定向凝固法生长多晶硅中位错密度降低的研究进展

位错可以通过缩短少数载流子寿命而严重限制多晶硅太阳电池的转换效率,随着对高转换效率的追求,研究多晶硅位错的重要性也随之增加.在介绍现有半导体晶体CRSS和HAS位错模型的基础上,归纳了定向凝固法生长多晶硅中应力、晶界、杂质、过冷度对位错形成的影响机制与缺陷腐蚀和原位检测等多种位错表征方法.重点阐述了控制固液界面形貌、籽晶、掺杂、硅锭制备工艺、硅片退火等技术对减少与抑制多晶硅位错的影响.最后,针对位错模型、位错表征以及多晶硅生长过程中位错的抑制和生长后位错密度降低技术进行了展望.     

热退火对多晶硅特性的影响

为研究热退火对太阳电池用多晶硅的影响,在750～1150℃,N2和O2环境下分别对硅片进行热处理.用傅里叶红外光谱仪和准稳态光电导衰减法测量退火前后的氧碳含量和少子寿命的变化.为了比较,对有相同氧碳含量的直拉硅片进行同样处理.结果发现:在多晶和单晶片中氧碳含量下降很小,意味着没有氧沉淀产生,晶界对碳行为影响不大.多晶硅片在N2和O2环境下,850、950和1150℃下退火,少子寿命都有很大提高,并且在O2中退火比N2中退火少子寿命上升得更多,可能由于在高温退火时大量杂质扩散到晶界处,减少了复合中心.另外,间隙硅原子填充了空位或复合中心从而导致寿命提高.     

热退火对多晶硅特性的影响

为研究热退火对太阳电池用多晶硅的影响,在750～1150℃,N2和O2环境下分别对硅片进行热处理.用傅里叶红外光谱仪和准稳态光电导衰减法测量退火前后的氧碳含量和少子寿命的变化.为了比较,对有相同氧碳含量的直拉硅片进行同样处理.结果发现:在多晶和单晶片中氧碳含量下降很小,意味着没有氧沉淀产生,晶界对碳行为影响不大.多晶硅片在N2和O2环境下,850、950和1150℃下退火,少子寿命都有很大提高,并且在O2中退火比N2中退火少子寿命上升得更多,可能由于在高温退火时大量杂质扩散到晶界处,减少了复合中心.另外,间隙硅原子填充了空位或复合中心从而导致寿命提高.     

原位退火对Si基CdTe材料的位错抑制研究

硅与碲镉汞之间的外延碲化镉缓冲层能够减小外延过程中产生的高达10⁷ cm^-2的位错密度,高温热退火是抑制材料位错的有效方法之一。传统的离位退火技术会导致工艺不稳定和杂质污染等,而原位退火则可有效解决这些问题。利用原位退火技术对分子束外延生长的硅基碲化镉材料进行了位错抑制研究。对厚度约为9■m的碲化镉材料进行了6个周期不同温度的热循环退火,并阐释了不同退火温度对硅基碲化镉材料位错的抑制效果。采用统计位错腐蚀坑密度的方法对比了退火前后材料的位错变化。可以发现,在退火温度为520℃时,位错密度可以达到1.2×10⁶ cm^-2,比未进行退火的CdTe材料的位错密度降低了半个数量级。     

氢等离子体原位清洁硅衬底表面

本文研究了在用氢等离子体原位清洁硅片表面过程中,衬底温度,等离子体能量,处理时间及退火工艺对衬底表面清洁及晶格损伤的影响.实验结果表明,较高的衬底温度,较低的等离子能量有利于得到高度清洁、晶格损伤可恢复完整的硅表面.衬底温度为室温时的等离子体处理对硅表面会引入不可恢复的永久性损伤(缺陷);等离子体处理后的退火对于恢复晶格完整是极其必要的.完善的等离子体清洁处理之后,在1000℃下利用硅烷减压外延生长的外延层中,层错密度和位错密度分别小于50个/厘米~2和 1×10~3个/厘米~2.     

单晶硅片磨削损伤的透射电子显微分析

为了揭示硅片自旋转磨削加工表面层损伤机理,采用透射电子显微镜对硅片磨削表面层损伤特性进行了分析.结果表明:粗磨Si片的损伤层中有大量微裂纹和高密度位错;半精磨和精磨si片的损伤层中除了微裂纹和位错外,还存在非晶硅和多晶硅(Si-I相和Si-III相).从粗磨到半精磨,Si片的非晶层厚度从约Onm增大到约110nm;从半精磨剑精磨,Si片的非品层厚度由约110nm减小至约30nm,且非晶层厚度的分布均匀性提高.从粗磨到精磨,Si片损伤深度、微裂纹深度及位错滑移深度逐渐减小,材料的去除方式由脆性断裂方式逐渐向塑性方式过渡.     

单晶硅片磨削损伤的透射电子显微分析

为了揭示硅片自旋转磨削加工表面层损伤机理,采用透射电子显微镜对硅片磨削表面层损伤特性进行了分析.结果表明:粗磨Si片的损伤层中有大量微裂纹和高密度位错;半精磨和精磨si片的损伤层中除了微裂纹和位错外,还存在非晶硅和多晶硅(Si-I相和Si-III相).从粗磨到半精磨,Si片的非晶层厚度从约Onm增大到约110nm;从半精磨剑精磨,Si片的非品层厚度由约110nm减小至约30nm,且非晶层厚度的分布均匀性提高.从粗磨到精磨,Si片损伤深度、微裂纹深度及位错滑移深度逐渐减小,材料的去除方式由脆性断裂方式逐渐向塑性方式过渡.     

Ar气氛下快速退火对CZ-Si单晶中FPD的影响

将Si片经Secco腐蚀液腐蚀,用光学显微镜和原子力显微镜(AFM)对CZ-Si单晶中的流动图形缺陷(FPD)的形貌、分布及结构进行了研究,对Si片进行了湿氧化处理并采用较新的快速退火方法(RTA),在Ar气氛下对Si片进行热处理,研究了退火温度和退火时间对FPD缺陷密度的影响.结果表明,FPDs缺陷在1 100 ℃以下非常稳定;但是在1 100 ℃以上的温度,尤其在1 200℃对Si片进行RTA处理后,Si片中FPD的密度大大降低,而且随着的退火时间的延长,密度不断下降.     

氢气退火对大直径直拉硅单晶中空洞型缺陷的影响

研究了氢退火对大直径直拉硅单晶中空洞型缺陷(voids)的影响.样品在1050～1200℃范围进行氢退火,退火前后样品上的流水花样缺陷(FPD)和晶体原生粒子(COP)在腐蚀后分别用微分干涉光学显微镜和激光记数器进行观察.实验结果表明在氢退火以后,FPD缺陷的密度随温度升高不变,而样品上的COP密度大量减少.分析可知,氢气退火仅仅消除了硅片表面的voids,而对于硅片体内的voids不产生影响,并在实验的基础上,讨论了氢退火消除voids的机理.     

氢气退火对大直径直拉硅单晶中空洞型缺陷的影响

研究了氢退火对大直径直拉硅单晶中空洞型缺陷(voids)的影响.样品在1050～1200℃范围进行氢退火,退火前后样品上的流水花样缺陷(FPD)和晶体原生粒子(COP)在腐蚀后分别用微分干涉光学显微镜和激光记数器进行观察.实验结果表明在氢退火以后,FPD缺陷的密度随温度升高不变,而样品上的COP密度大量减少.分析可知,氢气退火仅仅消除了硅片表面的voids,而对于硅片体内的voids不产生影响,并在实验的基础上,讨论了氢退火消除voids的机理.     

A study of mottling phenomenon on textured multicrystalline silicon wafers and its potential effects on solar cell performance

The mottling phenomenon refers to the appearance of irregular dark patterns on HF–HNO₃ acid etching textured multicrystalline silicon (mc-Si) wafers. The mottles have been identified as clusters of dislocation etch pits. In the acidic texturization, conditions favoring light reflectivity reduction usually lead to enhanced mottling. In a belief of adverse effect of the mottles to cell performance, light reflectivity reduction is more or less compromised in industry to avoid the mottling. The present study aims to identify whether appearance of the mottles alone really adversely affects the wafers minority carrier lifetime. Both serial examinations of an acid etched mc-Si wafer sample and parallel examinations of neighboring pairs of mc-Si wafer samples etched in acids of different HF/HNO₃ ratios were carried out. The results show that development of the mottling, i.e., growth of dislocation etch pits, does not deteriorate mc-Si wafers in their minority carriers lifetime; rather it even slightly increases the lifetimes. Light reflectivity measurement and modeling show that the mottles can contribute to reduction of light reflectivity, and ~3% relative reduction of reflectivity is expected for multicrystalline silicon wafers of ordinary level of dislocation density. Removal of the defected zone surrounding a dislocation by the etching is postulated as a reason for the observed mottling-enhancement of the lifetime. It is further postulated that, in texturization of mc-Si wafers for cell production, instead of compromising light reflectivity reduction to avoid the mottling, it may be better to pursue lower light reflectivity, allowing some extent of the mottling. Meanwhile, more attention should be paid to compatibility of the cone-shaped dislocation etch-pit with grid printing of solar cells.     

High‐efficiency solar cells on phosphorus gettered multicrystalline silicon substrates

Measurements of the dislocation density are compared with locally resolved measurements of carrier lifetime for p‐type multicrystalline silicon. A correlation between dislocation density and carrier recombination was found: high carrier lifetimes (>100 µs) were only measured in areas with low dislocation density (<10⁵ cm⁻²), in areas of high dislocation density (>10⁶ cm⁻²) relatively low lifetimes (<20 µs) were observed. In order to remove mobile impurities from the silicon, a phosphorus diffusion gettering process was applied. An increase of the carrier lifetime by about a factor of three was observed in lowly dislocated regions whereas in highly dislocated areas no gettering efficiency was observed. To test the effectiveness of the gettering in a solar cell manufacturing process, five different multicrystalline silicon materials from four manufacturers were phosphorus gettered. Base resistivity varied between 0·5 and 5 Ω cm for the boron‐ and gallium‐doped p‐type wafers which were used in this study. The high‐efficiency solar cell structure, which has led to the highest conversion efficiencies of multicrystalline silicon solar cells to date, was used to fabricate numerous solar cells with aperture areas of 1 and 4 cm². Efficiencies in the 20% range were achieved for all materials with an average value of 18%. Best efficiencies for 1 cm² (20·3%) and 4 cm² (19·8%) cells were achieved on 0·6 and 1·5 Ω cm, respectively. This proves that multicrystalline silicon of very different material specification can yield very high efficiencies if an appropriate cell process is applied. Copyright © 2006 John Wiley & Sons, Ltd.     

直拉单晶硅中氧沉淀的高温消融和再生长

重点研究了直拉(CZ)硅中氧沉淀在快速热处理(RTP)和常规炉退火过程中的高温消融以及再生长行为.实验发现,RTP是一种快速消融氧沉淀的有效方式,比常规炉退火消融氧沉淀更加显著.硅片经RTP消融处理后,在氧沉淀再生长退火过程中,硅中体微缺陷(BMD)的密度显著增加,BMD的平均尺寸略有增加;而经过常规炉退火消融处理后,在后续退火过程中,BMD的密度变化不大,但BMD的尺寸明显增大.氧沉淀消融处理后,后续退火的温度越高,氧沉淀的再生长越快.     

Effect of crystal defects on mechanical properties relevant to cutting of multicrystalline solar silicon

The effect of crystalline defects such as dislocations and grain boundary on the cutting behavior of multicrystalline solar silicon is investigated. Diamond scribing experiments reveal significant intra-granular variations in the critical depth of cut for ductile-to-brittle transition in the material. This is explained by characterizing the local dislocation density variations in (100) and (311) grains of a cast multicrystalline silicon wafer and measuring the corresponding elastic modulus, nanoindentation hardness, and fracture toughness. Measured elastic moduli are shown to be higher than theoretical values for defect-free single crystal silicon of the same crystallographic plane. For a given grain orientation, a higher dislocation density is shown to be correlated with higher fracture toughness and a larger critical depth of cut.     

热处理和淬火的未掺杂半绝缘LEC GaAs的均匀性

对未掺杂原生ＬＥＣＳＩＧａＡｓ单晶在５００～１１７０℃温度范围进行了单步、两步和三步热处理及淬火，研究了这种热处理对ＥＬ２分布的影响，并检测了位错和Ａｓ沉淀的变化。结果表明，６５０℃以上温度的热处理可以改善ＥＬ２分布均匀性，且在６５０～９５０℃温度范围的热处理中，ＥＬ２均匀性的改善与热处理后的降温速率无明显联系。此外，两步或三步热处理的样品中ＥＬ２分布甚至比单步热处理样品中更优。９５０℃以下的热处理和淬火对位错和Ａｓ沉淀无明显影响。但是１１７０℃热处理井淬火后位错密度增加大约３０％，Ａｓ沉淀消失。对经１１７０℃淬火的样品再进行８０Ｏ℃或９５０℃的热处理，Ａｓ沉淀重新出现。ＥＬ２分布的变化可能与点缺陷、位错和Ａｓ沉淀的相互作用有关。文中提出了这种相互作用的模型，利用该模型可解释不同条件热处理后ＥＬ２分布的变化。     

热处理气氛对直拉硅单晶中体缺陷的影响

研究了五种不同的热处理气氛对直拉硅中氧沉淀及其诱生缺陷的影响.实验结果表明,经过低-高退火处理的硅片继续在五种不同的气氛中高温退火,氧沉淀会部分溶解,其溶解量与热处理气氛没有明显的关系,但不同气氛中处理的硅片中体缺陷(BMDs)的分布不同.并对此现象的机理进行了讨论,认为热处理气氛影响了硅片中点缺陷的分布从而影响到BMDs的分布.此研究对集成电路生产中内吸杂工艺的保护气氛的选择有指导意义.     

NaOH-NaClO腐蚀液制备太阳电池用多晶硅绒面的研究

介绍了一种采用NaOH-NaClO混合腐蚀液制备多晶硅绒面的新方法。研究结果表明,当VNaOH:VNaClO=1:3,NaOH浓度为17%,腐蚀温度为80℃,腐蚀时间为20min时,能够得到均匀的沟壑状凹坑多晶硅绒面,腐蚀后硅片表面的反射率与未腐蚀的硅片表面的反射率相比,降低近30%。另外,与传统的HF:HNO3酸腐蚀工艺相比,这种新型腐蚀工艺不仅可以获得反射率更低的多晶硅绒面结构,而且反应过程中产生的具有高度活性的氯离子可以作为很好的吸杂剂,降低一些有害的金属杂质的活性以提高太阳电池的开路电压,同时也省去了在产业化生产过程中的盐酸处理,从而改善了生产环境。     

用于制备SOI材料的基于硅片键合和双层多孔硅剥离的薄外延硅膜转移技术

采用在阳极化反应时改变电流强度的办法 ,在高掺杂的 P型硅 (111)衬底上制备了具有不同多孔度的双层结构多孔硅层 .用超高真空电子束蒸发技术在多孔硅表面外延生长了一层高质量的单晶硅膜 .在室温下 ,该外延硅片同另一生长有热二氧化硅的硅片键合在一起 ,在随后的热处理过程中 ,键合对可在多孔硅处裂开 ,从而使外延的单晶硅膜转移到具有二氧化硅的衬底上以形成 SOI结构 .扫描电镜、剖面投射电镜、扩展电阻和霍尔测试表明 SOI样品具有较好的结构和电学性能     

Room temperature wafer bonding of silicon, oxidized silicon, and crystalline quartz

The use of plasma immersion as preparation for room temperature wafer bonding has been investigated. Silicon wafers have been successfully bonded at room temperature after exposure to oxygen or argon plasma. Oxidized silicon wafers and crystalline quartz have been bonded after exposure to oxygen plasma. The bonded interfaces exhibit very high surface energies, comparable to what can be achieved with annealing steps in the range of 600–800°C using normal wet chemical activation before bonding. The high mechanical stability obtained after bonding at room temperature is explained by an increased dynamic in water removal from the bonded interface allowing covalent bonds to be formed. Electrical measurements were used to investigate the usefulness of plasma bonded interfaces for electronic devices.     

Elimination of light‐induced degradation with gallium‐doped multicrystalline silicon wafers

Lifetime stability of gallium‐doped multicrystalline silicon wafers has been evaluated under illumination. Quality and stability of the Ga‐doped multicrystalline silicon wafers were intensively studied by means of quasi‐steady‐state photocondcutance lifetime measurement. Results show that as‐grown Ga‐doped multicrystalline silicon wafers have high lifetimes, and no significant degradation was observed under illumination. The Ga‐doped multicrystalline silicon wafers are a promising material for future photovoltaics. Copyright © 2003 John Wiley & Sons, Ltd.