Hard carbon microspheres with bimodal size distribution and hierarchical porosity via hydrothermal carbonization of trehalose.

Hydrothermal carbonization (HTC) is an efficient thermochemical method for the conversion of organic feedstock to carbonaceous solids. HTC of different saccharides is known to produce microspheres (MS) with mostly Gaussian size distribution, which are utilized as functional materials in various applications, both as pristine MS and as a precursor for hard carbon MS. Although the average size of the MS can be influenced by adjusting the process parameters, there is no reliable mechanism to affect their size distribution. Our results demonstrate that HTC of trehalose, in contrast to other saccharides, results in a distinctly bimodal sphere diameter distribution consisting of small spheres with diameters of (2.1 ± 0.2) µm and of large spheres with diameters of (10.4 ± 2.6) µm. Remarkably, after pyrolytic post-carbonization at 1000 °C the MS develop a multimodal pore size distribution with abundant macropores > 100 nm, mesopores > 10 nm and micropores < 2 nm, which were examined by small-angle X-ray scattering and visualized by charge-compensated helium ion microscopy. The bimodal size distribution and hierarchical porosity provide an extraordinary set of properties and potential variables for the tailored synthesis of hierarchical porous carbons, making trehalose-derived hard carbon MS a highly promising material for applications in catalysis, filtration, and energy storage devices.

Thickness-Varied Carbon Nanomembranes from Polycyclic Aromatic Hydrocarbons.

Despite the prospects of intrinsically porous planar nanomaterials in separation applications, their synthesis on a large scale remains challenging. In particular, preparing water-selective carbon nanomembranes (CNMs) from self-assembled monolayers (SAMs) is limited by the cost of epitaxial metal substrates and molecular precursors with specific chemical functionalities. In this work, we present a facile fabrication of CNMs from polycyclic aromatic hydrocarbons (PAHs) that are drop-cast onto arbitrary supports, including foils and metalized films. The electron-induced carbonization is shown to result in continuous membranes of variable thickness, and the material is characterized with a number of spectroscopic and microscopic techniques. Permeation measurements with freestanding membranes reveal a high degree of porosity, but the selectivity is found to strongly depend on the thickness. While the permeance of helium remains almost the same for 6.5 and 3.0 nm thick CNMs, water permeance increases by 2 orders of magnitude. We rationalize the membrane performance with the help of kinetic modeling and vapor adsorption experiments.

Element-Specific Detection of Sub-Nanosecond Spin-Transfer Torque in a Nanomagnet Ensemble.

Spin currents can exert spin-transfer torques on magnetic systems even in the limit of vanishingly small net magnetization, as recently shown for antiferromagnets. Here, we experimentally show that a spin-transfer torque is operative in a macroscopic ensemble of weakly interacting, randomly magnetized Co nanomagnets. We employ element- and time-resolved X-ray ferromagnetic resonance (XFMR) spectroscopy to directly detect subnanosecond dynamics of the Co nanomagnets, excited into precession with cone angle ≳0.003° by an oscillating spin current. XFMR measurements reveal that as the net moment of the ensemble decreases, the strength of the spin-transfer torque increases relative to those of magnetic field torques. Our findings point to spin-transfer torque as an effective way to manipulate the state of nanomagnet ensembles at subnanosecond time scales.

Field-Tunable 0-π-Transitions in SnTe Topological Crystalline Insulator SQUIDs.

The manifestation of spin-orbit interactions, long known to dramatically affect the band structure of heavy-element compounds, governs the physics in the surging class of topological matter. A particular example is found in the new family of topological crystalline insulators. In this systems transport occurs at the surfaces and spin-momentum locking yields crystal-symmetry protected spin-polarized transport. We investigated the current-phase relation of SnTe thin films connected to superconducting electrodes to form SQUID devices. Our results demonstrate that an assisting in-plane magnetic field component can induce 0-π-transitions. We attribute these findings to giant g-factors and large spin-orbit coupling of SnTe topological crystalline insulator, which provides a new platform for investigation of the interplay between spin-orbit physics and topological transport.

Size limits of magnetic-domain engineering in continuous in-plane exchange-bias prototype films.

Background: The application of superparamagnetic particles as biomolecular transporters in microfluidic systems for lab-on-a-chip applications crucially depends on the ability to control their motion. One approach for magnetic-particle motion control is the superposition of static magnetic stray field landscapes (MFLs) with dynamically varying external fields. These MFLs may emerge from magnetic domains engineered both in shape and in their local anisotropies. Motion control of smaller beads does necessarily need smaller magnetic patterns, i.e., MFLs varying on smaller lateral scales. The achievable size limit of engineered magnetic domains depends on the magnetic patterning method and on the magnetic anisotropies of the material system. Smallest patterns are expected to be in the range of the domain wall width of the particular material system. To explore these limits a patterning technology is needed with a spatial resolution significantly smaller than the domain wall width. Results: We demonstrate the application of a helium ion microscope with a beam diameter of 8 nm as a mask-less method for local domain patterning of magnetic thin-film systems. For a prototypical in-plane exchange-bias system the domain wall width has been investigated as a function of the angle between unidirectional anisotropy and domain wall. By shrinking the domain size of periodic domain stripes, we analyzed the influence of domain wall overlap on the domain stability. Finally, by changing the geometry of artificial two-dimensional domains, the influence of domain wall overlap and domain wall geometry on the ultimate domain size in the chosen system was analyzed. Conclusion: The application of a helium ion microscope for magnetic patterning has been shown. It allowed for exploring the fundamental limits of domain engineering in an in-plane exchange-bias thin film as a prototypical system. For two-dimensional domains the limit depends on the domain geometry. The relative orientation between domain wall and anisotropy axes is a crucial parameter and therefore influences the achievable minimum domain size dramatically.

Proximity-Induced Superconductivity and Quantum Interference in Topological Crystalline Insulator SnTe Thin-Film Devices.

Topological crystalline insulators represent a new state of matter, in which the electronic transport is governed by mirror-symmetry protected Dirac surface states. Due to the helical spin-polarization of these surface states, the proximity of topological crystalline matter to a nearby superconductor is predicted to induce unconventional superconductivity and, thus, to host Majorana physics. We report on the preparation and characterization of Nb-based superconducting quantum interference devices patterned on top of topological crystalline insulator SnTe thin films. The SnTe films show weak anti-localization, and the weak links of the superconducting quantum interference devices (SQUID) exhibit fully gapped proximity-induced superconductivity. Both properties give a coinciding coherence length of 120 nm. The SQUID oscillations induced by a magnetic field show 2π periodicity, possibly dominated by the bulk conductivity.

Quantitative Disentanglement of the Spin Seebeck, Proximity-Induced, and Ferromagnetic-Induced Anomalous Nernst Effect in Normal-Metal-Ferromagnet Bilayers.

We identify and investigate thermal spin transport phenomena in sputter-deposited Pt/NiFe_{2}O_{x} (4≥x≥0) bilayers. We separate the voltage generated by the spin Seebeck effect from the anomalous Nernst effect (ANE) contributions and even disentangle the ANE in the ferromagnet (FM) from the ANE produced by the Pt that is spin polarized due to its proximity to the FM. Further, we probe the dependence of these effects on the electrical conductivity and the band gap energy of the FM film varying from nearly insulating NiFe_{2}O_{4} to metallic Ni_{33}Fe_{67}. A proximity-induced ANE could only be identified in the metallic Pt/Ni_{33}Fe_{67} bilayer in contrast to Pt/NiFe_{2}O_{x} (x>0) samples. This is verified by the investigation of static magnetic proximity effects via x-ray resonant magnetic reflectivity.

Large magneto-Seebeck effect in magnetic tunnel junctions with half-metallic Heusler electrodes.

Spin caloritronics studies the interplay between charge-, heat- and spin-currents, which are initiated by temperature gradients in magnetic nanostructures. A plethora of new phenomena has been discovered that promises, e.g., to make wasted heat in electronic devices useable or to provide new read-out mechanisms for information. However, only few materials have been studied so far with Seebeck voltages of only some microvolt, which hampers applications. Here, we demonstrate that half-metallic Heusler compounds are hot candidates for enhancing spin-dependent thermoelectric effects. This becomes evident when considering the asymmetry of the spin-split density of electronic states around the Fermi level that determines the spin-dependent thermoelectric transport in magnetic tunnel junctions. We identify Co2FeAl and Co2FeSi Heusler compounds as ideal due to their energy gaps in the minority density of states, and demonstrate devices with substantially larger Seebeck voltages and tunnel magneto-Seebeck effect ratios than the commonly used Co-Fe-B-based junctions.

Quantitative separation of the anisotropic magnetothermopower and planar Nernst effect by the rotation of an in-plane thermal gradient.

A thermal gradient as the driving force for spin currents plays a key role in spin caloritronics. In this field the spin Seebeck effect (SSE) is of major interest and was investigated in terms of in-plane thermal gradients inducing perpendicular spin currents (transverse SSE) and out-of-plane thermal gradients generating parallel spin currents (longitudinal SSE). Up to now all spincaloric experiments employ a spatially fixed thermal gradient. Thus, anisotropic measurements with respect to well defined crystallographic directions were not possible. Here we introduce a new experiment that allows not only the in-plane rotation of the external magnetic field, but also the rotation of an in-plane thermal gradient controlled by optical temperature detection. As a consequence, the anisotropic magnetothermopower and the planar Nernst effect in a permalloy thin film can be measured simultaneously. Thus, the angular dependence of the magnetothermopower with respect to the magnetization direction reveals a phase shift, that allows the quantitative separation of the thermopower, the anisotropic magnetothermopower and the planar Nernst effect.

Tunnel Magnetoresistance Sensors with Magnetostrictive Electrodes: Strain Sensors.

Magnetostrictive tunnel magnetoresistance (TMR) sensors pose a bright perspective in micro- and nano-scale strain sensing technology. The behavior of TMR sensors under mechanical stress as well as their sensitivity to the applied stress depends on the magnetization configuration of magnetic tunnel junctions (MTJ)s with respect to the stress axis. Here, we propose a configuration resulting in an inverse effect on the tunnel resistance by tensile and compressive stresses. Numerical simulations, based on a modified Stoner-Wohlfarth (SW) model, are performed in order to understand the magnetization reversal of the sense layer and to find out the optimum bias magnetic field required for high strain sensitivity. At a bias field of -3.2 kA/m under a 0.2 × 10 - 3 strain, gauge factors of 2294 and -311 are calculated under tensile and compressive stresses, respectively. Modeling results are investigated experimentally on a round junction with a diameter of 30 ± 0.2 µ m using a four-point bending apparatus. The measured field and strain loops exhibit nearly the same trends as the calculated ones. Also, the gauge factors are in the same range. The junction exhibits gauge factors of 2150 ± 30 and -260 for tensile and compressive stresses, respectively, under a -3.2 kA/m bias magnetic field. The agreement of the experimental and modeling results approves the proposed configuration for high sensitivity and ability to detect both tensile and compressive stresses by a single TMR sensor.

Longitudinal spin Seebeck effect contribution in transverse spin Seebeck effect experiments in Pt/YIG and Pt/NFO.

The spin Seebeck effect, the generation of a spin current by a temperature gradient, has attracted great attention, but the interplay over a millimetre range along a thin ferromagnetic film as well as unintended side effects which hinder an unambiguous detection have evoked controversial discussions. Here, we investigate the inverse spin Hall voltage of a 10 nm thin Pt strip deposited on the magnetic insulators Y3Fe5O12 and NiFe2O4 with a temperature gradient in the film plane. We show characteristics typical of the spin Seebeck effect, although we do not observe the most striking features of the transverse spin Seebeck effect. Instead, we attribute the observed voltages to the longitudinal spin Seebeck effect generated by a contact tip induced parasitic out-of-plane temperature gradient, which depends on material, diameter and temperature of the tip.

A scanning probe microscope for magnetoresistive cantilevers utilizing a nested scanner design for large-area scans.

We describe an atomic force microscope (AFM) for the characterization of self-sensing tunneling magnetoresistive (TMR) cantilevers. Furthermore, we achieve a large scan-range with a nested scanner design of two independent piezo scanners: a small high resolution scanner with a scan range of 5 × 5 × 5 µm(3) is mounted on a large-area scanner with a scan range of 800 × 800 × 35 µm(3). In order to characterize TMR sensors on AFM cantilevers as deflection sensors, the AFM is equipped with a laser beam deflection setup to measure the deflection of the cantilevers independently. The instrument is based on a commercial AFM controller and capable to perform large-area scanning directly without stitching of images. Images obtained on different samples such as calibration standard, optical grating, EPROM chip, self-assembled monolayers and atomic step-edges of gold demonstrate the high stability of the nested scanner design and the performance of self-sensing TMR cantilevers.

On/off switching of bit readout in bias-enhanced tunnel magneto-Seebeck effect.

Thermoelectric effects in magnetic tunnel junctions are promising to serve as the basis for logic devices or memories in a "green" information technology. However, up to now the readout contrast achieved with Seebeck effects was magnitudes smaller compared to the well-established tunnel magnetoresistance effect. Here, we resolve this problem by demonstrating that the tunnel magneto-Seebeck effect (TMS) in CoFeB/MgO/CoFeB tunnel junctions can be switched on to a logic "1" state and off to "0" by simply changing the magnetic state of the CoFeB electrodes. This new functionality is achieved by combining a thermal gradient and an electric field. Our results show that the signal crosses zero and can be adjusted by tuning a bias voltage that is applied between the electrodes of the junction; hence, the name of the effect is bias-enhanced tunnel magneto-Seebeck effect (bTMS). Via the spin- and energy-dependent transmission of electrons in the junction, the bTMS effect can be configured using the bias voltage with much higher control than the tunnel magnetoresistance and even completely suppressed for only one magnetic configuration. Moreover, our measurements are a step towards the experimental realization of high TMS ratios without additional bias voltage, which are predicted for specific Co-Fe compositions.

Electronic structure and optical band gap determination of NiFe2O4.

In a theoretical study we investigate the electronic structure and band gap of the inverse spinel ferrite NiFe2O4. The experimental optical absorption spectrum is accurately reproduced by fitting the Tran-Blaha parameter in the modified Becke-Johnson potential. The accuracy of the commonly applied Tauc plot to find the optical gap is assessed based on the computed spectra and we find that this approach can lead to a misinterpretation of the experimental data. The minimum gap of NiFe2O4 is found to be a 1.53 eV wide indirect gap, which is located in the minority spin channel.

Time-resolved measurement of the tunnel magneto-Seebeck effect in a single magnetic tunnel junction.

Recently, several groups have reported spin-dependent thermoelectric effects in magnetic tunnel junctions. In this paper, we present a setup for time-resolved measurements of thermovoltages and thermocurrents of a single micro- to nanometer-scaled tunnel junction. An electrically modulated diode laser is used to create a temperature gradient across the tunnel junction layer stack. This laser modulation technique enables the recording of time-dependent thermovoltage signals with a temporal resolution only limited by the preamplifier for the thermovoltage. So far, time-dependent thermovoltage could not be interpreted. Now, with the setup presented in this paper, it is possible to distinguish different Seebeck voltage contributions to the overall measured voltage signal in the µs time regime. A model circuit is developed that explains those voltage contributions on different sample types. Further, it will be shown that a voltage signal arising from the magnetic tunnel junction can only be observed when the laser spot is directly centered on top of the magnetic tunnel junction, which allows a lateral separation of the effects.

Negative spin polarization of Mn2VGa probed by tunnel magnetoresistance.

The ferrimagnetic Heusler compound Mn(2)VGa is predicted to have a pseudogap in the majority spin channel, which should lead to a negative tunnel magnetoresistance (TMR). We synthesized epitaxial Mn(2)VGa thin films on MgO(001) substrates by dc and rf magnetron co-sputtering, resulting in nearly stoichiometric films. XRD analysis revealed a mostly B2 ordered structure for the films deposited at substrate temperatures of 350, 450, and 550 °C. Magnetic tunnel junctions with MgO barriers and CoFe counter-electrodes were fabricated. After post-annealing at up to T(a) = 425 °C negative TMR was obtained around zero bias, providing evidence for inverted spin polarization. The band structures of both electrodes were computed within the coherent potential approximation and used to calculate the TMR(V) characteristics, which were in good agreement with our experimental findings.

Local charge and spin currents in magnetothermal landscapes.

A scannable laser beam is used to generate local thermal gradients in metallic (Co2FeAl) or insulating (Y3Fe5O12) ferromagnetic thin films. We study the resulting local charge and spin currents that arise due to the anomalous Nernst effect (ANE) and the spin Seebeck effect (SSE), respectively. In the local ANE experiments, we detect the voltage in the Co2FeAl thin film plane as a function of the laser-spot position and external magnetic field magnitude and orientation. The local SSE effect is detected in a similar fashion by exploiting the inverse spin Hall effect in a Pt layer deposited on top of the Y3Fe5O12. Our findings establish local thermal spin and charge current generation as well as spin caloritronic domain imaging.

Seebeck effect in magnetic tunnel junctions.

Creating temperature gradients in magnetic nanostructures has resulted in a new research direction, that is, the combination of magneto- and thermoelectric effects. Here, we demonstrate the observation of one important effect of this class: the magneto-Seebeck effect. It is observed when a magnetic configuration changes the charge-based Seebeck coefficient. In particular, the Seebeck coefficient changes during the transition from a parallel to an antiparallel magnetic configuration in a tunnel junction. In this respect, it is the analogue to the tunnelling magnetoresistance. The Seebeck coefficients in parallel and antiparallel configurations are of the order of the voltages known from the charge-Seebeck effect. The size and sign of the effect can be controlled by the composition of the electrodes' atomic layers adjacent to the barrier and the temperature. The geometric centre of the electronic density of states relative to the Fermi level determines the size of the Seebeck effect. Experimentally, we realized 8.8% magneto-Seebeck effect, which results from a voltage change of about -8.7 µV K⁻¹ from the antiparallel to the parallel direction close to the predicted value of -12.1 µV K⁻¹. In contrast to the spin-Seebeck effect, it can be measured as a voltage change directly without conversion of a spin current.