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.     

化合物半导体材料的正电子寿命计算

在局域密度理论（LDA）和广义梯度理论（GGA）的基础上计算了ZnO,GaN,GaAs,SiC和InP五种化合物半导体材料中的正电子湮没信息,包括化合物半导体材料中的自由态正电子的湮没寿命;还有不同类型空位（单空位,双空位）附近俘获的束缚态正电子密度分布和湮没率分布,以及束缚态正电子的湮没寿命. 关键词： 半导体 正电子寿命     

Annealing effect on structure and green emission of ZnO nanopowder by decomposing precursors

ZnO nanopowder is successfully synthesized by annealing the precursors in oxygen gas using the chemical precipitation method. Structural and optical properties of thus synthesized ZnO nanopowder are characterized by scanning electron microscopy (SEM) and photoluminescence (PL). The morphology of ZnO nanopowders evolves from nanorod to cobble as annealing temperature increases from 500 to 1000~\du, while spiral structures are observed in the samples annealed at 900 and 1000~\du. The PL spectra of ZnO nanopowder consist of largely green and yellow emission bands. The green emission from ZnO nanopowder depends strongly on the annealing temperature with a peak intensity at a temperature lower than 800~℃ while the yellow emission is associated with interstitial oxygen \rm O_\i.     

Photoluminescence and positron annihilation spectroscopic investigation on a H(+) irradiated ZnO single crystal

Low temperature photoluminescence and room temperature positron annihilation spectroscopy have been employed to investigate the defects incorporated by 6?MeV H(+) ions in a hydrothermally grown ZnO single crystal. Prior to irradiation, the emission from donor bound excitons is at 3.378?eV (10?K). The irradiation creates an intense and narrow emission at 3.368?eV (10?K). The intensity of this peak is nearly four times that of the dominant near band edge peak of the pristine crystal. The characteristic features of the 3.368?eV emission indicate its origin as a 'hydrogen at oxygen vacancy' type defect. The positron annihilation lifetime measurement reveals a single component lifetime spectrum for both the unirradiated (164?±?1?ps) and irradiated crystal (175?±?1?ps). It reflects the fact that the positron lifetime and intensity of the new irradiation driven defect species are a little higher compared to those in the unirradiated crystal. However, the estimated defect concentration, even considering the high dynamic defect annihilation rate in ZnO, comes out to be ～4?×?10(17)?cm(-3) (using SRIM software). This is a very high defect concentration compared to the defect sensitivity of positron annihilation spectroscopy. A probable reason is the partial filling of the incorporated vacancies (positron traps), which in ZnO are zinc vacancies. The positron lifetime of ～175?ps (in irradiated ZnO) is consistent with recent theoretical calculations for partially hydrogen-filled zinc vacancies in ZnO. Passivation of oxygen vacancies by hydrogen is also reflected in the photoluminescence results. A possible reason for such vacancy filling (at both Zn and O sites) due to irradiation has also been discussed.     

AA 2037新型连铸铝合金热轧板退火的正电子湮没研究

应用正电子湮没等技术对AA 2037连铸铝合金热轧板不同温度退火下空位-溶质相互作用及沉淀相进行了研究， 研究表明：室温时效形成的主要是空位-铜复合体以及空位-镁-铜复合体；温度为200℃退火时由于过渡相的形成正电子平均寿命出现峰值，符合多普勒展宽谱的商谱中观察到锰信号的存在，表明形成了空位-镁-锰复合体或过渡相中可能存在锰；温度高于250℃时，随着过渡相变粗、溶解，锰信号消失，而铜信号增强，在350℃后铜信号达到饱和，温度为450℃左右时，稳定相形成. 关键词： 正电子湮没技术 空位-溶质复合体 沉淀 退火     

Influence of Annealing Treatment on Structural,Optical, Electric,and Thermoelectric Properties of MBE-Grown ZnO

In this paper, we have reported the influence of annealing treatment on structural, optical, electrical, and thermoelectric properties of MBE-grown ZnO on Si substrate. After growth, a set of as grown ZnO was annealed in oxygen environment at 500–800°C and another set was annealed in different environments (vacuum, oxygen, zinc, and vacuum + zinc) at 600°C for one hour in a programmable furnace. X-ray diffraction (XRD) results demonstrated that all annealed samples exhibited a major diffraction peak related to (002) plane. The full width at half maximum (FWHM) of this plane decreased and crystalline size increased for oxygen annealed sample and it increased when samples were annealed in zinc, vacuum, and successively annealed in vacuum and zinc. Further, photoluminescence spectrum revealed that the intensity of band edge emission increased and defect emission decreased as annealing temperature (oxygen environment) increased while it decreased for rest of annealing ambient. It is suspected that annealing in oxygen environment causes compensation of the oxygen vacancies by the incoming oxygen flux, while annealing in zinc and vacuum generates more oxygen vacancies. Hall and Seebeck measurements are also consistent with these arguments.     

Defect engineering of ZnO

The defect responsible for the transparent to red color change of nominally undoped ZnO bulk single crystals is investigated. Upon annealing in the presence of metallic Zn as reported by Halliburton et al. and also Ti and Zr a native defect forms with an energy level about 0.7 eV below the conduction band. This change is reversible upon annealing in oxygen. Optical transmission data along with positron depth profiles and annealing studies are combined to identify the defect as oxygen vacancies. Vacancy clustering occurs at about 500 °C if isolated zinc and oxygen vacancies. In the absence of zinc vacancies, clusters form at about 800 °C.     

The effects of fast neutron irradiation on oxygen in Czochralski silicon

The effects of fast neutron irradiation on oxygen atoms in Czochralski silicon (CZ-Si) are investigated systemically by using Fourier transform infrared (FTIR) spectrometer and positron annihilation technique (PAT). Through isochronal annealing, it is found that the trend of variation in interstitial oxygen concentration ([O_i]) in fast neutrons irradiated CZ-Si fluctuates largely with temperature increasing, especially between 500 and 700℃. After the CZ-Si is annealed at 600℃, the V₄ appearing as three-dimensional vacancy clusters causes the formation of the molecule-like oxygen clusters, and more importantly these dimers with small binding energies (0.1--1.0eV) can diffuse into the Si lattices more easily than single oxygen atoms, thereby leading to the strong oxygen agglomerations. When the CZ-Si is annealed at temperature increasing up to 700℃, three-dimensional vacancy clusters disappear and the oxygen agglomerations decompose into single oxygen atoms (O) at interstitial sites. Results from FTIR spectrometer and PAT provide an insight into the nature of the [O_i] at temperatures between 500 and 700℃. It turns out that the large fluctuation of [O_i] after short-time annealing from 500 to 700℃ results from the transformation of fast neutron irradiation defects.     

石墨和纳米碳中缺陷和电子动量的研究

用正电子湮没技术研究了石墨和纳米碳中的缺陷和电子动量. 结果表明, 纳米碳中缺陷的开空间和缺陷浓度分别大于和高于石墨晶体. 纳米碳中存在开空间小于单空位的自由体积以及开空间相当于约10个空位聚集体的微孔洞. 石墨晶体中的自由电子动量分布表现出显著的各向异性: 沿石墨晶体的\[0 001\]晶向的自由电子(即2Pz电子)的动量最大; 偏离该方向越大, 自由电子的动量越小; 垂直于\[0 001\]晶向的自由电子的动量最小. 而纳米碳中自由电子动量的分布表现出各向同性. The defects and electronic momenta in graphite and nanocrystalline carbon have been studied by positron annihilation techniques. The results show that the concentration and open volume of defects in nanocrystalline carbon are higher/larger than that in graphite. Two kinds of microdefects were found in the nanocrystalline carbon: free volume (with a size of smaller than that of a monovacancy) and microvoids (with a size of about ten monovacancies). The anisotropic distribution of electronic momentum was found in single crystalline graphite, the momentum of free electron shows a maximum value in \[0001\] direction, and decreases with the increase of the angle deviation from \[0001\] direction and then reaches a minimum value in the direction perpendicular to \[0001\]. However, this phenomenon was not found in nanocrystalline carbon since the distribution of electronic momentum is isotropic.     

质子辐照ZnO白漆光学退化的慢正电子湮没分析

 采用慢正电子湮没光谱研究低能质子辐照下ZnO白漆的光学退化。研究结果表明,随质子辐照注量的增加, 多普勒展宽谱的S参数逐渐减小,W参数逐渐增大。质子辐照下S-W参数拟合曲线的斜率发生改变。S参数的减小可以归结为锌空位含量的减少以及准正电子素的形成。准正电子素{单电离氧空位（捕获一个电子）+正电子}的形成,能够降低正电子湮没的速率,导致S参数减小。S参数的减小证实了质子辐照导致ZnO白漆中单电离氧空位数量的增加。S-W参数拟合曲线斜率的变化可以归结于质子辐照下双电离氧空位向单电离氧空位的转变。     

元素周期表中元素单晶基于局域密度理论的正电子寿命计算

在局域密度近似理论（LDA）的基础上用中性原子叠加模型和有限插分方法（SNA-FD）计算了元素周期表中各种元素单晶的正电子体寿命和单空位寿命.分析了不同结构的单晶中自由正电子的分布信息和湮没信息.元素单晶的正电子寿命计算值与文献中的实验测量值相符合,表明LDA基础上的SNA-FD方法可以作为单晶中正电子湮没理论计算的有效研究手段. 关键词： 局域密度近似理论 正电子寿命     

Luminescence mechanism of ZnO thin film investigated by XPS measurement

The effects of annealing environment on the luminescence characteristics of ZnO thin films that were deposited on SiO₂/Si substrates by reactive RF magnetron sputtering were investigated by X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). An analysis of the O 1s peak of ZnO film revealed that the concentration of oxygen vacancies increased with the annealing temperature from 600 °C to 900 °C under an ambient atmosphere. The PL results demonstrated that the intensity of green light emission at 523 nm also increased with temperature. Under various annealing atmospheres, the analyses of PL indicated that only one emission peak (523 nm) was obtained, indicating that only one class of defect was responsible for the green luminescence. The green light emission was strongest and the concentration of oxygen vacancies was highest when the ZnO film was annealed in ambient atmosphere at 900 °C. The results in this investigation show that the luminescence mechanism of the emission of green light from a ZnO thin film is associated primarily with oxygen vacancies. PACS 81.15.Cd; 81.40.Ef; 78.55.-m; 78.55.Et     

Preparation of p-type ZnO:(Al, N) by a combination of sol--gel and ion-implantation techniques

We report the preparation of p-type ZnO thin films on (0001) sapphire substrates by a combination of sol--gel and ion-implantation techniques. The results of the Hall-effect measurements carried out at room temperature indicate that the N-implanted ZnO:Al films annealed at 600\du\ have converted to p-type conduction with a hole concentration of $1.6\times10¹⁸cm^-3, a hole mobility of 3.67cm²/V.s and a minimum resistivity of 4.80cm.\Omega$. Ion-beam induced damage recovery has been investigated by x-ray diffraction (XRD), photoluminescence (PL) and optical transmittance measurements. Results show that diffraction peaks and PL intensities are decreased by N ion implantation, but they nearly recover after annealing at 600\du. Our results demonstrate a promising approach to fabricate p-type ZnO at a low cost.     

Annealing of vacancies in electron-irradiated α-iron

Positron lifetime studies are reported on the behaviour of vacancies in high-purity electron irradiated α-iron. Results show that already at temperatures around 220 K vacancies migrate and form agglomerates, which anneal out only well above room temperature. The decrease of monovacancy concentration at stage I_E around 130 K is also visible.     

Photoluminescence of ZnO nanowires dependent on O2 and Ar annealing

High-purity ZnO nanowires have been synthesized on Si substrates without the presence of a catalyst at 600 °C by a simple thermal vapor technique. Photoluminescence (PL) spectra of the annealed samples at 900 °C under oxygen and argon gases have been investigated. After O₂ or Ar annealing, the PL visible-emission intensity that is related to intrinsic defects (oxygen vacancies) is greatly reduced compared with as-grown ZnO nanowires because the oxygen-gas ions or oxygen interstitials diffuse into the oxygen vacancies during annealing process. The blue-band peak of the O₂- or Ar-annealed ZnO naonowires is also smaller than the green-band peak in the visible broadband because of the reduction of oxygen vacancies. Therefore, the main intrinsic defects (oxygen vacancies) of as-grown ZnO nanowires can be reduced by O₂ or Ar annealing, which is an important procedure for the development of advanced optoelectronic ZnO nanowire devices.     

高分子网络凝胶法制备ZnO超细粉体及其光学性能

采用高分子网络凝胶法制备球形ZnO超细粉体。通过聚乙烯醇(PVA)亚浓溶液交联网络的空间位阻作用,经过烧结,获得了具有球形形貌的粒径为1~3μm的ZnO粉体颗粒。利用X射线衍射(XRD)、扫描电镜(SEM)分析了不同PVA浓度以及退火温度对产物形貌、结构的影响,发现在PVA溶液浓度为5%,并且经500℃热处理所形成的ZnO球形颗粒最为均匀规整。研究了球形ZnO粉体的光致发光性能,室温下经325nm波长激发,观察到两个中心波长分别位于407,468nm的微弱的荧光发射带,在合适温度下,在385nm处还出现了较强的紫外峰。PL光谱表明,退火温度对ZnO的光致发光影响较大,随着退火温度升高,由于表面缺陷和结晶性能发生变化,407nm处发射峰逐渐减弱消失,而紫外发光先增强后减弱,经500℃热处理样品的紫外发光性能达到最佳。     

退火温度及退火气氛对ZnO薄膜的结构及发光性能的影响(英文)

采用脉冲激光沉积技术在Si/蓝宝石衬底上制备了ZnO薄膜,结合快速退火设备研究了不同退火温度(500~900℃)及退火气氛(N2,O2)对薄膜的结构及其发光性能的影响。并优化条件得到具有最小半峰全宽及最大晶粒尺寸的薄膜。X射线衍射(XRD)结果表明:氮气氛下退火的ZnO薄膜最佳退火温度为900℃;氧气氛下退火的ZnO薄膜最佳退火温度为800℃。红外(IR)光谱中,退火后Zn-O特征振动峰红移,说明在退火过程中,原子重新排布后占据较低能量位置;同样的退火温度下,氮气氛下退火的薄膜质量更优。同步辐射光电子能谱(synchrotron-based XPS)分别表征了未退火及N2,O2下900℃退火的ZnO薄膜,分峰拟合结果表明氧气氛下退火产生更多的氧空位。结构表征结合光致发光(PL)谱表明绿光的发光峰与氧空位有关。     

Positron annihilation studies on the migration of deformation induced vacancies in stainless steel AISI 316 L

Positron lifetime measurements were carried out at room temperature before and after isochronous annealing of cylindrical, machined fatigue specimens and of round slabs of austenitic stainless steel AISI 316 L deformed in compression. Annealing experiments are evaluated in terms of vacancy migration and sinking to grain boundaries and dislocations. The model assumes spherical grains with a homogeneous initial distribution of vacancies. A vacancy migration enthalpy of H^M _V=(0.9±0.15) eV was found. It is concluded that positron trapping at dislocation lines does not significantly contribute to positron lifetime measurements at room temperature and that single vacancies are the dominating positron traps. Positron annihilation depth profiling on cross-sectional areas prepared from machined specimens using a positron microprobe with 10 μm spatial resolution shows that machining of cylindrical specimens creates vacancies up to 5 mm below the surface. Received: 11 August 2000 / Accepted: 13 November 2000 / Published online: 28 February 2001     

Controlling oxygen vacancies and properties of ZnO

Intrinsic defects in semiconductors play crucial roles on their electrical and optical properties. In this article, we report on a facile method to control concentration of oxygen vacancies inside ZnO nanostructures and related physical properties based on adjustment of thermal transformation conditions from ZnO₂ to ZnO, including annealing atmosphere and temperature. ZnO₂ spheres assembled with nanoparticles were formed through the reaction between zinc nitrate and hydrogen peroxide. Significantly, it was found that the adopted temperature and atmosphere have remarkable impact on the concentration of oxygen vacancies, which was revealed by the variations of featured Raman scattering peaks at 584 cm⁻¹. Furthermore, with the increase of oxygen vacancies inside ZnO, the optical band-gap was found to red-shift 350 meV and the room-temperature ferromagnetism became stronger up to 1.6 emu/mg. The defect formation and evolution were discussed according to the chemical equilibrium of decomposition reaction under special local heating environment. This work demonstrated that ZnO₂ decomposition is an effective process to control the defect states inside ZnO and related properties.     

Co掺杂纳米ZnO微结构的正电子湮没研究

利用正电子湮没技术研究了10 at.% Co掺杂的Co₃O₄/ZnO纳米复合物中退火对缺陷的影响. 利用X射线衍射(XRD)测量了Co₃O₄/ZnO纳米复合物的结构和晶粒尺寸. 随着退火温度升高,Co₃O₄相逐步消失,ZnO晶粒尺寸也有显著增加. 经过1000 ℃以上退火后,Co₃O₄相完全消失,并出现了CoO的岩盐结构. 正电子湮没寿命测量显示出Co₃O₄ /ZnO纳米复合物中存在大量的Zn空位和空位团. 这些空位缺陷可能存在于纳米复合物的界面区域. 当退火温度达到700 ℃后Zn空位开始恢复,空位团也开始收缩. 900 ℃以上退火后,所有空位缺陷基本消失,正电子寿命接近ZnO完整晶格中的体态寿命值. 符合多普勒展宽谱测量也显示Co₃O₄ /ZnO纳米复合物经过900 ℃以上退火后电子动量分布与单晶ZnO基本一致,表明界面缺陷经过退火后得到消除. 关键词： ZnO 界面缺陷 正电子湮没