Self-organized growth of pyramidal clusters in epitaxial spinel CoCr2O4 films on rock salt MgO(001) substrates

Ferrimagnetic CoCr₂O₄ epitaxial thin films have been grown on MgO(001) substrates. The surface morphology of the films shows self-organized nanometric pyramids and hut clusters. The origins of this morphology are found in the anisotropy of the surface energy of CoCr₂O₄ and the epitaxial growth. A comparison with the growth on spinel MgAl₂O₄(001) substrates is done. It turns out that pyramids on MgO are typically larger and with a higher surface coverage than on MgAl₂O₄. These results open the possibility of fabricating hybrid structures of ferrimagnetic self-organized nanometric high aspect ratio objects on substrates of selected functionality. Tailoring the size of the objects can be achieved not only by deposition temperature and film thickness but also by appropriate selection of substrates. PACS 81.07.Bc; 68.65.-k     

Raman study of ultrathin Fe3O4 films on GaAs(001) substrate: stoichiometry,epitaxial orientation and strain

The growth and characterization of high‐quality ultrathin Fe₃O₄ films on semiconductor substrates is a key step for spintronic devices. A stable, single‐crystalline ultrathin Fe₃O₄ film on GaAs(001) substrate is obtained by post‐growth annealing of epitaxial Fe film with thicknesses of 5 and 12 nm in air. Raman spectroscopy shows a high ability to convincingly characterize the stoichiometry, epitaxial orientation and strain of such ultrathin Fe₃O₄ films. Polarized Raman spectroscopy confirms the unit cell of Fe₃O₄ films is rotated by 45° to match that of the Fe (001) layer on GaAs, which results in a built‐in strain of − 3.5% in Fe₃O₄ films. The phonon strain‐shift coefficient(−126 cm⁻¹) of the A_1g mode is proposed to probe strain effect and strain relaxation of thin Fe₃O₄ films on substrates. It can be used to identify whether the Fe layer is fully oxidized to Fe₃O₄ or not. Copyright © 2011 John Wiley & Sons, Ltd.     

Structural properties of high-quality sputtered Fe films on Al2O3(1120) and MgO(001) substrates

High-quality thin Fe films were deposited on MgO(001) and Al₂O₃(1120) substrates in the thickness range from 7 to 50 nm. The structural properties have been studied by out-of-plane and in-plane X-ray scattering experiments. From the out-of-plane measurements the electron density profile was determined together with interface and surface roughness parameters. Fe on Al₂O₃ grows along the [110]-direction with a structural coherence length comprising about the total film thick ness and a very small mosaicity. From in-plane scattering experiments a three-domain structure was observed. On MgO(001) substrates Fe grows in the [001]-direction, with the Fe [100]-axis parallel to the MgO [110]-axis. On both substrates, the Fe films exhibit a very small surface and interface roughness, indicative for a high quality of the sputtered samples.     

Growth and characterization of (001)-oriented Pb(Zr0.52Ti0.48)O3/LaNiO3/LaAlO3 heterostructures prepared by pulsed laser deposition

Completely (001)-oriented ferroelectric Pb(Zr_0.52Ti_0.48)O₃/LaNiO₃ heterostructures on single-crystal LaAlO₃(001) substrates have been successfully grown by pulsed laser deposition. X-ray-diffraction analyses (–2 scan, scan and scan) indicate that good out-of-plane orientation and in-plane alignment have been obtained with the epitaxial relationship of PZT(001)//LNO(001)//LAO(001) and PZT001//LNO001//LAO001. Scanning electron and atomic force microscopic images reveal very smooth LNO surfaces with roughness of about 0.4–0.6 nm. Based on a microstructural study of the LNO and PZT films, a layer-by-layer growth mode for the LNO growth is proposed, while island growth is dominant for the PZT films. Secondary ion mass spectroscopy analyses show that no distinct interdiffusion can be found between the PZT and LNO layers. P–E hysteresis loop measurements of the PZT films with LNO as bottom electrodes and Au as top electrodes were carried out at an applied voltage of 5 V. The best remanent polarization P_r and coercive field E_c were found to be 28 C/cm² and 74.5 kV/cm, respectively. PACS 81.15.Fg; 68.55.Jk; 77.22.Ej; 77.84.Bw; 68.65.Ac     

Characterization of epitaxial MgO growth on Si(001) surface

MgO epitaxial growth on a Si(001) surface by ultrahigh-vacuum molecular beam epitaxy was investigated. Epitaxial orientation and crystalline quality were characterized based on the three-dimensional reciprocal map obtained by Weissenberg RHEED. The epitaxial orientation and crystallinity were strongly dependent on the initial condition of the substrate. When MgO was deposited on a clean Si(001) surface at room temperature a MgO(001) film grew on the Si(001) substrate with two in-plane orientations:MgO[110]//Si[100] and MgO[100]//Si[100]. This is the first observation of MgO epitaxy with the former orientation, which has a smaller mismatch than the latter orientation. When the substrate was exposed to O₂ or thermally oxidized, the latterorientation predominantly grew on the substrate. Deposition of Mg on the substrate also produced the latter orientation. These results imply that nucleation sites on the initial substrate play an important role in determining the epitaxial orientation.     

Magnetic behavior and role of the antiphase boundaries in Fe3O4 epitaxial films sputtered on MgO (001)

Magnetite Fe₃O₄ films were grown on single crystal MgO (001) substrates using facing target sputtering technique. Conversion Electron M?ssbauer Spectroscopy and magneto optical polar Kerr spectra have confirmed the stoichiometric repartition of Fe cations corresponding to the inverse spinel structure and the electronic structure characteristic of bulk Fe₃O₄. Hysteresis loops carried out at room temperature show that, in a 1 T applied magnetic field, only 60% of the saturation magnetization is detected. This behavior is discussed in correlation to the antiphase boundaries (APBs) observed by electron microscopy. Magnetic force microscopy studies show that magnetic domains are larger than the mean distance between APBs. Received 2 July 2001     

Development of magnetic anisotropies in ultrathin epitaxial films of Fe(001) and Ni(001)

Ultrathin films, bcc Fe(001) on Ag(001), fcc Fe(001) on Cu(001) and Fe/Ni(001) bilayers on Ag, were grown by molecular beam epitaxy. A wide range of surface science tools were employed to establish the quality of epitaxial growth. Ferromagnetic resonance and Brillouin light scattering were used to extract the magnetic properties. Emphasis was placed on the study of magnetic anisotropies. Large uniaxial anisotropies with easy axis perpendicular to the film surface were observed in all ultrathin structures studied. These anisotropies were particularly strong in fcc Fe and bcc Fe films. In sufficiently thin samples the saturation magnetization was oriented perpendicularly to the film surface in the absence of an applied field. It has been demonstrated that in bcc Fe films the uniaxial perpendicular anisotropy originates at the film interfaces. In situ measurements indentified the strength of the uniaxial perpendicular anisotropy constant at the Fe/vacuum, Fe/Ag and Fe/Au interfaces asK _us = 0.96, 0.63, and 0.3 ergs/cm² respectively. The surface anisotropies deduced for [bulk Fe/noble metal] interfaces are in good agreement with the values obtained from ultrathin films. Hence the perpendicular surface ansiotropies originate in the broken symmetry at abrupt interfaces. An observed decrease in the cubic anisotropy in bcc Fe ultrathin films has been explained by the presence of a weak 4th order in-plane surface anisotropy,K _1S=0.012 ergs/cm². Fe/Ni bilayers were also investigated. Ni grew in the pure bcc structure for the first 3–6 ML and then transformed to a new structure which exhibited unique magnetic properties. Transformed ultrathin bilayers possessed large inplane 4th order anisotropies far surpassing those observed in bulk Fe and Ni. The large 4th order anisotropies originate in crystallographic defects formed during the Ni lattice transformation.     

Lattice deformation in thin BiFeO3 and Ba0.8Sr0.2TiO3 epitaxial films on (001)MgO single crystalline substrates

Bi_0.98Nd_0.02FeO₃ (BNFO) and Ba_0.8Sr_0.2TiO₃ (BST) epitaxial films produced by rf cathode sputtering on (001)MgO substrates are studied by means of XRD. The thickness dependences of uniform lattice deformations and linear dislocation density, generated due to epitaxial stress relaxation, are plotted.     

Structural and magnetic properties of pulsed laser deposited SrRuO3/CoFe2O4/La2/3Sr1/3MnO3 magnetic oxide heterostructures on SrTiO3(001) and MgO(001)

We report on the growth of all-oxide SrRuO₃/CoFe₂O₄/La_2/3Sr_1/3MnO₃ and La_2/3Sr_1/3MnO₃/CoFe₂O₄/SrRuO₃ heterostuctures on SrTiO₃(001) and MgO(001) substrates by pulsed laser deposition. Structural analyses by X-ray diffraction and transmission electron microscopy clearly indicate the preservation of epitaxial relations when the La_2/3Sr_1/3MnO₃ layer is grown first, whereas trilayers with SrRuO₃ at the bottom are more disordered. Both the substrate material and the deposition sequence strongly influence the formation of various structural defects such as interfacial dislocations and sub-grain structures, and this is clearly reflected by a reduction of the saturation magnetization in the top electrode. When the substrate material and the deposition sequence are correctly chosen, however, the magnetic moments of the La_2/3Sr_1/3MnO₃ and SrRuO₃ layers reverse independently, and the La_2/3Sr_1/3MnO₃ layer retains bulk-like magnetic properties.     

Sum-frequency generation and temperature-programed desorption studies of formic acid on MgO(001) surfaces

Adsorption and decomposition of formic acid on MgO(001) surfaces were studied by means of Sum-Frequency Generation (SFG), Temperature-Programed Desorption (TPD) and Atomic Force Microscopy (AFM). Formic acid was dissociatively adsorbed on MgO(001) surfaces at room temperature. From SFG and TPD measurements, the existence of several different types of formate species was deduced and all species mainly decomposed into CO and H₂O on raising the temperature of the substrate.Paper presented at the 129th WE-Heraeus-Seminar on Surface Studies by Nonlinear Laser Spectroscopies, Kassel, Germany, May 30 to June 1, 1994     

Step-like growth of Bi2Sr2CaCu2O8 films on off axis oriented (001) SrTiO3

High-quality Bi₂Sr₂CaCu₂O₈ (BSCCO) films were grown by means of pulsed-laser deposition on 10° off-axis oriented (001) SrTiO₃ substrates. The films exhibit a step-like morphology and they are properly oriented along the (001) direction. Their normal-state resistivity measured along the tilt (off-axis (100) direction of the substrate) was, typically, 260 times higher than that along the (010) direction. Such films reveal a transverse Seebeck-effect which significantly exceeds that observed with YBa₂Cu₃O₇ (YBCO).     

Direct comparison of anisotropic magnetoresistance and planar Hall effect in epitaxial Fe3O4 thin films

The angular dependence of anisotropic magnetoresistance (AMR) and planar Hall effect (PHE) were studied as a function of temperatures from the same epitaxial Fe₃O₄ film on MgO(001) substrates. The PHE contains only a twofold angular dependence, but the AMR below 200 K is constituted with both twofold and fourfold symmetric terms. Our results also prove that the origin of the fourfold symmetry of AMR is related to the lattice symmetry rather than the spin scattering near the antiphase boundaries.     

Structure and morphology of the reaction fronts during the formation of MgAl2O4 thin films by solid state reaction between R-cut sapphire substrates and MgO films

The thin-film spinel-forming solid state reaction between Al₂O₃ and MgO has been studied under initially non-coherent conditions. MgO films in (001) orientation on -cut sapphire single crystals were heated at 1100°C for 30 min or 1h. The film/substrate reaction proceeds via cation counterdiffusion as was revealed by a marker experiment. The MgAl₂O₄ films formed were predominantly (001) oriented, with an additional systematic tilt of about 5° of the spinel lattice around the [010] axis. The structure of the Al₂O₃ /MgAl₂O₄(001) and MgAl₂O₄(001)/MgO(001) reaction fronts has been investigated on cross section samples by high-resolution electron microscopy. It appeared that after starting from an incoherent interface, the Al₂O₃ /MgAl₂O₄(001) front assumes an almost fully coherent structure during the reaction. As a result the lattice misfit is reduced to 1%, and interfacial ledges are formed. The latter most probably play an active role in the necessary c.p.h. f.c.c. reconstruction of the oxygen sublattice. The MgAl₂O₄(001)/MgO(001) reaction front consists of coherent regions divided by misfit dislocations. During the reaction the former run ahead whereas the latter lag behind. As a result the morphology of the reaction front is bowed. The results confirm earlier observations of Carter and Schmalzried of the semicoherent Al₂O₃(00.1)/CoAl₂O₄(111) interface, thus strongly supporting the conclusion of a fundamental new phase transformation mechanism specific to oxide systems.Presented at the workshop on High-Voltage and High-Resolution Electron Microscopy, February 21–24, 1994, Stuttgart, Germany.     

Domain structure and optical property of epitaxial indium oxide film deposited on MgO(100) substrate

Indium oxide (In₂O₃) film has been deposited on MgO(100) substrate at 600 °C by metalorganic chemical vapor deposition (MOCVD). The crystal structure and epitaxial relationship of the sample were examined by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The results showed a clear epitaxial relationship of In₂O₃(111)||MgO(100) with In₂O₃[011?]||MgO<072> or In₂O₃[01$\overline{1}$]||MgO<011>. A multiple domain structure was found inside the In₂O₃ film and a theoretical model clarifying the geometrical relationships between each domain and the substrate has been proposed. Scanning electron microscopy (SEM) micrograph showed that the main surface features were triangle-shaped grains on the film. The absolute average transmittance of the obtained film in the visible range was over 93%.     

Epitaxial growth of InN on nearly lattice-matched (Mn,Zn)Fe2O4

We have grown InN films on nearly lattice-matched (Mn,Zn)Fe₂O₄ (111) substrates at low temperatures by pulsed laser deposition (PLD) and investigated their structural properties. InN films grown at substrate temperatures above 400 °C show poor crystallinity, and their in-plane epitaxial relationship is [10-10]InN//[11-2](Mn,Zn)Fe₂O₄, which means that their lattice mismatch is quite large (11%). By contrast, high quality InN films with flat surfaces can be grown at growth temperatures lower than 150 °C with the ideal in-plane epitaxial relationship of [11-20]InN//[11-2](Mn,Zn)Fe₂O₄, which produces lattice mismatches of as low as 2.0%. X-ray reflectivity measurements have revealed that the thickness of the interfacial layer between the InN and the substrates is reduced from 14 to 8.4 nm when the growth temperature is decreased from 400 °C to room temperature. This suppression of the interface reactions by reducing the growth temperature is probably responsible for the improvement in crystalline quality. These results indicate that the use of (Mn,Zn)Fe₂O₄ (111) substrates at low growth temperatures allows us to achieve nearly lattice matched epitaxial growth of InN.     

Growth of InN films on spinel substrates by pulsed laser deposition

We have grown InN films on MgAl₂O₄(111) substrates with atomically flat surfaces using pulsed laser deposition (PLD) and compared their structural properties with those grown on (Mn,Zn)Fe₂O₄(111) substrates. It has been revealed that InN(0001) films grow on MgAl₂O₄(111) with an in‐plane epitaxial relationship of InN[1 00] // MgAl₂O₄[1 0], achieving a lattice mismatch minimum. The InN films exhibited a clear sixfold rotational symmetry, without 30° rotational domains and with a full width at half maximum value of the InN 0002 rocking curve being 17.5 arcmin. Comparison between InN films grown on MgAl₂O₄ and those on (Mn,Zn)Fe₂O₄ led us to conclude that suppression of the interfacial reactions between the InN films and the substrate is inherently important to obtain high quality InN on substrates with a spinel structure. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

In situ RHEED analysis of epitaxial Gd2O3 thin films grown on Si (001)

Epitaxial Gd₂O₃ thin films were successfully grown on Si (001) substrates using a two-step approach by laser molecular-beam epitaxy. At the first step, a ～0.8 nm thin layer was deposited at the temperature of 200 ^°C as the buffer layer. Then the substrate temperature was increased to 650 ^°C and in situ annealing for 5 min, and a second Gd₂O₃ layer with a desired thickness was deposited. The whole growth process is monitored by in situ reflection high-energy electron diffraction (RHEED). In situ RHEED analysis of the growing film has revealed that the first Gd₂O₃ layer deposition and in situ annealing are the critical processes for the epitaxial growth of Gd₂O₃ film. The Gd₂O₃ film has a monoclinic phase characterized by X-ray diffraction. The high-resolution transmission electron microscopy image showed all the Gd₂O₃ layers have a little bending because of the stress. In addition, a 5–6 nm amorphous interfacial layer between the Gd₂O₃ film and Si substrate is due to the in situ high temperature annealing for a long time. The successful Gd₂O₃/Si epitaxial growth predicted a possibility to develop the new functional microelectronics devices.     

Magnetism of CrO overlayers on Fe(001)bcc surface: first principles calculations

Riva et al. [Surf. Sci. 621, 55 (2014)] as well as Calloni et al. [J. Phys.: Condens. Matter 26, 445001 (2014)] have studied the oxydation of Cr films deposited on Fe(001)bcc through low-energy electron diffraction, Auger electron spectroscopy and scanning tunneling microscopy. In the present work we perform a density functional approach within Quantum Expresso code in order to study structural and magnetic properties of CrO overlayers on Fe(001)bcc. The calculations are performed using DFT+U. The investigated systems include O/Cr/Fe(001)bcc, Cr/O/Fe(001)bcc, Cr_0.25O_0.75/Fe(001)bcc, as well as the O coverage O _x /Cr/Fe(001)bcc (x = 0.25; 0.50). We have found that the ordered CrO overlayer presents an antiferromagnetic coupling between Cr and Fe atoms. The O atoms are located closer to the Fe atoms of the surface than the Cr atoms. The ground state of the systems O/Cr/Fe(001)bcc and Cr/O/Fe(001)bcc corresponds to the O/Cr/Fe(001)bcc system with a magnetic coupling c(2 × 2). The effect of the O monolayer on Cr/Fe(001)bcc changes the ground state from p(1 × 1) ↓ to c(2 × 2) and produces an enhancement of the magnetic moments. The O _x overlayer on Cr/Fe(001)bcc produces an enhancement of the Cr magnetic moments.     

Highly oriented thin oxide films on single crystals of Fe-Si alloys II. The (111) surface of the substrate

In Part I (Czech. J. Phys.B 20 (1970), 994), orientational relationships in oxide films grown on the (001) surface of single crystals of some Fe-Si alloys have been described. Part II deals with highly oriented thin oxide films on the (111) surface of the substrate. Typical reflection high energy electron diffraction patterns are shown and orientational relationships between Fe₃O₄ and the substrate and between -Fe₂O₃ and Fe₃O₄ are given.The authors are indebted to Ing. B. Sesttk and Ing. S. Kadekovi (Institute of Physics, Czechoslovak Academy of Sciences) who made possible the preparation of single crystalline samples of Fe-Si alloys. The authors express their gratitude to members of the Institute of Solid State Physics, Czechoslovak Academy of Sciences, Dr. M. Rozsival for the possibility of the use of the electron diffraction apparatus, Dr. A. Linek for helpful discussion of some important problems and Miss J. Sikovi for computer calculations of structure factors.     

Thermal and irradiation induced interdiffusion in magnetite thin films grown on magnesium oxide (0 0 1) substrates

Epitaxial Fe₃O₄(0 0 1) thin films (with a thickness in the range of 10-20 nm) grown on MgO substrates were characterized using low-energy electron diffraction (LEED), conversion electron Mössbauer spectroscopy (CEMS) and investigated using Rutherford backscattering spectrometry (RBS), channeling (RBS-C) experiments and X-ray reflectometry (XRR). The Mg out-diffusion from the MgO substrate into the film was observed for the directly-deposited Fe₃O₄/MgO(0 0 1) films. For the Fe₃O₄/Fe/MgO(0 0 1) films, the Mg diffusion was prevented by the Fe layer and the surface layer is always a pure Fe₃O₄ layer. Annealing and ion beam mixing induced a very large interface zone having a spinel and/or wustite formula in the Fe₃O₄-on-Fe film system.