0000000000132710
AUTHOR
Vismants Zauls
Distribution of relaxation times in 0.5PMN-0.5PSN ceramics
Dielectric properties of chemically ordered and disordered 0.5PbMg1/3Nb2/3O3-0.5 PbSc1/2Nb1/2O3 (0.5PMN-0.5PSN) ceramics were investigated in frequency range from 20 Hz to 3 GHz by dielectric spectroscopy. The broad dielectric dispersion, similar to this typically obtained for relaxor ferroelectrics (RFE), was observed in both ceramics below 350 K. The frequency dependence of dielectric permittivity of these ceramics were analyzed in terms of the distribution of relaxation times and showed the splitting into two components at lower temperatures. The longest relaxation times part slows down following Vogel-Fulcher law with lower freezing temperature compare with typical RFE like PbMg1/3Nb2/3…
Influence of Structure Ordering, Defects and External Conditions on Properties of Ferroelectric Perovskites
Results of comprehensive studies of the (A’A“)(B’B”)O3-ferroelectric perovskites are reported. Examined compositions include Pb1-xLax(Zr0.65Ti0.35)1-x/4O3(PLZT), PbSc0.5Nb0.5O3(PSN), PbSc0.5Ta0.5O3(PST), and PMNT, PSNT and PLuNT pseudo-binary systems exhibiting pronounced dielectric, electrooptical, and electromechanical properties. Degree of ordering in the materials has been varied by chemical composition (modification, isomorphic ion substitution), by variation of technology (hot-pressing, specific thermal treatment, thin films), and by irradiation of different kind and intensity (γ-rays, electrons, neutrons).
Synthesis, modelling and characterisation of novel non-linear optical polymer containing indandionylpyridinium betaine units
Abstract In the present article we report about the synthesis, quantum chemical model calculations and non-linear optical characterisation of a novel polyurethane based polymer — a bipolar organic compound N -(indan-1,3-dion-2-yl)-4- N ′, N ′-dialkyaminopyridinium betaine (IPB) containing charged electron donor and electron acceptor groups covalently bonded to polyurethane polymer backbone. This newly synthesised IPB containing polymer can be regarded as a promising thermally stable organic non-linear optical material with a long time performance for photonics applications.
Effects of structure ordering, structure defects and external conditions on properties of complex ferroelectric perovskites
Abstract Structural rearrangements in lead-containing (A‘A’) (B’B“)O3 type perovskite compounds are caused by technological treatment, high-energy radiation and ambient conditions. Variation of structure ordering along with modification (substituted or defected solid solutions) may provide promising compositions for applications, e.g., cascade microcryogenic devices (PST solid solutions); efficient piezoelectric materials – here the new (1 – x)Pb(Lu1/2Nb1/2)O3 – xPbTiO3 system in the morphotropic region. The maximum values of the electromechanical coupling coefficients kp = 0·663, kt = 0·481, k 31 = 0·355 were attained in compositions PLuNT 59/41 (Tm = 353°C) near the morphotropic phase bou…
Formation of Optical Gradient in Chemical Solution-Derived PbZr[sub 0.52]Ti[sub 0.48]O[sub 3] Thin Films: Spectroscopic Ellipsometry Investigation
Investigation using a variable angle spectroscopic ellipsometer revealed the influence of sample preparation conditions on sol-gel PbZr 0.52 Ti 0.48 O 3 (PZT 52/48) thin-film homogeneity that allows identification and further optimization of thin-film performance. Separate crystallization of the layers determined the optical gradient appearance, irrespective of the chemical solvents used in this work. A more refined analysis showed that a refractive index gradient was apparent in the samples in which lattice parameters strongly changed with thickness. For these films, energy-dispersive X-ray spectroscopy analysis showed significant variation in Pb and Zr. Additionally, complex dielectric fu…
<title>Glass to ferroelectric phase transition induced by ac electric field in PbMg<formula><inf><roman>1/3</roman></inf></formula>Nb<formula><inf><roman>2/3</roman></inf></formula>O<formula><inf><roman>3</roman></inf></formula> thin films</title>
The nonlinear dielectric response of epitaxial heterostructures of relaxor ferroelectric PbMg1/3Nb2/3O3 thin films was experimentally studied using digital Fourier analysis. The amplitudes and the phase angles of the dielectric harmonics were determined as a function of temperature and the amplitude of the sinusoidal ac field. The response of the films was reconstructed assuming a linear contribution of the film-electrode interface capacitance. In the films at low amplitudes of ac field, a glass-like behavior was identified by a maximum in the third-order nonlinear dielectric permittivity around the freezing temperature, accompanied by a square field dependence of the amplitudes of the odd …
Langmuir-Blodgett films of indandione-1,3 pyridinium betaine. III: Linear dichroism and non-linear optical properties
Linear dichroism and second-harmonic generation (SHG) have been measured in Langmuir-Blodgett (LB) multilayers of Z-type structure of amphiphilic indandione-1,3 pyridinium betaine (IPB) with an aliphatic tail containing 17 carbon atoms (C171PB). The dichr
Thermal imaging in artificial nonlinear media
A method has been developed to determine the temperature distribution of ferroelectric surfaces and volumes. Based on the nonlinear optical effect of second harmonic generation (SHG) in highly nonlinear ferroelectric coating, demonstration of 2D thermosensing has been performed in the wide temperature range (77 K - 600 K). Physical concept of SHG thermal imaging, design of thermosensitive coating and experimental verification of the method has been discussed.
Interface Effects in Ferroelectric Thin Films
Dielectric, ferroelectric and piezoelectric characteristics in sol-gel derived and pulsed laser deposited (PLD) lead zirconate titanate (PZT), La modified lead titanate (PLT) and zirconate titanate (PLZT) ferroelectric thin films are investigated focusing on maintenance of thin film ferroelectric (FE) properties in a variety of thin film-electrodesubstrate interfaces. Interferometric studies of piezoelectric response of the heterostructures were performed with respect to a DC electrical bias and AC measurement frequency. The asymmetry of piezoelectric coefficient (d33) hysteresis, diminished values of d33, frequency-displacement and spot size — deformation behaviour in the ferroelectric het…
Thermo-optical mirror on a free ferrofluid surface
Here we report on the first, to our knowledge, direct experimental observation of giant thermo-optical mirror effect on the free surface of ferrofluid under He-Ne laser excitation. In our experiment a slightly focused laser beam of power in mW range is incident nearly normally to the surface, and a characteristic diffraction ring pattern has been observed in reflection mode. Concave surface deformation has been clearly observed at laser irradiated spot and has been explained in terms of lubrication theory approach for laser driven thermocapillary motion in thin layer of light absorbing fluid.
Optical Gradient of the Trapezium-Shaped NaNbO[sub 3] Thin Films Studied by Spectroscopic Ellipsometry
thin films were performed in the photon energy range of 1.24–4.96 eV.Effective values of the complex refractive index and thickness nonuniformity, roughness, and depth profile of the real part of therefractive index were evaluated. An increase of the refractive index with increasing of the sample thickness was observed anddiscussed.© 2008 The Electrochemical Society. DOI: 10.1149/1.2965786 All rights reserved.Manuscript submitted May 27, 2008; revised manuscript received July 7, 2008. Published August 19, 2008.
<title>Nonlinear optical properties of some indandione-1,3 pyridinium betaine derivatives</title>
In this paper nonlinear optical properties of indandione-1,3 pyridinium betaine (IPB) molecule and its novel amphiphilic derivatives have been studied. Hyper-Rayleigh scattering (HRS) has been used as a direct and accurate tool to determine effective hyperpolarizability (beta) of IPB derivatives dissolved in chloroform. Evaluation of hyperpolarizability gives an averaged values of (beta) from 140 multiplied by 10-30 to 450 multiplied by 10-30 esu. Disordering of molecular orientation for multilayer Langmuir-Blodgett films of compound C17-IPB has been studied by SHG techniques and discussed for different film thickness. It has been observed that orientation degree of the Z-type molecular str…
<title>Irradiation effects in lead zirconate thin films</title>
Lead zirconate PbZrO3 (PZ) and PbZr0.53Ti0.47O3 (PZT) sol-gel films with a thickness of up to 1.5 μm were deposited on TiO2/Pt/TiO2/SiO2/Si substrates by spin coating technique and heterostructures of the same composition as well as on Pb0.92La0.08 (Zr0.65Ti0.35)O3 (PLZT-8) (with a thickness of 0.4 μm) were pulse laser deposited (PLD) on Pt/Ti/SiO2/Si. Observation of a typical antiferroelectric (AFE) double hysteresis loop in obtained PZ heterostructures at room temperature was attributed to the superior dielectric strength in case of thin film materials. The thermal behavior of dielectric permittivity e of PZ film reveals a maximum near 225°C on heating and 219°C on cooling. The higher res…
Thermo‐optical investigations of NaNbO 3 thin films by spectral ellipsometry
In this work a spectroscopic ellipsometry was applied to the thermo-optical investigations of sodium niobate NaNbO3 (NN) thin films at the wide temperature range of 5–820 K. The temperature dependence of complex refractive index dispersions and optical bang energy of the direct allowed electron transitions were evaluated. Additionally dynamic scans of the main ellipsometric angles at the several fixed wave lengths of 300, 400, 500 and 635 nm were performed to acquire more detailed temperature dependences of the refractive index and extinction coefficient. Pronounced minima/maxima and substantial jumps in the temperature dependence of complex refractive index and band gap energy were found a…
Broad Distribution of Relaxation Times in 0.6PMN-0.4PZN Relaxor Ceramics
In this paper dielectric spectra of 0.6PMN-0.4PZN ceramic obtained from broadband dielectric spectroscopy is presented. Measurements revealed an unusual relaxor like nature. Two different processes in the dielectric spectra have been observed. High frequency, or short relaxation times, behaviour is typical for ferroelectric crystals. Longest relaxation times do not follow Vogel—Fulcher dependence, which is unusual for relaxors.
Compositional and Optical Gradient in Films of PbZrxTi1-xO3 (PZT) Family
Pb(ZrxTi1-x)O3 (PZT) (x = 0-1) films have attracted the attention of researchers for the past 30 years due to their excellent ferroelectric (FE) and electromechanical properties, which have led to the commercialization of thin PZT films for ferroelectric random access memory (FeRAM), forming a market of several millions USD annually. Ferroelectricity of perovskite oxide thin films, especially PZT thin films, can be exploited in semiconductor devices to achieve non-volatile random access memory (NVRAM) with high-speed access and long endurance, which can overcome the barriers, encountered in current semiconductor memory technologies. The ferroelectricity can be also exploited to voltage depe…
Antiferroelectric PbZrO3 thin films: structure, properties and irradiation effects
Abstract Irradiation effects on highly oriented antiferroelectric PbZrO 3 and ferroelectric Pb 0.92 La 0.08 (Zr 0.65 Ti 0.35 )O 3 thin films are investigated being exposed to neutron irradiation up to fluence 2*10 22 m −2 . The higher resistance of antiferroelectric PbZrO 3 thin films as compared to ferroelectric heterostructures to large fluences of neutron irradiation is recognized and discussed. Influence of two factors (structural and charge) was taken into account analysing irradiation effects on materials of different polarization states: ferroelectric PLZT (ceramics and thin films) and antiferroelectric PbZrO 3 films.
Distribution of the relaxation times of the new relaxor 0.4PSN–0.3PMN–0.3PZN ceramics
Abstract The real distribution function of the relaxation times g ( τ ) of the relaxor ferroelectric ceramics 0.4PSN–0.3PMN–0.3PZN is calculated from the experimental dielectric spectra obtained in the frequency range from 20 Hz to 1.25 GHz. Below the Burns temperature T B ≅ 380 K, where the clusters begin to appear on cooling, the distribution of the relaxation times is symmetrically shaped. On cooling, the permittivity and loss spectra strongly broaden and slow down. The g ( τ ) function becomes asymmetrically shaped and the second maximum appears. The width of the g ( τ ) function is calculated at different temperatures. The shortest relaxation time is of the order of 10 −12 s and it r…
Ferroelectric Behavior in Epitaxial Films of Relaxor PbMg1/3Nb2/3O3
The nonlinear dielectric response of epitaxial thin films of relaxor ferroelectric PbMg1/3Nb2/3O3 was experimentally studied using digital Fourier analysis. Change from glass-like to ferroelectric behavior was detected in a broad temperature range, at relatively low ac and/or dc electric fields, and at a time scale of seconds. The presence of interfaces and peculiar microstructure of thin films are suggested to determine such a specific behavior.
Anomalous Broad Distribution of Relaxation Times in Mixed PMN-PSN Ceramics
Dielectric permittivity of 0.8PMN-0.2PSN ceramic was measured in the frequency range from 20 Hz to 3 GHz. The typical ferroelectrics relaxor dielectric dispersion was observed. From the frequency dependence of complex dielectric permittivity, the distribution of relaxation times was calculated. The low frequency limit of the distribution of relaxation times diverges according to the Vogel–Fulcher law with the freezing temperature T f = 226 K which is lower than in PMN ceramics, obtained previously. The comparison of distributions of relaxation times between 0.8PMN-0.2PSN and pure PMN tends to the conclusion about smaller polar nano regions in 0.8PMN-0.2PSN ceramic.
Broadband Dielectric Spectroscopy of PSN-Rich PMN-PSN Ceramics
The broadband dielectric permittivity of ordered 0.1PMN-0.9PSN and disordered 0.2PMN-0.8PSN ceramics was investigated. The anomaly of dielectric permittivity is clearly seen in the region of 370 K for 0.1 PMN-0.9 PSN at all frequencies. 0.2 PMN-0.8 PSN shows relaxor behaviour with huge frequency dispersion below 350 K. Calculated distribution of relaxation times shows noticeable influence of polar nano regions to the total dielectric spectrum below 320 K with the longest relaxation times edge diverging according to the Vogel-Fulcher law. In 0.1 PMN-0.9 PSN two a little overlapped peaks present in the distribution of relaxation times, influenced by displacive lead motions at high frequencies…
Stability of the functional NLO polymers–optically induced depoling of the DMABI molecules in sPMMA matrix
Abstract Low polar order (PO) stability is the major problem of the polymer materials for nonlinear optical (NLO) applications. In this contribution we will show the results of PO stability investigations in the corona poled 3 wt.% DMABI + sPMMA guest–host system. Influence of the poling temperature on the building and stability of the polar order in the system will be presented. To characterize the stability, PO destruction has been caused by high intensity light. Polar order stability characteristics were obtained from the sample second harmonic generation intensity (SHI) time decays. We have found that the decay signal is the best fit to the sum of two exponentials. Several physical mode…
Synthesis and Characterization of Lead-Free (1-x)(K0.5Na0.5)Nb1-ySbyO3-xBaTiO3
In this study lead-free ceramics with a formula (1-x)(K0.5Na0.5)Nb1-ySbyO3-xBaTiO3 have been synthesized and studied. XRD studies showed that all compositions have perovskite structure with monoclinic or tetragonal cell depending on substitution level. KNN ceramics with BaTiO3 have more homogeneous structure and increased density in comparison with pure KNN or antimony substituted KNN. Dielectric measurements revealed diffuse phase transition.
Ceramics and Thin Films of Some New Pb(B 3+ ,Nb)TiO 3 -PbTiO 3 Systems
The structure, dielectric, and electromechanical properties of (1 m x )Pb(B 3+ ,Nb)TiO 3 - x PbTiO 3 binary systems (B = Lu, Er, Tb, Ho) are reported. The crystallographic features at the morphotropic phase boundary (MPB) between tetragonal P4mm and pseudo-monoclinic M phases are discussed with respect to electro-mechanical properties. Doping effect (with La 3+ ) on the properties of ceramic samples of pseudobinary Pb(Lu 1/2 Nb 1/2 )O 3 -PbTiO 3 (PLuNT) system has been investigated. Pb(Mg 1/3 Nb 2/3 )-PbTiO 3 (PT) solid solutions were studied under different processing conditions for obtaining ceramics of 100% perovskite structure with sufficient high j T EC ∼ 1 K near room temperature. The…
Structure and Physical Properties of Na1/2Bi1/2TiO3-CdTiO3Solid Solutions
Behaviour of ferroelectric properties in Na1/2Bi1/2TiO3-CdTiO3 solid solutions correlates with dependence of lattice symmetry versus concentration of constituents. However, some overlapping is observed in concentration range close to the morphotropic phase boundary. The properties of dielectric permittivity, characteristic for relaxor ferroelectrics, diminish, if concentration of CdTiO3 increases, but it is not influenced by the change of crystallographic symmetry. The electromechanical properties are mostly pronounced in the range of cubic-tetragonal morphotropic phase boundary.
SINTERING OF LEAD-FREE (K0.5Na0.5)NbO3 BASED SOLID SOLUTION
ABSTRACT In this study lead-free solid solution (K0.5Na0.5)NbO3 was prepared, structure, dielectric parameters of ceramics were investigated. The doping of sintering aids did not affect the crystallographic structure of the ceramics significantly; all ceramic samples had a single-phase perovskite structure. Added elements CdO, ZnO, MnO2, V2O5 effectively decreased the sintering temperature of KNN by 50°–80°C. All sintering aids influenced sinterability, microstructure and dielectric properties of ceramics. Dielectric constant for doped samples increased from 6000 up to 8000; Pr = 15 μC/cm2, Ec = 9 kV/cm, d33 = 110 pC/N, kp = 0.38 and Qm = 190 for MnO2 doped samples.
Pulsed laser deposition of relaxor ferroelectric films
Heterostructures of perovskite relaxor ferroelectric (RFE) thin films onto La 0.5 Sr 0.5 CoO bottom electrode layers were grown by pulsed laser deposition on MgO(100) crystal substrates. The films were highly oriented, with (h00) planes parallel to the substrate surface, and demonstrated good dielectric and ferroelectric quality at room temperature. The studies of the dielectric properties of the films over the frequency range of 20 Hz....100 kHz and over the temperature range of 0...350°C revealed relaxor type behavior in the films. A diffuse ferroelectric phase transition and a shift of the maximum dielectric permittivity towards higher temperatures with increasing frequency were observed…
NLO Polymers Containing as Active Chromophore in Dandionylpyridinium, Betaine Units: Synthesis, Modeling and Characterization
In present article we report about synthesis, quantum chemical model calculations, non-linear optical characterization and dependencies of the surface potential changes on irradiation with light of novel polyurethane based polymers, namely a bipolar organic compound N-(indan-1,3-dion-2-y1)-4-N’,N’dialkylaminopyridinium betaine (IPB) containing charged electron donor and electron acceptor groups covalently bonded to polyurethane polymer backbone. These newly synthesized IPB containing polymers could be regarded as a promising thermally stable organic non-linear optical materials with long time performance for photonic applications.
Modeling of trapped charge effects in ferroelectrics: application to piezoactuators
The strain response of lead zirconate titanate piezoelectric multilayer actuators have been measured up to 10 7 N/m 2 stress and the 3.10 6 V/m periodic unipolar driving voltage. An additional nonstationary strain component is detected. This effect is explained in terms of a simple solution of polarization kinetics specific for unipolar driving voltage. Preliminary experimentally assertions are given for space charge effects which manifest itself in the strain as well as charge plot after removing the mechanical load. It demonstrates that the static load free equilibrium of the actuator is not complete and the charge recently supported by the piezo voltage and then trapped forms a nonunifor…
Phase transitions and properties of perovskite ferroelectric ceramics and films for certain applications
Abstract The structure-properties relationships and phase transitions in perovskite ceramics, and films of PLZT, PLZST, PST, PSN, PMNT compounds are discussed with regard to ordering, relaxor behaviour, pronounced ferroelectric, electromechanical and electrocaloric properties. The theoretical approach is extended to the time dependent Ginsburg-Landau model. The evolution of dielectric properties in relaxors after the change of temperature and electric field creating an increase of dielectric permittivity is found to follow a logarithmic law of decay. A strong electromechanical response is observed in a number of thin films of different compositions.
Some New Ceramics and Thin Films of Pb(B 3+ ,Nb)TiO 3 -PbTiO 3 System
The structure, dielectric, and electromechanical properties of (1-x)Pb(B 3+ ,Nb)TiO 3 -xPbTiO 3 binary systems (B=Lu,Er,To,Ho) are reported. High values of the electromechanical coupling coefficien...
Novel second-order nonlinear optical polymer materials containing indandione derivativatives as a chromophore
Second order non linear optical (NLO) properties of sPMMA based host-guest systems containing eight dimethylaminobenzylidene -1, 3 - indandione (DMABI) related chromophores have been investigated by means of quantum chemical calculations and SHG experimental characterization. Ab initio calculations with basis set 6-31G were used for molecular geometry determination as well as in the calculations of molecular hyperpolarizability by FF approach. Influence of the chromophore concentration on the host-guest film NLO performance was obtained by SHG Maker fringe experiments. The highest value of d53233 =80 pm/V (frequency corrected value d033 =12 pm/V) at chromophore concentration 15 %wt have bee…
Raman Studies of Structural Phase Transitions in Perovskite Ferroelectric Sodium Niobate Solid Solutions
Raman spectra are sensitive to interactions between structural units and, consequently, may reflect fine rearrangements of the units of cation sublattice occuring at compositional changes affecting the phase equlibrium and ferroelectric properties of the crystal. Obtaining Raman spectra show the information on disordering of structural units depending on composition of the cation sublattice in real Li x Na 1 − x Ta y Nb 1 − y O 3 ferroelectrics. On the basis of experimental studies shown, that not only the frequency but also intensity of some “rigid” bands may serve as the function of order parameter of phase transition in Landau's theory of the second order phase transition.
Broadband dielectric spectroscopy of PSN ceramics
Abstract The complex dielectric permittivity of ordered and disordered PSN ceramics was measured in the frequency range from 20 Hz to 3 GHz. The anomaly of dielectric permittivity is clearly seen in the region of 115 °C for ordered PSN at all measured frequencies. Disordered PSN exhibits typical relaxor behaviour with a huge frequency dispersion below 125 °C. Calculated distribution of relaxation times shows noticeable influence of polar clusters to the total dielectric spectrum of disordered PSN below 80 °C with the longest relaxation times edge diverging according to the Vogel–Fulcher law. In the case of ordered PSN, two almost not overlapping peaks in the distribution of relaxation times…
Thermo-optical studies of NaNbO3thin films
Thermo-optical studies of sodium niobate NaNbO3 (NN) thin films, deposited by the pulsed laser ablation technique on Si/SrRuO3 substrates, were performed by spectroscopic ellipsometry in the temperature range 300-550°C. Optical constants at the room temperature were measured in the spectral range 250-1000 nm. Substantial changes in the refractive index temperature behaviour (taken at λ = 300 nm) were found at temperatures 370, 445, 503, 520, and 532°C, where the first and the last temperatures are the phase transitions P → R and S → T1, respectively. Other temperatures (445, 503, and 520°C) are suggested as the points of some local structural changes in the NN film.
Dynamics of Polar Clusters in PMN Ceramics: Comparison with PMN Single Crystal
The dielectric permittivity of PMN ceramics was measured in the frequency range from 20 Hz to 37 GHz. From the frequency dependence of the real and imaginary parts of dielectric permittivity, the distribution of relaxation times f(τ) was calculated. The f(τ) function broadens significantly, and the second maximum appears below the 270 K temperature. The dielectric response and also relaxation time distribution of PMN ceramics was compared with the previous results of PMN single crystal. The results showed that dynamics of polar nano regions in PMN ceramics is suppressed due to the small size of grains in the ceramics.