四氯化钛
锡
氮化钛
材料科学
氮化物
X射线光电子能谱
蚀刻(微加工)
分析化学(期刊)
钛
化学工程
化学
纳米技术
冶金
有机化学
图层(电子)
工程类
作者
Varun Sharma,Suresh Kondati Natarajan,Simon D. Elliott,Tom Blomberg,Suvi Haukka,M. E. Givens,M. Tuominen,Mikko Ritala
标识
DOI:10.1002/admi.202101085
摘要
Abstract Thermally activated chemical vapor‐phase etching of titanium nitride (TiN) is studied by utilizing either alternate exposures of niobium pentafluoride (NbF 5 ) and carbon tetrachloride (CCl 4 ) or by using CCl 4 alone. Nitrogen (N 2 ) gas purge steps are carried out in between every reactant exposure. Titanium nitride is etched in a non‐self‐limiting way by NbF 5 –CCl 4 based binary chemistry or by CCl 4 at temperatures between 370 and 460 °C. Spectroscopic ellipsometry and a weight balance are used to calculate the etch per cycle. For the binary chemistry, an etch per cycle of ≈0.8 Å is obtained for 0.5 and 3 s long exposures of NbF 5 and CCl 4 , respectively at 460 °C. On the contrary, under the same conditions, the etch process with CCl 4 alone gives an etch per cycle of about 0.5 Å. In the CCl 4 ‐only etch process, the thickness of TiN films removed at 460 °C varies linearly with the number of etch cycles. Furthermore, CCl 4 alone is able to etch TiN selectively over other materials such as Al 2 O 3 , SiO 2 , and Si 3 N 4 . X‐ray photoelectron spectroscopy and bright field transmission electron microscopy are used for studying the post‐etch surfaces. To understand possible reaction products and energetics, first‐principles calculations are carried out with density functional theory. From thermochemical analysis of possible reaction models, it is found that NbF 5 alone cannot etch TiN while CCl 4 alone can etch it at high temperatures. The predicted byproducts of the reaction between the CCl 4 gas molecules and TiN surface are TiCl 3 and ClCN. Similarly, TiF 4 , NbFCl 3 , and ClCN are predicted to be the likely products when TiN is exposed to both NbF 5 and CCl 4 . A more favorable etch reaction is predicted when TiN is exposed to both NbF 5 and CCl 4 (Δ G = −2.7 eV at 640 K) as compared to exposure to CCl 4 only (Δ G = −2 eV at 640 K) process. This indicates that an enhanced etch rate is possible when TiN is exposed alternately to both NbF 5 and CCl 4 , which is in close agreement with the experimental results.
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