臺灣博碩士論文加值系統

摘要
砷化鎵（Ga/As Gallium Arsenide）屬化合物半導體，在其磊晶製程使用砷
化氫氣體，從既往的文獻可以確定砷的環境流佈與人體危害有相當關聯性，由以
前的研究結果指出半導體晶圓廠離子植入機台維修作業時之砷作業環境測定結
果，但其空氣採樣樣品分析所偵測到的濃度大多很低且遠低於容鹵@度標準甚至
偵測不到。為瞭解化合物半導體廠作業人員的作業環境空氣中的暴露濃度，本研
究針對此製程機台的維修保養過程進行作業環境的空氣採樣，以瞭解作業人員的
可能暴露，另為推估化合物半導體廠砷化氫投入磊晶機台後砷的分佈，另進行廢
水採樣以瞭解整個砷的生命流程。故所以本研究包含為二個部份：第一為作業環
境砷的暴露採樣，第二為砷在製程的分佈推估採樣。
研究結果，作業環境測定皆低於偵測極限~0.00236mg/m3，均符合現有的法令
標準0.01mg/m3，設備維修人員若全程使用供氣式呼吸防護具，應可以有效保護維
修人員在進行維修保養過程不致有接觸砷及其化合物的機會，但是無塵室內機台
排列彼此相鄰，進行維修機台的過程若有氣體或微粒逸散則很容易會有擴散至鄰
近區域的人員，所以仍須多加注意。砷的生命流程顯示砷化氫投入機台後，約有
7.14%沈積於晶片與反應腔，60.92%於製程氣體補集器(process gas trap)捕集，
剩餘約31.73%進入尾氣洗滌塔(local scrubber)滌除，最後的0.21%由廠務端的
中央水洗塔(central scrubber)做最後的安全保護。此分佈結果大致符合機台在
製程氣體捕集器捕集大部份尾氣物質的設計。最後含砷廢水由化學處理單元將水
中砷轉變為含砷污泥，若廢水系統異常即可能導致放流水含砷濃度偏高的狀況。

ABSTRACT
Gallium Arsenide (Ga/As) is one of the semiconductors called “compound
semiconductor”. Arsine gas was used in the Ga/As epitaxy process. The arsenic
exposure in the environment has been known to strongly relate to the health hazards.
Previous studies on the work exposure of implanters in the semiconductor plants
showed very low or no detection of arsenic in the air sampling. To further understand
the work exposure of arsenic in the compound semiconductor plants, air sampling and
analysis during tool maintenance were performed. Furthermore to understand the
distribution of arsenic after the feed into the tool, wastewater sampling and analysis
were performed to assess the life cycle of the arsenic in the whole process. Thus, this
study comprised of two parts. The first part is the sampling and analysis of work
exposure of arsenic. The second part is the assessment of life cycle of arsenic in the
epitaxy process.
The results show that all work exposure sampling and analysis were lower than the
detection limits of 0.00236mg/m3, fulfill the requirement of current code requirement of
0.01 mg/m3. The maintenance staff can be protected properly from arsenic exposure if
self-breathing apparatus were used at all time. However as most tools were arranged
close to each other, other staff should be warned about the potential exposure. The life
cycle results show that 7.14% of arsenic feed was deposit on the wafer or in the reaction
chamber. 60.92% was collected in the process gas trap. The residual 31.73% entered the
local scrubbers. Only 0.21% entered the central scrubber. The results were in consistent
with the process gas trap where most exhaust materials should be trapped. Most
wastewater containing arsenic should be converted into arsenic sludge. However, it
should be noted that abnormal in the wastewater system may resulted in high
concentration in the effluent.

目 錄
頁次
中文提要 i
英文提要 ii
誌謝 iii
目錄 iv
表目錄 vii
圖目錄 ix
一、緒論 1
二、文獻探討 4
2.1 砷化鎵磊晶製程 4
2.1.1 半導體與化合物半導體的差異 4
2.1.2 半導體與化合物半導體的產品應用 5
2.1.3 化合物半導體的意義 7
2.1.4 化合物半導體磊晶的方法 7
2.1.5 化合物半導體員工的安全防護 9
2.2 砷的性質 10
2.2.1 砷的理化特性 10
2.2.2 砷的用途 14
2.2.3 砷的毒性效應 15
2.2.4 砷的代謝 16
v
2.2.5 砷的暴露標準 19
2.2.6 砷的生物偵測指標 21
三、材料與方法 24
3.1 研究對象 24
3.2 樣品的收集 24
3.2.1 作業環境空氣中砷的採樣 26
3.2.2 砷的分佈流程推估採樣 27
3.3 儀器與設備 28
3.3.1 採樣設備 28
3.3.2 分析儀器 29
3.3.3 試藥與試劑 30
3.4 分析方法 30
3.4.1 樣本分析方法 30
3.4.2 樣本分析前處理 31
3.4.3 分析方法的品管 33
四、分析結果 35
4.1 作業環境空氣採樣的濃度 35
4.2 砷的濃度分佈 38
五、討論 45
5.1 製程流程 45
5.2 砷的質量分佈 48
六、結論與建議 56
vi
參考文獻 59
附錄一 64
附錄二 75
附錄三 84
vii
表 目 錄
頁次
表2.1 週期表與半導體相關元素 4
表2.2 砷化鎵與矽元件特性比較 6
表2.3 化合物半導體磊晶生成法比較 8
表2.4 砷的物理性質 12
表2.5 砷化氫的物理性質 12
表2.6 砷及其無機化合物等相關物種名稱編號一覽表 13
表2.7 我國與其他國家空氣中砷及其無機化合物容鹵@度一覽表 20
表2.8 工業先進國家砷的生物偵測指標值 22
表4.1 空氣採樣濾紙分析結果 37
表4.2 第一次水樣含砷量分析結果 40
表4.3 第二次水樣含砷量分析結果 41
表4.4 第三次水樣含砷量分析結果 42
表4.5 分析方法品管-樣品重複分析 43
表4.6 分析方法品管-檢量線查核分析 43
表4.7 三次水樣砷濃度比較表 44
表5.1 三次水樣的砷質量重 48
表5.2 三次水樣的平均砷質量重與標準差 50
表5.3 砷在磊晶製程的分佈 52
viii
表5.4 Process Gas Trap 推估每部機台每日的砷捕集量 54
表5.5 進流水總砷與放流水總砷的比較 55
ix
圖 目 錄
頁次
圖2.1 人體內無機砷代謝途徑 18
圖3.1 砷化氫於製程的生命流程 25
圖3.2 空氣樣本採樣位置 26
圖3.3 含砷廢水的採集位置 28
圖4.1 空氣樣本濾紙分析檢量線 36
圖4.2 第一次水樣含砷量分析檢量線 38
圖4.3 第二次水樣含砷量分析檢量線 39
圖4.4 第三次水樣含砷量分析檢量線 39
圖5.1 砷化鎵磊晶製程流程 47
圖5.2 砷在磊晶製程分佈的比例 52
圖5.3 清洗區砷質量重與Process Gas Trap 捕集量比較 54
圖6.1 進流水總砷量與污泥總砷量比較 57

參 考 文 獻
1. ATSDR(2000)： Toxicological profiles for arsenic. U.S. Agency for
Toxic Substances and Disease Registry, Atlanta, GA.
2. Buchet, J.P., Lauwerys, R., Roels, H.(1981a)： Comparison of the
uinary excretion of arsenic metabolites after a single oral dose
of sodium arsenite, monomethylarsonate or dimethylarsinate in
man. Int. Arch. Occup. Environ. Health. 48:71-79.
3. Buchet, J.P., Lauwerys, R., Roels, H.(1981)：Urinary excretion
of inorganic arsenic and its metabolites after repeated ingestion
of sodium meta arsenite by volunteers. Int Arch Occup Environ
Health. 48：111-118.
4. Buchet, J.P., Lauwerys, R.(1985)：Study of inorganic arsenic
methylation by rat liver in vitro：relevance for interpretation
of observation in man. Arch Toxicol. 57：125-131.
5. Buchet, J.P., Lauwerys, R.(1987)：Study of factors influencing
the in vivo methylation of inorganic arsenic in rats. Toxicol Appl
Pharmacol. 91：65-74.
6. Chen, C.J., Chuang, Y.C., Lin, T.M., et al.(1985)： Malignant
neoplasms among residents of black foot disease –endemic area
in Taiwan:high arsenic artesian well water and cancers. Cancer
Res；45：5895-5899.
7. Chen, C.J., Chuang, Y.C., You, S.L., et al.(1986)： A
retrospective study on malignant neoplasms of bladder, lung and
liver in blackfoot disease endemic area in Taiwan. Br J Cancer；
53：399-405.
8. Chen, C. J.,wang, c.j.(1990)： Ecologicalation between arsenic
level in well water and age-adjusted mortality from malignant
neoplasms. Cancer Res；50：5470-5474.
9. Chiou, H.Y., Hsueh, Y.M., sieh, L.L. (1997)：Arsenic methylation
capacity, body retention, and null genotypes of glutathione
60
S-transferase M1 and T1 among current arsenic exposured residents
in Taiwan. Mutat Res. 386:197-207.
10. Crecelius, E.A.(1977)：Changes in the chemical speciation of
arsenic following ingestion by man. Environ Health Perspect. 19：
147-150.
11. Dagani,R.(1994)：New transistor class is based on chem.eng news
72-8.
12. Foa, V., Colombi, A., Maroni, M. et al. (1987)： Arsenic In:
biological indicators for the assessment of human exposure to
industrial chemicals.
13. Gerhartz, W., Yamamoyo, Y.S., Capbell, F.T. et al.(1985)：
Ullmann’s encyclopedia of industrial chemistry. Vol. A3
Germany：VCH Verlagsgesellschaft.
14. Hayes, R.B.(1997)： The carcinogenicity of metals in humans.
Cancer Causes Control. 8:371-385.
15. Hutchinson, T.C., Meema, K.M.(1987)：Lead, mercury, cadmium and
arsenic in the environment. Scientific Committee on problems of
the Environment (SCOPE).
16. Hatleild, B., Brailford, C., Carter, D.E.(1996)：Reaction of
arsine with hemoglobin.J. Toxicl. Environ Health. 47:145-157.
17. Hwang, Y.H., Lee, Z.Y., Wang, J.D. et al. (2002)：Monitoring of
arsenic exposure with speciated urinary inorganic arsenic
metabolites for ion implanter maintenance engineers. Environ
Res. 90:207-216.
18. IARC(1980)：IARC monographs on the evaluation of the carcinogenic
risk of chemicals to man:some metals and metallic compounds. IARC.
23.
19. IARC(1987) ： Evaluation of Carcinogenic Risks to Humans.
Supplement 7. Lyon, France, International Agency for Research on
Cancer, 100-106.
20. Lagerkvist, B.E.A., Linderholm, H., Nordberg, G.F.(1988)：Arsenic
and Raynaud’s phenomenon vasospastic tendency and excretion of
61
Arsenic in smelter workers before and after the summer vacation.
Int. Arch. Occup. Envorion. Health. 60:361-364.
21. Luster, M.I., Portier, C., Pait, D.G., White, K.F., Jennings, C.,
Munson, A.E, Rosenthal, G.J.（1994）：Risk assessment in
immunotoxicity I. Toxicol 18 200-210.
22. Malachowski, M.E. (1990)：An update on arsenic. Clin. Lab. Med.,
10：459-71.
23. Marafante, E.,Vahter, M.,Envall, J.(1985)： The role of the
methylation in the detoxification of arsenate in the rabbit. Chem
Biol Interac.;56:225-238.
24. Marafante, E.,Vahter, M., Norin, H., Envall, J., Sandstrom, M.,
Christakopoulos, A., Ryhage, R.(1987)：Biotransformation of
dimethylarsinic acid in mouse hamster and man. J Appl
Toxicol;7:111-117.
25. Nordwall, B.D.(1994)： Gallium Arsenide Chipsfind Commercial use.
Aviation week space Tech I40,54-55.
26. Parmeggiani, L.(1983)： Encyclopaedia of occupational health and
safety. Vol 1.International Labour Organisation.
27. Shenai-Khatkhate, Deodatta. V., Goyette, Randall j., Dripps,
Gregory. (2004)：Environment,health and safety issues for sources
used in MOVPE growth of compound semiconductors. Journal of
Crystal Growth 272:816~821.
28. Tam, G.K.H., Charbonneau, S.M., Bryce, F. et al. (1979) ：
Metabolism of inorganic arsenic in humans following oral
ingestion. Toxicol. Appl. Pharmacol. 50：310-322.
29. Thampson, D.J. (1993)： A chemical hypothesis for arsenic
methylation in mammals. Chem Biol Interac.;88:89-114.
30. Vahter, M.(1994)：Species differences in the metabolism of arsenic
compounds. App Org Chem. 8：175-182.
31. Vahter, M., Friberg, L., Rahnsten, B. et al.(1986)：Airborne
arsenic and urinary excretion of metabolites of inorganic arsenic
among smelter workers. Int. Arch. Occup. Environ. Health.
62
57:79-91.
32. Vahter, M., Marafante, E.(1988) ： In vivo methylation and
detoxification of arsenic in biological alkylation of heavy
elements, Craig PJ and Glockling F(Eds), Royal Society of
chemistry, U.K., p105-109 .
33. Venugopal, B., Luckey, T. D. (1978)： Metal toxicity in mammals.
plenum, New York.
34. Welch, K., Higgins, I., Oh, M. et al. (1982)：Arsenic exposure,
smoking and respiratory cancer in copper smelter Workers. Arch.
Environ Contam. Toxicol. 31(1):24-37.
35. Willardson, R.K.(1983)：Arsenic,in electronic,In arsenic -
industrial, biochemical. Environmental Perspective.
36. Wolff, S.P., Garner, A., Dean, R.T. (1986)：Free radicals, lipid
and protein degration. Trends Biochem. Sci., 11：27-31
37. World Health Organization (1981)：Environmental Health Criteria
18: Arsenic.
38. World Health Organization (1992)：Inorganic arsenic compounds
other than arsine .
39. Zybura, M.F.(1995)： Efficient computer aided design of GaAs and
InP millimeter wave transferred electron devices including
thermal analysis. Solid state Electron 38:873-880.
40. 莊達人 (1996)：VLSI製造技術 高立圖書有限公司.
41. 行政院勞工委員會(2003)：勞工作業環境空氣中有害物容鹵@度標準,
行政院勞工委員會.台北.
42. 行政院勞工委員會勞工安全衛生研究所：＂由勞工健康保護規則及國外
有關制度探討我國生物偵測技術之建立＂，29-49頁 (1993)
43. 行政院勞委會勞工安全衛生研究所（2003）：半導體砷作業勞工健康危
害評估.
44. 行政院勞委會勞工安全衛生研究所：採樣通則、分析方法之品質管制.
45. 行政院勞委會勞工安全衛生研究所：採樣分析建議方法-3002 砷.
46. 行政院環境保護署（2003）：污泥及沈積物中重金屬檢測方法-酸消化
法. NIEA R353.00C.
63
47. 行政院環境保護署（2004）：水中砷檢測方法-自動化連續流動式氫化
物原子吸收光譜法. NIEA W434.53B.
48. 邱弘毅， 葉錦瑩， 薛玉梅， 陳建仁 (1994)：台灣地區砷、汞、鎘及
其化合物之用途和用量調查研究。中華衛誌; 13: 113-125.
49. 黃偉益(1995) 碩士論文：飲用含砷井水與腦血管疾病相關性之流行病
學研究.
50. 陳相志（1997）碩士論文：晶圓製造廠離子植入機台維修保養工作之砷
暴露研究.
51. 林碧珍（2000）碩士論文：利用高效能液相層析及流動注入氫化產生原
子吸收光譜法進行尿液中砷物種之生物偵測研究.高雄
52. 顔士閔（2003）碩士論文：光電業含砷廢水處理-化學沈降和流體化床
法之評估.新竹.
53. 郭瑞雄（2004）碩士論文：銅泊製造工廠三氧化二砷作業勞工暴露風險
評估.高雄.