Rapid-thermal-anneal-based internal gettering for?germanium-doped Czochralski silicon

The internal gettering (IG) effects involved with a rapid thermal anneal (RTA) in germanium-doped Czochralski silicon (GCz-Si) wafer have been investigated. It was found that germanium doping could enhance the oxygen precipitation in bulk while shrinking the denuded zone width near the surface through pre-RTA at high temperature plus low–high temperature conventional furnace anneals. Rapid cooling rate after RTA was clarified to be beneficial for oxygen precipitation for GCz-Si wafer. It was suggested that the germanium doping could increase the vacancy concentration in Cz-Si during RTA by forming the germanium–vacancy complexes. In contrast to that in Cz-Si wafer, the smaller-sized higher-density oxygen precipitates were presented in the nucleation anneals, then followed RTA pretreatment while more oxygen precipitates survived during ramping processes after nucleation anneals in the GCz-Si wafer. Enhanced heterogeneous nucleation and reduced critical radius of precipitates associated with the germanium–vacancy complexes have been proposed for the oxygen precipitation enhancement.     

Enhancement of optoelectronic properties in multicrystalline silicon via combination of grooving grain boundaries and porous silicon gettering

In multi-crystalline silicon (mc-Si), the detrimental effect of impurities and grain boundaries (GBs) on charge carrier transport has driven the research focus since many years. In view of curing these limitations, we present an innovative method to enhance the optoelectronic performance of mc-Si wafers via a combination between GBs grooving and porous silicon (PS) gettering. A preferential grooving of GBs was achieved using the HF/HNO₃ based solution, the PS layers were formed on both sides of the samples using stain-etching method and the gettering experiment was performed at temperatures ranging from 750 to 900 °C. As a result, it has been shown that the rapid thermal annealing process with chemical grooving gives a positive trend of improvement of the electronic quality and found to be more efficient when used in combination with PS. After removing the PS layer, the minority carrier lifetime increases by a factor of more than 27. In addition, a significant enhancement of majority carrier mobility was obtained, which led to an important decrease of the resistivity.     

Precipitation of γ′ phase and helium bubbles during proton and α-particle irradiation of nickel–silicon

Segregation of silicon was induced by light-ion irradiation at elevated temperatures in Ni–8Si specimens. Its occurrence at external surfaces, helium-induced cavities, dislocation loops, coherent twin boundaries, grain boundaries, and precipitate-matrix interfaces has been investigated by transmission electron microscopy. Layers of ordered γ^′ (Ni₃Si) phase were formed at most of these point defect sinks. The behaviour of grain boundary precipitation was found to be exceptional in various respects. In particular, a high rate of precipitation distinguishes grain boundaries from all other kinds of point defect sinks investigated here. This phenomenon of rapid precipitation was found to be adjoined to precipitation-driven grain boundary migration and is attributed to a radiation-induced “discontinuous” precipitate reaction. Observations of helium bubble distributions created during α-particle irradiations at growing dislocation loops and at migrating grain boundaries are also briefly discussed.     

Correlation among grain boundary character,carbide precipitation and deformation in Alloy 690

The correlation among grain boundary character, carbide precipitation and deformation in the grain boundary engineering (GBE) treated Alloy 690 samples with and without pre-deformation aged at 715^oC for 15?h was analysed by scanning electron microscopy and electron backscatter diffraction. The fraction of low Σ coincidence site lattice (CSL) grain boundary was enhanced by GBE treatment. The fraction of Σ3 grain boundary decreased, and most of Σ9 and Σ27 grain boundaries disappeared in the deformed GBE samples. After aging treatment, bigger carbide precipitated at coherent Σ3 grain boundary, however, most of plate-like carbide precipitated at incoherent Σ3 grain boundary disappeared in the pre-deformed GBE samples. The larger carbide precipitated on the random grain boundary in the 5% pre-deformed sample, while smaller carbide can be observed in the 15% pre-deformed sample. During the in situ tensile test of the aged GBE samples, grain boundary carbide migrated with the grain boundary migration. The slip bands go across Σ3 grain boundary directly, but cannot go across other grain boundaries. The high density of carbide plate precipitated near incoherent Σ3 and Σ9 grain boundaries can resist the evolution of slip bands. Compared to the Σ3 and Σ9 grain boundaries, Σ27 and random grain boundaries are more easily to form microcrack during deformation. The initiation of grain boundary microcrack not only related to the character of grain boundary but also related to the character of nearby grain boundaries. The phase interface of carbide and matrix is another region to initiate the microcrack.     

Contribution of tilt boundaries to the total energy spectrum of grain boundaries in polycrystals

By measuring temperatures T _w for the transition from the incomplete to complete wetting of grain boundaries in poly- and bicrystals, the width of the spectrum of tilt grain boundaries and their contribution to the total energy spectrum of grain boundaries in polycrystals have been experimentally estimated. It has been shown that the tilt grain boundaries correspond to a rather narrow (only 5–10%) portion in the total energy spectrum of grain boundaries in polycrystals. In metals with a low stacking fault energy (copper, tin, zinc), the tilt grain boundaries belong to 10–20% of the grain boundaries with the highest transition temperatures T _w (hence, with low energies). In a metal with a high stacking fault energy (aluminum), the values of T _w for the tilt grain boundaries lie nearly in the middle between the minimum (T _w,min) and maximum (T _w,max) transition temperatures from the incomplete to complete wetting of grain boundaries. This means that grain boundaries with the structure corresponding to a lower energy than that of the symmetric twin boundaries (or stacking faults) can exist in aluminum.     

High-temperature oxygen and carbon aggregates in polycrystalline silicon

Abstract

EFG silicon ribbon and two kinds of polycrystalline silicon (SILSO and HEM) obtained by casting techniques, with different concentrations of oxygen and carbon impurities have undergone thermal treatments in the temperature range from 450 to 1300°C. Infrared spectroscopy was used to monitor changes in the concentration and configuration of various defects. The carbon-to-oxygen concentration ratio and the thermal history of the investigated materials proved to be of the paramount importance in the nucleation and growth of various precipitation phenomena at higher temperatures. As distinct from single crystal silicon, grain boundaries and high dislocation densities offer an additional source of impurities which may be seen by the infrared techniques upon their activation at higher temperatures.     

High-Temperature Behavior of SiO2 at Grain Boundaries in TZP

The chemical reaction between SiO₂ and tetragonal zirconia polycrystal (TZP) was directly observed using a TEM in-situ heating technique in order to understand the behavior of SiO₂ in TZP at high temperatures. Their dynamic interaction was recorded up to about 1400°C using a CCD camera-video system connected to the TEM. Most of SiO₂ phase dissolved into the ZrO₂ grains above 1300°C. On the other hand, during cooling from the high temperature to around 400°C, amorphous SiO₂ reprecipitated from the surface of ZrO₂ grains and formed a thin layer around the ZrO₂ grains. This result agrees well with the fact that silicon segregates in the vicinity of grain boundaries in SiO₂-doped TZP. In order to confirm the grain boundary segregation at high temperatures, we investigated grain boundaries in quenched specimens by high resolution electron microscopy (HREM), energy dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS). It was found that no amorphous phase was present between two adjacent grains in the quenched samples. EDS analysis revealed that silicon segregated at the grain boundaries and that the segregation layer was wider than that in as-sintered specimens. The electron energy loss near edge structure (ELNES) of O K-edge was measured from both grain boundary and grain interior in quenched specimen, and their spectra were interpreted by a first principles molecular-orbital (MO) calculation using the discrete-variational (DV)-X method.     

Effect of cooling rate on microstructure of friction-stir welded AA1100 aluminum alloy

In this work, the microstructural changes occurring during cooling of friction-stir welded aluminum alloy AA1100 were evaluated. To this end, friction-stir welding (FSW) was performed in a wide range of cooling rates of 20–62 K/s and the evolved microstructures were studied by using electron backscatter diffraction. Below 0.6 T_m (T_m being the melting point), the stir zone material was found to experience no significant changes during cooling. At higher FSW temperatures, however, notable changes occurred in the welded material, including grain growth, sharpening of texture, reduction of the fraction of high-angle boundaries and material softening.     

纯铜[0 1 1]倾侧型非共格∑3晶界结构稳定性分子动力学模拟研究

有研究表明, 非共格∑₃晶界的行为在中低层错能面心立方金属晶界 特征分布演化中发挥着重要作用. 为了掌握不同界面匹配的非共格∑₃晶界的特性, 本文利用分子动力学(MD)模拟方法首先研究了纯铜的[0 1 1]倾侧型 非共格∑₃晶界在700–1100 K温度范围内和常压下的结构稳定性. MD模拟采用原子间相互作用长程经验多体势, 步长为5×10^-15 s. 模拟结果表明: 所研究的五个非共格∑₃晶界, 其结构稳定性存在很大差异, 其一般规律是, 与(1 1 1)/(1 1 1)共格孪晶界之间的夹角(Φ角)越小, 晶界匹配值越大, 则非共格∑₃晶界越稳定; 反之亦然. Φ角最小的 (2 5 5)/(2 1 1)非共格∑₃晶界较稳定, 在退火过程中几乎不发生变化. 随着Φ角的增大, 非共格∑₃晶界不再稳定, 这类晶界会通过Miller指数较高一侧晶体每三层原子面合并为一层原子面 (或Miller指数较低一侧晶体每一层原子面分解为三层原子面)的机理 转变为亚稳的“台阶”状晶界, 台阶面部分地处于精确的能量极低 的{111}/{111}共格孪晶界上; 当提高温度退火时, 这种“台阶”状晶界最终会全部转变成稳定平直的{111}/{111}共格孪晶界. 关键词： 纯铜 ∑₃晶界')" href="#">非共格∑₃晶界 分子动力学模拟     

Effects of the triple junction types on the grain boundary carbide precipitation in a nickel-based superalloy,a statistical analysis

The morphology evolution of carbide precipitated on grain boundary nearby different triple junctions in grain boundary engineering (GBE) treated nickel-based Inconel Alloy 690 aged at 715°C for different time was investigated by scanning electron microscopy and electron backscatter diffraction. The results show that, the diversity of triple junction types was increased by GBE significantly. The size and morphology of grain boundary carbide were not only affected by the grain boundary character, but also the nearby grain boundary character at the triple junction. The higher Σ values of the nearby grain boundaries, the larger carbide precipitated on the other grain boundary. Based on the experimental results, the effects of grain boundary characters and triple junction types on the carbide precipitation behaviours are discussed.     

Transformations in the Grain Boundary Ensemble of M1 Copper Subjected to Equal-Channel Angular Pressing during Recrystallization Annealing

The grain structure of M1 copper subjected to equal-channel angular pressing (ECAP) and subsequent annealing at 593K for 1 h is studied by means of transmission electron microscopy and scanning electron microscopy with the diffraction of backscattered electrons. An increase in grain size and the formation of special boundaries (Σ3 twins both coherent and incoherent) are observed, along with the migration of high-energy Σ3 twins and common grain boundaries, the splitting of Σ9 special boundaries into Σ3 twins, and the splitting of common grain boundaries into Σ9 and Σ3 special boundaries. The local transformation of common grain boundaries into special boundaries also occurs. Particles of the Cu₂O phase are present on the migrating Σ3 twins and common grain boundaries.     

Large-scale black multi-crystalline silicon solar cell with conversion efficiency over 18 %

In this paper, large area multi-crystalline silicon (mc-Si) solar cells of 156 mm × 156 mm were fabricated by the combination of Ag-assisted etching and sodium hydroxide (NaOH) treatment. Scanning electron microscope, UV–Vis–NIR spectrophotometer, external quantum efficiency measurement system, and current–voltage test were used to characterize the etched black silicon wafers and the fabricated solar cells. It was found that, though the black mc-Si without NaOH treatment showed a lowest reflectance of 2.03 % in the wavelength of 400–900 nm, the maximum conversion efficiency came from the mc-Si solar cells produced by combination of Ag-assisted etching and NaOH treatment. Though the solar cell with additional NaOH treatment for 30 s presented a reflectance of 5.45 %, it presented the highest conversion efficiency of 18.03 %, which is 0.64 % higher than the traditional mc-Si solar cell (17.39 %) and much higher than that of the black mc-Si solar cell without NaOH treatment (16.24 %).     

Large crystalline grain growth using current-induced Joule heating

Electrical-current-induced Joule heating was applied to crystallization of 60-nm-thick amorphous silicon films formed on glass substrates. 3-7s-pulsed voltages were applied to silicon films connected with a capacitance in parallel. Coincident irradiation with 28-ns-pulsed excimer laser melted films partially and reduced its resistance. Complete melting for 12 7s and a low cooling rate at 1.1᎒⁸ K/s were achieved by Joule heating from electrical energy accumulated in the capacitance at 0.22 7F. For 7.4᎒¹⁷ cm^-3 phosphorus-doped films, analysis of temperature change in the electrical conductivity gave that the density of defect states localized at grain boundaries was 1.5᎒¹² cm^-2. Formation of 3.5-7m-long crystalline grains was observed by transmission electron micrograph. Preferential crystalline orientation was (110).     

Effects of milling-induced disorder on the lattice parameters and magnetic properties of hematite

A ball-milling treatment in air for 30 min is enough to reduce anhydrous bulk hematite (-Fe₂O₃) grains to nanometric sizes. For milling times, t_m, of 15, 30 min, 1 and 2 h, the crystals suffer an anisotropic lattice dilation, which is more pronounced for the smaller average grain sizes attained. Mössbauer and susceptibility results show that the process alters the effective Morin temperatures, T_M. The transition occurs less sharply than for the non-milled material and spreads over a maximum extent of 50 K for t_m=30 min. The susceptibility data indicate that the T_M for the fraction of material undergoes the transition shifts toward values not lower than 235 K. For t_m=10 h the transition is suppressed down to 12 K. Our results do not allow distinguishing bulk from surface regions of the grains. In addition, the disorder brought about by the milling reduces the magnetic response in the weak ferromagnetic state of -Fe₂O₃. The modification of T_M seems to depend mainly on the anisotropic dilation of the unit cell that affects the whole grain and it is related to the nanometric grain sizes achieved.     

Effect of the sintering temperature of ceramic manganites La0.7Mn1.3O3 ± Δ on their grain sizes, magnetic and electrical properties

The effect of the sintering temperature from 1070 to 1670 K of ceramic samples of lanthanum manganite La_0.7Mn_1.3O₃ on their grain size, structure, magnetic and resistive properties has been studied. An increase in the sintering temperature to 1270 K is shown to lead to an insignificant increase in the grain size and an increase in the density, fraction of the ferromagnetic phase in a grain, and colossal magnetoresistance. The ceramics sintering at temperatures higher than 1470 K is found to sharply increase the grain size; simultaneously, the grain takes a layered structure. The grain growth at these temperatures is established to be accompanied by manganese precipitation at the grain boundaries and likely in the grain interior. The increase in the sintering temperature is accompanied by appearance of a magnetically phase heterogeneity and a decrease in the Curie temperature and magnitude of the colossal magnetoresistance effect.     

Formation of copper silicides by high dose metal vapor vacuum arc ion implantation

Si(1 1 1) was implanted by copper ions with different doses and copper distribution in silicon matrix was obtained. The as-implanted samples were annealed at 300 and 540 °C, respectively. Formation of copper silicides in as-implanted and annealed samples were studied. Thermodynamics and kinetics of the reaction were found to be different from reaction at copper–silicon interface that was applied in conventional studies of copper–silicon interaction. The defects in silicon induced by implantation and formation of copper silicides were recognized by Si(2 2 2) X-ray diffraction (XRD).     

The role of diffusion in broadband infrared absorption in chalcogen-doped silicon

Sulfur doping of silicon beyond the solubility limit by femtosecond laser irradiation leads to near-unity broadband absorption of visible and infrared light and the realization of silicon-based infrared photodetectors. The nature of the infrared absorption is not yet well understood. Here we present a study on the reduction of infrared absorptance after various anneals of different temperatures and durations for three chalcogens (sulfur, selenium, and tellurium) dissolved into silicon by femtosecond laser irradiation. For sulfur doping, we irradiate silicon in SF₆ gas; for selenium and tellurium, we evaporate a film onto the silicon and irradiate in N₂ gas; lastly, as a control, we irradiated untreated silicon in N₂ gas. Our analysis shows that the deactivation of infrared absorption after thermal annealing is likely caused by dopant diffusion. We observe that a characteristic diffusion length—common to all three dopants—leads to the reduction of infrared absorption. Using diffusion theory, we suggest a model in which grain size of the resolidified surface layer can account for this characteristic diffusion length, indicating that deactivation of infrared absorptance may be caused by precipitation of the dopant at the grain boundaries.     

Superthermostability of nanoscale TIC-reinforced copper alloys manufactured by a two-step ball-milling process

A Cu-TiC alloy, with nanoscale TiC particles highly dispersed in the submicron-grained Cu matrix, was manufactured by a self-developed two-step ball-milling process on Cu, Ti and C powders. The thermostability of the composite was evaluated by high-temperature isothermal annealing treatments, with temperatures ranging from 727 to 1273 K. The semicoherent nanoscale TiC particles with Cu matrix, mainly located along the grain boundaries, were found to exhibit the promising trait of blocking grain boundary migrations, which leads to a super-stabilized microstructures up to approximately the melting point of copper (1223 K). Furthermore, the Cu-TiC alloys after annealing at 1323 K showed a slight decrease in Vickers hardness as well as the duplex microstructure due to selective grain growth, which were discussed in terms of hardness contributions from various mechanisms.