Self-implantation of Cz-Si: Clustering and annealing of defects

Observations of vacancy clusters formed in Czochralski (Cz) Si after high energy ion implantation are reported. Vacancy clusters were created by 2 MeV Si ion implantation of 1 × 10¹⁵ ions/cm² and after annealing between 600 and 650 °C. Doppler broadening measurements using a slow positron beam have been performed on the self-implanted Si samples, both as-implanted and after annealing between 200 and 700 °C for time intervals ranging from 15 to 120 min. No change in the S parameter was noted after the thermal treatment up to 500 °C. However, the divacancies (V₂) created as a consequence of the implantation were found to start agglomerating at 600 °C, forming vacancy clusters in two distinct layers below the surface; the first layer is up to 0.5 μm and the second layer is up to 2 μm. The S-W plots of the data suggest that clusters of the size of hexavacancies (V₆) could be formed in both layers after annealing for up to an hour at 600 °C or half an hour at 650 °C. After annealing for longer times, it is expected that vacancies are a mixture of V₆ and V₂, with V₆ most probably dominating in the first layer. Further annealing for longer times or higher temperatures breaks up the vacancy clusters or anneals them away.     

Synthesis and characterization of magnesium oxide nanocrystallites and probing the vacancy-type defects through positron annihilation studies

Magnesium oxide nanocrystallites exhibit certain abnormal characteristics when compared to those of other wide band gap oxide semiconductors in the sense they are most prone to water absorption and formation of a hydroxide layer on the surface. The problem can be rectified by heating and pure nanocrystallites can be synthesized with controllable sizes. Inevitably the defect properties are distinctly divided between two stages, the one with the hydroxide layer (region I) and the other after the removal of the layer by annealing (region II). The lattice parameters, the optical band gap and even the positron annihilation characteristics are conspicuous by their distinct behavior in the two stages of the surface configurations of nanoparticles. While region I was specific with the formation of positronium-hydrogen complexes that drastically altered the defect-specific positron lifetimes, pick-off annihilation of orthopositronium atoms marked region II. The vacancy clusters within the nanocrystallites also trapped positrons. They agglomerated due to the effect of the higher temperatures and resulted in the growth of the nanocrystallites. The coincidence Doppler broadening spectroscopic measurements supported these findings and all the more indicated the trapping of positrons additionally into the neutral divacancies and negatively charged trivacancies. This is apart from the Mg²⁺ monovacancies which acted as the dominant trapping centers for positrons.     

纳米MFe2O4（M=Ni,Zn）氧化物表面的光电子能谱

采用草酸共沉淀法制备了纳米MFe2O4（M=Ni,Zn）立方尖晶石粉体,分别用XRD、XPS等手段对所合成样品的相结构、表面元素状态进行了表征。Fe2p、O1s的XPS分析表明,氧化物表面存在Fe2＋及吸附态氧物种,氧空位的存在是形成反式尖晶石结构所致。     

Evidence of formation of tetravacancies in uniformly oxygen irradiated n-type silicon

High purity n-type silicon single crystal with resistivity in the order of 4000 Ω cm has been irradiated with high-energy oxygen ions at room temperature up to a fluence of 5E15 ions/cm². The energy of the beam was varied from 3 to 140 MeV using a rotating degrader to achieve a depthwise near-uniform implantation profile. Radiation induced defects and their dynamics have been studied using positron annihilation spectroscopy along with isochronal annealing up to 700 °C in steps of 50 °C for 30 min. After annealing the sample at 200 °C for 30 min, formation of silicon tetravacancies has been noticed. The formation of the tetravacancies was found to be due to agglomeration of divacancies present in the irradiated sample. An experimentally obtained positron lifetime value of 338±10 ps has been reported for silicon tetravacancies, which has a very close agreement with the value obtained from recent theoretical calculations. The tetravacancies were found to dissociate into trivacancy clusters upon further annealing. The trivacancies thus obtained were observed to agglomerate beyond 400 °C to form larger defect clusters. Finally, all the defects were found to anneal out after annealing the sample at 650 °C.     

Clusterization of vacancy defects in ZnO irradiated with 2 MeV O

Slow positrons have been used to study ZnO layers grown on a-axis sapphire and irradiated by 2 MeV O⁺ ions to fluences from 10¹² cm⁻² to 10¹⁷ cm⁻². At low fluences Zn vacancies are observed, and their introduction rate is estimated as 2000 cm⁻¹. At the highest fluences of 10¹⁶-10¹⁷ cm⁻² vacancy clusters are formed. The extent of the primary damage and its recovery is discussed.     

Angular correlation of scattered annihilation photons, to test the possibility of hidden variables in quantum theory

Angular correlations of the annihilation photons, Compton scattered by plastic scintillators and detected by means of NaI (T1) crystals, have been measured in order to test the possibility of deviations of the experimental results from the predictions of the quantum theory. In fact, Jauch and Bohm, starting with different motivations, both arrive at the possibility of a lower correlation ratio between the two orthogonal polarization states of the two photons than predicted by quantum theory. This in turn should give a lower azimuthal anisotropy in the angular correlations. Our experimental results compared with the theoretical predictions, after correction for finite geometry by means of a Montecarlo method, do not confirm quantum theory and exclude the hypotheses of Jauch and of Bohm. We are continuing the experiment in order to test wether the breakdown in the polarization correlation depends on the distance (spatial and/or temporal) between the two correlated scattering events, as suggested by Jauch. Paper A 34 presented at 3 rd Internat'l Conf. Positron Annihilation, Otaniemi, Finland (August 1973).     

Effect of thermal annealing on the structure and magnetism of Fe-doped ZnO nanocrystals synthesized by solid state reaction

High purity Fe₂O₃/ZnO nanocomposites were annealed in air at different temperatures between 100 and 1200 °C to get Fe-doped ZnO nanocrystals. The structure and grain size of the Fe₂O₃/ZnO nanocomposites were investigated by X-ray diffraction 2θ scans. Annealing induces an increase of the grain size from 25 to 195 nm and appearance of franklinite phase of ZnFe₂O₄. Positron annihilation measurements reveal large number of vacancy defects in the interface region of the Fe₂O₃/ZnO nanocomposites, and they are gradually recovered with increasing annealing temperature. After annealing at temperatures higher than 1000 °C, the number of vacancies decreases to the lower detection limit of positrons. Room temperature ferromagnetism can be observed in Fe-doped ZnO nanocrystals using physical properties measurement system. The ferromagnetism remains after annealing up to 1000 °C, suggesting that it is not related with the interfacial defects.     

Evolution of native point defects in ZnO bulk probed bypositron annihilation spectroscopy

This paper studies the evolution of native point defects with temperature in ZnO single crystals by positron lifetime and coincidence Doppler broadening (CDB) spectroscopy, combined with the calculated results of positron lifetime and electron momentum distribution. The calculated and experimental results of the positron lifetime in ZnO bulk ensure the presence of zinc monovacancy, and zinc monovacancy concentration begins to decrease above 600℃ annealing treatment. CDB is an effective method to distinguish the elemental species, here we combine this technique with calculated electron momentum distribution to determine the oxygen vacancies, which do not trap positrons due to their positive charge. The CDB spectra show that oxygen vacancies do not appear until 600℃ annealing treatment, and increase with the increase of annealing temperature. This study supports the idea that green luminescence has a close relation with oxygen vacancies.     

Structural, defect and optical properties of ZnO films grown under various O2/Ar gas ratios

Thin wurtzite (0 0 2) textured ZnO thin films were deposited on glass substrates by radio frequency magnetron sputtering under O₂/Ar ratios R varying from 0.05 to 1.0 at room temperature. The structure of, and defects in, the films were investigated by XRD, SEM and slow positron beam techniques. The XRD spectra showed that ZnO thin films were polycrystalline with hexagonal structure and a good c-axis orientation perpendicular to the substrate. The thickness, grain size and the crystalline quality of the films strongly depended on R; the larger grain size and thicker ZnO films were grown when R was lower. Positron beam Doppler broadening measurements showed that in low R films additional vacancy-type defects (e.g. Zn-related vacancy complexes or clusters) were formed. Photoluminescence spectra found that the film with R = 0.4 had the highest luminescence efficiency, in good agreement with the best c-axis preferential orientation. The transmittance spectra of the films decreased with decreasing R, due to the thickness effect. Correlations between microstructure, defect and optical properties are discussed.     

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.     

Correlation between ferromagnetism and defects in MgO nanocrystals studied by positron annihilation

High purity MgO nanopowders were pressed into pellets and annealed in air from 100 to 1400 °C. Variation of the microstructures was investigated by X-ray diffraction and positron annihilation spectroscopy. Annealing induces an increase in the MgO grain size from 27 to 60 nm with temperature increasing up to 1400 °C. Positron annihilation measurements reveal vacancy defects including Mg vacancies, vacancy clusters, microvoids and large pores in the grain boundary region. Rapid recovery of Mg monovacancies and vacancy clusters was observed after annealing above 1200 °C. Room temperature ferromagnetism was observed for MgO nanocrystals annealed at 100, 700, and 1000 °C. However, after 1400 °C annealing, MgO nanocrystals turn into diamagnetic. Our results suggest that the room temperature ferromagnetism in MgO nanocrystals might originate from the interfacial defects.     

Microstructural and magnetic properties of Ax:Zn1-xO (A=Mn,Gd and Mn/Gd) nanocrystals

We report the microstructural and magnetic properties of transition (3d) and rare earth (4f) metal substituted into the A_x:Zn_1?xO (A=Mn, Gd and Mn/Gd) nanocrystal samples synthesized by solgel method. The structural properties and morphology of all samples have been analysed using X-ray diffraction (XRD) method and scanning electron microscopy. The impurity phase in the XRD patterns for all samples is not seen, except (Mn/Gd):ZnO sample where a very weak secondary phase of Gd₂O₃ is observed. Due to the large mismatch of the ionic radii between Mn²⁺ and Gd³⁺ ions, the strain inside the matrix increases, unlike the crystallite size decreases with the substitution of Mn and Gd into ZnO system. A couple of additional vibration modes due to the dopant have been observed in Raman spectrum. The magnetic properties have been studied by vibrating sample magnetometer. The magnetic hysteresis shows that Mn:ZnO and Gd:ZnO have soft ferromagnetic (FM) behaviour, whereas (Mn/Gd):ZnO has strong FM behaviour at room temperature (RT). The enhancement of ferromagnetism (FM) in (Mn/Gd):ZnO sample might be related to short-range FM coupling between Mn²⁺ and Gd³⁺ ions via defects potential and/or strain-induced FM coupling due to the expansion lattice by doping. The experimental results indicate that RTFM can be achieved by co-substitution of 3d and 4f metals in ZnO which can be used in spintronics applications.     

Study of vacancy defects and their thermal stability in MeV Fe ion irradiated RAFM steel using positron beam Doppler broadening spectroscopy

Indian reduced activation ferritic-martensitic steel was irradiated with 1.1?MeV Fe ions to various doses from 1 to100?dpa at room temperature. The depth profiling of irradiation-induced vacancy-type defects and the defect-recovery under post-irradiation annealing was studied using variable low-energy positron beam Doppler broadening spectroscopy. The influence of irradiation-induced defects on the microstructural properties was studied by glancing incidence x-ray diffraction (GIXRD) and nanoindentation technique. Positron annihilation study showed the signatures of reduced vacancy concentration at the peak damage region due to injected interstitial effect from 30 to 100?dpa and the widening of vacancy-interstitial recombination-rich region towards the end of ion range with the increase in dose. The GIXRD results were analysed by modified Williamson–Hall plot method, and the variation of coherent domain size and micro-strain with irradiation dose was studied. Irradiation-induced hardening was observed in the nanoindentation study. The features observed in the GIXRD and nanoindentation study are correlated with the depth-resolved defect distribution observed in the positron annihilation study.     

Slow positron beam study of corrosion-related defects in pure iron

Corrosion-related defects of pure iron were investigated by measuring Doppler broadening energy spectra (DBES) of positron annihilation and positron annihilation lifetime (PAL). Defect profiles of the S-parameter from DBES as a function of positron incident energy up to 30 keV (i.e. ∼1 μm depth) were analyzed. The DBES data show that S-parameter increases as a function of positron incident energy (mean depth) after corrosion, and the increase in the S-parameter is larger near the surface than in the bulk due to corrosion. Furthermore, information on defect size from PAL data as a function of positron incident energy up to 10 keV (i.e. ∼0.2 μm depth) was analyzed. In the two-state trapping model, the lifetime τ₂ = 500 ps is ascribed to annihilation of positrons in voids with a size of the order of nanometer. τ₁, which decreases with depth from the surface to the bulk, is ascribed to the annihilation of positrons in dislocations and three-dimensional vacancy clusters. The corroded samples show a significant increase in τ₁ and the intensity I₂, and near the surface the corroded iron introduces both voids and large-size three-dimensional vacancy clusters. The size of vacancy clusters decreases with depth.     

Vacancy defects induced in sintered polished UO2 disks by helium implantation

Vacancy defects have been investigated in sintered polished and annealed uranium oxide disks. Slow positron beam coupled with Doppler broadening spectrometer was used to probe the track region of 1 MeV ³He ions implanted in uranium dioxide (UO₂) disks. The low and high momentum annihilation fractions, S and W, respectively, were measured in the first micrometer near surface region of the disks as a function of positron energy. The S and W values indicate that the 1 MeV He ions induce vacancy defects in the track region of their range. The vacancy defect depth distribution is heterogeneous. The positron trapping at these vacancy defects increases with the depth and with the implantation fluence indicating an increase of the vacancy defect concentration. The nature of the induced vacancy defects does not change with the fluence.     

Positron decay in polymers: Molecular weight dependence in polystyrene

The decay time τ_l ofo-Ps by the electron pickoff process has been measured in polystyrene as a function of molecular weight. For samples below their glass transition temperature τ_l is essentially independent of . In the low molecular weight region, , τ_l increased with decreasing in line with earlier theoretical predictions. The overall behaviour reflects closely the dependence of free volume on . The effects of molecular motion on τ_l are examined and it is concluded that the decay time is insensitive to such motions in polystyrene below the melting point, in contrast to what is observed in polytetrafluoroethylene.     

Synthesis and structural,magnetic characterization of Zn(Mn)O diluted magnetic semiconductor

The bulk samples with nominal composition Zn_1−x Mn_x O [x = 5% and 7%] were synthesized at 930 °C by Standard Solid State Reaction method. The structural analysis reveals the single phase nature. The Topography study indicates the distribution of the particles. Magnetic property was affirmed by Vibrating Sample Magnetometer, Zn_1−x Mn_x O (with x = 5%), low concentration of dopant shows good ferromagnetism compared to high concentration in Zn_1−x Mn_x O (with x = 7%).     

Co和Mn共掺杂ZnO铁磁性的第一性原理

基于密度泛函理论(DFT)的总体能量平面波超软赝势方法,结合广义梯度近似(GGA),对Co单独掺杂ZnO和(Co,Mn)共掺杂ZnO的32原子超原胞体系进行了几何结构优化,计算了纤锌矿结构ZnO、Co-ZnO及(Co,Mn)共掺杂ZnO的能带结构、电子态密度,并对此进行了详细的分析。计算结果表明,ZnO中单独掺杂Co元素显示出铁磁性行为,Mn的引入减弱了Co-ZnO的铁磁性。     

Positron annihilation in ionic crystals

Positron lifetime measurements were made on Ca²⁺ doped NaCl, Ba²⁺ doped NaCl and X-ray- and additively-coloured KCl crystals. In the NaCl(Ca) system a correlation which could be approximated by a power equation was found between the dopant concentration and the positron annihilation parameters. In the NaCl(Ba) system the decay parameters do not change significantly as expected and no significant difference in the decay parameters of the coloured and uncoloured crystals could be found. Paper C 4 presented at 3rd Internat'l Conf. Positron Annihilation, Otaniemi, Finland (August 1973).