Andreas Tschöpe

Rotational diffusion of magnetic nickel nanorods in colloidal dispersions

Colloidal dispersions of Ni nanorods were synthesized by pulsed electrodeposition of Ni into nanoporous aluminum oxide layers followed by dissolution of the templates. Geometrical characterization of the nanorods by transmission electron microscopy and scanning electron microscopy allowed us to determine the average length (100-250 nm) and diameter (20-40 nm) of the rods and to estimate the thickness of the polyvinylpyrrolidone surfactant layer. Due to their acicular shape, nanorods of the given size are uniaxial ferromagnetic single domain particles and exhibit a distinct anisotropic polarizability. These two characteristic properties are the physical basis for magnetic field-dependent optical transmission and allow us to investigate the rotational diffusion of the nanorods in liquid dispersion. In the present study, we employed AC magnetization measurements, dynamical light scattering and optical transmission measurements in a rotating magnetic field to determine the rotational diffusion coefficient. The results from all three methods were consistent and agree with theory within a factor of 2.

Low temperature processing of dense nanocrystalline yttrium-doped cerium oxide ceramics

Nanocrystalline cerium oxide ceramics of high homogeneity and nearly full density were prepared. The starting material was synthesized by the direct homogeneous precipitation method using hexamethylenetetramine (HMT). Two alternative routes for consolidation into green bodies were employed: (i) centrifugal casting of an electrostatically stabilized colloidal solution and (ii) cold isostatic pressing of dried ceria powder. The green bodies were sintered at temperatures between 700 and 1000°C. The sinter activities of both nanocrystalline materials were strongly enhanced if compared to microcrystalline ceria. Green bodies, which were generated by colloidal processing exhibited the highest sinter activities, associated with a unique pore structure. The effect of yttrium doping on the grain size after sintering at high temperatures was also investigated. The combination of yttrium doping and colloidal processing allowed for the synthesis of dense nanocrystalline cerium oxide ceramics by pressureless sintering.

Magnetic-field-dependent optical transmission of nickel nanorod colloidal dispersions

Aqueous dispersions of nickel nanorods, ≈13 nm in diameter and 40–160 nm in length, were synthesized using ac electrodeposition into porous alumina templates. The nanorods in suspension can be aligned by modest magnetic fields, which leads to a change in the optical transmittance of the dispersion. Optical transmission measurements with polarized and unpolarized light as a function of magnetic field were performed on suspensions of different particle concentration and varying aspect ratio of the nanoparticles. The experimental results were compared with a theoretical model in which the optical absorption of the nanorods is calculated from the polarizability of prolate ellipsoids in the quasistatic approximation. The magnetic field dependence is introduced in terms of the static orientational distribution function of magnetic moments in an external field. In addition, the relaxation dynamics of the optical transmission was studied, which allowed us to determine the rotational diffusion coefficient of the n...

Fabrication of all diamond scanning probes for nanoscale magnetometry

The electronic spin of the nitrogen vacancy (NV) center in diamond forms an atomically sized, highly sensitive sensor for magnetic fields. To harness the full potential of individual NV centers for sensing with high sensitivity and nanoscale spatial resolution, NV centers have to be incorporated into scanning probe structures enabling controlled scanning in close proximity to the sample surface. Here, we present an optimized procedure to fabricate single-crystal, all-diamond scanning probes starting from commercially available diamond and show a highly efficient and robust approach for integrating these devices in a generic atomic force microscope. Our scanning probes consisting of a scanning nanopillar (200 nm diameter, 1-2 μm length) on a thin (<1 μm) cantilever structure enable efficient light extraction from diamond in combination with a high magnetic field sensitivity (ηAC≈50±20nT/Hz). As a first application of our scanning probes, we image the magnetic stray field of a single Ni nanorod. We show that this stray field can be approximated by a single dipole and estimate the NV-to-sample distance to a few tens of nanometer, which sets the achievable resolution of our scanning probes.

Nanoscale rheometry of viscoelastic soft matter by oscillating field magneto-optical transmission using ferromagnetic nanorod colloidal probes

Nickel nanorods with an average length of 250–420u2009nm and diameter of 20–26u2009nm were prepared by pulsed current electrodeposition into porous aluminum oxide templates and dispersed as colloidal probes in water-based viscoelastic matrices. The ferromagnetic single domain nanorods were driven to rotational motion by an oscillating magnetic field. Nanorod rotation was detected using optical transmission of linearly polarized light providing a frequency-dependent complex magneto-optical response function. Quantitative data analysis was derived for the two most basic mechanical equivalents to viscoelastic materials, the Voigt-Kelvin and Maxwell model, respectively, and demonstrated by means of two examples. The transition from a viscous fluid towards a viscoelastic hydrogel with static shear elasticity was monitored by analyzing an isothermal series of magneto-optical measurements of a gelatin sol after temperature quench in terms of the Voigt-Kelvin model. Maxwell-type relaxation was investigated using CTAC/NaS...

Homogeneous Biosensing Based on Magnetic Particle Labels.

The growing availability of biomarker panels for molecular diagnostics is leading to an increasing need for fast and sensitive biosensing technologies that are applicable to point-of-care testing. In that regard, homogeneous measurement principles are especially relevant as they usually do not require extensive sample preparation procedures, thus reducing the total analysis time and maximizing ease-of-use. In this review, we focus on homogeneous biosensors for the in vitro detection of biomarkers. Within this broad range of biosensors, we concentrate on methods that apply magnetic particle labels. The advantage of such methods lies in the added possibility to manipulate the particle labels by applied magnetic fields, which can be exploited, for example, to decrease incubation times or to enhance the signal-to-noise-ratio of the measurement signal by applying frequency-selective detection. In our review, we discriminate the corresponding methods based on the nature of the acquired measurement signal, which can either be based on magnetic or optical detection. The underlying measurement principles of the different techniques are discussed, and biosensing examples for all techniques are reported, thereby demonstrating the broad applicability of homogeneous in vitro biosensing based on magnetic particle label actuation.

Influence of dipolar interactions on the angular-dependent coercivity of nickel nanocylinders

In this study the influence of dipolar interactions on the orientation-dependent magnetization behavior of an ensemble of single-domain nickel nanorods was investigated. The rods were synthesized by electrodeposition of nickel into porous alumina templates. Some of the rods were released from the oxide and embedded in gelatine hydrogels (ferrogel) at a sufficiently large average interparticle distance to suppress dipolar interactions. By comparing the orientation-dependent hystereses of the two ensembles in the template and the gel-matrix it could be shown that the dipolar interactions in the template considerably alter the functional form of the angular-dependent coercivity. Analysis of the magnetization curves for an angle of 60? between the rod-axes and the field revealed a significantly reduced coercivity of the template compared to the ferrogel, which could be directly attributed to a stray field induced magnetization reversal of a steadily increasing number of rods with increasing field strength. The magnetization curve of the template could be approximated by a weighted linear superposition of the hysteresis branches of the ferrogel. The magnetization reversal process of the rods was investigated by analyzing the angular-dependent coercivity of the non-interacting nanorods. Comparison of the functional form with analytical models and micromagnetic simulations emphasized the assumption of a localized magnetization reversal. Additionally, it could be shown that the nucleation field of rods with diameters in the range 18?29?nm tends to increase with increasing diameter.

Magnetic Nanorods: Genesis, Self-Organization and Applications

Magnetic-field-assisted self-assembly of magnetic dipole moment carrying iron nanoparticles is shown to result in the formation of magnetic and mechanically stiff nanoscale rods. The cooperative behavior of an ensemble of such rods and bundles thereof exhibits self-organized pattern formation on different length scales. Pattern formation on large length scales reveals great similarity with physical systems undergoing spinodal decomposition. Possible applications for dipolar magnetic nanorods in the field of perpendicular storage media are highlighted. We discuss an aerosol-synthesis-route allowing to prepare ferrofluids (FF) with shape-anisotropic particles constituting the magnetic phase immersed in the nonmagnetic carrier fluid. These so-called nanorod FF unveil a two orders of magnitude increase of viscosity enforced by an applied field of 10mT even at shear rates larger than 10-2s. This raises prospects for applications in microfluidics and MEMS.

Optical transmission versus ac magnetization measurements for monitoring colloidal Ni nanorod rotational dynamics

Ni nanorods with an average length nm and diameter nm were synthesized using the AAO template method. The magnetization and optical transmission of nanorod colloidal dispersions in alternating magnetic fields were measured and analyzed with the objective of comparing the intrinsic Brownian relaxation times obtained with the two methods. The different physical origin of the measured signal, related to different moments of the orientation distribution function, and the non-linear effects expected for the large magnetic moments of the Ni nanorods at common field amplitudes required a comprehensive modelling. The time-dependent magnetization and optical transmission in ac magnetic fields was derived by numerical solution of the Fokker–Planck equation. The simulated time-dependent magnetization and optical transmission at a given frequency and field amplitude were analyzed analogous to experimental data to determine characteristic relaxation frequencies. Empirical relationships were derived which enabled extraction of the intrinsic Brownian relaxation time from the characteristic frequencies measured in the non-linear regime. Despite large differences in the characteristic frequencies obtained from magnetization and optical transmission measurements, the retrieved intrinsic Brownian relaxation times were found to agree well. The potential of ac magnetic field-dependent optical transmission for biosensing applications was demonstrated by monitoring the adsorption of the protein gelatine on the nanorod labels.

Analysis of the static magnetic field-dependent optical transmission of Ni nanorod colloidal suspensions

The magnetic field-dependent optical transmission of dilute Ni nanorod aqueous suspensions was investigated. A series of four samples of nanorods were synthesized using the AAO template method and processed to stable colloids. The distributions of their length and diameter were characterized by analysis of TEM images and revealed average diameters of ∼25u2009nm and different lengths in the range of 60u2009nm–1100u2009nm. The collinear magnetic and optical anisotropy was studied by static field-dependent transmission measurements of linearly polarized light parallel and perpendicular to the magnetic field direction. The experimental results were modelled assuming the field-dependent orientation distribution function of a superparamagnetic ensemble for the uniaxial ferromagnetic nanorods in liquid dispersion and extinction cross sections for longitudinal and transversal optical polarization derived from different approaches, including the electrostatic approximation and the separation of variables method, both applied ...