Local ferroelectricity in SrTiO3 thin films

The temperature-dependent polarization of SrTiO3 thin films is investigated using confocal scanning optical microscopy. A homogeneous out-of-plane and an inhomogeneous in-plane ferroelectric phase are identified from images of the linear electro-optic response. Both hysteretic and nonhysteretic behavior are observed under a dc bias field. Unlike classical transitions in bulk ferroelectrics, local ferroelectricity is observed at temperatures far above the dielectric permittivity maximum. The results demonstrate the utility of local probe experiments in understanding inhomogeneous ferroelectrics.     

Effect of out-of-plane misfit strain on phase diagrams and ferroelectric properties of ferroelectric films in vertical nanocomposite structures

A phenomenological thermodynamic Landau–Devonshire theory is developed to investigate phase diagrams of epitaxial ferroelectric films with out-of-plane misfit strain induced by vertical nanocomposites. The thermodynamic potential of ferroelectric films is obtained based on the boundary conditions of three-dimensional clamping induced by the vertical nanocomposites. Our calculated results indicate that the out-of-plane misfit strain modulates the transition temperature and spontaneous polarization of ferroelectric films in a wide range even the substrate does not provide an effective in-plane misfit strain control. An enhanced critical transition temperature up to 803 °C in BaTiO₃ films under a tensile out-of-plane misfit strain is predicted, which is consistent with the experimental result very well. The polarization properties of BaTiO₃ films can also be effectively modulated by the out-of-plane misfit strain which is controlled by the volume fraction of nanopillars in the vertical nanocomposites. Our method provides a theoretical guide for the out-of-plane strain engineering of ferroelectric films.     

Anisotropic pinned/biased magnetization in SrRuO3/SrMnO3 superlattices

The exchange coupling at the interfaces of magnetic superlattices consisting of ferromagnetic SrRuO3 and antiferromagnetic SrMnO3 grown on (001) oriented SrTiO3 is studied with in-plane and out-of-plane orientations of the cooling magnetic field, with respect to the substrate plane. The magnetization of the in-plane, field cooled hysteresis loop is lower than the corresponding in-plane zero-field-cooled hysteresis loop. The out-of-plane field cooled hysteresis loop is shifted, from the origin, along the graphical magnetization axis. We attribute this irreversible rotation of the moment to the pinning/biasing of spin in the SrRuO3 layer in the vicinity of interfaces by the antiferromagnetic SrMnO3 layer.     

Ferromagneticlike closure domains in ferroelectric ultrathin films: first-principles simulations

We simulate from first principles the energetic, structural, and electronic properties of ferroelectric domains in ultrathin SrRuO_{3}/BaTiO_{3}/SrRuO_{3} ferroelectric capacitors in short circuit. The domains are stabilized down to two unit cells at zero temperature, adopting the form of a domain of closure, common in ferromagnetic thin films. The domains are closed by the in-plane relaxation of the atoms in the first SrO layer of the electrode, which behaves more like SrO in highly polarizable SrTiO3 than in metallic SrRuO3. Even if small, these lateral displacements are very important to stabilize the domains and might provide some hints to explain why some systems break into domains while others remain in a monodomain configuration. An analysis of the electrostatic potential reveals preferential points of pinning for charged defects at the ferroelectric-electrode interface, possibly playing a major role in film fatigue.     

Anisotropic polarization response of polar nanostructures in relaxor-type lead lanthanum zirconate titanate ferroelectric ceramics

Polar nanoregions (PNRs) in relaxor-type PLZT ferroelectric ceramics and their response to the out-of-plane, in-plane electric fields were investigated by the high-resolution piezoresponse force microscopy. Anisotropic polarization switching kinetic behaviors of PNRs were found in relaxor PLZT ceramics. Normal, stable ferroelectric domain states were formed through the coalescence of PNRs in the out-of-plane field, while in the high in-plane electric field, the polarization dynamic behaviors of PNRs show spatial inhomogeneity due to the anisotropy random fields in the ferroelectric PLZT ceramics.     

不同晶向SrTiO3上外延GaAs薄膜的光谱研究

利用MBE生长技术,成功地在不同晶向SrTiO3(100)(111)(110)衬底上生长了GaAs薄膜,利用显微Raman和荧光光谱（PL）对此进行了研究。实验结果表明,在不同晶向SrTiO3上生长的GaAs薄膜有不同的晶向和应力状态。荧光光谱（PL）研究表明在SrTiO3(100)(111)晶面上生长的GaAs薄膜的PL峰发生明显的蓝移。研究表明在SrTiO3(110)面上生长的GaAs薄膜和体单晶基本上一致,有更好的光学质量。     

Strain phase diagram and domain orientation in SrTiO3 thin films

SrTiO3 thin films were used as a model system to study the effects of strain and epitaxial constraint on structural phase transitions of perovskite films. The basic phenomena revealed will apply to a variety of important structural transitions including the ferroelectric transition. Highly strained SrTiO3 films were grown on different substrates, providing both compressive and tensile strain. The measured strain-temperature phase diagram is qualitatively consistent with theory; however, the increase in the phase transition temperature is much larger than predicted. Because of the epitaxial strain and substrate clamping, the SrTiO3 lattice is tetragonal at all temperatures. The phase transitions involve only changes in internal symmetry. The low temperature phase under tensile strain has a unique structure with orthorhombic Cmcm space group but a tetragonal lattice, an interesting consequence of epitaxial constraint.     

Electrical domain morphologies in compositionally graded ferroelectric films

We present a nonlinear thermodynamic formalism coupled with an electrostatic analysis of uniaxial n-layered compositionally graded heteroepitaxial ferroelectric films and extend this formalism to continuously graded ferroelectric films. We show that the domain morphology and its subsequent evolution in the presence of an electric field are determined by the spontaneous polarisation of the film induced through the compositional grading. The results for compositionally graded epitaxial (001) (Ba,Sr)TiO(3) and (001) Pb(Zr,Ti)O(3) films on (001)SrTiO(3) demonstrate that, while the domain morphologies in these two films are different in appearance, the dielectric displacement and the dielectric permittivity of such graded ferroelectric films exhibit a strong nonlinear behaviour which results in a high dielectric tunability. These findings indicate that it is possible to design specific domain structures that will yield desirable dielectric properties by controlling the strength of the compositional grading in the films.     

Ultrathin films of ferroelectric solid solutions under a residual depolarizing field

A first-principles-derived approach is developed to study the effects of depolarizing electric fields on the properties of Pb(Zr,Ti)O3 ultrathin films for different mechanical boundary conditions. A rich variety of ferroelectric phases and polarization patterns is found, depending on the interplay between strain and the amount of screening of surface charges. Examples include triclinic phases, monoclinic states with in-plane and/or out-of-plane components of the polarization, homogeneous and inhomogeneous tetragonal states, as well as peculiar laminar nanodomains.     

Resonance ultrasound spectroscopy with laser-Doppler interferometry for studying elastic properties of thin films

We propose an advanced method to determine the elastic-stiffness coefficients Cij of thin films using resonance ultrasound spectroscopy (RUS). It uses free-vibration resonance frequencies of a film/substrate layered solid and derives inversely the film's Cij from the resonance frequencies. We develop a piezoelectric tripod consisting of two pinducers and one support to place the specimen on it and measure the resonance frequencies with high enough accuracy. Furthermore, we achieve mode identification by measuring deformation distributions on the vibrating specimen surface using laser-Doppler interferometry. Accurate measurements of frequencies and correct mode identification are the keys for deducing reliable Cij of the film. We applied this technique to copper thin films deposited of Si substrates. The resulting film's Cij are considerably smaller than the bulk's Cij and show anisotropy between the out-of-plane direction and in-plane direction.     

Strain-induced ferroelectric phase transitions in incipient ferroelectric rutile TiO2

Uniaxial strain induced ferroelectric phase transitions in rutile TiO₂ are investigated by first-principles calculations. The calculated results show that the in-plane tensile strain induces rutile TiO₂, paraelectric phase with P_4-2/mnm (D_4h) space group, to a ferroelectric phase with P_m (C_s) space group,driven by the softening behaviour of the E_u1 mode. In addition, the out-of-plane tensile strain, vertical to the ab plane, leads to a ferroelectric phase with P_42nm (C_4v) space group, driven by the softening behaviour of the A_2u mode. The critical tensile strains are 3.7% in-plane and 4.0% out-of-plane, respectively. In addition, the in-plane compression strain, which has the same structure variation as out-of-plane tensile strain due to Poisson effect, leads the paraelectric rutile TiO₂ to a paraelectric phase with P_nnm (D_2h) space group driven by the softening behaviour of the B_1g mode. These results indicate that the sequence ferroelectric (or paraelectric) phase depends on the strain applied. The origin of ferroelectric stabilization in rutile TiO₂ is also discussed briefly in terms of strain induced Born effective charge transfer.     

Interface effects in ferroelectric PbTiO3 ultrathin films on a paraelectric substrate

Interface effects on the ferroelectric behavior of PbTiO3 ultrathin films deposited on a SrTiO3 substrate are investigated using an interatomic potential approach with parameters fitted to first-principles calculations. We find that the correlation of atomic displacements across the film-substrate interface is crucial for the stabilization of the ferroelectric state in films a few unit cells thick. We show that the minimum film thickness for the appearance of a spontaneous polarized domain state is not an intrinsic property of the ferroelectric film but depends on the polarizability of the paraelectric substrate. We also observe that the substrate displays an induced polarization with an unusual oscillatory behavior.     

Unusual behavior of the ferroelectric polarization in PbTiO3/SrTiO3 superlattices

Artificial PbTiO3/SrTiO3 superlattices were constructed using off-axis rf magnetron sputtering. X-ray diffraction and piezoelectric atomic force microscopy were used to study the evolution of the ferroelectric polarization as the ratio of PbTiO3 to SrTiO3 was changed. For PbTiO3 layer thicknesses larger than the 3-unit cell SrTiO3 thickness used in the structure, the polarization is found to be reduced as the thickness is decreased. This observation confirms the primary role of the depolarization field in the polarization reduction in thin films. For the samples with ratios of PbTiO3 to SrTiO3 of less than one, a surprising recovery of ferroelectricity that cannot be explained by electrostatic considerations was observed.     

Ideal soft mode-type quantum phase transition and phase coexistence at quantum critical point in 18O-exchanged SrTiO3

The quantum ferroelectric phase transition of 18O-exchanged SrTiO3 (x% exchanged SrTiO3 is abbreviated as STO18-x) was investigated by Raman scattering as a function of x. The result indicates the ideal soft mode-type quantum ferroelectric phase transition of STO18-x, where the 18O exchange enhances the softening of the soft mode by the suppression of quantum fluctuation. In the vicinity of the quantum critical point (x approximately xc=33%), the system results in the ferroelectric-paraelectric phase coexistence state, in clear contrast to the homogeneous ferroelectric phase in STO18-x, whose x is sufficiently larger than xc. Simultaneously, the softening of the soft mode becomes strongly rounded with the underdamped oscillation. The present result indicates that the sensitivity of the soft phonon vibration to the mass disorder is dramatically enhanced in the vicinity of the quantum critical point.     

Magnetic anisotropy of Fe films on GaAs(113)A substrates

We employ superconducting quantum interference device magnetometry to study the thickness dependence of in-plane and out-of-plane magnetic anisotropic properties of Fe films grown on high-index GaAs(113)A substrates by molecular beam epitaxy. The evolution of the in-plane magnetic anisotropy with film thickness is distinguished into two regions. First, for Fe film thicknesses ≤50 MLs, we observe an in-plane uniaxial magnetic anisotropy with the easy axis along the in-plane 〈332̄〉 axes. Second, for Fe film thicknesses ≥70 MLs, we observe a four-fold magnetic anisotropy with the easy axis along the in-plane 〈031̄〉 axes. The existence of an out-of-plane perpendicular magnetic anisotropy is also detected in ultrathin Fe films. Similar to Fe on GaAs(001), our results provide evidence for the interfacial origin of the in-plane uniaxial and out-of-plane perpendicular magnetic anisotropy. Both the uniaxial and the perpendicular interface anisotropy are found to be independent of the epitaxial orientation and are hence an intrinsic property of the Fe/GaAs interface. PACS 75.70.-i; 75.50.Bb; 81.15.Hi     

Superior electromechanical performance over PZT, in lead zinc niobate (PZN)–lead zirconium titanate (PZT) thin films

Strongly oriented thin films of lead zinc niobate (PZN)–lead zirconium titanate (PZT) with (La,Sr)CoO₃ lower electrodes were grown on MgO {001} substrates by pulsed laser deposition. The films were perovskite-dominated with strong in-plane and out-of-plane orientations. Room-temperature functional characterisation indicated that the films were ferroelectric, with dielectric constant ∼550 and loss tangent ∼0.08 at 1 kHz. The crystallographic strain, as a function of applied dc field, was monitored by in situ X-ray diffraction. The maximum electric-field-induced crystallographic strain (∼0.22%) was comparable to that observed in bulk, but at significantly greater field (∼150 kV cm^-1). The effective d₃₃ value obtained from the crystallographic strain data was around 150 pm V^-1, which is high for ferroelectric thin films 400 nm in thickness. The local polarisation-switching properties of the films were investigated using a piezo-response atomic force microscope. Domain maps for a 5×5 μm² region of material were recorded as a function of dc bias, and confirmed the ferroelectric switching behaviour. PACS 81.05.Je; 81.40.Vw; 68.37.Lp     

Electric-field-induced soft-mode hardening in SrTiO3 films

We have studied electric-field-induced Raman scattering in SrTiO3 thin films using an indium-tin-oxide/SrTiO3/SrRuO3 structure grown by pulsed laser deposition. The soft mode polarized along the field becomes Raman active. Experimental data for electric-field-induced hardening of the soft modes and the tuning of the static dielectric constant are in agreement described by the Lyddane-Sachs-Teller formalism. The markedly different behavior of the soft modes in thin films from that in the bulk is explained by the existence of local polar regions.     

Highly tunable photonic crystal filter for the terahertz range

By use of an incipient ferroelectric, SrTiO3, as a defect material inserted into a periodic structure of alternating layers of quartz and high-permittivity ceramic, thermal tuning of a single defect mode over the entire lowest forbidden band was obtained. The tunability of this compact structure reached 60%.     

Polar dependent in-plane electric transport of epitaxial ZnO thin films on SrTiO(3) substrates

Polar (001) and nonpolar (110) ZnO epitaxial thin films were grown on SrTiO(3) substrates by the pulsed laser deposition method and the in-plane electric transport was investigated. Both films display semiconducting behavior. The polar thin films have linear I-V relations with mobility increasing almost linearly with temperature. In contrast, for nonpolar ZnO thin films, the I-V curves are symmetric and nonlinear with room temperature resistivity 30 times larger than that of polar thin films. We conclude that in nonpolar ZnO thin films the bound polarization charge induced barrier limits the carrier transport. Instead, for polar thin films, the polar effect on the in-plane transport is negligible, and the charged dislocation scattering is dominant. Our observations suggest the polar effect should be considered in the design of ZnO related devices.     

Strain-gradient-induced polarization in SrTiO3 single crystals

Piezoelectricity is inherent only in noncentrosymmetric materials, but a piezoelectric response can also be obtained in centrosymmetric crystals if subjected to inhomogeneous deformation. This phenomenon, known as flexoelectricity, can significantly affect the functional properties of insulators, particularly thin films of high permittivity materials. We have measured strain-gradient-induced polarization in single crystals of paraelectric SrTiO3 as a function of temperature and orientation down to and below the 105 K phase transition. Estimates were obtained for all the components of the flexoelectric tensor, and calculations based on these indicate that local polarization around defects in SrTiO3 may exceed the largest ferroelectric polarizations. A sign reversal of the flexoelectric response detected below the phase transition suggests that the ferroelastic domain walls of SrTiO3 may be polar.