Thermal
atomic layer etching (ALE) can be performed using sequential
reactions based on surface modification followed by volatile release
of the modified surface layer. Surface modification can be accomplished
using fluorination. Volatile release can then be achieved using precursors
that undergo ligand-exchange reactions with the fluorinated surface
layer. Metal fluorides can be employed to model the fluorinated surface
layer. The ligand-exchange reaction between the precursor and the
metal fluoride can lead to spontaneous etching of the metal fluoride.
A new reactor with in situ quadrupole mass spectrometry
(QMS) was constructed to observe the volatile etch products from the
reaction of ligand-exchange precursors with metal fluoride powders.
The metal fluoride powders were AlF3, HfF4,
GaF3, InF3, and SnF4. The ligand-exchange
precursors were Al(CH3)3, SiCl4,
and TiCl4. A variety of studies were conducted including
Al(CH3)3 + AlF3, SiCl4 + HfF4, SiCl4 + InF3, TiCl4 + SnF4, Al(CH3)3 + GaF3, and SiCl4 + AlF3. The temperature-dependent in situ QMS studies revealed the many possibilities that
occur during the ligand-exchange reaction of precursors with metal
fluoride powders. Various categories of behavior were observed from
these studies: (i) Ligand exchange occurs at low temperature, but
metal etch products from the substrate are not observed until high
temperature. (ii) Ligand-exchange and metal etch products from the
substrate are observed at similar temperatures. (iii) Ligand exchange
occurs, but no metal etch products from the substrate are observed
up to a limiting temperature. Knowledge of these possibilities for
the ligand-exchange reaction between precursors and metal fluoride
powders during spontaneous etching helps to further the understanding
of thermal ALE.