Effect of thickness on magnetic phase coexistence and electrical transport in Nd0.51Sr0.49MnO3 films

We present the impact of the film thickness on the coexistence of various magnetic phases and its link to the magnetoresistance of Nd_0.51Sr_0.49MnO₃ thin films. These epitaxial films are deposited on LaAlO₃ (001) substrates by DC magnetron sputtering. Films with thicknesses of approximately 30 nm are found to be under full compressive strain while those with thicknesses ∼100 nm and beyond exhibit the presence of both strained and relaxed phases, as evidenced from X-ray diffraction studies. Both films exhibit multiple magnetic transitions controlled by strong electron correlations and phase coexistence. These films also display insulator–metal transitions (IMT) and colossal magnetoresistance (CMR) under moderate magnetic fields. Among the two set of films, only the 30-nm films show a weak signature of charge ordering at T≈50 K. Even at temperatures much lower than the IMT, the 30-nm films show huge magnetoresistance (MR) ∼80%. This suggests presence of softened charge-ordered insulating (COI) clusters that are transformed into ferromagnetic metallic (FMM) ones by the external magnetic field. In the 100-nm films, the corresponding MR is suppressed to less than 20%. Our study demonstrates that the softening of the COI phase is induced by the combined effect of the in-plane compressive strain and a slight reduction in Sr concentration.     

Photoassisted chemical solution deposition method for fabricating uniformly epitaxial VO2 films

Epitaxial VO₂ films were prepared on the TiO₂ (001) substrates by the excimer-laser-assisted metal–organic deposition (ELAMOD). The quality of the epitaxial films obtained by irradiation with a KrF laser was found to be affected by the film structure obtained after preheating at 500 or 300°C. When the films containing crystal domains, which were obtained by preheating at 500°C, were irradiated with the laser at room temperature under a base pressure of 250 Pa, epitaxial and polycrystalline VO₂ phases were simultaneously formed. In contrast, when the amorphous films containing organic components, which were obtained by preheating at 300°C, were irradiated with the laser at room temperature in air, a single phase of epitaxial VO₂ was formed. By using thermal simulations, we determined that the formation of the epitaxial phase was affected both by the temperature distribution within the film during the laser irradiation and by the laser intensity at the interface between the substrate and the film. The latter factor is considered to play a role in the nucleation of crystallization, causing the epitaxial phase to form preferentially compared to the polycrystalline phase in the amorphous matrix of the films. These results indicate that the ELAMOD process is effective for the fabrication of epitaxial VO₂ films at low temperature.     

Ferroelectric phase transitions in ultrathin films of BaTiO3

We present molecular dynamics simulations of a realistic model of an ultrathin film of BaTiO3 sandwiched between short-circuited electrodes to determine and understand effects of film thickness, epitaxial strain, and the nature of electrodes on its ferroelectric phase transitions as a function of temperature. We determine a full epitaxial strain-temperature phase diagram in the presence of perfect electrodes. Even with the vanishing depolarization field, we find that ferroelectric phase transitions to states with in-plane and out-of-plane components of polarization exhibit dependence on thickness; it arises from the interactions of local dipoles with their electrostatic images in the presence of electrodes. Secondly, in the presence of relatively bad metal electrodes which only partly compensate the surface charges and depolarization field, a qualitatively different phase with stripelike domains is stabilized at low temperature.     

Phenomenological description of phase transitions in thin BaTiO<Subscript>3</Subscript> films

Phase transitions in thin epitaxial films of BaTiO₃ are described phenomenologically in terms of Landau potentials with sixth-and eighth-order terms. It is established that the phase diagram depends on the electrostrictive constant Q ₁₂. The phase diagrams calculated for different values of Q ₁₂ available in the literature differ qualitatively. The dependence of the misfit strain of a film on the film tetragonality at room temperature is found, which makes it possible to determine the thermodynamic path in the phase diagram for a specific film. The dependences of the spontaneous polarization and dielectric constant of a film on the misfit strain at room temperature are constructed.     

Observation of ferroelectricity induced by defect dipoles in the strain-free epitaxial CaTiO3 thin film

CaTiO₃ is a well-known incipient ferroelectric material that does not undergo a ferroelectric phase transition in spite of the intriguing dielectric constant behavior. Especially, unlike a prototypical incipient ferroelectric SrTiO₃, the paraelectric state of CaTiO₃ cannot be easily destroyed by small perturbations, including cation doping and epitaxial strain. We present that a nearly strain-free epitaxial CaTiO₃ film grown at a low oxygen partial pressure exhibits polarization–voltage hysteresis loops and the distinct difference of piezoresponse force microscopy phase signals, implying that a ferroelectric phase is induced. Such results are shown even at room temperature. We suggest that the observed ferroelectric behavior in CaTiO₃ film comes from the defect dipoles composed of vacancies inside the film. Using electron-probe microanalysis and optical absorption spectra measurements, we found that CaTiO₃ film has considerable Ca and O vacancies, forming the localized defect state in electronic structure. This work highlights the importance of vacancies and their clusters, such as defect dipoles, in understanding the electronic properties of perovskite oxide thin films, including ferroelectricity.     

Formation of the ferroelectric domains in epitaxial PbTiO3 thin films grown by metalorganic chemical vapor deposition

3 thin films have been prepared by metalorganic chemical vapor deposition under reduced pressure. The formation of ferroelectric domains in films grown on SrTiO₃ and LaAlO₃ substrates was investigated by synchrotron radiation and Rutherford backscattering spectroscopy. Single-domain (3000-Å thick) and multi-domain (4500-Å thick) PbTiO₃ films were produced on SrTiO₃. For multi-domain PbTiO₃ film, the c-domain presented epitaxial structure with its c-axis perpendicular to the substrate surface, while a-domains aligned four-fold symmetrically with c-domains by 2.79^° off the c-axis of c-domains. In the film, the measured lattice constants (a, b and c) of the a- and c-domains were different from each other, indicating that the films suffered a modulated strain during domain formation. In contrast, both the a and c domains of films on LaAlO₃ were alternatively aligned on substrate with the a-axis of the a-domain and the c-axis of c-domains perpendicular to the substrate surface. Two-dimensional distribution of these domains is proposed and the formation of these kinds of domains is discussed. The surface morphology and phase transition process of single and multi domain PbTiO₃ film on SrTiO₃ were studied by atomic force microscope (AFM) and high temperature X-ray diffraction, respectively. Received: 15 August 1996/Accepted: 21 January 1997     

Structural transition of secondary phase oxide nanorods in epitaxial YBa2Cu3O7−δ films on vicinal substrates

A theoretical study of a structural transition of secondary phase oxide nanorods in epitaxial YBa₂Cu₃O_7?δ films on vicinal SrTiO₃ substrates is presented. Two possible types of film/substrate interface are considered, with one assuming complete coherence, while the other is defective as manifested by the presence of antiphase grain boundaries. Only in the former case does the increase of the vicinal angle of the substrate lead to a substantial change of the strain field in the film, resulting in a transition of the nanorod orientation from the normal to the in-plane direction of the film. The calculated threshold vicinal angle for the onset of the transition and lattice deformation of the YBa₂Cu₃O_7?δ film due to the inclusion of the nanorods is in very good agreement with experimental observations. This result sheds lights on the understanding of the role of the film/substrate lattice mismatch in controlling self-assembly of dopant nanostructures in matrix films.     

Film thickness dependence of electro-optic effect in epitaxial BaTiO3 thin films

Based on the phenomenological Landau-Devonshire theory, we investigate the film thickness dependence of ferroelectric and electro-optic properties of epitaxial BaTiO₃ thin films grown on SrTiO₃ and MgO substrates. By using the effective substrate lattice parameter concept, the film thickness dependence of misfit strain is incorporated into the theory. Therefore, the film thickness dependence of ferroelectric and electro-optic properties in epitaxial BaTiO₃ thin films can be explained. Moreover, a large quadratic electro-optic effect was obtained in the BaTiO₃ thin films, which is in good agreement with the experimental result of BaTiO₃ thin films on the MgO substrate.     

Pulsed laser deposition of a PBN:65 morphotropic phase boundary thin film with large electrostriction

We deposited epitaxial thin films of Morphotropic Phase Boundary (MPB) Pb_0.65Ba_0.35Nb₂O₆ (PBN:65) on MgO substrates using pulsed laser deposition. Afterwards, a novel transmission optical experiment was developed to measure the electric field-induced bending angle of the thin film sample using a divergent incident light. From which the electric field-induced strain was obtained, and it was used to calculate the electrostrictive constant of the PBN thin film. The result is 0.000875 μm²/V², and it is consistent with what we measured in the reflection experiment     

Ion-irradiation enhanced epitaxial growth of sol–gel TiO2 films

We report the epitaxial growth of sol–gel TiO₂ films by using ion-irradiation enhanced synthesis. Our present study shows that the ion-beam process can provide highly crystalline TiO₂ even at 350°C. Nuclear energy deposition at amorphous/crystalline interface plays a dominant role in the epitaxial growth of the films at the reduced temperature via a defect-migration mechanism. In addition, the ion irradiation allows for increasing the film density by balancing the crystallization rate and the escape rate of organic components.     

Epitaxial growth of PbTiO3 thin film on (110) NdGaO3 substrate by metalorganic chemical vapor deposition

(001) preferentially oriented PbTiO₃ thin films have been grown on (110) NdGaO₃ substrates by metalorganic chemical vapor deposition (MOCVD) under reduced pressure at 650°C. Atomic force microscopy (AFM) surface morphology of the as-deposited film showed the evidence of layer-by-layer growth in the MOCVD process. By using a grazing-angle scattering technique, a highly resolved Raman spectrum of the epitaxial PbTiO₃thin film on perovskite substrate was first time recorded. Other microstructure of the film, such as the element composition, the c-domain percentage and the epitaxial nature, were investigated by Rutherford backscattering spectrometry (RBS), x-ray θ ? 2θ diffraction patterns and x-ray φ scans, respectively. All measurements indicate that NdGaO₃single crystal, which used to be a substrate for the growth of high-T_c superconducting thin films, is also suitable for the growth of high quality PbTiO₃ thin film. This indicates the promising use of the NdGaO₃ for the integration of ferroelectric thin films and superconducting electrodes.     

Thickness-dependent transport properties of Sr4Fe6O13 epitaxial thin films

High-quality epitaxial thin films of Sr₄Fe₆O₁₃ have been deposited on NdGaO₃(001) substrates by pulsed laser deposition. The transport properties have been characterized by impedance spectroscopy. The temperature dependence of conductivity suggests a mechanism of adiabatic hopping by small polarons, in agreement with previous results in bulk samples. The transport properties show a clear dependence on the film thickness with the thinner films (10 nm) presenting conductivity values in oxygen one order of magnitude higher than the thicker ones (313 nm). We correlate this behaviour with the thickness dependence of the epitaxial strain.     

Wet‐Etching Induced Abnormal Phase Transition in Highly Strained VO2/TiO2 (001) Epitaxial Film

The metal–insulator transition (MIT) behavior in vanadium dioxide (VO₂) epitaxial film is known to be dramatically affected by interfacial stress due to lattice mismatching. For the VO₂/TiO₂ (001) system, there exists a considerable strain in ultra‐thin VO₂ thin film, which shows a lower T_c value close to room temperature. As the VO₂ epitaxial film grows thicker layer‐by‐layer along the “bottom‐up” route, the strain will be gradually relaxed and T_c will increase as well, until the MIT behavior becomes the same as that of bulk material with a T_c of about 68 °C. Whereas, in this study, we find that the VO₂/TiO₂ (001) film thinned by “top‐down” wet‐etching shows an abnormal variation in MIT, which accompanies the potential relaxation of film strain with thinning. It is observed that even when the strained VO₂ film is etched up to several nanometers, the MIT persists, and T_c will increase up to that of bulk material, showing the trend to a stress‐free ultra‐thin VO₂ film. The current findings demonstrate a facial chemical‐etching way to change interfacial strain and modulate the phase transition behavior of ultrathinVO₂ films, which can also be applied to other strained oxide films.     

Readdressing the issue of low-temperature resistivity minimum in La0.7Ca0.3MnO3 thin films

We have investigated the origin of low-temperature resistivity minima observed in epitaxial thin films of La_0.7Ca_0.3MnO₃ (thicknesses—300 Å and 3000 Å) using electrical and magneto-transport property measurements. We observe considerably smaller hysteresis in the magnetoresistance measurements for the thicker film than the thinner film. 300 Å film shows meta-stability in the resistivity measurements at low temperature and for this film the sample current ‘I’ shows large effect on the resistivity and its minima temperature. These observations suggest that the strain induces electronic intra grain inhomogeneity in these samples and these inhomogeneities consist of regions of different resistive phases. It appears that the high resistive phase prevents the transport of charge carriers between two low resistive regions thus giving rise to the resistivity minimum in these samples.     

Epitaxial growth of high-Tc superconducting Tl-Ca-Ba-Cu-O films by liquid phase epataxial process

Tl-Ca-Ba-Cu-O epitaxial films have been successfully grown on (001) MgO substrate by liquid phase epitaxial (LPE) process. The as-grown films showed an onset of superconductivity at about 140 K and zero resistance at 111 K. X-ray diffraction analysis suggests the films to be highly preferentially oriented with the c-axis perpendicular to the film surface. Observation from transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) revealed the presence of both Tl-Ca₂Ba₂Cu₃O_y and TlCa₂Ba₃Cu₄O_y phases.     

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.     

Epitaxial strain-induced magnetic anisotropy in Sm3Fe5O12 thin films grown by pulsed laser deposition

Sm₃Fe₅O₁₂ thin films of various thicknesses were grown on a (0 0 1)-oriented Gd₃Ga₅O₁₂ substrate by pulsed laser deposition. The crystal structure of the films was strongly dependent on film thickness. The lattice was strained for thinner films due to a lattice mismatch between the film and substrate. This lattice strain was relaxed when the film thickness exceeded a critical thickness of around 660 Å. It is suggested that the epitaxial strain induces uniaxial magnetic anisotropy with an out-of-plane magnetic easy axis.     

Magnetic and optical properties of epitaxial n-type Cu-doped ZnO thin films deposited on sapphire substrates

In this paper, we report on pulsed laser deposition of n-type Cu-doped ZnO thin films on c-plane sapphire substrates at 700°C. XRD and HRTEM were employed to study the epitaxial growth relationship between the Zn_1−x Cu _x O film and sapphire substrate. Absorption measurements showed excitonic nature of the thin films and a decrease in the bandgap energy with increased Cu concentration was observed. Such as-deposited films showed room temperature ferromagnetism with Curie temperature (T _c ) at around 320 K. The moment per Cu atom decreases as the Cu concentration increases. The largest magnetic moment about 0.81μ _B /Cu atom was observed for Zn_0.95Cu_0.05O thin films. The presence of any magnetic second phase was ruled out and the ferromagnetism was attributed to Cu ions substituted directly into the ZnO lattice.     

Pulsed laser deposition of BaGa<Subscript>2</Subscript>O<Subscript>4</Subscript>

This paper reports the first results obtained on monobarium gallate thin films grown on silicon and platinum coated substrates by pulsed laser deposition. The influence of oxygen background pressure and substrate (or post-annealing) temperature on the film properties was studied. The films were characterized by XRD, RHEED, AFM, photoelectron and electrical impedance spectroscopy. The structure analysis showed that the films crystallized into a hexagonal phase, most probably into (metastable) α-BaGa₂O₄. Depending on deposition conditions, films with different (from nearly epitaxial to polycrystalline) textures were obtained.     

Influence of the thickness on structural,magnetic and electrical properties of La0.7Ca0.3MnO3 thin film

We have studied the effect of thickness on the structural, magnetic and electrical properties of La_0.7Ca_0.3MnO₃ thin films prepared by pulsed laser deposition method using X-ray diffraction, electrical transport, magneto-transport and dc magnetization. X-ray diffraction pattern reflects that all films have c-axis epitaxial growth on LaAlO₃ substrate. The decrease in out-of-plane cell parameter specifies a progressive relaxation of in the plane compressive strain as the film thickness is increases. From the dc magnetization measurements, it is observed that ferromagnetic to paramagnetic transition temperature increases with increase in the film thickness. Magneto-resistance and temperature coefficient of resistance increases with film thickness and have maximum value near its metal to insulator transition temperature.