Silicon Nanocrystal Synthesis in Microplasma Reactor

Abstract

Nanocrystalline silicon particles with grains smaller than 5 nm are widely recognized as a key material in optoelectronic devices, lithium battery electrodes, and bio-medical labels. Another important characteristic is that silicon is an environmentally safe material that is used in numerous 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. In this study, we explore the possibility of microplasma technologies for efficient production of mono-dispersed nanocrystalline silicon particles on a micrometer-scale, continuous-flow plasma reactor operated at atmospheric pressure. Mixtures of argon, hydrogen, and silicon tetrachloride were activated using a very-high-frequency (144 MHz) power source in a capillary glass tube with volume of less than 1 μl. Fundamental plasma parameters of the microplasma were characterized using optical emission spectroscopy, which respectively indicated electron density of 10¹⁵ cm^-3, argon excitation temperature of 5000 K, and rotational temperature of 1500 K. Such high-density non-thermal reactive plasma can decompose silicon tetrachloride into atomic silicon to produce supersaturated silicon vapor, followed by gas-phase nucleation via three-body collision: particle synthesis in high-density plasma media is beneficial for promoting nucleation processes. In addition, further growth of silicon nuclei can be terminated in a short-residence-time reactor. Micro-Raman scattering spectra showed that as-deposited particles are mostly amorphous silicon with a small fraction of silicon nanocrystals. Transmission electron micrography confirmed individual 3-15 nm silicon nanocrystals. Although particles were not mono-dispersed, they were well separated and not coagulated.