The mechanisms of thermally stimulated depolarization in poly(diphenylene phthalide)

The nature of the charge formed in a thin poly(diphenylene phthalide) film was studied by thermally stimulated depolarization over the temperature range 170–373 K. The influence of the strength of a polarizing electric field and the rate of temperature changes on the depolarization current spectrum was demonstrated. Polarizing electric field intensity changed from 3 × 10⁵ to 7 × 10⁵ V/cm. The rates of temperature changes were 3, 5, and 10 K/min. The depolarization current spectra contained three regions. The first two low-temperature regions were interpreted using the dipole and volume charge approximations, respectively. It was assumed that, in the third region, where charge inversion was observed, near the electrode polarization occurred. The experimental data were used to estimate activation energies and the relative charge released during relaxation in the first and second regions. The suggestion was made that the ratio between various contributions to depolarization current could be changed by varying the polarization field value.     

Temperature dependence of the permittivity of PbWO<Subscript>4</Subscript> crystals in the range 290–550 K

The temperature dependence of the permittivity ε of PbWO₄ crystals is studied in the range T = 290–550 K at a frequency of 1 kHz. The ε(_T) dependences measured on heating and cooling are different. On heating, groups of narrow maxima at 290–330 K and 330–400 K are observed in the ε(_T) curves. The first group of peaks is dominant. High-temperature polarization produces an additional broad peak in the ε (_T) curve at 400 K. A linear ε(_T) dependence is observed in the range 400–470 K. Above 470 K, the variation in ε(_T) closely follows an exponential law. Restoring relaxation of ε in the range 25–30 at 290 K after high-temperature sample heating proceeds exponentially in a few stages. The features of ε(_T) curves are determined by the dipole polarization and the hopping mechanism of charge exchange between complex dipole associates. Such structural defects may be pairs of doubly charged lead and oxygen vacancies (diplons). These defects also form a basis for more complicated defect complexes with localized holes (or electrons) at the corresponding vacancies.     

Thermally stimulated depolarization currents and ionic conductivity of cubic lead fluoride containing small rare earth ions

Abstract

This work is concerned with thermally stimulated depolarization current (TSDC) and ionic conductivity studies in lead fluoride containing the small rare earths Dy, Ho, Er and Yb. The TSDC scans from 80 to 300 K show two peaks. For Pb_1?xEr_xF_2+x one is located at 106 K, and another, which is much stronger, occurs at about 160 K. The former is associated with a dipolar defect containing at least two rare earths and the latter is attributed to the development of F^? space charge during polarization of the sample. The activation energies obtained from both the high temperature TSDC peak and the ionic conductivity are the same, which corroborates the latter assignment. In addition, the ionic conductivity is shown to be independent of concentration. Those results can be understood of rare earth clustering, which is either absent or is unobservable dielectrically for large rare earths such as lanthanum, occurs extensively even at very low concentrations of the small rare earths. The explanation is that the majority of fluorine charge compensators are trapped by clusters.     

Study of the anisotropy of the dielectric response of Na<Subscript>1/2</Subscript>Bi<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> relaxor ferroelectric

The dielectric response, conductivity, and domain structure of (Na_1/2Bi_1/2)TiO₃ single crystals are studied in the temperature range of 290–750 K for the [100], [110], and [111] crystallographic directions. It is shown that the region of optical isotropization is observed in polarized light in the temperature range of 570–620 K. In this case, the birefringence (Δn) decreases and disappears (together with the image of the domain structure) for the [100] directions. The region of optical isotropization in the [111] directions is characterized by the disappearance of the image of the domain structure and by the existence of individual regions with partial quenching. The domain structure in the [110] directions remains distinguished against the background of a significant decrease in Δn in the indicated temperature range. The region of isotropization is also manifested in the temperature dependence of the imaginary part of the dielectric response and is determined by the isotropic character of the conductivity in the range of 570–620 K. The bulk conductivity has a thermally activated character with activation energies E _a = 50?60 meV at T < 500 K and E _a = 700?900 meV for T > 620 K. The low-frequency dispersion of the dielectric response is determined by the Maxwell–Wagner mechanism and is due to an increase in the ionic conductivity at temperatures above 620 K. The anisotropy of the susceptibility holds in the entire studied ranges of frequencies (25 Hz–1 MHz) and temperatures.     

Ion diffusion-controlled thermally stimulated processes in x-ray irradiated halide crystals

The ionic and ion diffusion-controlled thermally stimulated relaxation (TSR) processes in CaF₂, BaF₂, LiBaF₃ and KBr crystals were investigated above 290 K by means of the ionic conductivity, ionic thermally stimulated depolarisation current (TSDC) and thermal bleaching techniques. Under a DC field the halide crystals store large ionic space charge. We were able to detect in CaF₂, BaF₂, LiBaF₃ and KBr in the extrinsic ionic conductivity region a series of the ionic defect (the interstitial anion and/or anion vacancies - in fluorides; the cation vacancies - in KBr) release stages: 3-6 wide and overlapping ionic TSDC peaks. The correlated data of the ionic TSDC and the F band thermal show that above 290 K the TSR processes are initiated and controlled by the ionic defect thermal detrapping, migration and interaction with the localised electronic and ionic charges and colour centres. The ion diffusion-controlled TSR processes take place in the above halide crystals.     

Dielectric properties of the P(VDF<Subscript>60</Subscript>/Tr<Subscript>40</Subscript>) copolymer in the porous glass matrix

The dielectric properties and electrical conductivity of the composite material, which was prepared by incorporating the P(VDF₆₀/Tr₄₀) copolymer into the porous glass matrix (the average pore diameter is approximately equal to 320 nm), and the bulk sample of the P(VDF₆₀/Tr₄₀) copolymer have been investigated in the temperature range 290–440 K. It is revealed that the incorporated material is characterized by an increase in the melting temperature and a considerable decrease in the temperature at which the ferroelectric phase formed in polymer inclusions becomes unstable. It is shown that charge transfer in the composite material occurs predominantly through channels filled with the polymer.     

Study of thermal currents in powder β-spodumene ceramics doped with Cuo, FeO and TiO2

Ternary-phase ceramic system of Li₂O Al₂O₃ 4SiO₂ doped with CuO, FeO and TiO₂ has been prepared and subjected to dc electrical conductivity and thermally stimulated depolarization current (TSDC) measurements as a function of temperature (30-250 °C) and field strength. The electrical conductivity results are explained by assuming both ionic and electronic conduction mechanisms coexist with different contributions over the whole temperature range of experiments. TSDC spectra have been found to be characterized by a broad intense relaxation peak, which can be attributed to an ionic charge polarization. The broad relaxation transitions are apparently a result of the nonuniform nature of this process. Activation energies are calculated for both dc electrical conductivity and TSDC according to Arrhenius equation and initial rise method, respectively.     

Ionic,electronic and ion-diffusion controlled relaxation processes in CaF2, BaF2 and LiBaF3 crystals

Abstract

The ionic, electronic and anion-diffusion controlled thermally stimulated relaxation (TSR) processes at 80—700 K in CaF₂ BaF₂ and LiBaF₃ crystals (X-ray irradiated or non-irradiated) have been investigated by means of ionic conductivity, ionic thermally stimulated (TS) depolarization current (TSDC); as well as current (TSC), luminescence (TSL) and bleaching (TSB) techniques. Above 250—290 K broad and overlapping anion TSDC peaks and correlated TSB stages are detected. The TSB kinetics is initiated and controlled by anion detrapping and interaction with the localized charges, i.e., the anion-diffusion controlled TSR processes take place in fluorides. The TSL and TSC data for LiBaF₃ indicate that the lifetime and drift of electrons at 80—250 K is very small because of deep retrapping. The main TSL peaks at 132K, 170K and 220 K are caused by V_k center detrapping and hole-diffusion controlled tunnel recombination within pairs like {D_n e^?…V_k }.     

Ion diffusion-controlled thermally stimulated processes in X-ray irradiated halide crystals

The ionic and ion diffusion-controlled thermally stimulated relaxation (TSR) processes in CaF 2 , BaF 2 , LiBaF 3 and KBr crystals were investigated above 290 v K by means of the ionic conductivity, ionic thermally stimulated depolarisation current (TSDC) and thermal bleaching techniques. Under a DC field the halide crystals store large ionic space charge. We were able to detect in CaF 2 , BaF 2 , LiBaF 3 and KBr in the extrinsic ionic conductivity region a series of the ionic defect (the interstitial anion and/or anion vacancies - in fluorides; the cation vacancies - in KBr) release stages: 3-6 wide and overlapping ionic TSDC peaks. The correlated data of the ionic TSDC and the F band thermal evidence that above 290 v K the TSR processes are initiated and controlled by the ionic defect thermal detrapping, migration and interaction with the localised electronic and ionic charges and colour centres. The ion diffusion-controlled TSR processes take place in the above halide crystals.     

Polar behaviour induced by lithium in potassium tantalate ceramics

Polar behaviour in K(1-x)Li(x)TaO(3) ceramics with x = 0:02, 0.05 and 0.10, processed by the conventional solid state method, is studied by Raman spectroscopy and thermally stimulated depolarization current (TSDC) techniques between 10 and 290 K. The TO1 mode of KTaO(3) is revealed to harden in the whole temperature range and to split in the low-temperature range by Li doping. One splitting is observed for x = 0:02 and two consequent splittings are detected for x = 0:05 and 0.10. The temperatures, where TO1 mode splitting occurs, are found to correspond to those of the peaks of TSDC, and hence to the onset of the electric polarization. Such behaviour provides evidence for the order-disorder ferroelectric phase transition induced in KTaO(3) by lithium doping, which emerges from deformations of the cubic phase developed on cooling either in one (for x = 0:02) or two steps (for x = 0:05 and 0.10).     

Investigations on electric properties of polymers. X. Dielectric relaxation in polyphenylacetylenes studied by thermally stimulated depolarization currents

The thermally stimulated depolarization currents from polyphenylacetylenes with various isomeric structures (cis-cisoidal, cis-transoidal, and trans-cisoidal) were studied over the temperature range 200–360°K. The complexity of the spectra obtained depends on the isomeric structure of the polymer and, for the cis-transoidal one, in addition on its cis content. The ρ peak of the cis-cisoidal isomer was assigned to the Maxwell-Wagner polarization. The β₁ and β'₁ peaks, attributed to the cis and the trans fraction, respectively, arise from a single dipolar relaxation process, whereas β₂ peaks originate from a dipolar relaxation distributed in natural frequency. The molecular motions involved are not simple rotations about the formal single and C_α-phenyl bonds.     

Dielectric relaxation and ionic conductivity studies of LiCaPO<Subscript>4</Subscript>

The AC conductivity of the LiCaPO₄ compound has been measured in the temperature range 634–755 K and the frequency range 300 Hz–5 MHz. The impedance data were fitted to an equivalent circuit consisting of series combination of grains, grains boundary, and electrode elements. Dielectric data were analyzed using complex electrical modulus M* at various temperatures. The modulus plots are characterized by the presence of two relaxation peaks thermally activated. The activation energies obtained from the analysis of M″ (0.90 eV) and conductivity data (0.94 eV) are very close, revealing an ionic hopping mechanism.     

Effect of Polarization Temperature on the Chain Segment Motion and Space Charge Detrapping in Polyamide 610 Film Electrets

The effect of polarization temperature on the chain segment motion and charge trapping and detrapping in polyamide 610 films has been investigated by means of thermally stimulated depolarization current (TSDC) and wide-angle X-ray diffraction (WAXD). A small part of the amorphous phase of quenched polyamide 610 changes into the crystalline state with increasing polarization temperature. There are three current peaks (named α, ρ₁, and ρ₂ peak, respectively) in the TSDC spectra. The α peak corresponds to the glass transition, the ρ ₁ peak is attributed to space charge trapped in the amorphous phase, and interphase between crystalline and amorphous phases, and the ρ ₂ peak originates from space charge trapped in the crystalline phase. By analyzing the characteristic parameters of these peaks, it was found that the increase of polarization temperature induced a decrease of the chain segment mobility and promoted the creation of structural traps in polyamide 610. The decrease of the chain segment mobility in the amorphous phase made the intensity of the α peak weak and the activation energy increased. The higher the polarization temperature, the higher the degree of crystallinity and the more charge carriers trapped in the crystalline phase. So, the increase of polarization temperature made the intensity of the ρ ₂ peak strong and increased the stability of trapped charge in the crystalline phase. The increase of polarization temperature also made the intensity of the ρ ₁ peak strong and decreased the stability of trapped charge in the amorphous phase and interphase.     

退火与极化温度对尼龙11薄膜驻极体内陷阱能级分布的影响

用热释电技术研究了尼龙11薄膜驻极体制备过程中热处理与极化温度对驻极体陷阱能级分布的影响.结果显示，淬火驻极体的热释电流谱上存在四个空间电荷退陷阱电流峰，而在退火处理后则显示两个退陷阱电流峰.采用多点法对热释电流谱进行理论拟合可以将各个退陷阱电流峰分离并得到它们的陷阱深度参数.这些参数进一步表明，淬火尼龙11薄膜驻极体内存在四个空间电荷的陷阱能级，极化温度升高对它们的分布情况影响不大；退火处理后，陷阱能级减少为两个，且随着极化温度的升高，较浅的陷阱能级有明显向较深陷阱能级接近的趋势. 关键词： 尼龙11 薄膜驻极体 热释电 热处理     

The Chain Segment Motion and Traps in γ‐Irradiation Crystalline Nylon 1010

The chain segment motion, charge trapping and detrapping in γ‐irradiated nylon 1010 films (doses in the range 0–2,000 kGy were used) have been investigated by means of thermally stimulated depolarization current (TSDC). There are three current peaks (named α, ρ₁ and ρ₂, respectively) in the TSDC spectra, corrected by spontaneous current, above room temperature. By analyzing the characteristic parameters of the three peaks, it is found that the chain segment motion in the amorphous regions becomes more difficult at low irradiation dose (<100 kGy) and then becomes easier with further increasing irradiation dose. The stability of the traps at the crystalline‐amorphous interfaces increases at low irradiation dose (<500 kGy) and then decreases with further increasing irradiation dose; the irradiation promotes the creation of traps and the stability of traps in the crystalline regions.     

Estimation of the parameters of charge carriers in polymers in the vicinity of the threshold of thermally stimulated switching

The temperature dependences of the parameters of charge carriers in thin films of an electroactive poly(diphenylenephthalide) polymer are investigated in the range preceding the thermally stimulated electronic switching (110–400 K). The thermally stimulated current spectra and current-voltage characteristics are measured in the same temperature range. The parameters of charge carriers are estimated in the framework of the model of injection currents limited by the space charge. It is revealed that the charge carrier mobility decreases with an increase in the temperature in the range from 110 to 400 K. A correlation between the temperature behavior of the current-voltage characteristics and the thermally stimulated current spectra is established. The possible contribution of the Pool-Frenkel effect is considered, and the inference is made that the electric field plays an important role in the thermally stimulated electronic switching.     

Muon-spin-relaxation investigation of EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript>

The magnetic properties of the EuMn₂O₅ multiferroic (samples consisting of single crystals and ceramic samples) have been investigated by the muon-spin-relaxation (μSR) method in the temperature range of 10–300 K. Below the magnetic ordering temperature T _N = 40 K, the loss of the polarization of muons and the effect of the external magnetic field have been observed. Both phenomena can be explained by an additional channel of the depolarization of muons owing to the appearance of muons in a medium with a low electron density due to the charge separation process (the redistribution of the electron density in the phase transition process). The “memory” phenomenon has been revealed in a sample in the external magnetic field; the memory relaxation time depends on the size of the structure units of the samples (single crystals or ceramic grains).     

Mixed (ionic and hole) conductivity of Tl<Subscript>3</Subscript>VS<Subscript>4</Subscript> crystals

A model of mixed (ionic and hole) conductivity in Tl₃VS₄ crystals at close-to-room temperatures is proposed. The significant fraction of the ionic conductivity component (～70% of the total conductivity) is explained by the nonstoichiometric electrically active thallium vacancies, whose acceptor levels provide p-type conductivity. The characteristic time dependence of the voltage developing across a sample due to its polarization and depolarization is described using the diffusion theory of mixed conductivity previously developed by Yokota. The charge transport phenomena in Tl₃VS₄ are studied experimentally, and the data are processed according to the theoretical model.     

Effect of heating treatment on trap level distribution in polyamide 66 film electrets

The effect of heating treatment on the trap level distribution in polyamide 66 film electret is studied by thermally stimulated depolarization current （TSDC） technique. For annealed polyamide 66, there are three trap levels that respectively originate from space charge trapped in amorphous phase, interphase and crystalline phase. There is one peak that originates from space charge trapped in amorphous phase for quenched one. Using multi-point method to fit the experimental curves, the detrapping current peaks can be separated and the trap depth is obtained. The shallower trap levels trapped in amorphous phase and interphase are obviously close to the deeper trap level trapped in crystalline phase for annealed polyamide 66 as the polarization temperature increases, while the trap level distribution remains unaffected by polarization temperature for quenched one.     

Conductivity behavior of the new pyrophosphate NaNi<Subscript>1.5</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

NaNi_1.5P₂O₇ compound was obtained by the classic ceramic method at high temperature and was characterized by XRD. It was found to crystallize in the triclinic symmetry with the P-1 space group. The electrical conductivity and modulus characteristics of the system have been investigated in the temperature and the frequency range 586–723 K and 200 Hz–1 MHz, respectively, by means of impedance spectroscopy. The ac conductivity for grain contribution was interpreted using the universal Jonscher’s power law. The exponent s decreased with increasing temperature revealing that the conduction inside the studied material is insured by the correlated barrier hopping (CBH) model. The conduction mechanism was explained with the help of Elliot’s theory, and the Elliot’s parameters were determined. Thermodynamic parameters such as the free energy for dipole relaxation ΔG, the enthalpy ΔH, and the change in entropy ΔS have been calculated.