The impact of chemical bonding structure, porosity on electrical, mechanical, and thermal stress property of nano-clustering silica (NCS) low-k thin film have been investigated. NCS low-k thin films have been proved to have low dielectric constant with high elastic modulus. The direct incorporation of methyl (-CH3) groups by forming Si-CH3 bond could replace the conventional extra-step silylation process. The higher content Si-CH3 organic moieties had beneficial effect on the electrical properties of NCS low-k films.
The silica matrix TEOS/MTMS loading influenced on cross-link of Si-O-Si matrix. Higher TEOS content compared to MTMS produced higher Si-O-Si cross-link.
The structure directing agent/pore generator TPAOH concentration influenced the porosity in the way that lower TPAOH concentration produced smaller silica cluster, therefore as the smaller silica cluster can be packed more efficiently, hence producing smaller pores and lower porosity.
NCS2 to NCS5 porous low-k film has κ-value ranging from κ =2.3 to κ =2.8.
The silica matrix was composed by the addition of MTMS (Si-CH3) in balance with TEOS (Si-O-Si). Therefore high modulus porous low-k film was obtained (E~10GPa).
NCS2 through NCS5 film possessed spherical pore shape. The accommodation of Si-CH3 was equilibrated by the addition of Si-O precursor, in the agreement that the Si-O-Si linkage of NCS low-k film still preserved in the present of Si-CH3 groups. By adding more TPAOH, the porosity increased from NCS5 to NCS2 (micropores region enhancement) without causing much deterioration on mechanical modulus. Pore size was well controlled in the order of d<10nm with most population in the d=0.5nm.
In order to push κ-value <2.3, NCS1 porous low-k film was proposed with κ=2.0, that was obtained from less cross-link structure and higher porosity. The silica matrix
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was composed by higher content of MTMS (Si-CH3) instead of TEOS. But the modulus dropped to E=2.76GPa. Therefore, the incorporation of high methyl content and high porosity to NCS1 significantly reduced the κ value. Nevertheless, its Si-O-Si cross-linking was not rigid enough to sustain the thermal stress, therefore collapsed during thermal processing, formed elliptic cylindrical pore shape (din-plane=3.3nm dout-of-plane=1.9nm), and ultimately devastated the elastic modulus of final thin film.
In summary, in order to reduce dielectric constant and obtain higher elastic modulus of porous NCS low-k film, the appropriate precursor loading (MTMS/TEOS/TPAOH) must be taken into consideration. Since Si-O-Si matrix cross-linking and porosity greatly influenced the final property of porous NCS low-k film such as dielectric constant and elastic modulus.
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References
[1] M. T. Bohr, Tech. Digest IEEE Int. Electronic Device Meeting, 241 (1995).
[2] P. D. Moor, W. Ruythooren, P. Soussan, B. Swinnen, K. Baert, C. V.
Hoof, and E. Beyne, Mater. Res. Soc. Symp. Proc., 970, 0970-Y01-02 (2007).
[3] S. J. Martin, J. P. Godschalx, M. E. Mills, E. O. Shaffer II, and P. H.
Townsend, Adv. Mater., 12, 1769 (2000).
[4] J. L. Hedrick, R. D. Miller, C. J. Hawker, K. R. Carter, W. Volksen, D. Y.
[8] A. E. Braun, Semiconductor International, Low-k Bursts Into the Mainstream... Incrementally (2005)
[9] S. Lin, C. Jin, L. Lui, M. Tsai, M. Daniels, A. Gonzalez, J. T. Wetzel, K.A.
Monnig, P. A. Winebarger, S. Jang, D. Yu and M.S. Liang, in: Proc. IITC, 146 (2001).
Electrochem. Soc., 151, G882 (2004).
[15] K. D. Lee, E. T. Ogawa, S. Yoon, X. Lu, and P. S. Ho, Appl. Phys. Lett. , 82, 2032 (2003).
[16] G. Dixit, L. D. Cruz, S. Ahn., Y. Zheng, J. Chang, M. Naik, A. Demos, D.
95
Witty and H. Msaad, Proc. of the IEEE 2004 International Interconnect Technology Conference, 142 (2004).
[17] C. S. Yang and C. K. Choi, Curr. Appl. Phys., 6, 243 (2006).
[18] A. M. Padovani, L. Rhodes, L. Riester, G. Lohman, B. Tsuie, J. Conner, S. A.
B. Allen, and P. A. Kohla, Electrochem. and Solid-State Lett., 4, F25 (2001).
[19] G. Xu, J. He, E. Andideh, J. Bielefeld, and T. Scherban, Proc. of. The IEEE 2002 International Interconnect Technology Conference, 57 (2002).
[20] Z. Li, M. C. Johnson, M. Sun, E. T. Ryan, D. J. Earl, W. Maichen, J. I. Martin,
Ohha, M. Kase, H. Kitada, S. Satoh, N. Shimizu, I. Sugiura, F. Sugimoto, Y.
Setta, T. Tanka, N. Tamura, M. Nakaishi, Y. Nakata, J. Nakahira, N.
Nishikawa, A. Hasegawa, S. Fukuyama, K. Fujita, K. Hosaka, N. Horiguchi, H. Matsuyama, T. Minami, M. Minamizawa, H. Morioka, E. Yano, A.
Yamaguchi, K. Watanabe, T. Nakamura, and T. Sugii, Tech. Digest IEEE Int.
Electronic Device Meeting, 11.3.1 (2003).
[24] http://www.betasights.net/wordpress/?p=540
[25] I. Sugiura, N. Misawa, S. Otsuka, N. Nishikawa, Y. Iba, F. Sugimoto, Y. Setta, H. Sakai, Y. Koura, K. Nakano, T. Karasawa, Y. Ohkura, T. Kouno, H.
Watatani, Y. Nakata, Y. Mizushima, T. Suzuki, H. Kitada, N. Shimizu, S.
Nakai, M. Nakaishi, S. Fukuyama, T. Nakamura, E. Yano, M. Miyajima, and K. Watanabe, Microelec. Eng., 82, 380 (2005).
[26] K. Ito, R. S. Yu, K. Sato, K. Hirata, Y. Kobayashi, T. Kurihara, M. Egami, H.
96
Arao, A. Nakashima, and M. Komatsu, J. Appl. Phys. 98, 094307 (2005).
[27] G. E. Moore, Electronics, 38, 8 (1965).
[28] J. Singh, Semiconductor Devices: Basic Principles (John Wiley & Sons, New York, 2001), Chap. 10.
[29] “International technology roadmap for semiconductors," 2008. Update.
[30] P. T. Liu, T. C. Chang, Y. L. Yang, Y. F. Cheng and S. M. Sze, IEEE Trans. On Electronic Devices, 47, 1733 (2000).
[31] D. Edelstein, J. Heidenreich, R. Goldblatt, R. Schulz, L. Su, and J. Slattery, IEEE Int. Electronic Device Meeting, 1997, 773.
[32] R. D. Goldblatt, Proc. of Int'l Interconnect Technology Conference, 263, 261 (2000).
[35] 2008 ITRS Summer Public Conf.
[36] P. Atkins and J. de Paula, Atkins’ Physical Chemistry, 7th ed. (Oxford University Press, New York, 2002).
[37] S. O. Kasap, Principles of Electrical Engineering Materials and Devices (McGraw-Hill, New York, 1997), Chap. 7.
[38] K. J. Miller, H. B. Hollinger, J. Grebowicz, and B. Wunderlich, Macromolecules, 23, 3855 (1990).
[39] K. Maex, M. R. Baklanov, D. Shamiryan, F. Iacopi, S. H. Brongersma, and Z.
S. Yanovitskaya, J. Appl. Phys. 93, 8793 (2003).
[40] http://www.semiconductor.net/article/CA164243.html.
[42] V. L. Shannon, M. Z. Karim, Thin Solid Films, 270, 498 (1995).
97
[46] J. Bremmer, Y. Liu, K. Gruszynski and F. Dall, Mater. Res. Soc. Symp. Proc.,
37,476 (1997).
[47] Y. Liu, J. Bremmer, K. Gruszynski and F. Dall, VLSI Multilevel Interconnection Conf., 655, 1997, Santa Clara, CA.
[48] M. J. Loboda, Microelectron. Eng., 50, 15 (2000).
Peterson, and M. D. Bitner, Mater. Res. Soc. Symp. Proc., 766, E8.17.1 (2003).
[55] A trademark of Novellus Systems (http://www.novellus.com).
[56] A trademark of Applied Materials (www.appliedmaterials.com).
[57] S. J. Martin, J. P. Godschalx, M. E. Mills, E. O. Shaffer II, and P. H.
Townsend, Adv. Mater., 12, 1769 (2000).
[58] M. Fayolle, G. Passemard, M. Assous, D. Louis, A. Beverina, Y. Gobil, J.
Cluzel and L. Arnaud, Microelectron. Eng., 60, 119 (2002).
[59] T. Ramos, S. Wallace, and D. M. Smith, Mat. Res. Soc. Symp. Proc., 495, 279 Advanced Metallization Conferences (AMC)’’ Advanced Metallization and
98
Interconnect Systems for ULSI Applications, 445 (1996).
[63] C. Jin, J. D. Luttmer, D. M. Smith, and T. A. Ramos, MRS Bull. 22, 39 (1997).
[64] K. Chung, E. S. Moyer, and M. Spaulding, U.S. Patent No. 6,231,989 (2001).
[65] E. S. Moyer, K. Chung, M. Spauding, T. Deis, R. Boisvert, C. Saha, and J.
Bremmer, Proceedings of IITC, 1999.
[66] J. L. Hendrick, R. D. Miller, C. J. Hawker, K. R. Carter, W. Volksen, D. Y.
Yoon, and M. Trollsas, Adv. Mater., 10, 1049 (1998).
[67] M. Gallagher, N. Pugliano, J. Calvert, Y. You, R. Gore, N. Annan, M. Talley, S. Ibbitson, and A. Lamola, Presented at the MRS Spring Meeting, 2001.
[68] M. L. Che, J. Leu, Y. H. Chen, C. Y. Huang, and S. Choang , ECS Trans., 6, 591 (2007).
[69] Y. F. Lu, G. Z. Cao, R. P. Kale, S. Prabakar, G. P. Lopez, and C. J. Brinker, Chem. Mater., 11, 1223 (1999).
[70] M. R. Baklanov et al., Proceedings of the Advanced Metallization Conference Materials Research Society, Pittsburgh, PA, (2002).
[71] M. Petkov, M. H. Weber, K. G. Lynn, and K. P. Rodbell, Appl. Phys. Lett., 79, 3884 (2001).
[72] F. Iacopi et al., Microelectron. Eng. 64, 351 (2002).
[73] F. Ciaramella, V. Jousseaume, S. Maitrejean, M. Verdier, B. Remiat, A.
Zenasni, and G. Passemard, Thin Solid Films, 495, 124 (2006).
[74] K. Chung and S. Zhang, U.S. Patent No. 6,313,045 (2001).
[75] B. Zhong et al., Presented at the MRS Spring Meeting, 2002.
[76] Y. W. Chen, W. C. Wang, W. H. Yu, E. T. Kang, K. G. Neoh, R. H. Vora, C. K. Ong, L. F. Chen, C. K. Ong and L. F. Chen, J. Mater. Chem., 14, 1406 (2004).
99
Miller, Chem. Mater., 14, 3676 (2002).
[84] S. Yang, P. A. Mirau, C. S. Pai, O. Nalamasu, E. Reichmanis, J. C. Pai, Y. S.
Gidley, Adv. Funct. Mater., 14, 277 (2004).
[88] A. M. Padovani, L. Rhodes, S. A. B. Allen, and P. A. Kohl, J. Electrochem.
Soc., 149, F161 (2002).
100
[89] A. M. Padovani, L. Rhodes, S. A. B. Allen, and P. A. Kohl, J. Electrochem.
Soc., 149, F171 (2002).
[90] S. Z. Yu, T. K. S. Wong, X. Hu, K. Pita, and V. Ligatchev, J. Electrochem.
Soc., 151, F123 (2004).
[91] B. D. Lee, Y. H. Park, Y. T. Hwang, W. Oh, J. Yoon, and M. Ree, Nature Materials, 4, 147 (2005).
[92] H. W. Ro, K. J. Kim, P. Theato, D. W. Gidley, and D. Y. Yoon, Macromolecules, 38, 1031 (2005).
[93] B. J. Char, S. Kim, and K. Char, Macromol. Res., 13, 176 (2005).
[94] H. W. Ro, K. J. Kim, P. Theato, D. W. Gidley, and D. Y. Yoon, Macromolecules, 38, 1031 (2005).
[95] H. W. Su, W. C. Chen, Mat. Chem. and Phys., 114, 736 (2009).
[96] A. Zenasni, F. Ciaramella, V. Jousseaume, C. L. Cornec, and G. Passemard, J.
Electrochem. Soc., 154, G6 (2007).
[97] V. Jousseaume, A. Zenasni, L. Favennec, G. Gerbaud, M. Bardet, J. P. Simon, and A. Humbert, J. Electrochem. Soc., 154, G103 (2007).
[98] T.C. Chang, T.M. Tsai, P.T. Liu, C.W. Chen and T.Y. Tseng, Thin Solid Films, 469, 383 (2004).
[99] A. Zenasni, B. Remiat, C. Waldfried, C. L. Cornec, V. Jousseaume, and G.
Passemard, Thin Solid Films, 516, 1097 (2008).
[100] N. Kemeling, K. Matsushita, N. Tsuji, K. Kagami, M. Kato, S. Kaneko, H.
Sprey, D. Roest and N. Kobayashi, Microelec. Eng., 84, 2575 (2007).
[101] I. L. Berry III, C. Waldfried, and K. Durr, Mater. Res. Soc. Symp. Proc., 990, 0990-B02-01 (2007).
101
[102] E. Mickler, C. T. Lin, A. T. Krishnan, C. Jin, M. Jain, Proc. of the IEEE
2001 International Interconnect Technology Conference, 190 (2004).
[103] S. Li, Z. J. Li, and Y. S. Yan, Adv. Mater., 15, 1528 (2003).
[104] S. Li, J. N. Sun, Z. J. Li, H. G. Peng, D. Gidley, E. T. Ryan, and Y. S. Yan, J.
Phys. Chem. B, 108, 11689 (2004).
[105] Z. B. Wang, A. P. Mitra, H. T. Wang, L. M. Huang, Y. H. Yan, Adv.
McCullough, C. Taft, H. Lin, A. Simon, E. Simonyi, K. Malone, M.
Sankarapandian,D. Dunn, M. A. Zaitz, S. Cohen, N. Klymko, B. K. Moon, Z. Li, S. L, Y. Yan, J. Liu, P. S. Ho,Mater. Res. Soc. Symp. Proc., 863,
102
Maex, and J. A. Martens, Microporous and Mesoporous Materials, 118, 438 (2009).
[115] R. Aelion, A. Loebel, and F. Eirich, J. Am. Chem. Soc., 72, 5705 (1950) [116] G. Dixit, L. D. Cruz, S. Ahn, Y. Zheng, J. Chang, M. Naik, A. Demos, D.
Witty and H. Msaad, Proc. of the IEEE 2004 International Interconnect Technology Conference, 142 (2004).
[117] N, Tajima, T. Ohno, T. Hamada, K. Yoneda, S. Kondo, N. Kobayashi, M.
Shinriki, Y. Inaishi, K. Miyazawa, K. Sakota, S. Hasaka, and M. Inoeu, Jpn.
J. Appl. Phys., 46, 5970 (2007).
[118] C. S. Yang, and C. K. Choi, Curr. Appl. Phys., 6, 243 (2006).
[119] S.M. Bilodeau, A.S. Borovik, A.A. Ebbing, D.J Vestyck, C. Xu, J.F. Roeder, and T.H. Baum, Mat. Res. Soc. Symp. Proc., 812, F6.18.1 (2004).
[120] L.L. Chapelon, J. Vitiello, D. Neira, J. Torres, J.C. Royer, D. Barbier, F.
Naudin, G. Tas, P. Mukundhan, and J. Clerico, Microelec. Eng., 83, 2346 (2006).
[121] K. H. Lee, J. H. Yim, and M. R. Baklanov, Microporous and Mesoporous Materials, 94, 113 (2006).
[122] J.B. Vella, A.A. Volinsky, I.S. Adhihetty, N.V. Edwards, and W.W.
Gerberich, Mat. Res.Soc. Symp. Proc., 716, B12.13.1 (2002).
[123] M. P. Petkov, Mat. Res. Soc. Symp. Proc., 731, W5.20.1 (2002).
[124] Y. Liu, A. Knorr, W. L. Wu, D. Gidley, and B. Kastenmeier, Mater. Res. Soc.
Symp. Proc., 863, B3.1.1 (2005)
[125] N. Aoi, T. Fukuda and H. Yanazawa: Proc. Int. Interconnect Technology Conf., 72 (2002)..
[126] D.W. Krevelen, Properties of Polymers, 3rd edn., Elsevier, New York, (1990).
[127] S. Li, Proc. IEEE Int. Interconnect Technol. Conf., 146, (2001).
103
[128] S. Yang, P. A. Mirau, C. S. Pai, O. Nalamasu, E. Reichmanis, E. K. Lin, H. J.
Lee, D. W. Gidley, and J. N. Sun, Chem. Mater., 13, 2762 (2001).
[129] S. Eslava, M. R. Baklanov, A. V. Neimark, F. Iacopi, C. E. A. Kirschhock, K.
Maex, and J. A. Martens, Adv. Mater., 20, 3110 (2008).
[130] M. H. Ree, J. W. Yoon, and K. Y. Heo, J. Mater. Chem., 16, 685 (2006).
[131] P. Zaumseil, Innovations for High Performance Microelectronics, 497, Frankfurt (Oder) / Germany.
[132] http://staff.chess.cornell.edu/~smilgies/gisaxs/GISAXS.php [133] W. C. Oliver and G. M. Pharr, J. Mater. Res., 7, 1564 (1992). M. Ree, Macromolecules, 38, 3395 (2005).
[140] S. W. Yeh, K. H. Wei, Y. S. Sun, U. Jeng, K. S. Liang, Macromolecules, 37, 12 (2004).
[141] S. W. Yeh, K. H. Wei, Y. S. Sun, U. Jeng, K. S. Liang, Macromolecules., 37, 12 (2004).
[142] E. Y. Sheu, Phys. Rev. A., 45, 2428 (1992).
[143] A. Guinier and G. Fournet, Small Angle Scattering of X-Rays, (Wiley, New York, 1955).
[144] G. Porod, Small Angel X-ray Scattering, (Academic Press INC., London, New York, Eds, O.Glatter; O. Kratky, 1980). p. 17.
[145] U. S. Jeng, Y. S. Sun, H. J. Lee, C. H. Hsu, K. S. Liang, S. W. Yeh, K. H. Wei, Macromolecules., 37, 4617 (2004).
[146] D. H. Evertt, Pure Appl. Chem., 31, 579 (1972).
104
[147] V. Jousseaume, C. L. Cornec, F. Ciaramella, L. Favennec, A. Zenasni1, G.
Simon, J. P. Simon, G. Gerbaud, and G. Passemard, Mater. Res. Soc. Symp.
Proc., 914, 0914-F04-06 (2006).
[148] R.W. Rice, J. Mater. Sci., 40, 983 (2005).
[150] L. J. Gibson and M. F. Ashby, Cellular Solids: Structure and Properties, 2nd ed., Cambridge Univ. Press, Cambridge, UK (1997).
[151] K. K. Phani, S. K. Niyogi, and A. K. De, J. Mater. Sci. Lett., 7, 1253 (1988) [152] H. Miyosi, H. Matsuo, Y. Oku, H. Tanaka, K. Yamada, N. Mikami, S.
Takada, N. Hata and T. Kikkawa, Jpn. J. Appl. Phys., 43, 498 (2004).
[153] R. E. Williford, X. S. Li, R. S. Addleman, G. E. Fryxell, S. Baskaran, J. C.
Birnbaum, C. Coyle, T. S. Zemanian, C. Wang and A. R. Courtney, Microporous and Mesoporous Materials, 85, 260 (2005).
[154] N. Aoi, T. Fukuda and H. Yanazawa, Proc. Int. 2002 Interconnect
Technology Conf., California, 2002 (IEEE Press, New Jersey, 2002) p. 72.
[155] H. Miyoshi, H. Matsuo, Y. Oku, H. Tanaka, K. Yamada, N. Mikami, S.
Takada, N. Hata and T. Kikkawa, Jpn. J. Appl. Phys., 43, 498 (2004).
[156] H. Miyoshi, H. Matsuo, H. Tanaka, K. Yamada, Y. Oku, S. Takada, N. Hata and T. Kikkawa, Jpn. J. Appl. Phys., 44, 1161 (2005).
[157] R. W. Rice, J. Mater. Sci., 28, 2187 (1993).
Maex, and J. A. Martens, Microporous and Mesoporous Materials, 118, 458 (2009).