Crystallographic,magnetic, and electrical properties of thin <Emphasis Type="Italic">Re</Emphasis><Subscript>0.6</Subscript>Ba<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript> epitaxial films (<Emphasis Type="Italic">Re</Emphasis> = La,Pr, Nd,Gd)

Thin Re_0.6Ba_0.4MnO₃ epitaxial films (Re = La, Pr, Nd, Gd) grown on (001)SrTiO₃ and (001)ZrO₂(Y₂O₃) single crystal substrates have been prepared and studied. All the films were found to have a cubic perovskite structure, with the exception of the film with Re = La, which revealed rhombohedral distortion of the perovskite cell. The temperature dependences of the electrical resistivity and magnetoresistance pass through a maximum near the Curie point T_C, where the magnetoresistance reaches a colossal value. The magnetization isotherms M(H) are superpositions of a magnetization that is linear in field (like that of an antiferromagnet) and a weak spontaneous magnetization. The magnetic moment per formula unit is substantially smaller than that expected under complete ferro-or ferrimagnetic ordering. The magnetizations of samples cooled in a magnetic field (FC samples) and with no field applied (ZFC samples) differ by an amount that persists up to the highest measurement fields (50 kOe). The M(T) dependence obtained in strong magnetic fields is close to linear. Hysteresis loops of the FC samples are shifted along the field axis. The above magnetic and electric properties of thin films are explained in terms of two coexisting magnetic phases, which are due to strong s-d exchange coupling.     

Nonlinear dielectric response of epitaxial Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript> TiO<Subscript> 3</Subscript> thin films

Based on Landau-Devonshire (LD)-type phenomenological thermodynamic theory, the electric field dependence of the dielectric properties of tetragonal single-domain barium strontium titanate(Ba_1-xSr_xTiO₃) films on cubic substrates is theoretically investigated by taking into account the high order terms of the polarization. At room temperature, the nonlinear dielectric responses of epitaxial Ba_0.6Sr_0.4TiO₃ films are provided by adjusting the film thickness and growth temperature. The strong nonlinearity of relative dielectric constant and pyroelectric coefficient are attained around critical film thickness on MgO (69 nm) and LaAlO₃ (132 nm) substrates or critical growth temperature on MgO (337 °C) substrate with respect to epitaxy-induced lattice misfit and thermal stresses during deposition. This can be explained that small compressive stresses are effective to support high nonlinearity of dielectric constant and pyroelectric coefficient for Ba_0.6Sr_0.4TiO₃ films irrespective of whether they are on compressive substrate or tensile substrate. It is also predicted that a large tunability may be achieved by altering processing conditions, such as the film thickness and growth temperature for different substrates. Our theoretical results are in good agreement with the experimental data reported in literature.     

Magnetoelectric phenomena in manganites R<Subscript>0.6</Subscript>Ca<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript>(R = Pr,Nd) with charge ordering suppressed by a magnetic field

A change in electric polarization (up to 300 μC/m²) upon magnetic-field suppression of a charge-ordered antiferromagnetic state upon a transition to the ferromagnetic conducting phase (H _cr ～ 65–80 kOe at 4.2 K) is discovered in Pr_0.6Ca_0.4MnO₃ and Nd_0.6Ca_0.4MnO₃ single crystals. The transition is also accompanied by a jump in magnetization and magnetostriction. The dependence of the induced polarization sign on the polarity of the electric field in which the sample was preliminarily cooled indicates the existence of spontaneous electric polarization. The effect is the strongest in Nd_0.6Ca_0.4MnO₃ and is weaker by a factor of 5–10 in Pr_0.6Ca_0.4MnO₃, for which the tolerance factor is higher. The observed effect may be associated with recently predicted noncentrosymmetric structures in doped manganites with x ～ 0.5 (see D.V. Efremov, J. van den Brink, and D.I. Khomskii, Nature Materials 3, 853 (2004)), in which e _g electrons are not localized upon charge and orbital ordering at one manganese ion, but are distributed among neighboring ions, thus forming an ordered polar dimer structure.     

PLD and RF-PLD synthesis of Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> ferroelectric thin films for electrically controlled devices

Ba_0.6Sr_0.4TiO₃ (BST) bulk ceramic synthesized by solid state reaction was used as target for thin films grown by pulsed laser deposition (PLD) and radiofrequency beam assisted PLD (RF-PLD). The X-ray diffraction patterns indicate that the films exhibit a polycrystalline cubic structure with a distorted unit cell. Scanning Electron Microscopy investigations showed a columnar microstructure with size of spherical grains up to 150 nm. The capacitance–voltage (C–V) characteristics of the BST films were performed by applying a DC voltage up to 5 V. A value of 280 for dielectric constant and 12.5% electrical tunability of the BST capacitor have been measured at room temperature.     

Coercive field enhancement in microstructured (La<Subscript>0.4</Subscript>Pr<Subscript>0.6</Subscript>)<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> thin films

The perovskite material (La_0.4Pr_0.6)_0.67Ca_0.33MnO₃ (LPCMO) has complex electronic and magnetic behavior based on phase competition between ferromagnetic metallic (FMM) and insulating phases with similar free energies. Experimental evidence has indicated that in-plane stress anisotropy influences these phases and can affect electronic and magnetic properties. Here we investigate the roles that both stress and shape anisotropies may play in controlling the coercive field of the material. LPCMO thin films of various thicknesses (20, 25, and 30 nm) were deposited on (110) NdGaO₃ (NGO) substrates using pulsed laser deposition and the coercive fields were measured. Photolithography was then used to fabricate microstructured arrays of LPCMO on the NGO substrates for each of the films. The coercive fields of these arrays of LPCMO were compared to the behavior of the corresponding unpatterned LPCMO thin films across a range of temperatures. Microstructure arrays for the thicker (25 and 30 nm) films showed a substantial increase in the coercive field after forming the arrays, whereas a thinner film (20 nm) showed almost no change in the coercive field. Stress anisotropy continues to play a dominant role in the behavior of LPCMO thin films and dimensionality of the magnetic domains also influences the results. The films show 2D behavior when film thickness approaches the size of the critical radius for single-to-multidomain transitions. Making thicker films allows for 3D behavior and a role for shape anisotropy to influence the coercive fields.     

Memory effects in superparamagnetic La<Subscript>0.6</Subscript>Pb<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript> nanoparticles

Using different temperature and field protocols, the memory behaviors in the dc magnetization and magnetic relaxation are observed at temperature below blocking temperature T_B = 93 K in weakly interacting manganite La_0.6Pb_0.4MnO₃ nanoparticles. The results indicate that the magnetic dynamics of this nanoparticle system is strongly correlated with a wide distribution of particle relaxation times, which may arise from the particle weak interaction and distribution of the particle size.     

Iron-induced magnetic,transport and magnetoresistance behavior in Nd<Subscript>0.67</Subscript>Sr<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> epitaxial films

The effects of Fe doping on Mn site in the colossal magnetoresistive film, Nd_0.67Sr_0.33MnO₃ have been studied by preparing the series Nd_0.67Sr_0.33Mn_1-xFe_xO₃ (x=0,0.05 and 0.1). Upon doping, no structural changes have been found. However, the Curie temperature, the associated metal-to-insulator transition temperature and the magnetization decrease drastically with Fe doping. The resistivity in the paramagnetic regime for all the samples follows Emin–Holsteins theory of small polaron. The polaron activation energy, W_p and resistivity coefficient, A increase with Fe doping. This effect may be ascribed to the fact that upon Fe doping, the long-range ferromagnetic order is destroyed and, therefore, W_p is enhanced in the system. As compared to the La-based system, Fe doping has a stronger tendency to destabilize the long-range ferromagnetic order in the Nd-based system. Large MR (as high as 90%) observed in the epitaxial NSMFO film may be attributed to the good lattice-matching between the grown film and substrate. PACS 75.47.Gk; 75.47.Lx; 75.70.-i     

Electrical resistivity and magnetotransport properties of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> epitaxial films biaxially compressed by the substrate

The structure, electrical resistivity, and magnetoresistance of La_0.67Ba_0.33MnO₃(20 nm) films grown coherently on an La_0.3Sr_0.7Al_0.65Ta_0.35O₃(001) substrate with a lattice misfit of about 1% were studied. The rigid connection of the manganite layer with the bulk substrate brought about the unit cell distortion of the substrate (a _⊥/a _‖ = 1.02) and a decrease in the unit cell volume as compared to that of the corresponding bulk crystals (a _‖ and a _⊥ are the unit cell parameters measured in the substrate plane and along the surface normal, respectively). The temperature T _M ≈ 295 K, at which the electrical resistivity ρ of the (20 nm)La_0.67Ba_0.33MnO₃ films reached a maximum, was 40–45 K lower than that for the corresponding bulk crystals. The negative magnetoresistance (MR ≈ ?0.25 for μ₀ H = 1 T) attained a peak value at T _MR ≈ 270 K. The response of ρ to a magnetic field depended substantially on the angle between the current flow in the film and the direction of the magnetic field.     

Magnetotransport in thin epitaxial Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> films

The magnetoconductivity of thin Bi₂Se₃ films covered by a protective Se layer and grown at (111) BaF₂ substrates is studied. It is shown that the negative magnetoconductivity observed at low magnetic fields and caused by the effect of weak antilocalization, as well as the Shubnikov?de Haas oscillations at higher fields, is determined only by the magnetic field component perpendicular to the film plane. The obtained experimental results can be reasonably interpreted under the assumption that the studied films exhibit two-dimensional topologically protected electron states. Moreover, the contribution of these states to the total conductivity turns out to be the dominant one.     

Magnetotransport characteristics of strained La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> epitaxial manganite films

The electrical and magnetic characteristics of La_0.7Sr_0.3MnO₃ (LSMO) epitaxial manganite films are investigated by different methods under conditions when the crystal structure is strongly strained as a result of mismatch between the lattice parameters of the LSMO crystal and the substrate. Substrates with lattice parameters larger and smaller than the nominal lattice parameter of the LSMO crystal are used in experiments. It is shown that the behavior of the temperature dependence of the electrical resistance for the films in the low-temperature range does not depend on the strain of the film and agrees well with the results obtained from the calculations with allowance made for the interaction of electrons with magnetic excitations in the framework of the double-exchange model for systems with strongly correlated electronic states. Investigations of the magneto- optical Kerr effect have revealed that an insignificant (0.3%) orthorhombic distortion of the cubic lattice in the plane of the NdGaO₃(110) substrate leads to uniaxial anisotropy of the magnetization of the film, with the easy-magnetization axis lying in the substrate plane. However, LSMO films on substrates (((LaAlO₃)_0.3+(Sr₂AlTaO₆)_0.7)(001)) ensuring minimum strain of the films exhibit a biaxial anisotropy typical of cubic crystals. The study of the ferromagnetic resonance lines at a frequency of 9.76 GHz confirms the results of magnetooptical investigations and indicates that the ferromagnetic phase in the LSMO films is weakly inhomogeneous.     

Magnetoreflection and magnetooptical Kerr effect in La<Subscript>2/3</Subscript>Ba<Subscript>1/3</Subscript>MnO<Subscript>3</Subscript> films at room temperature

Results of studies of magnetooptical Kerr effect and magnetoreflection of natural light in La_2/3Ba_1/3MnO₃/SrTiO₃ films of different thickness are presented. The Kerr effect was shown to be the most prominent in visible and near IR range; magnetoreflection was found to achieve its maximum of about 10% in the mid-IR range near the room temperature. Physical mechanisms defining the value and sign of the effects and the influence of the thin-film state on the magnetooptical properties are discussed. Magnetoreflection is estimated in the framework of the magnetorefractive effect theory.     

Physical properties of Ba<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript> thin films

The behavior of material constants in ferroelectric Ba_0.8Sr_0.2TiO₃ thin films is studied depending on the misfit strain at room temperature in the context of nonlinear thermodynamic potential of the phenomenological theory. Some constants are found to undergo drastic changes with the alternating strain at the interfaces. The gathered results allow one to evaluate the material constants for a specific film and to outline the direction in searching the ways to synthesize films with the needed properties.     

Electro-optic properties of epitaxial Sr<Subscript>0.6</Subscript>Ba<Subscript>0.4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films grown on MgO substrates using Li<Subscript>x</Subscript>Ni<Subscript>2-x</Subscript>O buffer layer

Textured Li_xNi_2-xO (LNO) thin films have been fabricated on (001)MgO substrates by pulsed laser deposition technique. The as-deposited LNO films shows a conductivity of 2.5×10^-3 Ω m and possess a transmittance of about 35% in the visible region. Subsequent deposition of Sr_0.6Ba_0.4Nb₂O₆ (SBN60) thin film on these LNO-coated MgO substrates resulted in a textured SBN layer with a 〈001〉 orientation perpendicular to the substrate plane. Phi scans on the (221) plane of the SBN layer indicated that the films have two in-plane orientations with respect to the substrate. The SBN unit cells were rotated in the plane of the film by ± 8.2° as well as ± 45° with respect to the LNO/MgO substrate. Besides the highly (00l)-orientation, the SBN films also exhibited a dense microstructure as shown by scanning electron microscopy. The electro-optic coefficient (r₃₃) of the SBN film was measured to be 186 pm/V. On the basis of our results, we have demonstrated that the LNO film can be used as a buffer layer as well as a transparent bottom electrode for waveguide applications. The SBN/LNO heterostructure is also a suitable candidate for integrated electro-optics devices. PACS  42.79.Gn; 42.82.Et; 78.20.Ci     

Study of crystal and magnetic structures of manganite Pr<Subscript>0.7</Subscript>Ba<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at high pressure

The crystal and magnetic structures of manganite Pr_0.7Ba_0.3MnO₃ have been studied at high pressures of up to 5.1 GPa and temperatures from 10 to 300 K by means of the neutron diffraction. At normal pressure and a temperature T _C = 200 K, a ferromagnetic state forms in Pr_0.7Ba_0.3MnO₃. At high pressures P ≥ 1.9 GPa and T < T _N ≈ 153 K, a new antiferromagnetic state of A-type have been observed. Under high pressure, the Curie temperature T _C increases with the characteristic quantity dT _C/dP ≈ 2.4 K/GPa. A possible reason for the appearance of an A-type antiferromagnetic phase in Pr_0.7Ba_0.3MnO₃ at high pressures may be anisotropic uniaxial compression of oxygen octahedra along the b axis of the orthorhombic structure.     

Phase separation in a manganite La<Subscript>0.95</Subscript>Ba<Subscript>0.05</Subscript>MnO<Subscript>3</Subscript> crystal

The structure and magnetic states of a crystal of lightly doped manganite La_0.95Ba_0.05MnO₃ were studied using thermal-neutron diffraction, magnetic measurements, and electrical resistance data in a wide temperature range. It is shown that, in terms of its magnetic properties, the orthorhombic crystal is characterized by two order parameters, namely, antiferromagnetic (T _N = 123.6 K) and ferromagnetic (T _C = 136.7 K). The results obtained differ in detail from known information on the manganites La_0.95Ca_0.05MnO₃ and La_0.94Sr_0.06MnO₃. Two models of the magnetic state of the La_0.95Ba_0.05MnO₃ crystal are discussed, one of which is a model of a canted antiferromagnetic spin system and another is associated with the phase separation of the manganite. Arguments are advanced in favor of the coexistence in this crystal of the antiferromagnetic phase (about 87%) with a Mn⁴⁺ ion concentration of 0.048 and the 1/16-type charge-ordered ferromagnetic phase (about 13%) with a Mn⁴⁺ ion concentration of 0.0625. The specific features of the manganite studied are due to self-organization of the La_0.95Ba_0.05MnO₃ crystal lattice caused by the relatively large barium ion size.     

Elastic and kinetic properties of single-crystal La<Subscript>0.75</Subscript>Ba<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript>

An experimental study of the temperature behavior of longitudinal sound velocity, internal friction, electrical resistivity, and thermopower of single-crystal La_0.75Ba_0.25MnO₃ is reported. A structural transition accompanied by a large jump (18%) in the sound velocity was found to occur at T _S ≈170 K. Within the interval 156–350 K, the temperature dependences of the sound velocity and internal friction reveal a temperature hysteresis. An internal-friction peak due to relaxation processes was detected. The metallic and semiconducting regions are separated by a transition domain about 80 K wide lying below the Curie temperature T _C =300 K.     

La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> thin films on SrTiO<Subscript>3</Subscript> and CaTiO<Subscript>3</Subscript> buffered Si substrates: structural,static, and dynamic magnetic properties

Nearly 50-nm thick La_0.7Sr_0.3MnO₃ (LSMO) films were grown on Si substrates using molecular beam epitaxy on (001) Si substrates over-layered by a 20 nm thick SrTiO₃ (STO) or by a 20 nm thick CaTiO₃ (CTO) film. In addition, a reference LSMO film was directly deposited on a (001) STO substrate by pulsed laser deposition. For all the samples, X-ray diffraction revealed an excellent epitaxy of the LSMO film and small mosaicity around (001), with in-plane [100] and [010] cubic axes. The LSMO/CTO films are in-plane compressed while the LSMO/STO ones are in-plane extended. The temperature dependence of their static magnetic properties was studied using a SQUID, showing a Curie temperature overpassing 315 K for all the samples. Hysteresis loops performed at room temperature (294 K) with the help of a vibrating sample magnetometer (VSM) are also discussed. At 294 K Micro-strip ferromagnetic resonance (MS-FMR) was used to investigate the dynamic magnetic properties. It allows concluding to a strong anisotropy perpendicular to the films and to a weak fourfold in-plane anisotropy with easy axes along the [110] and [1[`1]0 1\bar{1}0 ] directions. Their values strongly depend on the studied sample and are presumably related to the strains suffered by the films.     

Nonlinear properties and paramagnet-to-ferromagnet transition in Nd<Subscript>0.7</Subscript>Ba<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> single crystal with metallic ground state

We present the results from studying the magnetic properties (linear and nonlinear susceptibilities and the depolarization of polarized neutrons) of Nd_{1 − x} Ba _x MnO₃ manganite, x = 0.3, with Curie temperature T _C ≈ 140 K and dielectric-to-metal transition temperature T _DM ≈ 129 K. Its critical behavior corresponds to that of an isotropic 3-D ferromagnet at temperatures above T*≈ 144 K, but a strong nonlinear response in weak magnetic fields and depolarization are observed at temperatures below T*. It is shown that this nontraditional behavior is related to the generation of ferromagnetic clusters in the paramagnetic matrix that form a conducting percolative network at temperatures near T _DM.     

Manganese doping effects on interband electronic transitions,lattice vibrations,and dielectric functions of perovskite-type Ba<Subscript>0.4</Subscript>Sr<Subscript>0.6</Subscript>TiO<Subscript>3</Subscript> ferroelectric ceramics

The Ba_0.4Sr_0.6−x Mn _x TiO₃ (BSMT) ceramics with different Mn composition (from 1% to 10%) have been prepared via the conventional solid-state reaction sintering. The X-ray diffraction analysis shows that the ceramics are polycrystalline with the single perovskite phase. The lattice vibrations and optical properties have been investigated using Raman scattering, spectroscopic ellipsometry (SE), and infrared reflectance spectra. It was found that the optical bandgap for the BSMT ceramics is varied between 3.40 and 3.65 eV. The three first-order Raman-active phonon modes can be observed, and the frequency of the A ₁(LO₃)/E(LO) mode shows a blue shift of 8 cm⁻¹ with the Mn composition, which can be attributed to the distortion of the TiO₆ octahedron. With increasing Mn composition, the frequency of the infrared-active TO₄ mode decreases from 532 to 520 cm⁻¹, owing to the local variation of the lattice constant induced by the Mn incorporation. Moreover, the optical functions of the ceramics from the far-infrared to ultraviolet region are obtained based on the SE and reflectance spectra, which is useful for the potential applications in ferroelectric-based optoelectronic devices.     

Effect of the substrate ferroelastic transition on epitaxial La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> films grown on LaAlO<Subscript>3</Subscript>

Thin films of La_0.7Sr_0.3MnO₃ were grown by molecular beam epitaxy on (001)LaAlO₃ crystals. High resolution X-ray diffraction analysis proves the presence of twins in the films at room temperature, showing that the twin structure of the substrate which forms at the ferroelastic transition at T_F = 813 K served as a template for the film microstructure. Magnetic measurements indicate a thermomagnetic irreversibility which is ascribed to the quenched disorder related to twinning and discussed in terms of coexisting ferromagnetic and spin disordered regions connected with the undeformed domain cores and strained domain walls respectively.