Synthesis of Silicon Nanocrystals in Microplasma Reactor

Abstract

Nanocrystalline silicon particles with a grain size of at least less than 10 nm are widely recognized as one of the key materials in optoelectronic devices, electrodes of lithium battery, bio-medical labels. There is also important character that silicon is safe material to the environment and easily gets involved in existing silicon technologies. To date, several synthesis methods such as sputtering, laser ablation, and plasma enhanced chemical vapor deposition (PECVD) based on low-pressure silane chemistry (SiH₄) have been developed for precise control of size and density distributions of silicon nanocrystals. We explore the possibility of microplasma technologies for the efficient production of mono-dispersed nanocrystalline silicon particles in a micrometer-scale, continuous-flow plasma reactor operated at atmospheric pressure.
Mixtures of argon, hydrogen, and silicon tetrachloride were activated using very high frequency (VHF = 144 MHz) power source in a capillary glass tube with a volume of less than 1 μ-liter. Fundamental plasma parameters of VHF capacitively coupled microplasma were characterized by optical emission spectroscopy, showing electron density of approximately 10¹⁵ cm^-3 and rotational temperature of 1500 K, respectively. Such high-density non-thermal reactive plasma has a capability of decomposing silicon tetrachloride into atomic silicon to produce supersaturated atomic silicon vapor, followed by gas phase nucleation via three-body collision. The particle synthesis in high-density plasma media is beneficial for promoting nucleation process. In addition, further growth of silicon nuclei was able to be favorably terminated in a short-residence time reactor. Micro Raman scattering spectrum showed that as-deposited particles were mostly amorphous silicon with small fraction of silicon nanocrystals. Transmission electron micrograph confirmed individual silicon nanocrystals of 3-15 nm size. Although those particles were not mono-dispersed, they were well separated and not coagulated.