표제지
목차
국문요약 16
I. 서론 19
II. 이론적 배경 22
2.1. 반도체 공정의 이해 22
2.1.1. 반도체 산업의 정의 22
2.1.2. 반도체 제조공정 흐름도 23
2.1.3. Photo 공정의 개요 26
2.1.4. Photo 공정에서 사용하는 화학물질 27
2.2. 화학물질 사고 통계 및 반도체 공정의 사고사례 29
2.2.1. 화학물질 사고현황 및 원인분석 29
2.2.2. 반도체 산업의 사고사례 30
2.3. 위험물의 특성 34
2.3.1. 제 4류 위험물의 정의 및 종류 34
2.3.2. 제 4류 위험물의 예방대책 및 소화방법 35
2.4. 화학물질 분류표시(GHS)와 물질안전보건자료(MSDS)의 이해 36
III. 인화점 및 자연발화온도, 폭발한계의 이론적 배경 37
3.1. 인화점 37
3.1.1. 인화성 액체의 분류기준 38
3.1.2. 물리적 위험성 분류 39
3.1.3. 인화성 액체의 판정논리 39
3.2. 자연발화온도(Autoignition Temperature, AIT) 41
3.2.1. 물리적 위험성 분류 42
3.2.2. 자연발화성 물질의 판정논리 42
3.3. 열발화 이론에 의한 자연발화온도와 발화지연시간 44
3.3.1. Semenov 모델 44
3.3.2. 자연발화온도에 관한 실험적 연구 46
3.4. 발화온도에 의한 발화시간 적용을 위한 다중회귀분석 47
3.5. 인화점과 자연발화온도에 영향을 주는 인자 49
3.6. 인화점에 의한 폭발한계 예측 50
3.7. 3성분계의 인화점 및 자연발화온도(AIT) 예측 방법 51
3.7.1. 경험식에 의거한 예측모델 51
3.7.2. 실험값과 예측값의 비교 방법 52
IV. 실험재료 및 측정방법 54
4.1. 실험재료 54
4.2. 인화점 실험 54
4.2.1. 인화점 측정장치 54
4.2.2. 인화점 측정방법 55
4.3. 자연발화온도 실험 56
4.3.1. 자연발화온도 측정장치 56
4.3.2. 자연발화온도 측정방법 57
V. 결과 및 고찰 58
5.1. 순수물질의 화재 및 폭발 특성치 분석 58
5.1.1. Isopropyl alcohol(IPA) 58
5.1.2. Hexamethyldisilazane(HMDS)의 인화점 측정 및 폭발한계 65
5.1.3. Propylene glycol monomethyl ether(PGME)의 인화점 측정 및 폭발한계 72
5.2. IPA + HMDS + PGME 3성분계의 인화점 79
5.2.1. 인화점 측정 79
5.2.2. 인화점 계산 81
5.3. IPA + HMDS + PGME 3성분계의 자연발화온도 84
5.3.1. IPA(0.2) + HMDS(0.7) + PGME(0.1)계의 자연발화온도 84
5.3.2. IPA(0.2) + HMDS(0.5) + PGME(0.3)계의 자연발화온도 88
5.3.3. IPA(0.2) + HMDS(0.3) + PGME(0.5)계의 자연발화온도 92
5.3.4. IPA(0.2) + HMDS(0.1) + PGMEr(0.7)계의 자연발화온도 96
5.3.5. IPA(0.3) + HMDS(0.5) + PGME(0.2)계의 자연발화온도 100
5.3.6. IPA(0.3) + HMDS(0.2) + PGME(0.5)계의 자연발화온도 104
5.3.7. IPA(0.5) + HMDS(0.4) + PGME(0.1)계의 자연발화온도 108
5.3.8. IPA(0.5) + HMDS(0.1) + PGME(0.4)계의 자연발화온도 112
5.3.9. IPA(0.7) + HMDS(0.2) + PGME(0.1)계의 자연발화온도 116
5.4. IPA + HMDS + PGME 3성분계의 조성변화에 대한 AIT 예측 120
VI. 결론 127
6.1. 순수물질의 인화점, 자연발화온도 및 폭발한계 127
6.2. IPA + HMDS + PGME 3성분계의 인화점 128
6.3. IPA + HMDS + PGME 3성분계의 자연발화온도 129
참고문헌 131
ABSTRACT 135
Table 1. Chemicals used in the photo process 28
Table 2. Cases of accidents caused by chemicals in the semiconductor manufacturing industry 31
Table 3. Criteria for determining flammable liquids 38
Table 4. Label elements of flammable liquids of GHS 39
Table 5. Label elements of autoignition material of GHS 42
Table 6. Constant value of pure substance 50
Table 7. Manufacturers and purity and experimental materials 54
Table 8. Flash points, AITs and explosion limits IPA by several references 59
Table 9. Estimated lower explosion limits(LEL) with experimental lower flash points of IPA 60
Table 10. Experimental ignition delay time by the AIT of IPA 63
Table 11. Flash points, AITs and explosion limits HMDS by several references 66
Table 12. Estimated lower explosion limits(LEL) with experimental lower flash points for HMDS 67
Table 13. Experimental ignition delay time by the AIT of HMDS 70
Table 14. Flash points, AITs and explosion limits PGME by several references 73
Table 15. Estimated lower explosion limits(LEL) with experimental lower flash points for PGME 74
Table 16. Experimental ignition delay time by the AIT of PGME 77
Table 17. Experimental and the calculated flash points for IPA(X₁) + HMDS(X₂) + PGME(X₃) system 82
Table 18. Experimental and calculated delay time by the AIT for IPA(0.2) + HMDS(0.7) + PGME(0.1) system 85
Table 19. Experimental and calculated delay time by the AIT for IPA(0.2) + HMDS(0.5) + PGME(0.3) system 89
Table 20. Experimental and calculated delay time by the AIT for IPA(0.2) + HMDS(0.3) + PGME(0.5) system 93
Table 21. Experimental and calculated delay time by the AIT for IPA(0.2) + HMDS(0.1) + PGME(0.7) system 97
Table 22. Experimental and calculated delay time by the AIT for IPA(0.3) + HMDS(0.5) + PGME(0.2) system 101
Table 23. Experimental and calculated delay time by the AIT for IPA(0.3) + HMDS(0.2) + PGME(0.5) system 105
Table 24. Experimental and calculated delay time by the AIT for IPA(0.5) + HMDS(0.4) + PGME(0.1) system 109
Table 25. Experimental and calculated delay time by the AIT for IPA(0.5) + HMDS(0.1) + PGME(0.4) system 113
Table 26. Experimental and calculated delay time by the AIT for IPA(0.7) + HMDS(0.2) + PGME(0.1) system 117
Table 27. Experimental and the predicted AITs of IPA(X₁) + HMDS(X₂) + PGME(X₃) system 121
Table 28. The predicted equation of activation energy by AIT of IPA + HMDS + PGME system 125
Fig. 1. Semiconductor applications. 23
Fig. 2. Semiconductor manufacturing process. 24
Fig. 3. Concept of photo process. 27
Fig. 4. Status of chemical accidents by cause. 29
Fig. 5. Washing process diagram and reactor equipment. 32
Fig. 6. Fire during filter cleaning in coating solution manufacturing process. 33
Fig. 7. HF leak accident site. 33
Fig. 8. Flash point for a pure substance by means of vapor pressure and flammable limit. 38
Fig. 9. Mixture determination logic of flammable liquids of GHS. 40
Fig. 10. Mixture determination logic of autoignition liquid of GHS. 43
Fig. 11. Photograph of Seta flash apparatus (Setaflash Series 8 Active Cool). 55
Fig. 12. Photograph autoignition temperature apparatus(ASTM E659-78). 56
Fig. 13. Monitoring program of AIT of IPA. 62
Fig. 14. Experimental and calculated ignition delay time for IPA. 64
Fig. 15. Monitoring program AIT of HMDS. 69
Fig. 16. Experimental and calculated ignition delay time for HMDS. 71
Fig. 17. Monitoring program of AIT of PGME. 76
Fig. 18. Experimental and calculated ignition delay time for PGME. 78
Fig. 19. Experimental flash point distribution of IPA + HMDS + PGME system. 80
Fig. 20. Experimental and Calculated flash points by Eqn.(32). 83
Fig. 21. Monitoring program of AIT of IPA(0.2) + HMDS(0.7) + PGME(0.1) system. 86
Fig. 22. Experimental and calculated ignition delay time for IPA(0.2) + HMDS(0.7) + PGME(0.1) system. 87
Fig. 23. Monitoring program of AIT of IPA(0.2) + HMDS(0.5) + PGME(0.3) system. 90
Fig. 24. Experimental and calculated ignition delay time for IPA(0.2) + HMDS(0.5) + PGME(0.3) system. 91
Fig. 25. Monitoring program of AIT of IPA(0.2) + HMDS(0.3) + PGME(0.5) system. 94
Fig. 26. Experimental and calculated ignition delay time for IPA(0.2) + HMDS(0.3) + PGME(0.5) system. 95
Fig. 27. Monitoring program of AIT of IPA(0.2) + HMDS(0.1) + PGME(0.7) system. 98
Fig. 28. Experimental and calculated ignition delay time for IPA(0.2) + HMDS(0.1) + PGME(0.7) system. 99
Fig. 29. Monitoring program of AIT of IPA(0.3) + HMDS(0.5) + PGME(0.2) system. 102
Fig. 30. Experimental and calculated ignition delay time for IPA(0.3) + HMDS(0.5) + PGME(0.2) system. 103
Fig. 31. Monitoring program of AIT of IPA(0.3) + HMDS(0.2) + PGME(0.5) system. 106
Fig. 32. Experimental and calculated ignition delay time for IPA(0.3) + HMDS(0.2) + PGME(0.5) system. 107
Fig. 33. Monitoring program of AIT of IPA(0.5) + HMDS(0.4) + PGME(0.1) system. 110
Fig. 34. Experimental and calculated ignition delay time for IPA(0.5) + HMDS(0.4) + PGME(0.1) system. 111
Fig. 35. Monitoring program of AIT of IPA(0.5) + HMDS(0.1) + PGME(0.4) system. 114
Fig. 36. Experimental and calculated ignition delay time for IPA(0.5) + HMDS(0.1) + PGME(0.4) system. 115
Fig. 37. Monitoring program of AIT of IPA(0.7) + HMDS(0.2) + PGME(0.1) system. 118
Fig. 38. Experimental and calculated ignition delay time for IPA(0.7) + HMDS(0.2) + PGME(0.1) system. 119
Fig. 39. Experimental autoignition temperature distribution of IPA + HMDS + PGME. 123
Fig. 40. Comparison of autoignition temperature Eqn.(53) with experiment data for IPA + HMDS + PGME system. 124