Optical emission spectroscopy of microwave-plasmas at atmospheric pressure applied to the growth of organosilicon and organotitanium nanopowders

Abstract

An atmospheric-pressure plasma sustained by an electromagnetic surface wave (SW) in the microwave regime combined with a bubbler/flash evaporator for the injection of liquid precursors was used to produce organosilicon and organotitanium nanopowders. Following the addition of hexamethyldisiloxane (HMDSO) vapors in the nominally pure argon plasma, optical emission spectra revealed the apparition of strong C2 molecular bands along with Si and Balmer H emission lines. Such features were not observed in our atmospheric-pressure Ar/HMDSO discharges controlled by dielectric barriers, indicating that microwave plasmas are characterized by much higher fragmentation levels of the precursors due to much higher electron densities. Emission spectra from the Ar/HMDSO SW plasma further showed a high-intensity continuum, the intensity of which decreased with time as powders started to form on the discharge tube walls. In presence of titanium isopropoxide (TTIP) vapors in the nominally pure Ar plasma, the emission was dominated by Ar and Ti lines, with no trace of carbon and no continuum. Fourier-Transform Infrared (FTIR) Spectroscopy of the powders formed in Ar/HMDSO plasmas showed very strong Si-(CH3)x and O-Si-(CH3)x bands, which is consistent with the formation of silicon oxycarbide. Transmission Electron Microscopy (TEM) further showed tube and sheet-like nanofeatures as well as larger structures consisting of agglomerated primary clusters. On the other hand, introduction of O2 in Ar/HMDSO plasmas produced only round-like nanoparticles with strong Si-O-Si bands and no trace of carbon, consistent with the formation of SiOx. The average size of the silica nanoparticles was 50 nm. FTIR spectra of powders formed in Ar/TTIP plasmas showed strong Ti-O signals, even without the addition of O2 in the gas phase. Corresponding TEM analysis showed nano- and agglomerated features comparable to those obtained in Ar/HMDSO although the average size of the titanate nanoparticles was smaller (10 nm). This set of data indicates that SW plasmas represent a promising parametric tool not only to achieve nanopowders with tailored properties for applications, but also for fundamental studies of nanodusty plasmas at atmospheric-pressure.