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Electrodeposition
Madhav Datta
4.1 Introduction
Electrodeposition is the process of cathodic deposition of metals, alloys, and other conducting materials from an electrolyte using an external potential (electric current) for the cation reduction process to occur at the working substrate. The deposition process is also known as electrolytic plating, electroplating, or simply plating. Electrodeposition is widely employed in a variety of applications ranging from coatings for wear and corrosion resistance to nanoscale feature fabrication for ultra-large-scale integration (ULSI). The deposition thickness may vary from few angstroms of uniformly deposited compact lms to electroformed structures that are millimeters thick. Compared to competing vacuum deposition processes, electrodeposition has emerged as more environmentally friendly and cost-effective micro/nanofabrication method. These features of electrodeposition make it an enabling technology for applications such as chip metallization and ipchip solder bumping. Electrodeposition has thus become an integral part of wafer processing fabs and an enabling technology in many aspects of microelectronic packaging. Although some aspects of electrodeposition still remain empirical, the gap between fundamental understanding and manufacturing application is narrowing [1]. In the following text the terms electrodeposition, electroplating, and plating are used synonymously. Advances in electrodeposition have played a major role in the phenomenal growth of storage, chip interconnects, microelectronic packaging, microelectromechanical systems (MEMS), and many other microelectronic and micromechanical components [210]. Some early examples of electrodeposition in the electronics industry include fabrication of printed circuit boards. Continued advances in plating processes for ne line wiring technology have contributed to the development of advanced boards and packages that are used today. Development of alloy plating
M. Datta (B) Cooligy Inc., 800 Maude Avenue, Mountain View, CA 94043, USA e-mail: mdatta@cooligy.com
Y. Shacham-Diamand et al. (eds.), Advanced Nanoscale ULSI Interconnects: Fundamentals and Applications, DOI 10.1007/978-0-387-95868-2_4, C Springer Science+Business Media, LLC 2009
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process, precision plating tool, and the application of through-mask plating for thin lm heads laid the foundation for the advances in electrochemical technology in the micro- and nanoelectronics industry [2]. Continued efforts on the development of novel magnetic materials and their precision plating have led to the advanced storage devices [3, 4]. Phenomenal advances in electroplating occurred in the last decade when it enabled a paradigm shift in chip making with the introduction of plated ip-chip technology and Cu metallization for chip interconnects [68]. Indeed, the material change from aluminum to copper for chip metallization has been heralded as a major breakthrough that will enable extension of Moores law beyond its earlier expectations. Other applications of electroplating in microelectronics include fabrication of connectors and interconnect, and metallization for multi-chip modules and other advanced packages [9]. These applications heavily relied on the advances in electroplating technologies which have been possible due to simultaneous progress in different areas. They include (i) continuous improvements and innovations in photolithography, (ii) fundamental understanding of the engineering principles that govern electrochemical micro- and nanofabrication processes and the ability to produce tailored materials and structures, and (iii) development of high yielding electrochemical processing tools that are compatible with ultra-clean semiconductor fabrications [10]. Some of these aspects are briey discussed below.
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of deposition. Internal stress that frequently develops in electrodeposits can cause cracking or loss of adhesion. Mismatch between substrate and deposit, grain coalescence during growth, and incorporation of additives or hydrogen may contribute to the internal stress. It is well known that electrodeposition under limiting current conditions leads to dendritic or powdery deposits [12, 13]. Therefore; the value of the operating current density with respect to the mass transport limited current density is a critical parameter for deposit morphology. Mass transport conditions at the wafer limit the rate of electroplating and inuences the current distribution and microstructure of the deposit. These criteria determine the thickness and uniformity of blanket deposited layers. In patterned plating, they also determine the shape evolution, leveling, and superlling. The current distribution in patterned plating is considered on three different scales: substrate scale, repeating pattern scale, and feature scale [14]. At the substrate level, the current distribution is governed by the overall cell geometry and the uniformity of current distribution is generally achieved by using auxiliary electrodes or current shielding concepts. On the pattern scale, the current distribution depends on the feature geometry and the spacing. Current density on a feature is higher when it is spaced farther away from a neighboring feature. On a feature scale, the current distribution evolves with time due to the continuously changing shape of the feature. The current distribution within the features is inuenced by the use of suitable additives [7, 14, 15]. Additives are widely employed in electroplating practice for grain rening, stress relieve, leveling, and brightening. Surfactants are also commonly added to plating electrolytes to facilitate evacuation of gas bubbles. A leveling agent is a suitably chosen additive that generally acts as an inhibitor for the metal deposition reaction. It is consumed at the cathode and its reaction rate is mass transport controlled [1518]. Since peaks are more accessible than valleys, they are more strongly inhibited by the additives, leading to preferential metal deposition into recess. These concepts have been used to develop understanding of superlling during dual-Damascene plating and to develop electroplating baths for Cu interconnects. Grain rening and brightening are related to inhibition which affects nucleation and growth. Early studies of the role of additives for the development of microstructure in electrodeposition were performed by Seiter and Fischer [19], who recognized the importance of inhibition for obtaining ne-grained deposits. Fishers concepts were further rened by Winand [20] and the factors affecting microstructure of electrodeposits were also discussed by Landolt [12]. The use of additives in electrodepositon of copper is a widely studied topic. Schimdt et al. [21] found that in a sulfate solution without additives copper nucleation on gold was three-dimensional. The presence of BTA decreased the size of nuclei and increased their number, while the presence of thiourea led to the formation of small at plates. Armstrong and Muller [22] found that BTA inhibits the growth of specic planes of copper but does not affect the number of nuclei. Kelly et al. [23] investigated the synergistic effects of adsorbed species using electrochemical methods and near eld microscopy. These authors demonstrated a strong synergistic effect between the adsorbed plating additive and the chloride ion. Such studies of the interactions between different additive species
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and their role in the nucleation and growth of deposits in nanostructures are of great importance to understand the mechanisms involved in Damascene plating of copper interconnects.
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Pulse reverse plating offers the possibility of achieving more uniform current distribution than in dc plating. In order to achieve this, the pulse parameters are so chosen that during the cathodic deposition cycle the current distribution is more uniform than during the anodic dissolution cycle. For example, one can apply a cathodic pulse corresponding to a relatively uniform secondary or tertiary current distribution, followed by a short high current density anodic pulse corresponding to a primary current distribution. The application of pulse reverse current is throughhole plating was studied by Pesco and Cheh [27]. Although the use of pc leads to a less uniform current distribution than the use of dc, pulse reverse plating was considered by the authors as a promising technique for improving current distribution. Wan et al. [28] investigated the applicability of pulse plating and pulse reverse plating in through-hole plating taking into account both the potential distribution and the prevailing mass transport conditions. From their theoretical analysis the authors concluded that throwing power is not improved by pulse plating but the use of pulse reverse plating may lead to more uniform deposits, in agreement with Pesco and Cheh [27]. Yung et al. [29] showed that the critical parameter characterizing the deposition rate in through-hole plating is proportional to L2 /r where L is the printed circuit board thickness and r is the hole radius. The current distribution therefore depends on the absolute dimension of the hole in addition to the aspect ratio.
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Additives that act as inhibitors tend to promote formation of ne equiaxial grains, which may lead to increased internal stress. Electrodeposited copper may contain non-equilibrium grain structures, which spontaneously recrystallize even at room temperature [35]. As a consequence, structure-dependent properties such as sheet resistance and internal stress of deposits may change slowly with time after deposition.
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Mathematical modeling work by Dukovic et al. [7, 14] assumed that the additives react under diffusion control while the metal deposition reaction is under activation controlled. Thus by optimizing the reaction rates (by varying additive concentration and adjusting the current density of Cu deposition), it is possible to obtain higher deposition rate at the bottom of via/trench. Moffat et al. [34, 3739] and West et al. [23, 40] explained the superconformal electrodeposition of copper by a curvature enhanced accelerator coverage model. The model is based on the assumptions that the local growth velocity is proportional to the surface coverage of the accelerator and the accelerator remains segregated at the metal/electrolyte interface during copper deposition. During deposit growth on nonplanar geometries, this leads to enrichment of the accelerator on the evolving concave surfaces and depletion on convex surfaces. This phenomenon gives rise to bottom-up superlling of submicrometer trenches and vias. In addition to the superlling property, these additives also inuence the deposit structure (hence stress) and roughness. It is evident that a delicate balance of respective additives is needed in the bath to obtain precise fabrication of void-free, nanoscale Cu interconnects that are to be uniformly laid on hundreds to thousands of chips in a 300 mm wafer.
References
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5. Romankiw, L. T. and Turner, D. (eds.): Electrodeposition Technology: Theory and Practice, PV 8617, Electrochemical Society Proceedings, New Jersey (1987) 6. Datta, M.; Shenoy, R. V.; Jahnes, C.; Andricacos, P. C.; Horkans, J.; Dukovic, J. O.; Romankiw, L. T.; Roeder, J.; Deligianni, H.; Nye, H.; Agarwala, B.; Tong, H. M.; and Totta, P. A.: Electrochemical fabrication of mechanically robust C4s. J. Electrochem. Soc. 142, 3779 (1995) 7. Andricacos, P. C.; Uzoh, C.; Dukovic, J. O.; Horkans, J.; and Deligianni, H.; Damascene copper electroplating for chip interconnections. IBM J. Res. Dev. 42, 567 (1998) 8. Datta, M.: Electrochemical processing technologies in chip fabrication: Challenges and opportunities. Electrochim. Acta. 48, 2975 (2003) 9. Seraphim, D. P.; Barr, D. E.; Chen, W. T.; Schmitt, G. P.; and Tummala, R. R.: In Microelectronic Packaging Handbook, Part III, 2nd edition, Tummala, R. R.; Rymaszewski, E. J.; and Klopfenstein, A. G. (eds.), Chapman and Hall, New York (1997) 10. Datta, M.: In New Trends in Electrochemical Technology, Microelectronic Packaging, Datta, M.; Osaka, T.; and Schultze, J. W. (eds.), CRC Press, New York, 3, 3 (2005) 11. Datta, M. and Landolt, D.: Fundamental aspects and applications of electrochemical microfabrication. Electrochim. Acta. 45, 2535 (2000) 12. Landolt D.: Electrochemical and materials science aspects of alloy deposition. Electrochim. Acta. 39, 1075 (1994) 13. Ibl, N.: In Comprehensive Treatise of Electrochemistry. Yeager, E.; Bockris, J. OM.; and Conway; B. (eds.), Plenum Press, New York 6(1), 133, 239, (1982) 14. Dukovic, J. O.: Feature-scale simulation of resist-patterned electrodeposition. IBM J. Res. Dev. 37(2), 125 (1993) 15. Madore, C.; Matlosz, M.; and Landolt, D.: Blocking inhibitors in cathodic leveling. I. Theoretical analysis. J. Electrochem. Soc. 143(12), 3927 (1996) 16. Kardos, O.: Current distribution on microproles, Part I, II, III. Plating, 61, 129, 229, 316 (1974) 17. Kruglikov, S. S.; Kudriavtsev, N. T.; Vorobiova, G. F.; and Antonov, A. Ya.: On the mechanism of levelling by addition agents in electrodeposition of metals. Electrochim. Acta. 10(3), 253 (1965) 18. Dukovic, J. and Tobias, C. W.: Simulation of leveling in electrodeposition. J. Electrochem. Soc. 137, 3748 (1990) 19. Seiter, H. and Fischer, H.: Electrocrystallization of metals. Z. Elektrochemie. 63, 249 (1959) 20. Winand, R.: Electrodeposition of metals and alloys-new results and perspectives. Electrochim. Acta. 39(8-9), 1109 (1994) 21. Schimdt, W. U.; Alkire, R. C.; and Gewirth, A.: Mechanic [sic] study of copper deposition onto gold surfaces by scaling and spectral analysis of in situ atomic force microscopic images. J. Electrochem. Soc. 143(10), 3122 (1996) 22. Armstrong, M. J. and Muller, R. H.: In situ scanning tunneling microscopy of copper deposition with Benzotriazole. J. Electrochem. Soc. 138(8), 2303 (1991) 23. Kelly, J. J.; Tian, C.; and West, A. C.: Leveling and microstructural effects of additives for copper electrodeposition. J. Electrochem. Soc. 146, 2540 (1999) 24. Ibl, N.: Some theoretical aspects of pulse electrolysis. Surface Technology. 10, 81 (1980) 25. Chin, D. T.: Mass transfer and current-potential relation in pulse electrolysis. J. Electrochem. Soc. 130, 1657 (1983) 26. Datta, M. and Landolt, D.: Experimental investigation of mass transport in pulse plating. Surface Technol. 25, 97 (1985) 27. Pesco, A. M. and Cheh, H. Y.: The current distribution within plated through-holes. J. Electrochem. Soc. 136(2), 408 (1989) 28. Wan, H. H.; Chang, R. Y.; and Yang, W. L.: Current distribution in a jet through-hole system during periodic electrolysis. J. Electrochem. Soc. 140(5), 1380 (1993) 29. Yung, E. K.; Romankiw, L. T.; and Alkire, R. C.: Plating of copper into through-holes and vias. J. Electrochem. Soc. 136(1), 206 (1989)
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30. Dini, J. W.: In Modern Electroplating. Schlesinger, M.; and Paunovic, M.: (eds.), 4th edition, Wiley Interscience, New York, 61 (2000) 31. Winnad, R.: Electrodeposition of metals and alloys-new results and perspectives. Electrochim. Acta. 39, 1091 (1994) 32. Donepudi, V. S.; Venkatachalapathy, R.; Ozemoyah, P. O.; Johnson, C. S.; and Prakash, J.: Electrodeposition of copper from sulfate electrolytes: Effects of Thiourea on resistivity and electrodeposition mechanism of copper. Electrochem. Solid-State Lett. 4(2), C, 13 (2001) 33. Landolt, D.: Electrodeposition science and technology in the last quarter of the twentieth century. J. Electrochem. Soc. 149(3), S, 9 (2002) 34. Moffat, T. P.; Bonewich, J. E.; Huber, W. H.; Stanishevsky, A.; Kelly, D. R.; Stafford, G. R.; and Josell, D.: Superconformal electrodeposition of copper in 50090 nm features. J. Electrochem. Soc. 147(12), 4524 (2000) 35. Cabral, C.; Andricacos, P. C.; Cignac, L. M.; and Noyan, I. C.: Room temperature annealing of damascene plated Cu chip metallization. Adv. Metallization Conf. Proc., ULSI XIV, 81 (1998) 36. Dubin, V. M.; Simka, H. S.; Shankar, S.; Moon, P.; Marieb, T.; and Datta, M.: In New trends in electrochemical technology, microelectronic packaging. Datta, M.; Osaka, T.; and Schultze, J. W. (eds.), CRC Press, New York. 3, 31 (2005) 37. Moffat, T. P.; Wheeler, D.; Huber, W. H.; and Josell, D.: Superconformal electrodeposition of copper. Electrochem. & Solid-State Lett. 4, C26 (2001) 38. Josell, D.; Wheeler, D.; Huber, W. H.; Bonevich, J. E.; and Moffat, T. P.: A simple equation for predicting superconformal electrodeposition in submicrometer trenches. J. Electrochem. Soc. 148, C767 (2001) 39. Wheeler, D.; Josell, D.; and Moffat, T. P.: Modeling of superconformal electrodeposition using the level set method. J. Electrochem. Soc. 150, C302 (2003) 40. West, A. C.; Mayer, S.; and Reid, J.: A superlling model that predicts bump formation. Electrochem. & Solid-State Lett. 4, C50 (2001)