銅具有比鋁高之擴散速率，容易擴散至其他材料中形成化合物，
因此必須在銅的上方或下方，以PVD 或者是CVD 的方式沈積一層緩
衝層(Buffer Layer)，目前緩衝層材料以Mo 或MoW 為主，其目的是
阻止銅金屬擴散進入玻璃基板或介電層中。
在本實驗中，以PVD 方式改變其沈積壓力及射頻功率成長Mo
薄膜，結果顯示：沈積壓力越低，會使得Mo 薄膜之晶粒尺寸越小、
表面粗糙度下降、雜質含量越低，因而電阻率降低；射頻功率增加，
Mo 薄膜之晶粒尺寸越大、雜質含量越低；但在100W 至250W 時，
射頻功率增加，表面粗糙度降低、電阻率降低。300W 至350W 時，
射頻功率增加，表面粗糙度增加、電阻率增加。
PVD 銅及電鍍銅具有良好的結晶性及低的表面粗糙度和低的電
阻率，其電阻率分別為5.47 及7.47μΩ-cm；而CVD 銅和無電鍍銅結
晶性較差、表面粗糙度以及電阻率均較PVD 銅、電鍍銅要來的高，
其電阻率分別為10.67μΩ-cm 及11.38μΩ-cm。
Cu(100nm)/Mo (37.5nm)/Si 多層膜結構在350℃至700℃溫度退
火30 分鐘，其失效溫度皆在650℃左右；而多層膜結構產生失效時，
銅原子之主要擴散路徑為晶界，並生成Cu3Si及Mo、Si化合物。
PVD 銅具有較高之擴散活化能0.948eV，但只比電鍍銅(0.946eV)
及無電鍍銅(0.943eV)高一點。PVD 銅具有優異的附著性，其附著能
約為2.46N/m，而無電鍍銅約為1.96N/m 較PVD 銅差，CVD 銅對於
基板具有最差之附著性，其附著能約為1.49N/m。
綜觀以上各種分析可以得知以PVD 方式成長銅膜具有最佳之結
晶性、表面粗糙度、電阻率、擴散活化能以及附著能。

The diffusion rate of copper (Cu) is higher than aluminum. It is easy to
diffuse into other materials to form the chemical compounds. Therefore, the
buffer layer can be deposited on above or below Cu films by the use of a
variety of technique including physical vapor deposition (PVD), and
chemical vapor deposition (CVD). Now, the components of buffer layer are
Mo or MoW. The purpose was prevented that metallic Cu diffuse into the
glass substrates or insulators.
In our study, the character of using PVD to achieve the deposition of
Molybdenum (Mo) film was examined. The deposition pressure decreased,
the grain sizes, surface roughness, impurities, and resistivity decreased. The
RF-power increased with the raise of the grain sizes, and the impurities of
films decreased. But the RF-power increased at 100W~250W, the surface
roughness and resistivity decreased; the RF-power increased at 300W~
350W, the surface roughness and resistivity increased
PVD Cu and electroplating Cu were good crystallization, low surface
roughness, and low resistivity. The resistivity of PVD Cu and electroplating
Cu are 5.47 μΩ-cm and 7.47 μΩ-cm, respectively. But CVD Cu and
electroless Cur were bad crystallization, high surface roughness, and high
resistivity. The character of PVD Cu and electroplating Cu are higher than
CVD Cu and electroless Cu. The resistivity of CVD Cu and electroless Cu
are 10.67 and 11.38 μΩ-cm, respectively.
Cu(100nm)/Mo(37.5nm)/Si multilayered structures were annealed at the
II
temperature of 350℃~700℃ for thirty minutes in vacuum system. The
failure temperatures of all samples were about 650℃. The main diffusion
path of Cu atom in The main failure diffusion paths of the copper atoms
were grain boundary, and the multilayered structures were formed
triangular-like Cu3Si, and MoxSiy compounds.
The diffusion activity energy of PVD copper (0.948eV) is higher than
electroplating Cu (0.946eV) and electroless Cu (0.943eV). Besides, PVD
copper was excellent adhesion. The adhesion energy on the substrate of
PVD Cu (2.46N/m) was higher than Electroless Cu (1,96eV) and CVD Cu
(1.49N/m).
Experiment results indicate that the growth of PVD copper own good
crystallization, low surface roughness, low resistivity, high activity energy,
and good adhesion energy.
III

1.P.G.LeComber,W.E.Spear,and A.Ghaith，Electronics.Letter, Vol.15,
pp.179, 1979.
2.W.E.Howard,J.Soc.Inform.Display,vol.3,no.3,p.127,1995.
3.N.Ibaraki,Mater.Chem.Phys.,vol.43,p220,1996.
4.M.Akiyama,S.Uchikoga,T.Sakakubo,T.Koizumi,and K.Suzuki, in Dig.
Soc. Inform. Displ. ,p10,1991.
5.L.Peter,Semiconductor International,Cover Story,P.64, September 1998.
6.G.S.Chae,H.S.Soh,W.H.Lee and J.G.Lee, J.Appl.Phys. 90, 411 (2001)
7.Tsujimura T,Kitahara H,Makita A,Fryer F,Batey J.Int Displ Res Conf,
1996. p.142.
8.劉繼文，雙鑲嵌結構製作技術及面臨之挑戰，電子月刊，Vol.6, No.8
(2000)88.
9.Yong Sup Hwang,Gyoo Chul Jo,Gee Sung Chae and In Jae Chung,
Copper Bus for TFT-LCD
10.http://www.chipworks.com/
11.C.-Y.Chen,J.-J.Chang,C.-Y.Sheu,C.-S.Chang,J.-H.Huang,”MoW-Al-
MoW Tri-layer Metal Dry Etching Technology for High Resolution
and Large-area LTPS TFT-LCD Panel”, AMLCD’03,(2003).
12.S.kawamota et al.,SID 98 Digest,35(1),1(1998)
13.Donal S. Gardner,Jin Onuki,Kazue Kudoo and Yutaka Misawa June
11-12, 1991 VMIC Conference.
14.H.Sirringhaus,S.D.Theiss,A.Kahn,and S.Wagner,IEEE ELECTRON
DEVICE LETTERS,VOL.18,NO.8,AUGUST 1997.
15.Toshiaki Arai,Atsuya Makita,Yasunobu Hiromasu,Hiroshi Takatsuji,
Thin Solid Films 383(2001)287-291
16.Sang Wook Lee,In Keun Woo,Kyu Sik Cho.Jin Jang,Journal of Non-
Crystalline Solids 299-302 (2002) 1351-1354.
17.Sang Wook Lee,Kyu Sik Cho,Byung Kwon Choo,and Jin Jang.
Member, IEEE IEE ELECTRON DEVICE LETTERS, VOL.23,
NO.6, JUNE 2002
114
18.N. Feldstein and J. A. Weiner, “Surface Characterization of Sensitized
and Activated Teflon,” J. Electrochem. Soc., Vol. 120, No.4, 1973,
p.745.
19.H.T. Ng, S. F. Y. Li, L. Chan, F. C. Loh, and K. L. Tan, “Sequential
Observation of Electroless Copper Deposition via Noncontact Atomic
Force Microscopy,” J. Appl. Electrochem., Vol. 145, 1995, pp.
3301-3307.
20.J. C. Fisher, J. Appl. Phys., 22 (1951) 74.
21.R. E. Hoffman and D. Turnbull, J. Appl. Phys., 23 (1951) 634.
22.M. Croset and G. Velasco, J. Vac. Sci. Technol., 9 (1971) 165.
23.R. S. Mishra, H. Jones, and G. W. Greenwood, J. Materials Sci. Lett, 7
(1988) 728.
24.R. S. Mishra, H. Jones, and G. W. Greenwood, Materials Sci.
Engineering, A117 (1989) 21.
25.N. P. Zulina, E. V. Bolberova, and I. M. Razumovskii, Acta mater., 44
(1996) 3625.
26.Q. Ma and R. W. Balluffi, Acta Metall. Mater., 41 (1993) 133.
27.A. Chatterjee and D. J. Fabian, Acta mater., 17 (1969) 1141.
28.Y. U. Mishin and I. M. Razumovskii, Acta Metall.mater.,40(1992)597.
29.P. Neuhaus, C. Herzig, and Q. Gust, Acta Metall. mater.,37(1989)587.
30.A. M. Brown and M. F. Ashby, Acta Metall. mater., 28 (1980) 1085.
31.S. M. Makin, A. H. Rowe, and A. D. LeClaire, Proc. Phy. Soc., 6
(1957) 545.
32.C. H. Ting and G. L. Pearson, J. Appl. Phys., 6 (1970) 2247.
33.L. G. Harrison, Trans. Faraday Sic., 57 (1961) 1191.
34.J. Li, A. Dasgupta, IEEE Trans. Reliability, 43 (1994) 2.
35.N.Feldstein and J.A.Weiner,”Surface Characterization of Sensitized
and Activated Teflon,” J.Electrochem. Soc., Vol.120,No.4,1973,P.145
36.O. Knotek, M. Bohmer, T. Leyendecker, J. Vac. Sci. Technol. A4
(1986) 2695.
37.W. L. Winterbottom, Acta Netall. 15 (1967) 303.
115
38.Michael Land and R. H. Dauskardt, Journal of Material Research, 15
(1) (2000) 203.
39.Y. Tsukamoto, H. Kuroda, A. Sato and H. Yamaguchi, Thin Solid
Films, 213 (1992) 220.
40.C. Y. Lee and K. L. Lin, Jpn. J. Appl. Phys., 33 (1994) 2684.
41.A. Furuya, N. Hosoi, and Y. Ohshita, J. Appl. Phys., 78 (10) (1995)
5989.
42.A. Furuya, and Y. Ohshita, J. Appl. Phys., 84 (9) (1998) 4941.
43.W. L. Winterbottom, Acta Metall., 15 (1967) 303.
44.Metals Referrence Book, 5th ed. (Butterworths, London, 1976).
45.Jui-Chang Chuang,Shuo-Lun Tu and Mao-Chieh Chen,Thin Solid
Films 346 (1999) 299-306
46.S.Luby,E.Majkova,M.Jergel,M.brunel,G.Leggieri,A.Luches,G.Majni,P.
Mengucci,Thin Solid Films(1996) 138-143
47.M. B. Chamberlain, Thin Solid Films, 91 (1982) 155.
48.K. Y. Lim, Y. S. Lee, Y. D. chung, I. W. Lyo, C. N. Whang, J. Y. Won,
and H. J. Kang, Appl. Phys. A 70 (2000) 431.
49.J. C. Lin, C. Lee, Electrochemical and Solid-State Letters, 2 (4) (1999)
181.
50.林俊成，RF 濺鍍成長TaNx 薄膜及其在積體電路之銅製程上的應
用，國立台灣科技大學化工所，(1999)
51.T. Oku, E. Kawakami, M. Uekuo, K. Takahiro, S. Yamaguchi and M.
Murakami, Applied Surface Science, 99 (1996) 265.
52.J. Imahori, T. Oku, and M. Murakami, Thin Solid Films, 301 (1997)
142.
53.Yu-Lin Kuo,Hisn-Hung Lee,Chiapyng Lee,Jing-Cheng Lin,Shau-Lin
Shue,Mong-Song Liang,and Brian J.Dianiels,Electrochemical and
Solid-State Letters,7(3) C35-C37(2004)
54.Thaddeus B. Massalski, Hiroaki Okamoto, P.R. Subramanian, Linda
Kacprzak., Binary alloy phase diagrams/editor-in-chief