慢正电子束流技术在金属/合金微观缺陷研究中的应用

正电子湮没谱学技术是研究材料微观结构非常有效的一种核谱学分析方法, 主要用于获取材料内部微观结构的分布信息, 特别是微观缺陷结构及其特性等传统表征方法难以获取的微观结构信息. 近年来, 在慢正电子束流技术快速发展的基础上, 正电子湮没谱学技术在薄膜材料表面和界面微观结构的研究中得到了广泛应用. 特别是该技术对空位型缺陷的高灵敏表征能力, 使其在金属/合金材料表面微观缺陷的形成机理、缺陷结构特性及其演化行为等研究方面具有独特的优势. 针对材料内部微观缺陷的形成、演化机理以及缺陷特性的研究, 如缺陷的微观结构、化学环境、电子密度和动量分布等, 正电子湮没谱学测量方法和表征分析技术已经发展成熟. 而能量连续可调的低能正电子束流, 进一步实现了薄膜材料表面微观结构深度分布信息的实验表征. 本文综述了慢正电子束流技术应用研究的最新进展, 主要围绕北京慢正电子束流装置在金属/合金材料微观缺陷的研究中对微观缺陷特性的表征和表面微观缺陷演化行为的应用研究成果展开论述.     

Design of a new type positron beam system

A new type positron beam system is being constructed in Wuhan university. The goal of this project is to build a positron beam which can measure positron lifetimes and has high moderation efficiency. The system utilizes a magnetically guided incident positron beam and the sample is biased to a high negative potential to achieve the desired implantation energies. A conventional tungsten moderator is replaced by a solid Ne moderator with high moderation efficiency (about 1%). A multi-functional target chamber for slow beam studies is designed, which can be used for positron annihilation lifetime spectroscopy (PALS), Doppler broadening (DB) and coincidence Doppler broadening (CDB) measurements.     

Tunable monoenergy positron annihilation spectroscopy of polyethylene glycol thin films

Doppler broadening and coincidence Doppler broadening of annihilation radiation experiments have been performed in three kinds of polyethylene glycol(PEG) membrane formed with different average molecular weight using the tunable monoenergy slow positron probe as a function of implantion energy. The obtained positron annihilation parameters are interpreted from two aspects: surface effect and differences in micro-structure or chemical environment of positron annihilation. The experimental results show that the regulation of densification of PEG molecular packing and distribution uniformity from the near surface layer to the bulk region in the film forming process can be well realized by changing its molecular weight. Combining a variable monoenergetic slow positron beam and these two positron annihilation spectroscopy methods is a powerful tool to study positron annihilation characteristics and for polymeric thin-film fine structure analysis.     

Diffusion Behavior of Cumulative He Doped in Cu/W Multilayer Nanofilms at Room Temperature

Cu/W multilayer nanofilms are prepared in pure Ar and He/Ar mixing atmosphere by the rf magnetron sputtering method.The cross-sectional morphology and the defect distribution of the Cu/W multilayer nanofilms are characterized by scanning electron microscopy and Doppler broadening positron annihilation spectroscopy.The results show that plenty of point defects can be produced by introducing He during the growth of the multilayer nanoGlms.With the increasing natural storage time,He located in the near surface of the Cu/W multilayer nanofilm at room temperature could be released gradually and induce the segregation of He-related defects due to the diffusion of He and defects.However,more He in the deep region spread along the interface of the Cu/W multilayer nanofilm.Meanwhile,the layer interfaces can still maintain their stability.     

Polymeric membrane studied using slow positron beam

A radioisotope slow positron beam has been built at the Chung Yuan Christian University in Taiwan for the research and development in membrane science and technology. Doppler broadening energy spectra and positron annihilation lifetime have been measured as a function of positron energy up to 30 keV in a polyamide membrane prepared by the interfacial polymerization between triethylenetetraamine (TETA) and trimesoyl chloride (TMC) on modified porous polyacrylonitrile (PAN) asymmetric membrane. The multilayer structures and free-volume depth profile for this asymmetric membrane system are obtained. Positron annihilation spectroscopy coupled with a slow beam could provide new information about size selectivity of transporting molecules and guidance for molecular designs in polymeric membranes.     

Chemical analysis using coincidence Doppler broadening and supporting first-principles theory: Applications to vacancy defects in compound semiconductors

The Doppler broadening of the positron annihilation radiation contains information on the chemical environment of vacancy defects trapping positrons in solids. The measured signal can, for instance, reveal impurity atoms situated next to vacancies. As compared to integrated quantities such as the positron annihilation rate or the annihilation line shape parameters, the full Doppler spectrum measured in the coincidence mode contains much more useful information for defect identification. This information, however, is indirect and complementary understanding is needed to fully interpret the results. First-principles calculations are a valuable tool in the analysis of measured spectra. One can construct an atomic-scale model for a given candidate defect, calculate from first principles the corresponding Doppler spectrum, and directly compare results between experiment and theory. In this paper we discuss recent examples of successful combinations of coincidence Doppler broadening measurements and supporting first-principles calculations. These demonstrate the predictive power of state-of-the-art calculations and the usefulness of such an approach in the chemical analysis of vacancy defects.     

北京慢正电子强束流运行性能测试

慢正电子强束流采用高能脉冲电子束流轰击金属钽靶, 以产生正负电子对的方式提供正电子, 作为慢正电子束流方法学研究和薄膜材料缺陷研究的束流基础. 本文是在该装置实现运行后, 对慢正电子束流的强度、能散、形貌等运行性能的测试工作的介绍, 以及慢正电子湮没多普勒测量系统的调试和标准样品的测量结果.     

Vacancy-solute complexes in aluminum

Several vacancy-solute complexes in the Al matrix are examined theoretically. In particular, these are V-Cu, V-Cd, V-In, V-Sn, V-Si and V-Fe. We concentrate on coincidence Doppler broadening (high momentum) profiles and positron lifetimes that bring complementary information about these defects. Positron calculations are carried out utilizing the atomic superposition method employing realistic atomic configurations obtained using an ab initio pseudopotential method. In this study we inspect to what extent such defects are detectable and differentiable using positron annihilation techniques. The influence of lattice relaxations around defects on the positron properties turns out to be important and is also debated. The obtained results are discussed in connection with experimental data published in literature.     

A positron remoderator for the high intensity positron source NEPOMUC

A remoderator for the high intensity positron source NEPOMUC was developed and installed at the beam facility. A beam of remoderated positrons could be produced with different energies and a diameter of less than 2 mm was obtained. The efficiency of the remoderation setup was determined to be 5%. Due to the brilliance of the remoderated beam, the measurements at the coincidence Doppler broadening spectrometer (CDBS) and at the positron annihilation induced Auger electron spectrometer (PAES) could be improved. The setup and functionality of the remoderation device is presented as well as the first measurements at the remoderator, CDBS and PAES.     

Slow positron beam study of nitrogen implanted CZ-Si subjected to rapid thermal processing

In this experiment, nitrogen ions were implanted into CZ-silicon wafer at 100 keV at room temperature with the fluence of 5 × 10¹⁵ N₂⁺/cm², followed by rapid thermal processing (RTP) at different temperatures. The single detector Doppler broadening and coincidence Doppler broadening measurements on slow positron beam were carried out to characterize the defects in the as-implanted silicon and RTP-treated samples. It is found that both nitrogen-vacancy complexes (N-Vsi) and oxygen-vacancy complexes (O-Vsi) produced by nitrogen implantation diffuse back to the sample surface upon annealing. But the N-Vsi and the O-Vsi complete with each other and give a summed effect on positron annihilation characteristics. It is shown that the N-Vsi win out the O-Vsi in as-implanted sample and by RTP at 650 °C, 750 °C, which make the S-parameter increase; O-Vsi plays a dominant role after annealing above 850 °C, which makes the S parameter decrease.     

Near-surface defects in hydrogen-plasma-treated boron-doped silicon studied by positron beam spectroscopy

Near-surface vacancy-type defects have been studied by positron beam spectroscopy in three boron-doped Si wafers; a control sample, second sample exposed to atomic hydrogen in electron cyclotron resonance (ECR) plasma, and a third sample annealed at 500 °C following plasma treatment. From the analysis of the Doppler broadening spectra, measured as a function of positron implantation depth, we obtain positron diffusion lengths of about 100 and 250 nm for the damaged layer and bulk of the wafer, respectively. For the plasma-treated wafer, our measurements provide a defect density of about 5×10¹⁷ cm^-3. Received: 4 September 1998 / Accepted: 5 January 1999 / Published online: 28 April 1999     

The study of native defects in as-grown GaAs by positron annihilation

A mono-energetic positron beam was applied for a study of native defects in GaAs. From measurements of Doppler broadening profiles and lifetime spectra of positrons, it was found that Ga-vacancies were introduced by Si-doping. On the other hand, for p-type GaAs, interstitial clusters were found to be introduced by Zn-doping. The observed species of defects are in agreement with those expected from the Fermi level.     

利用正电子湮没技术研究钾掺杂钨合金中的缺陷

钨合金中钾的掺杂会引入大量的缺陷,如尺寸几十纳米的钾泡、高密度的位错以及微米量级的晶粒带来的晶界等,这些缺陷的浓度和分布直接影响合金的服役性能.本文运用正电子湮没谱学方法研究钾掺杂钨合金中的缺陷信息,首先模拟计算了合金中各种缺陷的正电子湮没寿命,发现钾的嵌入对空位团、位错、晶界等缺陷的寿命影响很小;然后测量了不同钾含量掺杂钨合金样品的正电子湮没寿命谱,建立三态捕获模型,发现样品中有高的位错密度和低的空位团簇浓度,验证了钾对位错的钉扎作用,阐述了在钾泡形成初期是钾元素与空位团簇结合并逐渐长大的过程;最后使用慢正电子多普勒展宽谱技术表征了样品中缺陷随深度的均匀分布和大量存在,通过扩散长度的比较肯定了钾泡、晶界等缺陷的存在.     

Microstructural characterisation of a commercial Al–Cu–Mg alloy combining transmission electron microscopy and positron annihilation spectroscopy

Transmission electron microscopy and positron annihilation spectroscopy techniques were used to characterise the microstructure of the 2024 Al–Cu–Mg commercial alloy artificially aged with and without pre-deformation. In non-deformed samples, a very dense dispersion of small, needle-shaped particles, with mean size in the order of the nanometres, was observed homogeneously distributed in the matrix, together with a coarse distribution of S-phase precipitates. In pre-deformed samples, the needle-shape particles were not seen, only a high density of S-phase precipitates nucleated on dislocations. The needle-shaped particles were identified as solute-rich Guinier–Preston–Bagaryatski (GPB) zones by combining coincidence Doppler broadening positron annihilation measurements with TEM imaging. The relationship between the microstructure and measurements of hardness and positron lifetime evolution during artificial ageing is also discussed.     

A technique for positron spectroscopy of monovacancies formed by low-temperature ion implantation of silicon

A system for positron beam-based Doppler broadening spectroscopy of the formation and evolution of monovacancy defects in silicon is described. The apparatus allows in situ ion implantation at low temperatures (∼50 K) followed by positron beam assay. First measurements for 6 keV He implantation, at post-implant temperatures between 60 and 300 K are presented. Benefits and drawbacks of this system are discussed.     

Research for Crystallization of Metallic Glass Pd79.5Ni4Si16.5 by Slow Positron Beam

The monoenergetic slow positron beam was first used to study the crystalliation process of metallic glasses.The measurement of Doppler broadening spectra as a function of positron energy was made on the samples of metallic glass Pd_79.5Ni₄Si_16.5 in various states.It is shown that there are a number of the vacancy-like defects in the as-quenched state sample.Its crystallization started at the sample surface.Slow position beam turned out to be an effective probe to study the structural change of metallic glasses.     

Positron annihilation studies in ZnO nanoparticles

We report results on positron annihilation spectroscopic (PAS) studies using lifetime and coincidence Doppler broadening techniques in zinc oxide (ZnO) nanoparticles (4 to 40 nm) synthesized by solid state pyrolytic reaction followed by annealing in the temperature range of 200 ^°C to 800 ^°C. Positron lifetime in the nanoparticles are observed to be higher than bulk lifetime in all the cases. Theoretical calculation of lifetime indicates the presence of either Zn or (Zn, O) vacancy clusters which migrate and anneal out at high temperature. Comparison of ratio spectra from coincidence Doppler broadening measurement and calculated electron momentum distribution indicates the presence of either Zn or (Zn, O) vacancies. In addition, photoluminescence (PL) measurements have been carried out to examine the role of defects on the intensity of emission in the visible region.     

Two-dimensional melting of physisorbed submonolayers of argon and nitrogen

We have studied two-dimensional argon and nitrogen physisorbed on grafoil by conducting positron lifetime and Doppler broadening measurements as functions of adsorbate coverage and temperature. Positron lifetime and Doppler broadening parameters show turnarounds near one-half monolayer coverages at 77 K. The s parameter of the Doppler broadening spectra measured for one-half monolayer coverages of argon and nitrogen increases with temperature across the melting phase transition. We discuss the observed coverage and temperature effects following models based on Kosterlitz-Thouless-Nelson-Halperin-Young theory of two dimensional melting and positron localization in surface defects.     

Annealing Behaviour of Helium Bubbles in Titanium Films by Thermal Desorption Spectroscopy and Positron Beam Analysis

Helium-containing Ti Glms are prepared using magnetron sputtering in the helium-argon atmosphere. Isochronal annealing at different temperatures for an hour is employed to reveal the behaviour of helium bubble growth. Ion beam analysis is used to measure the retained helium content. Helium can release largely when annealing above 970K. A thermal helium desorption spectroscopy system is constructed for assessment of the evolution of helium bubbles in the annealed samples by linear heating （OAK/s） from room temperature to 1500K. Also, Doppler broadening measurements of positron annihilation radiation spectrum are performed by using changeable energy positron beam. Bubble coarsening evolves gradually below 680K, migration and coalescence of small bubbles dominates in the range of 68-970 K, and the Ostwald ripening mechanism enlarges the bubbles with a massive release above 970K.     

Spatially resolved investigation of thermally treated brass with a coincidence Doppler spectrometer

A spatially resolving coincidence Doppler spectrometer has been developed at the intense positron beam NEPOMUC at the nuclear research reactor FRMII in Garching near Munich. The positrons are focused onto the sample which is positioned in a vacuum chamber in order to achieve lateral resolution. The emitted annihilation radiation is detected by two facing germanium detectors in coincidence in order to enable background-free measurements. Since the measured spectra are not degraded by background, the high momentum region of the annihilation line can be precisely analysed. The positron beam structure is described and first measurements are presented in which thermally treated brass was investigated in order to determine the chemical environment of the positron at the annihilation site.