Effect of electric field on the dielectric permittivity of betaine phosphite crystals in the paraelectric phase

Temperature dependences of the dielectric permittivity of betaine phosphite crystals are studied both without and under application of an electric bias. It is shown that, in view of the fact that the high-temperature improper ferroelastic (antiferrodistorsive) phase transition at T _c1=355 K is nearly tricritical, the nonlinear temperature dependence of inverse dielectric permittivity in the paraelectric phase and the effect of the field on the dielectric permittivity can be described within a phenomenological model containing two coupled (polar and nonpolar) order parameters with a negative coupling coefficient. An analysis of the model revealed that, in the case where two phase transitions, a nonpolar and a ferroelectric one, can occur in the crystal, all of its dielectric properties, including the polarization response in a field, can be described by one dimensionless parameter a. For the crystal under study, we have a=?2.5. This value of the parameter corresponds to a second-order ferroelectric transition far from the tricritical point, at which a=?1. It is shown that the polarization response in the paraelectric phase in an electric field calculated within this model differs radically from that in the ferroelectric phase-transition model for which the Curie-Weiss law holds in the paraelectric phase.     

Ferroelectric phase transition in methylammonium tetrachloroaluminate crystals

Methylammonium tetrachloroaluminate (MATCAl) crystal have been found to undergo a phase transition at 100 K and show ferroelectricity along the a-axis below 100 K down to at least 77 K. The temperature dependence of permittivity fulfills the Curie-Weiss law both in the paraelectric and ferroelectric phase. The results of permittivity and spontaneous polarization measurements indicate the phase transition to be the second-order.     

Dielectric properties of betaine arsenate crystal near the phase transition

Dielectric measurements for single crystal of betaine arsenate (CH₃)₃NCH₂COO·H₃AsO₄ connected with the ferroelectric phase transition at 119 K were performed. The temperature dependence of electric permittivity was measured at dc electric fields up to 700 kV/m. The results show significant suppression of the dielectric constant by the application of dc field. Deviation from the classical behavior was observed. The electric permittivity was also measured in the paraelectric phase at constant temperature as a function of electric field intensity up to 700 kV/m. The electric permittivity might be well described by the classical relation with additional term including contribution to permittivity coming from clusters. The fit parameters indicate that the polar-clusters carries polarization P₀=0.7- with the clusters size of L=12-20 nm.     

Absence of relaxor-like ferroelectric phase transition in (Pb,Sr)TiO3 thin films

We have performed dielectric and micro-Raman spectroscopy measurements in the 298–673 K temperature range in polycrystalline Pb_0.50Sr_0.50TiO₃ thin films prepared by a soft chemical method. The phase transition have been investigated by dielectric measurements at various frequencies during the heating cycle. It was found that the temperature corresponding to the peak value of the dielectric constant is frequency-independent, indicating a non-relaxor ferroelectric behavior. However, the dielectric constant versus temperature curves associated with the ferroelectric to paraelectric phase transition showed a broad maximum peak at around 433 K. The observed behavior is explained in terms of a diffuse phase transition. The obtained Raman spectra indicate the presence of a local symmetry disorder, due to a higher strontium concentration in the host lattice. The monitoring of some modes, conducted in the Pb_0.50Sr_0.50TiO₃ thin films, showed that the ferroelectric tetragonal phase undergoes a transition to the paraelectric cubic phase at around 423 K. However, the Raman activity did not disappear, as would be expected from a transition to the cubic paraelectric phase. The strong Raman spectrum observed for this cubic phase is indicative that a diffuse-type phase transition is taking place. This behavior is attributed to distortions of the perovskite structure, allowing the persistence of low-symmetry phase features in cubic phase high above the transition temperature. This result is in contrast to the forbidden first-order Raman spectrum, which would be expected from a cubic paraelectric phase, such as the one observed at high temperature in pure PbTiO₃ perovskite. PACS 78.30.-j; 77.80.Bh; 64.70.Kb; 68.55.-a; 77.22.-a; 77.55.+f     

Dielectric relaxation spectroscopy of guest-host ferroelectric liquid crystals: influence of anthraquinone dye

The dielectric spectroscopy of a short pitch and high spontaneous polarization ferroelectric liquid crystal mixture and its guest-host derivatives with different wt/wt ratio of anthraquinone blue dichroic dye has been studied over a wide frequency range of 50 Hz-1 MHz. The increase in dye concentration results in the decrease of the permittivity of the material in the SmC* phase, however, an opposite effect is observed in the SmA phase. The influence of bias voltage on the dielectric parameters has also been investigated. A new relaxation mode has been observed with a relaxation frequency of ∼300 kHz and dielectric strength of ∼5 at room temperature.     

First-principles calculations of the dielectric and vibrational properties of ferroelectric and paraelectric BaAl2O4

First-principles calculations have been conducted to study the structural, dielectric, and vibrational properties of ferroelectric and paraelectric BaAl₂O₄. High-frequency and static dielectric constants, and phonon frequencies at the Brillouin zone center are reported. Both BaAl₂O₄ polymorphs are promising infrared-transparent materials due to their low electronic dielectric constants. The ferroelectric and paraelectric BaAl₂O₄ have much smaller permittivity compared to the classical ferroelectric materials. From an atomic nanostructure standpoint, the abnormally low permittivity of BaAl₂O₄ polymorphs is mainly related to low coordination numbers of Ba (9) and Al (4).     

Investigating the dielectric properties of potassium iodate polycrystals

Linear and nonlinear dielectric properties of KIO₃ polycrystalline samples are investigated. It is shown that linear dielectric permittivity ε' displays four anomalies corresponding to phase transitions in KIO₃. Anomalies of third-harmonic coefficient γ_3ω are observed at temperatures of 113, 263, and 345 K, corresponding to phase transitions between KIO₃ ferroelectric phases. It is established that the third-harmonic coefficient responsible for the nonlinearity of dielectric properties displays no anomalies during the transition to the paraelectric phase of KIO₃ at approximately 485 K. Possible reasons for there being no such anomaly are discussed.     

Dielectric studies of nanoporous alumina films filled with the Rochelle salt

Dielectric studies of nanoparticles of the Rochelle salt embedded in pores of porous alumina have been performed in the temperature range from 80 K to the decomposition temperature of the bulk Rochelle salt. It has been revealed that the permittivity exhibits an anomaly corresponding to the lower structural transition to the paraelectric phase, whereas the upper ferroelectric transition is shifted above the decomposition temperature in agreement with the recently published data. The temperature of the lower transition for nanoparticles in pores is found to decrease by 10 K. Possible physical factors that can be responsible for the broadening of the region of existence of the ferroelectric phase have been discussed.     

Shifting of transition temperature of ferroelectric liquid crystals due to addition of dye-An optical and dielectric study

In order to study the shifting of phase transition temperature of ferroelectric liquid crystals due to addition of dye molecules, we have investigated two ferroelectric liquid crystal materials (Felix 16/030 and Felix 16/100) and their five mixtures with Anthraquinone dye (1%, 2%, 3%, 4% and 5% wt/wt). The phase transition scheme has been investigated and analyzed by results obtained from the optical transmittance and the dielectric permittivity study with variation of temperature in the range of 30 to 100 °C. Both the samples clearly show the shifting of phase transition temperature with dye concentration, especially the SmC*-SmA phase transition temperature. It is also clear from the study that SmC*-SmA phase transition phenomenon also becomes stronger with the addition of dye molecules. A theoretical explanation has also been given for shifting of phase transition temperature. The amount of shift in transition temperature agrees well as obtained from optical and dielectric studies.     

Structural and electrical studies of Ba5RTi3V7O30 (R=Ho,Gd, La) compounds

The ferroelectric ceramics Ba₅RTi₃V₇O₃₀ (R=Ho, Gd, La) have been synthesized by solid-state reaction technique. Preliminary X-ray structural analysis confirmed a single-phase formation of the compound in orthorhombic structure. Surface morphology of the compounds was studied by scanning electron microscopy (SEM). Detailed studies of electrical properties (i.e., dielectric constant, loss tangent, ac conductivity) as a function of temperature (RT-773 K) and at four different frequencies (1 kHz, 10 kHz, 100 kHz and 1 MHz) show ferroelectric–paraelectric phase transition of the compounds of diffuse-type. The activation energy has been evaluated from ac conductivity following Arrhenius equation. The conductivity pattern shows that it is strongly frequency dependent and obeys Jonscher's power relation.     

X-ray study of the phase transition in RbHSeO4

The ferroelectric phase transition in RbHSeO₄ has been examined by precise measurements of the temperature dependence of the unit-cell parameters using the Bond technique. The transition, at T_c = 370.6 K, is of first order and the triclinic unit cell of the ferroelectric phase transforms to an equitranslational monoclinic cell in the paraelectric phase. In a temperature region of several K below T_c reflections belonging to both phases have been observed.     

Observation of87Rb NMR satellite transitions in the commensurate and incommensurate phases of Rb2ZnCl4

It is shown that the first order quadrupole split NMR satellite transition frequencies of the⁸⁷Rb nucleus can be detected in the paraelectric, incommensurate and ferroelectric phases of Rb₂ZnCl₄. From rotation patterns the electric field gradient tensor at the Rb sites is determined for the paraelectric phase. The data demonstrate a considerable influence of the structural changes in the incommensurate and ferroelectric phases on the observed NMR transition frequencies. For some crystal orientations the satellite transitions are followed through the incommensurate into the ferroelectric phase. Whereas in the former typical quasi continuous spectra are observed in the latter several sharp lines appear. The results are discussed in relation to the structural changes at the phase transitions.     

Effect of an organic dye on the ferroelectric phase transition in KH2PO4 (KDP)

This paper reports on the first measurement of the dielectric permittivity and heat capacity of a KDP crystal doped by Chicago Sky Blue organic dye within a temperature interval including the ferroelectric phase transition at T _c =122 K. Similar measurements were made on a pure KDP crystal under the same conditions for the sake of comparison. The heat capacities of the pure and doped crystals were shown to differ substantially within an interval 1 K wide in the vicinity of T _c , where an anomaly in the heat capacity of the doped crystal was observed to wash out without producing any change in the temperature position of its maximum. The doping reduces the permittivity in the polar phase markedly. The observed effects are associated with the influence of nonisomorphic defects on the ferroelectric phase transition in a piezoelectric crystal.     

Crystal growth and dielectric, mechanical, electrical and ferroelectric characterization of n-bromo succinimide doped triglycine sulphate crystals

Single crystals of triglycine sulphate (TGS) doped with n-bromo succinimide (NBS) were grown at ambient temperature by the slow evaporation technique. An aqueous solution containing 1-20 mol% of n-bromo succinimide as dopant was used for the growth of NBSTGS crystals. The incorporation of NBS in TGS crystals has been qualitatively confirmed by FTIR spectral data. The effect of the dopant on morphology and crystal properties was investigated. The cell parameters of the doped crystal were determined by the powder X-ray diffraction technique. The dielectric constant of NBS doped TGS crystal was calculated along the ferroelectric direction over the temperature range of 30-60 °C. The dielectric constant of NBSTGS crystals decrease with the increase in NBS concentration and considerable shift in the phase transition temperature (T_C) towards the higher temperature observed. Pyroelectric studies on doped TGS were carried out to determine the pyroelectric coefficient. The emergence of internal bias field due to doping was studied by collecting P-E hysteresis data. Temperature dependence of DC conductivity of the doped crystals was studied and gradual increase in the conductivity with the increase of dopant concentration was observed. The activation energy (ΔE) calculated was found to be lower in both the ferroelectric and the paraelectric phases for doped crystals compared to that of pure TGS. The micro-hardness studies were carried out at room temperature on thin plates cut perpendicular to the b-axis. Less doped TGS crystals show higher hardness values compared to pure TGS. Piezoelectric measurements were also carried out on 010 plates of doped TGS crystals at room temperature.     

Iminodiacetic acid doped ferroelectric triglycine sulphate crystal: Crystal growth and characterization

Single crystals of iminodiacetic acid (HN(CH₂COOH)₂) doped triglycine sulphate (IDATGS) crystals have been grown from aqueous solution containing 1-10 mol% of iminodiacetic acid at constant temperature by slow evaporation technique. The effects of different amounts of doping entities on the growth habit have been investigated. X-ray powder diffraction pattern for pure and doped TGS was collected to determine the lattice parameters. The grown crystals were subjected to Fourier transform infrared (FTIR) spectroscopy studies to find the presence of various functional groups qualitatively. The dielectric permittivity has been studied as a function of temperature. An increase in the transition temperature (49.2-49.7 °C) of IDATGS crystals is observed. The dielectric constant (ε′_max) of IDATGS crystals vary in the range 922-2410 compared to pure TGS (T_c=49.12 °C and ε′_max=3050). Curie Weiss constants C_p and C_f in the paraelectric and ferroelectric phases were determined. The transition temperature (T_c) is found to decrease with increase in dopant concentration. P-E hysteresis studies show the presence of internal bias field in the crystal. Piezoelectric measurements were also carried out at room temperature. Domain patterns on b-cut plates were observed using scanning electron microscope. The micro hardness studies reveal that the doped crystals are harder than the pure TGS crystals. The low dielectric constant, higher transition temperature, internal bias field and hardness suggest that IDATGS crystals could be a potential material for IR detectors.     

Variable-temperature Raman scattering and X-ray diffraction studies of Bi3.25Nd0.75Ti3O12 ceramics

Neodymium-substituted bismuth titanate (Bi_3.25Nd_0.75Ti₃O₁₂, BNT_0.75) ceramics was prepared by chemical co-precipitation along with calcinations. The lattice instability has been investigated by variable-temperature Raman scattering and X-ray diffraction. The results showed that there was an orthorhombic to pseudo-tetragonal phase transition at about 695 K, in terms of the evolution of temperature dependence of Raman scattering frequencies. Some changes at about 695 K in the XRD lines, the lattice parameters (a, b, and c) as well as the orthorhombic distortion b/a have been detected in the high temperature X-ray diffraction, which confirmed the conclusion that the BNT_0.75 ceramics undergoes a ferroelectric to paraelectric phase transition at about 695 K.     

Pyroelectric coefficient manipulation in doped TGS crystals

Pure and l-alanine doped Triglycine sulphate (TGS) crystals were grown in paraelectric phase (∼52 °C). Doped crystals show unequal growth rates along the ferroelectric axis. Pure TGS crystals show peculiar dielectric behavior in the ferroelectric phase, after crossing up and down the Curie point in two successive runs between room temperature and 80 °C. Much higher and unstable permittivity was found returning in the ferroelectric phase. At constant temperature (35 °C), permittivity follows a relaxation process, characterized by two relaxation times. l-Alanine doped TGS crystal shows more than one order of magnitude smaller permittivity and dielectric losses. Internal bias field of ∼1 kV/cm, induced by the dopant, made the crystal almost monodomain and pined polarization in one direction. Pyroelectric coefficient measurements were performed at constant heating rate of the samples, using a computer controlled He cryostat and Keithley 6517 electrometer. The temperature dependence of P⁺ polarization component, obtained by computer integration of the pyroelectric coefficient, was measured on a large temperature interval (−20/+80 °C). Pyroelectric coefficient of the doped samples was also measured by the same procedure, using a dc bias electric field, pointing in the opposite direction to the pined polarization. The polarization could be reversed, on the whole temperature range, by dc fields higher than bias or coercive field. Surprisingly, for the first time, the pyroelectric coefficient (p) was found constant on quite large temperature intervals. Doped TGS crystals show much smaller values of permittivity ?_r versus the pure one and consequently, get higher figure of merit M = p/?_r. The pyroelectric coefficient of this material can be tailored to become constant on a defined temperature range, under a dc field control. This characteristic makes this material valuable to be used as pyroelectric material for IR devices.     

Microwave dielectric dispersion in ferroelectric telluric acid ammonium phosphate

The paper presents the results of the investigation of dielectric dispersion in monoclinic telluric acid ammonium phosphate crystal over the frequency range 1 MHz to 77 GHz. It is shown that ferroelectric dispersion of the Debye type along the direction perpendicular to the plane (101) occurs in the frequency range 10⁸ to 10¹¹ Hz and is caused by a single relaxational soft mode. The relaxational soft mode is caused by the flipping motion of protons between two potential minima in a hydrogen bond. The frequency of the flipping proton mode in the paraelectric phase varies according to v_s = 0.94 (T – T_o ) GHz and decreases to 1.75 GHz at T_c = 317.3 K. The relaxational mode gives the main contribution to the high static dielectric permittivity of this crystal which fits the Curie-Weiss law. The results confirm the order-disorder nature of a proper ferroelectric phase transition of second order.     

Phase transitions in CuBiP2Se6 crystals

Investigation results of dielectric (20?Hz–1?MHz) properties of layered CuBiP₂Se₆ crystals are presented. The temperature dependence of the static dielectric permittivity reveals the first-order “displacive” antiferroelectric phase transition at T _c?=?136?K. In the paraelectric phase, at low frequencies, dielectric spectra are highly influenced by the high ionic conductivity with the activation energy of 2473?K (0.21?eV). In the antiferroelectric phase the electrical conductivity and its activation energy (531.1?K (0.045?eV)) are considerably smaller. At low temperatures, the temperature behaviour of the distribution of relaxation times reveals complex freezing phenomena. A part of long relaxation time distribution is strongly affected by external direct current (DC) electric field and it is obviously caused by antiferroelectric domain dynamics.     

Ferroelectric relaxor behavior in hafnium doped barium-titanate ceramic

Temperature and frequency dependence of the real (ε′) and imaginary (ε″) parts of the dielectric permitivity of cubic Ba(Ti_0.7Hf_0.3)O₃ ceramic has been studied in the temperature range of 100 K to 350 K at the frequencies 0.1 kHz, 1 kHz, 10 kHz, 100 kHz for the first time. Diffuse phase transition and frequency dispersion is observed in the permittivity-vs-temperature plots. This has been attributed to the occurrence of relaxor ferroelectric behavior. The observed relaxor behavior has been quantitatively characterized based on phenomenological parameters. A comparison with the Zr doped BaTiO₃ has also been presented. For Hf doped samples transmission electron microscopy (TEM) characterization do show the presence of highly disordered microstructure at length scales of few tens of nano-meters.