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研究生:李文山
研究生(外文):Wen- Shan Lee
論文名稱:高性能後化學機械研磨清洗技術之探討
論文名稱(外文):Investigation of High Performance Post CMP Cleaning Technologies
指導教授:葉清發
指導教授(外文):Ching-Fa Yeh
學位類別:碩士
校院名稱:國立交通大學
系所名稱:電資學院學程碩士班
學門:工程學門
學類:電資工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:英文
論文頁數:91
中文關鍵詞:化學機械研磨清洗技術
外文關鍵詞:chemical mechanical polish(CMP)cleaningbenzotriazole(BTA)copper
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在雙鑲嵌技術中銅化學機械研磨製程之化學機械研磨後清洗為一道非常重要之製程。減少介電材質表面的有機、銅污染殘餘物為本研究的目標。在我們的研究中,提出一項採用HAL緩衝氫氟酸加上後來臭氧超純水清洗的新式化學機械研磨清洗。在TXRF(全反射X光螢光分析儀)的分析中,和目前雙鑲嵌技術銅清洗製程中所使用的檸檬酸清洗相比,展現出較佳的介電質銅污染清洗成效。 此外,AFM(原子力顯微鏡)平坦度驗證也顯示出比檸檬酸清洗有更平滑的表面。TDS(熱分解質譜儀)用於檢查後化學機械研磨清洗後銅及介電質表面的有機殘餘物。在HAL緩衝氫氟酸浸泡後及臭氧超純水清洗後發現較少的有機殘餘物。這樣的清洗成效歸功於臭氧超純水清洗有機物的去除效果及HF蝕刻之結果。
除了上述的分析之外,還實施電性特性化以驗證在重要奈米元件清洗過程中所提出的清洗方法的實際成效。結果顯示所提出的清洗方式得到比目前使用的檸檬酸清洗較佳的漏電、崩潰、電荷崩潰性能。依據上述所有的實驗結果,我們的清洗方式為可行的且優於傳統式化學機械研磨清洗 。

Post CMP cleaning is an inevitable process for copper CMP in dual damascene technology. Minimizing organic, copper contamination residues on the dielectric surface is a goal of our investigation. In our study, a novel post CMP cleaning using HAL buffer HF solution and subsequent ozone water clean is proposed. From TRXRF (Total Reflection X-ray Fluorescence) and AFM (Atomic Force Microscope) roughness verification analysis, the new cleaning method has better copper clean performance compared to the citric clean, which is currently used in dual damascene copper clean process. TDS (Thermal Decomposition Spectrometer) is also used to check the organic residue on copper and dielectric surface after post CMP cleaning. Few organic residues are found in the clean process by using ozone water clean followed HAL buffer HF dip. The clean performance is attributed to the HF etching effect and the organic elimination effect of ozone water clean.
In addition to the above analysis, the electrical characterization is also performed to verify the actual effect the proposed clean approaches on the device cleaning process. The result shows that the proposed clean method has better leakage current, breakdown voltage, charge to breakdown performance than the citric clean. Based on all the experimental results mentioned above, our clean method is feasible and is superior to the conventional CMP clean.

Abstract (in Chinese)………………………………………………………………………………i
Abstract (in English)…………………………………………………ii
Acknowledgement…………………………………………………………iv
Contents……………………………………………………………………v
Table Captions…………………………………………………………vii
Figure Captions………………………………………………………viii
Chapter 1 Introduction
1.1 Background and Motivation…………………………………………1
1.2 Thesis Organization…………………………………………………4
Chapter 2 HAL Buffer HF plus Ozone Water Cleaning for Copper Contamination
2.1 Introduction……………………………………………………………5
2.2 Experiments……………………………………………………………6
2.3 Results and Discussion……………………………………………11
2.3.1 Analysis of Surface Roughness before/after Cleaning……11
2.3.2 Analysis of Copper Contamination before/after Cleaning……………………………………………………………………11
2.3.3 Electrical Characterization of LPD Gate Insulator before/after Cleaning for Copper Contamination…………………12
2.3.3.1 JE characteristic of LPD Capacitor ………………………12
2.3.3.2 Ebd characteristic of LPD Capacitor ……………………13
2.3.3.3 Qbd characteristic of LPD Capacitor………………………13
2.4 Summary…………………………………………………………………14
Chapter 3 HAL Buffer HF plus Ozone Water Cleaning for BTA Contamination
3.1 Introduction…………………………………………………………16
3.2 Experiments……………………………………………………………18
3.3 Results and Discussion……………………………………………23
3.3.1 Analysis of Surface Roughness before/after Cleaning……23
3.3.2 Analysis of BTA Contamination before/after Cleaning……23
3.3.3 Electrical Characterization of LPD Gate Insulator before/after Cleaning …………………………………………………24
3.3.3.1 JE characteristic of LPD Capacitor ………………………24
3.3.3.2 Ebd characteristic of LPD Capacitor………………………25
3.3.3.3 Qbd characteristic of LPD Capacitor……………………25
3.4 Summary…………………………………………………………………26
Chapter 4 Conclusions
4.1 Conclusions……………………………………………………………28
4.2 Future Work……………………………………………………………29
References…………………………………………………………………30

Reference
Chapter 1
[1] C.K. Hu. and JME. Harper, “ Copper interconnections and Reliability”Materials Chemistry and Physics. Vol 52, pp.5-16, 1998
[2] C. Steinbruchel, “ Patterning of copper for multilevel metallization:reactive ion etching and chemical mechanical polishing,” Applied Surface Science, Vol.91, pp.139-146, 1995.
[3] J.M.Steigerwald, et al.” Pattern geometry effect in chemical mechanical polishing of inlaid copper structures,” J. Electrochem. Soc., Vol.141, No.10, pp2842-2848, October 1994
[4] J.M.Steigerwald, et al.” Mechanism of copper removal during chemical mechanical polishing” J. Vac.Sci. Technol. B13(6), PP.2215-2218, Nov/Dec 1995
[5] J.M.Steigerwald, et al “Surface layer formation during the chemical mechanical polishing of copper thin films” Mat. Res. Soc. Symp. Proc.,Vol. 337, pp133-138, 1994
[6] F.B. Kaufman et al. “ Copper Photocorrosion Phenomenon during Post CMP Cleaning”
Electrochemical and Solid StateLetters3(3), pp.156-158, 2000.
Chapter 2
[1]HIROHISA et al.”Surface Active Buffered Hydrogen Fluoride Having Excellent Wettability for ULSI Processing” IEEE Trans. on Semiconductor Manufacturing vol.3 No.3 AUGUST 1990
[2]T. Shimono and M. Tsuji, Proceedings of 1ts Workshop on Ultra Clean Technology, 52, Ultra Clean Soc., Tokyo(1992)
[3]M. M. Heyns et al.”Cost Effective Cleaning for Advanced Si-Processing” 1985 IEDM pp.325
[4]James D et al. “Silicon VLSI Technology” 2000 Prentice Hall
[5]H. Uchida, N. Hirashita, and T. Ajioka, Technical Digest of IEDM, 405, SFO(1990)
[6]N. Fujino, Extended Abstracts of the 6 th International Symp. On Silicon Materials Science and Technology, 709, Montreal(1990)
[7]C. F. Yeh, C. L. Chen, and G. H. Lin,” The Physicochemical Properties and Growth of Oxides(SiO2-XFX ) by Liquid Phase Deposition with H2O Addition Only”, j. Electrochem. Soc., Vol.141, No.11, (1994), p3177
[8]C. L. Chen,”Investigation and Application of Room Temperature Liquid-Phase Deposited Silicon Oxide(SiO2-XFX )”, Doctoral Dissertation from Department of Electronic Engineering & Institute of Electronics, NCTU p39, p47
[9]J. Lee, I-C Chen, and C. Hu, 26th Annual Proceedings of the IEEE Reliability Physics Symposium, p131(1998)
[10]R. Moazzami, J. C. Lee, and C. Hu, IEEE Trans. On Electron Device 36, 2462(1989).
[11]Milton Ohring, “Reliability and Failure of Electronic Materials and Devices”, p.313.
[12]Jack C Lee et al., “Modeling and Characterization of Gate Oxide Reliability”, IEEE Transactions on Electron Devices, Vol. 35, No. 12, 2268 Dec., 1988
Chapter 3
[1]V. Nguyen et al. “Dependence of dishing on polish time and slurry chemistry in Cu CMP” Microelectronic Engineering, 50, pp.403-410, 2000.
[2]Cheng-Ging Chen, “Study on Chemical Mechanical Polishing in the Copper Damascene Process”, Master Thesis, NCTU
[3]Po-Lin Chen et al.”Study on Post Chemical Mechanical Polishing Cleaning in the Copper Damascene Process” Master Thesis of NTUT
[4]S.L. Cohen et al.”X-Ray Photoelectron Spectroscopy and Ellipsometry Studies of the Electrochemically Controlled Adsorption of Benzotriazole on Copper Surface”, Journal of Vacuum Science and Technology, Vol .8, No. 3, May/Jun 1990.
[5]C. Chadwick and T. Hashemi, Corrosion Science vol.18, page 39, 1978
[6]F. Mansfeld, T. Smith and E.P. Parry, Corrosion 27(1971) 289.
[7]G. W. Poling, Corrosion Science 10(1970) 350
[8]P.G. Fox, G. Lewis and P.J. Boden, Corrosion Science 19(1979)457
[9]J.M. Steigerwald et al. “ Chemical processes in the chemical mechanical polishing of copper”, Materials Chemistry and Physics, 41, pp. 217-228, March 1995.
[10]HIROHISA et al.”Surface Active Buffered Hydrogen Fluoride Having Excellent Wettability for ULSI Processing” IEEE Trans. on Semiconductor Manufacturing vol.3 No.3 AUGUST 1990
[11]T. Shimono and M. Tsuji: Proceedings of 1ts Workshop on Ultra Clean Technology, 52, Ultra Clean Soc., Tokyo(1992)
[12]M. M. Heyns et al.”Cost Effective Cleaning for Advanced Si-Processing” 1985 IEDM pp.325
[13]Geoff Rayner-Canham” Descriptive Inorganic Chemistry”, 2 th Edition, pp344, 353
[14]Geoff Rayner-Canham” Descriptive Inorganic Chemistry”, 2 th Edition, pp344, 353
[15]Tung Ming Pan et al.”Comparison of Novel Cleaning Solutions with Various Chelating Agent for Post CMP Cleaning on Poly-Si Film” IEEE Trans. on Semiconductor Manufacturing, vol. 14, No. 4, Nov. 2001
[16]C. F. Yeh, C. L. Chen, and G. H. Lin,” The Physicochemical Properties and Growth of Oxides(SiO2-XFX ) by Liquid Phase Deposition with H2O Addition Only”, j. Electrochem. Soc., Vol.141, No.11, (1994), p3177
[17]C. L. Chen,”Investigation and Application of Room Temperature Liquid-Phase Deposited Silicon Oxide(SiO2-XFX )”, Doctoral Dissertation from Department of Electronic Engineering & Institute of Electronics, NCTU p39, p47
[18]B. H. Chen “Investigation of High Quality LPD Insulator” Master thesis 2001, NCTU
[19]J. Lee, I-C Chen, and C. Hu, 26th Annual Proceedings of the IEEE Reliability Physics Symposium, p131(1998)
[20]R. Moazzami, J. C. Lee, and C. Hu, IEEE Trans. On Electron Device 36, 2462(1989).
[21]Milton Ohring, “Reliability and Failure of Electronic Materials and Devices”, p.313.
[22]Jack C Lee et al., “Modeling and Characterization of Gate Oxide Reliability”, IEEE Transactions on Electron Devices, Vol. 35, No. 12, 2268 Dec., 198

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