A first-principles study of phase transitions in ultrathin films of BaTiO3

We determine the effects of film thickness, epitaxial strain and the nature of electrodes on ferroelectric phase transitions in ultrathin films of BaTiO₃ using a first-principles effective Hamiltonian in classical molecular dynamics simulations. We present results for polarization and dielectric properties as a function of temperature and epitaxial strain, leading to size-dependent temperature-strain phase diagram for the films sandwiched between ‘perfect’ electrodes. In the presence of non-vanishing depolarization fields when non-ideal electrodes are used, we show that a stable stripe-domain phase is obtained at low temperatures. The electrostatic images in the presence of electrodes and their interaction with local dipoles in the film explain these observed phenomena.      

Modelling of the phase transitions sequence in KNbO3 and BaTiO3

Interatomic potentials are determined in the framework of the nonlinear oxygen polarizability model to describe the structural behavior of KNbO₃ and BaTiO₃ as a function of temperature. To this purpose, the adiabatic potential is evaluated for different ferroelectric distortions and the model potential parameters are improved by comparing with total energies from full-potential LMTO calculations. Phonon dispersion curves are computed to test if the model reproduces the pronounced two-dimensional character instabilities found by first-principles lattice dynamics using a linear response approach. Finally, the phase diagram for KNbO₃ is obtained through a constant-pressure molecular dynamics simulation.     

Structural phase transitions during high-energy ball milling of BaTiO3

Microstructural characterization of ball milled perovskite BaTiO₃ powders has been done by the modeling of X-ray diffraction profiles. The study reveals that on size reduction, BaTiO₃ powders undergo a continuous, displacive, and diffusionless dynamic phase transitions involving tetragonal (T), monoclinic (M), and orthorhombic (O) symmetry via the second-order type [T?→?(T?+?M)?→?(M?+?O)?→?O] when stimulated by a high-power pulse of pressure in a planetary mill. The order parameter, a phenomenological quantity to describe the general behavior of a system going through phase transitions has been estimated using spontaneous strain calculated from lattice parameters or physical distortions derived from atomic coordinates or both. At room temperature, BaTiO₃ nanoparticle achieved an orthorhombic phase when a critical size (<15?nm) has been reached at later stage of milling (≥70?h). Raman's study reveals similar structural phase transitions sequence on size reduction and TEM study reveals the corresponding particle diameter.     

Phase transitions in ultrathin ferroelectric polymer films and nanocrystals

The dielectric dispersion of nanocrystals of vinylidene fluoride—trifluoroethylene copolymer of 70/30 composition was investigated. A phase transition was revealed in ferroelectric nanocrystals at T = 100°C. A wide temperature hysteresis was observed, indicating a first-order phase transition.     

Ferroelectric Phase Transition of first Order in BaTiO3

A microscopic model of BaTiO₃ is treated to describe static phenomena near the ferroelectric phase transition. In addition to the polarization, changes of the lattice constant at fixed pressure are also considered. That leads to a new explanation of the first order character of the transition, which is carried out not only qualitatively but also quantitatively. We investigate the dependence on pressure and external field. Agreement with the experiment through the adjustment of the parameters of the theory is obtained.     

Ferroelectric polarization and resistive switching characteristics of ion beam assisted sputter deposited BaTiO3 thin films

In this work, 150 nm thick polycrystalline BaTiO₃ (BTO) films were deposited on Pt/TiO₂/SiO₂/Si substrate by ion beam assisted sputter deposition technique. The bias voltage dependent resistive switching (RS) and ferroelectric polarization characteristics of Au/BTO/Pt devices are investigated. The devices display the stable bipolar RS characteristics without an initial electroforming process. Fittings to current–voltage (I–V) curves suggest that low and high resistance states are governed, respectively, by filamentary model and trap controlled space charge limited conduction mechanism, where the oxygen vacancies act as traps. Presence of oxygen vacancies is evidenced from the photoluminescence spectrum. The devices also display P–V loops with remnant polarization (P_r) of 5.7 μC/cm² and a coercive electric field (E_c) of 173.0 kV/cm. The coupling between the ferroelectric polarization and RS effect in BTO films is demonstrated.     

Surface magnetic phase transitions in films

Using a simple Landau model, we discuss the different possibilities of generating magnetic effects at a second-order transition for films. Varying the sample size d$d$ and/or surface coupling γ$\gamma$ one can decrease or increase substantially the surface critical temperature _Ts$T_{\mathrm{s}}$ and the saturation magnetization _Ms$M_{\mathrm{s}}$. In the case of γ>0$\gamma >0$, _Ms$M_{\mathrm{s}}$ and _Ts$T_{\mathrm{s}}$ decrease from the bulk values as the film thickness is reduced. These theoretical results are in nice agreement with the experimental data on superconducting _MgB2${\mathrm{MgB}}_2$ thin films. By contrast, for γ<0$\gamma <0$, an enhancement of both quantities is expected. This extraordinary transition has rarely been observed experimentally and, usually, the situation is far from being clear. We analyze a new experiment on _NiFe2O4${\mathrm{NiFe}}_2{\mathrm{O}}_4$ ultra-thin films, where a very strong enhancement of the saturation magnetization is observed.     

Ferroelectric phase transitions in ionic conductors based on bismuth vadanate

Ceramic solid solutions (Bi_{1 ? x} La _x )₄V₂O_{11 ? z} (I), Bi₄(V_{1 ? x} Fe _x )₂O_{11 ? y} (II), and (Bi_{1 ? x} La _x )₄(V_0.96Fe_0.04)₂O_{11 ? y} (III) (x = 0–0.3, step Δx = 0.02) are prepared using solid-phase synthesis. The concentration and temperature ranges of stabilization of different polymorphic modifications, including the ranges of concentrations x corresponding to the stabilization of the ferroelectric phase, are established. It is revealed that an increase in the concentration x in the region of existence of the pseudoorthorhombic phase α of the solid solutions studied leads to a decrease in the transition temperature, smearing of the transition, and an increase in the width of the thermal hysteresis of the ferroelectric phase transition. The effect of compressing of the domain walls by oxygen vacancies was revealed in the samples from the region of existence of the ferroelectric α phase, and the effect of dielectric relaxation was detected in the samples from the region of existence of the orthorhombic phase β.     

Ferroelectric phase transition in Langmuir-Blodgett films of copper phthalocyanine

A ferroelectric phase transition is observed in Langmuir-Blodgett films prepared from substituted copper phthalocyanine molecules. The linear and nonlinear dielectric properties of the films and the switching of their spontaneous polarization are investigated in the temperature range of the phase transition. The observed features can be explained by the Landau-Ginzburg model of a first-order phase transition. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 9, 625–631 (10 November 1999)     

Spontaneous phase transitions in ferrite garnet films

Spontaneous phase transitions in ferrite garnet films have been studied. It has been shown that, with variations in the temperature, domain walls undergo phase transitions which cause spontaneous phase transitions in the lattice of cylindrical magnetic domains. The phase transition in a domain wall causes a spin-reorientation phase transition over the whole sample near the magnetic compensation point. The character of the phase transition in the domain wall determines the mechanism of the spin-reorientation phase transition.     

First-order magnetic phase transitions in thin films

Using the simple Landau model, we discuss near-surface magnetic effects for thin films corresponding to first-order phase transitions. The size effects observed in ultrathin ferroelectric films are in agreement with this theoretical interpretation. The presence of a weak external field is also formulated. The text was submitted by the authors in English.     

Determination of the phase transitions in BaTiO3 type crystals by using the theory of symmetry breaking: Etude des transitions de phase dans les cristaux du type BaTiO3 par la theorie des symetries brisees

Crystaks of the BaTiO₃ family showing the following sequence of phase transitions : tetragonal, orthorhombic, rhombohedral, are investigated. From the MASON-MATHIAS model based on a TiO₆ octahedron in which a Ti ion can be displaced along the different pseudo-cubic axes, these different polar structures are found by considering the possible lowering of the O_h symmetry associated with the non polar phase. By the appropriate orientation of the basis of the vector representation connected with the occurence of the polarisation $\text{P}$, the order-parameter of the phase transitions are determined for three cases (O_h → C_4v, C_2v, C_3v). The order of the transition is discussed. These parameters can be used for a thermodynamical investigation of the crystal based on an expansion of its free energy.     

Landau theory of phase transitions in thick films

A simple expression is used for the free energy density with a one-component order parameter, and the boundary conditions at the surfaces of a film of thickness L are given by means of an extrapolation length δ. Exact expressions are given for the critical temperature and the order parameter profile in terms of elliptic functions, and the nature of the phase transition is discussed.     

Ultrafast laser-induced phase transitions in amorphous GeSb films

Time-resolved measurements of the spectral dielectric function reveal new information about ultrafast phase transitions induced by femtosecond laser pulses in Sb-rich amorphous GeSb films. The excitation generates a nonthermal phase within 200 fs. The dielectric function of this phase differs from that of the crystalline phase, contrary to previous suggestions of a disorder-to-order transition. The observed dielectric function is close to that of the liquid phase, indicating an ultrafast transition from the amorphous phase to a different disordered state.     

Structural phase transitions in langmuir liquid crystal films

The isotherms of water molecule absorption on hyperfine Langmuir films made based on liquid crystals are investigated. A sharp increase in the adsorption capacity of the films at temperatures of 75°C (for a film with a thickness of ten monolayers) and 102°C (for a film with a thickness of five monolayers) has been revealed. This behavior is explained by structural phase transitions that take place at these temperatures.     

Temperature of phase transitions in thin two-layer metal films

It is experimentally established that the melting temperatures of Pb/Bi, Pb/Sn, Mg/Sn, Sn/Zn, and In/Zn two-layer films decrease with a decrease in their thickness.     

Ferroelectricity and tetragonality in ultrathin PbTiO3 films

The evolution of tetragonality with thickness has been probed in epitaxial c-axis oriented PbTiO3 films with thicknesses ranging from 500 down to 24 A. High resolution x ray pointed out a systematic decrease of the c-axis lattice parameter with decreasing film thickness below 200 A. Using a first-principles model Hamiltonian approach, the decrease in tetragonality is related to a reduction of the polarization attributed to the presence of a residual unscreened depolarizing field. It is shown that films below 50 A display a significantly reduced polarization but still remain ferroelectric.