A comparative microstructural study of compositionally up- and down-graded (Ba,Sr)TiO3 thin films epitaxially grown on (La,Sr)CoO3-covered MgO(100) substrates by pulsed laser deposition

We report a comparative study of the microstructure of compositionally graded (Ba_1-xSr_x)TiO₃ (BST) films with two compositionally graded directions, up and down, with respect to the substrate, which were deposited epitaxially on (La,Sr)CoO₃ (LSCO)-covered MgO(100) single-crystal substrates by pulsed laser deposition. Cross-sectional transmission electron microscopy (TEM) images and electron diffraction show that the graded films grow epitaxially with their (100) plane parallel to the (100) surface of the MgO single-crystal substrate, and with an in-plane orientation relationship of 〈001〉_BST//〈001〉_LSCO//〈001〉_MgO. The crystalline quality and surface morphology of the graded films are closely related to the direction of the compositional gradient built into the graded films. Down-graded films (starting with a BaTiO₃ layer at the film/substrate interface) have a much better crystalline quality and a smoother surface than the up-graded films (starting with a (Ba_0.75Sr_0.25)TiO₃ layer at the film/substrate interface). Obviously, the BaTiO₃ bottom layer in the down-graded film acts not only as a part of the graded film but also as an excellent seeding layer to enhance the crystallization of the subsequent film layers, resulting in a high crystalline quality of the down-graded film and an enhanced dielectric behavior. Planar (high-resolution) TEM images also demonstrate that down-graded films have a larger, and more uniform, grain size than up-graded films, and that the latter contain voids. PACS 81.15.-z; 77.55.+f; 68.37.Lp; 61.14.-x     

Effective Pyroelectric Coefficient and Polarization Offset of Compositionally Step-like Graded Ferroelectric Structures

In this paper, the effective pyroelectric coefficient and polarization offset of the compositionally step-like graded multilayer ferroelectric structures have been studied by use of the first-principles approach. It is exhibited that the dielectric gradient has a nontrivial influence on the effective pyroelectric coefficient, but has a little influence on the polarization offset; and the polarization gradient plays an important role in the abnormal hysteresis loop phenomenon of the compositionally step-like graded ferroelectric structures. Moreover, the origin of the polarization offset is explored, which can be attributed to the polarization gradient in the compositionally step-like graded structure.     

Theory of giant electromechanical response from ferroelectric bilayers with polydomain structures due to interlayer and interdomain coupling

The effect of interdomain ferroelastic coupling in ferroic multilayers is investigated theoretically. Specifically, we use nonlinear thermodynamics to analyze a heteroepitaxial ferroelectric PbZrxTi1-xO3 (PZT) bilayer consisting of (001) tetragonal (T) PZT and (001) rhombohedral (R) PZT films. We predict for certain misfit strain regimes that interlayer and interdomain interactions lead to an adaptive domain structure in both the T and R layers and result in significant enhancements in the piezoelectricity compared to single-layer films. Our results demonstrate that electrostatic, magnetostatic, and elastic interactions in ferroic multilayers can be a generic route to generate ultrahigh susceptibilities.     

Effect of concentration gradient on the first-, second- and third-order polarizabilities

The effect of concentration gradients on the polarizabilities of chemical systems of mixed composition is examined theoretically. It is found that the first-, second- and third-order polarizabilities all exhibit linear dependences on concentration gradient but nonlinear dependences on dielectric gradient. Furthermore, sample calculations imply that under selected conditions, concentration and/or dielectric gradient effects should be readily observable experimentally and indeed, under some conditions could dominate the experimental response. Examples of systems that might display the predicted effects include compositionally graded polymer, semiconductor, composite films, as well as thermally graded liquid mixtures and colloidal suspensions.     

Small- and strong-signal dielectric response in a single-crystal film of partially deuterated betaine phosphite

Poly- and single-crystal films of betaine phosphite deuterated to ∼20% have been grown by evaporation on NdGaO₃ (001) substrates with a preliminarily deposited planar interdigital structure of electrodes. The small-signal dielectric response in the 0.1–100.0-kHz frequency range has revealed a strong anomaly in capacitance upon the transition of the films to the ferroelectric state. Application of a bias field brings about suppression and a slight shift of the dielectric anomaly toward higher temperatures. The strong-signal dielectric response has been studied by the Sawyer-Tower method over the frequency range 0.06–3.00 kHz both in the para- and ferroelectric phases. In contrast to the case of a plane-parallel capacitor, in the planar structure studied, the dielectric hysteresis loops exhibit a very small coercivity at low frequencies, which grows with increasing frequency. This difference should be assigned to different domain structures formed in a planeparallel capacitor and in a planar structure in a saturating field. The growth of hysteresis with increasing frequency in a planar structure is considered to be associated with the domain wall motion.     

Nonlinear dielectric properties of planar structures based on ferroelectric betaine phosphite films

Ferroelectric films of partly deuterated betaine phosphite are grown on NdGaO₃(001) substrates with an interdigitated system of electrodes on their surfaces by evaporation at room temperature. These films have a high capacitance in the ferroelectric phase transition range. The dielectric nonlinearity of the grown structures is studied in small-signal and strong-signal response modes and in the intermediate region between these two modes by measuring the capacitance in a dc bias field, dielectric hysteresis loops, and the Fourier spectra of an output signal in the Sawyer-Tower circuit. In the phase transition range, the capacitance control ratio at a bias voltage U _bias = 40 V is K ? 7. The dielectric nonlinearity of the structures in the paraelectric phase is described by the Landau theory of second-order phase transitions. The additional contribution to the nonlinearity in the ferroelectric phase is related to the motion of domain walls and manifests itself when the input signal amplitude is higher than U _st ～ 0.7–1.0 V. The relaxation times of domain walls are determined from an analysis of the frequency dependences of the dielectric hysteresis.     

Preparation and characterization of PbTiO3–epoxy resin compositionally graded thick films

The preparation and properties of compositionally graded PbTiO₃ (PT)–epoxy resin (EPR) composite thick films are reported in this study. Various graded specimens were prepared using gravity casting method by embedding PT powders into the EPR matrix. The existence of a graded structure with two distinct phases, a good intermixing, some air pores, and different morphologies, was confirmed by scanning electron microscopy micrographs. The dielectric constants of these composites have values in the range 5–12 at the frequency of ～10⁴?Hz and about 3–13 at ～5?×?10^8?Hz. The composites with permittivity gradient act as a natural impedance match system in the frequency range 2–4?GHz, resulting in very low reflections. Therefore, the compositionally graded PT–EPR composite thick films are suitable as adapting impedance materials for microwave applications.     

Piezoelectric non-linearity in PbSc0.5Ta0.5O3 thin films

Epitaxial (001)-oriented PbSc_0.5Ta_0.5O₃ (PST) thin films were deposited by pulsed laser deposition. Local piezoelectric investigations performed by piezoelectric force microscopy show a dual slope for the piezoelectric coefficient. A piezoelectric coefficient of 3 pm/V was observed at voltages up to 0.8 V. However, at voltages above 0.8 V, there is a steep increase in piezoelectric coefficient mounting to 23.2 pm/V. This nonlinear piezoelectric response was observed to be irreversible in nature. In order to better understand this nonlinear behavior, voltage dependent dielectric constant measurements were performed. These confirmed that the piezoelectric non-linearity is indeed a manifestation of a dielectric non-linearity. In contrast to classical ferroelectric systems, the observed dielectric non-linearity in this relaxor material cannot be explained by the Rayleigh model. Thus the dielectric non-linearity in the PST films is tentatively explained as a manifestation of a percolation of the polar nano regions.     

Temperature-dependent ferroelectric and dielectric properties of Bi3.25La0.75Ti3O12 thin films

To investigate temperature-dependent ferroelectric and dielectric properties of ferroelectric films, Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were prepared on Pt-coated silicon substrates by pulsed laser deposition. The ferroelectric and dielectric behaviors have been studied in a wide temperature range from 80 K to room temperature. The saturated polarization (P_sat) decreases with decreasing temperature and decreasing electric field, whereas remnant polarization (P_r) shows a more complex temperature dependence. These results, which can be well explained based on a temperature-dependent charged defects-domain wall interaction model, might be helpful for further understanding the domain switching behavior. Based on these results, an alternative way to investigate temperature-dependent ferroelectric fatigue is proposed and experimentally carried out. The measured fatigue rate is found to be linearly dependent on temperature, consistent with the report on Pb(Zr,Ti)O₃ films. Temperature-dependent dielectric measurements of the films further confirm the above explanation.     

杂质分布设计对钛酸锶钡薄膜结构和性能的影响

用溶胶-凝胶方法在Pt/Ti/SiO₂/Si衬底上制备了Na⁺的不同浓度均匀掺杂和成分梯度掺杂(上梯度)钛酸锶钡(Ba_0.25Sr_0.75TiO₃)薄膜.电性能测试表明随着均匀掺杂浓度的增加，薄膜介电常数和损耗都减小，而漏电流先减小(掺杂浓度小于2.5mol%时)后又逐渐增加.场发射扫描电镜分析表明，均匀掺杂浓度增加到2.5mol%后薄膜表面呈疏松多孔状结构，这可能是导致漏电流又逐渐增大的原因.Na⁺的上梯度掺杂避免了掺杂浓度增加到2.5mol%后薄膜生长过程中出现的孔洞现象，于是薄膜的综合电性能得到了进一步提高.深入、系统地分析了杂质不同分布方式对薄膜结构和性能有不同影响的原因.     

Preparation of epitaxial compositionally graded (Ba1-xSrx)TiO3 thin films with enhanced dielectric properties

Epitaxial compositionally graded (Ba_1-xSr_x)TiO₃ (BST) (0.0x0.25) thin films were deposited on (100) LaAlO₃ substrates by pulsed laser ablation, the substrates having bottom electrodes made of 100-nm-thick conductive La_0.5Sr_0.5CoO₃ (LSCO). Extensive X-ray diffraction, rocking-curve, and -scan studies indicate that the graded films are (100)-oriented and exhibit good in-plane relationships of [010]_BST//[010]_LAO and [001]_BST//[001]_LAO. For the up-graded films with barium concentration (1-x) increasing across the film thickness in the direction from the film/substrate interface to the film surface, the full width at half maximum of the BST film (200) rocking curve and the surface roughness, examined by atomic force microscopy, were larger than those of the down-graded films with barium concentration decreasing from the film/substrate interface to the film surface. The dielectric properties of the graded films, measured using vertical structures, show that at room temperature, the dielectric constant (_r) and dissipation factor (cos) at 100 kHz were 380 and 0.013 for the up-graded films, and 650 and 0.010 for the down-graded films, respectively. The dielectric behavior was enhanced in the down-graded films, which was attributed to the fact that the pure BaTiO₃ layer in the down-graded BST films not only serves as a bottom layer but also acts as an excellent seeding layer for enhancing subsequent film growth, leading to better film crystallinity and larger grain sizes in the down-graded films. The graded BST films undergo a diffuse phase transition, giving a broad, flat capacitance-versus-temperature profile. With such a graded structure, it is possible to build a dielectric thin-film capacitor having a capacitance which has a low temperature dependence over a broad temperature regime. PACS 77.55.+f; 68.55.Jk; 81.15.Fg     

Pyroelectricity and compositionally graded ferroelectrics: a brief review of our theoretical approach

In the last decade, the properties of compositionally graded ferroelectric films (CGFF) have become an essential and very often addressed research topic of ferroelectric materials. Many theoretical discussions of CGFF have been already presented, however there are several drawbacks. This is the summary of the main results of the authors: (a) it is essential that the classical Landau free energy density will be modified by an additional term of the γP?grad?c type (c is the composition ratio of different atoms), (b) the experimentally observed shift of hysteresis loop along the polarization axis must be necessarily described by a kinetic equation. Our approach is limited, being based on the assumption that CGFF is an ideally nonconductive material. In this article we compare our approach to the available theories which consider the CGFF to be a semiconductor.     

Switching time dispersion and retention of bistable states in Langmuir-Blodgett ferroelectric films

Polarization switching and retention of each of the two polarized states in Langmuir—Blodgett (LB) ferroelectric films are studied using nonlinear dielectric spectroscopy. It is found that polarized states can be preserved for a long time, but the polarization dynamics in 10–40-nm-thick LB films is characterized by a considerable switching-time dispersion. In addition, ferroelectric LB films exhibit clearly manifested asymmetry of switching to states with opposite directions of polarization. To explain the experimental results, a polarization-switching model is proposed that takes into account the energy of interaction of a ferroelectric polymer with boundary surfaces. The effect of inhomogeneity of the LB film structure on the ferroelectric switching dynamics is also discussed.     

Pseudo-spin model of compositionally graded ferroelectrics

Recently, much attention has been focused on the study of compositionally graded ferroelectric films (CGFF). We devote this article to the microscopic theory of CGFF. Our theory is based on the transverse Ising pseudo-spin model. However the Hamiltonian used in recent papers does not contain the linear term in pseudo-spins. We show that it is necessary to modify the Ising Hamiltonian for homogenous material by addition of linear term in pseudo-spin. This term corresponds to the energy of the equivalent external field. Due to this term polarization is also included in the paraelectric phase.     

溶胶-凝胶法制备Pb(Zr1?xTix)O3复合梯度薄摸以及介电与热释电特性

"在Pt/Ti/SiO2/Si基片上用溶胶-凝胶法生长制备了PZT(Pb(Zr1-xTix)O3)复合梯度铁电薄膜． 薄膜最终结构由6层组成,"向上"梯度薄膜在Pt底电极上的第一层从PbZrO3开始,顶层是PZT(50/50),即第一层是PbZrO3,第二层PZT90/10 (10%Ti),第三层是PZT80/20,第四层PZT70/30,第五层PZT60/40,第六层PZT50/50．每一层与此相反的是"向下"梯度PZT薄膜．用X射线衍射、俄歇电子能谱和阻抗分析来研究梯度薄膜的结构与介电特性．600     

Ionic polarizability of conductive metal oxides and critical thickness for ferroelectricity in BaTiO3

We report a first-principles investigation of ultrathin BaTiO(3) films with SrRuO(3) electrodes. We find that the ionic relaxations in the metal-oxide electrode play a crucial role in stabilizing the ferroelectric phase. Comparison with frozen-phonon calculations shows that the degree of softness of the SrRuO(3) lattice has an essential impact on the screening of ferroelectric polarization in BaTiO(3). The critical thickness for ferroelectricity in BaTiO(3) is found to be 1.2 nm. The results of our calculations provide a possible explanation for the beneficial impact of oxide electrodes on the switching and dielectric properties of ferroelectric capacitors.     

Formation and thickness evolution of periodic twin domains in manganite films grown on SrTiO3(001) substrates

We present an extended synchrotron x-ray scattering study of the structure of thin manganite films grown on SrTiO3(001) substrates and reveal a new kind of misfit strain relaxation process which exploits twinning to adjust lattice mismatch. We show that this relaxation mechanism emerges in thin films as one-dimensional twinning waves which freeze out into a twin domain pattern as the manganite film continues to grow. A quantitative microscopic model which uses a matrix formalism is able to reproduce all x-ray features and provides a detailed insight into this novel relaxation mechanism. We further demonstrate how this twin angle pattern affects the transport properties in these functional films.     

Highly Strained Si Films with Ultra-low Dislocation Density Grown on Virtual Substrates of Thin Thickness

By using compositionally graded SiGe films as virtual substrates, tensile strained Si films with the strain of 1.5% and the threading dislocation density less than 1.0 × 10^5 cm-2 are successfully grown in micron size windows by molecular beam epitaxy （MBE）. The thickness of the virtual substrates was only 33Onto. On the surface of the s-Si films no cross-hatched lines resulting from misfit dislocations could be observed. We attribute these results to the edge-induced strain relaxation of the epitaxial films in windows, and the patterned virtual substrates with compositionally graded SiGe films.     

Influence of ambient oxygen pressure on the preferred orientation, microstructures, and dielectric properties of (Ba1-xSrx)TiO3 thin films with compositionally graded structures

Compositionally graded (Ba_1-xSr_x)TiO₃ (BST) thin films, with x decreasing from 0.25 to 0.0, were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by pulsed-laser ablation at 600 °C and under ambient oxygen pressures ranging from 50 to 400 mTorr. The influence of the ambient gas pressure on the preferred orientation, microstructures, and dielectric properties of compositionally graded BST films was investigated by X-ray diffraction, scanning electron microscopy, and dielectric frequency spectra, respectively. As the ambient oxygen pressure was increased, the preferred orientation evolved in the order: (100)+(110)(110)+(111) random orientation, and the surface roughness of the graded BST films also increased. The graded BST films deposited at high ambient oxygen pressures (300400 mTorr) exhibited a grainy structure with polycrystalline grains throughout the film thickness, whereas the graded films deposited at low ambient oxygen pressures (50200 mTorr) possessed a columnar structure. The evolution of the microstructure was ascribed to the different physical and chemical properties of the species that were incident onto the substrates at the various oxygen pressures. The dielectric properties of the graded BST films were dependent upon the ambient oxygen pressures. The graded BST films deposited at 200 mTorr exhibited the highest dielectric constant. PACS 77.55.+f; 77.22.Ch; 81.15.Fg