論文摘要
本篇論文共分為兩部分，我們使用低能電子繞射(LEED)、歐傑電子能譜(AES)、程溫脫附法(TPD)、二次離子質譜(SIMS)及同步輻射軟X光光電子光譜(SXPS)等表面分析技術，作為偵測材料表面鍵結狀態、組成以及結構在化學反應過程中改變的工具。在有關氣體分子在材料表面反應的研究，我們觀察在低溫100K時，一氧化碳(CO18)在Pd(110)單晶表面上鍵結吸附的情形，並且藉由改變表面的溫度或是照射同步輻射白光，觀看一氧化碳的吸附位置及狀態的改變，以及Pd(110)表面結構的變化。在低溫100K時，一氧化碳分子主要是吸附在bridge site，形成CO islands 結構。反應溫度升高時， CO islands的面積也隨著增加；當升溫至340K時，Pd(110)表面產生missing row重構面。而若Pd表面先吸附一氧化碳之後再照射同步輻射白光，將會有新的化學產物生成，其化學式分別為Cn(CO)及Cn(CO)2，隨著白光照射時間及Pd表面溫度的改變，這些產物在表面的數目也各有消長。另外，在有關蝕刻化學的研究上，我們選擇目前光電材料研究中最熱門的氮化鎵(GaN)為材質，而以蝕刻上最常使用的氯氣(Cl2)作為反應氣體。在低溫100K時，隨著氯氣曝露量的增加，GaCl為最先生成的產物，而GaCl2與GaCl3則分別在較高的曝露量(2L與6L)產生。當GaN表面達到飽合覆蓋量時，GaCl與GaCl2為主要的產物；隨著表面溫度不斷昇高，GaCl的含量逐漸下降，而GaCl2與GaCl3的含量慢慢多於GaCl，表示升溫過程中，GaCl會再進一步與氯原子形成含氯數較高且揮發性較高的產物。經由實驗結果，我們對於氯氣在GaN上蝕刻反應的機制能有較清楚的瞭解。

Abstract
About the chemical reaction of the adsorbed gas on material, we use the reaction of CO18 with the Pd(110) surface as a model system. The effect of the surface temperature and the exposure on the variation of the chemical state of CO18 present on the surface is measured by soft X-ray photoelectron spectroscopy (SXPS) which employs synchrotron radiation and temperature programmed desorption(TPD). Increasing the exposure at 100 K, the C1s spectrum exhibits two emission bands and is dominated by the photoemission of CO18 in bridge site. It appears that CO islands are formed, which is surrounded by a disordered sea. With increasing surface coverage increases the number and average size of islands reducing the number of molecules left in the disordered sea. When a CO-saturated surface is annealed to about 323 K, a CO-induced missing row reconstruction of the Pd(110)surface occurs. It is confirmed by theα3 state peak of CO18 in thermal desorption spectra data and new emission features at binding energies of 286.0 and 286.3 eV for CO bonding to bridge sites on the ridges and in the grooves of Pd(110).
When a CO-saturated surface is irradiated by synchrotron radiation white beam , the C 1s spectrum exhibits two emission bands and is dominated by lower binding-energy band. The lower binding-energy band which contains three deconvolution peaks assigns to new chemical species with general formula as Cn(CO) and Cn(CO)2. The effect of the irradiation time and the surface temperature on the variation of these new chemical species present on the surface is also discussed.
Regarding to the research of corrosion chemistry, we use GaN as a model substrate to study the etching reaction of chlorine on the nitride surface. The etching process of Cl on the surface is monitored at various substrate temperatures and chlorine exposures. Results from secondary ion mass spectrometric measurements reveal that the GaN surface is chlorinated upon chlorine exposure, with an increasing yield of the GaClx species formed on the surface at higher chlorine exposures. The chlorination reaction occurs stepwise, with gallium monochloride formed prior to the dichloride at 100K. The range of x also increases with the amount of chlorine exposed to GaN. The variation with the substrate temperature of the population of different Cl states on the surface is examined by coupling synchrotron-radiation core-level spectroscopy. A surface etching mechanism of GaN by chlorine is proposed based on the analysis of Ga3d core-level spectra.

第一章 緒論 1
1.1表面科學及其在半導體工業與觸媒催化之應用 1
1.2表面之重構現象(Reconstruction) 4
1.3一氧化碳吸附在Pd(110)單晶之反應機構 6
1.3.1簡介 6
1.3.2 CO-Pd之鍵結軌域研究 8
1.3.3 CO/Pd(110)之吸附位置研究 10
1.3.4 CO /Pd (110)之表面結構研究 13
1.3.5 CO/Pd(110)之氣體表面擴散研究 19
1.4 CO/Ni(110)、CO/Pd(110) 、CO/Pt(110)反應系統之比較 22
1.5 CO/Pd(111)、CO /Pd(110) 、CO/Pd(100)反應系統之比較 28
第二章 實驗儀器、方法與步驟 31
2.1 實驗之超高真空系統 31
2.2樣品處理及清潔 34
2.3實驗之氣體處理與氯氣製造器之製作 36
2.4表面分析技術之量測 37
2.4.1 低能電子繞射(LEED) 37
2.4.2 歐傑電子能譜 37
2.4.3 軟X光光電子發射能譜（SXPS） 39
2.4.4 二次離子質譜 39
2.4.5 層溫脫附法(TPD) 40
2.4.6 資料處理 42
第三章 實驗結果與討論 43
3.1 SXPS於分子吸附及蝕刻化學之研究 43
3.2一氧化碳在低溫吸附於Pd(110)表面之研究 44
3.3溫度對一氧化碳吸附於Pd(110)表面之影響研究 59
3.4 一氧化碳氧同位素於Pd (110)表面之程溫脫附實驗 62
3.5 照射同步輻射白光後對一氧化碳吸附於Pd (110)表面之影響研究
74
3.6蝕刻化學：氯氣(Chlorine)在氮化鎵(Gallium Nitride)表面之蝕刻反應研究 90
3.6.1 前言 90
3.6.2低溫蝕刻 94
3.6.2表面升溫的影響 95
第四章 結論117
Reference 122

Reference:
1. W.J.Kaiser, L.D.Bell, Phys. Rev. Lett. 60(1988)1406
2. R.J.Hamers, R.M.Tromp, J.E.Demuth, Phys. Rev. B34(1986)5343
3. T.Gritsch, D.Coulman, R.J.Behm, G. Ertl, Phys. Rev. Lett. 63(1989)1086
4. W.Moritz and D.Wolf, Surf. Sci.,163(1985)L655
5. I.K.Robison, Phys. Rev. Lett. 50(1983)1145
6. E.C.Sowa, M.A.van Hove, D.L.Adams, Surf. Sci. 199(1988)174
7. G.L.Kellog, Phys. Rev. Lett. 55(1985)2168
8. P.Ferry, W.Moritz, D.Wolf, Phys. Rev. B 38(1988)7275
9. D.J.Coulman, J.Wintterlin, R.J. Behm and G.Ertl, Phys. Rev. Lett.64(1990)1761
10. I.Stensgaard, L.Ruan, F.Besenbacher, F.Jensen and E.Laegsgarrd, Surf. Sci. 269/270(1992)81
11. T.Hashizume, M.Tanigichi, K.Motai, H.Lu, K.Tanaka, T.Sakurai, Jpn.J.Phys.30(1991)L1529
12. P.W.Murray, F.M.Leibsle, Y.Li, Q..Gau, M.Bowker, G.Thornton,V.R. Dhanak, K.C.Prince , R.Rosei, Phys. Rev. B 47(1993)12976
13. L.Ruan, I.Stensgaard, F.Benbacher, E.Lagsgaard, Phys. Rev. Lett. 71(1993)2963
14. S.H.Overbury, R.J.A. van den Oetelaar, Surf. Sci. 301(1994)313
15. D.R.Mullins, S.H.Overbury, Surf. Sci 210(1989)481
16. C.M. Chan, M.A. Van Hove, Surf. Sci. 171(1986)226
17. J.D.Wrigley, G.Ehrlich, Phys. Rev. Lett. 44(1980)661
18. G.Binnig, H.Rohrer,Ch.Gerber,E.Weibel, Surf. Sci.131(1983)L379
19. L.D.Marks, Phys. Rev. Lett. 51(1983)1000
20. S.H.Overbury,W.Heiland, D.M.Zehner, S.Datz, R.S. Thoe, Surf. Sci.109(1981) 238
21. M.Copel, T.Gustaffsson, Phys. Rev. Lett. 57(1986)723
22. D.Tomanek, H.J.Brocksch, K.H.Bennemann, Surf. Sci. 138(1984)
L129
23. H.J.Brocksch, K.H.Bennemann, Surf. Sci. 161(1985)321
24. M .S.Daw, Surf.Sci. 166(1986)L161
25. J .W.Davenport, M.Weinert. Phys. Rev. Lett. 58(1987)1382
26. K.M.Ho, K.P.Bohnen, Bull. Am. Phys. Soc. 32(1987)771
27. S.M.Foiles, Surf. Sci. 191(1987)L779
28. G.Blyholder, J. Phys.Chem. 68(1964)2772
29. B.GumHalter, K.Wandelt, Ph. Avouris, Phys. Rev. B37(1988)8048
30. Ph. Avouris, Physica Scripta. 35(1987)47
31. J.Yoshinobu, M.Kawai, S.I.Tanaka, K. Watanabe, Y. Matsumoto,M.Kamada, J. Electron Spect. Related Phenom. 88-91(1998)665
32. G. Ertl, P.Rau, Surf. Sci. 15(1969)443
33. H.Conrad, G.Ertl, J.Koch, E.E. Latta, Surf. Sci. 43(1974)462
34. J.He, P.R.Norton, J.Chem.Phys. 89(1988)1170
35. R.Raval, S.Haq, M.A.Harrison, G.Blyholder, D.A.King, Chem. Phys.Lett. 167(1990)391
36. R.M.Lambert , Surf. Sci. 49(1975)325
37. A.Wander, P.Hu, D.A.King, Chem. Phys. Lett. 201(1993)393
38. P.Hu, L.Morales de la Garza, R.Raval, D.A.King, Surf. Sci.
249(1991)1
39. R.Raval, S.Haq, M.A.Harrison, G.Blyholder, D.A.King, J. Electron Spect. Related Phenom. 54/55(1990)629
40. R.Raval, M.A.Harrison, D.A.King, Surf. Sci. 211/212(1989)61
41. M.G.Ramsey, F.P. Leisenberger, F.P.Netzer, A.J.Roberts, R.RavalSurf. Sci. 385(1997)207
42. I.Z.Jones, R.A.Bennett, M.Bower, Surf. Sci. 402-404(1998)595
43. A.Locatelli, B.Berna, S.Lizzit, G.Comelli, G.Cautero, G.Paolucci, R. Rosei, Phys. Rev. Lett. 73(1994)90
44. A.Locatelli, B.Berna, S.Lizzit, G.Comelli, G.Cautero, G.Paolucci, R. Rosei, Phys. Rev. B 54(1996)2839
45. M.A.Chesters, G.S.Mcdougall, M.E. Pemble, N.Sheppard, Surf. Sci.164(1985)425
46. J.Goschnick, M.Wolf, M.Grunze, W.N. Unertl, J.H.Block, J.Loboda-Cackovic, Surf. Sci. 178(1986)831
47. R.A.Bennett, S.Poulston, I.Z.Jones, M.Bowker, Surf. Sci. 401 (1998)831
48. C.J.Barnes, M.Q.Ding, M.Lindroos, R.D.Diehl, D.A.King, Surf. Sci.162(1985)59
49. C.J. Barnes, M.Lindroos, D.A.King, Surf. Sci. 201(1988)108
50. P.Hu, D.A.King, S.Crampin, M.H.Lee, M.C.Payne, Chem. Phys.
Lett. 230(1994)501
51. R.Ramprasad, K.M.Glassford, J.B.Adams, R.I.Masel, Surf. Sci.
360(1996)31
52. P.Hu, D.A.King, S.Crampin, M.H.Lee, M.C.Payne, J. Chem. Phys.107(1997)8103
53. X.D. Xiao, X.D. Zhu, W.Daum, Y.R.Shen, Phys. Rev. B 48(1993)
315
54. X.D. Xiao, X.D. Zhu, W.Daum, Y.R.Shen, Phys. Rev. B 46(1992)
9732
55. X.D. Xiao, X.D. Zhu, W.Daum, Y.R.Shen, Phys. Rev. Lett. 66
(1991)2352
56. H.H.Madden, J. Kuppers, G.Ertl, J. Chem. Phys. 58(1973)3401
57. K.Kilrer, A.C.Zettlemoyer, H.Leidheiser, J.Chem.Phys. 52(1970 )589
58. H.H. Madden, G.Etrl, Surf. Sci. 35(1973)211
59. C.M.Comrie, R.M.Lambert, Faraday Trans. I 7(1976)1659
60. R.W. McCabe, L.D.Schmidt, Surf. Sci. 60(1976)439
61. S.Haq, J.G. Love, D.A.King, Surf. Sci. 275(1992)170
62. D.J. Hannaman, M.A. Passler, Surf. Sci. 203(1988)449
63. B.Voigtlander, D.Bruchmann, S.Lehwald, H.Ibach, Surf. Sci. 225(1990)151
64. T.N.Talyer, P.J.Estrup, J. Vac. Sci. Technol., 10(1973)26
65. T.E.Jackman, J.A.Davies, D.P.Jackson, W.N.Unertl, Surf. Sci. 120(1982)Surf. Sci. 389
66. P.Hofmann, S.R.Bare, D.A.King, Surf. Sci. 117(1982)245
67. S.R.Bare, K.Griffiths, P.Hofmann, D.A.King, G.L.Nyberg,
N.V.Richardson, Surf. Sci. 120(1982)367
68. T.E.Jackson, W.N.Unertl, J.A.Davies, D.P.Jackson, P,R.Norton,J. Vac. Sci. Technol., 20(1982)607
69. D.Rieger, R.D.Schnell, W.Steinmann, Surf. Sci. 143(1984)157
70. S.Schwegmann, W.Tappe, U.Korte, Surf. Sci. 334(1995)55
71. R.Ducros, J.Fusy, Surf. Sci. 207(1988)L943
72. C.S.Feigerle, S.R.Desai, S.H. Overbury, J. Chem. Phys. 93(1990)787
73. G.R.Angelov, N.Memmel, E.Bertel, V.Dose, Surf. Sci. 251-252
(1991)965
74. G.Pacchioni, S.C.Chung, S.Kruger, N.Rosch, Surf. Sci. 392
(1997)173
75. B.E.Nieuwenhys, Surf. Sci. 105(1981)505
76. E.Bertel, N.Memmel, G.Rangelov, U.Bischler, Chem. Phys.
177(1993)337
77. S.C.Chung, S.Kruger, G. Pacchioni, N.Rosch, J. Chem. Phys. 102(1995)3695
78. S.C.Chung, S.Kruger, S.Ph.Ruzankin, G. Pacchioni, N.Rosch,
Chem. Phys. Lett. 248(1996)109
79. P.S.Bagus, W.Muller, Chem. Phys. Lett. 115(1985)540
80. G.Broden, G.Pirug, H.P.Bonzel, Surf. Sci. 72(1978)45
81. A.M.Bradshaw, F.M.Hoffmann, Surf. Sci. 72(1978)513
82. H.Ohtani, M.A.Van Hove, G.A.Somorjai, Surf. Sci. 187 (1987)
372
83. J.N.Andersen, M.Qvarford, R.Nyholm, S.L.Sorensen, C.Wigren
Chem. Phys. Lett. 67(1991)2822
84. A.Ortega, F.M.Hoffman, A.M.Bradshaw, Surf. Sci. 119(1982)79
85. J.P.Biberian, M.A.Van Hove, Surf. Sci. 118(1982)443
86. P.R. Norton, P.E.Binder, Surf. Sci. 169 (1986)L259
87. J.W.He, P.R.Norton, Surf. Sci. 195(1988)L199
88. L.Philippe, T.Hirayama, M.J.Ramage, G.Comtet, M.Rose, L.Hellner,G.Dujardin J. Chem. Phys. 106(1997)7072
89. V.M.Bermudez, J.Appl.Phys. 80(1996)1190
90. M.Wassermeier, A.Yamada, H.Yang, O.Brandt, J.Behend, K.H.Ploog Surf. Sci 385(1997)178
91. A.R.Smith, R.M.Freenstra, D.W.Greve, J.Neugebauer, J.E.Northrup,Phys. Rev. Lett. 79(1997)3934
92. A.R.Smith, R.M.Freenstra, D.W.Greve, M.S.Shin, M.Skowronski,J.Neugebauer, J.E.Northrup, J. Vac. Sci. Technol.B.16(1998)2242
93. H.Lee, D.B.Oberman, J.S.Harris, Appl. Phys. Lett. 67(1995)1754
94. D.Basak, M.T.Monojo, M.A.Sanchez-Garcia, F.J.Sanchez, E.Munoz,E.Calleja, Semicond. Sci. Technol. 12(1997)1654
95. L.Zhang, J.Ramer, J.Brown, K.Zheng, L.F.Lester, S.D.Hersee,
Appl. Phys. Lett. 68(1996)367
96. R.j.Shul, J.Howard, J.Vac. Sci. Technol. B 13(1995)2016
97. G.F.Mclane, L.Casas, Appl. Phys. Lett. 66(1995)3328
98. A.T.Ping, M.Asif Khan, I.Adesida, Appl. Phys. Lett. 67 (1995)1250
99. R.J.shul, G.B.McClellan, S.A.Casalnuovo, D.J.Reiger, Appl. Phys.Lett. 69(1996)1119
100. V.M.Bermudez, T.M.Jung, K.Doverspike, A.E.Wickenden,
J.Appl.Phys. 79(1996)110
101. V.M.Bermudez, D.D.Koleske, A.E.Wickenden, Appl. Surf. Sci
126 (1998)69
102. W.H.Hung, S.L.Wu, C.C.Chang, J. Phys.Chem. B 102(1998)1141
103. T.Halicioglu,T.Takai, W.A.Tiller, , in:The Structure of Surfaces, Eds. M.A. Van Hove and S.Y.Tong(Springer, Berlin,1985)p.231
104. K.Yyzaki, T.Yarimizu, K.Aooyagi, S.Ito, K.Kunimori, CatalysisToday 45(1998)129
105. G.Etl, Surf. Sci. 299/300(1994)742
106. P.A.Theil, R.J.Behm,P.R.Norton, G.Ertl., J.Chem.Phys.
78(1983)7437
107. G.Held, J.Schuler, W.Sklarek, H.-P. Steinruck, Surf. Sci. 398(1998)154
108. P.R.Norton, J.W.Goodale, E.B.Selkirk, Surf. Sci. 83(1979)189
109. M.Kiskinova, G.Pirug, H.P.Bonzel, Surf. Sci. 133(1983)321
110. L.A.DeLouise, E.J.White, N.Winograd, Surf. Sci. 147(1984)252
111. H.Antonsson, A.Nilsson, N.Maetensson, I.Panas, P.E.M. Siegbahn,J. Electron Spectrosc. Relat. Phenom. 54-55(1990)601
112. H.Tillborg, A.Nillson, N.Maetensson, Surf. Sci. 237(1992)47
113. V.R.Dhanak, A.Baraldi, G.Comeli, G.Paolucci, M.Kiskinova, A. Rosi, Surf. Sci. 295(1993)287
114. Peter A.Janssan, Deconvolution with Application in Spectroscopy, Academic Press, 1984
115. F.p.Netzer, T.E.Madey, J. Chem.Phys. 76(1982)710
116. J.B.Miller, H.R.Siddiqui, S.M.Gates, J.N.Russell, J.T.Yates,Jr.J. Chem. Phys. 87(1987)6725
117. D.Menzel, R.Gomer, J.Chem.Phys. 41(1964)3311
118. P.A.Redhead, Can. J. Phys. 42(1964)886
119. A.Rosenberg, P.J.Love, P.R.LaRoe, V.Rehn, C.C.Parks, Phys. Rev.B 31(1985)2634
120. G.Dujardin, L.Hellner, L.Philippe, M.J.Besnard-Ramage, P.Cirkel, Phys. Rev. B 48(1993)14592
121. A.Peremans, K.Fukutani, K.Mase, Y.Murata, Surf. Sci. 283
(1993)189
122. A.Peremans, K.Fukutani, K.Mase, Y.Murata, Phys.Rev. B
47(1993)4135
123. K.Al-Shamery, I.Beauport, H.J.Freund, H.Zacharis, Chem.Phys.
Lett. 222(1994)107
124. P.Avouris, R.E.Walkup, Annnu. Rev. Phys. Chem. 40(1989)179
125. D.Mezel, Nucl. Instrum. Methods B13(1986)507
126. H.T.Jonkman, J.Michl, J.Am.Chem.Soc. 63(1975)3656.
127. 物理雙月刊(第二十卷第二期)1998年4月 p240
128. 半導體學報(第二十卷第二期)1999年2月 p89
129. D.R.Lite(Ed.),CRC Handbook of Chemistry And Physics,
CRC Press, Boca Raton, FL, 1994
130. J.Massies, F.Lemmaire-Dezaly, J.Appl.Phy. 57(1985)237
131. P.Soukiassian, P.S.Mangat, Y.Huttel, Z.Hurych, ,B.Gruzza, A.Porte, J. Vac. Sci. Technol. B 11(1993)1603
132. N.D.Spencer, P.J.Goddard, P.W.Davies, M.Kitson, R.M.Lambert
J. Vac. Sci. Technol. A 1(1983)1554
133. Z.Stitar, L.L.Smith, R.F.Savis, J.Cryst.Growth 141(1994)11
134. W.R.L.Lambrecht, B.Segall, S.Strite, G.Martin, A.Agarwal, H.Morkoc, A.Rockett, Phys. Rev. B 50(1994)14155
135. J.Hedman, N.Martensson, Phys. Scr. 22(1980)176
136. L.A.DeLouise, J.Vac. Sci. Technol. A10(1992)1637
137. R.Carin, J.P.Deville, J.Werckmann, Surf. Interface Anal. 16(1990)65