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              <p>Cryogenic Atomic Layer Etching of SiO2 (“Cryo-ALE”) has been developed several years ago to address some limitations when it is performed at room temperature.The ALE process achieved under these last temperature conditions involves a C4F8 plasma in the modification step. This results in fluorocarbon deposition on the reactor walls, and eventually to process drifts, which affects reproducibility. Consequently, chamber cleaning is necessary. This can be addressed by flowing C4F8 in gas phase and cooling the SiO2 substrate at cryogenic temperature. C4F8 molecules are physisorbed only on the cooled surface and therefore, wall pollution is greatly reduced. The thin physisorbed C4F8 layer is then used as a reservoir to etch around one SiO2 monolayer in the subsequent Ar plasma of one ALE cycle.  Alternatively, a relevant approach consists in selecting a gas with a higher F/C ratio, which polymerizes much less than low F/C ratio gases such as C4F8. For instance, a CF4 plasma is in etching regime at room temperature and does not promote polymer deposition on the chamber walls at room temperature too. Nevertheless, it is shown by absorption spectroscopy that the sticking coefficient of CF radicals increases dramatically when the surface is cooled at cryogenic temperature. This means that a CF4 plasma can be used to deposit a fluorocarbon layer only on cooled surfaces, in particular SiO2. But the chamber walls, at room temperature, are polymerfree.  Consequently, a CF4 plasma can be used as a modification step in a SiO2 Cryo-ALE process. It is demonstrated that repeating cycles of a CF4 plasma step followed by an Ar plasma with low energy ion bombardment, with each cycle separated by a purge step, enables sequential etching of SiO2 cooled at cryogenic temperature. The EPC increases as the substrate temperature decreases and reaches 0.46 nm/cycle at -130°C. This process, provided deposition during CF4 plasma is well balanced with etching in the Ar removal step, exhibits a high synergy that can approach 100%.</p>
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