Formation process of Si3N4 particles on surface of Si ingots grown using silica crucibles with Si3N4 coating by noncontact crucible method

• Most of particles on the surface of ingots were found to be β-Si3N4.
• Particles originated from α-Si3N4 coating materials finally change to β-Si3N4.
• Some of Si3N4 particles attached on the surface of ingots acted as nucleation sites.
• β-Si3N4 particles on the surface of ingots had several morphologies.
• There are two cases to form floating Si3N4 particles on the melt surface.

A noncontact crucible method was used to investigate the process by which a Si3N4 coating material forms Si3N4 particles or precipitates on the surface of Si melts and ingots. Si ingots were grown using crucibles with and without a mixture of α- and β-Si3N4 particles. The oxygen and nitrogen concentrations in the ingots were measured by Fourier transform infrared spectrometry analysis. The nitrogen concentration in the ingots grown using crucibles with a Si3N4 coating was significantly higher than that in ingots grown using crucibles without a Si3N4 coating because the nitrogen from the Si3N4 coating material dissolved into the Si melt. From orientation image maps analyzed using electron backscattering diffraction patterns of SixNy particles on the surface of the ingots, it was clarified that most of the SixNy particles were β-Si3N4. This was also confirmed by X-ray diffraction measurements. The Si3N4 particles on the surface of the ingots had several morphologies such as needle-like, columnar, leaf-like, and hexagonal structures. There were two cases in which floating Si3N4 particles were formed on the surface of the Si melts, i.e., the removal and dissolution of the Si3N4 coating material. The removed or dissolved Si3N4 coating materials, which consisted of a mixture of α- and β-Si3N4 particles, are considered to have finally changed into β-Si3N4 in the form of transformers or precipitates on the surface of the Si melt, and these β-Si3N4 particles became attached to the surface of the ingots.