epa 96 e3 s2 02 01

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行政院環境保護署環境檢驗所 委託辦理九十六年度專案研究計畫 光電半導體產業排氣中全氟化物之 檢測技術建立計畫 期末報告書 計 畫 編 號: EPA-96-E3S2-02-01 執 行 時 間: 96 年 02 月 07 日 至 96 年 12 月 31 日 計畫主持人 : 蘇 仁 偉 執行機構:財團法人工業技術研究院 年 十二 月

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  • 1. EPA-96-E3S2-02-01 96 02 07 96 12 31

2. EPA-96-E3S2-02-01 96 2 96 12 96 2 96 12 1900 850 126.6 89.9 435.4 126.6 181 90.5 3 (Perfluorocarbons) (Optoelectronic and Semiconductor Industries) (Fourier Transform Infrared Spectrometer) ()e-mail 1003-5732688 3 7 03-5732660 13 6 03-5732686 9 3. The Establishment of Perfluorocarbons Emission Measurement Techniques forOptoelectronic and Semiconductor Industries.EPA-96-E3S2-02-0196/02/0796/12/3196/12/26356EPA96E3S20201.DOCMicrosoft Word 2003 4. Perfluorocarbons, Optoelectronic and Semiconductor Industries, FourierTransform Infrared Spectrometer300500 FTIR 6 PFCs PFCs PFCs SF 6 NF 3 PFCs 0.0003~0.0209 MMTCE L3 (6.5 ) PFCs C 3 F 8 C 2 F 6 0.0017~0.0133MMTCE 8 12 The objective of this study is to develop a testing method for qualitative and quantitative analysis of perfluorocompounds 5. (PFCs). Due to its strong absorbance of C-F bonding on mid infrared region, most PFCs demonstrate thousands times of global warming potential (GWP) than carbon dioxide. Even though PFCs emissions contribute less than 5% of total global warming gas emissions in carbon equivalent annually, it still draws great attention and pressure from regulatory agencies and environmental parties.The strong absorbance of C-F bonding on mid infrared region also makes Fourier Transform Infrared Spectroscopy (FTIR) an ideal instrument for measuring PFCs. A testing method was developed in this study. Possible interference caused by excess moisture and/or high temperature of waste stream on FTIR analysis was also evaluated. The results showed that quantitative analysis of FTIR was strongly affected by high relative humidity (>70%), especially low-concentration samples. It is because water also demonstrates strong absorbance in mid infrared region. High temperature also affected the quality of FTIRs quantitative analysis on PFCs.Finally, we have conducted monitoring PFC emissions from three semiconductor fabs and three TFT-LCD manufacturing plants. The results has demonstrated that FTIR is capable of qualitatively and quantitatively identifying PFCs from stack emissions and in atmospheric environment. 6. ............................................................................................................ 1-1 1.1 ........................................................................................................ 1-11.2 ...................................................................................................... 1-71.3 ............................................................................................ 1-7 ...................................................................................................... 2-1 2.1 PFCS .............................................................. 2-12.2 PFCS ....................................................................................... 2-22.2 FTIR PFCS ......................................................................... 2-8 .................................................................................. 3-1 3.1 ............................................................................................ 3-13.2 ........................................................................................ 3-43.3 .................................................................................... 3-7 3.3.1 ................................................................................................ 3-7 3.3.2 FTIR ................................................................................ 3-9 3.3.3 FTIR .............................................................................. 3-12 3.3.4 FTIR .............................................................................. 3-143.4 ...................................................................................................... 3-17 3.4.1 .................. 3-17 3.4.2 .......................................... 3-18 3.4.3 .............................................................................................. 3-22 .................................................................................................. 4-1 4.1 FTIR QA/QC .......................................................................................... 4-1 4.1.1 ............................................................................................ 4-1 4.1.2 .................................................................................... 4-4 4.1.3 ................................................................................................ 4-8 4.1.4 .......................................................................................... 4-10 4.1.5 .......................................................................................... 4-12 4.1.6 .................................................................................. 4-154.2 ................................................... 4-18 4.2.1 ...................................................................................... 4-18 4.2.2 ...................................................................................... 4-304.3 .............................................................................................. 4-45 4.3.1 .................................................................................. 4-45 I 7. 4.3.1.1 L1 .............................................................................................. 4-45 4.3.1.2 L2 .............................................................................................. 4-67 4.3.1.3 L3 .............................................................................................. 4-854.3.2 ............................................................................ 4-107 4.3.2.1 S1 ............................................................................................ 4-107 4.3.2.2 S2 ............................................................................................ 4-124 4.3.2.3 S3 ............................................................................................ 4-1444.3.3 ................................................................................ 4-166 4.4 PFCS ........................................................................................... 4-1694.4.1 ............................................................ 4-1694.4.2 PFC ............................................... 4-172 4.4 .................................................................................... 4-180................................................................................................ 5-15.1 ................................................................................................................ 5-1 5.2 ................................................................................................................ 5-4.................................................................................................... 6-1............................................................................................................................ 6-1 ............................................................ 1-1 ................................................................ 2-1 PFCS .................. 3-1 ........................................................................ 4-1 .................................................................... 5-1 II 8. 1- 1 1990~2006 ................................................... 1-2 1- 2 ............................... 1-3 2- 1 IPCC ............... 2-6 2- 2 PFCs ................................. 2-7 2- 3 88 OP-FTIR ......................................... 2-8 2- 4 87 VOC CC-FTIR .............. 2-9 3- 1 ....................................... 3-2 3- 2 ............................................................................... 3-3 3- 3 CF4 C2F6 ....................................................................... 3-4 3- 4FTIR ..................................................... 3-15 3- 5 PFCs .................................................................................... 3-21 3- 6 OP-FTIR ........................................................ 3-23 3- 7 CC-FTIR ........................................................ 3-24 3- 8 ............................................................. 3-25 4- 1 ................................................................................... 4-6 4- 2 ....................................................................................... 4-9 4- 3 ......................................................................................4-11 4- 4 ......................................................................................... 4-14 4- 5 PFCs .......................................... 4-19 4- 6 ..................................................... 4-26 4- 7 ()............................................... 4-27 4- 8 ............................................................................. 4-29 4- 9 PFCs .......................................... 4-30 4- 10 PFCs ..................................................... 4-39 4- 11 PFCs ..................................................... 4-40 4- 12 PFCs ..................................................... 4-41 4- 13 PFCs ......................... 4-42 III 9. 4- 14 ........................................................... 4-44 4- 15 L1 PFCs ........................................................ 4-48 4- 16 L1 .................................................................. 4-50 4- 17 L1 .......................................................................... 4-51 4- 18 L1 ........................................... 4-54 4- 19 L1 PFCs MMTCE ................................................. 4-55 4- 20 L1 OP-FTIR ..................................................... 4-60 4- 21 L1 .................................................. 4-65 4- 22 L2 PFCs ........................................................ 4-69 4- 23 L2 .................................................................. 4-70 4- 24 L2 ....................................................................... 4-71 4- 25 L2 P01 ...................................... 4-73 4- 26 L2 P02 ...................................... 4-73 4- 27 L2 P04 ...................................... 4-74 4- 28 L2 P05 ...................................... 4-74 4- 29 L2 PFCs MMTCE ................................................. 4-75 4- 30 L2 OP-FTIR ................................................................. 4-80 4- 31 L2 .................................................. 4-81 4- 32 L3 PFCs ........................................................... 4-87 4- 33 L3 .................................................................. 4-88 4- 34 L3 .......................................................................... 4-90 4- 35 L3 P01 ...................................... 4-92 4- 36 L3 P02 ...................................... 4-92 4- 37 L3 P03 ...................................... 4-92 4- 38 L3 P07 ...................................... 4-93 4- 39 L3 P08 ...................................... 4-94 4- 40 L3 P09 ...................................... 4-95 4- 41 L3 PFCs MMTCE .................................................. 4-97 4- 42 L3 OP-FTIR ...................................................................103IV 10. 4- 43 L3 ................................................ 4-104 4- 44 S1 PFCs ......................................................... 4-109 4- 45 S1 .................................................................4-110 4- 46 S1 .........................................................................4-111 4- 47 S1 P01 .....................................4-112 4- 48 S1 P02 .....................................4-113 4- 49 S1 P03 .....................................4-114 4- 50 S1 PFCs MMTCE ..................................................4-116 4- 51 S1 OP-FTIR ................................................ 4-122 4- 52 ................................................................................. 4-123 4- 53 S2 PFCs ......................................................... 4-126 4- 54 S2 ................................................................ 4-127 4- 55 S2 ........................................................................ 4-129 4- 56 S2 P01 .................................... 4-130 4- 57 S2 P02 .................................... 4-131 4- 58 S2 P03 .................................... 4-132 4- 59 S2 P04 .................................... 4-133 4- 60 S2 P05 .................................... 4-134 4- 61 S2 P06 .................................... 4-135 4- 62 S2 P08 .................................... 4-136 4- 63 S2 PFCs MMTCE ................................................ 4-137 4- 64 S2 OP-FTIR ................................................ 4-143 4- 65 S3 PFCs ......................................................... 4-146 4- 66 S3 ................................................................ 4-147 4- 67 S3 ........................................................................ 4-149 4- 68 S3 P01 .................................... 4-150 4- 69 S3 P02 .................................... 4-151 4- 70 S3 P03 .................................... 4-151 4- 71 S3 P04 .................................... 4-152 V 11. 4- 72 S3 P05 .................................... 4-153 4- 73 S3 P06 .................................... 4-154 4- 74 S3 P07 .................................... 4-155 4- 75 S3 PFCs MMTCE ................................................. 4-157 4- 76 S3 OP-FTIR ................................................... 4-163 4- 77 PFC ....................................... 4-167 4- 78 .................................................................... 4-168 4- 79 ............................................................. 4-171 4- 80 ................................................................ 4-172 4- 81 WSC PFCs ..................................................... 4-174 4- 82 TSIA PFCs ......................................................... 4-176 4- 83 TTLA PFCs ....................................................... 4-177VI 12. 1- 1 1990~2000 ............................................... 1-3 1- 2 ....................................................................................... 1-5 2- 1 ........................................................................... 2-9 2- 2 ..................................................................... 2-10 3- 1 PFCs ....................................................................3-11 3- 2 ..................................................................... 3-12 3- 3 ............................................................................. 3-21 3- 4 CC-FTIR ........................................................ 3-22 3- 5 OP-FTIR ........................................................ 3-23 4- 1 ........................................................................... 4-3 4- 2 - 2480-2520 cm-1 ........................................................... 4-6 4- 3 - 968-1008cm-1 .............................................................. 4-7 4- 4 ..................................................................................... 4-13 4- 5 ................................................................. 4-16 4- 6 ..................................... 4-17 4- 7 PFCs ............................................................... 4-19 4- 8 PFCs ....................................... 4-20 4- 9 PFCs ............................................... 4-24 4- 10 PFCs ................................. 4-25 4- 11 PFCs ..................................................... 4-28 4- 12 ............................................................... 4-31 4- 13 ................................................................................... 4-31 4- 14 ....................................................................... 4-34 4- 15 PFCs ............................................. 4-35 4- 16 PFCs ............................................. 4-36 4- 17 PFCs ............................................. 4-37 VII 13. 4- 18 PFCs ..................................................................... 4-42 4- 19 ....................................................................... 4-43 4- 20 L1 .................................................................................. 4-47 4- 21 20 m 28.5 m FTIR ......................................... 4-49 4- 22 L1 .................................................................. 4-49 4- 23L1 PFCs ............................................ 4-53 4- 24L1 PFCs .................................................................... 4-55 4- 25 L1 .............................................................................. 4-57 4- 26 L1 ...................................... 4-57 4- 27 L1 .......................................................................... 4-58 4- 28 L1 OP-FTIR PFCs .......... 4-62 4- 29 OP-FTIR L1 PFCs .......... 4-63 4- 30 L1 OP-FTIR ................. 4-64 4- 31 L1 PFCs ............................................... 4-66 4- 32L2 PFCs ............................................................ 4-68 4- 33L2 PFCs ........................................ 4-72 4- 34 L2 PFCs ....................................................... 4-75 4- 35 L2 .............................................................................. 4-76 4- 36 L2 .............................................................................. 4-78 4- 37L2 PFCs ................................................................ 4-83 4- 38 L2 NH3 N2O .................................................... 4-83 4- 39 L2 OP-FTIR ..................................... 4-84 4- 40 L3 PFCs ............................................................... 4-86 4- 41 L3 PFCs ........................................... 4-91 4- 42 L3 PFCs ....................................................... 4-98 4- 43 L3 PFCs ....................................................................... 4-98 4- 44 L3 OP-FTIR ............................................................. 4-99 4- 45 L3 ............................................................................ 4-101 4- 46 L3 OP-FTIR -1 ....................... 4-105VIII 14. 4- 47 L3 OP-FTIR -2 ....................... 4-106 4- 48 S1 ............................................................................ 4-108 4- 49 S1 PFCs ..........................................4-111 4- 50 S1 PFCs ......................................................4-117 4- 51 S1 PFCs ......................................................................4-117 4- 52 S1 OP-FTIR .................................................................4-118 4- 53 S1 ..................................4-119 4- 54 S1 ..................................................................... 4-120 4- 55 S1 OP-FTIR PFCs ..... 4-121 4- 56 S1 PFCs .......................................... 4-123 4- 57 S2 PFCs ............................................................. 4-125 4- 58 S2 PFCs ............................................. 4-130 4- 59 S2 PFCs ..................................................... 4-138 4- 60 S2 PFCs ..................................................................... 4-138 4- 61 S2 OP-FTIR ................................................................ 4-139 4- 62 S2 ................................. 4-140 4- 63 S2 ..................................................................... 4-141 4- 64 S2 ............................................ 4-142 4- 65 S3 PFCs ............................................................. 4-145 4- 66 S3 PFCs ......................................... 4-150 4- 67 S3 PFCs ..................................................... 4-158 4- 68 S3 PFCs ..................................................................... 4-158 4- 69 S3 OP-FTIR ................................................................ 4-159 4- 70 S3 ................................. 4-160 4- 71 S3 ..................................................................... 4-161 4- 72 S3 OP-FTIR PFCs ..... 4-164 4- 73 S3 PFCs .......................................... 4-165 4- 74 ............................................................ 4-173 4- 75 WSC PFCs ..................................................... 4-174 IX 15. 4- 76 PFCs .................................................................. 4-175 4- 77 TSIA PFCs ................................................................. 4-177 4- 78 TTLA PFCs ............................................................... 4-178X 16. () :() :() PFCs PFCs FTIR PFCs () FTIR () XI 17. 4.1 FTIR PFCs QA/QC 4.2 PFCs FTIR FTIR PFCs 4.3 FTIR FTIR PFCs 4.4 PFCs () ()XII 18. EPA-96-E3S2-02-01 96 02 07 96 12 31 1,900 FTIR 6 PFCs PFCs PFCs SF6 NF3 PFCs 0.0003~0.0209 MMTCE L3 (6.5 ) PFCs C3F8 C2F6 0.0017~0.0133MMTCE 8 12 The objective of this study is to develop a testing method for qualitative and quantitative analysis of perfluorocompounds (PFCs). Due to its strong absorbance of C-F bonding on mid infrared region, most PFCs demonstrate thousands times ofXIII 19. global warming potential (GWP) than carbon dioxide. Even though PFCs emissions contribute less than 5% of total global warming gas emissions in carbon equivalent annually, it still draws great attention and pressure from regulatory agencies and environmental parties. The strong absorbance of C-F bonding on mid infrared region also makes Fourier Transform Infrared Spectroscopy (FTIR) an ideal instrument for measuring PFCs. A testing method was developed in this study. Possible interference caused by excess moisture and/or high temperature of waste stream on FTIR analysis was also evaluated. The results showed that quantitative analysis of FTIR was strongly affected by high relative humidity (>70%), especially low-concentration samples. It is because water also demonstrates strong absorbance in mid infrared region. High temperature also affected the quality of FTIRs quantitative analysis on PFCs. Finally, we have conducted monitoring PFC emissions from three semiconductor fabs and three TFT-LCD manufacturing plants. The results has demonstrated that FTIR is capable of qualitatively and quantitatively identifying PFCs from stack emissions and in atmospheric environment. 1997 12 1 11 CO2CH4 N2O 1990 (HFCs)(Prefluorocompounds, PFCs) SF6 1995 PFCs C-F CO2 85% PFCs 2% PFCs (Global Warming Potential, GWP) CO2PFCs PFCs PFCs XIV 20. PFC (SemiconductorManufacturing Technology, SEMATECH) PFC Protocol forFTIR Measurements of Fluorinated Compounds in Semiconductor Process ToolExhaustFourier Transform Infrared Spectormetery,FTIR CF4C2F6C3F8CHF3NF3 SF6 PFC Local ScrubberCentral Scrubber PFCs FTIR PFCs (Taiwan Semiconductor Industrial Association, TSIA)(World Semiconductor Council, WSC) CF4C2F6SF6NF3CHF3C3F8 PFCs PFCs 96 FTIR PFCs FTIR PFCs PFCs XV 21. 11 PFCs PFCs Close Cell-FTIR (CC-FTIR) Open Path-FTIR (OP-F TIR) 11 17 6 72 900 ()(1)(2) (3)FTIR (4) PFCs 6 PFCs PFCs T/CR() FTIR (absorption coefficient) PFCs CF4 CHF3C2F6 C3F8 PFCs PFCs PFCs NF3 SF6 (100 ppb )PFCs C3F8 C2F6 PFCs SF6 NF3 PFCs SF6 NF3 PFCs SF6 SF6 SO2F2 L2 SF6 0.0209 MMTCE L3 0.0003 MMTCEL1 0.0012XVI 22. MMTCE PFCs C3F8 C2F6 TSIA TSIA PFCs C2F6 C3F8 C2F68 S1 S2 12 S3 8 S1 S2 S3 S1 S2 0.0123 0.0133 MMTCE S3 0.0017MMTCEPFCs SF6 CF4C2F6 SF6 C3F8 PFCs C3F8 C2F6 C3F8 TTLA TSIA 2006 2006 (TTLA) 0.422 MMTCE PFC SF6 87.7% 0.0224 MMTCESF6 97.1%2006 TSIA 1.23 MMTCEC2F6 44% 0.0273 MMTCE C2F6 18.9%C3F8 44.8% CF4 23% PFCs PFCs PFCs SF6 NF3 PFCs XVII 23. 0.0003~0.0209 MMTCE PFCs C3F8 C2F6 0.0017~0.0133MMTCE ()PFCs PFCs 80 PFCs 50%~80% FTIR PFCs PFCs () ( 70%) PFCs PFCs ()(PFCs SF6) 3.2% SF6 TTLA TSIA 2010 10% PFCs PFCs XVIII 24. 1.1 1997 12 1 11 CO2 CH4 N2O 1990 (HFCs) (Prefluorocompounds, PFCs) SF6 1995 2001 7 2002 CO2 261.7 1990 CO2(97.5%) 1- 1 1- 1 1 1990 1997 1990 1994 CO2 1994 1995 1996 1997 CO2 HFCs 1998 2000 1997 1998/1999 HFCs PFCs SF6 2000 HFCs CH4 CO2 PFCs SF6 1999 20012002 2000 20 CO2CH4 HFCs PFCs SF61-1 25. 1999 2003 2002 2003 PFCs SF6 2% CO2 CH4 HFCs 2003 1990 2003 1- 1 1990~2006 CO2 equivalent() Year CO2 CH4 N2OHFCSPFCSSF6 Total 1990132,525.0213,928.67 13,999.60NENE NE 178,349.14 1991140,979.3615,116.43 14,886.20NENE NE 189,018.67 1992151,279.9517,575.32 14,827.30 702.00 NE NE 202,515.03 1993164,242.5118,821.88 15,190.001,638.00NE NE 218,321.71 1994173,343.8320,043.87 15,543.401,521.00NE NE 230,799.56 1995179,417.4917,995.95 15,500.001,755.00NE NE 234,970.48 1996189,569.4418,292.68 15,927.802,808.00NE NE 246,801.92 1997203,442.5219,193.58 14,064.703,276.00NE NE 260,272.35 1998216,093.5019,312.44 13,649.30 17,454.63607.76 61.42287,512.77 1999221,577.3920,160.21 13,528.40 16,712.27 1,367.5298.95293,881.76 2000238,953.5812,492.90 11,739.705,584.10 2,736.15 114.48292,068.02 2001246,565.5352,063.41 12,967.30 18,776.85 1,371.8698.95351,297.71 2002261,732.0358,613.52 12,784.40 18,216.65 1,371.8698.95373,269.66 2003267,228.65 9,792.00 12,588.904,452.60 5,435.20 202.50320,158.95 2004244,723.80 8,029.90 10,727.901,906.60 5,133.305,170.00 275,691.50 2005251,209.7013,927.60 10,345.80 623.303,813.305,206.70 285,126.40 2006258,043.20 7,195.60 10,743.201,210.00 4,033.304,693.30 285,918.60 1-2 26. 400000 SF6 PFCS350000 N2O HFCS CO2 Equivalent ( 300000 CO2 CH4 250000200000 150000100000 5000001990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 1- 1 1990~2006 PFCs C-F CO2 85% PFCs 2% PFCs(Global Warming Potential, GWP) CO2 1- 2 GWP100 CO2 CWP100 1 CF4 C2F6 5700 11900 CO2 1- 1 PFCs 1998 PFCs 1- 2 GreenhouseAtmospheric LifetimeGlobal WarmingGas(Years)Potential (GWP100) CO2 5-200 1C2F61000011900Chamber cleanCF4 50000 5700Chamber clean CHF3260 12000 Film etching gas 1-3 27. NF3740 10800Chamber clean C3F8 243 14800Chamber clean SF6 3200 22200 Film etching gas C4F83200 10000 Film etching gas The IPCC Third Assessment Report: Climate Change 2001PFCs (anode effect)PFCs CF4 C2F6 () PFCs PFCs PFCs PFCs TFT ()( PDPTFT LCD)(PDA) 1- 2 1-4 28. TFT LCD PDP PDA ()()() 1- 2 PFCs PFCs 1- 2 PFCs PFC (Semiconductor Manufacturing Technology, SEMATECH)PFC Protocol for FTIR Measurements of Fluorinated Compounds inSemiconductor Process Tool Exhaust Fourier Transform Infrared Spectormetery, FTIR CF4C2F6C3F8CHF3NF3 SF6 PFC Local ScrubberCentral Scrubber PFCs FTIR PFCs 1-5 29. (Taiwan Semiconductor Industrial Association, TSIA)(World Semiconductor Council, WSC) CF4C2F6SF6NF3CHF3C3F8 PFCs PFCs PFCs 1-6 30. 1.2 1.3 50807090 100RH 3 3 1-7 31. 2.1 PFCs PFCs (TFT-LCD) PFCs PFCs (Perfluormethane, CF4)(perfluoroethane, C2F6)(Perfluoropropane, C3F8)(Trifluoromethane, CHF3)(Sulfur Hexafluoride, SF6)(Nitrogen Trifluoride, NF3)(Chemical Vapor Deposition,CVD)(dry etch)PFCs 2: 1. (CVD):C2F6NF3CF4 2. (Dry etch):: (Poly Silicon Etch)CF4SF6(Nitride Etch)CF4SF6CHF3 (Oxide Etch)CF4C2F6C4F8CHF3 (Metal Etch)CF4SF6CHF3 (TiN Etch)SF6CHF3 (Tungsten Etch)SF6 2002 3 2002 PFCs 1.36MMTCE(million metric tons carbon equivalent) C2F6 59% CF4 SF6 19% 13%NF3 6%2-1 32. 80% CVD 20% PFCs 20% 80% PFCs SF6 91% NF3 6% PFCs (World Semiconductor Council, WSC)(Taiwan Semiconductor Industrial Association, TSIA) 2010 1995 10% WSC 2- 2 2010 0.82 (Taiwan TFT-LCDAssociation, TTLA) 2004 8 27 PFCs 90% TTLA (TSIA) 2010 PFCs 1997 1999 1998* 90%42.2 PFCs PFCs (1) (AlternativeChemistries)(2)(Process Optimization)(3)(Recovery andRecycle)(4)(Abatement)(1997~2003) PFC 2-2 33. (1999~2003 )(CVD/Chamber Clean)(2003~2007 )(Etch)(2006~2011 ) PFC 567 (1) GWP() GWP PFCs PECVD C3F8 CF4 C2F6 C2F6 CF4 10%(Million Metric Tons of Carbon Equivalent,MMTCE)C3F8 CF4 C2F6 70%C3F8 ClF3TFAA(Trifluoroacetic Anhydride)CF3I NF3 (2) PFCs PFCs Epson (Fujimi et al., 2001) C2F6 (200 400 600sccm) O2 (400 700 1,000 sccm) RF (180590999 mm)RF (500600700 W)(0510torr) CVD C2F6O2 RF PFCs C2F6 2/3 20~25% 40~45% PFCs 3/4 2010 WSC 2-3 34. (3) /( CF4C2F6N2)8(4) : A. PFCs PFCs 1200(H2 CH4)/ 1200 PFCs CO2HFCOF2 Deltech CDO Eco Phoenix IV Edwards TPU 4214 B. (500~750) PFCs Hitachi NF3SF6CF4CHF3C2F6C3F8 C4F8 (500~750) 100% C. :( 3000)()(surface wave) PFCs2-4 35. (radical)ETC Dry Scrubber C2F6 C5F8 CF4 100%100% 70%IPCC Tier 2b 2- 12-5 36. 2- 1 IPCC CF 4 C2F6 CHF 3 C3F8 C4F8 NF 3 SF 6 Hot Tubes0.10.3 NT NT NT 0.50.1 Fueled combustions 0.90.9 0.90.90.90.90.9 Plasma(with additive H 2 0 vapors) 0.9NT0.9NT 0.90.90.9 Plasma(with additive O 2 vapors) 0.9NT0.9NT 0.90.80.8 Catalytic0.90.9 0.90.90.90.90.9 Cryogenic absorption 0.70.9 0.9NT NT NT 0.9 Membrane Separration 0.80.9 NT NT NT NT 0.9 NT 2-6 37. 2- 2 PFCs TSIA 2002 C 3 F 8 C 2 F 6 2004 WSC ( ) 2001 PFCs 2005 MOU 2006 JSIA 1990 PFCs ( ) 1997 4 EIAJ PFCs 1993 NF 3 PFCs HFCs PFCs SIA 1990 PFCs ( ) 1996 SIASEMATECH PFCs SEMATECH PFCs (IntelMotorolaTIAppliedMaterialNovellusLamAir LiquidAir ProductDu PontPraxair) 2001 3 2004 2010 KSIA PFCs ( ) 1997 12 PFCs KSIA PFCs PFCs 1995 PFCs PFCs ESIA 1997 PFCs ( ) 1997 PFCs 2001 PFCs 2005 2010 2-7 38. 2.2 FTIR PFCs FTIR PFCs 2- 3 88 Open Path Fourier Transform Infrared Spectrometry,OP-FTIR PFCs SF6C2F6 CF4 PFCs PFCs 2- 3 88 OP-FTIR (ppb)(ppb) (ppb) (ppb) 19.7 2.17 23.8 1.45 151.08 -- -- 24.9 1.27 21.7 0.49 2.9 0.041.1 0.02 551.750.59 1075.58 138.9 6.95 130.84.93 2.2 0.04 -- -- 2.8 0.02 -- -- 60.06 -- -- 174.36.9 -- -- 107.66.3 -- -- -- -- 20.03 -- --6.9 0.12 -- -- 660 28.72 -- -- 32.5 0.16 88 1 2- 4 2-8 39. Close Cell Fourier Transform Infrared Spectrometry,CC-FTIR PFCs C2F6CF4CHF3 SF6 2- 4 87 VOC CC-FTIR A VOCA VOCA VOC ()Exhaust #1 Exhaust #2 Exhaust #3 (ppm) (ppm) (ppm)(ppm) (ppm) (ppm)SIH4 0.280.52 1.12 3.58C2F6 3.2517.7 0.771.27 10.3334CF40.450.73 0.521.01 45.99 128N2O 13.85 37.518.5770CHF3 0.511.03 0.320.980.57 1.01CO 0.1 1.3 1.166.741.18 5.68SF60.140.28 0.25 2.80.08 0.17 2- 1 PFCs CC-FTIR PFCs 0.050 0.045 0.040 Emission rate (kg/h)0.035 0.030 0.025 0.0440.020 0.015 0.0100.0150.005 0.0030.000 NF3SF6SiH4 2- 1 2-9 40. 2- 2 CC-FTIR CF4C2F6 SF6(N2O) 1.000.900.80Emission rate (kg/h) 0.700.600.500.934 0.400.300.20 0.338 0.243 0.10 0.1710.026 0.0100.002 0.00N2OC2F6CF4C9F21NSF6 C4F8C8F16O 2- 2 2-10 41. (carbontetrafluoride, CF4) (hexafluoroethane, C2F6) (nitrogen trifluoride, NF3)(trifluoromethane, CHF3)(sulfur hexafluoride, SF6)(perfluoropropane, C3F8) 3.1 PFCs(Perflourinatrd Compounds) 1998 (Monterey) PFCs CHF3 PFCs CF4C2F6C3F8CHF3NF3 SF6 PFCs (NF3 ) PFCs (GWP,Global Warming Potential)(Lifetime) 3- 1 CF4C2F6C3F8 SF6 CHF3 NF3 CO2 PFC 3- 2 PFCs NF3 PFCs PFCs 3-1 42. NF3 SF6 (TWA) 10 ppm 1000 ppm NF3 PFCs SF6 PFCs (MSDS AIR LIQUIDE ) 3- 1 Global Warming Gas Formula Common NameLifetime (Years) Potential (100 yrs) C2F6Halocarbon 11610,000 12,500 CF4 Halocarbon 14 50,0006,300 CHF3Halocarbon 23250 12,100 SF6 Sulfur Hexafluoride 3,20024,900 NF3 Nitrogen Trifluoride50 7406,300 - 13,100 C3F8 Perfluoropropane 2,600 7,000 CO2 Carbon Dioxide50 2001 3-2 43. 3- 2 MP BPVP Relative densityRelative densityWater solubility Chemical CAS No. OdorMW () ()(at 20) gas(air=1)liquid(water=1) (mg/l) Hexafluoroethane (C2F6) 76-16-4 --138-101-78.2 30 bar 4.8 1.23 insoluble Carbon Tetrafluoride (CF4) 75-73-0 -- 88-184-128 -- 3 -- 20 Trifluoromethane (CHF3) 75-46-7Ethereal70-155-82.2 41.6 bar 2.41.4 1080 Sulfur Hexafluoride (SF6)2551-62-4--146-50.8-6421 bar5 1.441 Nitrogen Trifluoride (NF3)7783-54-2Moldy71-207-129 --2.41.561 Perfluoropropane (C3F8) 76-19-7Ethereal 188-183-36.77.7 bar 6.51.4 -- 3-3 44. 3.2 PFC PFC emissions from primary aluminum production CF4 C2F6 0.1 ppmv CF4 C2F6 0.001 ppmv (GasChromatography, GC)(Mass Spectrometry, MS)(GasChromatography / Mass Spectrometry, GC/MS)(Infrared, IR)(Tunable Diode Laser, TDLAS)(Fourier TransformInfrared Spectroscopy, FTIR) 3- 3 CF4 C2F6 Roberts Marks FTIR CF4 C2F6 CF4 C2F6FTIR GC/MS 3- 3 CF4 C2F6 Mass Spectrometry CF4 (MS) C2F6 Infrared (IR)CF4 C2F6 Tunable Diode Laser CF4 (TDLAS)C2F6 Fourier Transform Infrared CF4 Spectroscopy (FTIR)C2F6 Gas Chromatography (GC) Gas Chromatography / CF4 Mass SpectrometryC2F6 (GC/MS) Roberts, R. and J. Marks, 1994 (Gas3-4 45. Chromatography/ Mass Spectroscopy, GC/MS)(FourierTransform Infrared, FTIR) FTIR SEMATECH FTIR Beer-Lambert 1998 3M Dr. Reagan Rho Squared, Inc. Dr. Plummer NIST Protocol for FTIR Measurements of FluorinatedCompounds in Semiconductor Process Tool Exhaust (SemiconductorManufacturing Technology, SEMATECH) FTIR CF4C2F6C3F8CHF3NF3 SF6 PFCs SiF4COF2WF6CO2CO HF Protocol for Measurement of Tetrafluoromethane (CF4) and[9] Hexafluoroethane (C2F6) Emissions from Primary Aluminum Production CF4 C2F6 canister GC/MS FTIR GC/MS 0.05 ppmv(CF4) 0.04 ppmv(C2F6) FTIR 10m FTIR(HgCdTe or MCT )CF4 0.7ppbv C2F6 1.1 ppbvFTIRMethod 320 VOCs(Hazardous Air Pollutants, HAPs)3MZazzeraReagenFTIRVOCsPFCsHAPsC3F81 ppm-meter50 ppm-meter C3F8FTIRR0.9994FTIRPFCs3-5 46. (Non-Dispersive InfraRed, NDIR) FTIR PFC NDIR FTIRBeer-Lambert FTIR NDIR (bandpass) PFC PFC NDIR PFC PFCs NDIR(Photometer, CLEANSENS) PFCs 1 ppm PFCs FTIR PFCs FTIR 3-6 47. 3.3 3.3.1 interferogram FTIR FTIR FTIR FTIR FTIR Beer-Lambert FTIR FTIRClose-Cell FTIR CC-FTIR FTIR(Open Path-FTIR OP-FTIR) FTIR :1 FTIR (1974 ) IR ()3-7 48. FTIR OP-FTIR CC-FTIR () GC/MASS FTIR H2O CO2 8001200 cm-1 H2O CO2 (6004000cm-1) OP-FTIR H2O, CO2 ( FTIR )CC- FTIR H2O CO2 close cell () H2O CO2 CC-FTIR 2OP-FTIR 3-8 49. (Telescope)(bistatic, )(monostatic, ) ()(4cm-1 )( 0.06cm-1)()3.3.2 FTIR FTIR (unique)(N2O2)3-9 50. 14 ( N15N16O15N14N16OH2OHDOD2O ) Bellamy Silverstein 12 SpectrometricIdentification of Organic Compounds Nakamoto IR Colthup Introduction to Infrared and RamanSpectroscopy(Pesticides) Aldrich The AldrichLibrary of FT-IR Spectra 164 cm-1 1 cm-1 Rao Molecular Spectroscopy: Modern Research 0.5 cm-1 0.25 cm-1 Ethylene 949.5 cm-1 949.25949.75 (Shift) 95% () 3- 1 PFCs FTIR 3-10 51. (subtraction)FTIR 3- 2 3- 2 3- 2 3- 2ozone 3- 2 () 1 CF4, 3.63 ppm -m, 25C, 1atm N2.8 CHF3, 2.80 ppm-m, 25C, 1atm N2 C2F6, 516.8 ppm-m, 25C, 1atm N2 .6Arbi tray YC3F8, 33.0 ppm-m, 25C, 1atm N2 .4NF3, 81.8 ppm -m, 25C, 1atm N2 .2SF6, 5.23 ppm -m, 25C, 1atm N20 1400 1200 1000Wavenumbe r (cm-1) 800 3- 1 PFCs 3-11 52. Sample Spectrum.4Reference, Water Sample, Water subtracted Reference,Ozone Absorbance 0 Sample, Ozone subtractedReference, Acetone -.4Sample, Acetone subtractedReference, Acrylonitrile -.8Sample, Acrylonitrile subtracted 1200 11001000 900 Arbitrary X 3- 2 3.3.3 FTIR FTIR (Classical Least Squares)FTIR As Ar k k i ( Asi Ari ) k=2 ( Ari ) i3-12 53. Asi i Ari i k Cs kCr ( Cr ) Asi Asi1k1Csl Asi2k2Cs2 Asi3k3Cs3 Asi Asi1Asi2Asi3 AKC () Beers Law AKC k-matrix (CLS)K K=ArCrt (CrCrt)-1 Ct C (transpose matrix) K kij K Asi=kijCsj AsKCs(inverse matrix)K-1 Cs K-1 As Cs=(Kt K)-1KtAs Cs Csi k-matrix K k-matrixk-matrix (CLS) script script script FTIR 1 IR 3-13 54. 23 scriptscript 4 script script 25% script script 5 script 3.3.4 FTIR ETG Galactic LC U.S. EPA Infrared Analysis OP-FTIR 3- 4 300 3-14 55. 3- 4 FTIR 1-PenteneChloroacetophenoneMethyl chloroform 1,1-Dichloroethane Chlorobenzene Methyl ethyl ketone 1,1-Dimethyl hydrazine Chlorodifluoromethane Methyl formate 1,1,1-TrichloroethaneChloroethaneMethyl hydrazine 1,1,1,2-TetrachloroethaneChloroformMethyl iodide 1,1,1,2-TetrafluoroethaneChloromethane Methyl isoamyl ketone 1,1,2-TrichloroethaneChloromethyl methyl ether Methyl isobutyl ketone 1,1,2,2-TetrachloroethaneChloropentafluoroethane Methyl mercaptan 1,1,2,2-TetrafluoroethaneChloroprene Methyl methacrylate 1,1,2-TrichloroethaneChlorotetrafluoroethane Methyl nitrite 1,1,2-TrifluoroethaneChlorotrifluoroethylene Methyl tert-butyl ether 1,1-Dichloro-1-fluoro ethane ChlorotrifluoromethaneMethyl vinyl ether 1,1-Dichloroethene cis-1,2 DichloroethyleneMethyl vinyl ketone 1,1-Dimethyl hydrazine CO2(much) Methylene chloride 1,2-DibromoethaneCrotonaldehydem-Xylene 1,2-DibromoethaneCumenen,n-Diethyl aniline 1,2-Dichloroethane Cyclohexane n,n-Dimethyl formamide 1,2-DichlorotetrafluoroethaneCyclopenteneNaphthalene 1,2,3-Propanetriol w/methylCyclohexanone n-Butyl acetate oxirane 1,2,3-Trichloropropane Cyclohexene n-Butyl alcohol 1,2,4-Trichlorobenzene Cyclopropanen-Butyraldehyde 1,2,4-Trimethyl benzeneDethyl ethern-Heptane 1,2-Dibromo-3-chloropropaneDibromomethanen-Hexane 1,2-Dichloroethene Dichlorodifluoromethane Nitric acid 1,2-DichloropropaneDichloroethyl ether Nitric oxide 1,2-EpoxybutaneDichloromethane Nitro benzeneDichloromethane (methylene 1,2-Propylenimine Nitro ethanechloride) 1,3 ButadieneDichlorotrifluoroethane Nitro methane 1,3-DichloropropaneDichlorovos Nitrogen dioxide 1,3-DichloropropeneDiethyl amine Nitrogen dioxide (and N2O4) 1,4-DioxaneDiethyl ether Nitrogen trifluoride 1,4-DichlorobenzeneDiethyl ketoneNitroso benzene 1-ButanolDifluoroethaneNitrosomorpholine 1-Chloro-1,1-difluoro ethane Diisopropyl ether Nitrous acid 1-PenteneDimethyl carbamoyl chloride Nitrous oxide 2,2,4-Trimethylpentane Dimethyl ethern-Nitrosodimethylamine 2,4,5-TrichlorophenolDimethyl formamiden-Nitrosomorpholine 2,4,6-TrichlorophenolDimethyl sulfiden-Octane 2,4-Toluene diisocyanate Dimethyl phthalaten-Propanol 3-15 56. 2-Amino-2-methyl-1-propanolDinitrogen tetroxiden-Propyl acetate 2-Butanone Dodecanen-Propyl nitrate 2-Chloro-1,3-butadiene Epichlorohydrin n-Propyl benzene 2-Chloroacetophenone Ethaneo-Cresol 2-ChlorotolueneEthanol o-Dichlorobenzene 2-Hexanone Ethyl acetate o-Xylene 2-Methyl 1-pentene Ethyl acrylateo-Dichlorobenzene 2-Methyl 2-buteneEthyl benzene o-Toluidine 2-Methyl 2-pentene Ethyl butyrateOxygen difluoride 2-Methyl butaneEthyl chlorideo-Xylene 2-Methyl pentane Ethyl formate Ozone 2-Methyl-1-pentene Ethyl vinyl ether p-Dichlorobenzene 2-Methyl-2-pentene Ethylbenzenep-Cresol 2-Nitropropane EthylenePentafluoroethane 2-PenteneEthylene dibromidePentane 3-Methyl 1-buteneEthylene dichloride Perfluorobutane 3-Methyl pentane Ethylene oxidePerfluorohexane 4-ChlorotolueneEthylidene dichloride Perfluoromethane 4-Methyl 2-pentene Exxon 87 gasoline Perfluoropropane 55% DibutylFluoro benzenePerfluoropropene Acetaldehyde Fluorobenzene Peroxy acetyl nitrate (main bands) Acetic acidFluoroethanePhenol Acetic acid, monomer and dimer Fluoromethane Phosgene Aceto nitrileFormaldehydePhosgene (Carbonyl chloride) AcetoneFormic acid (monomer) Phosphine Acetonitrile Furan Phosphorus trichloride Acetophenone Glyceryl trinitrate Propane Acetyl ChlorideHexachloro-1,3-butadienePropionaldehyde AcetyleneHexachlorobutadiene Propionic acid Acrolein Hexachlorocyclopentadiene Propionic acid, monomer and dimer Acrylic acid HexachloroethanePropionic acid, mostly monomer Acrylic acid monomer Hexamethylphosphoramide Propylene Acrylic acid, monomer and dimer Hexane Propylene dichloride Acrylic acid, mostly monomer Hexyl acetate Propylene glycol methyl ether acetate Acrylo nitrile Hydrazine Propylene oxide Allyl alcoholHydrogen bromidePropyleneimine Allyl chloride Hydrogen chloride p-Xylene Alpha-pinene Hydrogen cyanideQuinoline AmmoniaHydrogen fluoride Silane AnalineHydrogen iodide Silicon tetrafluoride Arsine Hydrogen peroxide SOCl2 (Thionyl chloride) Benzaldehyde Hydrogen sulfideStyrene 3-16 57. BenzeneIodomethane Styrene oxide Benzotrichloride Iodopentafluoroethane Sulfur dioxide Benzyl chlorideIodotrifluoromethaneSulfur hexafluoride Beta-pineneIsobutane Sulfur monochloride (S2Cl2) bis-Chloromethyl ether IsobutanolSulfuryl fluoride bis-Dichloroethyl etherIsobutylene Tertiary butyl benzene Boron trichlorideIsocyanic acidTetrachloroethylene Boron trifluorideIso-OctaneTetraethoxy silane bis-PropiolactoneIsophoroneTetrafluoromethane Bromo methaneIsopreneTetrahydrofuran Bromobenzene Isopropanol Tetrahydrothiophene Bromochloromethane IsopropylbenzeneThionyl fluoride Bromoform (Tribromo methane) K-1 keroseneThiophene Bromomethane Maleic anhydrideToluene Bromotrifluoromethanem-CresolTributyl phosphate Butadienem-Dichlorobenzene Trichloroethylene Butane MesityleneTrichlorofluoromethane Butyl acetatem-xyleneTrichlorotrifluoroethane Carbon dioxide m-Dichlorobenzene Triethylamine Carbon disulfide Methane Trifluoroethane Carbon monoxideMethanolTrifluoromethane Carbon tetrachloride Methyl acetateVinyl acetate Carbon tetrafluoride Methyl acrylate Vinyl bromide Carbonyl fluorideMethyl amineVinyl chloride Carbonyl sulfide Methyl bromideVinylidene chloride Chloroacetic acidMethyl chloride Water3.4 3.4.1 (nitrous oxide, N2O) PFC 3-17 58. (TSIA) TFT-LCD (TTLA)/ 3.4.2 (5080(70%90% 100%RH) FTIR FTIR(CC-FTIR) PFC CC-FTIR (extractive cell)FTIR PFC (extractive cell) FTIR FTIR PFCs FTIR 30 901(1) 6506,000 cm-1 (2) 0.04 cm-1(3) (Resolution) : 1.0 cm-1(4) (Beamsplitter & Optical materials) : ZnSe (, ())(5) (Detector) : MCT 12 , 650~5,000cm-1. (6) (IR source) : (7) (Scanning & Data acquisition control)He/NeLaser 3-18 59. (8) (Interferometer) : a ()() - Michelsonand linear force motor driving b - ()(with incredible resistance to low frequency vibrationinterference)(9) Ethernet USB ()() 100MBPS(10) () 7 2(Gas cell) (1) (Gas cell) Multi-pass White cell structure, path-length:302m. 120 ;() ZnSe (2)(Transfer Optics)( ) (Gascell Sample Compartment)(Path-length) 3(1) 15m 120 TEFLON (2) 15 L/min (3) (a) : 0~360 : : 3-19 60. 1.1m/s : 3: 1.3m(b) : 0~60 m/s: : 1.0m/s: 0.3m/s : 2.7m:100m/s(4) (a) -40to 60 0.5 -40to 60(b) 0.8100% RH 2% (0-90%)3% (90%-100%)(5) 660-810mmHg1%(6) 4.5CMM 10-3torr Gas cell 10-1 torr 3- 3 PFCs PFCs NIST SF6CF4C3F8C2F6NF3 CHF3 PFCs 3- 5 3-20 61. FTIR T P S MFC M Sample S M PFCs P S MFC Dry GasN2 P SMFC Wet GasN2 3- 3 3- 5 PFCs (ppm) Sulfur Hexafluoride SF650 TetrafluoromethaneCF4 100 PerfluoropropaneC3F8100 Perfluoroethane C2F6500 Nitrogen trifluorideNF3 500 TrifluoromethaneCHF35003-21 62. 3.4.3 PFCs PFCs CC-FTIR 60 () PFC 3- 4(FTIR) 20 GAS CELL CC-FTIR 3- 4 CC-FTIR FTIR(Open Path FTIR,OP-FTIR) OP-FTIR OP-FTIR 3- 5OP-FTIR 5 64 (scans) 288 864 FTIR FTIR 3 FTIR 3-22 63. N15NW10NE 5W 33.49%E 1510 5 5 1015 5 SW10SE15S 1~22~3 3~4 4~5 5~6>6 3- 5 OP-FTIR OP-FTIR CC-FTIR 3- 6 OP-FTIR ETGBomen 1cm-1 Zn-Se Beamspliter QA cell 15 Window-base software MCT dectector OP-FTIR Telescope LC (Galactic )MDA Closure 10400 3-23 64. 3- 7 CC-FTIR Midac 1cm-1 Zn-Se Beamspliter Cell 7 2cm,10cm,1m,3m,10m,20m,45m Cell Window-base software MCT dectector LC (Galactic )MDA Closure PFCs CVD CF4 C2F6 C3F8 Local Scrubber PFCs Local Scrubber PFCs 3- 8 S1 S2 S3 L2 5 L3 6 L1 2.5 3-24 65. 3- 8 / S1Fab 5 8 0.18m1997 40k S28F8 0.15m2000 40kS312B 1290nm2005 45kL1Fab 5 52005 180k L2L6A 62005 120KL3- 2.5 1997 50k3-25 66. 4.1 FTIR QA/QC USEPA TO-16 USEPATO-16 USEPA Method 320 4.1.1 : FTIR :1. S/N 2. FTIR 1cm - 1 (450 ) 4-1 67. FTIR 1cm - 1 (450 )3. : 1 cm-120m450 0.15m FTIR 30 : 4- 1 Y 0-40 0 4-2 68. 45.0040.0035.0030.0025.0020.00 15.0010.005.00 0.00 4500 4000 3500 3000 2500 2000 1500 1000 500 -5.00 Wave number(cm - 1 ) 4- 1 4-3 69. 4.1.2 : (root mean squarenoise:RMSN) (root mean square noise difference ; RMSD noise ) :n Ai AM : 80 988 cm - 12500 cm - 1 4400 cm - 1 FTIR 1 cm - 1 968~1008 cm - 12480~2520 cm - 14380~4420 cm - 1 ( ) 4-4 70. 1 cm20m640.15m968~1008 cm2480~2520 cm80 TO-16 968~1008 cm 2480~2520 cm 4380~4420 cm MCT 4000 cm PFCs 3200 cm 4380~4420 cm 4- 1 4- 2 4- 3 1.39E-04 2.12E-04 1.59E-05 1.38E-05 9.08 E-05~1.86E-04 1.7 E-04~2.54 E-04 4-5 71. 4- 1 968 cm-1~1008 cm-1 2480 cm-1~2520 cm-111.30E-042.26E-0421.64E-042.13E-0431.23E-041.94E-0441.24E-042.00E-0451.44E-042.13E-0461.46E-042.29E-041.39E-042.12E-04 1.59E-051.38E-059.08 E-05~1.86 E-041.7 E-04~2.54 E-04 4- 2 - 2480-2520 cm-1 4-6 72. 4- 3 - 968-1008cm-14-7 73. 4.1.3 :U.S.EPA TO-16 : 16 15 15 (cell) : 4- 2 16 15 28.5m NF 3 CHF 3 10ppb NF 3 CHF 3 NF 3 CHF 3 4-8 74. 4- 2 CF4C2F6 SF6 NF3C3F8CHF3 10.359-0.279 0.008 -22.32 0.522 0.9242-0.240 -0.242 -0.58214.271.388 3.2663-0.099 0.8290.816 10.66-0.810 -2.56640.439-0.685 -0.560-22.57 0.366-1.5475-0.2860.113 -0.28319.720.170 4.4806-0.015 0.2510.993 6.240-1.375 -8.58970.019-0.243 0.084 4.0601.435 7.1598-0.108 0.438-0.6382.843-0.075 -3.87990.182-0.540 0.516 -31.13 0.471 13.1710 -0.251 -0.362 -0.38717.420.138-10.8611 0.0900.872-0.61110.740.486-1.04512 0.444-0.154 0.863 -10.57 -2.4483.53613 -0.144 0.0420.362 11.101.661 9.70914 -0.294 -0.712 -1.758-1.101 -0.434 -5.10215 0.2360.4520.022 -3.840 -0.033 -2.0040.240.520.78 14.421.19 7.770.731.562.35 43.263.5723.31 ppb 4-9 75. 4.1.4 15 15% :1. FTIR 2. ( )3. Cell Purge Cell4. Cell Purge Cell5. Cell 15 6. 7. ; 4- 3 0.15%-2.13% 15% C 3 F 8 NF 3 4-10 76. 4- 3 SF6CF4C3F8 C2F6 NF3 CHF3 11.1662.4222.421 11.590 11.24511.38021.1682.4202.382 11.598 11.65511.41331.1602.4172.360 11.599 11.58211.51541.1522.4182.264 11.598 11.61611.45451.1652.4222.247 11.587 11.46311.53761.1562.4242.292 11.564 11.53511.53371.1612.4232.296 11.563 11.41411.48681.1572.4232.315 11.567 11.38911.56191.1522.4252.317 11.568 11.23211.42610 1.1562.4212.331 11.581 11.46711.56611 1.1622.4282.315 11.556 11.60011.55312 1.1552.4192.325 11.596 11.63811.43513 1.1582.4262.357 11.605 11.55611.38314 1.1572.4142.401 11.602 11.61111.47415 1.1672.4202.284 11.610 11.27211.412 1.1592.4222.327 11.586 11.48511.475 0.0050.0040.0500.0180.146 0.066 0.45%0.15% 2.13%0.15% 1.27% 0.57% pp m- m4-11 77. 4.1.5 : : 85%-115% :1. FTIR 2. ( )3. Cell Purge Cell C14. Cell C25. Purge Cell C3 6. C1 C2 C3 7. C2-2/1(C1+C3) 8. 9. 100 4-12 78. : 4- 4 4- 4 CF 4 85%-115% 85%-115% 450.00 120.0% 400.00 100.0%350.00 300.00 80.0%Concentration (ppm)250.00 60.0%200.00 150.00 40.0% 100.00 20.0% 50.00 0.00 0.0% SF6 CF4C3F8 C2F6 NF3 CHF3 4- 4 4-13 79. 4- 4 SF6CF4C3F8 C2F6 NF3CHF3 1 40.7685.2181.22405.48 407.03405.36 2 40.5384.8981.59406.87 408.34401.24 3 40.6585.1182.70407.21 405.46399.42 4 40.6184.7284.25407.10 407.41402.58 5 40.9584.9180.14407.36 395.50400.4240.7084.9781.98406.81 404.75401.80 40.3280.8080.00402.40 401.60402.40100.9% 105.2% 102.5% 101.1% 100.8%99.9% ppb4-14 80. 4.1.6 FTIR 1. 400 FTIR 25 2. ( 500cm - 1 -700cm - 1 ) 500cm - 1 -700cm - 1 FTIR 3. 50 4. 987cm - 1 2500 - 1 4000 - 1 5. 6. FTIR 4-15 81. : 4- 5 OP-FTIR 50-350 ( 25-175 ) 50 500cm - 1 -700cm - 1 ( 4- 6) 350 OP-FTIR 50-350 FTIR 25-175 70602500cm-1 50 987cm-140304000cm-1 2010 0 2575 125175 225 275 4- 5 4-16 82. =10.75 m 60 40 200 400 03000 2000 1000 Wave number (cm-1) 4- 6 4-17 83. 4.2 (5080(70%90% 100%RH) FTIR FTIR(CC-FTIR) 28.5 m PFCs FTIR PFCs 3 3 FTIR PFCs 40 654.2.1 25405060 80 SF6CF4C3F8C2F6NF3 CHF3 PFCs 4- 5 PFCs 500 4- 5 PFCs FTIR PFCs 10 700~1300cm-1 IR C3F8 C2F6 C3F8 C2F6 C3F8 C3F8 986~1021 cm-1 PFCs 4- 7 4-18 84. 4- 5 PFCs (ppm) (ppm) Sulfur Hexafluoride SF6 500.1 Tetrafluoromethane CF4100 0.2 PerfluoropropaneC3F8100 0.2 Perfluoroethane C2F6500 1.0 Nitrogen trifluoride NF3500 1.0 Trifluoromethane CHF3 500 1.0CHF3 1113-1198 cm-1 NF3 858-953 cm-1 C2F6 1222-1282 cm-1 C3F8 981-1030 cm-1 CF4 1228-1310 cm-1 SF6916-965 cm-115001400 13001200 1100 1000900800 700 Wavenumber(cm-1) 4- 7 PFCs 4- 8 847.17 cm-1 25 27.64 50 26.49 80 22.164-19 85. 30 25 40 25 50 65 20 80Arbitray Y 15 10 5 04500 4000 35003000 2500 2000 1500 1000 500 0Wavenumber (cm-1) 4- 8 PFCs 4-20 86. 4- 9 4- 10 SF6 25 50 947.46 cm-1 80 945.53 cm-1 C2F6 4- 6 4- 7 1 C2F6NF3 CHF3 25 1 ppm 80C2F6 561 ppbNF3 682 ppb CHF3 781 ppb 4- 11 PFCs 13(10 ~ 40)(>200)13 T C 300K C*T/300-4-21 87. PVnRTP(atm)V(liter)n(mole)R(atm-liter/mole-oK)T(oK)(n/V)(oK) 25(298 oK) 40(313 oK) 25 95.2% SF6 25 100.47 ppb 40 95.66 ppb 87.85 92% FTIR FTIR Beer-Lamberts LawAlog(Io/I)CL Io (absorbance)I(absorbance)(1/ppm-m)C(ppm)L(path length, m)(2005) PFCs ()(Cm)4-22 88. (CTC) Ratio(R)(Cm/CTC) PFC R(Ratio)aTb() 4- 8 PFC PFC PFC Ci(T)Ci(25oC){298/(T+273)}Ri(T) Ci(T)PFCi T Ci(25 C) PFCi 25oC o T(oC) Ri(T) PFCi T ( 4- 8) FTIR PFCs FTIR (1) PFCs (2) PFCs - PFCs -(3) FTIR 4-23 89. 0.40 C2F60.3525400.305065 0.25 Absorbance CHF3 80 CF40.200.15 NF3 SF60.100.05C3F80.001300 1250 1200 1150 1100 1050 1000 950900 850 800-1Wavenumber (cm ) 4- 9 PFCs 4-24 90. 0.0800.200250.070 250.180 40400.1600.060 50500.140 650.050Absorbance65 Absorbance 0.120 80800.0400.100 0.0300.080 0.0600.020 0.0400.0100.0200.0000.000 965960955950 945940 935 9301295 1290 12851280 1275 12701265 Wavenumber (cm-1)Wavenumber (cm-1)SF6CF40.0160.400250.014 250.350 40400.0120.300 5050 650.010Absorbance650.250 Absorbance 80800.0080.200 0.0060.150 0.0040.100 0.0020.050 0.0000.000 1030 1020 10101000990 9801280 1270 12601250 1240 12301220 Wavenumber (cm-1)Wavenumber (cm-1) C3F8C2F60.1200.20025250.1800.100 40400.160 50500.1400.080 65Absorbance65 Absorbance 0.120 80800.0600.100 0.0800.040 0.060 0.0400.020 0.0200.0000.000 940930920 910 900 890 880 8701180 1170 11601150 1140 11301120 Wavenumber (cm-1)Wavenumber (cm-1) NF3CHF3 4- 10 PFCs 4-25 91. 4- 6 SF6CF4C3F82540 50 65 80 2540 50658025405065 801100.56 87.88 80.43 72.04 61.57 199.79 171.15153.44 133.88 110.05 201.02 201.60 185.82 179.91164.89 2100.53 87.70 80.22 72.05 61.74 199.65 171.00153.65 133.95 109.53 203.26 202.73 187.16 178.37164.48 3100.47 87.66 80.40 71.99 61.73 199.82 170.90153.74 134.01 109.51 202.71 201.81 184.89 178.87166.59 4100.39 87.74 80.31 71.93 61.61 199.76 170.74153.79 133.61 109.57 202.97 202.38 185.52 177.53165.29 5100.41 87.98 80.42 72.09 61.72 199.88 171.18153.62 133.51 109.28 201.98 203.74 185.39 179.99167.50 6100.43 87.99 80.15 71.95 61.72 199.78 171.28153.75 133.45 109.42 201.89 202.03 184.20 181.45164.15 7100.55 87.89 80.46 71.99 61.39 199.72 171.28154.07 133.39 109.24 201.82 203.72 184.08 180.17162.46 8100.41 87.77 80.49 71.87 61.35 200.05 171.52153.84 133.35 109.25 201.45 202.71 183.83 179.31163.86 9100.57 88.07 80.44 71.94 61.63 200.08 171.16153.96 133.32 109.10 201.81 203.49 184.89 179.97165.71 10 100.37 87.84 80.31 72.00 61.76 199.88 171.43153.79 133.19 109.08 201.61 203.36 183.93 178.20162.97 100.47 87.85 80.36 71.98 61.62 199.84 171.16153.77 133.57 109.40 202.05 202.76 184.97 179.38164.79 ppb 4-26 92. 4- 7 () C2F6 NF3CHF32540506580254050658025405065 80 1 996.53 858.32 774.39 676.64 563.20 998.88 892.36 823.13 764.69 681.80 996.32 918.07 885.14 839.36782.642 996.61 856.28 772.62 676.63 561.91 1000.80891.35 825.76 763.71 683.29 996.92 917.43 883.91 839.72780.653 997.15 859.58 775.55 676.73 561.50 1001.56893.35 823.48 764.81 682.41 998.22 918.87 885.20 841.32780.834 997.72 856.97 773.25 676.24 562.17 1000.45890.86 824.50 763.65 681.71 997.46 917.23 884.99 840.78780.675 997.46 858.19 773.75 675.65 561.09 1001.15891.42 822.41 764.24 681.69 997.05 917.80 883.98 842.26779.726 997.62 858.19 774.04 675.66 561.55 1001.25891.91 823.54 764.77 682.60 997.58 918.18 884.62 840.99779.347 997.38 858.74 773.17 675.68 560.47 999.91 891.52 824.50 763.10 681.61 998.26 919.16 885.89 842.33781.938 997.31 858.61 774.93 675.45 560.84 1000.82890.92 824.55 765.38 680.83 997.82 917.07 885.66 841.24780.319 997.31 857.05 773.46 675.06 560.35 1000.90892.29 822.84 763.90 681.90 997.37 918.61 886.42 841.66779.8610996.85 856.52 774.64 674.15 559.80 1000.34892.86 824.26 762.89 681.12 996.38 917.63 886.87 840.43780.53 997.19 857.79 773.94 675.79 561.29 1000.61891.89 823.90 764.11 681.89 997.34 918.01 885.27 841.01780.65ppb4-27 93. 1200 1000800SF6CF4 (ppb)C3F8 600C2F6NF3CHF3 4002000 290 300 310 320330 340 350 360 (K) 4- 11 PFCs 4-28 94. 4- 8 SF6CF4 C3F8 C2F6 NF3 CHF3 RatioRatioRatioRatio Ratio Ratio (K)CmCTCCmCTCCmCTCCmCTC CmCTCCmCTC (Cm/CTC) (Cm/CTC) (Cm/CTC) (Cm/CTC)(Cm/CTC)(Cm/CTC) 298 100.47 199.84 202.05 997.19 1000.61 997.34 313 87.85 95.66 0.92 171.16 190.26 0.90 202.76 192.37 1.05 857.79 949.40 0.90 891.89 952.660.94 918.01 949.540.97 323 80.36 92.69 0.87 153.77 184.37 0.83 184.97 186.41 0.99 773.94 920.01 0.84 823.9 923.16 0.89 885.27 920.150.96 338 71.98 88.58 0.81 133.57 176.19 0.76 179.38 178.14 1.01 675.79 879.18 0.77 764.11 882.190.87 841.01 879.310.96 353 61.62 84.82 0.73 109.4 168.700.65 164.79 170.57 0.97 561.29 841.82 0.67 681.89 844.710.81 780.65 841.950.93 R= -205.76T + 502.96R= -159.34T + 456.94 R = -363.64T + 690.05 R = -168T + 465.46R = -291.56T + 587.53R = -786.75T + 1082.3RatioaT+bR20.9949 0.9970.2963 0.99730.9809 0.9159 Cm CTC 4-29 95. 4.2.2 70%90% 100%(1.5%) PFCs PFCs 4- 9 4- 12 PFCs 4- 13 4- 9 PFCs (ppb) (ppm) Sulfur Hexafluoride SF650160808Tetrafluoromethane CF4100320 160 16PerfluoropropaneC3F8100320 160 16Perfluoroethane C2F6500 1600 800 80Nitrogen trifluoride NF3500 1600 800 80TrifluoromethaneCHF3500 1600 800 80 4-30 96. FTIR TP S MFC M Sample S M PFCs P S MFC Dry GasN2 P SMFC Wet Gas N2 4- 12 4- 13 4-31 97. PFCs 130ml/min 1.5 l/min PFCs FTIR FTIR FTIR 1cm-1 16 1 700~1300cm-1 IR C3F8 C2F6 C3F8 C2F6 C3F8 C3F8 986~1021 cm-1 PFCs 4- 7 PFCs (130ml/min) PFCs FTIR PFCs IR IR 4- 14 FTIR 987.48 cm-1 IR 27.77 70% 24.97 100% 23.40IR 700~1300cm-1 800~1000 cm-1 1000~1200 cm-1 ()4-32 98. 4- 15 4- 16 4- 17 PFCs PFCs ( 4- 15) PFCs PFCs 70%90% 100% PFCs PFCs PFCs ( 4- 16 4- 17) PFCs PFCs 1000cm-1 PFCs 1000cm-1~1150cm-1 4-33 99. 3027.77Dry(1%) 26.3170% 24.97 2523.4090%100%20 Arbitray Y15 10 5 0 4500 40003500 300025002000 1500 1000 500 0Wavenumber (cm-1) 4- 14 4-34 100. SF68ppb, CF416ppb, C3F816ppb, C2F680ppb, NF380ppb, CHF380ppb100%RH90%RH70%RH Dry 1300 1250 120011501100 1050 1000950 900850 800Wavenumber(cm-1) 4- 15 PFCs 4-35 101. SF680ppb, CF4160ppb, C3F8160ppb, C2F6800ppb, NF3800ppb, CHF3800ppb100%RH 90%RH 70%RH Dry1300 1250 1200 1150 1100 10501000950900850 800 Wavenumber(cm-1) 4- 16 PFCs 4-36 102. SF6160ppb, CF4320ppb, C3F8320ppb, C2F61600ppb, NF31600ppb, CHF31600ppb100%RH90%RH70%RH Dry 1300 1250 1200 1150 1100 1050 1000 950 900 850 800Wavenumber(cm-1) 4- 17 PFCs 4-37 103. 4- 10 4- 11 4- 12 PFCs PFCs C3F8 C2F6 PFCs 70%90% 100% SF6 NF3 100%SF6 NF3 86.2% 44.9% SF6 NF3 PFCs ( 4- 18)SF6 NF3 916~965 cm-1 858~953cm-1 CF4C2F6 CHF3 C3F8 PFCs C3F8 SF6 NF3 CF4 CHF3 4-38 104. 4- 10 PFCs SF6CF4 C3F8 Dry 70% 90%100% Dry70%90%100%Dry70%90%100% 1 8.1 7.8 7.0 6.8 16.2------ 14.1 -- ---- 2 8.1 7.7 6.9 6.8 16.3------ 14.1 -- ---- 3 8.0 7.9 7.1 7.2 16.2------ 14.8 -- ---- 4 8.0 7.6 7.1 6.9 16.2------ 13.6 -- ---- 5 8.0 7.3 7.1 6.8 16.2------ 14.2 -- ---- (ppb) 8.1 7.7 7.0 6.9 16.2------ 14.2 -- ---- (ppb) 81616(%)100.995.987.686.2 101.4------ 88.5 -- ---- C2F6 NF3 CHF3 Dry 70% 90%100% Dry70%90%100%Dry70%90%100% 1 79.9 ------ 81.577.064.237.0 80.3 -- ---- 2 79.5 ------ 80.975.362.937.7 80.5 -- ---- 3 79.1 ------ 81.676.160.636.4 79.8 -- ---- 4 78.3 ------ 80.976.360.534.9 80.1 -- ---- 5 77.9 ------ 80.275.855.933.5 79.2 -- ---- (ppb) 78.9 ------ 81.076.160.835.9 80.0 -- ---- (ppb) 80 8080(%) 98.7 ------101.295.176.044.9100.0 -- ----4-39 105. 4- 11 PFCs SF6 CF4 C3F8 Dry70%90% 100%Dry70% 90%100%Dry70%90%100% 1 81.5 80.0 80.8 81.2160.9145.8 146.7 154.5168.3158.8144.978.7 2 81.3 80.0 80.9 81.0160.8146.0 147.2 154.7168.2162.2145.877.7 3 81.3 80.2 81.0 80.7160.7146.2 147.4 154.6168.0159.0147.076.8 4 81.4 80.1 80.9 80.5160.6146.4 147.8 154.2168.5164.2146.873.5 5 81.4 79.9 81.0 80.4161.0146.5 147.8 154.0169.5157.9146.872.5 (ppb) 81.4 80.1 80.9 80.8160.8146.2 147.4 154.4168.5160.4146.375.8 (ppb)80160 160(%)101.7100.1101.1101.0100.5 91.492.196.5105.3100.3 91.447.4 C2F6NF3 CHF3 Dry70%90% 100%Dry70% 90%100%Dry70%90%100% 1801.5855.8862.1888.1811.6808.4 816.7 767.7806.6772.5775.6 849.6 2801.2858.2863.0885.3811.9810.3 818.4 766.6807.8773.1777.2 848.2 3801.4858.9864.3885.6811.0809.8 818.0 765.6805.8773.7776.6 849.0 4800.5859.2864.5884.3810.4808.5 819.1 762.6807.4770.6779.3 848.9 5802.2860.0866.5880.2811.7806.2 819.4 759.3808.5769.1779.4 844.4 (ppb)801.4858.4864.1884.7811.3808.6 818.3 764.4807.2771.8777.6 848.0 (ppb)800 800 800(%)100.2107.3108.0110.6101.4101.1 102.395.5100.9 96.5 97.2 106.04-40 106. 4- 12 PFCs SF6 CF4 C3F8 Dry70%90%100%Dry 70%90% 100%Dry70%90% 100% 1159.9 159.4160.0160.4 317286.1 288.5 298.3 317.1323.9295.7 208.0 2160.1 159.7160.1160.1317.1 286.2 288.4 297.5 317.5322.3295.5 209.2 3159.9 159.8160.1160.3316.9 286.6 288.3 297.9 316.9324.7294.2 208.6 4160.2 159.7160.1160.0317.2 286.7 288.5 298.1 317.7324.0295.0 207.1 5160.0 159.7160.0160.1317.2 286.8 288.4 298.4 319.7325.5294.5 205.1 (ppb)160.0 159.7160.1160.2317.1 286.5 288.4 298.1317.8 324.1295.0 207.6 (ppb)160 320 320(%)100.099.8100.0100.1 99.189.590.193.1 99.3 101.3 92.264.9 C2F6NF3 CHF3 Dry70%90%100%Dry 70%90% 100%Dry70%90% 100% 1 1583.31636.2 1650.8 1675.3 1594.2 1611.7 1612.01535.51587.1 1585.9 1571.21634.2 2 1584.11638.2 1650.9 1673.6 1594.4 1614.2 1610.11534.71589.9 1587.0 1571.21635.1 3 1583.31640.0 1651.2 1673.5 1593.9 1615.8 1610.91534.31589.3 1588.7 1571.61637.4 4 1585.51642.3 1650.1 1674.8 1595.7 1617.7 1610.81534.11590.9 1590.5 1570.11634.3 5 1584.81642.4 1651.9 1673.2 1595.1 1617.9 1611.51533.61589.6 1591.9 1571.11633.5 (ppb) 1584.21639.8 1651.0 1674.1 1594.6 1615.4 1611.01534.51589.4 1588.8 1571.01634.9 (ppb)160016001600(%) 99.0 102.5103.2104.6 99.7 101.0 100.795.9 99.399.3 98.2 102.24-41 107. CHF3 1113-1198 cm-1NF3 858-953 cm-1 C2F6 1222-1282 cm-1 C3F8 981-1030 cm-1 CF4 1228-1310 cm-1SF6916-965 cm-1 Water 125011501050950 850 750Wavenumber(cm-1) 4- 18 PFCs PFCs PFCs 4- 13 FTIR PFCs FTIR FTIR 4- 19 4- 13 PFCs (ppm) (ppm)Sulfur Hexafluoride SF6 50 0.35Tetrafluoromethane CF4 1000.7Perfluoropropane C3F81000.7PerfluoroethaneC2F65003.5Nitrogen trifluoride NF3 5003.5Trifluoromethane CHF35003.54-42 108. 4- 19 4- 14 PFCs 91.4%46.8%SF6 NF3 C2F6 CF4 1200 cm-1 C3F8 CHF3 91.4% 46.8% PFCs 4-43 109. 4- 14 SF6CF4 C3F8C2F6NF3CHF3 (91.4%) (46.8%) (91.4%) (46.8%) (91.4%) (46.8%) (91.4%) (46.8%) (91.4%) (46.8%) (91.4%) (46.8%) 1 352.9353.1623.1612.1 603.5 657.0 3574.1 3546.2 3552.1 3534.8 3412.9 3481.1 2 353.5353.6623.0612.5 602.7 657.2 3564.3 3544.6 3551.2 3535.5 3420.4 3485.5 3 353.1353.9623.6613.0 603.5 658.1 3568.0 3553.0 3557.7 3535.0 3422.8 3488.1 4 353.2352.9624.2612.1 606.0 656.7 3558.2 3557.2 3555.3 3536.4 3417.2 3479.1 5 353.7354.1624.2612.4 606.9 657.5 3582.4 3546.7 3558.7 3538.1 3416.8 3488.0 6 354.2353.7624.7613.8 603.9 658.5 3569.0 3555.7 3563.1 3540.5 3423.3 3487.5 7 353.4353.3624.5613.1 603.6 658.3 3573.3 3544.2 3560.9 3538.6 3421.7 3484.1 8 354.1353.1624.3613.0 604.5 656.2 3582.4 3554.7 3566.1 3540.8 3432.5 3485.1 9 353.8353.2625.6612.9 606.2 658.5 3589.2 3546.1 3565.5 3541.6 3426.8 3482.510 353.6354.0624.0613.8 599.7 660.6 3577.4 3565.1 3564.2 3544.5 3425.9 3490.2 (ppb) 353.5353.5624.1612.9 604.0 657.9 3573.8 3551.4 3559.5 3538.6 3422.0 3485.1 (ppb)350 700700350035003500(%) 101.0101.0 89.2 87.686.394.0102.1101.5101.7101.1 97.8 99.6 4-44 110. 4.3 PFCs PFCs CC-FTIR 60 () PFC FTIR(Open Path FTIR,OP-FTIR) OP-FTIR OP-FTIR OP-FTIR 5 64 (scans) 864 FTIR 4.3.1 4.3.1.1 L1 L1 1992 2.5 370 mm 470mm 2.45 10.4 TFT-LCD()1. Close-Cell FTIR 4- 20 L14-45 111. 4- 15 PFC SF6 NF3 (A01)(P01) Local Scrubber Local Scrubber HF L1 (A01)(A01)(P01)(FTIR) (FTIR) 20 ( 4- 21) 28.5 FTIR ( 4- 21) 4- 22 4-46 112. P03E01 E02 160 P01 A01 E03 160 P05 A02E04 E05 180 P02(A03P07(E06 P06 180A05 E07 E08 THC HCl... .. 4- 20 L1 4-47 113. 4- 15 L1 PFCs 1.2.3.4. 5.6.7.8. P019. 1.AL 2.He3.ITO 4.5.6.7. 4-48 114. 20m CC-FTIR28.5m CC-FTIR 4- 21 20 m 28.5 m FTIR Vacuum Pump VacuumPump28.5m CC-FTIR20m CC-FTIRStack (P001)Scrubber (A001)inlet outlet 4- 22 L1 4-49 115. PFCs 96 7 11 11:53 14:48 2 55 156 330 CMMinlet outlet 24.4 22.6 64.7 % 83.2 % FTIR 4- 16 4- 16 L1 L1L1-P01(inlet) L1-P01(outlet) 96 7 11 156(CMM)330()24.4 22.6(% rh) 64.7 83.2(m)2028.5()33.6 35.8(% rh) 41.9 34.7FTIR (mmHg) -136 -278 2.(A01) 4- 17 NF3SF6N2OSiH4SO2F2CH3COOH SiF4 PFCs NF3 SF6 NF3 SF6 SiH4 CH3COOH N2OSO2F2 SiF4 NF3SF6N2OSiH4 SO2F2PFCs NF3 SF6 CH3COOH SiF4 L1 (outlet)PFCs 4-50 116. 4- 17 L1 P01(Inlet) P01(Outlet) Nitrogen trifluorideNF3 1170312.33 45 1056 282.7631.6 Sulfur Hexafluoride SF6362120.98 10332 123.427.01 Nitrous Oxide N2O 1880 27.91 50 134129.5335.1 SilaneSiH4 349 60.74 5529866.5538.6 Sulfuryl Fluoride SO2F21324.71 2511211.5917.5 Acetic Acid CH3COOH 2633111.96 70 49 Silicon Tetrafluoride SiF4 145 42.27 55 38.6 PFCs ppb4-51 117. NF3 1056 ppb 283 ppb SF6 332 ppb 123 ppb NF3 SF6 L1 A01 PFCs 4- 23 PFCs 2.6 ppm 112 ppb 28.5 m FTIR 6N2OSiH4 SO2F2SF CC-FTIR FTIR FTIR FTIR 4- 18 NF3SF6 N2O NF3 CH3COOH 4-52 118. 350 312300 283 250 Concentration (ppb) 200150121123100500 inletoutletinletoutlet NF3SF6P01 4- 23 L1 PFCs 4-53 119. 4- 18 L1 400inlet350Concentration (ppb)outlet300250200 SF6150100 5000 1020 30405060 7080 90 100 110 120 130 140 15014001200inletConcentration (ppb)1000outlet 800NF3 600 400 200001020 304050 6070 80 90 100 110 120 130 140 150140inlet120Concentration (ppb)outlet100 80 SO2F260 40 2000 1020 30405060 7080 90 100 110 120 130 140 1502000 inletConcentration (ppb)1500 outlet 1000 N2O 500001020 304050 6070 80 90 100 110 120 130 140 150400inlet350Concentration (ppb)outlet300250200 SiH4 150100 5000 1020 30405060 7080 90 100 110 120 130 140 150 160140 Concentration (ppb) inlet120100 80 SiF460 40 2000 10 20304050 607080 90 100 110 120 130 140 1503000 2500Concentration (ppb) inlet2000 1500 CH3COOH1000500 001020 304050 6070 80 90 100 110 120 130 140 150 4-54 120. PFCs PFCs Local Scrubber PFCs (Million MetricTons Carbon EquivalentMMTCE): GWP Q (Kg) PFCs NF3 SF6 4- 19 PFCs NF3 SF6 0.016kg/h 0.015kg/h 142 kg 128 kg L1 P01 NF3 SF6 0.00042MMTCE 0.000774 MMTCE 0.0012 MMTCEL1 PFCs 4- 24 4- 19 L1 PFCs MMTCE GWP MMTCE g/mole CMM ppbKg/hKg/yr NF3 71.0 10800 2830.016 142 0.000420330 0.0012 SF6146.0 22200 1230.015 128 0.000774 NF3 37%SF663% 4- 24L1 PFCs 4-55 121. 1. L1 4- 25Open Path Fourier Transform InfraRed OP-FTIR 50400 OP-FTIR 3 5 288 864 96/07/11 20:18 96/07/15 01:57 78 945 7 FTIR 2 161 L1 OP-FTIR 4- 25 4-56 122. 4- 25 L1 2. 4- 26 4- 27 0.12 / 360270 ( ) 180 90 0 07/07/1107/07/1207/07/1307/07/14 07/07/15 07/07/1686 ( / ) 42 0 07/07/1107/07/1207/07/1307/07/14 07/07/15 07/07/16 4- 26 L1 4-57 123. Total( 0.1~2 2~3 3~44~55~6>6 (6 WNW0.00%2.86% 2.33%0.64% 0.32% 0.00% 0.00% 6.14% NW 0.00%1.06% 0.64%0.11% 0.11% 0.00% 0.00% 1.91% NNW0.00%0.85% 0.32%0.11% 0.00% 0.00% 0.00% 1.27% 15.57% 59.85% 15.89% 6.36% 2.01% 0.21% 0.11% 4- 27 L1 4-58 124. 3. L1 OP-FTIR 4- 20 8 PFCs PFCs 326ppb C2F6 SF6 SF6 SF6 PFCs Chemical Vapor Deposition, CVD CF4 CHF3C2F6C3F8SF6NF3Cl2CCl4CCl3FCCl2F2 CClF3 CF4CHF3C2F6C3F8SF6NF3 (PFCs) PFCs Chemical Vapor Deposition, CVD CVD SiH4 300 CVD4-59 125. 4- 20 L1 OP-FTIR 0 Compound(ppb)(ppb) (ppb)(ppb) Isopropanol (CH3)2CHOH 423.76 13.11 20.87% 8000 1000 0.00% Nitrous Oxide N2O 73.16.29 46.19%---- -- Silane SiH4 45.611.76 35.81% 100-- -- unpleasant odor AmmoniaNH335.64 3.1 49.47% 1000430.00%, PerfluoroethaneC2F6 25.24 0.9 21.61%---- -- Tetrafluoromethane CF4 6.550.218.90%---- -- Perfluoropropane C3F86.110.030.53%---- -- Sulfur HexafluorideSF6 3.750.17 44.60% 20000-- -- 1. PFCs 2. -- 3. A/50A 4. Odor Thresholds for Chemicals with Established Occupational Health Standards, American Industrial Hygiene Association,1989. 4-60 126. SiH4 CVD CVD(LowPressure CVDLPCVD) CVD(Plasma-Enhanced CVDPECVD)LPCVD(1~0.5 Torr) PECVD CVD(Radical) N2O SiH4 PECVD :SiH4(g) + 2N2O(g) SiO2(s) + 2N2(g) + 2H2(g) PECVD SiO2 H N C3F8 PECVD CF4 C2F6 C2F6 CF4 10%(Million Metric Tons of Carbon Equivalent, MMTCE)C3F8 CF4 C2F6 70% C3F8 IPAIPA PFCs SF6 SF6 3.75ppb 20000ppb 8 4- 28 OP-FTIR L1 PFCsC2F6CF4C3F8SF6-C2F6 PFCs 7/137/15 C2F6 OP-FTIR 4-61 127. 30 25 Perfluoroethane 20 (ppb) 15 C2F61050 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/168 Tetrafluoromethane6 (ppb)4 CF42 0 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/168 Perfluoropropane6 (ppb)4 C3F82 0 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/164 Sulfur Hexafluoride3(ppb)2 SF61 0 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/16 360270 ( ) 180 90 0 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/16765 ( / )4 3210 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/16 4- 28 L1 OP-FTIR PFCs CF4C3F8SF6 10ppb OP-FTIR 4- 29 FTIR PFCs PFCs 4-62 128. 4- 29 OP-FTIR L1 PFCs 4-63 129. PFCs 4- 30 - 500 400 Isopropanol 300(ppb) IPA 200 1000 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/16 80 Nitrous Oxide 60 (ppb) 40 N2O 20 0 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/16 50 40 30 Silane (ppb) SiH420 100 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/16 4030 Ammonia(ppb) 20 NH3 10 0 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/16 360270 ( ) 180 90 0 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/16765 ( / )4 3210 07/07/11 07/07/12 07/07/13 07/07/14 07/07/15 07/07/16 4- 30 L1 OP-FTIR 4-64 130. 4- 31 IPA N2O IPA N2O SiH4 NH3 8 4- 21 +1 -1 CF4 N2O 0.441 4- 21 L1 SF6 NH3 SiH4 IPAC2F6 CF4 C3F8 N2OSF61NH3 0.3771SiH40.007 -0.0461IPA 0.377 0.225 -0.0021C2F60.023 -0.093 0.151 -0.049 1CF4 0.187 0.2250.025 0.129 0.1031C3F80.098 0.295 -0.023 0.038-0.018 0.215 1N2O0.23 0.313 -0.025 0.142-0.001 0.441 0.094 1 OP-FTIR 4- 31C2F6 CF4 C3F8 SF6 OP-FTIR C2F6 CF4C3F8 SF6 L1 CF4C3F8 L1 L1 PFCs SF64-65 131. 4- 31 L1 PFCs 4-66 132. 4.3.1.2 L2 L2 1100 mm1300 mm TFT-LCD 5 2005 18 17 20 27 PFCs PFCs ()1. Close-Cell FTIR PFCs 4- 32 L2 4- 22 PFC 4- 32 4- 22 (CVD)PFCs (NF3) P05 CVD PFCs (SF6) PFCs P01~P04 PFCs P01~P04 CVD P05 P03 CVD (FTIR) 28.5 1/4 Teflon L2 PFCs 96 9 12 13 100 FTIR 1cm-1 16 1 100 4-67 133. 4- 23 4- 32 L2 PFCs 4-68 134. 4- 22 L2 PFCs 1./(1%)2.3. 4.5. CVD P05 6. 7.8.9.10.1.ITO P012. P023. P034. P045.6. 4-69 135. 4- 23 L2 L2 L2-P01 L2-P02L2-P04 L2-P05 CVD 96 9 12 ~13 100 (CMM)300 300 300700 () 26.8 25.325.2 27.6 (% rh)79.1 85.484.6 86.6 (m) 28.5 () 31.4 30.329.1 38.9 (% rh)56.6 57.965.1 39.4 FTIR (mmHg) 16 1718-4052. L2 PFCs 4- 24(SF6)(SO2F2)(N2O)(SiH4)(CH3COOH)(NH3)(C6H12O3,) PFCs SF6SF6N2OSiH4SO2F2CH3COOH NH3SO2F2 SF6 PGMEA CVD CVD P01P02 P04 SF6 SO2F2 N2O CVD SiH4 PGMEA 4-70 136. 4- 24L2 CVD P01P02P04P05 Sulfur Hexafluoride SF61517 18741191 1899 956 1556 -- -- Sulfuryl Fluoride SO2F2 182876 238 1208 794 1510 -- -- Nitrous Oxide N2O -- --20.5 390 4.23 175 -- -- SilaneSiH4-- ---- ---- --95.4 371 Acetic Acid CH3COOH -- ---- --103 2855 -- -- Ammonia NH3 19.7 646 -- ---- ---- -- PGMEA C6H12O3 -- ---- ---- --34.2 2904-71 137. L2 PFCs SF6 P01 1517 ppb 1874 ppb P02 P04 1191 ppb 956 ppb 1000 ppb SF6 Local Scrubber SF6 L2 CVD Local Scrubber PFCs SF6 NF3 PFCs CVD L2 PFCs 4- 33 PFCs SO2F2 SF6 182 ppb238 ppb 794ppb P04 N2O P02 P04 SiH4 CVD P05 95.4 ppb P04 2.9 ppm 103 ppb16001517 140011911200956Concentration (ppb)1000800600400200 0 P01 P02 P04SF6 4- 33 L2 PFCs L2 4- 25 4-28 P01P02 P04 SF6 SO2F2 SO2F2 SF6 4-72 138. P04 28 34 2.9 ppm 4- 25 L2 P01 2000 Concentration 1500 (ppb) 1000SF6 500 0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 1000800 Concentration600 (ppb)400 SO2F22000 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 800 Concentration 600 (ppb) 400NH3200 0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 4- 26 L2 P02 2000 Concentration 1500 (ppb) 1000SF6 500 0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 1500 Concentration 1000 (ppb) SO2F25000 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 500 400 Concentration 300 (ppb) 200N2O100 0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 1004-73 139. 4- 27 L2 P04 2000Concentration1500(ppb)1000 SF650000 5101520253035404550556065707580859095 1002000Concentration1500(ppb)1000SO2F2 50000 5101520253035404550556065707580859095 100200Concentration150(ppb)100 N2O5000 5101520253035404550556065707580859095 10030002500Concentration2000(ppb)1500 CH3COOH1000 500 00 5101520253035404550556065707580859095 100 4- 28 L2 P05 400 Concentration300 (ppb)200SiH410000 5 101520253035404550556065707580859095100400 Concentration300 (ppb)200 PGMEA10000 5 1015202530354045505560657075808590951004-74 140. PFCs PFCs (GWP) PFCs (Million Metric Tons CarbonEquivalentMMTCE) 4- 29 4- 34 L2 PFCs SF6 CVD P01P02 P03 0.00870.0068 0.0055 MMTCE L2 PFCs 0.0209MMTCE 4- 29 L2 PFCs MMTCE SF6 Kg/hr MMTCE P01 0.163 0.00870.0087 P02 0.128 0.00680.0068 0.0209 P04 0.103 0.00550.0055:MMTCE1.00E-02 9.00E-03 SF68.00E-03 7.00E-03 6.00E-03MMTCE5.00E-03 4.00E-03 3.00E-03 2.00E-03 1.00E-03 0.00E+00 P01 P02 P04 L2 4- 34 L2 PFCs 4-75 141. 1. L2 TFT-LCD L2 1100mm 1300mm 6 27 27 L2 OP-FTIR 2007/9/13 16:40 2007/9/18 03:44 4.5 1115 OP-FTIR L2 () 156 (OP-FTIR path length312 )OP-FTIR IC PFCs OP-FTIR 4- 35 156 mL2 4- 35 L2 4-76 142. 2. 0.36% 53%3 m/sec(3m/sec OP-FTIR L2 L2 L2 4- 36 L2 4-77 143. (m/s)Total((6)N1.26%2.70% 1.53%0.81%1.08%1.26% 1.35%8.72%NNE1.71%4.13% 2.16%2.34%2.52%1.35% 2.43% 14.91%NE 1.26%1.80% 0.63%0.81%0.27%0.54% 0.36%4.40% L2 ENE2.34%5.66% 0.36%0.18%0.09%0.18% 0.18%6.65% N20E2.25%4.76% 0.18%0.00%0.00%0.00% 0.00%4.94%NW 15NE 10ESE1.08%5.66% 1.80%0.09%0.00%0.09% 0.09%7.73% 5SE 0.09%1.89% 1.08%0.27%0.00%0.09% 0.00%3.32% W14.91%E SSE0.18%1.08% 1.53%1.08%0.00%0.18% 0.09%3.95% 20 15 105 510 1520 5S0.09%0.09% 0.00%0.00%0.18%0.00% 0.09%0.36% 10SSW0.09%0.45% 0.09%0.09%0.00%0.00% 0.09%0.72%SW 15SE 20 SW 0.00%0.63% 0.18%0.18%0.09%0.09% 0.00%1.17% SWSW0.54%0.81% 0.18%0.09%0.18%0.18% 0.36%1.80% 0.5~2 2~3 3~4 4~5 5~6>6W0.36%0.90% 0.45%0.45%0.09%0.09% 0.09%2.07%WNW0.54%1.44% 0.36%0.18%0.18%0.00% 0.00%2.16%NW 1.35%1.53% 0.81%1.35%0.54%0.54% 0.18%4.94%NNW1.80%3.77% 4.22%3.14%2.07%2.61% 1.44% 17.25%14.91%37.29% 15.54% 11.05%7.28%7.19% 6.74% 4- 36 L2 4-78 144. 3. L2 4 1115 (1115 FTIR ) 10 () PFCs CVD VOCs - PFCs 10 ppb 8.8 ppb1115 0.11 ppb>0.0 ppb 11.77% 131/1115 4.76%(53 /1115 ) 2.88%(32 )/ 6.5 ppb/0.05 ppb 5.3 ppb/0.05 ppb IPCC CVD (Si3N4)CVD N 162.9ppb 4.69 ppb>0.0 32.97%41% L2 97.7 ppb 5.51 ppb PFCsL2 5% 121.9 ppb 111.3 ppb 55.4 ppb85.1 ppb 31.5 ppbL2 OP-FTIR 4- 30 4-79 145. 4- 30 L2 OP-FTIR 0 Compound (ppb) (ppb) (ppb) (ppb) Sulfur HexafluorideSF68.8 0.11 11.77%-- -- -- PerfluoroethaneC2F6 6.5 0.05 4.76% -- -- -- Tetrafluoromethane CF45.3 0.05 2.88% -- -- -- Nitrous OxideN2O162.9 4.69 32.97%-- -- -- ,, AmmoniaNH3 97.7 5.51 41.06% 1000 43 3.50% StyreneC6H5C2H3 121.9 0.270.36% 1000 4.70.36% / MethanolCH3OH 111.3 0.944.49% 4000 3300 0.00% Ethyl Acetate CH3COOC2H5 55.4 0.130.63% 8000 5.60.54% ,, Dichloromethane CH2Cl2 85.1 0.261.17% 1000 10000000 0.00% Cyclohexane C6H1231.5 0.496.74% 6000 5200.00% // 1. PFCs 2. -- 3. A/50A 4. Odor Thresholds for Chemicals with Established Occupational Health Standards, American Industrial Hygiene Association,1989. 4-80 146. A B / 0.5 50% 4- 31 2 CF4 C2F6 50.6% PFCs CF4C2F6 SF6 SF6 L2 PFC CF4C2F6 SF6 73.8% 70% 50% 4- 31 L2 EthylDichloro-L2SF6 Styrene NH3 CF4 C2F6 MethanolN2O CyclohexaneAcetate methaneSF6 1Styrene0.22 1NH3 -0.034 -0.005 1CF4 -0.005 -0.008 0.0811C2F6 0.1 -0.008 0.0920.5061Methanol-0.025 -0.008 -0.024 -0.012-0.0021Ethyl Acetate -0.008 -0.003 -0.012 -0.01 -0.0090.496 1Dichloromethane -0.015 -0.005 -0.025 -0.013-0.0130.6990.7381N2O -0.018 -0.01 0.054 0.343 0.386-0.043-0.02 -0.0281Cyclohexane -0.004 -0.009 -0.024 -0.015-0.0210.016-0.01 -0.006-0.041L2 PFCs L2 SF6 45 L2 SF6 L2 L2 CF4 L2L2 4-81 147. CF4 C2F6 4- 37 L2 PFCs N2O CO2 PFCs SF6 N2O IPCC N2O 310 ppb(Chemical Vapor Deposition, CVD) N2O NH3N CVD (Point-Of-Use Abatement, POU Abatement)local scrubber PFCs NH3/N2O NOxN2O NH3/( 4- 38)N2O 90 L2 N2O NH3 NH3 L2 OP-FTIR L2 4 L2 L2 L2 ( 4- 39)4-82 148. 4- 37 L2 PFCs 4- 38 L2 NH3 N2O 4-83 149. 4- 39 L2 OP-FTIR 4-84 150. 4.3.1.3 L3 L3 1500 mm1800 mm TFT-LCD 6 2005 12 32 37 15 17 PFCs PFCs ()1. Close-Cell FTIR PFCs 4- 40 L3 PFCs 4- 32 PFC PFCs PFCs A06 A01~A05 P01~P05 A07~A09 P07~P09 CVD (P01~P03) CVD (P07~P09) PFCs (FTIR) 28.5 1/4 Teflon L3 PFCs 96 10 30 ~31 60 FTIR 1cm-1 16 1 60 4- 33 4-85 151. 4- 40 L3 PFCs 4-86 152. 4- 32 L3 PFCs 1.7.2.8. P04 3. 9. CVD P054.10. P06 5. 11.6.12.1. P012. P023. P03 4. P045. P056.7.4-87 153. 4- 33 L3 L3L3-P01 L3-P02L3-P03L3-P07 L3-P08 L3-P09 CVD 96 10 30 ~31 60(CMM)230.47 220.99227.03260.93 261.46 254.35() 23.1 22.324.524.6 25.5 25.5(% rh)91.5 94.388.298.1 97.7 97.4(m) 28.5() 28.9 27.426.426.2 27.1 28.3(% rh)57.1 62.868.376.9 72.7 66.6FTIR (mmHg)-98-99 -99 -95-96-984-88 154. 2. L3 PFCs 4- 34 L3 (SF6)(CF4)(NF3)(CH3F)(CH2F2)(N2O)(SiH4) (NH3) PFCs SF6NF3 CF4 CF4CH3F CH2F2 CF4CH3F CH2F2 SF6 NF3 (P01~P03) SF6 NH3 CVD (P07~P09) SF6 4- 41 L3 PFCs PFCs SF6 PFCs 6.85 ppb~8.24 ppb 8.76 ppb CVD NF3 CF4 PFCs NF3 59.4 ppb~71.1 ppb P08 P08 315 ppb CVD CF4 3.16ppb~5.20ppb P07 59.2 ppb CVD HFCs CH3F CH2F2CH3F 81 ppb~101 ppbCH2F2s 10.6 ppb~16.5 ppb HFCs N2O CVD 6.1 ppm~6.7 ppm 10.1 ppm N2O (GWP) PFCs(GWP N2O=296) L3 4- 35~ 4-40 SF6 NH3 CVD CH3FCH2F2 CF4 CH4 CH3FCH2F2 CH3FCH2F2 CF4 4-89 155. 4- 34 L3 CVD P01P02P03P07P08P09 Sulfur HexafluorideSF66.857.48 7.55 7.938.24 8.76-- ---- ---- -- Tetrafluoromethane CF4-- ---- ---- -- 5.2059.2 3.6135.3 3.1644.1 Nitrogen trifluoride NF3-- ---- ---- -- 61.5 230 71.1 315 59.4274 FluoromethaneCH3F -- ---- ---- -- 81.0 520 94.1568 101560 DifluoromethaneCH2F2-- ---- ---- -- 10.682.4 14.722116.5131 Nitrous OxideN2O-- ---- ---- -- 6671 10381 6690 10013 6083 10541 Silane SiH4 -- ---- ---- -- 22482707 2296 27701780 2345 AmmoniaNH3 15.38 146.792.4111.21 14.3178.25 78.7 329764 948 5.0647.2 4-90 156. 8071.1 70 61.5 59.4 60 Concentration (ppb) 50 40 30 20 107.51 8.246.85 5.203.61 3.16 0SF6SF6SF6CF4NF3CF4 NF3CF4NF3 P01P02P03 P07 P08P09 CVD 4- 41 L3 PFCs 4-91 157. 4- 35 L3 P01 8Concentration6 (ppb)4SF62 00 5 10152025 3035 40 45 50 55 60 200Concentration150 (ppb)100NH350 00 5101520 2530 35 40 45 50 55 60 4- 36 L3 P02 108Concentration6 (ppb)SF6 4200 5 10152025 3035 40 45 50 55 60 1210Concentration 8 (ppb) 6NH34 2 00 5 10152025 3035 40 45 50 55 60 4- 37 L3 P03 108Concentration6 (ppb)SF6 4200 5 10152025 3035 40 45 50 55 60 10080Concentration60 (ppb)NH3 402000 5101520 2530 35 40 45 50 55 60 4-92 158. 4- 38 L3 P07 8060 Concentration (ppb) 40CF4 20 00 5 101520253035404550 55 60250 200 Concentration 150 (ppb) NF3 1005000 5 101520253035404550 55 60600 500 Concentration 400 (ppb) 300 CH3F200 100 00 5 101520253035404550 55 6010080 Concentration60 (ppb) CH2F2402000 5 101520253035404550 55 6012000 10000 Concentration8000 (ppb)6000 N2O40002000 00 510152025303540 4550 55 603000 2500 Concentration 2000 (ppb) 1500 SiH4100050000 51015202530 35404550 55 60400300 Concentration (ppb) 200 NH3 100 00 5 101520253035404550 55 60 4-93 159. 4- 39 L3 P08 4030 Concentration (ppb) 20CF4 10 00 5 1015202530354045 50 55 60400300 Concentration (ppb) 200NF3 100 00 5 1015202530354045 50 55 60600 500 Concentration 400 (ppb) 300CH3F 200 100 00 5 1015202530354045 50 55 60250 200 Concentration 150 (ppb) CH2F2 1005000 5 1015202530354045 50 55 6012000 10000 Concentration8000 (ppb)6000N2O 40002000 00 510152025303540 45 50 55 603000 2500 Concentration 2000 (ppb) 1500SiH4 100050000 51015202530 354045 50 55 601000800 Concentration600 (ppb)NH3 40020000 51015202530 354045 50 55 60 4-94 160. 4- 40 L3 P09 50 40 Concentration 30 (ppb)CF420 1000 5 101520253035404550 55 60300 250 Concentration 200 (ppb) 150 NF3 10050 00 5 101520253035404550 55 60600 500 Concentration 400 (ppb) 300 CH3F200 100 00 5 101520253035404550 55 60150 Concentration 100 (ppb) CH2F250 00 5 101520253035404550 55 6012000 10000 Concentration8000 (ppb)6000 N2O40002000 00 510152025303540 4550 55 602500 2000 Concentration 1500 (ppb) SiH4100050000 51015202530 35404550 55 6050 40 Concentration 30 (ppb) NH3 20 1000 5 101520253035404550 55 60 4-95 161. L3 PFCs PFCs (GWP) PFCs (Million Metric Tons CarbonEquivalentMMTCE) 4- 41 4- 42 L3 PFCs SF6NF3 CF4 4- 42 L3 PFCs PFCs SF6 CVD NF3 CH4 PFCs CVD NF3 2.24E-04MMTCE SF6(9.71E-05MMTCE) PFCs 0.00033MMTCE 4- 43 PFCs NF3 68% SF6 29% 4-96 162. 4- 41 L3 PFCs MMTCE NF3 SF6 CF4 kg/hMMTCE kg/hMMTCE kg/hMMTCE P01---- 5.66E-04 3.00E-05---- 3.00E-05 P02---- 5.95E-04 3.16E-05---- 3.16E-05 P03---- 6.70E-04 3.56E-05---- 3.56E-05 P07 2.80E-03 7.21E-05---- 2.93E-04 3.99E-06 7.61E-05 CVD P08 3.24E-03 8.36E-05---- 2.04E-04 2.77E-06 8.64E-05 P09 2.63E-03 6.79E-05---- 1.74E-04 2.36E-06 7.03E-05 8.67E-03 2.24E-04 1.83E-03 9.71E-05 6.70E-04 9.13E-06 0.00033 :MMTCE 4-97 163. 1.00E-04 CF49.00E-05 SF6 NF38.00E-05 7.00E-05 6.00E-05MMTCE5.00E-05 4.00E-05 3.00E-05 2.00E-05 1.00E-05 0.00E+00 P01P02P03 P07 P08 P09 CVDL3 4- 42 L3 PFCs CF43% SF6 29% NF3 68% 4- 43 L3 PFCs 4-98 164. 1. L3 TFT-LCD 1500mm1850mm 32 TFT-LCD LEDL2 OP-FTIR 144 288 FTIR (path length)OP-FTIR 4-44 L3 144 m 4- 44 L3 OP-FTIR 2. L2 61%90 90% 10 (6WNW0.00%1.02% 1.40% 0.76% 0.13% 0.13% 0.00%3.43% NW 0.13%1.90% 0.76% 1.14% 0.63% 1.02% 1.27%6.73% NNW0.00%2.41% 2.54% 1.90% 2.03% 0.89% 3.05%12.82% 0.38%17.13% 18.15% 18.40% 15.48% 11.93% 18.53% 4- 45 L3 4-101 167. 3. OP-FTIR 2007/10/31 15:30 2007/11/05 10:18 4.5 1483 (1483 FTIR ) 4.5 OP-FTIR (propylene glycol monomethyl etheracetate, PGMEA) 4- 42 L3 OP-FTIR SF6 PFCs 2.5 ppb 0.03 ppb(1483 )SF6 (>OP-FTIR ) 51%50% L3 SF6SF6 L3 SF6 SF6 1 ppb SF6 100 FTIR 50% 50% 8.6 ppb 1.27 ppb (silane, SiH4) 8.7 ppb 0.11 ppb PECVD CVD OP-FTIR (PGMEA) 28.6 ppb 0.52 ppbPGMEA 6.8 ppb 0.26 ppb VOC () PGMEA L3 L3 4-102 168. 4- 42 L3 OP-FTIR 0 Compound (ppb) (ppb) (ppb) (ppb) Sulfur HexafluorideSF6 2.54 0.03 50.98% 20000 ---- Nitrous OxideN2O 8.58 1.27 54.01%-- ---- Silane SiH48.65 0.11 18.81%100---- unpleasant odor MethanolCH3OH 28.57 0.52 11.13% 400033000.00% Propylene Glycol C6H12O36.76 0.26 20.63% 2000 25 0.00% Methyl Ether Acetate,, AmmoniaNH3 2.56 0.11 10.99% 1000 43 0.00% 5. PFCs 6. -- 7. A/50A 8. Odor Thresholds for Chemicals with Established Occupational Health Standards, American Industrial Hygiene Association,1989.4-103 169. L3 L3 4- 43 L3 4- 43 L3 L3Methanol Silane SF6 PGMEA NH3 N2OMethanol1Silane0.0951 SF6 0.02 0.0151 PGMEA0.057 0.2620.2511NH3 0.006 0.1370.063 0.282 1N2O 0.027 0.1370.051 0.1690.0981L3 90 OP-FTIR L3 OP-FTIR OP-FTIR OP-FTIR 4- 46 4- 47 L3 / 4-104 170. 3 2.5SF6 (ppb) 2 1.5SF61 0.5 0 10/3110/3111/0111/0111/0211/02 11/03 11/03 11/04 11/0411/05 11/05 11/06 00:0012:0000:0012:0000:0012:00 00:00 12:00 00:00 12:0000:00 12:00 00:00 108N2O (ppb)64 N2O2010/31 10/3111/0111/0111/02 11/0211/03 11/03 11/04 11/0411/05 11/05 11/0600:00 12:0000:0012:0000:00 12:0000:00 12:00 00:00 12:0000:00 12:00 00:00108Silane (ppb)64 Silane 2010/3110/3111/0111/01 11/0211/02 11/03 11/03 11/04 11/0411/05 11/05 11/0600:0012:0000:0012:00 00:0012:00 00:00 12:00 00:00 12:0000:00 12:00 00:00 360270 ( ) 180 90010/31 10/3111/0111/0111/02 11/0211/03 11/03 11/04 11/0411/05 11/05 11/0600:00 12:0000:0012:0000:00 12:0000:00 12:00 00:00 12:0000:00 12:00 00:00 14 12 ( / ) 1086 42010/31 10/3111/0111/0111/02 11/0211/03 11/03 11/04 11/0411/05 11/05 11/0600:00 12:0000:0012:0000:00 12:0000:00 12:00 00:00 12:0000:00 12:00 00:00 4- 46 L3 OP-FTIR -1 4-105 171. 35Methanol (ppb) 30 25 20 15 Methanol105010/3110/3111/0111/0111/0211/0211/03 11/03 11/04 11/04 11/05 11/05 11/0600:0012:0000:0012:0000:0012:0000:00 12:00 00:00 12:00 00:00 12:00 00:00 8 PGMEA (ppb)64 PGMEA2010/31 10/3111/0111/0111/0211/0211/0311/03 11/04 11/04 11/05 11/05 11/0600:00 12:0000:0012:0000:0012:0000:0012:00 00:00 12:00 00:00 12:00 00:003 Ammonia (ppb) 2.5 2 1.5 NH3 1 0.5 0 10/3110/3111/0111/0111/0211/0211/0311/03 11/04 11/04 11/05 11/05 11/06 00:0012:0000:0012:0000:0012:0000:0012:00 00:00 12:00 00:00 12:00 00:00360270 ( ) 180 90010/31 10/3111/0111/0111/0211/0211/0311/03 11/04 11/04 11/05 11/05 11/0600:00 12:0000:0012:0000:0012:0000:0012:00 00:00 12:00 00:00 12:00 00:0014 12 ( / ) 108642010/31 10/3111/0111/0111/0211/0211/0311/03 11/04 11/04 11/05 11/05 11/0600:00 12:0000:0012:0000:0012:0000:0012:00 00:00 12:00 00:00 12:00 00:00 4- 47 L3 OP-FTIR -2 4-106 172. 4.3.2 4.3.2.1 S1 S1 8 0.18 1997 PFCs PFCs()1. Close-Cell FTIR PFCs 4- 48 S1 4- 44 PFC PFCs PFCs PFCs P01P02 P03 PFCs PFCs P01P02 P03 PFCs (FTIR) 28.5 1/4 Teflon S1 PFCs 96 9 7 90 FTIR 1cm-1 16 1 90 4-107 173. 4- 45 5 E101 A101VOC01P04 ST-VEX-01E102 A102 VOC02 P05 ST-VEX-01A104E103 A103SEX01 VOC03A105E104 A111 P01 ST-SEX-01SEX02 AEX01P02A106E105 A112 P06 ST-SEX-01SEX03 AEX02ST-AEX-01 P03 ST-SEX-01A107 E106 A113SEX04 AEX03 A108 T101SEX05A109 T102SEX06 A110 T103SEX07 T104 T104 4- 48 S1 4-108 174. 4- 44 S1 PFCs 1.11. 2. 12. 3. 13. 4. 14. 5. 15. 6. 16.-1.2 (T-LC) 7. 17. 8. 18. 9.19. P01 10. P02 1.13.(1%) P03 2.O2/He(30%) 14. 3. 15. 4.16. 5. 17.(Slurry) 6. 18.PH3/He(1%) 7. 19.O2/He(0.5%) 8. 20.(TEOS) 9. 21. 10. 22.CH4/Ar 11. 23.(TEPO) 12.24.(TEB) 4-109 175. 4- 45 S1 S1 S1-P01S1-P02S1-P03 96 9 7 90 (CMM)342.42032.2489.7 ()20.921.322.1 (% rh) 83.482.783.2 (m)28.5 m ()30.430.730.4 (% rh) 46.144.646.7 FTIR (mmHg) -522-506-4842. S1 PFCs 4- 46 S1 (SF6)(CF4)(C3F8)(C2F6)(CHF3)(N2O)(SiH4) PFCs SF6CF4C3F8C2F6 CHF3 PFCs SF6 CF4 C3F8 P01 P03 C2F6 P02 P03 CHF3 P03 PFCs N2O SiH4 4- 49 S1 PFCs PFCs CF4 P03 527 ppb 995 ppb P01 426 ppb PFCs P01 C3F8 625 ppb 1.15 ppmSF6 P03 11 ppbCHF3 P03 64.6 ppb 145 ppb4-110 176. PFCs N2O SiH4N2O 2.4 ppm~5.4 ppm P03 SiH4 116 ppb~220 ppb P01 : S1 4- 47~ 4- 49 4- 46 S1 P01P02 P03 Sulfur HexafluorideSF66.137.12.520.810.6124 Tetrafluoromethane CF44261219 479 1094527 995 Perfluoropropane C3F8 6251149 -- --9.7 165.9 PerfluoroethaneC2F6---- 29.1 370 231.1 1417 Trifluoromethane CHF3---- -- -- 64.6145 Nitrous OxideN2O4830 9567 237336285366 7834 Silane SiH4 220473206334116 269700625 600527 500 479 Concentration (ppb) 426 400300 23120010065296.1 2.510 11 0 CF4 C3F8 SF6CF4 C2F6SF6 CF4C3F8 C2F6CHF3 SF6 P01 P02P03 4- 49 S1 PFCs 4-111 177. 4- 47 S1 P01 4030 Concentration (ppb) 20SF610 00 5 101520253035404550556065 70 75 80 85 901500 Concentration 1000 (ppb)CF4 500 00 510152025303540 45 50 556065 70 75 80 85 901500 Concentration 1000 (ppb)C3F8500 00 510152025303540 45 50 556065 70 75 80 85 9012000 10000 Concentration8000 (ppb)6000N2O 40002000 00 51015202530354045505560 65 70 75 80 85 90500 400 Concentration 300 (ppb)SiH4 200 10000 510 1520253035404550556065 70 75 80 85 904-112 178. 4- 48 S1 P02 2520Concentration15(ppb) SF610 5 0 0 5 1015202530354045 5055 60 65 70 75 80 85 90 12001000Concentration 800(ppb) 600 CF4 400 200 0 0 510152025303540 4550 55 60 65 70 75 80 85 90 400 300Concentration(ppb)200 C2F6 1000 0 510 15202530354045 5055 60 65 70 75 80 85 90 4000 3000Concentration(ppb)2000 N2O10000 0 510152025303540 4550 55 60 65 70 75 80 85 90 400 300Concentration(ppb)200 SiH4 1000 0 510 15202530354045 5055 60 65 70 75 80 85 90 4-113 179. 4- 49 S1 P03 150 Concentration 100 (ppb)SF6 500 0 5 101520253035404550 55 60 65 70 75 80 85 901200 1000 Concentration800 (ppb)600CF4 4002000 0 5 101520253035404550 55 60 65 70 75 80 85 90200150 Concentration (ppb) 100C3F8500 0 5 101520253035404550 55 60 65 70 75 80 85 901500 Concentration 1000 (ppb)C2F65000 0 5 101520253035404550 55 60 65 70 75 80 85 90200150 Concentration (ppb) 100 CHF3 500 0 5 101520253035404550 55 60 65 70 75 80 85 90100008000 Concentration6000 (ppb)N2O 40002000 0 0 51015202530354045 50 55 60 65 70 75 80 85 90300 250 Concentration 200 (ppb) 150SiH4 10050 0 0 5 101520253035404550 55 60 65 70 75 80 85 90 4-114 180. S1 PFCs PFCs (GWP) PFCs (Million Metric Tons CarbonEquivalentMMTCE) 4- 50 4- 50 PFCs 4- 51 S1 PFCs CF4C3F8C2F6SF6 CHF3 4- 51 S1 PFCs C2F6 38% 4.66E-03 MMTCE 4- 50 P03 P02 PFCs CF4 35% 4.27E-03 MMTCE P03 C3F8 PFCs 18%SF6 CHF3 4% 5% PFCs PFCs 0.0123MMTCE4-115 181. 4- 50 S1 PFCs MMTCE CF4C3F8 C2F6SF6 CHF3 Kg/h MMTCE Kg/hMMTCE Kg/h MMTCE Kg/hMMTCE Kg/hMMTCE P011.87E-01 4.29E-04 5.86E-01 2.03E-03 -- -- 4.47E-034.00E-05-- -- 2.50E-03 P023.54E-02 6.90E-04-- -- 3.37E-03 1.37E-04 3.09E-04 2.35E-05-- -- 8.51E-04P035.57E-02 3.15E-03 2.19E-03 1.87E-04 3.83E-02 4.52E-03 1.86E-034.09E-04 5.43E-03 6.47E-04 8.92E-03 2.78E-01 4.27E-03 5.88E-01 2.22E-03 4.17E-02 4.66E-03 6.64E-034.72E-04 5.43E-03 6.47E-040.0123MMTCE 4-116 182. 1.00E-02CHF3 9.00E-03 SF6C2F6 8.00E-03 C3F8CF4 7.00E-03 6.00E-03 MMTCE 5.00E-03 4.00E-03 3.00E-03 2.00E-03 1.00E-03 0.00E+00 P01P02P03 S1 4- 50 S1 PFCs CHF3 SF65% 4%CF4 35% C2F6 38%C3F818% 4- 51 S1 PFCs 4-117 183. 1. 96/09/07 11:05 96/09/11 11:27 95 1140 9 FTIR 2 116 S1 OP-FTIR 4- 52 4- 52 S1 OP-FTIR 2. 4-118 184. 4- 53 4- 54 90% 41% 26.7% 22.2% 26 / 2 m/sec 4.3% 2 m/sec ~ 4 m/sec 360270 ( ) 180 90 0 07/09/07 07/09/08 07/09/0907/09/10 07/09/11 07/09/1286 ( / ) 42 0 07/09/07 07/09/08 07/09/0907/09/10 07/09/11 07/09/12 4- 53 S1 4-119 185. Total( 0.1~2 2~33~44~5 5~6 >6 (6 WSW 0.00%0.00% 0.09%0.00%0.00%0.00% 0.00%0.09% W 0.00%0.18% 0.18%0.09%0.09%0.00% 0.00%0.53% WNW 0.00%0.26% 0.18%0.09%0.09%0.09% 0.00%0.70% NW0.00%0.18% 0.61%0.35%0.09%0.00% 0.00%1.23% NNW 0.00%0.00% 0.18%0.18%0.35%0.09% 0.00%0.79% 0.00%4.30% 32.81% 41.93% 15.79% 4.56% 0.61% 4- 54S1 4-120 186. 3. S1 OP-FTIR 4- 51 5 PFCs PFCs 110ppb CF4 9.41ppb C2F6 41 PFCs 4- 55 10 Tetrafluoromethane86 (ppb) CF4420 07/09/07 07/09/08 07/09/09 07/09/10 07/09/11 07/09/12 10 Perfluoroethane86(ppb) C2F6 420 07/09/07 07/09/08 07/09/09 07/09/10 07/09/11 07/09/12 10 Sulfur Hexafluoride86(ppb) SF6420 07/0