Structure-Related Electronic and Magnetic Properties in Ultrathin Epitaxial NixFe3-xO4 Films on MgO(001).

Off-stoichiometric NixFe3-xO4 ultrathin films (x < 2.1) with varying Ni content x and thickness 16 (±2) nm were grown on MgO(001) by reactive molecular beam epitaxy. Synchrotron-based high-resolution X-ray diffraction measurements reveal vertical compressive strain for all films, resulting from a lateral pseudomorphic adaption of the film to the substrate lattice without any strain relaxation. Complete crystallinity with smooth interfaces and surfaces is obtained independent of the Ni content x. For x < 1 an expected successive conversion from Fe3O4 to NiFe2O4 is observed, whereas local transformation into NiO structures is observed for films with Ni content x > 1. However, angle-resolved hard X-ray photoelectron spectroscopy measurements indicate homogeneous cationic distributions without strictly separated phases independent of the Ni content, while X-ray absorption spectroscopy shows that also for x > 1, not all Fe2+ cations are substituted by Ni2+ cations. The ferrimagnetic behavior, as observed by superconducting quantum interference device magnetometry, is characterized by decreasing saturation magnetization due to the formation of antiferromagnetic NiO parts.

Real-Time Monitoring of Strain Accumulation and Relief during Epitaxy of Ultrathin Co Ferrite Films with Varied Co Content.

Ultrathin CoxFe3-xO4 films of high structural quality and with different Co content (x = 0.6-1.2) were prepared by reactive molecular beam epitaxy on MgO(001) substrates. Epitaxy of these ferrite films is extensively monitored by means of time-resolved (operando) X-ray diffraction recorded in out-of-plane geometry to characterize the temporal evolution of the film structure. The Co ferrite films show high crystalline ordering and smooth film interfaces independent of their Co content. All CoxFe3-xO4 films exhibit enhanced compressive out-of-plane strain during the early stages of growth, which partly releases with increasing film thickness. When the Co content of the ferrite films increases, the vertical-layer distances increase, accompanied by slightly increasing film roughnesses. The latter result is supported by surface-sensitive low-energy electron diffraction as well as X-ray reflectivity measurements on the final films. In contrast, the substrate-film interface roughness decreases with increasing Co content, which is confirmed with X-ray reflectivity measurements. In addition, the composition and electronic structure of the ferrite films is characterized by means of hard X-ray photoelectron spectroscopy performed after film growth. The experiments reveal the expected increasing Fe3+/Fe2+ cation ratios for a higher Co content.

Click-Functionalization of Silanized Carbon Nanotubes: From Inorganic Heterostructures to Biosensing Nanohybrids.

Here we present an approach to functionalize silanized single-walled carbon nanotubes (SWNTs) through copper-free click chemistry for the assembly of inorganic and biological nanohybrids. The nanotube functionalization route involves silanization and strain-promoted azide-alkyne cycloaddition reactions (SPACC). This was characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and Fourier transform infra-red spectroscopy. Silane-azide-functionalized SWNTs were immobilized from solution onto patterned substrates through dielectrophoresis (DEP). We demonstrate the general applicability of our strategy for the functionalization of SWNTs with metal nanoparticles (gold nanoparticles), fluorescent dyes (Alexa Fluor 647) and biomolecules (aptamers). In this regard, dopamine-binding aptamers were conjugated to the functionalized SWNTs to perform real-time detection of dopamine at different concentrations. Additionally, the chemical route is shown to selectively functionalize individual nanotubes grown on the surface of silicon substrates, contributing towards future nano electronic device applications.

Influence of Oxygen Plasma on the Growth and Stability of Epitaxial NiCo2O4 Ultrathin Films on Various Substrates.

In this work, we investigated the influence of oxygen plasma on the growth of nickel cobaltite (NiCo2O4) thin films compared to growth in a molecular oxygen atmosphere. The films were grown on MgO(001), MgAl2O4(001) and SrTiO3(001) substrates by oxygen plasma (atmosphere of activated oxygen)-assisted and reactive molecular beam epitaxy (molecular oxygen atmosphere). Soft X-ray photoelectron spectroscopy showed that only the use of oxygen plasma led to a spectrum characteristic of (NiCo2O4). Low energy electron diffraction measurements were conducted to obtain information on the structure of the film surfaces. The results proved the formation of a spinel surface structure for films grown with oxygen plasma, while the formation of a rock salt structure was observed for growth with molecular oxygen. To determine the film thickness, X-ray reflectivity measurements were performed. If oxygen plasma were used to grow (NiCo2O4) films, this would result in lower film thicknesses compared to growth using molecular oxygen although the cation flux was kept constant during deposition. Additional X-ray diffraction experiments delivered structural information about the bulk structure of the film. All films had a rock salt bulk structure after exposure to ambient conditions. Angle-resolved hard X-ray photoelectron spectroscopy revealed a homogeneous depth distribution of cations of the grown film, but no typical (NiCo2O4) spectrum anymore. Thus, on the one hand, (NiCo2O4) films with a spinel structure prepared using activated oxygen were not stable under ambient conditions. The structure of these films was transformed into NiCo oxide with a rock salt structure. On the other hand, it was not possible to form (NiCo2O4) films using molecular oxygen. These films had a rock salt structure that was stable under ambient conditions.

Reactive Additive Capillary Stamping with Double Network Hydrogel-Derived Aerogel Stamps under Solvothermal Conditions.

Integration of solvothermal reaction products into complex thin-layer architectures is frequently achieved by combinations of layer transfer and subtractive lithography, whereas direct additive substrate patterning with solvothermal reaction products has remained challenging. We report reactive additive capillary stamping under solvothermal conditions as a parallel contact-lithographic access to patterns of solvothermal reaction products in thin-layer configurations. To this end, corresponding precursor inks are infiltrated into mechanically robust mesoporous aerogel stamps derived from double-network hydrogels. The stamp is then brought into contact with a substrate to be patterned under solvothermal reaction conditions inside an autoclave. The precursor ink forms liquid bridges between the topographic surface pattern of the stamp and the substrate. Evaporation-driven enrichment of the precursors in these liquid bridges, along with their liquid-bridge-guided conversion into the solvothermal reaction products, yields large-area submicron patterns of the solvothermal reaction products replicating the stamp topography. For example, we prepared thin hybrid films, which contained ordered monolayers of superparamagnetic submicron nickel ferrite dots prepared by solvothermal capillary stamping surrounded by nickel electrodeposited in a second orthogonal substrate functionalization step. The submicron nickel ferrite dots acted as a magnetic hardener, halving the remanence of the ferromagnetic nickel layer. In this way, thin-layer electromechanical systems, transformers, and positioning systems may be customized.

Real-Time Monitoring the Growth of Epitaxial CoxFe3-xO4 Ultrathin Films on Nb-Doped SrTiO3(001) via Reactive Molecular Beam Epitaxy by Means of Operando HAXPES.

In this work, we present a comprehensive study on real-time monitoring the growth of epitaxial CoxFe3-xO4 thin films grown on SrTiO3(001) substrates via reactive molecular beam epitaxy. The growth process was monitored during evaporation by means of time resolved operando hard X-ray photoelectron spectroscopy (HAXPES). We prepared ultrathin ferrite films using different oxygen partial pressures, showing pure metallic, light oxidic, and cobalt ferrite-like growth. Additional X-ray diffraction measurements confirm HAXPES results.

Magnetoelectric Response of Laminated Cantilevers Comprising a Magnetoactive Elastomer and a Piezoelectric Polymer, in Pulsed Uniform Magnetic Fields.

The voltage response to pulsed uniform magnetic fields and the accompanying bending deformations of laminated cantilever structures are investigated experimentally in detail. The structures comprise a magnetoactive elastomer (MAE) slab and a commercially available piezoelectric polymer multilayer. The magnetic field is applied vertically and the laminated structures are customarily fixed in the horizontal plane or, alternatively, slightly tilted upwards or downwards. Six different MAE compositions incorporating three concentrations of carbonyl iron particles (70 wt%, 75 wt% and 80 wt%) and two elastomer matrices of different stiffness are used. The dependences of the generated voltage and the cantilever's deflection on the composition of the MAE layer and its thickness are obtained. The appearance of the voltage between the electrodes of a piezoelectric material upon application of a magnetic field is considered as a manifestation of the direct magnetoelectric (ME) effect in a composite laminated structure. The ME voltage response increases with the increasing total quantity of the soft-magnetic filler in the MAE layer. The relationship between the generated voltage and the cantilever's deflection is established. The highest observed peak voltage around 5.5 V is about 8.5-fold higher than previously reported values. The quasi-static ME voltage coefficient for this type of ME heterostructures is about 50 V/A in the magnetic field of ≈100 kA/m, obtained for the first time. The results could be useful for the development of magnetic field sensors and energy harvesting devices relying on these novel polymer composites.

Phenolic Resin Dual-Use Stamps for Capillary Stamping and Decal Transfer Printing.

We report an optimized two-step thermopolymerization process carried out in contact with micropatterned molds that yields porous phenolic resin dual-use stamps with topographically micropatterned contact surfaces. With these stamps, two different parallel additive substrate manufacturing methods can be executed: capillary stamping and decal transfer microlithography. Under moderate contact pressures, the porous phenolic resin stamps are used for nondestructive ink transfer to substrates by capillary stamping. Continuous ink supply through the pore systems to the contact surfaces of the porous phenolic resin stamps enables multiple successive stamp-substrate contacts for lithographic ink deposition under ambient conditions. No deterioration of the quality of the deposited pattern occurs, and no interruptions for ink replenishment are required. Under a high contact pressure, porous phenolic resin stamps are used for decal transfer printing. In this way, the tips of the stamps' contact elements are lithographically transferred to counterpart substrates. The granular nature of the phenolic resin facilitates the rupture of the contact elements upon stamp retraction. The deposited phenolic resin micropatterns characterized by abundance of exposed hydroxyl groups are used as generic anchoring sites for further application-specific functionalizations. As an example, we deposited phenolic resin micropatterns on quartz crystal microbalance resonators and further functionalized them with polyethylenimine for preconcentration sensing of humidity and gaseous formic acid. We envision that also preconcentration coatings for other sensing methods, such as attenuated total reflection infrared spectroscopy and surface plasmon resonance spectroscopy, are accessible by this functionalization algorithm.

Cationic Ordering and Its Influence on the Magnetic Properties of Co-Rich Cobalt Ferrite Thin Films Prepared by Reactive Solid Phase Epitaxy on Nb-Doped SrTiO3(001).

Here, we present the (element-specific) magnetic properties and cation ordering for ultrathin Co-rich cobalt ferrite films. Two Co-rich CoxFe3-xO4 films with different stoichiometry (x=1.1 and x=1.4) have been formed by reactive solid phase epitaxy due to post-deposition annealing from epitaxial CoO/Fe3O4 bilayers deposited before on Nb-doped SrTiO3(001). The electronic structure, stoichiometry and homogeneity of the cation distribution of the resulting cobalt ferrite films were verified by angle-resolved hard X-ray photoelectron spectroscopy. From X-ray magnetic circular dichroism measurements, the occupancies of the different sublattices were determined using charge-transfer multiplet calculations. For both ferrite films, a partially inverse spinel structure is found with increased amount of Co3+ cations in the low-spin state on octahedral sites for the Co1.4Fe1.6O4 film. These findings concur with the results obtained by superconducting quantum interference device measurements. Further, the latter measurements revealed the presence of an additional soft magnetic phase probably due to cobalt ferrite islands emerging from the surface, as suggested by atomic force microscope measurements.

Close-packed silane nanodot arrays by capillary nanostamping coupled with heterocyclic silane ring opening.

We report the parallel generation of close-packed ordered silane nanodot arrays with nanodot diameters of few 100 nm and nearest-neighbor distances in the one-micron range. Capillary nanostamping of heterocyclic silanes coupled with ring-opening triggered by hydroxyl groups at the substrate surfaces yields nanodots consisting of silane monolayers with exposed terminal functional groups. Using spongy mesoporous silica stamps with methyl-terminated mesopore walls inert towards the heterocyclic silanes, we could manually perform multiple successive stamping cycles under ambient conditions without interruptions for ink refilling. Further functionalizations include the synthesis of polymer nanobrushes on the silane nanodots by surface-initiated atom-transfer radical polymerization. Proteins-of-interest fused to the HaloTag were site-specifically captured to silane nanodots functionalized by copper-free reactions with azide derivatives. Thus, bioorthogonal functionalization for bioanalytics with a spatial resolution in the one-micron range may be realized on solid supports compatible with fluorescence-based optical microscopy. The feature sizes of the silane nanodot arrays match well the length scales characteristic of a variety of biomolecular submicroscopic organizations in living cells, thus representing a compromise between miniaturization and the resolution limit of optical microscopy for sensitive high-throughput bioanalytics.

Impact of Strain and Morphology on Magnetic Properties of Fe3O4/NiO Bilayers Grown on Nb:SrTiO3(001) and MgO(001).

We present a comparative study of the morphology and structural as well as magnetic properties of crystalline Fe3O4/NiO bilayers grown on both MgO(001) and SrTiO3(001) substrates by reactive molecular beam epitaxy. These structures were investigated by means of X-ray photoelectron spectroscopy, low-energy electron diffraction, X-ray reflectivity and diffraction, as well as vibrating sample magnetometry. While the lattice mismatch of NiO grown on MgO(001) was only 0.8%, it was exposed to a lateral lattice mismatch of −6.9% if grown on SrTiO3. In the case of Fe3O4, the misfit strain on MgO(001) and SrTiO3(001) amounted to 0.3% and −7.5%, respectively. To clarify the relaxation process of the bilayer system, the film thicknesses of the magnetite and nickel oxide films were varied between 5 and 20 nm. While NiO films were well ordered on both substrates, Fe3O4 films grown on NiO/SrTiO3 exhibited a higher surface roughness as well as lower structural ordering compared to films grown on NiO/MgO. Further, NiO films grew pseudomorphic in the investigated thickness range on MgO substrates without any indication of relaxation, whereas on SrTiO3 the NiO films showed strong strain relaxation. Fe3O4 films also exhibited strong relaxation, even for films of 5 nm thickness on both NiO/MgO and NiO/SrTiO3. The magnetite layers on both substrates showed a fourfold magnetic in-plane anisotropy with magnetic easy axes pointing in 100 directions. The coercive field was strongly enhanced for magnetite grown on NiO/SrTiO3 due to the higher density of structural defects, compared to magnetite grown on NiO/MgO.

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.

Electro-oxidation of a cobalt based steel in LiOH: a non-noble metal based electro-catalyst suitable for durable water-splitting in an acidic milieu.

The use of proton exchange membrane (PEM) electrolyzers is the method of choice for the conversion of solar energy when frequently occurring changes of the current load are an issue. However, this technique requires electrolytes with low pH. All oxygen evolving electrodes working durably and actively in acids contain IrOx. Due to their scarcity and high acquisition costs, noble elements like Pt, Ru and Ir need to be replaced by earth abundant elements. We have evaluated a cobalt containing steel for use as an oxygen-forming electrode in H2SO4. We found that the dissolving of ingredients out of the steel electrode at oxidative potential in sulfuric acid, which is a well-known, serious issue, can be substantially reduced when the steel is electro-oxidized in LiOH prior to electrocatalysis. Under optimized synthesis conditions a cobalt-containing tool steel was rendered into a durable oxygen evolution reaction (OER) electrocatalyst (weight loss: 39 µg mm-2 after 50 000 s of chronopotentiometry at pH 1) that exhibits overpotentials down to 574 mV at 10 mA cm-2 current density at pH 1. Focused ion beam SEM (FIB-SEM) was successfully used to create a structure-stability relationship.

Characterization of multifunctional ß-NaEuF4/NaGdF4 core-shell nanoparticles with narrow size distribution.

The properties of ß-NaEuF4/NaGdF4 core-shell nanocrystals have been thoroughly investigated. Nanoparticles with narrow size distribution and an overall diameter of ∼22 nm have been produced with either small ß-NaEuF4 cores (∼3 nm diameter) or large ß-NaEuF4 cores (∼18 nm diameter). The structural properties and core-shell formation are investigated by X-ray diffraction, transmission electron microscopy and electron paramagnetic resonance, respectively. Optical luminescence measurements and X-ray photoelectron spectroscopy are employed to gain information about the optical emission bands and valence states of the rare earth constituents. Magnetic characterization is performed by SQUID and X-ray magnetic circular dichroism measurements at the rare earth M(4,5) edges. The characterization of the core-shell nanoparticles by means of these complementary techniques demonstrates that partial intermixing of core and shell materials takes place, and a significant fraction of europium is present in the divalent state which has significant influence on the magnetic properties. Hence, we obtained a combination of red emitting Eu(3+) ions and paramagnetic Gd(3+) ions, which may be highly valuable for potential future applications.

Controlling the physics and chemistry of binary and ternary praseodymium and cerium oxide systems.

Rare earth praseodymium and cerium oxides have attracted intense research interest in the last few decades, due to their intriguing chemical and physical characteristics. An understanding of the correlation between structure and properties, in particular the surface chemistry, is urgently required for their application in microelectronics, catalysis, optics and other fields. Such an understanding is, however, hampered by the complexity of rare earth oxide materials and experimental methods for their characterisation. Here, we report recent progress in studying high-quality, single crystalline, praseodymium and cerium oxide films as well as ternary alloys grown on Si(111) substrates. Using these well-defined systems and based on a systematic multi-technique surface science approach, the corresponding physical and chemical properties, such as the surface structure, the surface morphology, the bulk-surface interaction and the oxygen storage/release capability, are explored in detail. We show that specifically the crystalline structure and the oxygen stoichiometry of the oxide thin films can be well controlled by the film preparation method. This work leads to a comprehensive understanding of the properties of rare earth oxides and highlights the applications of these versatile materials. Furthermore, methanol adsorption studies are performed on binary and ternary rare earth oxide thin films, demonstrating the feasibility of employing such systems for model catalytic studies. Specifically for ceria systems, we find considerable stability against normal environmental conditions so that they can be considered as a "materials bridge" between surface science models and real catalysts.

Oxidized Mild Steel S235: An Efficient Anode for Electrocatalytically Initiated Water Splitting.

The surface of steel S235 was oxidized by Cl2 gas and checked for its electrocatalytic efficiency regarding oxygen formation in aqueous solution. If exposed to humid Cl2 gas for 110 min, steel S235 became an electrocatalyst that exhibits an overpotential for the oxygen evolution reaction (OER) of 462 mV at 1 mA cm(-2) at pH 7. The OER activity of the same sample at pH 13 was moderate (347 mV overpotential at 2.0 mA cm(-2) current density) in comparison with OER electrocatalysts developed recently. Potential versus time plots measured at a constant current demonstrate the sufficient stability of all samples under catalysis conditions at pH 7 and 13 for tens of hours. High-resolution X-ray photoelectron spectra could be reasonably resolved with the proviso that Fe2 O3 , FeO(OH), MnO(OH), and Mn2 O3 are the predominant Fe and Mn species on the surface of the oxidized steel S235.

Tunnel junction based memristors as artificial synapses.

We prepared magnesia, tantalum oxide, and barium titanate based tunnel junction structures and investigated their memristive properties. The low amplitudes of the resistance change in these types of junctions are the major obstacle for their use. Here, we increased the amplitude of the resistance change from 10% up to 100%. Utilizing the memristive properties, we looked into the use of the junction structures as artificial synapses. We observed analogs of long-term potentiation, long-term depression and spike-time dependent plasticity in these simple two terminal devices. Finally, we suggest a possible pathway of these devices toward their integration in neuromorphic systems for storing analog synaptic weights and supporting the implementation of biologically plausible learning mechanisms.

Plasma Enhanced Complete Oxidation of Ultrathin Epitaxial Praseodymia Films on Si(111).

Praseodymia films have been exposed to oxygen plasma at room temperature after deposition on Si(111) via molecular beam epitaxy. Different parameters as film thickness, exposure time and flux during plasma treatment have been varied to study their influence on the oxygen plasma oxidation process. The surface near regions have been investigated by means of X-ray photoelectron spectroscopy showing that the plasma treatment transforms the stoichiometry of the films from Pr2O3 to PrO2. Closer inspection of the bulk properties of the films by means of synchrotron radiation based X-ray reflectometry and diffraction confirms this transformation if the films are thicker than some critical thickness of 6 nm. The layer distance of these films is extremely small verifying the completeness of the plasma oxidation process. Thinner films, however, cannot be transformed completely. For all films, less oxidized very thin interlayers are detected by these experimental techniques.