Thermal atomic layer etching (ALE) is one promising method to achieve atomic level precision and high conformality over three-dimensional structures that can further enable the manufacturing of gate-all-around devices. Initially, an ALE process using CF4/NH3/Ar remote plasma exposure followed by infrared (IR) annealing was studied on SiCO films. The process showed self-limiting behavior and achieved an etch per cycle (EPC) of 0.2 nm/cycle. To increase the EPC, an O2 remote plasma exposure step was added before the CF4/NH3/Ar plasma exposure step in the ALE cycle. The process achieved an EPC of 1.0 nm/cycle. Measurements of the EPC of the SiCO film showed self-limiting behavior in both the O2 and CF4/NH3/Ar steps. X-ray photoelectron spectroscopy results showed an increase in atomic concentration (AC) of oxygen while the AC of carbon decreased following the exposure of the film to an O2 remote plasma. The results indicate that methyl groups (-CH3) in the top layers of the film are being replaced by hydroxyl (-OH) groups and Si-O-Si bonding. The N1s spectrum showed the formation of an ammonium fluorosilicate (NH4)2SiF6-based surface-modified layer following exposure to a CF4/NH3/Ar remote plasma. IR annealing of the film showed desorption of the ammonium fluorosilicate surface-modified layer and the return to an as grown SiCO film surface composition.

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