C4F8-based plasmas are widely used for semiconductor oxide processing because they can selectively form fluorocarbon passivation layers on surfaces such as HfO2. Here, we show that the chemical reactivity of C4F8 plasmas can be systematically tuned by...
C4F8-based plasmas are widely used for semiconductor oxide processing because they can selectively form fluorocarbon passivation layers on surfaces such as HfO2. Here, we show that the chemical reactivity of C4F8 plasmas can be systematically tuned by diluted gases such as N2 and CH4. Furthermore, we find that the chamber wall alternates between acting as a radical sink and a radical source, depending on its surface condition. For example, adding N2 to C4F8 plasmas increased the Si etch depth from 58 to 168 nm as the N2 flow rose from 0 to 30 sccm, consistent with gas-phase consumption of CF2 by N and the formation of CN, as confirmed by optical absorption spectroscopy and actinometry. During Si etching, volatile SiFx species such as SiF4 tended to accumulate on the wall, while C4F8 plasmas simultaneously formed a fluorocarbon-rich layer that acted as an active reservoir under subsequent plasma exposure. However, in successive processing runs, this wall film thickness reached a steady state rather than continuously increasing, indicating that plasma-wall interactions constrained further growth. Under such conditions, CF2 originating from the wall influenced substrate uniformity. In contrast, in C4F8/CH4 plasma processes, the chamber wall was maintained in a clean state across runs, thereby minimizing wall-derived effects, and substrate-dependent carbon film growth was achieved by varying the gas flow-rate ratio R = CH4/(C4F8 + CH4). These results identify gas-ratio dilution as a practical level at which C4F8-based plasmas can be tuned and demonstrate that optical absorption spectroscopy provides a direct pathway to monitor the governing radical chemistry, enabling improved control of etch-process uniformity and selectivity in advanced oxide fabrication.