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Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model

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WO₃ and W Thermal Atomic Layer Etching Using "Conversion-Fluorination" and "Oxidation-Conversion-Fluorination"

Nicholas R Johnson¹, Steven M George¹

¹Department of Chemistry and Biochemistry, and ‡Department of Mechanical Engineering, University of Colorado , Boulder, Colorado 80309, United States.

ACS Applied Materials & Interfaces

|September 7, 2017

Summary

New thermal atomic layer etching (ALE) methods were developed for tungsten oxide (WO3) and tungsten (W) using sequential, self-limiting reactions. These processes enable precise etching of W and WO3 films for advanced material applications.

Keywords:

W WO3 atomic layer etching conversion etching fluorination oxidation

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Area of Science:

Materials Science
Chemical Engineering
Surface Chemistry

Background:

Atomic Layer Etching (ALE) is crucial for precise thin-film deposition and removal in microelectronics.
Developing selective and self-limiting etching processes for refractory metals and their oxides remains a challenge.

Purpose of the Study:

To demonstrate novel thermal ALE mechanisms for tungsten oxide (WO3) and tungsten (W).
To investigate the self-limiting nature and etch rates of these new processes.
To explore the potential for etching other metal materials.

Main Methods:

Utilized a "conversion-fluorination" mechanism with boron trichloride (BCl3) and hydrogen fluoride (HF) for WO3 ALE.
Employed an "oxidation-conversion-fluorination" mechanism with O2/O3, BCl3, and HF for W ALE.
Applied in situ spectroscopic ellipsometry (SE) to monitor film thickness and reaction progress.

Main Results:

Achieved self-limiting ALE for WO3 with etch rates up to 4.19 Å/cycle at 207 °C.
Demonstrated selective etching of W using a three-step process, with etch rates of ~2.5 Å/cycle at 207 °C.
Confirmed that W acts as an etch stop for the WO3 etching process.

Conclusions:

New thermal ALE mechanisms based on sequential, self-limiting reactions have been successfully developed for WO3 and W.
These methods offer precise control over etching processes and are adaptable for other metal materials.
The demonstrated etch stop capability of W is significant for selective etching applications.