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}     

Dielectric relaxation spectrum of water studied by the site—site generalized Langevin/modified mode-coupling theory

The dielectric relaxation spectrum of water is calculated from the site-site generalized Langevin/modified mode-coupling theory. The main part of the relaxation follows the Debye-type function, and a small deviation from the Debye relaxation is found on the high-frequency side. This tendency is consistent with recent experiments, although the absolute relaxation time does not agree with the experimental value quantitatively. The time development of the longitudinal polarization function resembles the dielectric part of the memory function, and we consider that this is because the dielectric friction dominates the collective reorientation of the dipole moment of water. We performed calculations with different dielectric constants using the reference interaction-site model integral equation, and found that the large gap between the time scales of the dielectric relaxation and the longitudinal polarization relaxation causes the Debye-type dielectric relaxation in our theory when the dielectric friction is dominant in the friction on the collective reorientation of the dipole moment. Namely, the longitudinal polarization relaxation is fast enough to be considered as a white noise to the dielectric relaxation process, so that the relaxation becomes a Markov process. The large gap between the two relaxation times originates from a large local field correction owing to the large dielectric constant of water. It is also suggested that the deviation from the Debye relaxation at the high-frequency side is the manifestation of the slow memory caused by the long-time part of the longitudinal polarization relaxation in the low-wavenumber region.     

One-dimensional semiconductor in a polar solvent: Solvation and low-frequency dynamics of an excess charge carrier

Due to solvation, excess charge carriers on 1d semiconductor nanostructures immersed in polar solvents undergo self-localization into polaronic states. Using a simplified theoretical model for small-diameter structures, we study low-frequency dynamical properties of resulting 1d adiabatic polarons. The combined microscopic dynamics of the electronic charge density and the solvent leads to macroscopic Langevin dynamics of a polaron and to the appearance of local dielectric relaxation modes. Polaron mobility is evaluated as a function of system parameters. Numerical estimates indicate that the solvated carriers can have mobilities orders of magnitude lower than the intrinsic values.     

Reaction dynamics for heavy particle charge transfer reactions in polar solvents and ion dielectric friction

The authors' theory of a solvent's influence on heavy particle charge transfer reactions in polar solvents with complex frequency-dependent dielectric constant is applied to treat the dielectric friction on a moving ion. The aim is to demonstrate a relation between the approach used in the theory and other approaches used for treating solute-solvent Coulomb interactions. As a result Zwanzig's formula is recovered. In addition, because this formula is derived by the other method, the relationship between the dielectric friction and the dynamics of nonequilibrium solvent polarization is demonstrated in a very transparent manner.     

Dielectric Dispersion Study of Poly(vinyl Pyrrolidone)–Polar Solvent Solutions in the Frequency Range 20 Hz–1 MHz

Influence of polar solvents environment and polymer concentrations on the electrical properties (complex dielectric constant, ac electrical conductivity, complex electric modulus and complex impedance) of the solutions of poly(vinyl pyrrolidone) (PVP) in polar solvents, namely water, ethyl alcohol, ethylene glycol, diethylene glycol, poly(ethylene glycol), glycerol, dimethyl sulfoxide and dimethyl formamide, have been investigated in the frequency range 20 Hz–1 MHz at 25°C. Comparative analysis of the dielectric dispersion curves confirms that the solvent molecular size and number of its hydroxyl groups, and the solutions viscosity, are the major factors which governs the PVP chain segmental motion. The ionic conduction and electrode polarization phenomena has a dominant influence on the large increase of complex dielectric constant values of the solutions of PVP‐polar solvent in the lower frequency region. The values of relaxation times corresponding to these phenomena are also reported.     

The influence of the inertial medium relaxation component on the kinetics of “hot” transitions

The probabilities of “hot” electronic transitions for inertial (Gauss correlation function) and diffusion (exponential correlation function) polar solvent relaxation modes were calculated. It was shown that the probabilities of transitions for inertial and diffusion relaxation could differ by two-three times. The possibility and conditions of the replacement of the inertial by diffusion relaxation component were studied in the simulation of electronic transition kinetics in real solvents.     

时域介电谱方法及其应用

提出了微分和二次微分时域介电谱方法。极化响应可描述为exp[-(t/τ)^α]类型若干个分得很开的峰,峰的线型决定α,它有1和1/2两个典型值.极化机构种类和峰的个数相等,峰高给出各机构对极化贡献的成份.响应时间τ由峰的位置定决,谱线的分离说明习惯设α=1而令τ有连续分布的看法缺乏根据,在石蜡中观察到温度升高时,指数增大,石蜡熔解过程中出现时域谱线分裂,从中可得到分子链运动的许多信息。     

On the dynamics of band Jahn-Teller systems with A15-structure

We construct a thermodynamic model for a system of electronic d-bands coupled to the elastic lattice. For the electronic fluctuations a Debye-type of relaxation, for the lattice displacement a modified elastic equation of motion is assumed. As a result a coupling of certain acoustic and relaxational modes is found leading to a soft mode instability. For non-vanishing external fields displacement and dielectric response functions are derived. The special case for wavevector q[110] is worked out explicitly. A comparison between the present phenomenological model and a microscopic multiple-band electron-phonon transport theory, recently given by the author, reveals remarkable agreement between both approaches.     

Fluctuations of the relaxation time in one-dimensional systems

The direct interaction of electrons with impurity field is represented as interelectronic interaction of a special kind which is called “dissipative”. This type of interaction is responsible for relaxation process and generally leads to fluctuations of the relaxation time. The probability distribution function for the mean free time of electrons is found in the white-noise approximation for a one-dimensional conductor. It is shown that the dielectric response function can be obtained in this case by averaging relevant expression over the fluctuations of the relaxation time.     

CaCu3Ti4O12 陶瓷介电模量响应特性的研究

由于CaCu₃Ti₄O₁₂巨介电常数陶瓷的低频区直流电导较大, 本文采用模量 M"-f频谱表征与分析了低频和高频的两个松弛极化过程. 研究认为, 这两个特征峰属于晶界区Schottky 势垒耗尽层边缘深陷阱的电子松弛过程, 其中高频松弛峰起源于晶粒本征缺陷的电子松弛过程, 而低频松弛峰则为与氧空位有关的松弛极化过程. 对于CaCu₃Ti₄O₁₂这类低频下具有高直流电导的陶瓷材料, 采用模量频谱能更有效地分析研究其损耗极化机理. 关键词： 3Ti₄O₁₂陶瓷')" href="#">CaCu₃Ti₄O₁₂陶瓷 模量 松弛过程 电导     

金红石相纳米块材TiO2的介电特性

研究了不同制备压力下成型的以金红石相为主的纳米二氧化钛介电常数的频率谱和温度谱。在频率谱上发现,当频率ω<0.1kHz时,随着测量频率的下降,介电常数迅速升高,低频下的介电常数比高频区的介电常数高1—2个数量级。并且随着样品加压压力的提高,介电常数升高,在与之相对应的介电损耗谱上,随着样品加压压力的提高,损耗值下降,损耗峰向低频区位移。对1.0GPa压力下成型的样品,其介电常数随测量温度的升高,分别在50℃和300℃出现两个峰值。经分析得出,影响金红石相纳米二氧化钛介电行为的微观机制主要为晶粒内部的电子松弛极化和界面中的电偶极矩的转向极化,50℃峰对应于电于松弛极化,而300℃峰则对应于电偶极矩的转向极化。 关键词：     

Optical and electronic properties of pure and fully hydrogenated SiC and GeC nanosheets: first-principles study

In this work, the electronic and linear optical properties of pure and fully hydrogenated SiC and GeC nanosheets have been studied using the full potential linearized augmented plane wave method within the density functional theory. Our study on SiC and GeC has confirmed their potential applications in electronic devices. The dielectric tensor is derived within the random phase approximation. The dielectric function, reflectivity, energy loss function and refraction index of these nanosheets for parallel (E||X) and perpendicular (E||Z) electric field polarization directions are well described. It is observed that hydrogenated nanosheets have semiconductor behavior with anisotropic optical spectra for both E||X and E||Z polarization direction. Also, hydrogenated nanosheets provide new electronic transitions between their neighboring atoms.     

Dielectric constant of solvents at nano to bulk regimes: linear response theory and statistical mechanics-based approaches

Statistical mechanics and generalised linear response theory based approaches are employed to derive the analytical expressions for size-dependent dielectric constant and normalised orientation polarisation of solvents. As an illustrative example, water is considered and the dielectric constants for the same are calculated over the entire range of water clusters. Our results reveal that the dielectric constant and normalised orientation polarisation are monotonically increasing with the increase in the number of solvent molecules and converge to the respective bulk values in the thermodynamic limit. More importantly, the dielectric constant of water is found to be independent of the nature, geometry and microscopic charges of the non-spherical ions. This finding offers a new platform for calculating the hydration energy and orientation polarisation based on linear response theory for different kinds of ions in the solvent medium.     

Dielectric spectroscopy on aqueous solutions of some zwitterionic amino acids

The complex (electric) permittivity of aqueous solutions of dipolar solutes has been measured as a function of frequency between 1 MHz and 40 GHz. Solutes are the isomers DL-2-aminobutyric acid, DL-3-aminobutyric acid, and 4-aminobutyric acid, and also 6-aminohexanoic acid. The measured dielectric spectra show two dispersion/dielectric loss regions, one due to the orientational diffusion of the solute molecules the other one due to the dielectric relaxation of the solvent water. A relaxation spectral function based on a model of the solutions has been fitted to the measured frequency dependence of the complex permittivity. The values for the electric dipole moment and reorientation time of the zwitterionic part of the solute particles derived by this analysis from the measurements fairly agree with theoretical predictions. Quite remarkably, the dipole moment in solution of 4-aminobutyric acid and 6-aminohexanoic acid up to remarkably high solute concentrations is nearly constant. A noteworthy result for the hydration water of the amino acids is, that its relaxation time is almost independent of the solute dipole moment.     

Polarization in organic molecular crystals and charge-transfer salts

Polarization in insulators is a general phenomenon that extends over nanometer distances. Two special cases illustrate recent theoretical progress. Polarization energies of localized charges in organic molecular crystals exceed the bandwidth and redistribute the charge density. A systematic treatment of electronic polarization is summarized in the limit of zero intermolecular overlap for pentacene crystals or thin films on metallic substrates, with special attention to the transport gap for producing a separated electron–hole pair and the optical dielectric tensor of the crystal. When overlap cannot be neglected, the general formulation of polarization in extended insulators is in terms of the exact ground state's phase. This formulation is applied to organic charge-transfer (CT) salts whose correlated electronic structure is described by one-dimensional Peierls–Hubbard models. Near the Peierls instability, coupling to lattice modes generates large peaks in the dielectric response that is primarily due to lattice vibrations. Comparisons with experiment are mentioned for both organic molecular crystals and CT salts.     

Quasistationary current contributions in electronic devices

In an electronic device, the current supplied to the electrodes is related to different types of processes inside the device: current density, change in spontaneous polarization, and change in dielectric properties. Two expressions for the electrode current are derived: one is based on the time derivative of the Shockley-Ramo theorem, the other on the time derivative of the dielectric tensor. This result is illustrated for a switching liquid crystal device and a two-dimensional flux tube.     

Lindhard dielectric function in the relaxation-time approximation and generalized linear response theory

Within a generalized linear response theory, an expression for the dielectric function is derived which allows to include the effect of collisions. Former attempts to include collisions into the Lindhard dielectric function by a relaxation time are discussed and systematic improvements are outlined.     

Laurdan and Prodan as Polarity-Sensitive Fluorescent Membrane Probes

The steady-state and dynamic fluorescence spectral properties of 2-dimethylamino-6-lauroylnaphthalene (LAURDAN) and several other naphthalene derivatives are summarized to illustrate their sensitivity to the polarity of the environment. Results obtained both in solvents of different polarity and in phospholipid vesicles in two phase states are presented. The emission red shift observed in polar solvents and in the phospholipid liquid–crystalline phase is explained on the basis of dipolar relaxation of solvent molecules surrounding the fluorescent naphthalene moiety of these probes. In phospholipid environments, experimental evidence is shown that excludes the intramolecular relative reorientation of the dimethylamino and carbonyl groups in the naphthalene and the reorientation of the entire fluorescent moiety. The solvent dipolar relaxation observed for LAURDAN and PRODAN in phospholipid bilayers has been attributed to a small number of water molecules present at the membrane interface. A comparison between LAURDAN emission in phospholipid vesicles prepared in D₂O and in H₂O is also presented. The definition and the derivation of the generalized polarization function are also discussed.     

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.