On the role of group I elements in ZnO

Diffusion of Li, Na and K into single-crystal substrates of ZnO was performed. We compare the results with ZnO epitaxial films doped with the respective elements during growth. The diffused and in-situ doped layers were studied using mass spectroscopy and low temperature photoluminescence spectroscopy. Li and Na are known to produce deep acceptor centers which give rise to shallow donor to deep acceptor recombinations in the visible spectral region. We will demonstrate that shallow acceptors are also introduced, having binding energies around 300 meV. A donor–acceptor pair recombination (zero phonon line at 3.05 eV) with LO phonon replica is observed. We further investigated bulk ZnO crystals which contained the deep Li acceptor by thermal treatments under H₂ atmospheres. With increasing annealing temperature shallow donors are introduced as monitored by EPR while the EPR signal of the neutral Li acceptors decreases. Quite unexpectedly, the shallow Li acceptor centre which is not present in the as-grown state is also created. PACS 71.55.Gs; 78.55.Et; 76.30.Da     

Cathodoluminescence from deformed ZnO ceramics

Cathodoluminescence of deformed ZnO ceramics is studied in a scanning electron microscope based cathodoluminescence measurement system. Mechanical damage of the surface produces the decrease of the CL emission and a shift of the emission peak to higher wavelengths. The possible influence of oxygen vacancies on the observed effects is discussed.     

The luminescence of ZnO ceramics

The luminescence properties of ZnO ceramics with grains 100–5000 nm sintered by different techniques from nanopowders were studied. The luminescence decay times were compared with that obtained for ZnO single crystal. The temperature dependence of non-exponential decay of defect luminescence (2.0–2.6 eV) was measured in wide time, intensity and temperature range. The luminescence decay kinetic at T ≤ 20 K shows the decay close to I(t) ～ t^?1 dependence. At temperature region 50–250 K the decay kinetics is more complicate since the TSL was observed in this temperature region. It is shown that the luminescence properties of NP and ceramics strongly depend on defect distribution on grains surface and the volume/surface ratio determine the luminescence decay in ZnO nanostructures and ceramics.     

Unipolar characteristics of ZnO ceramics

The paper presents research on unipolar characteristics of ZnO ceramics. Dielectric response analysis is generally known method to characterize electrical properties of materials. It becomes important method for non-destructive testing. Recently, the possibilities and limitations of this method to reflect the deterioration processes due to thermal and electrical stress were investigated. The method is based on measuring the conduction and dielectric or polarization response. Present investigations are bringing extension to this research by high-energy pulse loading of samples that are used e.g. in production of gapless overvoltage protections. Moreover, the variations of characteristics due to pulse energy stress of samples are investigated.     

Localized luminescence in ZnO: Mn ceramics

Experimental conditions leading to the appearance of a Mn-related green emission band in ZnO ceramics are investigated. The emission has been found to be associated with the presence of small luminescent particles in the matrix.     

ZnO压敏陶瓷的介电谱

在-160℃-200℃温度范围内、0.1 Hz-0.1 MHz频率范围内测量了 ZnO压敏陶瓷的介电频谱, 发现可以采用电导率谱低频端的类直流特性来表征晶界Schottky势垒的电子输运过程, 获得的Schottky势垒高度为0.77 eV. 基于背靠背双Schottky势垒模型, 提出当存在直流偏压时, 势垒高度将随直流偏压线性增大. 基于此势垒模型计算了ZnO压敏陶瓷单晶界的直流偏压大小, 进而计算出晶粒平均尺寸为6.8 μm, 该理论值与通过扫描电子显微镜断面照片获得的测量值的偏差在5%以内. 可见采用介电谱不但可以获得势垒高度实现电气性能的表征, 还能获得晶粒尺寸实现显微结构的表征.     

Physical meaning of conductivity spectra for ZnO ceramics

With the help of broadband dielectric spectroscopy in a wide temperature and frequency range, the conductivity spectra of ZnO polycrystalline ceramics are measured and the direct-current-like (DC-like) conductivity and relaxation polarization conductivity are observed successively along the frequency axis. According to the classical Debye theory and Cole-Cole equation, the physical meanings of the two conductivities are discussed. It is found that the DC-like conductivity corresponds to electron transportation over the Schottky barrier at the grainboundary. The relaxation polarization conductivity corresponds to electronic trap relaxation of intrinsic point defects (zinc interstitial and oxygen vacancy). When in the high frequency region, the relaxation conductivity obeys the universal law with the index n equal to the index α in the Cole-Cole equation as an indictor of disorder degree.     

Photoluminescence of ZnO ceramics sintered with a flux

ZnO ceramics both with and without boric acid as a flux were sintered at $T_S=800\text{–}1200{}^{°}C$ and their luminescent characteristics were compared. In obtained samples UV as well as visible emission bands were observed. The addition of the flux was shown to cause the increase of grain size and the improvement of crystalline quality of the ceramics, which was ascribed to the creation of a liquid phase during the sintering process. It was found that the adding of 1 wt% of boric acid to ZnO powder allowed ceramics preparation without any pressing of the starting materials, in this case $T_S=950{}^{°}C$ being enough to obtain firm and dense ceramics. This ceramics had higher intensity of UV emission and lower intensity of visible emission than ceramics sintered without the flux.     

High temperature thermoelectric properties of Nb-doped ZnO ceramics

Solid-state reaction processing technique was used to prepare Zn_xNb_1−xO (0≤x≤0.02) polycrystalline bulk samples. In the present study, we find that their lattice parameters a and c tend to decrease with increasing amount of Nb additive. The electrical conductivity of all the Zn_1−xNb_xO samples increased with increasing temperature, indicating a semiconducting behavior in the measured temperature range. The addition of Nb₂O₅ to ZnO led to an increase in the electrical conductivity and a decrease in the absolute value of the Seebeck coefficient. The best performance at 1000 K has been observed for nominal 0.5 at% Nb-doped ZnO, with an electrical resistivity of about 73.13 (S cm⁻¹) and Seebeck coefficient of ∼257.36 μV K⁻¹, corresponding to a power factor (S²σ) of 4.84×10⁻⁴ Wm⁻¹ K⁻². The thermal conductivity, κ, of the oxide decreased as compared to pure ZnO. The figure of merit ZT values of ZnO-doped Nb₂O₅ samples are higher than the ZnO pure sample, demonstrating that the Nb₂O₅ addition is fairly effective for enhancing thermoelectric properties.     

Optical properties of ZnO related to the dc sputtering power

Zinc oxide thin films were sputter deposited on (100) silicon substrates at 250 ^○C substrates temperature via reactive unbalanced dc magnetron process using pure zinc target and argon/oxygen gases. The influence of the applied dc sputtering power (between 100 to 250 Watts, step 50 Watts) on the optical properties of the grown films was systematically investigated by variable angle of incidence spectroscopic ellipsometry (VASE) technique. The refractive indices were found to follow the second-order Sellmeier dispersion relation. However, Cauchy-like dispersion model was formulated to account for the absorption tail and excitonic structure near the direct band gap. The optical properties such as refractive indices, extinction coefficients, optical band gaps, Urbach's energies, excitonic binding structure and absorption coefficients of the grown films were reported as a function of dc power in the photon energy range between 1.2 eV and 4.2 eV. The films were found to be polycrystalline with (002) preferred orientation.     

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}     

Metal-nonmetal transition in the boron group elements

Structural competition in boron group elements has been studied by means of ab initio calculations. For boron we predict a structural change alpha-B-->alpha-Ga accompanied by a nonmetal-metal transition at a pressure of about 74 GPa. For Al and Ga we find an icosahedron based elemental modification (alpha-B) 0.22 and 0.05 eV/atom, respectively, higher in energy than the corresponding metallic ground state structures. In particular, the low energy difference for Ga raises expectations into the experimental feasibility of new modifications for these elements, especially in nanosized systems.     

Emission and excitation spectra of ZnO:Ga and ZnO:Ga,N ceramics

The spectral characteristics of ZnO:Ga and ZnO:Ga,N ceramics prepared by uniaxial hot pressing have been investigated. At room temperature, the edge (exciton) band at 3.12 eV dominates in the luminescence spectra of ZnO:Ga, while a wide luminescence band at 2.37 eV, which is likely to be due to zinc vacancies, is observed in the spectra of ZnO:Ga,N. Upon heating, the edge band maximum shifts to lower energies and the bandwidth increases. The extrapolated position of the edge-band maximum at zero temperature, E _m (0) = 3.367 ± 0.005 eV, is in agreement with the data for thin zinc oxide films. The luminescence excitation spectra in the range from 3 to 6.5 eV are reported and the mechanism of energy transfer to excitons and luminescence centers is considered.     

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.     

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     

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.     

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.     

Quantum and super-quantum group related to the Alexander-Conway polynomial

We describe the quasitriangular structure (universal R-matrix) on the nonstandard quantum group U_q(H₁, H₂, X^±) associated to the Alexander-Conway matrix solution of the Yang-Baxter equation. We show that this Hopf algebra is connected with the super-Hopf algebra U_qgl(1 | 1) by a general process of superization.     

Radiation resistance of boron nitride and related ceramics to low-energy electron irradiation

The radiation resistance of heat-proof ceramics based on boron nitride (BN + Si₃N₄ and BN + SiO₂), which are proposed to be used as structural materials in space ion engines, to low-energy electron irradiation has been investigated.