The optical control of domain structures in ferroelectrics is of great interest. In the present work, we demonstrate the reliable creation of charged domain walls - conductive channels in otherwise insulating barium titanate - by a combined effect of light and electric field. We propose a scenario for the documented process, in which the bulk photovoltaic effect plays the key role, providing charge screening at the walls. Our scenario is supported by the results of phase-field simulations. The results are of interest for future reconfigurable electronic and opto-electronic devices.
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 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.
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.
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…
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.
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 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…
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$0.03) for aftershocks in PZT and extend the barium titanate studies to a wider range of temperature.
The phonon dispersion curves of cubic BaTiO_3 have been computed within a first-principles approach and the results compared to the experimental data. The curves obtained are very similar to those reported for KNbO_3 by Yu and Krakauer [Phys. Rev. Lett. 74, 4067 (1995)]. They reveal that correlated atomic displacements along <100> chains are at the origin of the ferroelectric instability. A simplified model illustrates that spontaneous collective displacements will occur when a dozen of aligned atoms are coupled. The longitudinal interatomic force constant between nearest neighbour Ti and O at…
The Born effective charge tensors of Barium Titanate have been calculated for each of its 4 phases. Large effective charges of Ti and O, also predicted by shell model calculations and made plausible by a simplified model, reflect the partial covalent character of the chemical bond. A band by band decomposition confirms that orbital hybridization is not restricted to Ti and O atoms but also involves Ba which appears more covalent than generally assumed. Our calculations reveal a strong dependence of the effective charges on the atomic positions contrasting with a relative insensitivity on isotr…
Single phase barium titanate-bismuth ferrite ((1-x)BaTi$_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…
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…
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…
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.
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 …
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…
The bulk photovoltaic effect (BPE) leads to the generation of a photocurrent from an asymmetric material. Despite drawing much attention due to its ability to generate photovoltages above the band gap ($E_g$), it is considered a weak effect due to the low generated photocurrents. Here, we show that a remarkably high photoresponse can be achieved by exploiting the BPE in simple planar BaTiO$_3$ (BTO) films, solely by tuning their fundamental ferroelectric properties via strain and growth orientation induced by epitaxial growth on different substrates. We find a non-monotonic dependence of the r…
Correct phenomenological description of ferroelectric phase transitions in barium titanate requires accounting for eighth-order terms in the free energy expansion, in addition to the conventional sixth-order contributions. Another unusual feature of BaTiO_3 crystal is that the coefficients B_1 and B_2 of the terms P_x^4 and P_x^2*P_y^2 in the Landau expansion depend on the temperature. It is shown that the temperature dependence of B_1 and B_2 may be caused by thermal fluctuations of the polarization, provided the fourth-order anharmonicity is anomalously small, i. e. the nonlinearity of P^4 t…
Precise specific heat of barium titanate single crystals of different quality has been measured with special attention to the temperature region above the ferroelectric phase transition. It is shown that excess specific heat of the multiaxial barium titanate in the paraelectric phase has a fluctuation nature and its temperature dependence is in accordance with the theoretical predictions of Levanyuk theory for multiaxial ferroelectrics. In this study the first observation of fluctuation contribution to the specific heat is presented.
The bandgap energy values for the ferroelectric BaTiO3-based solid solutions with isovalent substitution Ba1-x SrxTiO3, BaZrxTi1-xO3 and BaSnxTi1-xO3 were determined using diffuse reflectance spectra. While the corresponding unit cell volume follows Vegard's law in accordance with the different ionic radii of the ionic substitutions, the bandgap values depict non-linear compositional dependences for all the solid solutions. The effect is considerably large for BaZrxTi1-xO3 and BaSnxTi1-xO3 solutions, depicting a bandgap linear compositional dependence up to x=0.6, for x>0.6 BaZrxTi1-xO3 compou…
First principle calculations were performed to study the ground state electronic properties of Barium titanate within the density functional theory (DFT). In our DFT computations, we used Vosko-Wilk-Nusair correlation energy functional and generalized gradient approximation (GGA) exchange and correlation energy functional as suggested by Perdew and Wang (PWGGA). The band structure, total density of states (DOS) and partial DOS have been systematically conducted to investigate the electronic configuration of this prototype ferroelectric perovskits compound. The band gap was 1.92 eV within our a…
Electric Charge Transport and Dielectric Properties of the Barium Titanate Ceramics Obtained by Spark-Plasma Sintering with Different Carbon Content
Institute of Physics of the National Academy of Sciences of Ukraine（乌克兰国家科学院物理研究所）；Educational Scientific Institute of High Technologies, Taras Shevchenko National University of Kyiv（基辅塔拉斯舍甫琴科国立大学高等技术教育科学研究所）；Frantsevich Institute for Problems in Materials Science, National Academy of Sciences of Ukraine（乌克兰国家科学院弗兰采维奇材料科学问题研究所）；Department of Chemistry, Stockholm University（斯德哥尔摩大学化学系）；Department of Physical Materials Science and Heat Treatment, National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”（乌克兰国立技术大学“伊戈尔·西科尔斯基基辅理工学院”物理材料科学与热处理系）
Impact of Carbon Contamination on the Low-Temperature Electric Conduction of the Spark-Plasma Sintered Barium Titanate Ceramics
Institute of Physics of the National Academy of Sciences of Ukraine（乌克兰国家科学院物理研究所）；Frantsevich Institute for Problems in Materials Science, National Academy of Sciences of Ukraine（乌克兰国家科学院弗兰特谢维奇材料科学问题研究所）；V. Lashkarev Institute of Semiconductor Physics, National Academy of Sciences of Ukraine（乌克兰国家科学院瓦·拉舍列夫半导体物理研究所）
Ba{[Gax,Tax]Ti(1-2x)}O3 ceramics with x equal to 0, 0.0025, 0.005, 0.01, 0.025 and 0.05 have been prepared by conventional solid-state reaction. Structural and dielectric characterization have been performed to investigate the effect of dipole-pair substitution concentration on the macroscopic dielectric properties. Ba{[Gax,Tax]Ti(1-2x)}O3 evolves from a classic ferroelectric to a diffuse phase transition (DPT) as x increases. Ba{[Gax,Tax]Ti(1-2x)}O3 for x > or = 0.01 possesses diffuseness parameters comparable to Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) and recently reported (Ba0.97Pr0.03)(Ti0.9425Ce…
Hybrid Barium Titanate Waveguide Designs For Efficient Nonlinear Frequency Conversion
Fraunhofer Institute for Applied Optics and Precision Engineering IOF（弗劳恩霍夫应用光学和精密工程研究所）；Institute of Applied Physics, Abbe Center of Photonics, Friedrich Schiller University Jena（耶拿弗里德里希·席勒大学阿贝光子学中心应用物理研究所）；Max Planck School of Photonics（马克斯·普朗克光子学校）
Diluted magnetic semiconductors possessing intrinsic static magnetism at high temperatures represent a promising class of multifunctional materials with high application potential in spintronics and magneto-optics. In the hexagonal Fe-doped diluted magnetic oxide, 6H-BaTiO$_{3-δ}$, room-temperature ferromagnetism has been previously reported. Ferromagnetism is broadly accepted as an intrinsic property of this material, despite its unusual dependence on doping concentration and processing conditions. However, the here reported combination of bulk magnetization and complementary in-depth local-p…
We have investigated the size effect in lead zirconate titanate (PZT) thin films with a range of manganese (Mn) doping concentrations. We found that the size effect in the conventional Pt/PZT/Pt thin-film capacitors could be systematically reduced and almost completely eliminated by increasing Mn doping concentration. The interfacial layer at the electrode-film interface appears to disappear almost entirely for the PZT films with 2% Mn doping levels, confirmed by the fits using the conventional in-series capacitor model. Our work indicates that the size effect in ferroelectrics is extrinsic in…
Following the recent discovery of a bulk photovoltaic effect in the Pb[(Mg1/3Nb2/3)0.68Ti0.32]O3 crystal, we report here more than one order of magnitude improvement of photovoltaicity as well as its poling dependence in the related composition of lead magnesium niobate-lead titanate noted Pb[(Mg1/3Nb2/3)0.7Ti0.30]O3. Photocurrent measurements versus light intensity reveal a fascinating hysteretic charge carriers dynamics clearly demonstrating charge generation, trapping and release processes.
Ferroelectric photovoltaic materials are an alternative to semiconductor-based photovoltaics and offer the advantage of above bandgap photovoltage generation. However, there are few known compounds, and photovoltaic efficiencies remain low. Here, we report the discovery of a photovoltaic effect in undoped lead magnesium niobate-lead titanate crystal and a significant improvement in the photovoltaic response under suitable electric fields and temperatures. The photovoltaic effect is maximum near the electric-field-driven ferroelectric dipole reorientation, and increases threefold near the Curie…
This study is carried out using first principles density functional theory calculations within gpaw code. Atomic size effect is analyzed and investigated by doping either Li, Cs or both on Barium doped BiFeO$_3$ (BFO) which belongs to monoclinic $P2_1/m$ space group. The calculated results reveal that Cs doped BFO had significantly improved photocurrent density seemingly due to broadened absorption peaks and biplasmons generation. Co-doping two atoms with large size difference have a significant effect on plasmon width and peak than doping with a single and small sized atom. At higher photon e…
Phonon Hall effect (PHE) has attracted a lot of attention in recent years with many theoretical and experimental explorations published. While experiments work on complicated materials, theoretical studies are still hovering around the phenomenon-based models. Moreover, previous microscopic theory was found unable to explain large thermal Hall conductivity obtained by experiments in strontium titanate (STO). Therefore, as a first attempt to bridge this gap, we implement first-principles calculations to explore the PHE in real materials. Our work provides a new benchmark of the PHE in sodium ch…
We present a first-principles study of 180-degree ferroelectric domain walls in tetragonal barium titanate. The theory is based on an effective Hamiltonian that has previously been determined from first-principles ultrasoft-pseudopotential calculations. Statistical properties are investigated using Monte Carlo simulations. We compute the domain-wall energy, free energy, and thickness, analyze the behavior of the ferroelectric order parameter in the interior of the domain wall, and study its spatial fluctuations. An abrupt reversal of the polarization is found, unlike the gradual rotation typic…
Vortices consisting of $90^\circ$ quadrant domains are rarely observed in ferroelectrics. Although experiments show polarization flux closures with stripe domains, it is as yet unclear why pure single vortices are not commonly observed. Here we model and explore the energy of polarization patterns with vortex and stripe domains, formed on the square cross-section of a barium titanate nanowire. Using phase-field simulations, we calculate the associated energy of polarization patterns as a function of nanowire width. Further, we demonstrate the effects of surface energy and electrical boundary c…
The influence of flexoelectric coupling on the internal structure of neutral domain walls in tetragonal phase of perovskite ferroelectrics is studied. The effect is shown to lower the symmetry of 180-degree walls which are oblique with respect to the cubic crystallographic axes, while {100} and {110} walls stay "untouched". Being of the Ising type in the absence of the flexoelectric interaction, the oblique domain walls acquire a new polarization component with a structure qualitatively different from the classical Bloch-wall structure. In contrast to the Bloch-type walls, where the polarizati…
