Determination of the vapour pressure curves and vaporization enthalpies of hafnium alkoxides using thermogravimetric analysis.

Abstract

In order to identify a volatile metallo-organic precursor for the deposition of hafnium oxide (HfO2) films for atomic layer deposition (ALD) applications, the evaporative properties of hafnium alkoxides (hafnium isopropoxide, hafnium n-propoxide and hafnium n-butoxide) were investigated using thermogravimetric analysis. These hafnium alkoxide samples were synthesized by the electrochemical method and characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance and inductively coupled plasma analysis techniques. The characterization results indicated that the products were 99.997% high-purity hafnium alkoxides and could meet the requirement of purity considering the usage of making HfO2 gate oxide by ALD. Synthesized samples were subjected to a simultaneous thermogravimetric–differential thermal analysis unit at 10 K min−1 in a dry nitrogen atmosphere flowing at 100 ml min−1. Benzoic acid was used to calculate a calibration constant, which could then be inserted into a modified Langmuir equation to calculate vapour pressure curves for hafnium isopropoxide and hafnium n-propoxide. Detailed vapour pressure data for the HfO2 precursor hafnium alkoxides were determined. The vapour pressure curve of hafnium isopropoxide was constructed within the first stage, and calculated to be lnp = 31.157 (±0.200)−13130.57 (±56.50)/T. Hafnium n-propoxide and hafnium n-butoxide were simultaneously undergoing evaporation and decomposition, thus making calculations invalid.