Kinetics of TiN Chemical Vapor Deposition Process using TiCl<sub>4</sub>and NH<sub>3</sub>for ULSI Diffusion Barrier Applications: Relationship between Step Coverage and NH<sub>3</sub>Partial Pressure

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  • Jun Keeyoung
    Department of Materials Engineering, School of Engineering, The University of Tokyo
  • Egashira Yasuyuki
    Division of Chemical Engineering, Department of Chemical Engineering, Osaka University
  • Shimogaki Yukihiro
    Department of Materials Engineering, School of Engineering, The University of Tokyo

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  • Kinetics of TiN Chemical Vapor Deposition Process using TiCl4 and NH3 for ULSI Diffusion Barrier Applications: Relationship between Step Coverage and NH3 Partial Pressure

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TiN films were deposited by chemical vapor deposition (CVD) using NH3 and TiCl4 as the source precursors. The effect of partial pressures of TiCl4 (PTiCl<SUB>4</SUB>) and NH3 (PNH<SUB>3</SUB>) on the growth rate and step coverage quality of these TiN films was measured, revealing the growth rate of TiN films followed the Langmuir–Hinshelwood (L–H) type isotherm as a function of PTiCl<SUB>4</SUB>. The sticking probability of film-forming species was estimated from the step coverage profile simulated by using the Monte Carlo method. The relationship between the sticking probability of Ti-containing species and PNH<SUB>3</SUB> was investigated, revealing that the sticking probability in the 1st-order kinetic regime depended on PNH<SUB>3</SUB>. The effect of NH3 on the growth kinetics could be expressed by G.R.×ρTiN=[ksKCTiCl<SUB>4</SUB>⁄(1+KCTiCl<SUB>4</SUB>)]·(CNH<SUB>3</SUB>)2 in the wide range of PTiCl<SUB>4</SUB>. The reason for 2nd-order reaction for PNH<SUB>3</SUB> is not clear yet, but the rate equation suggests the complicated gas-phase and/or surface reaction chemistries to form TiN.

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