Influence of epitaxial growth on phase competition in Pr0.5Sr0.5MnO3 films

A series of Pr_0.5Sr_0.5MnO₃ (PSMO) films with various thickness were epitaxially grown on substrates of (0 0 1)-oriented (LaAlO₃)_0.3(SrAl_0.5Ta_0.5O₃)_0.7 (LSAT), LaAlO₃ (LAO) and SrTiO₃ (STO), and (0 1 1)-oriented STO using pulse laser deposition. Influence of epitaxial growth on phase competition was investigated. A ferromagnetic metal to antiferromagnetic insulator (FMM-AFI) transition upon cooling is present in both largely compressed situations deposited on LAO (0 0 1) and tensile cases deposited on STO (0 0 1) but absent in little strained films grown on LSAT (0 0 1), indicating that the antiferromagnetic insulating state is favored by strains. On the other hand, the 400 nm films deposited on (0 1 1)-oriented STO as well as LAO substrates show FMM-AFI transition. These results reveal that both the orientation of epitaxial growth and substrate-induced strain affect the FMM-AFI transition.     

Exchange bias in (1 1 0)-orientated Bi0.9La0.1FeO3/La0.5Ca0.5MnO3 films

We performed a systematic study on the exchange bias in (1 1 0)-orientated Bi_0.9La_0.1FeO₃/La_0.5Ca_0.5MnO₃ (BLFO/LCMO) heterostructure with a fixed BLFO film thickness of 600 nm and different LCMO layers ranging from t=0 to 30 nm. The LCMO is found to be weakly ferromagnetic, with the Curie temperature descending from ∼225 K to 0 as the layer thickness decreases from 30 nm to 3 nm. The main magnetic contributions come from the BLFO film, and the areal magnetization ratio is 1:0.07 for t=5 nm and 1:0.82 for t=30 nm for BLFO to LCMO at the temperature of 5 K. Further experiments show the presence of significant exchange bias, and it is, at the temperature of 10 K, ∼40 Oe for t=0 and ∼260 Oe for t=30 nm. The exchange bias reduces dramatically upon warming and disappears above the blocking temperature of the spin-glasslike behavior observed in the samples. The possible origin for exchange bias is discussed.     

Half Ca-doped LaMnO3 films on (0 0 1) SLAO and STO substrate studied by magnetization and transport measurements

In this study, La_0.5Ca_0.5MnO₃ (LCMO) films, at the boundary between ferromagnetic metallic and charge-ordered antiferromagnetic insulator according to the bulk phase diagram, were epitaxially grown on (0 0 1) SrTiO₃ (STO) and SrLaAlO₄ (SLAO) substrates by pulsed laser deposition technique. The films were analyzed by X-ray diffraction, magnetization and magnetoresistance measurements. A considerably higher magnetization was measured for 290-nm-thick film on SLAO substrate compared to the film on STO substrate, although both films have the same chemical composition, thickness and epitaxial orientation. The film on SLAO shows a metal-insulator (MI) transition, which occurs at higher temperatures with increasing applied magnetic field, whereas only insulating behavior was observed for the 290-nm-thick film on STO except for the highest applied magnetic field (7 T). In addition, transport measurements were performed and analyzed by Mott's variable range hopping (VRH) model to correlate the resistivity of the films with the Jahn-Teller strain (ε_J−T) in the structure.     

Role of crystal orientation on the magnetic properties of CoFe2O4 thin films grown on Si (1 0 0) and Al2O3 (0 0 0 1) substrates using pulsed laser deposition

We report the influence of crystal orientation on the magnetic properties of CoFe₂O₄ (CFO) thin films grown on single crystal Si (1 0 0) and c-cut sapphire (Al₂O₃) (0 0 0 1) substrates using pulsed laser deposition technique. The thickness was varied from 200 to 50 nm for CFO films grown on Si substrates, while it was fixed at 200 nm for CFO films grown on Al₂O₃ substrates. We observed that the 200 and 100 nm thick CFO-Si films grew in both (1 1 1) and (3 1 1) directions and displayed out-of-plane anisotropy, whereas the 50 nm thick CFO-Si film showed only an (1 1 1) orientation and an in-plane anisotropy. The 200 nm thick CFO film grown on an Al₂O₃ substrate was also found to show a complete (1 1 1) orientation and a strong in-plane anisotropy. These observations pointed to a definite relation between the crystalline orientation and the observed magnetic anisotropy in the CFO thin films.     

Structure and electronic properties calculation of ultrathin α-Al2O3 films on (0 0 0 1) α-Cr2O3 templates

Ab initio total energy Hartree-Fock calculations of ultrathin films of α-Al₂O₃ on (0 0 0 1) α-Cr₂O₃ templates are presented. The surface relaxation, the in-plane reconstruction and the surface and strain energies of the slabs are studied as a function of alumina film thickness. The surface Al layer is found to relax inwards considerably, with the magnitude of the inwards relaxation depending on the thickness of the ultrathin alumina film in a non-linear manner. The calculations also reveal that ultrathin films of alumina lower the surface energy of (0 0 0 1) α-chromia substrates. This indicates that the (0 0 0 1) α-chromia surface provides favourable conditions for the templated growth of α-alumina. However, increasing the alumina film thickness is found to give rise to a significant increase in strain energy. Finally, the electronic properties at the surface of the (0 0 0 1) α-Al₂O₃/α-Cr₂O₃ slabs are investigated. Here it is found that the alumina coating gives rise to an increase in the covalency of the bonds at the surface of the slabs. In contrast, the influence of an alumina layer on the electrostatic potential at the surface of the chromia slab is relatively minor, which should also be beneficial for the templated growth of α-alumina on (0 0 0 1) α-chromia substrates.     

Growth of superconducting FeSe0.5Te0.5 thin films by pulsed-laser deposition

FeSe_0.5Te_0.5 thin films with PbO-type structure are successfully grown on MgO(1 0 0) and LaSrAlO₄(0 0 1) substrates from FeSe_0.5Te_0.5 or FeSe_0.5Te_0.75 polycrystalline targets by pulsed-laser deposition. The film deposited on the MgO substrate (film thickness ∼ 55 nm) shows superconductivity at 10.6 K (onset) and 9.2 K (zero resistivity). On the other hand, the film deposited on the LaSrAlO₄ substrate (film thickness ∼ 250 nm) exhibits superconductivity at 5.4 K (onset) and 2.7 K (zero resistivity). This suggests the strong influence of substrate materials and/or the c-axis length to superconducting properties of FeSe_0.5Te_0.5 thin films.     

Growth temperature dependence of the hysteretic behavior of Ni0.5Zn0.5Fe2O4 thin films

Herein, a discussion of the effect of deposition temperature on the magnetic behavior of Ni_0.5Zn_0.5Fe₂O₄ thin films. The thin films were grown by r.f. sputtering technique on (1 0 0) MgO single-crystal substrates at deposition temperatures ranging between 400 and 800 °C. The grain boundary microstructure was analyzed via atomic force microscopy (AFM). AFM images show that grain size (φ∼70-112 nm) increases with increasing deposition temperature, according to a diffusion growth model. From magneto-optical Kerr effect (MOKE) measurements at room temperature, coercive fields, H_c, between 37and 131 Oe were measured. The coercive field, H_c, as a function of grain size, reaches a maximum value of 131 Oe for φ ∼93 nm, while the relative saturation magnetization exhibits a minimum value at this grain size. The behaviors observed were interpreted as the existence of a critical size for the transition from single- to multi-domain regime. The saturation magnetization (21 emu/g<M_s<60 emu/g) was employed to quantify the critical magnetic intergranular correlation length (L_c≈166 nm), where a single-grain to coupled-grain behavior transition occurs. Experimental hysteresis loops were fitted by the Jiles-Atherton model (JAM). The value of the k-parameter of the JAM fitted by means of this model (k/μ_o∼50 A m²) was correlated to the domain size from the behavior of k, we observed a maximum in the density of defects for the sample with φ∼93 nm.     

Dynamic phase separation as revealed by the strong resistance relaxation in epitaxially shear-strained La0.67Ca0.33MnO3/NdGaO3(0 0 1) thin-films

Strong phase competitions between the ferromagnetic metal and the charge-ordered-insulator have been induced in a wide temperature range of 10-256 K for the shear-strained La_0.67Ca_0.33MnO₃/NdGaO₃(0 0 1) films. Based on various magnetotransport measurements, the mobility of phase boundaries was inferred to change dramatically with temperature. In the high temperature range where the phase boundaries are movable, strong relaxation in resistivity was observed, while at the frozen temperatures lower than 40 K it is weakened. The resistivities tend to relax in accordance with the phase transitions driven by the temperature or magnetic field in the phase separation (PS) background. Moreover, to our surprise, while the melting fields of the insulating phase varied with film thicknesses, for a given film however, they stay unchanged when started with different phase fractions produced by the field or thermal cycling. The results show a crucial role of the inherent strain state in determining PS and phase competitions in these epitaxial thin films.     

Lead-free ferroelectric BaTiO3 doped-(Na0.5Bi0.5)TiO3 thin films processed by pulsed laser deposition technique

The difficulties in synthesizing phase pure BaTiO₃ doped-(Na_0.5Bi_0.5)TiO₃ are known. In this work, we reporting the optimized pulsed laser deposition (PLD) conditions for obtaining pure phase 0.92(Na_0.5Bi_0.5)TiO₃-0.08BaTiO₃, (BNT-BT_0.08), thin films. Dielectric, ferroelectric and piezoelectric properties of BNT-BT_0.08, thin films deposited by PLD on Pt/TiO₂/SiO₂/Si substrates are investigated in this paper. Perovskite structure of BNT-BT_0.08 thin films with random orientation of nanocrystallites has been obtained by deposition at 600 °C. The relative dielectric constant and loss tangent at 100 kHz, of BNT-BT_0.08 thin film with 530 nm thickness, were 820 and 0.13, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 22 μC/cm² and a coercive field of 120 kV/cm. The piezoresponse force microscopy (PFM) data showed that most of the grains seem to be constituted of single ferroelectric domain. The as-deposited BNT-BT_0.08 thin film is ferroelectric at the nanoscale level and piezoelectric.     

Structure, dielectric and ferroelectric properties of highly (1 0 0)-oriented BaTiO3 grown under low-temperature conditions

The highly (1 0 0)-oriented BaTiO₃ thin films were fabricated on LaNiO₃(1 0 0)/Pt/Ti/SiO₂/Si substrates under low-temperature conditions. Substrate temperatures throughout the fabrication process remained at or below 400 °C, which allows this process to be compatible with many materials commonly used in integrated circuit manufacturing. X-ray diffraction data provided the evidence for single BaTiO₃ phase. Field-emission scanning electron microscopy was used to study the columnar structure of the films. The dielectric properties as a function of frequency in the range of 1 kHz to 1 MHz was obtained. The room temperature remanent polarization (2P_r) and coercive field were found to be ∼5 μC/cm² and 50 kV/cm, respectively. The BTO film maintains an excellent fatigue-free character even after 10⁹ switching cycles.     

Depth-dependent fct to fcc strain relaxation in CoxNi1−x/Cu3Au(1 0 0) alloy films

Co_xNi_1−x/Cu₃Au(1 0 0) with x ? 11% was prepared at room temperature to study the strain relaxation and their correlation with the spin-reorientation transition. The vertical interlayer distance relaxed from 1.66 Å (fct) to 1.76 Å (fcc) while the thickness increased from 8 ML to 18 ML. Such rapid strain relaxation with thickness was attributed to the larger lattice mismatch between Co_xNi_1−x and Cu₃Au(1 0 0) (η ∼ −6.5%). The smooth change for crystalline structure was observed during strain relaxation process in which the crystalline structure seems irrespective of the alloy composition. To explain the strain relaxation, a phenomenological model was proposed. We provide a physical picture that the deeper layers may not relax while the surface layer start to relax. This assumption is based on the several experimental studies. Using the strain averaged from all layers of thin film as the volume strain of magneto-elastic anisotropy energy, the interrelation between strain relaxation and spin reorientation transition can be well described in a Néel type magneto-elastic model.     

Out-of-plane low field anisotropic magnetoresistance in Nd0.51Sr0.49MnO3 thin films

A comparative study of the out-of-plane anisotropic magnetoresistance (AMR) in single crystalline and polycrystalline thin films of phase separated manganite Nd_0.51Sr_0.49MnO₃ has been carried out. On-axis DC magnetron sputtering was used to deposit the single crystalline films (30 and 100 nm in thickness) on single crystal (0 0 1) LaAlO₃ (LAO) and polycrystalline films (100 nm) on (1 0 0) Yttrium-stabilized ZrO₂ (YSZ) substrates. The in-plane and out-of-plane magnetotransport properties of these films differ significantly. A large low field AMR is observed in all the films. AMR shows a peak below the insulator-metal transition temperature in the single crystalline films, while the same increases monotonically in the polycrystalline film. Relatively larger low field AMR (∼20% at T=78 K and H=1.7 kOe) in the polycrystalline films suggests the dominance of the shape anisotropy.     

Solid phase epitaxy of Ge films on CaF2/Si(1 1 1)

At room temperature deposited Ge films (thickness < 3 nm) homogeneously wet CaF₂/Si(1 1 1). The films are crystalline but exhibit granular structure. The grain size decreases with increasing film thickness. The quality of the homogeneous films is improved by annealing up to 200 °C. Ge films break up into islands if higher annealing temperatures are used as demonstrated combining spot profile analysis low energy electron diffraction (SPA-LEED) with auger electron spectroscopy (AES). Annealing up to 600 °C reduces the lateral size of the Ge islands while the surface fraction covered by Ge islands is constant. The CaF₂ film is decomposed if higher annealing temperatures are used. This effect is probably due to the formation of GeF_x complexes which desorb at these temperatures.     

Magnetoresistance of magnetite thin films grown by pulsed laser deposition on GaAs(1 0 0) and Al2O3(0 0 0 1)

Magnetotransport properties of magnetite thin films deposited on gallium arsenide and sapphire substrates at growth temperatures between 473 and 673 K are presented. The films were grown by UV pulsed laser ablation in reactive atmospheres of O₂ and Ar, at working pressure of 8 × 10⁻² Pa. Film stoichiometry was determined in the range from Fe_2.95O₄ to Fe_2.97O₄. Randomly oriented polycrystalline thin films were grown on GaAs(1 0 0) while for the Al₂O₃(0 0 0 1) substrates the films developed a (1 1 1) preferred orientation. Interfacial Fe³⁺ diffusion was found for both substrates affecting the magnetic behaviour. The temperature dependence of the resistance and magnetoresistance of the films were measured for fields up to 6 T. Negative magnetoresistance values of ∼5% at room temperature and ∼10% at 90 K were obtained for the as-deposited magnetite films either on GaAs(1 0 0) or Al₂O₃(0 0 0 1).     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

Effect of crystallinity of Co layer on perpendicular exchange bias in Au-capped ultrathin Co film on Cr2O3(0 0 0 1) thin film

The effect of the crystalline quality of ultrathin Co films on perpendicular exchange bias (PEB) has been investigated using a Au/Co/Au/α-Cr₂O₃ thin film grown on a Ag-buffered Si(1 1 1) substrate. Our investigation is based on the effect of the Au spacer layer on the crystalline quality of the Co layer and the resultant changes in PEB. An α-Cr₂O₃(0 0 0 1)layer is fabricated by the thermal oxidization of a Cr(1 1 0) thin film. The structural properties of the α-Cr₂O₃(0 0 0 1) layer including the cross-sectional structure, lattice parameters, and valence state have been investigated. The fabricated α-Cr₂O₃(0 0 0 1) layer contains twin domains and has slightly smaller lattice parametersthan those of bulk-Cr₂O₃. The valence state of the Cr₂O₃(0 0 0 1) layer is similar to that of bulk Cr₂O₃. The ultrathin Co film directly grown on the α-Cr₂O₃(0 0 0 1) deposited by an e-beam evaporator is polycrystalline. The insertion of a Au spacer layer with a thickness below 0.5 nm improves the crystalline quality of Co, probably resulting in hcp-Co(0 0 0 1). Perpendicular magnetic anisotropy (PMA) appears below the Néel temperature of Cr₂O₃ for all the investigated films. Although the PMA appears independently of the crystallinequality of Co, PEB is affected by the crystalline quality of Co. For the polycrystalline Co film, PEB is low, however, a high PEB is observed for the Co films whose in-plane atom arrangement is identical to that of Cr³⁺ in Cr₂O₃(0 0 0 1). The results are qualitatively discussed on the basis of the direct exchange coupling between Cr and Co at the interface as the dominant coupling mechanism.     

Structure, magnetic and electrical transport properties of cosputtered Fe0.5Ge0.5 nanocomposite films

Fe_0.5Ge_0.5 nanocomposite films with different film thicknesses were fabricated using cosputtering. The films are composed of Ge, Fe and Fe₃Ge₂, and are ferromagnetic at room temperature. The saturation magnetization and magnetic interaction including dipolar interaction and exchange coupling increase with the increasing film thickness. The electrical conductance mechanism turns from metallic to semiconducting and the saturation Hall resistivity ρ_xys increases with the decreasing film thickness. At 28 nm, ρ_xys is ∼137 μΩ cm at 2 K, about 150 times larger than that of pure Fe film (0.9 μΩ cm) and four orders larger than that of bulk Fe. The ρ_xy-H curves of all the films show the same linearity character in low-field range even though the temperature-independent slope is different at different film thicknesses. At high temperatures, the skew scattering mechanism is dominant. At low temperatures, side-jump effect should be dominant at large resistivity ρ_xx regime for the thin films, and the skew scattering is dominant at small ρ_xx regime for the thick films.     

Molecular dynamics simulation of the (0 0 0 1) α-Al2O3 and α-Cr2O3 surfaces

A simple, rigid pair-potential model is applied to investigate the dynamics of the (0 0 0 1) α-Al₂O₃ and α-Cr₂O₃ surfaces using the molecular dynamics technique. The simulations employ a two-stage equilibration process: in the first stage the simulation-cell size is determined via the constant-stress ensemble, and in the second stage the equilibration of the size-corrected simulation cell is continued in the canonical ensemble. The thermal expansion coefficients of bulk alumina and chromia are evaluated as a function of temperature. Furthermore, the surface relaxation and mean-square displacement of the atoms versus depth into the slab are calculated, and their behaviour in the surface region analysed in detail. The calculations show that even moderate temperatures (∼400 °C) give rise to displacements of the atoms at the surface which are similar to the lattice mismatch between α-alumina and chromia. This will help in the initial nucleation stage during thin film growth, and thus facilitate the deposition of α-Al₂O₃ on (0 0 0 1) α-Cr₂O₃ templates.     

Magnetotransport properties of epitaxial Pr0.5Ca0.5MnO3 films grown by a solution technique

Epitaxial Pr_0.5Ca_0.5MnO₃ films have been synthesized on (0 0 1) SrTiO₃ substrate using a chemical solution deposition technique and two-step post-annealing process. The zero field resistivity of the films shows semiconducting behavior and a characteristic of charge ordering is observed at 230 K. The resistivity of the 10 nm film did not show any effect with the magnetic field. However, melting of charge ordering was observed for the 120 nm film at an applied magnetic field of 4 T. Large decrease in the resistivity of the 120 nm film (<100 K) resulted in magnetoresistance of nearly −100% at 75 K.     

Initial oxidation kinetics and energetics of Cu0.5Au0.5 (0 0 1) film investigated by in situ ultrahigh vacuum transmission electron microscopy

The initial oxidation behavior of Cu_0.5Au_0.5 (0 0 1) thin film was investigated by in situ ultrahigh vacuum transmission electron microscopy to model nano-oxidation of alloys with one active component and one noble component. The formation of irregular-shaped octahedron Cu₂O islands with cube-on-cube crystallographic orientation to the substrate film was observed at all temperature studied. The energetics of Cu₂O nucleation for Cu and Cu_0.5Au_0.5 oxidation was compared. Cu_0.5Au_0.5 oxidation has lower nucleation activation energy due to the reduced mismatch strain between Cu₂O and Cu_0.5Au_0.5 films. On the other hand, the reaction kinetics for Cu_0.5Au_0.5 alloy oxidation is slower due to the higher diffusion activation energy of Cu.