Add time:07/26/2019         Source:sciencedirect.com

Titanium nitride (TiN) can be deposited using the organometallic precursor tetrakis(dimethylamino)titanium (Ti[N(CH3)2]4) (TDMAT). Deviations from conformal TiN film growth have been observed in trench structures using TDMAT. This nonconformal deposition may be associated with readsorption and site blocking by the dimethylamine (HN(CH3)2) (DMA) reaction product. To understand the deviations from conformal TiN deposition in trench structures, the adsorption and desorption kinetics for TDMAT and DMA were measured on a sputter-deposited TiN surface using laser induced thermal desorption (LITD) techniques. The LITD measurements revealed that DMA has a higher sticking coefficient than TDMAT. The sticking coefficients for both TDMAT and DMA were also dependent on surface coverage. The initial sticking coefficient for TDMAT is S0=0.23 with a coverage-dependence approximated by S(θ)=0.25 exp(−4.7 θ) where θ is the normalized surface coverage. The initial sticking coefficient for DMA is S0=0.70 and the coverage-dependence is approximated by S(θ)=0.86 exp(−3.7 θ). The observed desorption kinetics of DMA following TDMAT and DMA exposures on TiN were also coverage-dependent. The isothermal desorption measurements could be fit using a simple first-order desorption rate expression, kd=νdexp[−Ed(θ)/RT] where E(θ) is the coverage-dependent desorption energy, Ed(θ)=E0−E1θ. Assuming a desorption preexponential of νd=1×1013 s−1, the observed isothermal desorption measurements for DMA desorption following both TDMAT and DMA exposures could be fit using E0=29.1 kcal mol−1 and E1=8.2 kcal mol−1. These measured adsorption and desorption kinetics are consistent with DMA readsorption as a major contributor to nonconformal TiN growth in trench structures using TDMAT.

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