Wenxiang Zhang,Yinhui Li,Yue Wu,Yu Fu,Shuhui Chen,Zhonghui Zhang,Songjie He,Tong Yan,Heping Ma
Recovering of high value-added perfluorinated electronic specialty gases (F-gases) in plasma etching waste gas is a challenging task in the silicon-based semiconductor industry. In recent years, the adsorptive separation technology based on porous materials has been regarded as a effective strategy to capture and recover F-gases due to its energy-saving and high operational feasibility. Herein, two porous organic polymers (POPs) with fluorinated skeleton structure (termed POPTrA-4F and POPTrA-8F) were developed to selective capture and recycle of F-gases in plasma etching exhaust gas. Single-component gas adsorption and IAST calculation show that two fluorinated porous polymers can selectively capture F-gases from mixed gas. Theoretical simulations based on DFT reveal the selective adsorption mechanism of fluorinated polymers to F-gases at molecular level, and give the binding energy between polymers and gas molecules. Furthermore, time-dependent adsorption rate tests and dynamic breakthrough experiments confirm that two fluorinated polymers could preferentially adsorb F-gases and exhibit excellent cycling durability. These results demonstrate that fluorine-functionalized POPs have great potential to effectively capture and recover F-gases in plasma etching exhaust gas.
Wenxiang Zhang,Yue Wu,Yinhui Li,Shuhui Chen,Yu Fu,Zhonghui Zhang,Tong Yan,Shanshan Wang,Heping Ma
Efficiently capturing and recycling perfluorinated electron specialty gases (F-gases) with severe greenhouse effects (e.g., long atmospheric lifetime and high global warming potential) from etching exhaust is of great significance to the semiconductor industry. The adsorption separation technique based on a porous adsorbent is considered as an economical and effective method to remove the F-gases in the semiconductor exhaust, benefiting from its low energy consumption and high operational feasibility. Herein, two fluorinated microporous polymers (termed POPTrB-4F and POPTrB-8F) have been synthesized via direct C–H arylation polycondensation. Motivated by their fluorinated pore structure and sturdy covalent bond linkage mode, the separation performances of POPTrB-4F/8F for F-gases under both equilibrium and kinetic conditions were systematically studied. Both experimental results and theoretical calculations show that these two fluorinated polymers can selectively capture F-gases from the simulated etching exhaust. Impressively, the ideal adsorbed solution theory selectivity of POPTrB-4F and POPTrB-8F to SF6 reached 62.88 and 51.55, respectively, at 298.15 K and 1 bar. Moreover, the mechanisms of gas adsorption and separation in porous organic polymers have also been profoundly revealed through simulation calculations based on the density functional theory. These results suggest the possibility of exploiting these fluorinated microporous polymers for the separation of F-gases in an eco-friendly way.
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