Difference between chemical structures of the interface at the Al-oxide tunneling barrier prepared by plasma or by radical oxidation

We have studied chemical structures of the interface between the Al-oxide tunneling barrier and the underlying Co₉₀Fe₁₀ layer in magnetic tunnel junctions when a 1-nm thick metallic Al barrier was oxidized by two different methods: plasma oxidation and radical oxidation. Our chemical analyses confirmed that the underlying CoFe layer was unavoidably attacked by oxygen during the oxidation and that this left different oxide states at the AlO_x/CoFe interface, depending on the oxidation method. The radical oxidation required long oxidation time for optimizing tunneling performance and resulted in a large amount of oxygen at the interface, which, in turn, resulted in the formation of mostly α-Fe₂O₃ and Al₂O₃. Conversely, the plasma oxidation required a relatively short oxidation time for optimization and left FeO as a dominant phase at the interface. Our results also show that the thermal treatment helped AlO_x, an oxygen-deficient phase, to be re-oxidized and transformed into Al₂O₃, the thermodynamically stable stoichiometric phase. The oxygen that diffused from the reduced CoFe layer into the barrier is likely responsible for this oxygen enrichment. We show that such differences in the chemical structure of the interface are critical clues to understanding what causes the change in tunneling properties of magnetic tunnel junctions.     

Dynamics and instability of solid-state dewetting

Spontaneous dewetting of solid thin films proceeds by edge retraction of film edges and/or by heterogeneous void growth. Classical 1D and 2D continuous models of the evolution of a dewetting film, based on surface diffusion mechanisms, predict that in the long-time limit dewetting obeys universal scaling laws. In this paper, we review 1D and 2D predictions and recent experimental results. For this purpose, using Si(001)/SiO₂ and Ge(001)/SiO₂ single-crystalline thin films in different geometries, we have been able to compare theoretical predictions to experimental results obtained by combining in situ LEEM and ex situ AFM measurements. For dewetting from film edges, experimental results partially differ from continuous models predictions. More precisely, because of the crystallographic anisotropy: (i) the facetted edges remain stable during dewetting (they simply recede at constant shape) while poorly or un-facetted edges are unstable (they recede by finger formation); (ii) rim formation, induced by mass-conservation condition, proceeds in a layer-by-layer mode and is limited by 2D nucleation properties on the top of the rim; (iii) the island generation mechanism differs from the mass shedding behaviour predicted by 1D models. For dewetting mechanisms involving void growth, different behaviours are reported and discussed. For thin Si(001)/SiO₂ films, the corners of the opening square-shaped voids lead to a local destabilisation of the growing voids. For thin Ge(001)/SiO₂ films, the side of the voids invariably turns instable and forms tip dendrites whose branch density depends on the temperature and the initial film thickness. Finally, ultra-thin films, more sensitive to local fluctuations, dewet in a fractal geometry.     

CoFe-based granular alloys: the role of the metallic matrix

RF-sputtered CoFe-NM granular alloys (NM=Ag, Cu) with CoFe volume content, x_v, ranging from 0.10 to 0.45 have been studied. These two series of samples show similar features depending on the synthesis conditions and post-deposition annealing treatments, revealing the strong dependence of magnetotransport properties on microstructure. Three different regimes have been observed as x_v is increased: the classical giant magnetoresistance (GMR) regime at low ferromagnetic contents; at intermediate x_v, a domain structure appears, and GMR and anisotropic magnetoresistance (AMR) together with domain wall scattering are observed; and a third regime at x_v close but below the volume percolation threshold, where the two latter contributions still coexist, while the GMR contribution has been suppressed by strong magnetic correlations. The role of the metallic matrix is crucial to determine the crossover ferromagnetic contents between these three regimes, which depend on the relative immiscibility of CoFe either in the Ag or Cu matrices and the diffusivity of Ag and Cu. Moreover, the metallic matrix settles the degree of CoFe segregation, sample crystallisation and texture, which are responsible for the magnetotransport properties.     

Giant magnetoresistance in Cu–Co films electrodeposited on n-Si

High quality Cu–Co alloy films with excellent metallic luster have been electrolytically deposited directly onto n-Si (1 0 0) substrate, thereby eliminating the need of a conducting seed layer, which is otherwise required when the films were grown on insulating substrates (Al₂O₃). The as-deposited Cu–Co films exhibit relatively higher magnetoresistance (MR) in comparison with the as-deposited films on Al₂O₃ under identical conditions. The observed increase in MR could be attributed to the reduced substrate current shunting. The MR further improves to 2.67% (at H=10 kOe) with vacuum annealing (at 425°C for 30 min) of the films on Si. This has been ascribed to the separation of Cu and Co phases resulting in a magnetic granular nanostructure. This value of MR of annealed films on Si is, however, lower in comparison with the value obtained for annealed films deposited on Al₂O₃. Glancing angle X-ray diffraction (GAXRD) has revealed the formation of copper silicide in these samples, which is responsible for the lower value of MR. Thus we have observed good MR with a copper silicide host matrix.     

Antiferromagnet IrMn thickness dependence in exchange-biased perpendicular magnetic anisotropy based on CoFe/Pt/CoFe/[IrMn(tIrMn)] multilayers

The effect of the antiferromagnetic IrMn thickness upon the magnetic properties of CoFe/Pt/CoFe/[IrMn(t_IrMn)] multilayers is studied. An oscillatory interlayer coupling (IEC) has been shown in pinned CoFe/Pt(t_Pt)/CoFe/IrMn multilayers with perpendicular anisotropy. The period of oscillation corresponds to about 2 monolayers of Pt. The oscillatory behavior of IEC depends on the nonmagnetic metallic Pt thickness and is thought to be related to the antiferromagnetic ordering induced by the IrMn layer. From the extraordinary Hall voltage amplitude (EHA) curves as function of IrMn thickness, we report that the oscillation dependence of IEC for the [CoFe/Pt/CoFe] multilayer system induced by IrMn with spacer-layer thickness is a important features of perpendicular exchange biased system.     

Evidence for replacing zinc with cobalt and iron atoms in epitaxial ZnO:CoFe-diluted magnetic semiconductors

The structure and local environment of ZnO:CoFe were investigated. An epitaxial structure of ZnO thin film doped with CoFe on Al₂O₃ substrate was confirmed by XRD. By fitting the Zn EXAFS spectra, the bond distances and coordination numbers of Zn atoms in the ZnO:CoFe show that Co and Fe ions replace some positions of zinc atoms. The XANES study of Zn and O also show that CoFe cluster formation in this system can be excluded.     

Glassy carbon - A promising substrate material for pulsed laser deposition of thin Li1+xMn2O4−δ electrodes

The spinel LiMn₂O₄ is a promising candidate for future battery applications. If used as a positive electrode in a battery, the charging capacity of such a battery element is limited by the formation of a solid electrolyte interphase like layer between the electrolyte and the spinel. To study the electrolyte-electrode interaction during electrochemical cycling, spinel thin films are deposited as model electrodes on glassy carbon substrates by pulsed laser ablation. The obtained polycrystalline oxide thin films show a well defined surface morphology and are electrochemical active. Adhesion of these thin films on glassy carbon is in general poor, but can be improved considerably by a surface pretreatment or adding a thin metallic coating to the substrate prior deposition. The best adhesion is obtained for films deposited on argon plasma pretreated as well as Pt coated glassy carbon substrates. During the electrochemical characterization of Li_1.06Mn₂O_3.8 thin film electrodes, no additional reactions of the substrate are observed independent of the used electrolyte. The best cycle stability is achieved for films on Pt coated glassy carbon substrates.     

Magnetic and structural study of Cu-doped TiO2 thin films

Transparent pure and Cu-doped (2.5, 5 and 10 at.%) anatase TiO₂ thin films were grown by pulsed laser deposition technique on LaAlO₃ substrates. The samples were structurally characterized by X-ray absorption spectroscopy and X-ray diffraction. The magnetic properties were measured using a SQUID. All films have a FM-like behaviour. In the case of the Cu-doped samples, the magnetic cycles are almost independent of the Cu concentration. Cu atoms are forming CuO and/or substituting Ti in TiO₂. The thermal treatment in air promotes the CuO segregation. Since CuO is antiferromagnetic, the magnetic signals present in the films could be assigned to Cu substitutionally replacing cations in TiO₂.     

An in situ iron-57 Mössbauer spectroscopic investigation of the reduction of ironcerium oxide catalysts in different gaseous reducing agents

The formation of iron-cerium oxide catalysts by the treatment in hydrogen or carbon monoxide of air-dried precipitates has been monitored in situ by⁵⁷Fe Mössbauer spectroscopy. The results show that the initial calcination of the precipitates in air induces phase segregation and the formation of small concentrations of large particle α-iron(III) oxide in combination with cerium dioxide. Treatment of the solid in hydrogen at 450°C results in the facile reduction of α-Fe₂O₃ to metallic iron which is unaffected by exposure to a reactant gaseous mixture of carbon monoxide and hydrogen. Exposure of the biphasic material formed in air to carbon monoxide at similar temperatures induces the reduction of α-Fe₂O₃ to Fe₃O₄ and metallic iron and the subsequent formation of iron carbide. The carbided catalyst is not changed by exposure to a mixture of carbon monoxide and hydrogen. In distinct contrast the cerium orthoferrite of composition CeFeO₃ suffers only slight reduction when treated in hydrogen and shows a very limited amenability to carbide formation when treated in carbon monoxide.     

Synthesis and characterization of nanostructured bimetallic films on α-Al2O3 substrates using electroless deposition

The Pt-Pd and Pd-Ag nanostructured bimetallic films on porous α-Al₂O₃ substrates are successfully synthesized by chemical deposition using lyotropic liquid crystalline templating strategy. The co-reduction of two metallic species in the presence of liquid crystalline phase by hydrazine hydrate produces hexagonal nanostructured Pt-Pd and lamellar nanostructured Pd-Ag films. Low-angle X-ray diffraction (XRD) and transmission electron microscopy (TEM) studies show the ordered nanostructure of both Pt-Pd and Pd-Ag films. The energy dispersive X-ray (EDX) and wide-angle XRD analyses of the bimetallic films have verified the coexistence and uniform distribution of constituent metallic species. By taking into account of catalytic activities, well-defined nanochannels and higher surface areas, the nanostructured bimetallic films might have application potential in microreactors.     

Fabrication of high performance Gd–Ba–Cu–O single grains in air using a practical melt processing technique

A practical processing route for the fabrication of LRE-Ba–Cu–O single grain superconductors has been developed at the University of Cambridge based on a generic, Mg-doped Nd-123 melt textured seed and suppression of the formation of the solid solution phase in air by enriching the precursors with higher Ba concentration. The processing of high performance Gd–Ba–Cu–O single grains using this processing route is described. The Mg-doped generic seed crystal has been used effectively to promote heterogeneous nucleation via a cold-seeding process. The Gd/Ba solid solution has been suppressed by enriching Gd–Ba–Cu–O precursor powders with two different Ba-rich compositions. This involved adding BaO₂ and GdBa₆Cu₃O_y (Gd-163) (a novel Ba-rich second phase) to the precursor powders, respectively. The Gd-163 phase has been observed not only to suppress formation of the solid solution phase, but also to promote increased heterogeneous grain size. A detailed further study has been carried out with an initial aim of optimizing the BaO₂ and Gd-163 phase content of the precursor composition to produce a single grain almost free of solid solution. Based on the optimized parameters, large single grain Gd–Ba–Cu–O superconductors have been fabricated in an air atmosphere and demonstrated to exhibit record trapped magnetic fields for this material melt processed in air in relatively small single grain samples. The trapped fields of samples produced in air atmosphere are at least comparable to those processed under reduced oxygen partial pressure.     

Magnetic field-induced cluster formation and variation of magneto-optical signals in zinc-substituted ferrofluids

Fine magnetic particles (size≅100 Å) belonging to the series Zn_xFe_1−xFe₂O₄ were synthesized by cold co-precipitation methods and their structural properties were evaluated using X-ray diffraction. Magnetization studies have been carried out using vibrating sample magnetometry (VSM) showing near-zero loss loop characteristics. Ferrofluids were then prepared employing these fine magnetic powders using oleic acid as surfactant and kerosene as carrier liquid by modifying the usually reported synthesis technique in order to induce anisotropy and enhance the magneto-optical signals. Liquid thin films of these fluids were prepared and field-induced laser transmission through these films was studied. The transmitted light intensity decreases at the centre with applied magnetic field in a linear fashion when subjected to low magnetic fields and saturate at higher fields. This is in accordance with the saturation in cluster formation. The pattern exhibited by these films in the presence of different magnetic fields was observed with the help of a CCD camera and was recorded photographically.     

Effects of controlling Cu spacer inter-diffusion by diffusion barriers on the magnetic and electrical stability of GMR spin-valve devices

An ultra-thin Co or CoFe diffusion barrier inserted at the NiFe/Cu interfaces was revealed to effectively control the electrical and magnetic stability of NiFe/Cu/NiFe-based giant magnetoresistance (GMR) spin-valve spintronics devices (SVSDs) operating at high current density. It was found that the activation energy, E_a, related to the electromigration (EM)-induced inter-diffusion process for the patterned NiFe(3)/Cu(2)/NiFe(3 nm) magnetic multi-layered devices (MMLD) was remarkably increased from 0.52±0.2 eV to 1.17±0.16 eV after the insertion of an ultra-thin Co diffusion barrier at the NiFe/Cu interfaces. The dramatically reduced “current shunting paths” from the Cu spacer to the NiFe thin films and the development of “self-healing process” resulted from the effectively restrained Cu inter-diffusion (intermixing with Ni atoms) due to the diffusion barriers were found to be primarily responsible for the improvement of electrical and magnetic stability. The further investigation on the effects of controlling Cu spacer inter-diffusion by diffusion barriers on the EM and thermomigration (TM)-induced magnetic degradation was carried out for the NiFe/(Co or Co₉₀Fe₁₀)/Cu/(Co or Co₉₀Fe₁₀)/NiFe/FeMn top exchange-biased GMR (EBGMR) SVSDs electrically stressed under the applied DC current density of J=2.5×10⁷ A/cm² (I=16.5∼17.25 mA). It was clearly confirmed that the Co and the CoFe diffusion barriers effectively control the Cu spacer inter-diffusion resulting in a smaller reduction in both GMR ratio and exchange bias field of the EBGMR SVSDs. Furthermore, it was obviously observed that the effects of CoFe diffusion barrier on controlling the Cu spacer inter-diffusion are more significant than that of Co. The effectively reduced Mn atomic inter-diffusion at the NiFe/FeMn interface and the well-maintained interfacial spin-dependent scattering resulted from the control of EM and TM-induced Cu spacer inter-diffusion were the main physical reasons for the significant improvement of magnetic and electrical degradation of top EBGMR SVSDs.     

Synthetic Co50Pt50/Ru/CoFe hard–soft trilayer in spin valves

The influence of deposition power and seedlayer on the properties of hard magnet Co₅₀Pt₅₀ was studied. Co₅₀Pt₅₀(/Co₉₀Fe₁₀)/Ru/Co₉₀Fe₁₀ trilayer was used as pining/pinned layer in spin valves. The influences of different hard layer, soft layer and free layer on exchange bias, interlayer coupling, and magnetoresistance (MR) ratio were studied. Weak antiferromagnetic interlayer coupling was obtained by adjusting the thickness of hard and soft layers. MR of a spin valve with structure Cr2/CoFe0.5/CoPt4/CoFe0.5/Ru0.8/CoFe2.2/Cu2.05/CoFe2.6/Cu1.1/Ta1 reached 10.68% (unit in nm), which is comparable to those of IrMn-based synthetic spin valves. The increment of the coercivity of the free layer is mainly due to the static magnetic interaction between the hard layer and the free layer.     

Formation of V2O3 nanocrystals by thermal reduction of V2O5 thin films

We report the formation of homogeneous and stable V₂O₃ nanocrystals, directly from V₂O₅ thin films, at 600 °C, as observed by using in situ electron microscopy experiments. Thermally-induced reduction of V₂O₅ thin films in vacuum is remarkably different when compared to reduction of V₂O₅ single crystals and results in the formation of nanophase V₂O₃. Thermally grown V₂O₃ nanocrystals exhibit hexagon or square shape and are stable at higher temperature as well as room temperature. The formation of stable nanocrystals through the reduction process in a non-chemical environment (vacuum) could provide a basis for understanding the complex processes of vanadium oxide phase transitions and for controlling the chemical processes to produce oxide nanocrystals.     

Dewetting processes in a cylindrical geometry

Dewetting of liquid films of water-glycerol solutions of different viscosities has been studied experimentally in PVC cylindrical tubes. In contrast with plane surfaces, the dewetting capillary number Ca_vd increases with the film thickness h₀ over a large part of the experimental range and follows a same global trend independent of viscosity as a function of h₀. This increase is only partly explained by variations of the capillary driving force predicted in a recent theoretical work for a cylindrical geometry. An additional explanation is suggested, based on different spatial distributions of the viscous dissipation in the dewetting bump in the planar and cylindrical geometries. This mechanism is investigated for films of different thicknesses in a numerical model assuming a polynomial variation of the liquid thickness with distance in the bump region.     

Isotope effect for transport and magnetic properties of La 0.35 Pr 0.35 Ca 0.3 MnO 3 thin films

The effect of ¹⁶ O → ¹⁸ O isotope substitution on electrical resistivity, magnetoresistance, and ac magnetic susceptibility was studied for La_0.35Pr_0.35Ca_0.3MnO₃ epitaxial thin films deposited onto LaAlO₃ and SrTiO₃ substrates. For the films on LaAlO₃, the isotope substitution resulted in the reversible transition from a metal-like to insulating state. The applied magnetic field ( H ≥ 2 T) transformed the sample with ¹⁸O back to the metallic state. The films on SrTiO₃ remained metallic at low temperatures for both ¹⁶O and ¹⁸O, but the shift of the resistivity peak corresponding to onset of metallic state exceeded 63 K after ¹⁶ O → ¹⁸ O substitution. The temperature dependence of both resistivity and magnetic susceptibility was characterized by hysteresis, especially pronounced in the case of the films on LaAlO₃. Such a behavior gives certain indications of the phase separation characteristic of interplay between ferromagnetism and charge ordering. Received 11 February 2000 and Received in final form 13 September 2000     

Manipulating Bonding at a Cu/(0001)Al2O3 Interface by Different Substrate Cleaning Processes

Growth of Cu films on (0001)Al₂O₃ substrates can result in metallic Cu—Al or ionic-covalent Cu—O bonds at atomically abrupt interfaces. The type of bonding depends on the substrate cleaning procedure prior to film growth. Cu films deposited on Ar⁺-ion sputter-cleaned substrates exhibit interfacial Cu-L_2,3, Al-L_2,3 and O-K energy-loss near-edge structures that indicate the formation of metallic Cu—Al bonds at the Cu/Al₂O₃ interface. In contrast, growth on chemically cleaned -Al₂O₃ substrates results in interfacial energy-loss near-edge structures that suggest Cu—O bonding at the interface. The experimental electron energy-loss spectroscopic results are compared to calculated spectra, and the mechanisms causing the changes in the atomic and electronic structure are addressed.     

Ultraviolet-induced erasable photochromism in bilayer metal oxide films

We demonstrate that the optical transmittance of bilayer samples consisting of pyrolytically coated amorphous Mg-Sn-O and metal oxide films such as In₂O₃ and SnO₂ decreases upon ultraviolet illumination, but can be recovered by annealing in air at ∼300 ^°C. Spectral, structural, and compositional studies suggest that this photochromic phenomenon is induced by photoelectronic excitation in the Mg-Sn-O film, electron injection into the metal oxide, which becomes negatively charged, and subsequent formation of metallic particles, which absorb and/or scatter visible light.     

First nucleation steps of vanadium oxide thin films studied by XPS inelastic peak shape analysis

The initial states of deposition of vanadium oxide thin films have been studied by analysis of the peak shape (both inelastic background and elastic contributions) of X-ray photoemission spectra (XPS) after successive deposition experiments. This study has permitted to assess the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of a XPS spectrometer. Thin films of vanadium oxide have been prepared on Al₂O₃ and TiO₂ by means of thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition. The thin films prepared by the first two procedures consisted of V₂O₄, while those prepared by the latter had a V₂O₅ stoichiometry. The analysis of the inelastic background of the photoemission spectra has shown that the films prepared by thermal evaporation on Al₂O₃ are formed by big particles that only cover completely the surface of the substrate when their height reaches 16 nm. By contrast, the thin films prepared with assistance of ions on Al₂O₃ or with plasma on TiO₂ consist of smaller particles that succeed in covering the substrate surface already for a height of approximately 4 nm. Thin films prepared by plasma-assisted deposition on Al₂O₃ depict an intermediate situation where the substrate is completely covered when the particles have a height of approximately 6 nm. The type of substrates, differences in the deposition procedure or the activation of the adatoms by ion bombardment are some of the factors that are accounted for by to explain the different observed behaviours.