Constant dielectric loss in disordered ionic conductors: Theoretical aspects

Cooperative charge relaxation within a random system of electrostatically interacting defect centers provides a mechanism for a “nearly constant dielectric loss” (NCL) response in structurally disordered ionic conductors. Pertinent models based on statistical mechanics are reviewed briefly. In addition, we present a theoretical frame for the problem of how two kinds of ionic motion, hopping migration and NCL-type local charge relaxation, are superimposed in the total ac-response. Using renewal theory, the modification of NCL-spectra due to hopping is calculated in terms of the waiting time distribution for ionic hops. In the special case of Poissonian hops with average rate λ the modified complex dielectric susceptibility in the NCL-regime is obtained by analytic continuation from the corresponding susceptibility in the absence of hops. Implications with respect to the crossover between hopping transport and NCL-behavior are discussed.     

Dielectric property of CaCu3Ti4O12 thin film grown on Nb-doped SrTiO3(100) single crystal

Thin film of CaCu₃Ti₄O₁₂ (CCTO) has been deposited on Nb-doped SrTiO₃(100) single crystal using pulsed laser deposition. The dielectric constant and AC conductivity of CCTO film in the metal–insulator–metal capacitor configuration over a wide temperature (80 to 500 K) and frequency (100 Hz to 1 MHz) range have been measured. The small dielectric dispersion with frequency observed in the lower temperature region (<300 K) indicates the presence of small defects in the deposited CCTO thin film. The frequency-dependent AC conductivity at lower temperature indicates the hopping conduction. The dielectric dispersion data has been analyzed in the light of both conductivity relaxation and Debye type relaxation with a distribution of relaxation times. Origin of dielectric dispersion is attributed to the distribution of barrier heights such that some charge carriers are confined between long-range potential wells associated with defects and give rise to dipolar polarization, while those carriers which do not encounter long-range potential well give rise to DC conductivity.     

Surface and near-surface passivation, chemical reaction, and Schottky barrier formation at ZnO surfaces and interfaces

Using a combination of depth-resolved cathodoluminescence spectroscopy, electronic transport, and surface science techniques, we have demonstrated the primary role of native defects within ZnO single crystals as well as native defects created by metallization on metal-ZnO Schottky barrier heights and their ideality factors. Native defects and impurities resident within the ZnO depletion region as well as defects extending into the bulk from the intimate metal-ZnO interface contribute to barrier thinning of, carrier hopping across, and tunneling through these Schottky barriers. Chemical reactions at clean ZnO-metal interfaces lead to metal-specific eutectic or oxide formation with pronounced transport effects. These results highlight the importance of bulk crystal quality, surface cleaning, metal interaction, and post-metallization annealing for controlling Schottky barriers.     

Studies of dielectric and impedance properties of KCa2V5O15 ceramics

A polycrystalline sample, KCa₂V₅O₁₅, with tungsten bronze structure was prepared by a mixed-oxide method at low temperature (i.e., at 630 °C). A preliminary structural analysis of the compound showed an orthorhombic crystal structure at room temperature. Surface morphology of the compound was studied by scanning electron microscopy (SEM). Two dielectric anomalies at 131 and 275 °C were observed in the temperature dependency of dielectric response at various frequencies, which may be attributed to the ferroelastic-ferroelectric and ferroelectric-paraelectric transitions, respectively. The nature of variation of the electrical conductivity, and value of activation energy of different temperature regions, suggest that the conduction process is of mixed-type (i.e., ionic-polaronic and space charge generated from the oxygen ion vacancies). The impedance plots showed only bulk contributions, and non-Debye type of relaxation process occurs in the material. A hopping mechanism of electrical transport processes in the system is evident from the modulus analysis. The activation energy of the compound (calculated both from loss and modulus spectrum) is same, and hence the relaxation process may be attributed to the same type of charge carriers.     

Dopant size dependent variable range hopping conduction in polyaniline nanorods

The present work investigates the electrical transport and dielectric relaxation of polyaniline (PAni) nanorods doped with organic camphorsulfonic acid (CSA) and inorganic hydrochloric acid (HCl) synthesized by interfacial polymerization technique. High resolution transmission electron micrographs (HRTEM) depict that initially spherical nuclei directionally grow into nanorods and CSA doped PAni produces more uniform and aligned structures. The electrical transport studies reveal that the CSA doped nanorods follow 1D Mott variable-range hopping (VRH), whereas the HCl doped nanorods exhibit 2D VRH conduction mechanism. The value of interchain charge transfer integral is found to be higher for smaller size HCl doped PAni than that for larger size CSA doped PAni. The resistivity measurements exhibit semiconducting behavior for both organic and inorganic dopants and the resistivity of the CSA doped nanorods is found to be smaller than that of the HCl doped nanorods. The dielectric relaxation studies suggest Debye type relaxation with a single relaxation peak for both the dopants and the relaxation time of the carriers of the CSA doped PAni nanorods is smaller than that of the HCl doped nanorods.     

Charge transfer between ZnO crystals and dye layers

The interaction between crystal and adsorbed dye molecules has been studied under well defined conditions by measurements of field effect and spectrally sensitized photoconductivity. The (101&#x0304;0) surfaces of n-type ZnO crystals (band gap 3.3 eV) are cleaned in ultrahigh vacuum. A pretreatment with atomic hydrogen produces an accumulation layer. Merocyanine (polymethine) dye molecules are deposited by sublimation in the same vacuum (coverage (1–2000) × 10¹⁴ cm^?2. Optical excitation of the dye causes a sensitized photoconductivity in the ZnO crystal close to the surface. The spectra distribution resembles the absorption spectrum of the dye with a maximum at 2.3 eV. An electric field applied perpendicular to the dye covered surface induces charge carriers in the crystal and changes the surface conductivity (field effect). Additional excitation of the dye by light causes a slow relaxation of the field-induced change of surface conductivity. This relaxation is observed for both signs of the field. Furthermore a memory of the dye covered crystals has been found. It can be programmed by field and light, read out via the surface conductivity and quenched by light. A phenomenological model for relaxation and memory is refined by kinetic equations and by considerations about charge transport within the dye layer. The observations can only be explained by a charge transfer between crystal and dye operating in both directions. From these results the following conclusion is drawn for the mechanism of spectrally sensitized photoconductivity of the present system: An electron transfer between dye molecules and crystal represents the decisive step rather than an energy transfer.     

Dielectric relaxation and ac conductivity behavior of carboxyl functionalized multiwalled carbon nanotubes/poly (vinyl alcohol) composites

We study the dielectric relaxation and ac conductivity behavior of MWCNT-COOH/Polyvinyl alcohol nanocomposite films in the temperature (T) range 303–423 K and in the frequency (f) range 0.1 Hz–1 MHz. The dielectric constant increases with an increase in temperature and also with an increase in MWCNT-COOH loading into the polymer matrix, as a result of interfacial polarization. The permittivity data were found to fit well with the modified Cole-Cole equation. Temperature dependent values of the relaxation times, free charge carrier conductivity and space charge carrier conductivity were extracted from the equation. An observed increment in the ac conductivity for the nanocomposites was analysed by a Jonscher power law which suggests that the correlated barrier hopping is the dominant charge transport mechanism for the nanocomposite films. The electric modulus study revealed deviations from ideal Debye-type behavior which are explained by considering a generalized susceptibility function. XRD and DSC results show an increase in the degree of crystallinity.     

Modelling of diffusion and conductivity relaxation of oxide ceramics

A two-dimensional square grain model has been applied to simulate simultaneously the diffusion process and relaxation of the dc conduction of polycrystalline oxide materials due to a sudden change of the oxygen partial pressure of the surrounding gas phase. The numerical calculations are performed by employing the finite element approach. The grains are squares of equal side length (average grain size) and the grain boundaries may consist of thin slabs of uniform thickness. An additional (space charge) layer adjacent to the grain boundary cores (thin slabs) either blocking (depletion layer) or highly conductive for electronic charge carriers may surround the grains. The electronic transport number of the mixed ionic-electronic conducting oxide ceramics may be close to unity (predominant electronic conduction). If the chemical diffusion coefficient of the neutral mobile component (oxygen) of the grain boundary core regions is assumed to be higher by many orders of magnitude than that in the bulk, the simulated relaxation curves for mass transport (diffusion) and dc conduction can deviate remarkably from each other. Deviations between the relaxation of mass transport and dc conduction are found in the case of considerably different electronic conductivities of grain boundary core regions, space charge layers, and bulk. On the contrary, the relaxation curves of mass transport and electronic conductivity are in perfect coincidence, when either effective medium diffusion occurs or the effective conductivity is unaffected by the individual conductivities of core regions and possible space charge layers, i.e. the grain boundary resistivity is negligible.     

Structural and dielectric properties of undoped ZnO pellets prepared by solid state route

Undoped zinc oxide has been prepared at various growth temperatures by a conventional sintering process. The crystal structures of the prepared samples were studied by X-ray diffraction. The frequency-dependent dielectric dispersion of all the sintered ZnO ceramics was investigated in the temperature range from ?100 to 30 °C and in the frequency range from 1 Hz to 10 MHz by broadband dielectric spectroscopy. An analysis of the complex permittivity and electric modulus as a function of frequency has been performed assuming a distribution of relaxation times. The pellet sintered at 900 °C showed the lowest value of the dielectric strength. The temperature dependent of the parameter α is discussed. While the charge transport through the grain and grain boundary regions was examined by impedance spectroscopy. Activation energy values extracted from conduction measurements were found to be in the range of 0.09 and 0.3 eV.     

Switching and memory effects governed by the hopping mechanism of charge carrier transfer in composite films based on conducting polymers and inorganic nanoparticles

The switching and memory effects in composite films based on conducting polymers [poly(phenylenevinylene), thiophene, and carbazole derivatives] and inorganic nanoparticles (ZnO, Si) are investigated. It is established that the introduction of inorganic nanoparticles (ZnO, Si) exhibiting strong acceptor properties into polymer materials leads to the appearance of memory effects, which manifest themselves in the transition of the polymer from a low-conductivity state to a high-conductivity state. For a number of composites, this transition is accompanied by the formation of a region with a negative differential resistance and a hysteresis in the current-voltage characteristics. It is demonstrated that the observed effects are determined by the mechanism of charge carrier transfer in the composite. In particular, the main mechanism of transport in films based on thiophene derivatives is associated with electrical conduction due to the tunneling of charge carriers between conducting regions embedded in a nonconducting matrix, whereas the dominant mechanism of transport in “polymer-semiconductor nanoparticle” composite films is hopping conduction, which is responsible for the effects observed in these objects.     

Electronic relaxation of deep bulk trap and interface state in ZnO ceramics

This paper investigates the electronic relaxation of deep bulk trap and interface state in ZnO ceramics based on dielectric spectra measured in a wide range of temperature, frequency and bias, in addition to the steady state response. It discusses the nature of net current flowing over the barrier affected by interface state, and then obtains temperature-dependent barrier height by approximate calculation from steady I--V (current--voltage) characteristics. Additional conductance and capacitance arising from deep bulk trap relaxation are calculated based on the displacement of the cross point between deep bulk trap and Fermi level under small AC signal. From the resonances due to deep bulk trap relaxation on dielectric spectra, the activation energies are obtained as 0.22 eV and 0.35 eV, which are consistent with the electronic levels of the main defect interstitial Zn and vacancy oxygen in the depletion layer. Under moderate bias, another resonance due to interface relaxation is shown on the dielectric spectra. The DC-like conductance is also observed in high temperature region on dielectric spectra, and the activation energy is much smaller than the barrier height in steady state condition, which is attributed to the displacement current coming from the shallow bulk trap relaxation or other factors.     

Hopping and drift mechanisms of photoconductivity in ZnO:Li films

The mechanisms of dark- and photoconductivity in ZnO:Li films are investigated. The obtained results are interpreted on the basis of hopping mechanism of charge carriers transport for the dark conductivity and the hopping or drift mechanism for the photoconductivity depending on the energy of an exciting photon. For photons with the energy more than the forbidden band gap the drift mechanism of carriers transport takes place, while for photons with the energy less than the forbidden band gap the hopping mechanism takes place.     

Charge transfer in thin polymer films of polyarylenephthalides

Transitions from an insulating state to a high-conductivity state are observed in thin polymer films of polyarylenephthalides. The temperature dependences of the conductivity for thin films of wide-band-gap polymer insulators are determined, the relaxation of excess charge is investigated, and the mechanisms of charge transfer in the temperature range preceding the transition to the high-conductivity state are revealed. It is shown that hopping transport over trap states in the band gap is the main mechanism of charge transfer in polyarylenephthalide film.     

Investigation of MWS Relaxation in Nylon 1010 using Dielectric Relaxation Spectroscopy

Maxwell–Wagner–Sillars (MWS) relaxation in nylon 1010, arising from charge carriers accumulated at the interphase between amorphous and crystalline regions, has been investigated by means of dielectric relaxation spectra. In the frequency spectra of nylon 1010, dielectric permittivity showed high values at low frequencies originating from charge carrier movement. For the MWS relaxation, the dielectric strength was independent of temperature. The results revealed that there is a transition temperature, located between 110 and 120°C, resulting in the separation of two different charge carrier movement mechanisms. Below and above this transition temperature, the temperature dependence of the MWS relaxation time follows the Vogel–Tammann–Fulcher type, showing that the charge carrier transport is governed by the motion of the polymer chains. The change of charge carrier movement mechanisms is due to the onset of polymer chain motion in the interphase.     

Refractive index,band gap energy,dielectric constant and polarizability calculations of ferroelectric Ethylenediaminium Tetrachlorozincate crystal

Single crystal of Ethylenediaminium Tetrachlorozincate has been grown by slow evaporation method. The single crystal XRD study confirms the orthorhombic structure of the crystal. The presence of functional group vibrations are ascertained through FTIR and Raman studies. In optical studies, the insulating behaviour of the material is established by Tauc plot. The refractive index and the real dielectric constant of the crystal are calculated. The electronic polarizability in the high frequency optical region is also calculated from the dielectric constant values by using the Clausius–Mossotti equation. The large value of dielectric constant is identified through dielectric studies and it points to the ferroelectric behaviour of the material. Further an experimental study confirms the ferroelectric behaviour of the material. The total polarizability of the crystal owing to the space charge, dipole, ionic and electronic polarizability contributions is obtained experimentally, and it matches well with the theoretically obtained value from Penn analysis. Further, Plasmon energy and Fermi energy of the material are also calculated using Penn analysis.     

Selective spreading and jetting of electrically driven dielectric films

We study the electrically driven spreading of dielectric liquid films in wedge-shaped gaps across which a potential difference is applied. Our experiments are in a little-studied regime where, throughout the dynamics, the electrical relaxation time is long compared to the time for charge to be convected by the fluid motion. We observe that at a critical normal electric field the hump-shaped leading edge undergoes an instability in the form of a single Taylor cone and periodic jetting ensues, after which traveling waves occur along the trailing thin film. We propose a convection-dominated mechanism for charge transport to describe the observed dynamics and rationalize the viscosity dependence of the self-excited dynamics.     

Dielectric relaxation and AC conduction of an AgTlSe2 semiconductor in the solid and liquid states

Measurements of the dielectric properties of AgTlSe₂ in the solid and liquid states were carried out in a wide range of frequencies and temperatures. The material displayed dielectric dispersion, and a loss peak was observed. Cole-Cole diagrams have been used to determine the distribution parameter (a) and the molecular relaxation time (). The process of dielectric relaxation (loss) and ac conduction was attributed to the correlated barrier hopping model suggested by Elliott for amorphous solids, where two carriers simultaneously hop over a barrier between charged defectD ⁺ andD ^– states.     

ZnO压敏陶瓷中缺陷的介电谱研究

从理论上证明了介电松弛过程在介电谱上等效于电子松弛过程,认为室温下10⁵Hz处特征损耗峰起源于耗尽层处本征缺陷所形成的电子陷阱.在-130—20℃范围内测量了三种配方ZnO陶瓷的介电频谱,发现ZnO压敏陶瓷室温下10⁵Hz处的特征损耗峰在低温下分裂为两个特征峰,认为它们起源于耗尽层中的本征缺陷(锌填隙或/和氧空位)的电子松弛过程.发现ZnO-Bi₂O₃二元系陶瓷特征峰仅仅由锌填隙引起,而ZnO-Bi_{2关键词： ZnO压敏陶瓷 本征缺陷 介电谱 热处理}     

Small polaron hopping conduction mechanism in Ni-doped LaFeO3

The electrical transport properties of LaFe_{1? x} Ni _x O₃ (0.1 ≤ x ≤ 0.6) bulk samples were investigated over a wide temperature range, i.e. 9–300 K. Powder x-ray diffraction patterns at room temperature showed that all samples were formed in a single phase. However, a structural transformation was observed from orthorhombic (Pnma) to rhombohedral crystal symmetry at x > 0.5 in Ni-doped samples, which is supported by the electrical transport analysis. Temperature-dependent resistivity data were fitted using Mott's variable-range hopping model for a limited range of temperatures to calculate the hopping distance and the density of states at Fermi level. It was found that all parameters vary systematically with an increase in Ni concentration. Moreover, the resistivity data were also fitted using the small polaron hopping (SPH) model. The non-adiabatic SPH conduction mechanism is followed up to 50% Ni concentration, whereas an adiabatic hopping conduction mechanism is active above it. Such a change in the conduction mechanism is accompanied by subtle electronically induced structural changes involving Fe³⁺–O–Fe³⁺ and Fe³⁺–O–Ni³⁺ bond angles and bond lengths. Thus, we suggest that the transport properties can be explained according to the additional delocalization of charge carriers induced by Ni doping.