Decomposition of SF6 in an RF Plasma Environment

Abstract

Sulfur hexafluoride (SF₆)-contained gas is a common pollutant emitted during the etching process used in the semiconductor industry. This study demonstrated the application of radio-frequency (RF) plasma in the decomposition of SF₆. The decomposition fraction of SF₆ [η_SF6 (C_in–C_out)/C_in x 100%] and the mole fraction profile of the products were investigated as functions of input power and feed O₂/SF₆ ratio in an SiO₂ reactor. The species detected in both SF₆/Ar and SF₆/O₂/Ar RF plasmas were SiF₄, SO₂, F₂, SO₂F₂, SOF₂, SOF₄, S₂F₁₀, S₂OF₁₀, S₂O₂F₁₀, and SF₄. The results revealed that at 40 W, η_SF6 exceeded 99%, and the reaction products were almost all converted into stable compounds such as SiF₄, SO₂, and F₂ with or without the addition of oxygen. Sulfur oxyfluorides such as SO₂F₂, SOF₂, SOF₄, S₂OF₁₀, and S₂O₂F₁₀ were produced only below 40 W. The results of this work can be used to design a plasma/chemical system for online use in a series of a manufacturing process to treat SF₆-containing exhaust gases.     

Total toxicity equivalents emissions of SF6, CHF3, and CCl2F2 decomposed in a RF plasma environment

Sulfur hexafluorine compound (SF6), trifluoromethane (CHF3) and diclorodifluoromethane (CCl2F2) are extensively used in the semiconductor industry. They are global warming gases. Most studies have addressed the effective decomposition of fluorine compounds, rather than the toxicity of decomposed by-products. Hence, the concepts of toxicity equivalents (TEQs) were applied in this work. The results indicated that HF and SiF4 were the two greatest contributors of TEQ to the SF6/H2/Ar plasma system, while F2 and SiF4 were the two greatest contributors to the SF6/O2/Ar system. Additionally, SiF4 and HF were the two greatest contributors of TEQ to both the CHF3/H2/Ar and CHF3/O2/Ar plasma systems. HF and HCl were the two greatest contributors of TEQ to the CCl2F2/H2/Ar plasma system, and Cl2 and COCl2 were the two greatest contributors to the CCl2F2/O2/Ar system. HCl and HF can be recovered using wet scrubbing, which reduces the toxicity of these emission gases. Consequently, the hydrogen-based plasma system was a better alternative for treating gases that contained SF6, CHF3 and CCl2F2 from the TEQs point of view.     

用能权交易制度能否提升能源利用效率?

用能权交易制度作为绿色发展理念实践中的重大制度创新,是推进生态文明体制改革的重大举措。实施用能权交易制度对于提高能源利用效率、实现能耗总量和强度"双控"目标具有重要的意义。文章以用能权交易试点作为切入点,基于2006—2019年全国30个省份的面板数据,运用双重差分法考察了用能权交易制度对能源利用效率的影响与作用机制。研究结果表明,用能权交易制度能够显著提升能源利用效率。具体而言,使试点省份单位地区生产总值能耗下降5.78%。机制检验表明,用能权交易制度主要通过推动绿色技术创新提高能源利用效率。异质性分析表明,用能权交易制度对能源利用效率的提升作用会随着节能潜力的升高呈现递减趋势,用能权交易制度对节能潜力较高的河南和四川能源利用效率能够发挥显著推动作用,而对节能潜力较低的浙江和福建影响并不显著。此外,文章还发现,用能权交易制度存在环境红利,在推动能源利用效率提升的同时,能够有效降低二氧化硫和二氧化碳的排放。在经过平行趋势检验、结构断点检验、PSM-DID、安慰剂检验以及其他稳健性检验后,文章结论依旧成立。由此得出,在用能权交易市场建设过程中,要及时总结试点经验、逐步扩大试点范围,并且要不断完善监管机制,以降低制度性交易成本,推动能源高效配置合理使用,同时还应该坚持因地制宜,从实际出发制定和实施具有本地特色的用能权交易配套措施。     

建立全球环境保护协调发展的格局

在分析全球环境恶化几个特点的基础上,分析了造成环境恶化的多重因素,认为把全球环境恶化归结于发展中国家是不恰当的。并且指出,应该采取协调发展的方针。最后,提出了全球环境问题上应该采取的若干对策,如强化政府对环境的管理职能,开展环境问题上的国际合作,建立全球性环境保护的仲裁机构等。     

An integrated approach for identification of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) pollutant sources based on human blood contents

Background, aim, and scope  

This study developed an integrated approach to identify pollutant sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of workers based on their blood contents.     

论资源开发区域的环境保护：以内蒙古呼伦贝尔为例

本文以我国一个重要的资源开发区域——内蒙古呼伦贝尔为案例,分析了该区域在资源开发中造成的种种环境问题和引发这些问题的背景因素,据此提出了加强环境保护的措施。作者认为呼伦贝尔出现的环境问题在我国资源开发区域带有一定的典型性,这种状况提醒我们,就发展中大国来说,在资源开发过程中绝不能忽视而只能加强环境保护工作,对我国中西部生态环境脆弱的资源开发区域尤应如此。     

Exposure and health-risk assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) for sinter plant workers

This study was set out to assess polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) exposures and health-risk impact posed on sinter plant workers. One sinter plant located in southern Taiwan was selected and their workers were divided into four exposure groups based on their work tasks, including raw material charging workers, sintering grate workers, shredding workers, and others. Results show that their mean total PCDD/F and the corresponding total I-TEQ exposure levels shared the same trend as: shredding workers>others>sintering grate workers>raw material charging workers. For all selected exposure groups, their PCDD/F exposures were dominated by the particle phase contents. Congener profiles of the gaseous+particle phase PCDD/Fs were found with more fractions of high chlorinated congeners than low chlorinated congeners. The lifetime average daily doses (LADDs) and their resultant excess cancer risks (ECRs) found for sinter plant workers were higher than those residents living at the residential area and rural area, but were lower than those living at the nearby of the selected sinter plant, urban area, industrial area. Considering ECRs of the sinter plant workers were still higher than 10(-6) suggesting the need for adopting proper control measurements for reducing workers' PCDD/F exposures, particularly for those sinter zone workers.     

Decomposition of SF6 in an RF plasma environment

Sulfur hexafluoride (SFd)-contained gas is a common pollutant emitted during the etching process used in the semiconductor industry. This study demonstrated the application of radio-frequency (RF) plasma in the decomposition of SF6. The decomposition fraction of SF6 [etaSF6 (C(in)-C(out))/C(in) x 100%] and the mole fraction profile of the products were investigated as functions of input power and feed O2/SF6 ratio in an SiO2 reactor. The species detected in both SF6/Ar and SF6/O2/ Ar RF plasmas were SiF4, SO2, Fe2, SO2F2, SOF2, SOF4, S2F10, S2OF10, S2O2F10, and SF4. The results revealed that at 40 W, etaSF6 exceeded 99%, and the reaction products were almost all converted into stable compounds such as SiF4, SO2, and F2 with or without the addition of oxygen. Sulfur oxyfluorides such as SO2F2, SOF2, SOF4, S2OF10, and S2O2F10 were produced only below 40 W. The results of this work can be used to design a plasma/chemical system for online use in a series of a manufacturing process to treat SF6-containing exhaust gases.     

碱渣高压湿式氧化(WAO)出水在污水场的综合利用

根据进入污水处理场的WAO出水的性质，在污水处理生化系统的承受能力范围内充分利用其碱性，以达到降低生化系统碱耗及污水处理前端因调节pH而产生的酸耗，节约能源、降低处理费用。     

Particle size distributions and health-related exposures of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of sinter plant workers

This study measured particle size distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in two workplace atmospheres of the sintering grate and rough roll shredder in a sintering plant, and to assess their workers’ health-related exposures. We found that the PCDD/F concentration of the sintering grate (site A = 14.47 pg m⁻³) was lower than that of the rough roll shredder (site B = 17.20 pg m⁻³). Particle size distributions of PCDD/Fs were in the form of the unimodal with the mass median aerodynamic diameter (MMAD) of 4.74 μm and 5.23 μm, and geometric standard deviation (σ_g) of 3.15 and 2.15 for the site A and B, respectively. The above results suggest that the workplace of the site A had a less fraction of coarse particles than that of the site B. The estimated PCDD/F concentrations of the inhalable fraction (11.0 pg m⁻³) and thoracic fraction (8.89 pg m⁻³) of the site A were lower than those of the site B (12.4 and 9.39 pg m⁻³, respectively). But to the contrary the estimated respirable fraction of the site A (5.05 pg m⁻³) was slightly higher than that of the site B (4.93 pg m⁻³). Our results clearly indicate the importance to conduct particle size segregating samplings for assessing human PCDD/F exposures.