Defect characterization of slow-cooled and quenched samples of calcium-copper-titanate through positron annihilation spectroscopy

Abstract

Positron annihilation lifetime and Doppler-broadened gamma-ray spectra have been analyzed for slow-cooled and thermally quenched polycrystalline samples of calcium-copper-titanate. Two positron lifetimes revealing the characteristic defects in the respective samples were carefully analyzed to compare and contrast the significance of their origin and implication. A third component arising from positronium formation at the powdered particle surfaces has been considered in the analysis although its significance is lost in its very small intensity (～ 1.1–1.2%). In the quenched sample, the defect-specific long positron lifetime (τ₂) is found to larger and the mean lifetime smaller while its intensity I₂ is found drastically smaller and the concentration of defects less by an order of magnitude as compared to the slow-cooled sample. The observed changes in electrical parameters of slow-cooled and quenched samples were found to have correlations with the positron annihilation lifetime and Doppler-broadened lineshape parameters.     

Lifetime of Positrons in Nanostructured Nonstoichiometric Silver Sulfide Ag<Subscript>2–δ</Subscript>S

The lifetime of positrons in nanostructured nonstoichiometric silver sulfide Ag_2–δS samples with average nanoparticle sizes from 44 to 230 nm has been measured. It has been found that the lifetime spectra of Ag_2?δS nanoparticles include two components corresponding to the capture and annihilation of positrons in two types of defects: structural vacancies of the metallic sublattice and vacancy clusters at the interfaces between nanoparticles. The long surface component depends on the size of silver sulfide particles and indicates a difference in their defect structure.     

Positron lifetime measurements on electron irradiation damage in amorphous Pd80Si20 and Cu50Ti50 alloys

Positron lifetime measurements were performed on amorphous Pd₈₀Si₂₀ and Cu₅₀Ti₅₀ alloys irradiated with 3MeV electrons at 20K. The irradiation was found to increase the mean positron lifetime in both specimens indicating the presence of vacancy-like radiation damage. Isochronal annealing between 77 K and 300 K resulted in a continuous reduction of the positron lifetime, which suggests a gradual recovery of the irradiation induced defects.     

退火处理Fe43Co43Hf7B6Cu1非晶合金的正电子湮没研究

对熔体急冷法制备的Fe₄₃Co₄₃Hf₇B₆Cu₁非晶合金进行了200,300,400和500 ℃保温30 min的退火处理,用正电子湮没寿命谱、X射线衍射、穆斯堡尔谱等方法研究了退火后试样的结构及结构缺陷变化.结果表明,在非晶合金的制备态,正电子主要在非晶基体相空位尺寸的自由体积中湮没,湮没寿命τ₁为158.4 ps,强度I₁关键词： 43Co₄₃Hf₇B₆Cu₁非晶')" href="#">Fe₄₃Co₄₃Hf₇B₆Cu₁非晶 退火处理 正电子湮没寿命 结构与结构缺陷     

Behaviour of vacancies in dilute Fe–Re alloys: a positron annihilation study

Positron annihilation lifetime spectroscopy was used in a room temperature study of the influence of heat treatment on behaviour of vacancies in Fe_0.97Re_0.03 and Fe_0.94Re_0.06 alloys. In this experiment, the vacancies were created during the formation and further mechanical processing of the iron systems under consideration so the lifetime spectra of positrons were collected at least twice. The first samples were taken just after the melting process in an arc furnace, and the second ones were taken for the specimens annealed at 1,270 K and then cold-rolled at room temperature. After that, the spectra were measured for all studied samples after annealing at some temperatures gradually increasing from 300 to 1,270 K. It was found that vacancy-Re pairs are the dominant type of structural defects in alloys just after the melting process. In the case of alloys after a cold rolling process, the dominant type of structural defects is vacancies associated with edge dislocations. Moreover, for cold-rolled samples annealed at 473–573 K, the growth of the vacancy clusters associated with edge dislocations is observed by an increase in the mean positron lifetime. Finally, at temperatures above 573 K, vacancy clusters associated with edge dislocations as well as vacancy-Re pairs become unstable, and freely migrating vacancies sink at grain boundaries.     

Influence of free volume and medium-range order on the deformation response of rapidly solidified and bulk Zr-based (Zr52Ti6Al10Cu18Ni14) metallic glass

Free volume and medium-range order (MRO) present in rapidly solidified ribbons (RSRs) and bulk metallic glasses (BMGs) of Zr₅₂Ti₆Al₁₀Cu₁₈Ni₁₄ have been probed by high resolution electron microscopy, fluctuation microscopy, positron annihilation and differential scanning calorimetry. In the as-solidified condition, RSRs showed higher free volume and lower MRO in comparison to BMGs. Within BMGs, the central regions showed higher MRO and lower free volume than the peripheral regions. Uniform deformation of BMGs and RSRs modified their structures, where in, free volume increased in the former and reduced in the latter. These changes in structures led to work hardening in RSRs and work softening in BMGs. Such behaviour could be explained by invoking a concept of critical free volume in the glass phase. For samples (in as-solidified condition) having free volume higher than the critical value, free volume decreased with deformation and showed work-hardening behaviour. In contrast, the work softening behaviour was noticed in samples having free volume lower than the critical free volume.     

氧含量对BiFeOδ多晶陶瓷介电特性的影响

采用固相反应法制备了不同含氧量的BiFeO_δ多晶陶瓷样品，利用HP4294A阻抗分析仪测量了样品的介电特性随频率和氧含量的变化，用正电子湮没寿命谱学的方法研究了样品中因氧含量的变化所引起的结构缺陷. 实验结果表明：引入氧空位和氧填隙离子缺陷都会使介电常数减小，而介电损耗则随氧含量的增加而增加，二者的变化范围均在10%—35%之间；对不同氧含量的BiFeO_δ样品，介电常数和介电损耗随测量频率的增加而减小. 氧空位的引入使得局域电子密度变小，正电子平均寿命τ_m增加. 在氧含量δ=2.99时电子密度最大(n_e=3.90×10²³/cm³)，继续增加氧含量对正电子寿命与局域电子密度的影响不大. BiFeO_δ样品的介电常数和介电损耗随氧含量的变化可以在空间电荷限制电导的框架下来理解.     

Defects in electron irradiated amorphous SiO2 probed by positron annihilation

Defects in 3-MeV electron irradiated amorphous (a-) SiO₂ were studied by the positron annihilation technique. A high formation probability of positronium (Ps) was found for un-irradiated a-SiO₂ specimens. These Ps atoms were considered to be trapped by vacancy-type defects. The formation probability of Ps was drastically decreased by the electron irradiation. This fact can be attributed to an introduction of vacancy-type defects such as oxygen vacancies by the electron irradiation and a resultant trapping of positrons by such defects.     

EPR investigation of a-Si:H aerosol particles formed under silane thermal decomposition

The dangling bond defects were investigated in a-Si:H particles formed under silane thermal decomposition in flow reactor. EPR together with hydrogen evolution method were used. The experimental results allowed us to conclude that there are two kinds of dangling bond defects in a-Si:H aerosol particles. The defects of the first kind are localized on the surface of interconnected microvoids and microchannels (surface dangling bonds) and those of the second kind are embedded in amorphous silicon network (volume dangling bonds). The thermal equilibration of dangling bonds and temperature dependence of equilibrium dangling bond concentration were investigated. It was found that at temperatures > 400 K the dangling bond concentrationNApplied Magnetic Resonance _s reversibly depends on sample temperature. The volume dangling bond concentration increases with temperature increasing (the effective activation energy of dangling bond formationU > 0), and the surface dangling bond concentration decreases with temperature increasing (U < 0). It has been found that EPR line is considerably asymmetric for samples with high hydrogen content and for low hydrogen content the EPR line is weakly asymmetric. A conclusion was drawn that the asymmetry degree depends on amorphous silicon lattice distortions. This conclusion has been confirmed by EPR spectra simulations.     

中频磁脉冲处理Fe52Co34Hf7B6Cu1非晶合金的正电子湮没研究

对熔体急冷法制备的非晶合金 Fe₅₂Co₃₄Hf₇B₆Cu₁ 进行了不同频率的中频磁脉冲处理, 用透射电子显微镜、穆斯堡尔谱、正电子湮没寿命谱等方法研究了处 理前后试样的微观结构及结构缺陷变化. 结果表明,经中频磁脉冲处理后,样品发生了部分纳米晶化, 晶化量随磁脉冲频率增加而增加, 当磁脉冲频率为2000 Hz时, 晶化量达33.1%; 在淬态非晶样品中, 正电子在类单空位中的湮没寿命τ₁为150.5 ps, 强度 I₁为77.7%, 在微孔洞中的湮没寿命τ₂为349.7 ps,强度I₂为22.3%; 随磁脉冲频率的增加, τ₁, τ₂值呈现减小的变化趋势, 与淬态非晶相比, I₁有所增加, I₂下降, τ₁, τ₂的平均值τ大幅降低.     

Medium range ordering and some magnetic properties of amorphous Fe90Zr7B3 alloy

High-resolution electron microscopy (HREM) reveals in the as-quenched Fe₉₀Zr₇B₃ alloy the existence of medium range ordered (MRO) regions 1-2 nm in size. Transmission Mössbauer spectroscopy confirms that these regions are α-Fe MRO ones. Above the Curie point of the amorphous phase (T_C=(257±2)K) they behave like non-interacting superparamagnetic particles with the magnetization decreasing linearly with the temperature. For these particles the average magnetic moment of 390μ_B and the average size of 1.7 nm, in excellent agreement with HREM observations, were estimated. The maximum of the isothermal magnetic entropy change at the maximum magnetizing field induction of 2 T occurs at the Curie temperature of the amorphous phase and equals to 1.05 Jkg⁻¹ K⁻¹. The magnetic entropy changes exhibit the linear dependence on the maximum magnetizing field induction in the range 0.5-2 T below, near and above T_C. Such correlations are attributed to superparamagnetic behavior of α-Fe MRO regions.     

Positrons and electron-irradiation induced defects in the layered semiconductor InSe

The positron annihilation characteristics of the layered semiconductor InSe have been investigated. No evidence for low temperature positron trapping is found in as-grown and heavily deformed InSe. The temperature dependence of the S-parameter in these sample exhibits an increase rate in good agreement with the linear expansion coefficient along the c-axis. The positron lifetime spectra of electron-irradiated 0.01% Sn-doped InSe show a long-lifetime component of 336 ps which is tentatively attributed to positrons trapped at isolated In vacancies. Isochronal annealing experiments performed on these samples show that the recovery of the positron lifetime measured at 77K is accomplished in two stages. The first, starting after annealing at 150K, could be induced by the formation of complexes (V_In-Sn_In). The second stage, observed at temperatures T375K, is attributed to the dissociation of these complexes and subsequent annealing of the In vacancies.     

Effect ofV K centers on positron annihilation in KCl and Ag-doped KCl

Positron lifetime spectra have been measured at 77 K for KCl and Ag-doped KCl before and after x-irradiation at 77 K and after annealing at room temperature. Radiation at 77 K reduces the intensity of the intermediate lifetime (τ₂) component. Radiation-induced defects were monitored optically and by ESR. The experiment shows that the changes observed in the positron decay are associated with the presence ofV _K centers.     

Magnetic structure and properties of a bulk Fe72Al5P10Ga2C6B4Si1 alloy in the amorphous and nanocrystalline states

The structure forming under controlled crystallization of a bulk Fe₇₂Al₅P₁₀Ga₂C₆B₄Si₁ amorphous alloy has been studied using differential scanning calorimetry, transmission electron microscopy, and x-ray diffraction. Crystallization of the alloy was established to result in the formation of a nanocrystalline structure consisting of three phases. The domain structure and magnetic properties of amorphous and nanocrystalline samples were investigated using the magnetooptic indicating film technique (MOIF) and a vibrating-sample magnetometer. The coercive force and the saturation magnetization of the amorphous samples were found to be 1 Oe and 130 emu/g, respectively. It was shown that the formation of the nanocrystalline structure entails a dramatic decrease in domain size (down to 1–4 μm) as compared to an amorphous sample (∼1 mm). Simultaneously, a decrease in the saturation magnetization and a strong increase in the coercive force of the samples were observed. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 5, 2004, pp. 858–863. Original Russian Text Copyright ? 2004 by Abrosimova, Aronin, Kabanov, Matveev, Molokanov.     

正电子湮没谱和光致发光谱研究掺锌GaSb质子辐照缺陷

用正电子湮没谱和光致发光谱研究了质子辐照后掺锌GaSb中的缺陷.通过分析正电子的缺陷寿命τ₂及强度I₂的变化发现,在高能质子的辐照下产生了双空位缺陷V_GaV_Sb,可能同时产生了小的空位团.正电子平均寿命τ_av和S参数随着质子辐照剂量的变化也证明了这一结论.通过分析不同质子辐照剂量下掺锌GaS     

Comparative study on the hydrogen storage capacity of crystalline and amorphous nanomaterials of MoO<Subscript>3</Subscript>: effect of a catalytic Pd capping

Hydrogen storage capacities were investigated for two forms of MoO₃ nanomaterial, amorphous of low crystallinity, and other highly crystalline, using the quartz crystal microbalance technique. Effect of a catalytic Pd capping on the nanomaterials was evaluated. MoO₃ materials were grown using the gas condensation method, and both the amorphous and crystalline samples were composed of orthorhombic phases with Mo⁶⁺ oxidation state. For 4-min measurements, uncapped amorphous MoO₃ achieved a higher storage capacity than its crystalline counterpart, while Pd-capped samples exhibited lower values due to slower kinetics. Then, Pd-capped samples were measured using longer H2 exposure times of 30 min, finding that Pd-capped crystalline MoO₃ sample exhibited higher hydrogen storage capacity than its amorphous counterpart. Pd capping was found to affect the hydrogenation of the underlying oxide layer, mainly due to differences in long-range order and layered structure between crystalline and amorphous MoO₃ samples.     

First-principles study of the segregation of boron dopants near the interface between crystalline Si and amorphous SiO2

We investigate the stability of boron dopants near the interface between crystalline Si and amorphous SiO₂ through first-principles density functional calculations. An interstitial B is found to be more stable in amorphous SiO₂ than in Si, so that B dopants tend to segregate to the interface. When defects exist in amorphous SiO₂, the stability of B is greatly enhanced, especially around Si floating bond defects, while it is not significantly affected near Si–Si dimers, which are formed by O-vacancy defects.     

Microstructure of polycarbonate seen by positrons as an in-situ probe

Positron Annihilation Lifetime Spectroscopy (PALS) is used to probe the micro-structural changes in the polymer polycarbonate in terms of the changes in free volume hole size and their content as a function of temperature. The measured spectra are best fitted to three lifetime component analysis. The average hole size in the amorphous regions is determined from the measured Ortho Positronium (O-Ps) lifetime ₃ by following the treatment of Nakanishi et al. On the other hand, information about defects in the crystalline regions is revealed by trapped positrons lifetime ₂. In this polymer the average hole radius varies from 2.71 Å to 2.77 Å. The present study indicates that this polymer has a glass transition temperature of 152°C. Further, we have calculated the trapping rates in the ordered and disordered regions of the polymer based on Goldanskii's kinetic equations and an attempt is made for the first time to estimate the activation energy in the amorphous and crystalline regions separately.     

In‐plane and out‐of‐plane defects of graphite bombarded by H,D and He investigated by atomic force and Raman microscopies

Graphite samples exposed to H, D and He plasma at fluencies from 10¹⁶ to 10¹⁸ cm⁻² have been investigated by means of atomic force and Raman microscopies. The ion energy was varied between 40 and 800 eV, and the ion incidence was either perpendicular (Highly Oriented Pyrolitic Graphite) or parallel (carbon/carbon composite) to the basal plane. When increasing the impinging ion energy, the growth of nanometric domes at the surface has been observed by atomic force microscopy and the incident kinetic energy has been found as the parameter determining their height. Two different Raman signatures related to (1) a graphitic nano‐crystalline component similar to that of a 10¹⁴ cm⁻² bombarded 1‐, 2‐ and 3‐layer graphene, and to (2) an amorphous component, have been evidenced. Polarization studies have revealed that these components are related to regions with either in‐plane or out‐of‐plane disorder, coexisting in the material. These Raman studies have also revealed that both the defect–defect distance in the first case and the aromatic domain size in the second case are typically 1 nm. When the number of vacancies created in the material increases, the number of in‐plane defects decreases to the benefit of the out‐of‐plane defects. Copyright © 2014 John Wiley & Sons, Ltd.     

Crystallization of Fe-B amorphous alloy powders produced by chemical reduction

The crystallization behaviour of the Fe?B amorphous alloy powders prepared by the chemical reduction method has been investigated by Mössbauer spectroscopy. In comparison to amorphous ribbons prepared by melt-spinning, a different crystallization behaviour has been observed. After annealing the amorphous samples entirely crystallized into three crystalline phases: α-Fe, Fe₃B, and Fe₂B. In the case of Fe₈₀B₂₀ amorphous alloy ribbons produced by melt-spinning technique eutectic crystallization is commonly observed and results in the crystalline phases: α-Fe and Fe₃B. This kind of crystallization was not observed in the chemically prepared samples. The metastable tetragonal Fe₃B phase transformed completely into α-Fe and Fe₂B after annealing at 973 K for one hour.