In the present study, structural changes due to gradual doping of Sr in BaTiO3 were investigated by both x-ray and neutron powder diffraction techniques. Ba1-xSrxTiO3 (x=0.0, 0.5 and 1.0) samples were synthesized by PVA evaporation method and purity was confirmed by x-ray diffraction experiment. After that, neutron diffraction experiments were carried out and diffraction data were analyzed by Rietveld least-square data refinement method using the computer program RIETAN-2000 and FullProf to determine various crystallographic structural parameters. The cation and anion position coordinates were also determined from the data refinement method which confirmed that Ba and Sr atoms possess tetrahedral A site and Ti atoms possess octahedral B site for all three samples BaTiO3, Ba0.5Sr0.5TiO3, and SrTiO3, respectively. Moreover, the lattice parameter values indicate, Ba1-xSrxTiO3 structure undergoes a phase transition from tetragonal to cubic somewhere before x=0.5. The concurrences between observed and calculated profiles were excellent and well consistent with the previously reported values. Furthermore, MEM based analysis was done for charge density measurement.
The powder of barium titanate (BaTiO3) synthesized by solid state was characterised by spherical grains of the average size about 500 nm. The double mechanical activation and calcination of raw materials was necessary to receive the monophase material. In order to improve the mouldability, the obtained barium titanate powder was granulated in spray drier. Pellets and beams from BaTiO3 granulate were manufactured by both uniaxial and isostatic pressing. The properties of barium titanate material at each stage of its fabrication (powder, granulate, sintered material) influencing on its applicati…
We present a study of the local strain effects associated with vacancy defects in strontium titanate and report the first calculations of elastic dipole tensors and chemical strains for point defects in perovskites. The combination of local and long-range results will enable determination of x-ray scattering signatures that can be compared with experiments. We find that the oxygen vacancy possesses a special property -- a highly anisotropic elastic dipole tensor which almost vanishes upon averaging over all possible defect orientations. Moreover, through direct comparison with experimental mea…
We have used energy filtered x-ray photoelectron emission microscopy (XPEEM) and synchrotron radiation to measure the grain orientation dependence of the work function of a sintered niobium doped strontium titanate ceramic. A significant spread in work function values is found. Grain orientation and surface reducing/oxidizing conditions are the main factors in determining the work function. Energy filtered XPEEM looks ideally suited for analysis of other technologically interesting polycrystalline samples.
We demonstrate an approach for calculating temperature-dependent quantum and anharmonic effects with beyond density-functional theory accuracy. By combining machine-learned potentials and the stochastic self-consistent harmonic approximation, we investigate the cubic to tetragonal transition in strontium titanate and show that the paraelectric phase is stabilized by anharmonic quantum fluctuations. We find that a quantitative understanding of the quantum paraelectric behavior requires a higher-level treatment of electronic correlation effects via the random phase approximation. This approach e…
We investigated the ferroelectric properties of strontium titanate (STO) thin films deposited on SrTiO3 (001) substrate with SrRuO3 electrodes. The STO layer was grown coherently on the SrTiO3 substrate without in-plane lattice relaxation, but its out-of-plane lattice constant increased with a decrease in the oxygen pressure during deposition. Using piezoresponse force microscopy and P-V measurements, we showed that our tetragonal STO films possess room-temperature ferroelectricity. We discuss the possible origins of the observed ferroelectricity.
We study the electrocaloric effect in the classic ferroelectric BaTiO3 through a series of phase transitions driven by applied electric field and temperature. We find both negative and positive electrocaloric effects, with the negative electrocaloric effect, where temperature decreases with applied field, in monoclinic phases. Macroscopic polarization rotation is evident through the monoclinic and orthorhombic phases under applied field, and is responsible for the negative electrocaloric effect.
The surface composition of polycrystalline niobium-doped strontium titanate (SrTiO3 : Nb) is studied using X-ray photoelectron emission microscopy (XPEEM) for many grain orientations in order to characterise the surface chemistry with high spatial resolution. The surface sensitivity is maximised by the use of soft X-ray synchrotron radiation (SR). The grain orientation is determined by electron backscattering diffraction (EBSD). Stereographic plots are used to show the correlation between surface composition and orientation for several grains. Predominant surface terminations are assigned to m…
In this comment to [S. Lenjer, O. F. Schirmer, H. Hesse, and Th. W. Kool, Phys. Rev. B {\bf 66}, 165106 (2002)] we discuss the electronic structure of oxygen vacancies in perovskites. First principles computations are in favour of rather deep levels in these vacancies, and Lenjer et al suggest that the electrons' interaction energy is negative, but data on electroconductivity are against.
Monodispersed strontium titanate nanoparticles were prepared and studied in detail. It is found that ~10 nm as-prepared stoichiometric nanoparticles are in a polar structural state (with possibly ferroelectric properties) over a broad temperature range. A tetragonal structure, with possible reduction of the electronic hybridization is found as the particle size is reduced. In the 10 nm particles, no change in the local Ti-off centering is seen between 20 and 300 K. The results indicate that nanoscale motifs of SrTiO3 may be utilized in data storage as assembled nano-particle arrays in applicat…
Time-dependent speckle pattern of paraelectric barium titanate observed in a soft x-ray laser pump-probe measurement is theoretically investigated as a correlated optical response to the pump and probe pulses. The scattering probability is calculated based on a model with coupled soft x-ray photon and ferroelectric phonon mode. It is found that the speckle variation is related with the relaxation dynamics of ferroelectric clusters created by the pump pulse. Additionally, critical slowing down of cluster relaxation arises on decreasing temperature towards the paraelectric-ferroelectric transiti…
We present current-voltage studies of very thin (ca. 77 nm) barium titanate single crystals up to 1.3 GV/m applied field. These show that the mechanism of leakage current at high fields is that of space charge limited conduction (SCLC) in a regime with a continuous distribution of traps, according to the original model of Rose [Phys. Rev. 97, 1537 (1955)]. This study represents a factor of x5 in field compared with the early studies of BaTiO3 conduction [A. Branwood et al., Proc. Phys. Soc. London 79, 1161 (1962)]. Comparison is also given with ceramic multilayer barium titanate capacitors, wh…
Several defect configurations including oxygen vacancies have been investigated as possible origins of the reported room-temperature ferroelectricity of strontium titanate (STO) thin films [Appl. Phys. Letts. 91, 042908 (2007)]. First-principles calculations revealed that the Sr-O-O vacancy complexes create deep localized states in the band gap of SrTiO3 without affecting its insulating property. These results are in agreement with electronic structural changes determined from optical transmission and X-ray absorption measurements. This work opens the way to exploiting oxygen vacancies and the…
The Landau theory of phase transitions of Ba0.8Sr0.2TiO3 thin film under external electric field applied in the planar geometry is developed. The interfacial van-der-Waals field Ez=1.1x10^8 V/m oriented normal to the film-substrate interface was introduced in to the model calculation to explain experimentally observed behavior of the polarization as a function of planar electric field. The Ez - misfit strain phase diagram of the film is constructed and discussed.
The results of positron annihilation lifetime spectroscopy measurements on undoped, electron irradiated, and Nb doped SrTiO3 single crystals are reported. Perfect lattice and vacancy defect positron lifetimes were calculated using two different first-principles schemes. The Sr vacancy defect related positron lifetime was obtained from measurements on Nb doped, electron irradiated, and vacuum annealed samples. Undoped crystals showed a defect lifetime component dominated by trapping to Ti vacancy related defects.
Goldstone-mediated polar instability in hexagonal barium titanate
University of Warwick（华威大学）；Durham University（杜伦大学）；Luxembourg Institute of Science and Technology（卢森堡科学与技术研究所）；European Synchrotron Radiation Facility（欧洲同步辐射装置）；Institut Laue-Langevin（朗之万研究所）
We investigate the influence of quantum effects on the dielectric and piezoelectric properties of barium titanate in its (low-temperature) rhombohedral phase, and show the strongly anharmonic character of this system even at low temperature. For this purpose, we perform path-integral molecular-dynamics simulations under fixed pressure and fixed temperature, using an efficient Langevin thermostat-barostat, and an effective hamiltonian derived from first-principles calculations. The quantum fluctuations are shown to significantly enhance the static dielectric susceptibility (~ by a factor 2) and…
It is well known that disordered relaxor ferroelectrics exhibit local polar correlations. The origin of localized fields that disrupt long range polar order for different substitution types, however, is unclear. Currently, it is known that substituents of the same valence as Ti4+ at the B-site of barium titanate lattice produce random disruption of Ti-O-Ti chains that induces relaxor behavior. On the other hand, investigating lattice disruption and relaxor behavior resulting from substituents of different valence at the B-site is more complex due to the simultaneous occurrence of charge imbala…
The magnetic and electronic properties of strontium titanate with different carbon dopant configurations are explored using first-principles calculations with a generalized gradient approximation (GGA) and the GGA+U approach. Our results show that the structural stability, electronic properties and magnetic properties of C-doped SrTiO3 strongly depend on the distance between carbon dopants. In both GGA and GGA+U calculations, the doping structure is mostly stable with a nonmagnetic feature when the carbon dopants are nearest neighbors, which can be ascribed to the formation of a C-C dimer pair…
Multiferroicity can be induced in strontium titanate by applying biaxial strain, resulting in the coexistence of both ferroelectric and antiferrodistortive domains. The magnitude and sign of the strain imposed on the lattice by design can be used to tune the phase transitions and interactions between these two phenomena. Using optical second harmonic generation, we report a transition from centrosymmetric 4/mmm phase to ferroelectric mm2, followed by an antiferrodistortive transition to a coupled ferroelastic-ferroelectric mm2 phase in a strontium titanate thin film strained in biaxial tension…
The thermodynamic and kinetic properties of mono and di-vacancy defects in cubic (para-electric) barium titanate are studied by means of density-functional theory calculations. It is determined which vacancy types prevail for given thermodynamic boundary conditions. The calculations confirm the established picture that vacancies occur in their nominal charge states almost over the entire band gap. For the dominating range of the band gap the di-vacancy binding energies are constant and negative. The system, therefore, strives to achieve a state in which under metal-rich (oxygen-rich) condition…
For many applications, it is important to measure the local work function of a surface with high lateral resolution. Low-energy electron microscopy is regularly employed to this end since it is, in principle, very well suited as it combines high-resolution imaging with high sensitivity to local electrostatic potentials. For surfaces with areas of different work function, however, lateral electrostatic fields inevitably associated with work function discontinuities deflect the low-energy electrons and thereby cause artifacts near these discontinuities. We use ray-tracing simulations to show tha…
Previous studies of Barkhausen noise in PZT have been limited to the energy spectrum (slew rate response voltages versus time), showing agreement with avalanche models; in barium titanate other exponents have been measured acoustically, but only at ambient temperatures. In the present study we report the Omori exponent (-0.95$\pm$0.03) for aftershocks in PZT and extend the barium titanate studies to a wider range of temperature.
The phonon dispersion curves of cubic BaTiO_3 have been computed within a first-principles approach and the results compared to the experimental data. The curves obtained are very similar to those reported for KNbO_3 by Yu and Krakauer [Phys. Rev. Lett. 74, 4067 (1995)]. They reveal that correlated atomic displacements along <100> chains are at the origin of the ferroelectric instability. A simplified model illustrates that spontaneous collective displacements will occur when a dozen of aligned atoms are coupled. The longitudinal interatomic force constant between nearest neighbour Ti and O at…
Emphasizing the contribution of Professor Roger A Cowley, FRS to the Theory of Raman Scattering from crystals, the development of the Theory of Raman cattering since 1928 has been briefly discussed. Some experimental studies of Strontium Titanate using Inelastic Neutron Scattering, Raman Scattering, Electro- paramagnetic resonance measurement and X-ray & Gamma Ray techniques has been briefly discussed. Using Schwabl's semi-phenomenological theory for the soft mode and central peak, we have developed (a) a one-phonon Green's function exhibiting the three peaked structure and (b) a two phonon Gr…
Density functional theory calculations of twin-domain walls in strontium titanate are presented. The two possible domain walls are characterized. The domain wall type is set by the relative phase of the octahedral rotations in the body-centered-tetragonal SrTiO$_3$ on either side of the domain wall. The width of the domain walls is estimated to be approximately 3 nm.
Ferroelectric domain structure evolution induced by an external electric field was investigated by means of nematic liquid crystal (NLC) method in two strontium-barium niobate single crystals of nominal composition: Sr_{0.70}Ba_{0.30}Nb_{2}O_{6} (SBN:70 - relaxor) and Sr_{0.26}Ba_{0.74}Nb_{2}O_{6} (SBN:26 - ferroelectric). Our results provide evidence that the broad phase transition and frequency dispersion that are exhibited in SBN:70 crystal have a strong link to the configuration of ferroelectric microdomains. The large leakage current revealed in SBN:26 may compensate internal charges acti…
We report an experimental demonstration of thermal tuning of resonance frequency in a planar terahertz metamaterial consisting of a gold split-ring resonator array fabricated on a bulk single crystal strontium titanate (SrTiO3) substrate. Cooling the metamaterial starting from 409 K down to 150 K causes about 50% shift in resonance frequency as compare to its room temperature resonance, and there is very little variation in resonance strength. The resonance shift is due to the temperature-dependent refractive index (or the dielectric constant) of the strontium titanate. The experiment opens up…
We report self-consistent ab-initio electronic, structural, elastic, and optical properties of cubic SrTiO$_{3}$ perovskite. Our non-relativistic calculations employed a generalized gradient approximation (GGA) potential and the linear combination of atomic orbitals (LCAO) formalism. The distinctive feature of our computations stem from solving self-consistently the system of equations describing the GGA, using the Bagayoko-Zhao-Williams (BZW) method. Our results are in agreement with experimental ones where the later are available. In particular, our theoretical, indirect band gap of 3.24 eV,…
We present the first systematic {\em ab initio} study of anti-ferrodistortive (AFD) order in Ruddlesden-Popper (RP) phases of strontium titanate, Sr$_{1+n}$Ti$_n$O$_{3n+1}$, as a function of both compressive epitaxial strain and phase number $n$. We find all RP phases to exhibit AFD order under a significant range of strains, recovering the bulk AFD order as $\sim 1/n^2$. A Ginzburg-Landau Hamiltonian generalized to include inter-octahedral interactions reproduces our {\em ab initio} results well, opening a pathway to understanding other nanostructured perovskite systems.
The Born effective charge tensors of Barium Titanate have been calculated for each of its 4 phases. Large effective charges of Ti and O, also predicted by shell model calculations and made plausible by a simplified model, reflect the partial covalent character of the chemical bond. A band by band decomposition confirms that orbital hybridization is not restricted to Ti and O atoms but also involves Ba which appears more covalent than generally assumed. Our calculations reveal a strong dependence of the effective charges on the atomic positions contrasting with a relative insensitivity on isotr…
Single phase barium titanate-bismuth ferrite ((1-x)BaTi$_3$-(x)BiFe$_3$, BTO-BFO) solid solutions were prepared using citric acid and ethylene glycol assisted sol-gel synthesis method. Depending on the dopant content the samples are characterized by tetragonal, tetragonal-pseudocubic, pseudocubic and rhombohedral structure as confirmed by Raman spectroscopy and XRD measurements. An increase of the BFO content leads to a reduction in the cell parameters accompanied by a decrease in polar distortion of the unit cell wherein an average particle size increases from 60 up to 350 nm. Non zero piezor…
Raman Spectroscopic measurements are carried out to investigate the structural phase transitions as a function of composition in modified sodium niobate [(1-x) NaNbO3-xBaTiO3:NNBTx] for x=0.0 to 0.15 at room temperature. The characteristic antiferroelectric modes at around 93.4 and 123.6cm-1alongwith a mode at 155.5 cm-1were found to disappear across the structural phase transition from antiferroelectric orthorhombic phase (Pbcm) to ferroelectric orthorhombic phase (Pmc21) phase for x>0.02. The redistribution of intensities and positions of the Raman lines in bending (150-350 cm-1) and stretch…
The surfaces of metal oxides often are reconstructed with a geometry and composition that is considerably different from a simple termination of the bulk. Such structures can also be viewed as ultrathin films, epitaxed on a substrate. Here, the reconstructions of the SrTiO3 (110) surface are studied combining scanning tunneling microscopy, transmission electron diffraction, and X-ray absorption spectroscopy, and analyzed with density functional theory calculations. While SrTiO3 (110) invariably terminates with an overlayer of titania, with increasing density its structure switches from nx1 and…
The dielectric properties of strontium titanate (SrTiO$_3$) have previously been reported from room temperature to low temperatures with conflicting results. In this work, precision measurement of the permittivity is undertaken by simultaneously measuring transverse electric and transverse magnetic resonant modes within a single crystal. It is unequivocally shown that the permittivity is isotropic at room temperature with a permittivity of order $316.3\pm2.2$ by measuring multiple modes of different electric field polarisations. As the crystal is cooled to 5 K and undergoes well known phase tr…
The local structure and oxidation state of the cobalt impurity in SrTiO$_3$ is studied by X-ray absorption fine structure (XAFS) spectroscopy. The synthesis conditions, under which cobalt predominantly (up to 76%) substitutes the atoms at the $A$ site of the perovskite structure, is found for SrTiO$_3$(Co) samples. By varying the synthesis conditions, it is possible to appreciably change the ratio between the concentrations of cobalt atoms incorporated into the $A$ and $B$ sites. It is established that the oxidation state of cobalt is +2 at the $A$ site and +3 at the $B$ site. It is revealed t…
Strontium titanate is a wide-gap semiconductor avoiding a ferroelectric instability thanks to quantum fluctuations. This proximity leads to strong screening of static Coulomb interaction and paves the way for the emergence of a very dilute metal with extremely mobile carriers at liquid-helium temperature. Upon warming, mobility decreases by several orders of magnitude. Yet, metallicity persists above room temperature even when the apparent mean-free-path falls below the electron wavelength. The superconducting instability survives at exceptionally low concentrations and beyond the boundaries o…
Hexagonal BaTiO_3 undergoes a structural phase transition to an orthorhombic C222_1 phase at T_0 = 222 K. The transition is driven by a soft optical mode with E_2u symmetry whose couplings force the appearance of a spontaneous E_2g strain (improper ferroelastic character). Staying within the same E_2u subspace, the system could in principle settle into a second (not observed) orthorhombic phase (Cmc2_1). We have carried out a first-principles investigation of these questions, studying the structure of the existing C222_1 and the "virtual" Cmc2_1 phases, and describing the spontaneous E_2g stra…
Stoichiometric Epitaxial Strontium Titanate Thin Films on Silicon by High-Temperature Sr Segregation
Imec；Department of Materials Engineering (MTM), KU Leuven（荷语鲁汶大学材料工程系）；Physics Department, Jean Monnet University（圣艾蒂安让·穆内大学物理系）；Department of Information Technology (INTEC), Photonics Research Group, Ghent University（根特大学信息与科技学院光子学研究组）
The experimentally observed temperature dependence of the quartic coefficients in the Landau-Devonshire expansion for BaTiO_3 is naturally accounted for within a proper fluctuation model. It is explained, in particular, why one of the quartic coefficients varies with temperature above T_c while the second is constant. The tetragonal phase in BaTiO_3 is argued to exist essentially due to the thermal fluctuations, while the true Landau-Devonshire expansion with temperature-independent coefficients favours the rhombohedral ferroelectric phase. Certain conclusions concerning the temperature depend…
Polarized Raman spectra of the epitaxial Ba0.5Sr0.5TiO3 film, bi-color BaTiO3/Ba0.5Sr0.5TiO3 superlattice, and tri-color BaTiO3/Ba0.5Sr0.5TiO3/SrTiO3 superlattice were studied in a broad temperature range of 80-700 K. Based on the temperature dependence of the polar modes we determined the phase transitions temperatures in the studied heterostructures. In the sub-THz frequency range of the Y(XZ)Y spectra, we revealed the coexistence of the Debye-type central peak and soft mode in bi-color BaTiO3/Ba0.5Sr0.5TiO3 superlattice.
We investigate the effects of strain on superconductivity with particular reference to SrTiO$_3$. Assuming that a ferroelectric mode that softens under tensile strain is responsible for the coupling, an increase in the critical temperature and range of carrier densities for superconductivity is predicted, while the peak of the superconducting dome shifts towards lower carrier densities. Using a Ginzburg-Landau approach in 2D, we find a linear dependence of the critical temperature on strain: if the couplings between the order parameter and strains in different directions differ while their sum…
In this Article, we report on the observation of ferroelectric domain pattern in the whole volume of the ferroelectric barium titanate single crystal by means of the digital holographic microscopy (DHM). Our particular implementation of DHM is based on the Mach-Zehnder interferometer and the numerical processing of data employs the angular spectrum method. A modification of the DHM technique, which allows a fast and accurate determination of the domain walls, i.e. narrow regions separating the antiparallel domains, is presented. Accuracy and sensitivity of the method are discussed. Using this …
We investigated the nanosecond-scale time decay of the blue-green light emitted by nominally pure SrTiO$_3$ following the absorption of an intense picosecond laser pulse generating a high density of electron-hole pairs. Two independent components are identified in the fluorescence signal that show a different dynamics with varying excitation intensity, and which can be respectively modeled as a bimolecular and unimolecolar process. An interpretation of the observed recombination kinetics in terms of interacting electron and hole polarons is proposed.
We report measurements of the thermal Hall effect in single crystals of both pristine and isotopically substituted strontium titanate. We discovered a two orders of magnitude difference in the thermal Hall conductivity between $SrTi^{16}O_3$ and $^{18}O$-enriched $SrTi^{18}O_3$ samples. In most temperature ranges, the magnitude of thermal Hall conductivity ($κ_{xy}$) in $SrTi^{18}O_3$ is proportional to the magnitude of the longitudinal thermal conductivity ($κ_{xx}$), which suggests a phonon-mediated thermal Hall effect. However, they deviate in the temperature of their maxima, and the therma…
The stability, electronic structure, optical and thermoelectric properties of Te-doped BaTiO3 are investigated by first-principal calculation based on the density functional theory and Boltzmann transport theory implemented in WIEN2K and BoltzTraP simulation program. This study is carried out by applying LDA + TB-mBJ potential. Formation energy of each doped structure is calculated to examine the stability and feasibility of the synthesis. Incorporating Te into BaTiO3 efficiently reduces the electronic band gap and the level of band gap reduction can be controlled by varying the amount of dopa…
