本研究先以真空磁控濺鍍方式在矽基材上沉積奈米尺寸(10 nm &
5 nm)的銦錫氧化物薄膜(Indium Tin Oxide, ITO)，再以電鍍方式，
在銦錫氧化物薄膜上沉積銅金屬層，接著以快速退火爐(Rapid
Thermal Annealing, RTA)在真空與氬:氫(95:5)的氣氛下進行
300~800 ℃的熱處理，持溫五分鐘。所有試片分別以四點探針
(four-point probe)、X 光繞射儀(XRD)、掃描式電子顯微鏡及穿透
式電子顯微鏡(TEM)等儀器來分析ITO 阻障層之片電阻值、相、表面
和界面微觀結構以瞭解真阻障效果。
為改善電鍍銅膜與ITO 薄膜間之剝離現象，在ITO 薄膜上再以真
空磁控濺沉積一層釕(Ru)金屬層來改善電鍍銅膜與ITO 鍍膜間的結
合性；接著以無電鍍方式在電鍍銅膜上沉積CoWP 薄膜做為覆蓋層，
以防止電鍍銅膜在熱處理溫度作用下產生聚集。
最後以真空濺鍍及無電鍍在ITO/Si 沉積銅金屬層，藉此比較電
鍍、無電鍍及真空磁控濺鍍三種方式所沉積之銅膜對ITO 阻障層有何
種影響。實驗結果顯示電鍍及無電鍍所製備之Cu/ITO/Si 試片可有效
抵擋銅原子擴散達600 ℃；以真空磁控濺鍍所製備之試片，其失效
溫度為700 ℃。

In the research, the effect of electroplating Copper (Cu) film on
Indium Tin Oxide (ITO) diffusion barrier was studied, improved by
additional treatments and finally compared with electroless Cu and
magnetron sputter Cu film.
First, silicon (Si) substrate was deposited ITO thin film with 10 and
5 nm thickness by Magnetron Sputter in vacuum, separately, then electro
Cu film was electroplated onto it, and annealed at 300 to 800 ℃ for 5 min
in rapid thermal annealing (RTA) furnace in vacuum and atmosphere of
Ar and H2 with a volume ratio of 95:5, respectively. The microstructure,
phase, and sheet resistance of various Cu/ITO/Si sample were observed
and measured by transmission electron microscopy (TEM), scanning
electron microscopy (SEM), X-ray diffractometer (XRD), and four-point
probe.
To improve the interface between Cu and ITO film, a seed layer of
ruthenium (Ru) film with 5 nm thickness was coated onto ITO film by
Magnetron sputter before electroplating Cu process. And to inhibit Cu
agglomeration in annealing process, a capping layer of Co-W-P film was
electroless plated onto Cu film.
Finally, the influence of Cu film Cu/ITO/Si by electroplating,
Electroless plating and Magnetron Sputtering process on ITO diffusion
barrier was inrestigated. The results show that Cu film in Cu/ITO/Si,
which was deposited by electroplating and electroless plating process
could hinder the diffusion of Cu up to 600 ℃; the Cu film by magnetron
sputtering process in vacuum failed at 700 ℃.

摘要.....................................................Ⅰ
Abstract .......................................................Ⅱ
目錄..........................................................Ⅴ
圖目錄........................................................Ⅸ
表目錄......................................................ⅩⅤ
第一章 序論....................................................1
第二章 文獻回顧................................................3
2-1 銅金屬化製程............................................3
2-2 擴散阻障層..............................................6
2-3 銦錫氧化物.............................................. 7
2-4 薄膜沉積方式............................................ 9
2-4-1 真空磁控濺鍍......................................9
2-4-2 電鍍..............................................9
2-4-3 無電鍍............................................ 10
第三章 實驗步驟及分析方法..................................... 12
3-1 製程................................................... 12
3-1-1 試片前處理....................................... 13
3-1-2 沉積ITO 薄膜..................................... 14
3-1-3 ITO 薄膜上電鍍Cu................................. 15
3-1-4 無電鍍CoWP 析鍍................................. 16
3-1-5 無電鍍Cu析鍍.................................... 17
3-1-6 RTA熱處理....................................... 17
3-2 試片量測與分析......................................... 18
3-2-1 四點探針 (Four-Point Probe) ......................... 18
3-2-2 X 光繞射儀 (XRD)................................. 18
3-2-3 掃瞄式電子顯微鏡 (SEM)........................... 19
3-2-4 透式電子顯微鏡 (TEM)............................. 20
3-2-4-1 TEM 試片製作.................................. 21
第四章 實驗結果與討論......................................... 24
4-1 Cu/ITO/Si 真空與Ar+H2(5%)熱處理........................ 24
4-1-1 ITO 初鍍膜前置處理............................... 24
4-1-2 Cu/ITO/Si真空與Ar+H2(5%)熱處理之電性量測分析.... 24
4-1-3 Cu/ITO/Si 真空與Ar+H2(5%)熱處理之SEM 表面形貌
分析................................................... 25
4-1-4 Cu/ITO/Si真空與Ar+H2(5%)熱處理之XRD 繞射分析... 27
4-1-5 Cu/ITO/Si真空與Ar+H2(5%)熱處理之TEM 顯微結構
分析................................................... 28
4-2 Cu/Ru(5 nm)/ITO(5 nm)/Si................................. 51
4-2-1 Cu/Ru/ITO/Si之電性量測分析....................... 51
4-2-2 Cu/Ru/ITO/Si之SEM 表面形貌分析.................. 51
4-2-3 Cu/Ru/ITO/Si之XRD 繞射分析...................... 52
4-2-4 Cu/Ru/ITO/Si之TEM 顯微結構分析.................. 52
4-3 Cu/ITO(5 nm)/Si ......................................... 63
4-3-1 Cu/ITO(5 nm)/Si之電性量測分析..................... 63
4-3-2 Cu/ITO(5 nm)/Si之SEM 表面形貌分析................ 63
4-3-3 Cu/ITO(5 nm)/Si之XRD 繞射分析.................... 64
4-3-4 Cu/ITO(5 nm)/Si之TEM 顯微結構分析................ 64
4-4 CoWP/Cu/Ru(5 nm)/ITO (5 nm)/Si .......................... 72
4-4-1 CoWP/Cu/Ru/ITO/Si 之電性量測...................... 72
4-4-2 CoWP/Cu/Ru/ITO/Si之SEM 表面形貌分析............ 72
4-4-3 CoWP/Cu/Ru/ITO/Si之XRD 繞射分析................ 74
4-4-4 CoWP/Cu/Ru/ITO/Si之TEM 顯微結構分析............ 74
4-5 Sputter & Electroless ..................................... 87
4-5-1 Sputter & Electroless 之電性量測..................... 87
4-5-2 Sputter & Electroless 之SEM 表面形貌分析............ 87
4-5-3 Sputter & Electroless 之XRD 繞射分析................ 88
4-5-4 Sputter & Electroless 之TEM 顯微結構分析............ 89
第五章 結論.................................................. 106
參考文獻..................................................... 107

1. MT. Bohr, Interconnect scaling – the real limiter to high performance ULSI,
Int. Electr. Dev. Meet. Technical digest. 241(1995)
2. C.-A Chang, J. Appl. Phys. 67, 566-569(1990)
3. A.A. Istratov and E.R. Weber, J. Electrochem, Soc., 149, G21(2002)
4. S.P Murarka, Microelectron. Eng., 37, 29(1997)
5. G. Granqvist, A. Hultaker, Thin Solid Films, 411, 1(2002).
6. A.K. Kulkarni, K.H. Schulz, T.S. Lim, M. Khan, Thin Solid Films, 308-309,
1(1997)
7. H. Yumoto, T. Inoue, S.J. Li, Sako, K. Nishiyama, Thin Solid Films, 345, 38
(1999).
8. S.E. Dyer, O.J.Gregory, P.S. Amons, A. Bruins Slot(1996) Thin Solid Films,
288, p.279.
9. S-P Heng et al., 1995 International Symposium on VLSI TSA, p.164.
10. L. D. Burke, G. M. Bruton, J. A. Collins, Electrochimica Acta, 44, p1467
(1997).
11. J. M. Sterigerwald, S. P. Murarka, R. J. Gutmann and D. J. Duquette, Mater.
Chem. Phys., 41. 217 (1995).
12. C. W. Kannta, S. G. Bombardier, W. J. Cote, W. R. Hill, et al. IEEE VMIC
Conf, 144(1991).
13. C.Y. Chen, J.S. Jeng, and J.S. Chen, Thin Solid Films, 420-421 (2002) 398.
14. S.R. Burgess, H. Donohue, K. Buchanan, N. Rimmer, and P. Rich,
Microelectron. Eng., 64 (2002) 307.
15. T. Laurila, K. Zeng, J. K. Kivilahti, J. Molarius, and I. Suni, J. Appl. Phys.,
91 (2002) 5391.
16. L. W. Lai , J. S. Chen and Wu-Shiung Hsu, JOURNAL OF APPLIED
PHYSICS VOLUME 94, (8)( 2003)5396
17. H.Y. Cheng, Y.C .Chen, C.M. Lee, R.J. Chung, and T.S. Chin, J.
Electrochem. Soc., 153 (2006) G685
18. J.S. Fang, H.L. Chang, G.S. Chen, and P.Y. Lee, Rev. Adv. Mater. Sci., 5
(2003) 510 .
19. A. Kohn, M. Eizenberg, Y. Shacham-Diamand, Y. Sverdlov, Materials
Science and Engineering A302 (2001) 18-25.
20. A. Kohn, M. Eizenberg, Y. Shacham-Diamand, B. Israel, Y. Sverdlov,
Microelectronin Engineering 55 (2001) 297-303.
21. Yosi Shacham-Diamand, Barak Israel, Yelena Sverdlov, Microelectronic
- 108 -
Engineering 55 (2001) 313-322.
22. A. Kohn, M. Eizenberg, Y. Shacham-Diamand, Applied Surface Science
212-213 (2003) 367-372.
23. H.Y. Wong, N.F. Mohd Shukor, N. Amin, Microelectronics Journal 38 (2007)
777.
24. X-P Qu, J-J Tan, M. Zhou, T. Chen, Q. Xie, G-P Ru, and B-Z Li, Appl. Phys.
88, 151923 (2006).
25. H. Enoki and J. Echigoya and H. Suto, J. Mat. Sci.26, 4110 (1991).
26. C. M. Liu, W. L. Liu, W. J. Chen, S. H. Hsieh, T. K. Tsai, and L. C. Yang, J.
Electrochem. Soc., 152 (3) G234-239 (2005).
27. O. Chyan, T.N. Arunagiri, T. Ponnuswamy, J. Electrochem. Soc. 150, C347
(2003).
28. T.N. Arunagiri, Y. Zheng, O.Chyan, M. El-Bouanani, M.J. Kim, K.H. Chen,
C.T. Wu, L.C. Chen, Appl. Phys. Lett. 86, 083104 (2005).
29. M. Damayanti, T. Sritharan, S.G. Mhaisalker, Z.H. Gan, Appl. Phys. Lett. 88,
044101 (2006).