Browsing by Author "Givens, Michael E."

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Combining Experimental and DFT Investigation of the Mechanism Involved in Thermal Etching of Titanium Nitride Using Alternate Exposures of NbF5 and CCl4, or CCl4 Only
(2021-11-23) Sharma, Varun; Kondati Natarajan, Suresh; Elliott, Simon D.; Blomberg, Tom; Haukka, Suvi; Givens, Michael E.; Tuominen, Marko; Ritala, Mikko
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Thermally activated chemical vapor-phase etching of titanium nitride (TiN) is studied by utilizing either alternate exposures of niobium pentafluoride (NbF5) and carbon tetrachloride (CCl4) or by using CCl4 alone. Nitrogen (N2) gas purge steps are carried out in between every reactant exposure. Titanium nitride is etched in a non-self-limiting way by NbF5–CCl4 based binary chemistry or by CCl4 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 NbF5 and CCl4, respectively at 460 °C. On the contrary, under the same conditions, the etch process with CCl4 alone gives an etch per cycle of about 0.5 Å. In the CCl4-only etch process, the thickness of TiN films removed at 460 °C varies linearly with the number of etch cycles. Furthermore, CCl4 alone is able to etch TiN selectively over other materials such as Al2O3, SiO2, and Si3N4. 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 NbF5 alone cannot etch TiN while CCl4 alone can etch it at high temperatures. The predicted byproducts of the reaction between the CCl4 gas molecules and TiN surface are TiCl3 and ClCN. Similarly, TiF4, NbFCl3, and ClCN are predicted to be the likely products when TiN is exposed to both NbF5 and CCl4. A more favorable etch reaction is predicted when TiN is exposed to both NbF5 and CCl4 (ΔG = −2.7 eV at 640 K) as compared to exposure to CCl4 only (ΔG = −2 eV at 640 K) process. This indicates that an enhanced etch rate is possible when TiN is exposed alternately to both NbF5 and CCl4, which is in close agreement with the experimental results.
Thermal Atomic Layer Etching of Aluminum Oxide (Al2O3) Using Sequential Exposures of Niobium Pentafluoride (NbF5) and Carbon Tetrachloride (CCl4): A Combined Experimental and Density Functional Theory Study of the Etch Mechanism
(2021-04-27) Sharma, Varun; Blomberg, Tom; Haukka, Suvi; Givens, Michael E.; Tuominen, Marko; Ritala, Mikko; Elliott, Simon
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Thermal atomic layer etching (ALEt) of amorphous Al2O3 was performed by alternate exposures of niobium pentafluoride (NbF5) and carbon tetrachloride (CCl4). The ALEt of Al2O3 is observed at temperatures from 380 to 460 °C. The etched thickness and the etch rate were determined using spectroscopic ellipsometry and verified by X-ray reflectivity. The maximum etch rate of about 1.4 Å/cycle and a linear increase of the removed film thickness with the number of etch cycles were obtained at a temperature of 460 °C. With the help of density functional theory calculations, an etch mechanism is proposed where NbF5 converts part of the Al2O3 surface into an AlF3 or aluminum oxyfluoride layer, which upon reacting with CCl4 is converted into volatile halide-containing byproducts, thus etching away the converted portion of the material. Consistent with this, a significant surface fluorine content of about 55 at. % was revealed when the elemental depth profile analysis of a thick NbF5-Treated Al2O3 layer was performed by X-ray photoelectron spectroscopy. The surface morphology of the reference, pre-, and postetch Al2O3 surfaces was analyzed using atomic force microscopy and bright-field transmission electron microscopy. Moreover, it is found that this process chemistry is able to etch Al2O3 selectively over silicon dioxide (SiO2) and silicon nitride (Si3N4).