本論文主要是探討以射頻磁控濺鍍（RF magnetron sputterig）之方式所沉積之TiNx阻障層抵抗銅原子擴散的能力。主要是以射頻磁控濺鍍法沉積不同氮含量之TiNx薄膜，進行晶粒大小、結晶結構、晶粒排列與化學組成等分析，並對Cu/TiNx/Si多層膜進行退火，由HRTEM等儀器對退火前後之多層膜試樣進行分析，以所獲得的分析結果及銅原子在阻障層中之擴散係數，來討論阻障層中氮含量及阻障層厚度對阻障特性的影響。
實驗結果顯示，氮含量的增加，使得具有六方最密堆積結構
之金屬鈦薄膜轉變成結構較為穩定之氮化鈦岩鹽結構(rock-salt structure)，並由於氮原子的不斷提供，薄膜結構由柱狀(column)結構轉變為微結晶（nanocrystalline）結構，當提供此微晶結構足夠的熱能（高溫退火）後，則會轉變為柱狀結構。
由TEM的分析發現在多層膜系統中，主要是因為銅原子的擴散而造成阻障層之失效。以四點探針量測的片電阻值變化率來判定TiNx阻障層之失效時間（threshold time），並配合擴散平均長度
L=2（Dt）1/2的公式，可計算得到銅原子在不同組成之擴散阻障層中之擴散係數。
由HRTEM分析發現，在阻障層厚度變薄後，單位阻障層厚度之總晶界長度增加許多，銅原子在阻障層中之總擴散路徑變長，擴散係數因此而降低，因此在超大型積體電路中，採用較薄厚度之氮化鈦阻障層，既可降低阻障層的電阻值又可降低銅的擴散係數，是非常有利的作為。

The study is to evaluate the obstructing capability of TiNx films to Cu diffusion. The TiNx films were deposited by RF magnetron-sputtering system. The grain size, crystal structure, crystal arrangement, chemical composition and other characteristics of TiNx films were also analyzed. Before and after annealing, behavior for Cu/TiNx/Si multilayered samples were investigated by HRTEM and other instruments. By combining all materials analyses with how diffusion coefficients of copper in TiNx diffusion barriers, the nitrogen content and TiNx thickness affect the diffusion coefficient of Cu in TiNx films were revealed.
The experimental results indicate that the crystalline structure of TiNx film was changed from Hexagonal metal Ti to stable rock-salt TiN structure with the raise of N2/Ar flow ratio. And, microstructure changed from the column structure to nanocrystalline structure as the increase in N2/Ar flow ratio. Having sufficient energy（After annealing at high temperatrures）, the nanocrystalline structure is back to column structure.
We found out that barrier failure was due to Cu atoms diffusing through the TiNx layer in Cu/TiNx/Si multilayered sample. The failure time (threshold time) of TiNx films was estimated from the sheet resistance curves by FPP. Combining failure time with formula L（the average diffusion length of atoms）= 2(Dt)1/2 got diffusion coefficients of copper in TiNx diffusion barriers.
HRTEM shows that the boundary length in thin barrier films would be more than thicker barrier films. In ULSI, the advantages of using thinner TiNx barrier include lower resistivity of diffusion barrier and diffusion coefficient of copper in TiNx diffusion barrier.

1.ITRS, Executive Summary of the 2003 Edition, p.39.
2.S-P Heng et al.,1995 International Symposium on VLSI TSA, p.164.
3.ITRS, Interconnect of the 2004 Update, p.3∼ p.9.
4. Werner Steinhoegl, Guenther Schindler and Manfred Engelhardt, 〝Unraveling the Mysteries Behind Size Effects in Metallization Systems〞, Infineon Technologies（2005,5,1）.
5.C. Y. Chang, S. M. Sze, ULSI Technology,the McGraw-Hill, p.663,1996.
6.Abhishek Gupta, “Diffusion Characteristics Of Copper In Novel Metallic Films”, North Carolina State University.
7.張勁燕,“深次微米矽製程技術”, p.219.
8.Thaddeus B. Massalski et al.,〝Binary Alloy Phase Diagram〞,vol.1.
9.Shacham-Diamand, Y., Li, J.,Olowlafe, J.O., Russel, S., Tamou, Y., Mayer, J. W., Proc. 9 Bienn Univ. Gov. Ind. Microelectron Symp. Pabl by IEEE Service Center, Piscataway, NJ, USA(IEEE cat. n 91ch3027-0), p.210-215.
10.A. E. Kaloyeros and E. Eisenbraun, Annu. Rev. Mater. Sci. 30(2000)363.
11.M.-A. Nicolet, Thin Solid Films, 52(1978)415.
12.楊文祿、吳其昌, 深次微米元件後段金屬連線技術, 真空科技, 十二卷二期, p.44-45 ,1999.
13.W. Nelson, Proc. Int. Symp. Hybrid Microelectronics, 1969, Dallas,Texas, International Society of Hybrid Microelectronics,Montgomery,U.S.A,p.413（1969）.
14.C.-K. Hu , J. M. E. Harper, Materials chemistry and Physics, 52（1998）5.
15.W.H. Teh, L.T. Koh, S.M. Chen, J. Xie, C.Y. Li, and P.D.Foo ,Electron. Lett. 37, (2001) 660.
16. S. M. Rossnagel and H. Kim, J. Vac. Sci. Technol., B 21 (6) (2003)2550.
17.Katsutaka Sasaki,Hidekazu Miyake,Statoko Shinkai,Yoshio Abe and Hideto Yanagisawa,Jpn. J. Appl. Phys.,40（2001） 4661.
18.Cheng-Shi Chen et al., J. Vac. Sci. Technol. ,B 22(3) (2004)1075.
19.Huseyin Kizil, Christoph Steinbruchel, Thin Solid Films , 449 (2004)158.
20.Mayumi B. Takeyama et al., J. Vac. Sci. Technol. ,B 22 (5)( 2004)2542.
21. R. Hubner et al.,Thin Solid Films,458 (2004) 237.
22.S. Balakumar, Tohru Hara, Rakesh Kumar, Takamasa Wakabayashi,and Minoru Uchida, Electrochemical and Solid-State Letters, 7 (8)（2004）G175.
23.H.C. Kim and T.L. Alford , Thin Solid Films , 449 (2004)6.
24.Wang SQ. , Mater. Res. Soc. Bull, 19（1994）30.
25.Uh J, Aeen M, Leusink G, Webb D, Hillman J. T hin Solid Films(1997)308.
26.Sa-Kyun Rha , Won-Jun Lee , Seung-Yun Lee , Yong-Sup Hwang ,Yoon-Jik Lee ,Dong-Il Kim , Dong-Won Kim , Soung-Soon Chun ,Chong-Ook Park , Thin Solid Films ,320 (1998) 134.
27.Ki Tae Nam, Arindom Datta, Soo-Hyun Kim, and Ki-Bum Kim,79（2001）2549.
28.Katz A, Feingold A, Pearton S, Nakahara S and Ellington M, et al., J.Appl. Phys. ,70（1991）1666.
29.張鼎張、胡榮治,金屬化學氣相沉積在積體電路技術的發展,真空科技,十二卷二期,1999, p.35-43.
30. Ho PS. , Thin Solid Films ,96（1982）301.
31. Park K, Kim K, Raaijmakers I, Ngan K., J. Appl. Phys., 80(10)(1996)5674.
32. A. E. Kaloyeros and E. Eisenbraun, Annu. Rev. Mater. Sci, 30（2000)363.
33.Shewmon PG. ,Diffusion in Solids, New York,McGraw Hill,1963.
34.J.C. Fisher , J. Appl. Phys., 22 (1951)74.
35.Y. Mishin and Chr. Herzig Mater. Sci. Eng. ,A 260 (1999)55.
36.行政院國家科學委員會精密儀器發展中心,〝真空科技與應用〞 ,2002.
37.Thaddeus B. Massalski et al.,〝Binary Alloy Phase Diagram〞,vol.1.
38. D.A. Porter and K.E. Easterling,“Phase Transformations in Metals and Alloys”,Nelson Thrones, p.130.
39. M.Moriyama, T.Kawazoe , M.T anaka , M.Murakami, Thin Solid Films, 416 (2002) 136.
40.Michel Barsoum,〝Fundamentals of Ceramics〞, McGraw- Hill ,p.197.