Manufacturing semiconductor devices requires advanced patterning technologies, including reactive ion etching (RIE) based on the synergistic interactions between ions and etch gas. However, these interactions weaken as devices continuously scale down to sub‐nanoscale, primarily attributed to the diminished transport of radicals and ions into the small features. This leads to a significant decrease in etch rate (ER). Here, a novel synergistic interaction involving ions, surface‐adsorbed chemistries, and materials at cryogenic temperatures is found to exhibit a significant increase in the ER of SiO2 using CF4/H2 plasmas. The ER increases twofold when plasma with H2/(CF4 + H2) = 33% is used and the substrate temperature is lowered from 20 to −60 °C. The adsorption of HF and H2O on the SiO2 surface at cryogenic temperatures is confirmed using in situ Fourier transform infrared spectroscopy. The synergistic interactions of the surface‐adsorbed HF/H2O as etching catalysts and plasma species result in the ER enhancement. Therefore, a mechanism called “pseudo‐wet plasma etching” is proposed to explain the cryogenic etching process. This synergy demonstrates that the enhanced etch process is determined by the surface interactions between ions, surface‐adsorbed chemistry, and the material being etched, rather than interactions between ion and gas phase, as observed in the conventional RIE.
Manufacturing semiconductor devices requires advanced patterning technologies, including reactive ion etching (RIE) based on the synergistic interactions between ions and etch gas. However, these interactions weaken as devices continuously scale down to sub‐nanoscale, primarily attributed to the diminished transport of radicals and ions into the small features. This leads to a significant decrease in etch rate (ER). Here, a novel synergistic interaction involving ions, surface‐adsorbed chemistries, and materials at cryogenic temperatures is found to exhibit a significant increase in the ER of SiO2 using CF4/H2 plasmas. The ER increases twofold when plasma with H2/(CF4 + H2) = 33% is used and the substrate temperature is lowered from 20 to −60 °C. The adsorption of HF and H2O on the SiO2 surface at cryogenic temperatures is confirmed using in situ Fourier transform infrared spectroscopy. The synergistic interactions of the surface‐adsorbed HF/H2O as etching catalysts and plasma species result in the ER enhancement. Therefore, a mechanism called “pseudo‐wet plasma etching” is proposed to explain the cryogenic etching process. This synergy demonstrates that the enhanced etch process is determined by the surface interactions between ions, surface‐adsorbed chemistry, and the material being etched, rather than interactions between ion and gas phase, as observed in the conventional RIE.
SiNx:H film deposition via plasma-enhanced chemical vapor deposition has been widely used in semiconductor devices. However, the relationship between the chemical bonds and the physical and chemical properties has rarely been studied for films deposited using tools in terms of the actual volume production. In this study, we investigated the effects of the deposition conditions on the H-related chemical bonding, physical and chemical properties, yield, and quality of SiNx:H films used as passivation layers at the 28 nm technology node. The radiofrequency (RF) power, electrode plate spacing, temperature, chamber pressure, and SiH4:NH3 gas flow ratio were selected as the deposition parameters. The results show a clear relationship between the H-related chemical bonds and the examined film properties. The difference in the refractive index (RI) and breakdown field (EB) of the SiNx:H films is mainly attributed to the change in the Si–H:N–H ratio. As the Si–H:N–H ratio increased, the RI and EB showed linear growth and exponential downward trends, respectively. In addition, compared with the Si–H:N–H ratio, the total Si–H and N–H contents had a greater impact on the wet etching rates of the SiNx:H films, but the stress was not entirely dependent on the total Si–H and N–H contents. Notably, excessive electrode plate spacing can lead to a significant undesired increase in the non-uniformity and surface roughness of SiNx:H films. This study provides industry-level processing guidance for the development of advanced silicon nitride film deposition technology.
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