多晶硅锭中硬质夹杂性质与形成机理研究
摘要
晶体硅太阳电池是太阳电池中的主导产品,市场占有量达90%以上。由于多晶硅太阳能电池片是以太阳能级硅或电子级硅的头尾料和碎料为原料。因此,相对单晶硅而言,多晶硅锭中含有较多的杂质。多晶硅锭中硬质夹杂的出现使得在硅锭切割过程中硅片出现脊纹而报废,甚至由于硬质夹杂存在而造成包括断线停机、硅块报废等损失。为此,研究多晶硅锭中硬质夹杂性质及其形成对生产具有重大指导意义。
本文通过对多晶硅片脊纹、断线停机的形成原因进行分析;利用KeyenceVHX-100型3D高景深显微镜、配备了特征X射线能谱仪的HITACH S-3000N型扫描电镜、X射线衍射仪(Bruker D8 Focus型)对多晶硅锭中出现的硬质夹杂进行形貌、物相观察,发现造成硅片脊纹和断线停机主要原因是由于硬质夹杂物—块体状的β-SiC和棒状β-Si_3N_4的存在。β-SiC附着在β-Si_3N_4上形成团簇状,硅锭顶部颗粒直径达100μm以上,团簇后增大至几百微米;硅锭中部夹杂物较少,但也能找到直径在100μm左右的夹杂物。
进一步通过理论分析发现硅中碳、氮主要来源于原料、铸锭过程器件挥发、生成气体以及保护气。对SiC、Si_3N_4形成热力学、动力学分析发现它们都应该形成于凝固后,而不是凝固前。通过实验,再利用上述仪器以及SDT-Q600型DSC-TGA、Nicolet 380型傅立叶变换红外光谱仪(FTIR)验证了理论分析。并根据所得结果提出了解决措施建议。
Crystalline silicon solar cell is the dominant products in the solar cells industry, its market share amounts up to 90%. Multi-crystalline silicon solar cells produced by solar grade silicon or the craniocaudal electronic grade silicon material and debris as raw materials. Therefore, compared with monocrystalline silicon, multi-crystalline silicon ingot contains more impurities. The rigid inclusions in multi-crystalline silicon ingots affects surface quality of multi-crystalline silicon wafers, and threatens the wire cutting process of the wafer production from multi-crystalline silicon ingot. Furthermore, they may cause wire broken in the cutting processes. To sum up, studying the formation and nature of the hard inclusions in the multicrystalline silicon ingot is great significant for production.
Through the analysis of the reason about the ridges formation on polysilicon chip and the sawing wire breaken. Scanning electron microscope associated with energy spectrometer for characteristic X-ray, 3D digital microscope and X-ray diffract meter have been used to analyze the inclusions's surface morphology and phase in a directionally solidified multi-crystalline silicon ingot. The results indicate a high density of large SiC and Si_3N_4 particles in the top layer of the ingot andβ-SiC attached to theβ-Si_3N_4 surface and become cluster-formation. The density decreases rapidly with depth. In the middle of the ingot, very few and fine SiC inclusions can be found, though large SiC particles(~100μm) do exist sometime.
It has been further found that the carbon and nitrogen in the silicon ingot comes mainly from raw materials by theoretical analysis, the product between devices in directionally solidified process and the protection gas. Analysissing the SiC and Si_3N_4 formed thermodynamics and kinetics showed that all of them should be formed not in the solidification, but after the solidification. The equipments, such as energy spectrometer for characteristic X-ray, 3D digital microscope, X-ray diffract meter , DSC-TGA and FTIR, are used to verify the theoretical analysis.With respect to the results,possible solutions for reducing of SiC inclusions in multi-crystalline silicon ingot are suggested.
本文通过对多晶硅片脊纹、断线停机的形成原因进行分析;利用KeyenceVHX-100型3D高景深显微镜、配备了特征X射线能谱仪的HITACH S-3000N型扫描电镜、X射线衍射仪(Bruker D8 Focus型)对多晶硅锭中出现的硬质夹杂进行形貌、物相观察,发现造成硅片脊纹和断线停机主要原因是由于硬质夹杂物—块体状的β-SiC和棒状β-Si_3N_4的存在。β-SiC附着在β-Si_3N_4上形成团簇状,硅锭顶部颗粒直径达100μm以上,团簇后增大至几百微米;硅锭中部夹杂物较少,但也能找到直径在100μm左右的夹杂物。
进一步通过理论分析发现硅中碳、氮主要来源于原料、铸锭过程器件挥发、生成气体以及保护气。对SiC、Si_3N_4形成热力学、动力学分析发现它们都应该形成于凝固后,而不是凝固前。通过实验,再利用上述仪器以及SDT-Q600型DSC-TGA、Nicolet 380型傅立叶变换红外光谱仪(FTIR)验证了理论分析。并根据所得结果提出了解决措施建议。
Crystalline silicon solar cell is the dominant products in the solar cells industry, its market share amounts up to 90%. Multi-crystalline silicon solar cells produced by solar grade silicon or the craniocaudal electronic grade silicon material and debris as raw materials. Therefore, compared with monocrystalline silicon, multi-crystalline silicon ingot contains more impurities. The rigid inclusions in multi-crystalline silicon ingots affects surface quality of multi-crystalline silicon wafers, and threatens the wire cutting process of the wafer production from multi-crystalline silicon ingot. Furthermore, they may cause wire broken in the cutting processes. To sum up, studying the formation and nature of the hard inclusions in the multicrystalline silicon ingot is great significant for production.
Through the analysis of the reason about the ridges formation on polysilicon chip and the sawing wire breaken. Scanning electron microscope associated with energy spectrometer for characteristic X-ray, 3D digital microscope and X-ray diffract meter have been used to analyze the inclusions's surface morphology and phase in a directionally solidified multi-crystalline silicon ingot. The results indicate a high density of large SiC and Si_3N_4 particles in the top layer of the ingot andβ-SiC attached to theβ-Si_3N_4 surface and become cluster-formation. The density decreases rapidly with depth. In the middle of the ingot, very few and fine SiC inclusions can be found, though large SiC particles(~100μm) do exist sometime.
It has been further found that the carbon and nitrogen in the silicon ingot comes mainly from raw materials by theoretical analysis, the product between devices in directionally solidified process and the protection gas. Analysissing the SiC and Si_3N_4 formed thermodynamics and kinetics showed that all of them should be formed not in the solidification, but after the solidification. The equipments, such as energy spectrometer for characteristic X-ray, 3D digital microscope, X-ray diffract meter , DSC-TGA and FTIR, are used to verify the theoretical analysis.With respect to the results,possible solutions for reducing of SiC inclusions in multi-crystalline silicon ingot are suggested.
引文
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