High-temperature phase transitions in the improper ferroelectric KIO3

The ac conductivity (σ_ac) and dielectric permittivity (?) are determined in the temperature range 300?K?T3 compound. The results indicated that the compound behaves as an improper ferroelectric and undergoes a ferroelectric phase transition from a high temperature rhombohedral phase I to a low temperature monoclinic phase II at T _c?=?(486?±?1)?K. A second structural phase transition was observed around 345?K. The conductivity varies with temperature range and for T?>?428?K intrinsic conduction prevails. Different activation energies in the different temperature regions were calculated. The frequency dependence of σ(ω) was found to follow the universal dynamic response [σ(ω)∝(ω) ^s(T)]. The thermal behaviour of the frequency exponent s(T) suggests the hopping over the barrier model rather than the quantum mechanical tunneling model for the conduction mechanism.     

Dielectric behavior and low temperature phase transition in NH4IO3

The electrical properties namely ac conductivity σ(ω,?T) and the complex dielectric permittivity (ε*) are measured at selected frequencies (5–100?kHz) as function of temperature (95?K?T?4IO₃. The ferroelectric hysteresis loops and the X-ray diffraction pattern are also measured. The analysis of the data indicates that the compound undergoes a structural phase transition at ～103?K and the behavior of σ(ω,?T) obeys the power law. The trend of the temperature dependence of the angular frequency exponent s (0?s?4IO₃; (2) the data indicate that the compound undergoes a structural phase transition at 103?K; (3) the originality of this transition has been confirmed by X-ray diffraction; (4) no evidence for the existence of a ferroelectric transition at 103?K as mentioned earlier; and (5) the quantum mechanical tunneling is proposed as the main mechanism of the electric conduction.     

Characterization of organic–inorganic hybrid layered perovskite and intercalated compound (n-C12H25NH3)2ZnCl4

We report on some electrical properties and solid–solid phase transitions of organic–inorganic hybrid layered halide perovskite and intercalated compound (n-C₁₂H₂₅NH₃)₂ZnCl₄ which is one member of the long-chain compounds of the series (n-C_nH_2n+1NH₃)_2,(n = 8–18). The complex dielectric permittivity ?*(ω,T) and the ac conductivity σ (ω,T) were measured as functions of temperature 100 K < T < 390 K and frequency 5 kHz < f < 100 kHz. Moreover, the differential scanning calorimetery and the differential thermal analysis thermograms were performed. The analysis of our data confirms the existence of a structural phase transition at T ≈ (362?±?2) K, where the compound changes its state from intercalation to non-intercalation with a drastic increase in the c-axis by about 16.4%.

The behavior of the frequency-dependent conductivity follows the Jonscher universal power law: σ (ω, T) α?^s(?,T). The mechanism of electrical conduction in the low-temperature phase (phase II) can be described as quantum mechanical tunneling model.     

Some characterizations of a new metal–organic framework (n-C14H29NH3)2CdCl4 and the role of hydrogen bonding

A cadmium-based organic–inorganic hybrid (n-C₁₄H₂₉NH₃)₂CdCl₄ is synthesized and characterized, thermally and dielectrically. The differential scanning calorimetery (DSC) and the differential thermal analysis (DTA) thermograms were performed in a suitable range of temperature. The general feature of each thermogram indicates that the hybrid undergoes two structural phase transitions at T_major ≈ 351.5?K and T_minor ≈ 344.66?K in addition to an intermediate temperature which is located at ≈346.8?K. For further confirmation of the observed phase transitions, the complex dielectric permittivity ε* (ω,T)?=?ε′(ω,T) – iε″(ω,T) and ac conductivity σ_ac(ω,T) were accurately measured in the wide range of temperature 100?K<T<400?K at some suitable range of frequencies. The data evidenced the existence of such transitions. Comparison with other hybrids reveals the absence of the odd–even effect whereas the transition temperature increases with the increase of the chain length. The mechanism of proton transfer and kink defects was outlined.     

Dielectric properties and relaxation behavior of [TMA]2Zn0.5Cu0.5Cl4 compound

The [TMA]₂Zn_0.5Cu_0.5Cl₄ hybrid material was prepared and its dielectric spectra were measured in the 10⁻¹ Hz-10⁶ Hz frequency range and 200-305 K temperature interval. The dielectric permittivity showed a ferroelectric-paraelectric phase transition at 293 K. Double relaxation peaks are observed in the imaginary part of the electrical modulus, suggesting the presence of grain and grain boundary in the sample. The frequency dependent conductivity was interpreted in term of Jonscher's law: σ(ω)=σ_dc+Aωⁿ. The temperature dependent of the dc conductivity (σ_dc) was well described by the Arrhenius equation: σ_dcT=σ_o×exp(−E_a/kT).     

AC conductivity and dielectric behavior of bulk Furfurylidenemalononitrile

AC conductivity and dielectric behavior for bulk Furfurylidenemalononitrile have been studied over a temperature range (293–333 K) and frequency range (50–5×10⁶ Hz). The frequency dependence of ac conductivity, σ_ac, has been investigated by the universal power law, σ_ac(ω)=Aω^s. The variation of the frequency exponent (s) with temperature was analyzed in terms of different conduction mechanisms, and it was found that the correlated barrier hopping (CBH) model is the predominant conduction mechanism. The temperature dependence of σ_ac(ω) showed a linear increase with the increase in temperature at different frequencies. The ac activation energy was determined at different frequencies. Dielectric data were analyzed using complex permittivity and complex electric modulus for bulk Furfurylidenemalononitrile at various temperatures.     

Dielectric spectroscopy characteristics of ferroelectric Pb0.77K0.26Li0.2Ti0.25Nb1.8O6 ceramics

Temperature and frequency dependence of dielectric constant and conductivity properties of Pb_0.77K_0.26Li_0.2Ti_0.25Nb_1.8O₆ (PKLTN) ceramics are modelled through the universal dielectric response (UDR). Partial substitution of Ti⁴⁺ for Nb⁵⁺ was compensated by charge and the creation of oxygen vacancies according to the Kroger-Vink notation. The electrons released by this reaction are captured by Nb⁵⁺ and Ti⁴⁺ to generate Nb³⁺ and/or Ti³⁺. The hopping of electrons between Nb⁵⁺–Nb³⁺ and Ti⁴⁺–Ti³⁺ are believed to participate in conductivity. Characterization of the dielectric constant has been performed from room temperature to 590°C in the frequency range from 45 Hz to 5 MHz. The measured dielectric constant obeyed Jonscher's dielectric dispersion relations: ε ^l = ε _∞ + sin(n(T)π/2)(a(T)/ε ₀)(ω^{n ( T )?1}) and ε ^ll = σ/iε ₀ ω + cos(n(T)π/2)(a(T)/ε ₀)(ω^{n ( T )?1}). Cole-Cole plots inclined at an angle (1 ? n(T))π/2 and followed the trend of universal material behavior ε _∞ + A(T)(ω^{n ( T )?1}). The exponent n(T) and coefficient A(T) = (a(T)S/L) exhibited a minimum and maximum at T _c = 425°C, respectively. The conductivity studies show the contribution of the hopping of bound charge carriers to conduction in PKLTN.     

Temperature dependence of Bi2O3 structural parameters close to the α–δ phase transition

This article presents the results of in situ X-ray powder diffraction, Raman spectroscopy, and electrical impedance spectroscopy of the α-phase of Bi₂O₃, at 0.1 MPa in the temperature range below and above the α–δ-phase transition. This work demonstrated subtle nonlinear temperature variations of the cell parameters, of the hard-mode Raman shift, and of the activation energy of electrical conductivity in the temperature range about 100–120°C below the α–δ phase transition temperature T _Tr ≈ 725°C in Bi₂O₃. At T < 600°C, the linear variation of the inverse dielectric susceptibility (χ ^?1) correlates well with the hard mode frequency shift Δ(ω ²) of Raman A_1g mode as Δ(χ ^?1)/Δ(ω ²) ≈ 5.5 × 10^?7 cm². A structural model describing the mechanism of O^2? anion distribution and electric dipole disordering in the vicinity of T _Tr is discussed.     

Transport properties in non-oxide perovskite ferroelectric relaxors

Electric transport in a Cu-doped Cd salt [(CH₂)₃(NH₃)₂Cd_{1? x} Cu _x Cl₄, x?=?0.0, 0.07, 0.395 and 0.69] was investigated in the frequency range 60?Hz–100?kHz and the temperature range 290–450?K. The conductivity increases with increasing copper doping. Samples with x?=?0.0 and 0.07 undergo phase transitions at 374?K and 369?K, respectively. Ferroelectric relaxor-like behaviour appears for x?=?0.395 and 0.69. The conduction mechanism of the samples with x?=?0.0 and 0.07 depends on the temperature region. Below the transition temperatures chlorine vacancy and proton hopping prevails, whereas above the transition temperatures mainly proton conduction dominates. Transport in the new non-oxide ferroelectric relaxors, where x?=?0.395 and 0.69, can be explained by the jump relaxation model where proton and ionic hopping contribute to the conductivity throughout the whole temperature range.     

Super-linear frequency dependence of ac conductivity of disordered Ag2S–Sb2S3 at cryogenic temperatures

The ac conductivity of a new class of disordered solids, i.e. mechanochemically synthesized amorphous fast ion conducting Ag₂S–Sb₂S₃ materials, has been investigated in the audio frequency range (10–10⁷?Hz) down to cryogenic temperatures (～10?K). The conductivity spectra exhibit the usual signature of a disordered system at higher temperatures, well described by the Jonscher power law (JPL) i.e., σ′(ω)?=?σ _dc?+?A(T)ω*, although the frequency exponent (n?<?1) is found to be a weak function of temperature. However, as the temperature is lowered, the frequency width of the σ _dc region decreases gradually and that of the JPL region increases. Eventually, the σ _dc region disappears and the JPL region alone dominates the spectrum. However, at the lowest temperatures, both the σ _dc and JPL regions disappear and σ′(ω) obeys a super-linear power law (SPL) (σ′?∝?ω^m , m?≥?1). It is observed that the SPL has strikingly similar characteristics to the well-established nearly-constant-loss (NCL) behaviour corresponding to m?=?1. Both SPL and NCL appear in the same time–temperature (low-temperature/low-frequency) domain. Furthermore, in both cases the conductivity is a distinctly weak function of temperature but quite sensitive to frequency, and the SPL/NCL?→?JPL crossover frequency is thermally activated with almost the same energy as the ac activation energy. The presence of the SPL is further manifested in the form of a well-defined minimum in the dielectric loss, ε″(ω), spectra. It is therefore proposed that the entire low-temperature/low-frequency spectra can be described by a modified Jonscher power law, σ′(ω)?=?σ _dc(T)?+?A(T) ωⁿ ?+?B(T)ω^m , m?=?1 (NCL), m?>?1 (SPL), where the second term with n?<?1 accounts for the JPL and the third term with m?≥?1 accounts for SPL/NCL. The results and some other low-temperature/low-frequency conductivity data are consistent with an asymmetric double well potential (ADWP) model.     

Dielectric and conduction mechanism studies of PVA-orthophosphoric acid polymer electrolyte

Polyvinyl alcohol (PVA)-based proton conducting polymer electrolytes have been prepared by the solution cast technique. The conductivity is observed to increase from 10⁻⁹ to 10⁻⁴ S cm⁻¹ as a result of orthophosphoric acid (H₃PO₄) addition. The plot of conductivity vs temperature shows that a phase transition occurred at 343 K in the sample PVA-33 wt% H₃PO₄. The β-relaxation peak is observed at 313 K. The glass transition temperature of PVA-33 wt% H₃PO₄ is 343 K. Orthophosphoric acid seems to play a dual role, i.e., as a proton source and as a plasticizer. The ac conductivity σ _ac = Aω ^s was also calculated in the temperature range from 303 to 353 K. The conduction mechanism was inferred by plotting the graph of s vs T from which the conduction mechanism for sample PVA-17 wt% H₃PO₄ was inferred to occur by way of the overlapping large polaron tunneling (OLPT) model and the conduction mechanism for the sample PVA-33 wt% H₃PO₄ by way of the correlated barrier height (CBH) model.     

AC conductivity analysis and dielectric relaxation behavior of (C6H20N3)BiBr6.H2O

The N‐(3‐ammoniumpropyl)‐1,3 diammoniumpropane hexabromobismuthate (III) monohydrate exhibits a structural phase transition at T = 330 °K, which has been characterized by differential scanning calorimetric. The alternating current electrical conductivity and the dielectric relaxation properties of the (C₆H₂₀N₃)BiBr₆.H₂O compound have been investigated by means of impedance spectroscopy measurements over a wide range of frequencies and temperatures, 100 Hz–1 MHz and 290–355 °K, respectively. The Z′ and Z″ versus frequency plots are well fitted to an equivalent circuit consisting of series of combination of grains and grain boundary elements. The frequency dependent alternating current conductivity is well described by Jonscher's universal power law: σ(ω,T) = σ_DC(T) + A(T)ω^s(T). The nature of direct current conductivity variation suggests the Arrhenius type of electrical conductivity. Furthermore, the modulus plots can be characterized by full width at half height or in terms of a non‐experiential decay function φ(t) = exp(?t/τ)^β. The variation of the value of these elements with temperatures confirmed the result detected by differential scanning calorimetry measurements. Thus, the near values of activation energies obtained from the impedance and modulus spectra confirm that the transport is through an ion hopping mechanism. Copyright © 2015 John Wiley & Sons, Ltd.     

AC conductivity and dielectric properties of bulk tungsten trioxide (WO3)

AC conductivity and dielectric properties of tungsten trioxide (WO₃) in a pellet form were studied in the frequency range from 42 Hz to 5 MHz with a variation of temperature in the range from 303 K to 463 K. AC conductivity, σ_ac(ω) was found to be a function of ω^s where ω is the angular frequency and s is the frequency exponent. The values of s were found to be less than unity and decrease with increasing temperature, which supports the correlated barrier hopping mechanism (CBH) as the dominant mechanism for the conduction in WO₃. The dielectric constant (ε′) and dielectric loss (ε″) were measured. The Cole–Cole diagram determined complex impedance for different temperatures.     

DSC study of superionic phase transition in (NH4)4H2(SeO4)3 single crystals

DSC and complex impedance studies of the protonic conductor (NH₄)₄H₂(SeO₄)₃, which undergoes a superionic phase transition of first order at T_s = 378 K show that the activation energy of ionic conductivity d(lg σ)/dt and the ordering enthalpy ΔC_p of the crystal are proportional: d(lg σ)/dT = XΔC_p/RT_s + const, as found for MAg₄I₅ crystals undergoing a second-order superionic phase transition. Thus the short-range order environment of the species involved in fast-ion transport plays the main role in the superionic phase transition. This is also supported by the value of the entropy change at T_s, ΔS = 43 J/mole·K. A new metastable phase was found to be induced on heating the (NH₄)₄H₂(SeO₄)₃ crystal above T_s.     

Atomic 6p-Tl0 centers in ferroelectric Rb2ZnCl4 crystals

Abstract

Several Tl⁰ (6s²6p ¹)-type paramagnetic centers, produced by low temperature X-ray irradiation, were observed and studied by electron spin resonance (ESR) in the orthorhombic ferroelectric phase of thallium doped Rb₂ZnCl₄ crystals. The centers were formed by electron trapping at Tl⁺ ions localized substitutionally at Rb⁺ sites. The number and properties of the observed centers account for the tripling of the unit cell in the ferroelectric phase.     

Structural Phase Transition and the Dielectric Permittivity of the Model Lipid Bilayer [(CH2)12(NH3)2]CuCl4

Structural phase transitions in the lipid-like bilayer material [(CH₂)₁₂(NH₃)₂]CuCl₄ have been observed using differential thermal scanning. The compound shows an irreversible thermochromic transition at ? 465 K and three reversible transitions at T ₁ = 433 ± 4 K and T ₂ = 411 ± 2 K and T ₃ = 358 K. The transition at 350 K is ascribed to chain melting. The other two correspond to crystalline phase transformation.

Phase (IV) T₃ = 358 ± 2K Phase (III) T₂ = 411 ± 2K Phase (II) T₁ = 433 ± 4K Phase (I)

Dielectric permittivity is studied as a function of temperature in the range 300-440 K and frequency, range (60 Hz-100 kHz). It confirms the observed transitions. The dielectric permittivity reflects rotational and conformational transitions for the compound. The variation of the real part of the conductivity with temperature is thermally activated in the temperature range above 350 K, with frequency-dependent activation energy, the values of activation energy lie in the range of ionic hopping. The dependence of the conductivity on frequency follows the universal power law σ = σ₀ + A(T) ω ^{s ( T )} with 0<s<1. Comparison of this material with other members of the series is discussed     

Mn2+doping-induced-effects on commensuration and incommensuration of potassium zinc chloride crystal

Undoped and Mn²⁺-doped with different concentrations of potassium zinc chloride (KZC) crystals were grown from aqueous solutions by slow evaporation. The dielectric constant (ε), dielectric losses (tan?δ) and ac conductivity (σ_ac) of the crystals in the ferroelectric-commensurate, incommensurate and normal phases have been measured as a function of frequency, in the range 1–100?kHz, and temperature, in the range 300–580?K. Virgin samples were subjected to measurements of the frequency dependence at selected temperatures and measurements of the temperature dependence was then followed using the same samples. The increase of ε with T could be due to a combination of conductivity, structural variations and discommensuration (DC) formation and pinning as well. The increase of tan?δ with temperature was attributed to relaxation loss in addition to conduction loss, which increases more rapidly with temperature. The ac conductivity (σ_ac) and tan?δ along the polar axis of KZC increased significantly with increasing Mn²⁺ content while ε decreased. σ_ac changed with frequency according to a power law of the form σ_ac?=?f? ^s where 0.15<s<1.27. A linear decrease of ε and tan?δ with increasing the frequency was also found. The obtained results were treated by considering the effect of Mn²⁺-doping on stripples nucleation, DC evolution/annihilation, DC-lattice formation and DCs pinning by the crystal lattice and/or structural defects for virgin and thermally treated samples.     

Influence of Pr dopant on the dielectric properties and Curie temperatures of Ba1−3x Pr2x Ti0.95Sn0.05O3 (0.01≤x≤0.05) ceramics

Three perovskite-structured ceramic phases Ba_1?3x Pr_2x Ti_0.95Sn_0.05O₃ (BPTS-x) with x=0.01, 0.03, and 0.05 have been synthesized by solid-state reaction method. Obtained BPTS-x ceramics were investigated by X-ray diffraction and dielectric properties measurements. Analysis of all the ceramic samples using X-ray diffraction method at room temperature and its Rietveld refinement inferred rhombohedric structure with the space group $R\bar{3}c$ . The temperature variation of real permittivity gives evidence of the ferroelectric phase transition and of the relaxation behavior. With increasing Pr concentration, the degree of diffuse phase transition was enhanced, and a linear reduction in the transition temperature was produced. The conductivity spectra have been investigated by the Jonscher universal power law (σ(ω)=σ _dc+Aω ^s ) and attributed to hopping conduction mechanism.     

Influence of nanocrystalline phases on the electrical properties of lithium titanate phosphate glass ceramics mixed with Ga2O3 nanocrystals

Several glass ceramic compositions dispersed with Ga₂O₃ nanocrystals, in the series samples (100???x)[0.4Li₂O–0.1TiO₂–0.5P₂O₅]?+?xGa₂O₃ with x?=?0, 2, 4, 6, 8, and 10?mol% of Ga₂O₃ were synthesized via high-energy ball milling technique and labeled as lithium gallium titanate phosphate glass (LTPG _x ) (x is the mol% of Ga₂O₃ nanocrystals). The compositions have been selected on the basis of thermal stability data obtained from differential thermal analysis. X-ray diffraction studies indicate nanocrystalline phase formation in the controlled crystallized glasses. The variation of electrical conductivity was explained in the light of growth of nanocrystalline phases. The best bulk conductivity (σ?=?7.03?×?10^?4?S?cm^?1, at 303?K) was achieved by the sample containing 8?mol% of Ga₂O₃ nanocrystals content, labeled as LTPG₈ sample. The activation energy for conduction (E_{a σ} ) is obtained from the temperature dependent of conductivity data, which is fitted to Arrhenius equation. The single super curve in the scaling spectra suggested the temperature-independent relaxation phenomenon.