Defects in Fast-Neutron Irradiated Nitrogen-Doped Czochralski Silicon after Annealing at High Temperature

Fast-neutron irradiated nitrogen-doped Czochralski silicon(NCZ-Si)was annealed at 1100℃for different time,then FTIR and optical microscope were used to study the behavior of oxygen.It is found that[Oi]increase at the early stage then decrease along with the increasing of anneal time.High density induced-defects can be found in the cleavage plane.By comparing NCZ-Si with Czochralski silicon(CZ-Si),[Oi]in NCZ-Si decrease more after anneal 24 h.

Impact of Heat Shield Structure in the Growth Process of Czochralski Silicon Derived from Numerical Simulation

Further development of the photovoltaic industry is restricted by the productivity of mono-crystalline silicon technology due to its requirements of low cost and high efficient photocells. The heat shield is not only the important part of the thermal field in Czochralski（Cz） mono-crystalline silicon furnace, but also one of the most important factors influencing the silicon crystal growth. Large-diameter Cz-Si crystal growth process is taken as the study object, Based on FEM numerical simulation, different heat shield structures are analyzed to investigate the heater power, the melt-crystal interface shape, the argon flow field, and the oxygen concentration at the melt-crystal interface in the process of large Cz-Si crystal growth. The impact of these factors on the growth efficiency and crystal quality are analyzed. The results show that the oxygen concentration on the melt-crystal interface and the power consumption of the heater stay high due to the lack of a heat shield in the crystal growth system. Argon circumfluence is generated on the external side of the right angle heat shield. By the right-angle heat shield, the speed of gas flow is lowered on the melt free surface, and the temperature gradient of the free surface is increased around the melt-crystal interface. It is not conducive for the stable growth of crystal. The shape of the melt-crystal interface and the argon circulation above the melt free surface are improved by the inclined heat shield. Compared with the others, the system pulling rate is increased and the lowest oxygen concentration is achieved at the melt-crystal interface with the composite heat shield. By the adoption of the optimized composite heat shield in experiment, the real melt-crystal interface shapes and its deformation laws obtained by Quick Pull Separation Method at different pulling rates agree with the simulation results. The results show that the method of simulation is feasible. The proposed research provides the theoretical foundation for the thermal field design of the large diameter Cz-Si monocrystalline growth.

Annealing behaviors of vacancy in varied neutron irradiated Czochralski silicon

The difference of annealing behaviors of vacancy-oxygen complex (VO) in varied dose neutron irradiated Czochralski silicon: (S1 5×1017 n/cm3 and S2 1.07×1019 n/cm3) were studied. The results show that the VO is one of the main defects formed in neutron irradiated Czochralski silicon (CZ-Si). In this defect, oxygen atom shares a vacancy, it is bonded to two silicon neighbors. Annealed at 200 ℃, divacancies are trapped by interstitial oxygen(Oi) to form V2O (840 cm-1). With the decrease of the 829 cm-1 (VO) three infrared absorption bands at 825 cm-1 (V2O2), 834 cm-1 (V2O3) and 840 cm-1 (V2O) will rise after annealed at temperature range of 200-500 ℃. After annealed at 450-500 ℃ the main absorption bands in S1 sample are 834 cm-1, 825 cm-1 and 889 cm-1 (VO2), in S2 is 825 cm-1. Annealing of A-center in varied neutron irradiated CZ-Si is suggested to consist of two processes. The first is due to trapping of VO by Oi in low dose neutron irradiated CZ-Si (S1) and the second is due to capture the wandering vacancy by VO, etc, in high dose neutron irradiated CZ-Si (S2), the VO2 plays an important role in the annealing of A-center. With the increase of the irradiation dose, the annealing behavior of A-center is changed.

Influence of rapid thermal process on intrinsic gettering in fast neutron irradiated Czochralski silicon

A rapid thermal process (RTP) was first introduced into the intrinsic gettering (IG) processes of fast neutron irradiated Czochralski (CZ) silicon. The effect of RTP conditions on bulk microdefects (BMDs) and denuded zone (DZ) was investigated. Fourier transform infrared absorption spectrometer (FTIR) was used to measure the concentration of interstitial oxygen ([Oi]). Bulk microdefects were observed by optical microscope. The results show that, according to the variation of [Oi], it is found that RTP doesn’t change the processes of oxygen precipitation in fast neutron irradiated Czochralski silicon. Perfect denuded zone, dense oxygen precipitates and defects form in the bulk of irradiated samples. With increasing temperature of RTP, the width of denuded zone decreases. Increasing RTP cooling rate, the density of Bulk microdefects increases. DZ forms in the sample that annealed in nitrogen atmosphere.

Influence of co-precipitation of copper and nickel on the formation of a denuded zone in Czochralski silicon

The influence of co-precipitation of copper and nickel on the formation of a denuded zone （DZ） in Czochralski silicon （Cz Si） was systematically investigated by means of etching and optical microscopy （OM）. It was found that, for conventional high-low-high annealing （CFA）, the DZ could be obtained in all specimens contaminated by copper and nickel co-impurity at different steps of the heat treatment, indicating that no copper precipitates or nickel precipitates were generated in the region just below the surface. However, for rapid thermal annealing （RTA）-low-high annealing, the tendency is not the same; the DZ could not be found in the specimen which was contaminated by copper and nickel contamination before the first RTA annealing. On the basis of the experimental results, it was supposed that the concentration and distribution of the vacancies generating during the RTA can influence the distribution of copper precipitation and nickel precipitation along the cross-section of Cz Si significantly, and thus influence the formation of the DZ to a great extent.

Statistical analysis of recombination properties of the boronoxygen defect in p-type Czochralski silicon

This paper presents the application of lifetime spectroscopy to the study of carrier-induced degradation ascribed to the boron-oxygen （BO） defect. Specifically, a large data set of p-type silicon samples is used to investigate two important aspects of carrier lifetime analysis： ① the methods used to extract the recombination lifetime associated with the defect and ② the underlying assumption that cartier injection does not affect lifetime components unrelated to the defect. The results demonstrate that the capture cross section ratio associated with the donor level of the BO defect （kl） vary widely depending on the specific method used to extract the defect-specific recombination lifetime. For the data set studied here, it was also found that illumination used to form the defect caused minor, but statistically significant changes in the surface passivation used. This violation of the fundamental assumption could be accounted for by applying appropriate curve fitting methods, resulting in an improved estimate of k1 （11.90±0.45） for the fully formed BO defect when modeled using the donor level alone. Illumination also appeared to cause a minor, apparently injectionindependent change in lifetime that could not be attributed to the donor level of the BO defect alone and is likely related to the acceptor level of the BO defect. While specific to the BO defect, this study has implications for the use of lifetime spectroscopy to study other carrier induced defects. Finally, we demonstrate the use of a unit-less regression goodness-of-fit metric for lifetime data that is easy to interpret and accounts for repeatability error.

Microstructure of flow pattern defects in boron-doped Czochralski-grown silicon

The morphology and microstructure of flow pattern defects （FPDs） in lightly boron-doped Czochralski-grown silicon （Cz-Si） crystals were investigated using optical microscopy and atomic force microscopy. The experimental results showed that the morphology of FPDs was parabola-like with several steps. Single-type and dual-type voids were found on the tip of FPDs and two heaves exist on the left and right sides of the void. All the results have proved that FPDs were void-type defects. These results are very useful to investigate FPDs in Cz-Si wafers further and explain the annihilation of FPDs during high-temperature annealing.

Experiment and numerical simulation of melt convection and oxygen distribution in 400-mm Czochralski silicon crystal growth

Single-crystalline silicon materials with large dimensions have been widely used as assemblies in plasma silicon etching machines.However,information about large-diameter low-cost preparation technology has not been sufficiently reported.In this paper,it was focused on the preparation of 400-mm silicon（100） crystal lightly doped with boron from 28-in.hot zones.Resistivity uniformity and oxygen concentration of the silicon crystal were investigated by direct-current（DC） four-point probes method and Fourier transform infrared spectroscopy（FTIR）,respectively.The global heat transfer,melt flow and oxygen distribution were calculated by finite element method（FEM）.The results show that 28-in.hot zones can replace conventional 32 in.ones to grow 400-mm-diameter silicon single crystals.The change in crucible diameter can save energy,reduce cost and improve efficiency.The trend of oxygen distribution obtained in calculations is in good agreement with experimental values.The present model can well predict the 400-mm-diameter silicon crystal growth and is essential for the optimization of furnace design and process condition.

Microstructure of flow pattern defects in boron-doped Czochralski-grown silicon

The morphology and microstructure of flow pattern defects (FPDs) in lightly boron-doped Czochralski-grown silicon (Cz-Si) crystals were investigated using optical microscopy and atomic force microscopy. The experimental results showed that the morphology of FPDs was parabola-like with several steps. Single-type and dual-type voids were found on the tip of FPDs and two heaves exist on the left and right sides of the void. All the results have proved that FPDs were void-type defects. These results are very useful to investigate FPDs in Cz-Si wafers further and explain the annihilation of FPDs during high-temperature annealing.

直拉法单晶硅生长原理、工艺及展望

碳达峰、碳中和理念提出后,太阳能作为一种可再生绿色能源备受关注。单晶硅作为主要的光伏材料,其质量决定着太阳能电池效率的高低,为了降低成本和提高产能,人们对单晶硅提出越来越高的要求。直拉法(CZ法)是单晶硅的主要制备方法,其生产效率高,可实现自动化,直拉单晶硅市场占比超过90%,目前正朝着大尺寸、N型、薄片化、低氧低碳的方向发展。然而随着晶棒尺寸增大,热场变化更加复杂,现有CZ工艺难以满足市场需求。未来降低度电成本仍是晶硅光伏发展的驱动力,应通过技术革新、产业标准化、成本控制等手段推动光伏产业发展。本文介绍了CZ法生长单晶硅的基本原理和生长工艺,分别对缺陷控制、热场优化、氧含量控制等进行了分析,在总结工艺现状和单晶生长特点的基础上对直拉法生长单晶硅的发展方向进行了展望。

The Splittings of p_± States in Infrared Spectra of Thermal Donors in Silicon

p -type CZ silicon crystals annealed at 450℃ have been investigated by low temperature infrared spectroscopy with high resolusion. It has been shown that the 2p± and 3p± bands of neutral thermal donors TD~° are all split into two bands, which have not been reported before. In addition, the concentrations ofindi- vidual TD_i and total TD have been derived from the heights of 2po bands, and the boron concentrations de- rived from that of 320 cm^(-1) band. The room temperature resistivities of samples have been evaluated and the comparison with practically measured resistivities have been made.

Influence of Ring Oxidation-Induced Stack Faults on Efficiency in Silicon Solar Cells

We observe a strong correlation between the ring oxidation-induced stack faults （OISF） formed in the course of phosphor diffusion and the efficiency of Czochralski-grown silicon solar cells. The main reason for ring-OISF formation and growth in substrate is the silicon oxidation and phosphorus diffusion process induced silicon selfinterstitial point defect during POCI3 diffusion. The decreasing of minority carrier diffusion length in crystal silicon solar cell induced by ring-OISF defects is identified to be one of the major causes of efficiency loss.

基于ISOMAP-DE-SVM的Cz单晶硅等径阶段掉苞预测

针对目测法无法及时发现直拉单晶硅在等径生长阶段发生的掉苞问题,本文提出一种基于ISOMAP-DE-SVM的掉苞预测模型,可以在掉苞现象发生之前发出警告。首先剔除方差较小的参数,采用斯皮尔曼相关系数法剔除冗余参数,采用最大互信息法检验剩余参数的非线性相关性;然后将关键参数的均值和标准差作为等度量映射和多维放缩的输入,得到两份样本数据;最后将这两份样本数据分别输入到经过差分算法、遗传算法优化的支持向量机预测模型,得到4份预测结果。预测结果表明:基于ISOMAP-DE-SVM的预测模型具有收敛速度快、准确度高的特点,平均预测准确率可以达到96%;同时,所使用的方法揭示了单晶硅等径阶段的数据具有非线性特点。通过实际应用验证表明模型具有一定的工程实用价值。

横向磁场下坩埚转速对半导体级直拉单晶硅熔体中流场与氧浓度的影响机制

利用ANSYS有限元软件分析了横向磁场下不同坩埚转速对200 mm半导体级直拉单晶硅的流场及氧浓度的影响。研究结果表明:在横向磁场下,硅熔体的流场和氧浓度分布呈三维非对称性,熔体对流形式主要包括泰勒-普劳德曼漩涡、浮力-热毛细漩涡及次漩涡,其中前两者有助于氧挥发,而次漩涡则起到抑制作用。当坩埚转速较低(0.5~1.0 r/min)时,较弱的熔体对流强度导致坩埚壁与固液界面间的热传导效率低,氧主要以扩散机制迁移至固液界面,熔硅中氧浓度高;当坩埚转速较高(2~2.5 r/min)时,氧通过强对流形式迁移至固液界面。随着坩埚转速增加,次漩涡和浮力-热毛细漩涡的作用强度提高,浮力-热毛细漩涡影响区域远离自由表面,使硅熔体中的氧浓度呈先下降后上升的趋势。数值模拟结果与实验结果均表明,在横向磁场条件下优选1.5 r/min的坩埚转速可获得平均氧浓度较低的单晶硅。上述分析结果可以为横向磁场下半导体级单晶硅拉晶参数优化提供参考依据。

直拉单晶硅中的缺陷形成机理及控制方法

半导体级单晶硅作为半导体产业链中的重要原材料,其杂质、缺陷等品质对电子器件和集成电路的性能起着至关重要的作用。单晶硅生长和加工过程都不可避免地会形成各种缺陷。鉴于直拉法是目前主流的单晶硅制造方法,针对直拉法半导体级单晶硅制造技术中的晶体缺陷工程问题进行了探讨。简要介绍了半导体级单晶硅中各种晶体缺陷以及它们的形成机理。最后,总结了控制缺陷形成的主要方法。

高拉速对Ф300 mm单晶硅点缺陷分布及生产能耗的影响

大尺寸直拉单晶硅的“增效降本”是当前光伏企业急需解决的问题。本文采用有限元体积法对Ф300 mm直拉单晶硅生长过程分别进行稳态和非稳态全局模拟,研究提高拉晶速率对直拉单晶硅生长过程中的固液界面、点缺陷分布以及生长能耗的影响。结果表明:拉晶速率提高为1.6 mm/min时固液界面的偏移量为33 mm,不会影响晶体的稳定生长;拉晶速率对晶体中点缺陷的分布起决定性作用,提高拉晶速率不仅能降低自间隙点缺陷的浓度,而且使晶棒内V/G始终高于临界值;且拉晶速率对功率消耗影响较大,提高拉晶速率后晶体生长时间减少了46.4%,单根晶体生长消耗功率降低了约4.97%。优化和控制适宜的拉晶速率有利于低成本地生长特定点缺陷分布甚至无点缺陷单晶硅,为提高大尺寸直拉单晶硅质量、降低生产能耗提供一定的理论支持。

基于模糊神经网络的模型预测硅单晶直径控制

为了生产大尺寸、高质量、低能耗的直拉单晶硅棒,文中通过在直拉硅单晶生产车间采集的大量数据,通过模糊神经网络(Fuzzy Neural Networks,FNN)和模型预测控制(Model predic-tive control,MPC)进行建模,得到了等径阶段的直径预测模型和直径控制模型.直径预测模型测试结果表明:平均相对误差仅为0.0287%,预测精度极高.通过仿真并与常规PID控制进行对比分析得出,MPC比常规PID控制的调节速度快53.66%,并且MPC的控制过程非常稳定,其超调量基本为0;由加热器功率调控变化过程可知,MPC减少了调节过程的能耗,并提高了热场稳定性及单晶硅棒质量.通过预测模型建立的直径控制模型能提高控制精度并促进硅单晶高质量生产.

热氧化法钝化硅片的少数载流子寿命

用高频光电导衰减法 (PCD)研究了热氧化钝化对直拉硅少子寿命的影响 .在 70 0～ 110 0℃范围热氧化不同时间 (0 .5～ 4 h)对直拉硅片表面进行钝化 ,实验结果表明 ,在 10 0 0℃下热氧化对硅片表面钝化的效果最好 ;而且发现热氧化 1.5 h后硅片的少子寿命值达到最大值 ,接近于其真实值 ,而随着热氧化时间的延长 (>1.5 h)少子寿命将会降低 ,这是由于直拉硅中过饱和的氧会沉淀下来形成氧沉淀 ,成为新的少子复合中心 .

微氮硅单晶中的空洞型原生缺陷

研究了掺氮和不掺氮直拉硅单晶中 ,空洞型原生缺陷 (voids)的分布行为和其退火性质 .从两种晶体不同位置取样 ,观察与大尺寸 voids相关的流水花样缺陷 (FPD)沿晶体轴向的分布 ,然后在 10 5 0～ 12 5 0℃下 Ar气中退火不同时间 .实验结果表明在掺氮直拉硅中与较大尺寸 voids相关的 FPD缺陷的密度大量减少 ,其体内这种 FPD缺陷的退火行为与不掺氮直拉硅一样 ,在高温下才能被有效的消除 .这表明在直拉硅中掺氮可以抑制大尺寸的 voids的产生 ,而且掺氮硅中

大直径直拉硅中氮对原生氧沉淀的影响

研究了在大直径直拉硅单晶中掺氮 (N )对原生氧沉淀的影响 .通过高温一步退火 (10 5 0℃ )和低 -高温两步退火 (80 0℃ +10 5 0℃ )发现在掺 N直拉 (NCZ)硅中氧沉淀的行为与一般直拉 (CZ)硅是大不相同的 ,经过高温一步退火后 ,在氧化诱生层错环 (OSF- ring)区氧沉淀的量要小于空洞型缺陷 (voids)区 ,而经过低 -高温两步退火后 ,OSF-ring区的氧沉淀量要远远大于 voids区 .由此可得 ,在晶体生长过程中 ,N通过改变硅晶体中空位的浓度及其分布从而改变原生氧沉淀的尺寸和分布 .并在此基础上讨论了在大直径 NCZ硅中掺 N影响原生氧沉淀的机理 .