnetic contrast agent Endorem, over an extended frequency range (1-60 MHz). The marked increase of the transverse relaxivity r2 at a clinical magnetic field stren…
A linear combination of spherically symmetric heat sources is shown to provide optimal stationary thermal distribution in magnetic hyperthermia. Furthermore, such spatial location of heat sources produces suitable temperature distribution in biological medium even for assemblies of magnetic nanoparticles with a moderate value of specific absorption rate (SAR), of the order of 100 - 150 W/g. We also demonstrate the advantage of using assemblies of magnetic nanocapsules consisting of metallic iron nanoparticles covered with non magnetic shells of sufficient thickness in magnetic hyperthermia. Ba…
Iron oxide nanoparticles have tremendous scientific and technological potential in a broad range of technologies, from energy applications to biomedicine. To improve their performance, single-crystalline and defect-free nanoparticles have thus far been aspired. However, in several recent studies defect-rich nanoparticles outperform their defect-free counterparts in magnetic hyperthermia and magnetic particle imaging. Here, an overview on the state-of-the-art of design and characterization of defects and resulting spin disorder in magnetic nanoparticles is presented with a focus on iron oxide n…
Techniques to reliably pick and place single nanoparticles into functional assemblies are required to incorporate exotic nanoparticles into standard electronic circuits. In this paper we explore the use of electric fields to drive and direct the assembly process, which has the advantage of being able to control the nano-assembly process at the single nanoparticle level. To achieve this, we design an electrostatic gating system, thus enabling a voltage controllable nanoparticle picking technique. Using the nonlinear Poisson-Boltzmann equation, we can successfully characterise the parameters req…
There is so far no clear-cut experimental analysis that can determine whether dipole-dipole interactions enhance or reduce the blocking temperature $T_{B}$ of nanoparticle assemblies. It seems that the samples play a central role in the problem and therefore, their geometry should most likely be the key factor in this issue. Yet, in a previous work, Jönsson and Garcia-Palacios did investigate theoretically this problem in a weak-interaction limit and without the presence of an external DC field. Based on symmetry arguments they reached the conclusion that the variation of the relaxation rate i…
The influence of the crystal structure inhomogeneities on the magnetic properties of cobalt nanoparticles with different aspect ratio and spherical nanoparticles of chromium dioxide, cobalt ferrite and magnetite has been studied by means of numerical simulation. The polycrystalline nanoparticles are modeled by means of subdivision of the nanoparticle volume into tightly bound single-crystal granules with randomly distributed directions of the easy anisotropy axes. The probability of appearance of quasi uniform and vortex states in sufficiently large assemblies of polycrystalline nanoparticles …
The elements of the magneto-dipole (MD) interaction matrix are calculated for a pair of oriented spheroidal magnetic nanoparticles with a semiaxes ratio a/b = 1.25, 1.5, 2.0 and 3.0 as a function of the distance between the particle centers. It is shown that the spherical approximation for MD interaction matrix is incorrect already at aspect ratios a/b > 1.25, if the distance R between the particle centers is of the order of particle sizes. However, for moderate particle aspect ratios, a/b < 1.5, the first order correction to spherical approximation with respect to a corresponding small parame…
Homogeneous single phase GdCrO3 nanoparticles are synthesized by a modified-hydrothermal synthesis. The sample shows a compensation temperature at 128 K, below which the DC magnetization becomes negative and positive at low temperatures due to the competition between the two sublattice magnetization. At Néel temperature (168K), the line width and the intensity show an abrupt transition, revealed from electron paramagnetic resonance spectroscopy.
To evaluate the self-heating effects of FeCo magnetic nanoparticles, the surface oxidized FeCo nanoparticles were synthesized by co-precipitation method with the reduction reaction without any post treatments. As-synthesized FeCo nanoparticles exhibited the mean diameter of about 39 nm with the oxidized shell thickness of about 4-5 nm. The saturation magnetization and coercivity were obtained 172 emu/g and 268 Oe at 300 K, respectively. The heat elevation of the FeCo magnetic colloid was measured under alternating magnetic fields of 76, 102, and 127 Oe with selectable frequencies of 190, 250 a…
A mean field model is presented for the configuration dependent effective demagnetizing and anisotropy fields in assemblies of exchange decoupled magnetic particles of arbitrary shape which are expressed in terms of the demagnetizing factors of the particles and the volumetric shape containing the assembly. Perpendicularly magnetized 2D assemblies have been considered, for which it is shown that the demagnetizing field is lower than the continuous thin film. As an example of these 2D systems, arrays of bistable cylindrical nanowires have been characterized by remanence curves as well as ferrom…
The stochastic Landau-Lifshitz equation is used to investigate the relaxation process and equilibrium magnetization of interacting assembly of superparamagnetic nanoparticles uniformly distributed in a nonmagnetic matrix. For weakly interacting assembly the equilibrium magnetization is shown to deviate significantly from the Langevin law in the range of moderate and large magnetic fields due to the influence of magnetic anisotropy energy. For dense assemblies with noticeable influence of the magneto-dipole interaction a significant dependence of the initial susceptibility on the assembly densi…
The magnetic properties of Fe$_3$O$_4$ nanoparticle assemblies have been investigated in detail through a combination of vibrating sample magnetometry and muon spin relaxation ($μ$SR) techniques. Two samples with average particle sizes of 5 nm and 20 nm, respectively, were studied. For both samples, the magnetometry and $μ$SR results exhibit clear signatures of the superparmagnetic state at high temperature and the magnetically blocked state at low temperature. The $μ$SR data demonstrate that the transition from the superparamagnetic to the blocked state occurs gradually throughout the sample …
A detailed numerical simulation of quasistatic hysteresis loops of dense clusters of interacting magnetic nanoparticles is carried out. Both clusters of magnetically soft and magnetically hard nanoparticles are considered. The clusters are characterized by an average particle diameter D, the cluster radius Rc, the particle saturation magnetization Ms, and the uniaxial anisotropy constant K. The number of particles in the cluster varies between Np = 30 - 120. The particle centers are randomly distributed within the cluster, their easy anisotropy axes being randomly oriented. It is shown that a …
Remote sensing of magnetic nanoparticles has exciting applications for magnetic nanoparticle hyperthermia and molecular detection. We introduce, simulate, and experimentally demonstrate an innovation---a sensing coil that is geometrically decoupled from the excitation field---for magnetic nanoparticle spectroscopy that increases the flexibility and capabilities of remote detection. The decoupling enhances the sensitivity absolutely; to small amounts of nanoparticles, and relatively; to small changes in the nanoparticle dynamics. We adapt a previous spectroscopic method that measures the relaxa…
The properties of natural and artificial assemblies of interacting elements, ranging from Quarks to Galaxies, are at the heart of Physics. The collective response and dynamics of such assemblies are dictated by the intrinsic dynamical properties of the building blocks, the nature of their interactions and topological constraints. Here we report on the relaxation dynamics of the magnetization of artificial assemblies of mesoscopic spins. In our model nano-magnetic system - square artificial spin ice - we are able to control the geometrical arrangement and interaction strength between the magnet…
Magnetization dynamics in the system of magnetic nanoclusters with randomly distributed properties are studied by means of computer simulations. The main attention is paid to the possibility of coherent magnetization reversal from a strongly nonequilibrium state with a mean cluster magnetization directed opposite to an external magnetic field. Magnetic nanoclusters are known to be characterized by large magnetic anisotropy and strong dipole interactions. It is also impossible to produce a number of nanoclusters with identical properties. As a result, any realistic system of nanoclusters is com…
The complex permittivity and permeability of superparamagnetic iron-oxide nanoparticles has been quantified using a circular waveguide assembly with a static magnetic field to align the nanoparticle's magnetization. The high sensitivity of the measurement provides the precise resonant feature of nanoparticles. The complex permeability in the vicinity of ferromagnetic resonance (FMR) is in agreement with the nanoparticle's measured magnetization via conventional magnetometry. A rigorous and self-consistent measure of complex permittivities and permeabilities of nanoparticles is crucial to ascer…
We present a systematic numerical modeling investigation of magnetization dynamics and thermal magnetic moment fluctuations of single magnetic domain nanoparticles in a configuration applicable to enhancing inductive magnetic resonance detection signal to noise ratio (SNR). Previous proposals for oriented anisotropic single magnetic domain nanoparticle amplification of magnetic flux in MRI coil focused only on the coil pick-up voltage signal enhancement. Here we extend the analysis to the numerical evaluation of the SNR by modeling the inherent thermal magnetic noise introduced into the detect…
We report evidence of the magnetization reversal in nanoparticles by surface acoustic waves (SAWs). The experimental system consists of isolated magnetite nanoparticles dispersed on a piezoelectric substrate. Magnetic relaxation from a saturated state becomes significantly enhanced in the presence of the SAW at a constant temperature of the substrate. The dependence of the relaxation on SAW power and frequency has been investigated. The effect is explained by the effective ac magnetic field generated by the SAW in the nanoparticles.
Thermomagnetic measurements are used to obtain the size distribution and anisotropy of magnetic nanoparticles. An analytical transformation method is described which utilizes temperature-dependent zero-field cooling (ZFC) magnetization data to provide a quantitative measurement of the average diameter and relative abundance of superparamagnetic nanoparticles. Applying this method to self-assembled MnAs nanoparticles in MnAs-GaAs composite films reveals a log-normal size distribution and reduced anisotropy for nanoparticles compared to bulk materials. This analytical technique holds promise for…
We present Vinamax, a simulation tool for nanoparticles that aims at simulating magnetization dynamics on very large timescales. To this end, each in dividual nanoparticle is approximated by a macrospin. Vinamax numerically solves the Landau-Lifshitz equation by adopting a dipole approximation method, while temperature effects can be taken into account with two stochastic methods. It describes the influence of demagnetizing and anisotropy fields on magnetic nanoparticles at finite temperatures in a space and time-dependent externally applied field. Vinamax can be used in biomedical research wh…
Magnetosomes, i.e. nanoparticles synthesized in nature by magnetotactic bacteria, are very promising for use in magnetic hyperthermia for the cancer treatment. Using the solution of the stochastic Landau-Lifshitz equation we calculate the specific absorption rate in an alternating magnetic field of assemblies of magnetosome chains depending on the particle size, the distance between particles in a chain, and the angle of the applied magnetic field with respect to the chain axis. The dependence of specific absorption rate on the distance between the chain particles is shown to have a bell-shape…
Superparamagnetic nanoparticles containing hundreds and thousands of coupled electron spins are on the boundary between classical and quantum behavior, and demonstrate features which are typical for paramagnetic spins and absent in macroscopic ferromagnetic systems. In order to better understand the evolution of magnetization dynamics from quantum to classical behavior with the increase in the system size, we study the electron magnetic resonance signal in suspensions of iron oxide nanoparticles as the function of the particle size. The experimental data are compared with numerical simulations…
