ZnO压敏陶瓷介电损耗的温度谱研究

利用Novocontrol宽频介电谱仪在-100—20 ℃温度范围内测量了ZnO-Bi₂O₃系压敏陶瓷的介电频谱,其频率范围为10^-2—10⁶ Hz. 研究表明： ZnO压敏陶瓷特征损耗峰的活化能分别为0.26和0.36 eV,结合实验条件、理论计算结果及其他现象的分析排除了特征损耗峰源于阴极电子注入、夹层极化和偶极子转向极化的可能.热刺激电流（TSC）谱共出现三个峰,其中高温峰对应于TSC实验加压过程引入的热离子极化,而中温峰和低温峰对应于介电损耗峰. 在分析的基础上,提出了ZnO压敏陶瓷的特征损耗峰起源于耗尽层内本征缺陷的电子弛豫过程. 关键词： ZnO压敏陶瓷 本征缺陷 介电谱 热刺激电流     

直流老化及热处理对ZnO压敏陶瓷缺陷结构的影响

在电场为3.2 kV/cm, 电流密度为50 mA/cm²条件下对ZnO压敏陶瓷进行了115 h的直流老化, 研究了直流老化对ZnO压敏陶瓷电气性能及缺陷结构的影响. 发现直流老化115 h 后ZnO压敏陶瓷的电位梯度、非线性系数分别从2845 V/cm, 38.3下降到51.6 V/cm, 1.1, 介电损耗中的缺陷松弛峰被增大的直流电导掩盖, 电模量中只观察到一个缺陷松弛峰, 低频区交流电导率急剧增大并且相应的电导活化能从0.84 eV下降到只有0.083 eV. 通过对直流老化后的ZnO压敏陶瓷在800 ℃进行12 h 的热处理, 发现其电气性能和介电性能都得到了良好的恢复并有一定的增强, 电位梯度、非线性系数恢复到3085 V/cm, 50.8, 电导活化能上升到0.88 eV. 另外, 其本征氧空位缺陷松弛峰也得到了一定的抑制. 因此, 认为热处理过程中氧在晶界处的扩散作用对ZnO压敏陶瓷的直流老化恢复起到了关键作用. 关键词： ZnO压敏陶瓷 介电性能 直流老化 热处理     

Thermally stimulated current and high temperature resistivity measurements of 4H semi-insulating silicon carbide

High purity semi-insulating 4H SiC single crystals have potential applications for room temperature radiation detectors because of the wide band gap and radiation hardness. To control carrier lifetime, a key parameter for high performance radiation detectors, it is important to understand the nature of the deep traps in this material. For this purpose, we have successfully applied thermally stimulated current (TSC) and high temperature resistivity measurements to investigate deep level centers in semi-insulating 4H SiC samples grown by physical vapor transport. High temperature resistivity measurements showed that the resistivity at elevated temperatures is controlled by the deep level with an activation energy of 1.56 eV. The dominant traps revealed by TSC measurements were at 1.1-1.2 eV. The deep trap levels in 4H-SiC samples, the impurity and point defect nature of TSC traps peaked at ∼106 K (0.23 eV), ∼126 K (0.32 eV), ∼370 K (0.95 eV), ∼456 K (1.1-1.2 eV) are discussed.     

Radiation-induced electronic and ionic charge storage and release in sapphire

Radiation-induced thermally stimulated relaxation (TSR) processes in the reduced f -Al 2 O 3 (sapphire) crystal were investigated at 290-650 v K by means of the TS current (TSC), ionic depolarisation current (TSDC) and electron emission (TSEE) techniques. After thermal (ionic) polarisation of sapphire wide (～75 v K) and asymmetric ionic dipolar TSDC peak at T max , 590 v K (disorientation of the anion vacancy-related dipoles) was detected. This peak correlates with the wide TSEE peak at T max , 615 v K, the radiation-induced electrical degradation (RIED) yield rise above 550 v K ( T max , 745 v K) and the chromium emission line broadening in ruby. Above 450-500 v K the anion vacancy hopping (migration) starts. This can lead to lattice dynamic disordering and anion vacancy diffusion-controlled processes in sapphire (especially in vacuo near the sample surface, grain boundaries, dislocations) in various TSR (TSC, TSDC, TS heat release and bleaching) and RIED phenomena. Surface structure and impurity content, surrounding atmosphere (vacuum or air) and electric fields determine these phenomena.     

ZnO薄膜微结构变化对光电特性的影响

使用脉冲激光淀积(PLD)技术在n型Si衬底上沉积氧化锌(ZnO)薄膜,在O2气氛下对样品进行了500℃(Sample1,S1),600℃(Sample2,S2),700℃(Sample3,S3)和800℃(Sample4,S4)退火,随后进行了X射线衍射(XRD)谱,椭偏光折射率,热激电流(TSC)和电容-电压(C-V)的测量。研究发现:S1中晶界的电子陷阱由高浓度的深能级杂质(Zni)提供的电子填充,该能级位于ET=EC-0.24±0.08eV。S3中出现与中性施主(D0)有关的深能级中心,其ET=EC-0.13±0.03eV,推测D0的出现与高温氧气条件退火下晶界处形成的复合体缺陷有关。XRD和椭偏光折射率测量结果表明:氧气对ZnO薄膜微结构的修饰是改变ZnO/Si结构光电特性的主要因素。     

Thermally stimulated luminescence properties of BaY 2 F 8 :Ce Crystals

Wavelength resolved thermally stimulated luminescence (TSL) measurements were performed on BaY 2 F 8 :1.8 v mol% Ce crystals after X-ray irradiation at 10 v K and at 300 v K, in order to obtain preliminary information about both trap levels and recombination centres. After irradiation at 10 v K, the TSL glow curve shows the presence of a strong peak at 50 v K, together with additional structures at approximately 20 and 170 v K. The TSL spectrum is dominated by the characteristic doublet emission due to transitions from the lowest energy level of the 5d configuration to the spin-orbit split 2 F ground state of Ce 3+ . Above RT, the glow curve exhibits a peak at 60 v C, whose spectrum is again dominated by Ce 3+ emission. The TSL emission is in accordance with radio-luminescence (RL) spectra performed in the 10-300 v K region. Moreover, RL spectra at temperatures lower than 200 v K display an additional weak high energy band at around 4.5 v eV assigned to host lattice transitions.     

Near-infrared photoluminescence and thermally stimulated current in Cu3Ga5Se9 layered crystals: A comparative study

Near-infrared photoluminescence (PL) and thermally stimulated current (TSC) spectra of Cu₃Ga₅Se₉ layered crystals grown by Bridgman method have been studied in the photon energy region of 1.35–1.46 eV and the temperature range of 15–115 K (PL) and 10–170 K (TSC). An infrared PL band centered at 1.42 eV was revealed at T = 15 K. Radiative transitions from shallow donor level placed at 20 meV to moderately deep acceptor level at 310 meV were suggested to be the reason of the observed PL band. TSC curve of Cu₃Ga₅Se₉ crystal exhibited one broad peak at nearly 88 K. The thermal activation energy of traps was found to be 22 meV. An energy level diagram demonstrating the transitions in the crystal band gap was plotted taking account of results of PL and TSC experiments conducted below room temperature.     

MULTI-ACTIVATION ENERGY DENSITY DISTRIBUTION AND THERMALLY STIMULATED CURRENT OF ELECTRIC DIPOLES IN CONDENSED MATTER

The physical meaning of the transcendental function in traditional thermally stimulated current (TSC) equation of electric dipoles with a single activation energy was first analyzed. Then a simple formula obtained directly from the tested TSC for calculating activation energy parameter, etc., was deduced. Numerical calculation showed that the exact TSC agrees with the approximated one very well. Further analysis found a limiting condition for the discrete to continuous activation energy density distribution and a criterion for discriminating the contributions to TSC by depolarization of the dipoles with multi-activation energy from those with a single one.     

Photoenhancement of the photoconductivity (PC) of electron irradiated semiconducting diamond

The spectrum of the non-enhanced PC of electron irradiated semiconducting diamond extends from the UV towards the visible and near infrared. It's long wavelength tail was found in the present work to exhibit a well defined threshold shifted with temperature from about 1.5eV at 76 K to about 1.25 eV at 500 K. Pre-illumination in the “UV-band” produced an enhanced PC band with a temperature independent threshold at 1.08 0.03 eV. This photoenhanced band was found to be closely related to a thermally-simulated current peak (TSC) at 500 K with an activation energy of 0.50 eV excited by the pre-illumination in the UV-band. The prhotenhanced band was bleached out thermally with the exhaustion of the TSC peak below 600 K. Some of the characteristics of the photoenhanced band including the linear dependence of the square root of the PC on photon energy may suggest that internal photoemission of holes plays a role in the formation of this band.     

ZnO压敏陶瓷缺陷结构表征及冲击老化机理研究

对多元ZnO压敏陶瓷电阻片进行了多达14000次的大电流冲击老化试验, 通过显微结构、电气性能及介电特性的测量对其缺陷结构进行了表征, 并研究了缺陷结构与大电流冲击老化之间的关系. 试验表明多次大电流冲击老化导致试样的电气性能明显下降, 发现ZnO压敏陶瓷的几何效应不仅受控于晶粒还与晶界密切相关. 另外, 通过介电谱分析观察到ZnO压敏陶瓷存在四种缺陷弛豫过程, 低温-60 ℃下的两个缺陷弛豫峰激活能约为0.24 eV和0.35 eV, 认为它们分别对应着本征的锌填隙缺陷L(Zn_i^··)和氧空位缺陷L(V_O^·)并且不受冲击老化的影响. 高温80℃以上两个松弛峰的活化能约为0.71 eV和0.84 eV, 认为它们分别对应着非本征的晶间相电子陷阱L(ingr)和晶界处界面态陷阱L(gb). 发现大电流冲击后, 仅界面态陷阱激活能从0.84 eV降低到0.76 eV, 认为界面态陷阱主要控制着ZnO压敏陶瓷的电气性能和稳定性.     

An investigation on the variations in properties of Ni+ irradiated ZnO thin films

ZnO thin films, irradiated by 80 MeV Ni⁺ ions, were analysed with the help of different characterization techniques like X-ray diffraction, optical absorption, transmission, photoluminescence (PL), electrical resistivity, photosensitivity (PS) and thermally stimulated current (TSC) measurements. Crystallinity and absorption edge were hardly affected by irradiation. PL spectrum of pristine sample showed a broad peak at 517 nm, whereas irradiated film had two emissions at 517 and 590 nm. Intensity ratio between these two emissions (I₅₁₇/I₅₉₀) decreased with the fluence, and finally at a fluence of 3×10¹³ ions/cm², the emission at 517 nm completely disappeared. Electrical resistivity of the sample irradiated with a fluence of 1×10¹³ ions/cm² drastically increased. However, on increasing the fluence to 3×10¹³ ions/cm², resistivity decreased, probably due the onset of hopping conduction through defects. PS also decreased due to irradiation. TSC measurements on pristine sample could reveal only one defect level at 0.6 eV, due to interstitia1 zinc (Zn_I). But, irradiation at a fluence of 1×10¹² ions/cm², resulted in three different defect levels as per TSC studies. Interestingly, the sample irradiated at a fluence of 3×10¹³ ions/cm² had only one defect level corresponding to a deep donor. The possible origin of these defect levels is also discussed in the paper.     

Thermal ionization of impurity centers in Fe-doped Bi12SiO20 and Bi12GeO20 crystals

The spectral and temperature dependence of the optical absorption and thermally stimulated depolarization currents in Fe-doped Bi₁₂SiO₂₀ and Bi₁₂GeO₂₀ crystals are investigated in the photon energy range 1.36–3.46 eV and temperature 85–750 K. The results show thermally induced electron redistribution between donor and acceptor levels and defect association-dissociation processes and are discussed using the configuration-coordinate model. Fiz. Tverd. Tela (St. Petersburg) 41, 1006–1011 (June 1999)     

Shallow traps in pure KTaO 3 crystals

We made Thermally Stimulated Conductivity (TSC), Thermoluminescence (TL) and Electron Spin Resonance (ESR) measurements on single crystals of potassium tantalate in the temperature range 4.2-290 v K. We revealed two sorts of O m shallow hole centers which are responsible for Photoconductivity (PC) and Photoluminescence (PL) enhancement. Both O m centers were identified by their ESR spectra. We show that these centers serve as radiative electron-hole recombination centers. The measurements of TSC and TL after UV irradiation revealed several glow peaks at temperatures 18-30 v K and 65-70 v K. Both TSC and TL are attributed to the thermal ionization of the same shallow donor centers related with oxygen vacancies. Experimental data were treated in a simple one-trap/one-recombination center model, which takes into account the presence of "thermally disconnected" deep electron traps.     

Effect of point defects on luminescence characteristics of ZnO ceramics

Photo- and thermally stimulated luminescence of ZnO ceramics are produced by uniaxial hot pressing. The luminescence spectra of ceramics contain a wide band with a maximum at 500 nm, for which oxygen vacancies V_O are responsible, and a narrow band with a maximum at 385 nm, which is of exciton nature. It follows from luminescence excitation spectra that the exciton energy is transferred to luminescence centers in ZnO. An analysis of the thermally stimulated luminescence curves allowed detection of a set of discrete levels of point defects with activation energies of 25, 45, 510, 590 meV, and defects with continuous energy distributions in the range of 50–100 meV. The parameters of some of the detected defects are characteristic of a lithium impurity and hydrogen centers. The photoluminescence kinetics are studied in a wide temperature range.     

Theory of modified thermally stimulated current and direct determination of trap level distribution

In order to investigate the trap level distribution in polymer films, a new method is proposed based on modified thermally stimulated current (TSC) theory and numerical calculation of the TSC measurement. In this method, a new function is defined to weight the contribution of every trap level to the external current. The demarcation energy is used to study the trap emptying process. The modified TSC theory shows that only the electrons with trap levels very close to the demarcation energy can significantly contribute to the external circuit at any instant temperature. Based on this method, the trap level distribution of the DuPont original polyimide film 100HN and nanocomposite polyimide film 100CR are investigated as an application example. The effectiveness of the method is confirmed by the experiments. The experimental results show that the trap level density in the 100CR PI films is about six times larger than that in the 100HN PI films through the investigated trap level ranges 06–1.3 eV. The increased traps in 100CR should be introduced by nanofillers, probably come from the interfaces formed between nanofillers and the polymer matrix.     

Thermally stimulated currents in ice. Correction for orientational defects

The Bernal and Fowler model of ice [1] has been supplemented with modern ideas about relaxing defects arising as a result of migration of a proton along hydrogen bonds [2, 3]. We develop a theory for thermally stimulated currents (TSC) in hexagonal ice. We propose a kinetic equation taking into account relaxation of the structural defects supporting proton conductivity in the crystals. We obtain formulas qualitatively describing thermally stimulated depolarization currents and also a formula for calculating the activation energy for structural defects, allowing us to compare with experiment. Due to the unwieldiness of the calculations, we present only the derivation of the kinetic equations and analysis of the solution.Karaganda Polytechnical Institute. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 93–98, February, 1994.     

Electrical properties of n-type GaS single crystals

Hall effect and Thermally Stimulated Currents (TSC) measurements have been carried out with the current flowing perpendicular to the c-axis on n-GaS crystals grown both from the melt by the Bridgman-Stockbarger method and from the vapour by chemical transport with iodine. An impurity hopping conduction with an activation energy of 0.2 eV has been evidenced in the range of temperatures between 200 and 300 K. The results of TSC measurements indicate the iodine as being responsible for a donor level at 0.44 eV from the conduction band.     

Energy spectrum of electron trapping centers in CuInAsS<Subscript>3</Subscript>

This paper presents the results of the investigation of the energy spectrum of electronic states due to trapping centers, the role of which in CuInAsS₃ is played by lattice defects. The results of the analysis of the thermally stimulated current curves of CuInAsS₃ demonstrate that the energy spectrum of trapping centers is localized under the bottom of the conduction band in the energy range E _C–(0.14–0.35) eV.     

TSC measurements and their correlation with photocurrent techniques

Deep level energy spectroscopy using the thermal release of trapped charge in pn junctions or Schottky barriers has recently been suggested as a useful method for evaluating deep level parameters in semiconductors [1, 2]. Although the measurements of thermally stimulated currents (TSC) may be a rapid method the use of which simplifies the investigation of known deep centers, considerable difficulties arise when TSC measurements are used for the characterization of unknown deep levels.     

Characteristics of traps in TlInS2 single crystals

Characteristics of charge traps in TlInS₂ single crystals are investigated by the use of thermally stimulated current (TSC) technique. The TSC spectra of the sample from 80 K to 300 K are recorded at a constant heating rate. The spectra reveal that there are several trapping levels associated with the complex structure of overlapping peaks. The experimental results indicate that the traps in TlInS₂ associated with the spectra in the measuring range of temperature obey the monomolecular (first order) kinetics. Thus, the spectra are resolved into first order shaped peaks by the use of computerized best fit procedure. The trapping parameters; such as the energy depth, temperature dependent frequency factor and capture cross section, together with concentrations of the corresponding six discrete levels are computed. These centers all having low capture cross sections with strong temperature dependence are found to be at the energies of 0.11 eV, 0.22 eV, 0.25 eV, 0.26 eV, 0.29 eV and 0.30 eV with high concentrations of 6.6 × 10¹⁶, 2.0 × 10¹⁷, 3.3 × 10¹⁷, 9.6 × 10¹⁶, 2.3 × 10¹⁷ and 4.0 × 10¹⁷ cm^?3, respectively.