Surface functionalization of silicon substrates via graft polymerization

SURFACE FUNCTIONALIZATION OF SILICON SUBSTRATES VIA GRAFT POLYMERIZATION YU WEIHONG (B. ENG., M. ENG.) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMICAL AND BIOMOLECULAR ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2004 ACKNOWLEDGEMENTS This dissertation would not have been completed without many people’s help. They made this time special and memorable for me. The author is deeply indebted to Professor Kang En Tang and Professor Neoh Koon Gee, for their constant guidance, encouragement, and valuable discussion through this work, and detailed criticism on the manuscript. The author wishes to express his thank to all my colleagues in Surface and Interface Molecular Engineering and Design (SIMED) lab for his kind help and support. It is a great time working with coworkers. In particular, this work is succeeded owing to Dr. Ling Qi Dan for sharing the valuable experience of synthesis and Dr. Ying Lei for useful discussions. The research scholarship provided by National University of Singapore is also gratefully acknowledged. Finally, special thanks are to my wife, daughter, and parents for their continuous love and support. i TABLE OF CONTENTS Page Acknowledgement i Table of Contents ii Summary iv Lists of Tables vi Lists of Figures vii Lists of Symbols xii Chapter Introduction Chapter Literature Survey 10 2.1 Surface Functionalization of Silicon Substrates via SelfAssembled Monolayers 11 2.2 Surface Functionalization via Layer-By-Layer Approach 22 2.3 Surface Functionalization via Grafted Polymer Chains 24 2.4 Living Free Radical Polymerization 35 2.5 Surface Functionalization with Polymer Chains for Application in Microelectronics Industry 41 2.6 Viologen-Functionalized Surface: Preparation and Applications 45 Chapter Functionalization of Hydrogen-Terminated Silicon via Surface-Initiated Atom Transfer Radical Polymerization 49 3.1 Experimental 50 3.2 Results and Discussion 60 3.3 Conclusions 93 ii Chapter Functionalization of Hydrogen-Terminated Silicon via Surface-Initiated Reversible Addition-Fragmentation Chain Transfer Polymerization of 4-Vinylbenzyl Chloride and Coupling of Viologen 4.1 Experimental 94 95 4.2 Results and Discussion 104 4.3 Conclusions 128 Chapter Functionalization of Silicon Surface via Plasma Graft Polymerization and its Application in Electroless Plating of Copper 129 5.1 Experimental 130 5.2 Results and Discussion 134 5.3 Conclusions 155 Chapter Functionalization of Dielectric SiLK Coated Silicon Surface via UV-induced Graft Copolymerization and its Application in Electroless Metallization 156 6.1 Experimental 157 6.2 Results and Discussion 162 6.3 Conclusions 182 Chapter Conclusions 183 References 186 List of Publications 206 iii SUMMARY Surface functionalization with polymer chains was investigated as an effective and versatile approach for the control of the surface properties. Controlled grafting of welldefined and functional polymer brushes on the hydrogen-terminated Si(100) substrates (the Si-H substrates) was carried out via surface-initiated living free radical polymerization (ATRP and RAFT) polymerization. Surface initiators were immobilized on the Si-H substrates in three consecutive steps: (i) coupling of an ω– unsaturated alkyl ester to the Si-H surface under UV irradiation, (ii) reduction of the ester groups by LiAlH4, and (iii) esterification of the surface-tethered hydroxyl groups with 2-bromoisobutyryl bromide (for ATRP) or 4,4’-azobis(4-cyanopentanoic acid) (for RAFT polymerization). Homopolymer brushes of methyl methacrylate (MMA), (2-dimethylamino)ethyl methacrylate (DMAEMA), poly(ethylene glycol) methacrylate (PEGMA), and glycidyl methacrylates (GMA) were prepared by surface-initiated ATRP. The rate of surface-initiated ATRP of GMA was enhanced in aqueous mixture (DMF/water) medium. The epoxy functional groups on the resulting Si-g-PGMA surface were preserved quantitatively. Diblock copolymer brushes consisting of PMMA and PDMAEMA blocks were obtained on the silicon surfaces using either type of the homopolymer brushes as the macroinitiators for ATRP of the second monomer. On the other hand, homopolymer brushes of 4-vinylbenzyl chloride (VBC) were prepared by surface-initiated RAFT polymerization on the Si-H surface with the immobilized azo initiators. The benzyl chloride groups of the grafted VBC polymer (PVBC) were subsequently derivatized into the viologen groups (Si-g-viologen surface). The redox-responsive property of the Si-g-viologen surfaces was demonstrated by photoreduction of the surface adsorbed Pd(II) and Au(III) ions to their respective metallic form. Electroless plating of copper could be carried out iv effectively on the Si-g-viologen surface with the photo-reduced palladium metal. Living free radical polymerization from the Si-H surfaces allowed the preparation of polymeric-inorganic hybrid materials with well-structured surface and interface. Surface functionalization of oriented single crystal silicon substrate is also carried out by plasma graft polymerization of 4-vinylpyridine (4VP). The pyridine functional groups of the plasma polymerized 4VP (pp-4VP) films could be retained, to a certain extent, under proper glow discharge conditions, such as a low input RF power. AFM images revealed that the pp-4VP-grafted Si(100) (pp-4VP-Si) surfaces remained relatively smooth. The grafted pp-4VP film on the Si(100) surface was used not only as the chemisorption sites for the palladium complexes (without the need for prior sensitization by SnCl2 ) during the electroless plating of copper, but also as an adhesion promotion layer for the electrolessly deposited copper. Surface modification of SiLK® film coated silicon wafer (SiLK-Si substrate) was carried out via UV-induced graft copolymerization. The 4VP, 2-vinylpyridine (2VP) and vinylimidazole (VIDz) graft copolymerized SiLK-Si surfaces could be activated via Sn-free process for the electroless metallization. The Sn-free process involved initially the chemisorption of palladium, in the complex form, on the pyridine or imidazole group of the graft polymer. The palladium complex underwent a reduction to Pd metal in the electroless copper or nickel plating bath prior to the initiation of the electroless metal deposition. The 4VP, 2VP and VIDz graft copolymerized SiLK-Si surfaces exhibited the enhanced adhesion with electrolessly deposited copper and nickel. v LIST OF TABLES Table 3.1 Chemical compositions, contact angle, film thickness, and surface coverage of the graft-polymerized silicon surfaces Table 3.2 Contact angle, film thickness, and surface composition of the diblock copolymer brushes grafted on the hydrogen-terminated silicon surfaces via ATRP Table 3.3 Chemical compositions, contact angle, film thickness, and surface coverage of the GMA graft-polymerized silicon surfaces Table 4.1 Chemical composition and film thickness of the Si-g-PVBC and Si-gviologen surfaces Table 4.2 Comparison of the adhesion strength of the electrolessly deposited copper with the Si-H, the Si-g-PVBC, and the Si-g-viologen surfaces Table 5.1 Effect of plasma graft polymerization of 4VP on the Si(100) surface on the adhesion strength of electrolessly plated copper Table 6.1 Comparison of the adhesion strength of the electrolessly deposited copper or nickel on the pristine, plasma-treated and grafted-modified SiLK-Si substrate surfaces vi LIST OF FIGURES Figure 3.1 Schematic diagram illustrating the processes of immobilization of surface initiators and surface graft polymerization via ATRP from the bromoesterfunctionalized silicon surface. Figure 3.2 XPS Si 2p core-level spectra of (a) the pristine Si(100) and (b) the Si-H surface, C 1s core-level spectra of (c) the Si-R1COOCH3 surface and (d) the Si-R2OH surface, and (e) C 1s and (f) Br 3d core-level spectra of the SiR3Br surface. Figure 3.3 XPS C1s core-level spectra of the Si-R3Br surface subjected to ATRP of (a) MMA, (b) DMAEMA, (c) PEGMA. Reaction conditions are shown in Table 3.1. Figure 3.4 Dependence of the thickness of the PMMA layer, grown from the Si-R3Br surface via ATRP, on (a) polymerization time, and (b) molecular weight (Mn) of the “free” PMMA formed in the solution. Reaction condition: [MMA] : [EBiB] : [CuBr] : [HMTETA] = 300 : : : 1, [MMA] = 4.7 M, solvent: anisole/acetonitrile = 1/1 (v/v), temp: 70 °C. Figure 3.5 The relationships (a) between ln([M0]/[M]) and polymerization time; (b) between Mn and monomer conversion (see Figure 3.4 for reaction conditions) Figure 3.6 AFM images of (a) the Si-H surface, (b) the Si-R3Br surface, and (c) the Sig-PMMA surface (PMMA thickness = 9.5 nm). Figure 3.7 XPS C 1s core-level spectra of (a) the PMMA-b-PDMAEMA and (b) PDMAEMA-b-PMMA block copolymer brushes on the silicon surface (the thickness values of the initial homopolymer and block copolymer brushes are given in Table 3.2). Figure 3.8 XPS (a) wide scan and (b) C1s core-level spectra of the Si-R3Br surface subjected to ATRP of GMA at room temperature in a mixed DMF/H2O medium for h. Figure 3.9 Reflectance FT-IR spectra of (a) the Si-g-PGMA surface (surface coverage = 28 mg/m2) and (b) the surface after subjected to reaction with M ethylenediamine in DMF at room temperature. vii Figure 3.10 AFM images of (a) Si-g-PGMA surface and (b) the Si-g-PGMA-NH2 (PGMA thickness = nm). Figure 3.11 Dependence of the thickness of the PGMA layer, grown from the Si-R3Br surface via ATRP on polymerization time in (a) DMF/Water medium and (b) DMF. Figure 3.12 XPS (a) C 1s and (b) F 1s core-level spectra of Si-g-PGMA-b-PFS surface. Figure 3.13 Schematic diagram illustrating the plausible reactions of the epoxy group with ethylenediamine Figure 3.14 XPS (a) C 1s and (b) N 1s core-level spectra of the Si-g-PGMA-NH2 surface. Figure 4.1 Schematic diagram illustrating the process for synthesis of chain transfer agent, cumyl dithiobenzoate Figure 4.2 Schematic diagram illustrating the processes of RAFT-mediated graft polymerization of VBC on the Si-H surface and functionalization of the VBC graft-polymerized Si surface with viologen. Figure 4.3 XPS (a) N 1s core-level spectrum of the Si-R3AZO surface and (b) C 1s and Cl 2p core-level spectra of the Si-g-PVBC surface. Figure 4.4 XPS (a) C 1s and (b) F 1s core-level spectra of the Si-g-PVBC-b-PFS surface. Figure 4.5 Dependence of the thickness of the PVBC layer, grown from the Si-R3AZO surface via RAFT polymerization, on (a) polymerization time and (b) molecular weight ( M n ) of the free PVBC formed in the solution. Reaction conditions: [VBC]:[CTA]:[AIBN] = 950:1:0.5, [VBC] = 5.7 M, solvent: DMF, temp: 80˚C. Figure 4.6 The relationship (a) between ln([M0]/[M]) and polymerization time, and (b) between M n and monomer conversion (CTA: cumyl phenyldithioacetate; other reaction conditions are similar to those indicated in Figure 4.6) viii Figure 4.7 Schematic diagram illustrating the chemical structures of the grafted VBC polymer on the Si-H surface (a) before and (b) after the coupling of viologen. Figure 4.8 XPS (a) N 1s and (b) Cl 2p core-level spectra of the Si-g-viologen surface prepared by reacting the Si-g-PVBC surface with an equimolar mixture of dichloro-p-xylene and bipyridine in DMF at 60 ºC for 20 h. Figure 4.9 Schematic diagram illustrating the process of electron mediation by the Sig-viologen surface during the photo-reduction of surface adsorbed Pd(II) ions. Figure 4.10 XPS Pd 3d core-level spectra of the Si-g-viologen surface ([N]/[C] = 0.02) (a) after immersion in the Pd(NO3)2 acid solution for 10 min, and (b) subjected to UV irradiation under an argon atmosphere for 30 min. XPS Au 4f core-level spectra of the Si-g-viologen surface ([N]/[C] = 0.02) (c) after immersion in the AuCl3 acid solution for 10 min, and (d) subjected to UV irradiation under an argon atmosphere for 30 min. Figure 4.11 AFM images of (a) the Si-H surface, (b) the Si-R3AZO surface and (c) the Si-g-PVBC surface ([Cl]/[C] = 0.09), and (d) the Si-g-viologen surface ([N]/[C] = 0.02). Figure 5.1 Schematic diagram of the plasma graft polymerization apparatus. Figure 5.2 Schematic diagram illustrating the processes of Ar plasma pretreatment, plasma graft polymerization, surface activation, and electroless plating of copper on the Si(100) surface. Figure 5.3 XPS wide scan and N 1s core-level spectra of (a) pristine Si(100) surface and the pp-4VP-Si surfaces prepared at input RF powers of (b) W and (c) 70 W on Ar plasma-pretreated silicon substrates. (Ar carrier gas flow rate = 20 sccm, system pressure = 100 Pa, monomer temperature = 0°C, and plasma deposition time = 45 s). Figure 5.4 FTIR spectra of (a) the 4VP homopolymer, and the pp-4VP films deposited on KBr discs at the input RF powers of (b) W and (c) 70 W. (Ar carrier gas flow rate = 20 sccm, system pressure = 100 Pa, monomer temperature = 0°C, and plasma deposition time = min). Figure 5.5 The plausible processes of molecular rearrangements of the activated 4VP molecules and radicals under low and high energy glow discharge condition. ix Ejaz, M., S. Yamamoto, K. Ohno, Y. Tsujii and T. Fukuda. Controlled Graft Polymerization of Methyl Methacrylate on Silicon Substrate by the Combined Use of the Langmuir-Blodgett and Atom Transfer Radical Polymerization Techniques, Macromolecules, 31, pp.5934-5936. 1998. Elkin, B., J. Mayer, B. Schindler and U. Vohrer. Wettability, Chemical and Morphological Data of Hydrophobic Layers by Plasma Polymerization on Smooth Substrates, Surf. Coatings Technol., 119, pp.836-840. 1999. Ellaboudy, A.S., P.J. Oconner, and J.C. Tou. Correlated Electron Spin-Resonance and Infrared Spectroscopic Study of the Postformation Auto-Oxidation Phenomenon in Plasma-Polymerized 4-Vinylpyridine Films, J. Appl. Polym. Sci., 60, pp.637-647. 1996. Frechet J.M.J. and M. J. Farrall. In Chemistry and Properties of Crosslinked Polymers. Ed. by S. S. Labana, pp.59-83, New Yeork: Academic Press. 1977. Freeman, W.M., D.J. Robertson and K.E. Vrana. Fundamentals of DNA Hybridization Arrays for Gene Expression Analysis, Biotechniques, 29, pp.1042-1042. 2000. Georger, M.K., R.P.N.Vergin, P.M.Kazmaier and G.K.Hamer. Narrow MoleculeWeight Resins by a Free-Radical Polymerization Process, Macromolecules, 26, pp.2987-2988. 1993. Goldblatt, R. D., B. Agarwala, M. B. Anand, E. P. Barth, G. A. Biery, Z. G. Chen, S. Cohen, J. B. Connolly, A. Cowley, T. Dalton, S. K. Das, C. R. Davis, A. Deutsch, C. DeWan, D. C. Edelstein, P. A. Emmi, C.G. Faltermeier, J. A. Fitzsimmons, J. Hedrick, J. E. Heidenreich, C. K. Hu, J. P. Hummel, P. Jones, E. Kaltalioglu, B. E. Kastenmeier, M. Krishnan, W. F. Landers, E. Liniger, J. Liu, N. E. Lustig, S. Malhotra, D. K. Manger, V. McGahay, R.Mih, H. A. Nye, S. Purushothaman, H. A. Rathore, S.C. Seo, T. M. Shaw, A. H. Simon, T. A. Spooner, M. Stetter, R. A. Wachnik, and J. G. Ryan. A High Performance 0.13µm Copper BEOL Technology with Low-k Dielectric. In Proc.3rd International Interconnect Tech. Conf., June 2000, San Francisco, CA, USA, pp. 261-263. Guyard, C. and B. Despax. Laser Writing on Gold-Containing Hydrocarbon Matrix Films Deposited by a Technique Combining Cathodic Sputtering with Hydrocarbon Plasma Polymerization, Surf. Coatings Technol., 119, pp.638-642. 1999. Hable, C.T., R.M. Crooks and M.S. Wrighton. pH-Dependent Charge Trapping by Quinones Electrostatically Bound in An Electrode-Confined Benzylviologen Polymer, J. Phys. Chem., 93, pp.1190-1192. 1989. Hadjian, J., R. Pilard and P. Bianco. J. Electroanal. Chem., 184, pp.391. 1985. 191 Hamers, R.J., S.K. Coulter, M.D. Ellison, J.S. Hovis, D.F. Padowitz, M.P. Schwartz, C.M. Greenlief and J.N. Russell. Cycloaddition Chemistry of Organic Molecules with Semiconductor Surfaces, Acc. Chem. Res., 33, pp.617-624. 2000. Han, L.C.M., R.B. Timmons, W.W. Lee, Y.Y. Chen and Z.B. Hu, Pulsed Plasma Polymerization of Pentafluorostyrene: Synthesis of Low Dielectric Constant Films, J. Appl. Phys., 84, pp.439-444. 1998. Hansen, K.M., H.F. Ji, G.H. Wu, R. Datar, R. Cote, A. Majumdar and T. Thundat. Cantilever-Based Optical Deflection Assay for Discrimination of DNA SingleNucleotide Mismatches, Anal. Chem., 73, pp.1567-1571. 2001. Hawker, C.J., A.W. Bosman and E. Harth. New Polymer Synthesis by Nitroxide Mediated Living Radical Polymerizations, Chem. Rev., 101, pp.3661-3688. 2001. He, J., S.N. Patitsas, K.F. Preston, R.A. Wolkow and D.D.M. Wayner. Covalent Bonding of Thiophenes to Si(111) by a Halogenation/Thienylation Route, Chem. Phys. Lett., 286, pp.508-514. 1998. He, P.G., T. Takahashi, T. Hoshi, J. Anzai, Y. Suzuki and T. Osa. Preparation of Enzyme Multilayers on Electrode Surface by Use of Avidin and Biotin-Labeled Enzyme For Biosensor Applications, Materials Sci. & Eng. C – Biomimetic Materials Sensors and Systems, 2, pp.103-106. 1994. Heeg, J., U. Schubert and F. Küchenmeister. Surface Chemistry of Planarized SiLKFilms Studied by XPS, Mikrochim. Acta, 133, pp.113-117. 2000. Hertler, W.R., D.Y. Sogah and F.P. Boettcher. Group-Transfer Polymerization on a Polymeric Support, Macromolecules, 23, pp.1264-1268. 1990. Higashi, G.S., Y.J. Chabal, G.W. Trucks and K. Raghavachari. Ideal Hydrogen Termination of the Si(1 1) Surface, Appl. Phys. Lett. 56, pp. 656-658. 1990 Huang, W.X., G.L. Baker and M.L. Bruening. Controlled Synthesis of Cross-Linked Ultrathin Polymer Films by Using Surface-Initiated Atom Transfer Radical Polymerization, Angew. Chem. Int. Edit., 40, pp.1510-1513. 2001. Huang, W.X., J.B. Kim, M.L. Bruening and G.L. Baker. Functionalization of Surfaces by Water-Accelerated Atom Transfer Radical Polymerization of Hydroxyethyl Methacrylate and Subsequent Derivatization, Macromolecules, 35, pp.1175-1179. 2002. Huang, X. and M.J. Wirth. Surface Initiation of Living Radical Polymerization for Growth of Tethered Chains of Low Polydispersity, Macromolecules, 32, pp.1694-1696. 1999. 192 Huang, Y.C., J. Flidr, T.A. Newton and M.A. Hines. Effects of Dynamic Step-Step Repulsion and Autocatalysis on the Morphology of Etched Si(111) Surfaces, Phys. Rev. Lett., 80, pp.4462-4465. 1998. Husseman, M., E.E. Malmström, M. McNamara, M. Mate, D. Mecerreyes, D. G. Benoit, J.L. Hedrick, P. Mansky, E. Huang, T.P. Russell and C.J. Hawker. Controlled Synthesis of Polymer Brushes by "Living" Free Radical Polymerization Techniques, Macromolecules, 32, pp.1424-1431. 1999. Ikeda, M., H. Kudo, R. Shinohara, F. Shimpuku, M. Yamada, and Y. Furumura. Integration of Organic Low-K Material with Cu-Damascene Employing Novel Process, Proc. st International Interconnect Technology Conf (IITC), San Francisco, CA, pp. 131-133. 1998. Inagaki, N. Plasma Surface Modification and Plasma Polymerization. Chap. 5, Lancaster, PA: Technomic. 1996. Inagaki, N., S. Tasaka, and M. Masumoto. Improved Adhesion between Kapton Film and Copper Metal by Plasma Graft Polymerization of Vinylimidazole, Macromolecules, 29, pp.1642-1648. 1996. Ingall, M.D.K., C.H. Honeyman, J.V. Mercure, P.A. Bianconi and R.R. Kunz. Surface Functionalization and Imaging using Monolayers and Surface-Grafted Polymer Layers, J. Am. Chem. Soc., 121, pp.3607-3613. 1999. Ito, Y., M. Inaba, D. J. Chung and Y. Imanishi, Control of Water Permeation by pH and Ionic-Strength Through a Porous Membrane Having Poly(carboxylic Acid) Surface-Grafted, Macromolecules, 25, pp.7313-7316. 1992. Jackson, R.L. Pd+2/Poly(acrylic acid) Thin-Films as Catalysts for Electroless Copper Deposition – Mechanism of Catalyst Formation, J. Electrochem. Soc., 137, pp.95-101. 1990. Jankova, K. and S. Hvilsted. Preparation of Poly(2,3,4,5,6-pentafluorostyrene) and Block Copolymers with Styrene by ATRP. Macromolecules, 36, pp.1753-1758. 2003. Jastrzebski, Z.D. The Nature and Properties of Engineering Materials, 3rd Ed., p.618, John Wiley and Sons, NY. 1987 Ji, H.F., T. Thundat, R. Dabestani, G.M. Brown, P.F. Britt and P.V. Bonnesen. Ultrasensitive Detection of CrO42- Using a Microcantilever Sensor, Analytical Chem., 73, pp.1572-1576. 2001. Jones, D.M. and W.T.S. Huck, Controlled Surface-Initiated Polymerizatiions in Aqueous Media. Adv. Mater., 16, pp.1256-1259. 2001. 193 Jordan, R. and A.Ulman. Surface Initiated Living Cationic Polymerization of 2Oxazolines, J. Am. Chem. Soc., 120, pp.243-247. 1998. Jordan, R., A. Ulman, J.F. Kang, M.H. Rafailovich and J. Sokolov. Surface-Initiated Anionic Polymerization of Styrene by Means of Self-Assembled Monolayers, J. Am. Chem. Soc., 121, pp.1016-1022. 1999. Juang, A., O.A. Scherman, R.H. Grubbs and N.S. Lewis. Formation of Covalently Attached Polymer Overlayers on Si(111) Surfaces using Ring-Opening Metathesis Polymerization Methods, Langmuir, 17, pp.1321-1323. 2001. Kamigaito, M., T. Ando and M. Sawamoto. Metal-Catalyzed Living Radical polymerization, Chem. Rev., 101, pp.3689-3745. 2001. Kamogawa, H. and M. Nanasawa. Effect of Temperature on the Color Developed by Near-Ultraviolet Light for 4,4’-Bipyridinium Slats (Viologens) Embedded in Poly(1Vinyl-2-pyrrolidone) Matrix, Bull. Chem. Soc. Jpn., 66, pp.2443-2445. 1993. Kang, E.T. and Y. Zhang. Surface Modification of Fluoropolymers via Molecules Design, Adv. Mater., 12, pp.1481-1494. 2000. Kang, E.T., K.G. Neoh, K.L. Tan and D.J. Liaw. Surface Graft Copolymerization and Grafting of Polymers for Adhesion Improvement. In Adhesion Promotion TechniquesTechnological Applications, ed by K.L. Mittal and A. Pizzi, pp.289-323. New York: Marcel Dekker. 1999. Kang, E.T., K.G. Neoh, and Y. Ikada., in Encyclopedia of Surface and Colloid Science, ed by A. Hubbard, pp. 2320-2340. New York: Marcel Dekker. 2000. Kato, K., E. Uchida, E.T. Kang, Y. Uyama and Y. Ikada. Polymer Surface with Graft Chains, Prog. Polym. Sci., 28, pp.209-259. 2003. Kato, M., M. Kamgaito, M. Sawamoto and T. Higashimura. Polymerization of Methyl Methacrylate with the Carbon Tetrachloride Dichlorotris(triphenylphosphine)ruthenium(II) Methylaluminum Bis(2,6-di-tertbutylphenoxide) Initiating System- possiblity of Living Radical Polymerization, Macromolecules, 28, pp.1721-1723. 1995. Keller P. and A. Moradpour, J. Am. Chem. Soc., 102, pp.7193. 1980 Kickelbick, G., U. Reinohl, T.S. Ertel, A. Weber, H. Bertagnolli, K. Matyjaszewski. Extended X-ray Absorption Fine Structure Analysis of the Bipyridine Copper Complexes in Atom Transfer Radical Polymerization. Inorg. Chem., 40, pp.6-8. 2001 Kim, J.B., W.X. Huang, M.L. Bruening, G.L. Baker. Synthesis of Triblock Copolymer Brushes by Surface-Initiated Atom Transfer Radical Polymerization. Macromolecules, 35, pp.5410-5416. 2002. 194 Kim, N.Y., N.L. Jeon, I.S. Choi, S. Takami, Y. Harada, K.R. Finnie, G.S. Girolami, R.G. Nuzzo, G.M. Whitesides and P.E. Laibinis. Surface-Initiated Ring-Opening Metathesis Polymerization on Si/SiO2, Macromolecules, 33, pp.2793-2795. 2000. Konecny, R. and D.J. Doren. Theoretical Prediction of a Facile Diels-Alder Reaction on the Si(100)-2x1 Surface, J. Am. Chem. Soc., 119, pp.11098-11099. 1997. Kotov, N.A. Layer-by-Layer Self-Assembly: The Contribution of Hydrophobic Interactions, Nanostructured Materials, 12, pp.789-796. 1999. Le, T.P., G. Moad, E. Rizzardo and S.H.Hang. WO Patent 98/01478 Lenigk, R., M. Carles, N.Y. Ip and N.J. Sucher. Surface Characterization of a SiliconChip-Based DNA Microarray, Langmuir, 17, pp.2497-2501. 2001. Leroy, E., O.M. Kuttel, L. Schlapbach, L. Giraud and T. Jenny. Chemical Vapor Deposition of Diamond Growth Using a Chemical Precursor, Appl. Phys. Lett., 73, pp.1050-1052. 1998. Li J., Y. Shacham-Diamand, and J. W. Mayer. Copper Deposition and ThermalStability Issues in Copper-based Metallization for ULSI Technology, Mater. Sci. Reports, 9, pp.1-51. 1992. Linford, M.R. and C.E.D. Chidsey. Alkyl Monolayers Covalently Bonded to Silicon Surfaces, J. Am. Chem. Soc., 115, pp.12631-12632. 1993. Linford, M.R., P. Fenter, P.M. Eisenberger and C.E.D. Chidsey. Alkyl Monolayers on Silicon Prepared from 1-Alkenes and Hydrogen-Terminated Silicon, J. Am. Chem. Soc., 117, pp.3145-3155. 1995 Liu, H.B. and R.J. Hamers. Stereoselectivity in Molecule-Surface Reactions: Adsorption of Ethylene on the Silicon(001) Surface, J. Am. Chem. Soc., 119, pp.75937594. 1997 . Liu, X., K.G. Neoh, Luping Zhao and E T. Kang, Surface Functionalization of Glass and Polymeric Substrates via Graft Copolymerization of Viologen in an Aqueous Medium, Langmuir, 18, pp.2914-2921. 2002. Lvov, Y., G. Decher and G. Sukhorukov. Assembly of Thin-Films by Means of Successive Deposition of Alternate Layers of DNA and Poly(allylamine), Macromolecules, 26, pp.5396-5399. 1993. Lyons, A.M., M.J. Vasile, E.M. Pearce, and J.V. Waszeza. Copper Chloride Complexes with Poly(2-vinylpyridine) - Preparation and Redox Properties, Macromolecules, 21, pp.3125-3134. 1988. 195 Maboudian, R. Surface Processes in MEMS Technology, Surf. Sci. Reports, 30, pp. 209-270. 1998. MacBeath, G., S.L. Schreiber. Printing Proteins as Microarrays for High-Throughput Function Determination, Science, 289, pp.1760-1763. 2000. Maier, G. Low Dielectric Constant Polymers for Microelectronics, Prog. Polym. Sci., 26, pp.3-65. 2001. Mallory, G.O. and J.B. Hajdu. (ed). Electroless Plating: Fundamentals and Applications. Orlando: AESF. 1990. Mance, A.M., R.A. Waldo and A.A. Dow. Interactions of Electroless Catalysts with Plasam-Oxidized Surfaces of Polystyrene-Based Resins, J. Electrochem. Soc., 136, pp.1667-1671. 1989. Mansky, P., Y. Liu, E. Huang, T.P. Russell and C. Hawker. Controlling PolymerSurface Interactions with Random Copolymer Brushes, Science, 275, pp.1458-1460. 1997. Mao, G.Z., Y.H. Tsao, M. Tirrell, H.T. Davis, V. Hessel and H. Ringsfdorf. Interactions, Structures And Stability of Photoreactive Bolaform Amphiphile Multilayers, Langmuir, 11, pp.942-952. 1995. Martin, S.J., J.P. Godschalx, M.E. Mills, E.O. Shaffer and P.H. Townsend. Development of a Low-Dielectric-Constant Polymer for the Fabrication of Integrated Circuit Interconnect, Adv. Mater., 12, pp.1769-1778. 2000. Matyjaszewski, K. and J. Xia. Atom Transfer Radical Polymerization, Chem. Rev., 101, pp.2921-2990. 2001. Matyjaszewski, K., P.J. Miller, N. Shukla, B. Immaraporn, A. Gelman, B.B. Luokala, T.M. Siclovan, G. Kickelbick, T. Vallant, H. Hoffmann and T. Pakula. Polymers at Interfaces: Using Atom Transfer Radical Polymerization in the Controlled Growth of Homopolymers and Block Copolymers from Silicon Surfaces in the Absence of Untethered Sacrificial Initiator, Macromolecules, 32, pp.8716-8724. 1999. May, C.A. Epoxy Resins: Chemistry and Technology. New York: Dekker. 1988. Minko, S., A. Sidorenko, M. Stamm, G. Gafijchuk, V. Senkovsky and S. Voronov. Radical Polymerization Initiated from a Solid Substrate. 2. Study of the Grafting Layer Growth on the Silica Surface by In Situ Ellipsometry, Macromolecules, 32, pp.45324538. 1999. Miura, T., M. Niwano, D. Shoji and N. Miyamoto. Kinetics of Oxidation on Hydrogen-Terminated Si(100) and (111) Surfaces Stored in Air, J. Appl. Phys., 79, pp.4373-4380. 1996. 196 Moad, G. and D.H. Solomon. The Chemistry of Free Radical Polymerization. Oxford: Pergamon. 1995. Moad, G, J. Chiefari, Y.K. Chong, J. Krstina, R.T.A. Mayadunne, A. Postma, E. Rizzardo, S.H. Thang, Living free radical polymerization with reversible additionfragmentation chain transfer (the life of RAFT), Polym. Inter. 49, pp.993-1001. 2000. Monk, P.M.S. The Viologens: Physicochemical Properties, Synthesis and Applications of the Salts of 4,4'-Bipyridine. Chichester, UK: John Wiley & Sons. 1998. Mori, H., A. Boker, G. Krausch and A.H.E. Muller. Surface-Grafted Hyperbranched Polymers via Self-Condensing Atom Transfer Radical Polymerization from Silicon surfaces, Macromolecules, 34, pp.6871-6882. 2001. Morrison, R.T. and R.N. Boyd. Organic Chemistry, pp. 20-22, Boston: Allyn and Bacon. 1983. Mortimer, R.J. and J.L. Dillingham. Electrochromic 1,1'-Dialkyl-4,4'-bipyridiliumincorporated Nafion Electrodes, J. Electrochem. Soc., 144, pp.1549-1553. 1997 Munakata, M., S. Kitagawa, A. Asahara and H. Masuda, Bull. Chem. Soc. Jpn. 60, 1927. 1987. Nakahara, S. and Y. Okinaka. Microstructure and Mechanical-Properties of Electroless Copper – Depositions, Annu. Rev. Mater. Sci., 21, pp.93-129. 1991. Nalwa, H.S.(ed). Silicon-Based Materials and Devices: Materials and Processing. Vol. 1, New York: Academic Press. 2001. Ng, S.W., K.G. Neoh, Y.T. Wong, J.T. Sampanthar and E.T. Kang. Surface Graft Copolymerization of Viologens on Polymeric Substrates, Langmuir, 17, pp.1766-1772. 2001. Ninham, B.W. and V. Yaminsky. Ion Binding and Ion Specificity: The Hofmeister Effect and Onsager and Lifshitz Theories, Langmuir, 13, pp.2097-2108. 1997. Okada, T., and Y. Ikada. Modification of Silicon Surface by Graft-Polymerization of Acrylamide with Corona Discharge, Makromol Chem, 192, pp.1705-1713. 1991. Okinaka, Y. and T. Osaka. Electroless Deposition Processes: Fundamentals and Applications. in Advances in Electrochemical Science and Engineering, Vol3, H. Gerischer and C.W. Tobias, Editiors, pp55-116. Weinheim: VCH. 1993. Park, K.K. and S.Y. Han. Convenient Reduction of Azobenzenes and Azoxybenzenes to Hydrazobenzenes by Sodium Dithionite using Dioctylviologen as An Electron Transfer Catalyst, Tetrahedron Lett., 37, pp.6721-6724. 1996. 197 Park, K.K., C.H. Oh and W.J. Sim. Chemoselective Reduction of Nitroarenes and Nitroalkanes by Sodium Dithionite Using Octylviologen as An Electron-Transfer Catalyst, J. Org. Chem., 60, pp.6202-6204. 1995. Pascual, S., B. Coutin, M. Tardi, K. Polton and J.P. Vairon. Homogeneous Atom Transfer Radical Polymerization of Styrene Initiated by 1-Chloro-l-phenylethane Copper(I) Chloride Bipyridine in the Presence of Dimethylformamide, Macromolecues, 32, pp.1432-1437. 1999. Perrier, S.; Haddleton, D. M. Effect of Water on Copper Mediated Living Radical Polymerization. Macromol Symp. 182, pp.261-272. 2002. Perrin D.D. and W.L.F.Armaregon. Purification of Laboratory Chemicals. Oxford: Pergamon Press. 1988. Prucker, O. and J. Rühe. Mechanism of Radical Chain Polymerizations Initiated by Azo Compounds Covalently Bound to the Surface of Spherical Particles, Macromolecules, 31, pp.602-613. 1998. Prucker, O. and J. Rühe. Synthesis of Poly(styrene) Monolayers Attached to High Surface Area Silica Gels through Self-Assembled Monolayers of Azo Initiators, Macromolecules, 31, pp.592-601. 1998a. Prucker, O., C.A. Naumann, J. Ruhe, W. Knoll and C.W. Frank. Photochemical Attachment of Polymer Films to Solid Surfaces via Monolayers of Benzophenone Derivatives, J. Am. Chem. Soc., 121, pp.8766-8770. 1999b. Pyun, J. and K. Matyjaszewski. Synthesis of Nanocomposite Organic/Inorganic Hybrid Materials Using Controlled/”Living” Radical Polymerization, Chem. Mater., 13, pp.3436-3448. 2001. Quinn, J.F., E. Rizzardo and T.P. Davis. Ambient Temperature Reversible AdditionFragmwntation Chain Transfer Polymerisation, Chem. Commun., pp.1044-1045. 2001. Rajagopal, A., C. Gregoire, J.J. Lemaire, J.J. Pireaux, M.R. Baklanov, S. Vanhaelemeersch, K. Maex and J.J. Waeterloos. Surface Characterization of a Low Dielectric Constant Polymer-SiLK* Polymer, and Investigation of Its Interface with Cu, J. Vac. Sci. Technol. B, 17, pp.2336-2340. 1999. Rivas, B.L. H.A.Maturana and E. Pereira. Metal-Ion Binding-Properties of Synthetic Vinyl Resins, Angew Makromol Chem., 220, pp.61-74. 1994. Sagiv, J. Organized Monolayers by Adsorption. 1. Formation and Structure of Oleophobic Mixed Monolayers on Solid Surfaces, J. Am. Chem. Soc., 102, pp.92-98. 1980. 198 Sampanthar, J.T., K.G. Neoh, S.W. Ng, E.T. Kang and K.L. Tan. Flexible Smart Window via Surface Graft Copolymerization of Viologen on Polyethylene, Adv. Mater., 12, pp.1536-1539. 2000. Sandrin, L., M.S. Silverstein, and E. Sacher. Fluorine Incorporation in PlasmaPolymerized Octofluorocyclobutane, Hexafluoropropylene and Trifluoroethylene, Polymer, 42, pp.3761-3769. 2001. Shah, R.R., D. Merreceyes, M. Husemann, I. Rees, N.L. Abbott, C.J. Hawker and J.L. Hedrick. Using Atom Transfer Radical Polymerization to Amplify Monolayers of Initiators Patterned by Microcontact Printing into Polymer Brushes for Pattern Transfer, Macromolecules, 33, pp.597-605. 2000. Sharma, S., R.W. Johnson and T.A. Desai. Ultrathin Poly(ethylene glycol) Films for Silicon-Based Microdevices, Appl. Surf. Sci., 206, pp.218-229. 2003. Shimazaki, Y., M Mitsuishi, S. Ito and M. Yamamoto. Alternate Adsorption of Polymers on a Gold Surface through the Charge-Transfer Interaction, Macromolecules, 32, pp.8220-8223. 1999. Shu, C.F. and M.S. Wrighton. Synthesis and Charge-Transport Properties of Polymers Derived from the Oxidation of 1-Hydro-1’-(6-(pyrrol-1-yl)hexyl)-4,4’-bipyridinium Bis(Hexafluorophosphate) and Demonstration of A pH-Sensitive Microelectrochemical Transistors Derived from the Redox Properties of A Conventional Redox Center, J. Phys. Chem., 92, pp.5221-5229. 1988. Sidorenko, A., S. Minko, K. Schenk-Meuser, H. Duschner and M. Stamm. Switching of Polymer Brushes, Langmuir, 15, pp.8349-8355. 1999. Sieval, A.B., A.L., Demirel, J.W.M., Nissink, M.R., Linford, J.H., van der Maas, W.H., de Jeu, H., Zuilhof and E.J.R., Sudholter. Highly Stable Si-C Linked Functionalized Monolayers on the Silicon (100) Surface, Langmuir, 14, pp.1759-1768. 1998 Sieval, A.B., V. Vleeming, H. Zuilhof and E.J.R. Sudholter. An Improved Method for the Preparation of Organic Monolayers of 1-Alkenes on Hydrogen-Terminated Silicon Surfaces, Langmuir, 15, pp.8288-8291. 1999. Silberzan, P., L. Leger, D. Ausserre and J.J. Benattar. Silanation of Silica Surfaces –A New Method of Constructing Pure and Mixed Monolayers, Langmuir, 7, pp.1647-1651. 1991. Sofia, S.J., V. Premnath and E.W. Merrill. Poly(ethylene oxide) Grafted to Silicon Surfaces: Grafting Density and Protein Adsorption, Macromolecules, 31, pp.50595070. 1998. Stears, R.L., T. Martinsky, and M. Schena. Trends in Microarray Analysis. Nature Medicine, 9, pp.140-145. 2003. 199 Stewart, M.P. and J.M. Buriak. Photopatterned Hydrosilylation on Porous Silicon, Angew. Chem. Int. Edit., 37, pp.3257-3260. 1998. Stewart, M.P. and J.M. Buriak. Exciton-Mediated Hydrosilylation on Photoluminescent Nanocrystalline Silicon, J. Am. Chem. Soc., 123, pp.7821-7830. 2001. Strother, T., W. Cai, X.S. Zhao, R.J. Hamers and L.M. Smith. Synthesis and Characterization of DNA-Modified Silicon (111) Surfaces, J. Am. Chem. Soc., 122, pp.1205-1209. 2000. Sung, M.M., G.J. Kluth, O.W. Yauw and R. Maboudian, Thermal Behavior of Alkyl Monolayers on Silicon Surfaces, Langmuir, 13, pp.6164-6168. 1997. Suzuki M., A. Kishida, H. Iwata and Y. Ikada. Graft Copolymerization of Acrylamide onto a Polyethylene Surface Pretreated with Glow Discharge, Macromolecules, 19, pp.1804-1808. 1986. Sze, S.M. The Physics of Semiconductor Devices. New York: Wiley. 1981. Tan, K.L., L.L. Woon, H.K. Wong, E.T. Kang and K.G. Neoh. Surface Modification of Plasma-Pretreated Poly(tetrafluoroethylene) Films by Graft-Coplymerization, Macromolecules, 26, pp.2832-2836. 1993. Teplyakov, A.V., M.J. Kong and S.F. Bent. Vibrational Spectroscopic Studies of Diels-Alder Reactions with the Si(100)-2x1 Surface as a Dienophile J. Am. Chem. Soc., 119, pp.11100-11101. 1997. Terry, J., M.R. Linford, C. Wigren, R.Y.,Cao, P. Pianetta and C.E.D. Chidsey. Determination of the Bonding of Alkyl Monolayers to the Si(111) Surface Using Chemical-Shift, Scanned-Energy Photoelectron Diffraction, Appl. Phys. Lett., 71, pp.1056-1058. 1997a. Terry, J., R. Mo, C. Wigren, R.Y. Cao, G. Mount, P. Pianetta, M.R. Linford and C.E.D. Chidsey. Reactivity of the H-Si (111) Surface, Nuclear Instrument Methods Phys. Res. Sect. B, 133, pp.94-101.1997b. Tillman, N., A. Ulman and T. L. Penner. Formation of Multilayers by Self-Assembly, Langmuir, 5, pp.101-111. 1989. Townsend, P.H., S.J. Martin, J. Godschalx, D.R. Romer, D.W. Smith, Jr., D. Castillo, R. DeVries, G. Buske, N. Rondan, S. Froelicher, J. Marshall, E.O. Shaffer, and J.H. Im. SiLK Polymer Coating with Low Dielectric Constant and High Thermal Stability for ULSI Interlayer Dielectric, Mater. Res. Soc. Symp. Proc., 476, pp.9-17. 1997. 200 Tsubokawa, N., A. Kogure, K. Maruyama, Y. Sone and M. Shimomura. GraftPolymerization of Vinyl Monomers from Inorganic Ultrafine Particles Initiated by Azo Groups Introduced onto the Surface, Polym. J., 22, pp.827-833. 1990. Tsujii, Y., M. Ejaz, K. Sato, A. Goto and T. Fukuda. Mechanism and Kinetics of RAFT-Mediated Graft Polymerization of Styrene on a Solid Surface. 1. Experimental Evidence of Surface Radical Migration, Macromolecules, 34, pp. 8872-8878. 2001. Tsukahara, K. and R.G. Wilkins, Inorg. Chem., 24, pp.3399. 1985. Uchida, T., K. Senda, G.K. Vinogradov and S. Morita. Plasma Polymerized Acetylene Thin Film by Pulsed Discharge, Thin Solid Films, 282, pp.536-538. 1996. Ulman, A. Formation and Structure of Self-Assembled Monolayers, Chem. Rev., 96, pp.1533-1554. 1996. Uyama, Y., K. Kato and Y. Ikada. Surface Modification of Polymers by Grafting, Adv. Polym. Sci., 137, pp.1-39. 1998. Van Ooij, W.J. Interfacial Interactions Between Polymers and Other Materials and Their Effects on Bond Durability. In Physicochemical Aspects of Polymer Surface. Vol. 2, ed by K.L. Mittal, pp.1035-1092. New York: Plenum Press. 1983. Vitale, M., N.B. Castagnola, N.J. Ortins, A. Brooks, A. Vaidyalingham and P.K. Dutta. Intrazeolitic Photochemical Charge Separation for Ru(bpy)(3)(2+)-Bipyridinium System: Role of the Zeolite Structure, J. Phys. Chem. B, 103, pp.2408-2416. 1999 von Werne, T. and T.E. Patten. Atom Transfer Radical Polymerization from Nanoparticles: A Tool for the Preparation of Well-Defined Hybrid Nanostructures and for Understanding the Chemistry of Controlled/"Living" Radical Polymerizations from Surfaces, J. Am. Chem. Soc., 123, pp.7497-7505. 2001. Waltenburg, H.N. and J.T. Yates Jr. Surface Chemistry of Silicon, Chem. Rev., 95, pp.1589-1673. 1995. Wang, J.S. and K. Matyjaszewski. Controlled Living Radical Polymerization -Halogen Atom-Transfer Radical Polymerization Promoted By a Cu(I)/CU(II) Redox Process, Macromolecules, 28, pp.7901-7910. 1995. Wang, P., K.L. Tan and E.T. Kang. Surface Modification of Poly(tetrafluoroethylene) Films via Grafting of Poly(ethylene glycol) for Reduction in Protein Adsorption, J. Biomater. Sci. Polym. Edn., 11, pp.169-186. 2000. Wang, P., K.L. Tan, E.T. Kang and K.G. Neoh. Surface Functionalization of Low Density Polyethylene Films with Grafted Poly(ethylene glycol) Derivatives, J. Material Chem., 11, pp.2951-2957. 2001. 201 Wang, X.S. and S.P. Armes. Facile Atom Transfer Radical Polymerization of Methoxy-Capped Oligo(ethylene glycol) Methacrylate in Aqueous Media at Ambient Temperature, Macromolecules, 33, pp.6640-6647. 2000. Wayner, D.D.M. and R.A. Wolkow. Organic Modification of Hydrogen Terminated Silicon Surfaces, J. Chem. Soc. Perk T., 2, pp.23-34. 2002. Weck, M., J.J.; Jackiw, R.R. Rossi, P.S. Weiss and R.H. Grubbs. Ring-Opening Metathesis Polymerization from Surfaces, J. Am. Chem. Soc., 121, pp.4088-4089. 1999. Weigl, B.H. and P. Yager. Microfluidics - Microfluidic Diffusion-based Separation and Detection, Science, 283, pp.346-347. 1999. Weimer, M.W., H. Chen, E.P. Giannelis and D.Y. Sogah. Direct Synthesis of Dispersed Nanocomposites by In Situ Living Free Radical Polymerization Using a Silicate-Anchored Initiator, J. Am. Chem. Soc., 121, pp.1615-1616. 1999. Wojtyk, J.T.C., M. Tomietto, R. Boukherroub and D.D.M. Wayner. "Reagentless" Micropatterning of Organics on Silicon Surfaces: Control of Hydrophobic/Hydrophilic Domains, J. Am. Chem. Soc., 123, pp.1535-1536. 2001. Wolkow, R.A. Controlled Molecular Adsorption on Silicon: Laying a Foundation for Molecular Devices, Annu. Rev. Phys. Chem., 50, pp.413-441. 1999. Wu, S.Y., E.T. Kang, K.G. Neoh, H.S. Han and K.L. Tan. Surface Modification of Poly(tetrafluoroethylene) Films by Graft Copolymerization for Adhesion Improvement with Evaporated Copper, Macromolecules, 32, pp.186-193. 1999. Xu, D., E.T. Kang; K.G. Neoh; Y. Zhang; A.A.O. Tay; S.S. Ang, M.C.Y. Lo and K. Vaidyanathan. Selective Electroless Plating of Copper on (100)-Oriented Single Crystal Silicon Surface Modified by UV-Induced Coupling of 4-Vinylpyridine with the H-Terminated Silicon, J. Phys. Chem. B, 106, pp.12508-12516. 2002 Xue, G., Q.P. Dai and S. G. Jiang. Chemical-Reactions of Imidazole with Metallic Silver Studied by the Use of SERS and XPS Techniques, J. Am. Chem. Soc., 110, pp.2393-2395. 1988. Xue, G., G.Q. Shi, J.F. Ding, W.M. Chang and R.S. Chen. Complex-Induced Coupling Effect - Adhesion of Some Polymers to Copper Metal Promoted by Benzimidazole, J. Adhes. Sci. Technol., 4, pp.723-732. 1990. Yamamoto, S., M. Ejaz, Y. Tsujii and T. Fukuda. Surface Interaction Forces of WellDefined, High-Density Polymer Brushes Studied by Atomic Force Microscopy. 1. Effect of Chain Length, Macromolecules, 33, pp. 5602-5607. 2000a. 202 Yamamoto, S., M. Ejaz, Y. Tsujii and T. Fukuda. Surface Interaction Forces of WellDefined, High-Density Polymer Brushes Studied by Atomic Force Microscopy. 2. Effect of Graft Density, Macromolecules, 33, pp.5608-5612. 2000b. Yang, G.H., E.T. Kang and K.G. Neoh. Surface Modification of Poly(tetrafluoroethylene) Films by Plasma Polymerization of Glycidyl Methacrylate and its Relevance to the Electroless Deposition of Copper, J. Polym. Sci. Part A: Polym. Chem., 38, pp.3498-3509. 2000. Yang, G.H., E.T. Kang, K.G. Neoh, Y. Zhang and K. L. Tan. Surface Graft Copolymerization of Poly(tetrafluoroethylene) Films with N-containing Vinyl Monomers for the Electroless Plating of Copper, Langmuir, 17, pp.211-218. 2001a. Yang, G.H., E.T. Kang, K. G., Neoh, Y. Zhang, and K.L. Tan. Electroless Deposition of Copper on Polyimide Films Modified by Surface Graft Copolymerization with Nitrogen-Containing Vinyl Monomers, Colloid Polym. Sci., 279, pp.745-753. 2001b. Yang, X.G., J.X. Shi, S. Johnson and B. Swanson. Growth of Ultrathin Covalently Attached Polymer Films: Uniform Thin Films for Chemical Microsensors, Langmuir, 14, pp.1505-1507. 1998. Yasuda, H. (ed). Plasma Polymerization. Chap. 3, New York: Academic Press. 1985. Yates, J.T. A New Opportunity in Silicon-Based Microelectronics, Science, 279, pp.335-336. 1998. Yen, P.C. Improved ABS Plastic Activating Treatment for Electroless Copper Plating, Polymer, 36, pp.3399-3400. 1995. Yu, Z.J., E.T. Kang, K.G. Neoh and K.L. Tan. Surface Passivation of Epoxy Resin with a Covalently Adhered Poly(tetrafluoroethylene) Layer, Surf. Coat. Tech., 138, pp.48-55. 2001. Yu, Z.J., E.T. Kang and K.G. Neoh. Electroless Plating of Copper on Poly(tetrafluoroethylene) Films Modified by Surface Graft Copolymerization and Quaternization, J. Electrochem. Soc., 149, pp.C10-C17. 2002. Yuk, S.H., S.H. Cho and S.H. Lee. pH/Temperature-Responsive Polymer Composed of Poly((N,N-dimethylamino)ethyl Methacrylate-co-Ethylacrylamide), Macromolecules, 30, pp.6856-6859. 1997. Zazzera, L.A., J.F. Evans, M. Deruelle, M. Tirrell, C.R. Kessel and P. Mckeown. Bonding Organic Molecules to Hydrogen-Terminated Silicon Wafers, J. Electrochem. Soc., 144, pp.2184-2189. 1997. Zee, F. and J. W. Judy. Micromachined Polymer-based Chemical Gas Sensor Array, Sensors and Actuators B, 72, pp.120-128. 2001. 203 Zen, J.M. and C.W. Lo. A Glucose Sensor Made of An Enzymatic Clay-Modified Electrode and Methyl Viologen Mediator, Anal. Chem., 68, pp.2635-2640. 1996. Zeng, F., Y. Shen, S. Zhu and R. Pelton. Synthesis and Characterization of CombBranched Polyelectrolytes. 1. Preparation of Cationic Macromonomer of 2(Dimethylamino)ethyl Methacrylate by Atom Transfer Radical Polymerization, Macromolecules, 33, pp.1628-1635. 2000. Zhang, J. F., C.Q. Cui, T.B. Lim, E.T. Kang and K.G. Neoh, Chemical Modification of Silicon (100) Surface via UV-Induced Graft Polymerization, Chem. Mater., 11, pp.1061-1068. 1999. Zhang, Y., K.L. Tan, G.H. Yang, X.P. Zou, and E.T. Kang. Thermal Imidization of Poly(amic acid) on Si(100) Surface Modified by Plasma Polymerization of Glycidyl Methacrylate, J. Adhesion Sci. Technol., 14, pp.1723-1744. 2000. Zhang, F., E.T. Kang, K.G. Neoh, P. Wang and K.L. Tan, Surface Modification of Stainless Steel by Grafting of Poly(ethylene glycol) for Reduction in Protein Adsorption, Biomaterials, 22, pp.1541-1548. 2001a. Zhang, F., E.T. Kang, K.G. Neoh and W. Huang. Modification of Gold Surface by Grafting of Poly(ethylene glycol) for Reduction in Protein Adsorption and Platelet Adhesion, J. Biomater. Sci. Polym. Edn., 12, pp.515-531. 2001b. Zhang, Y. K.L. Tan, B.Y. Liaw, D.J. Liaw, E.T. Kang, and K.G. Neoh. Thermal Imidization of Fluorinated Poly(amic acid)s on Si(100) Surfaces Modified by Plasma Polymerization and Deposition of Glycidyl Methacrylate, Langmuir, 17, pp.2265-2274. 2001c. Zhang, Y. Surface Modification of Silicon and Polymeric Dielectrics via Graft Polymerization and its Relevance to Adhesion Enhancement, Ph.D Thesis, National University of Singapore. 2001d. Zhang, Y., K.L. Tan, G.H. Yang, E.T. Kang, and K.G. Neoh. Electroless Plating of Copper and Nickel via a Sn-free Process on Polyimide Films Modified by Surface Graft Copolymerization with 1-Vinylimidazole, J. Electrochem. Soc., 148, pp.C574C582. 2001e. Zhang, Y., K. L. Tan, B.Y. Liaw, D.J.Liaw, E.T. Kang, K.G. Neoh. Thermal Imidization of Fluorinated Poly(amic acid) Precursors on a Glycidyl Methacrylate Graft-Polymerized Si(100) Surface, J. Vac. Sci. Tech. A, 19, pp.547-556. 2001f. Zhao, B. and W.J. Brittain. Synthesis of Tethered Polystyrene-block-Poly(methyl methacrylate) Monolayer on a Silicate Substrate by Sequential Carbocationic Polymerization and Atom Transfer Radical Polymerization, J. Am. Chem. Soc., 121, pp.3557-3558. 1999 204 Zhao, B. and W.J. Brittain. Polymer Brushes: Surface-Immobilized Macromolecules, Prog. Polym. Sci., 25, pp.667-710. 2000a. Zhao, B. and W.J. Brittain. Synthesis, Characterization, and Properties of Tethered Polystyrene-b-Polyacrylate Brushes on Flat Silicate Substrates, Macromolecules, 33, pp.8813-8820. 2000b. Zhao, B., W.J. Brittain, W. Zhou and S.Z.D. Cheng. AFM Study of Tethered Ppolystyrene-b-Poly(methyl methacrylate) and Polystyrene-b-Poly(methyl acrylate) Brushes on Flat Silicate Substrates, Macromolecules, 33, pp.8821-8827. 2000. Zhao, L.P., K.G. Neoh and E.T. Kang. Photoinduced and Thermal-Activated Doping of Polyaniline, Chem. Mater., 14, pp.1098-1106. 2002. Zhu, X.Y. Organic Monolayers on Silicon: Microprinting, Micromachines, and Microarrrays, Acta Physico-Chemica Sinca, 18, pp.855-864. 2002. Zou, X.P., E.T. Kang, K.G. Neoh, C.Q. Cui and T.B. Lim. Surface Modification of Poly(tetrafluoroethylene) Films by Plasma Polymerization of Glycidyl Methacrylate for Adhesion Enhancement with Evaporated Copper, Polymer, 42, pp.6409-6418. 2001. 205 LIST OF PUBLICATIONS 1. Yu, W.H., Y. Zhang, E.T. Kang, K.G. Neoh, S.Y. Wu and Y.F. Chow. Electroless Plating of Copper via a Sn-Free Process on Dielectric SiLK® Surface Modified by UV-induced Graft Copolymerization with 4Vinylpyridine and 1-Vinylimidazole, J. Electrochem. Soc., 149, pp.C521-C528. 2002. 2. Yu, W.H., E.T. Kang and K.G. Neoh. Electroless Plating of Copper on (100)Oriented Single Crystal Silicon Substrates Modified by Plasma Graft Polymerization of 4-Vinylpyridine, J. Electrochem. Soc., 149, pp.C592-C599. 2002. 3. Yu, W.H., Y. Zhang, E.T. Kang, K.G. Neoh, S.Y. Wu and Y.F. Chow. Electroless Metallization of Dielectric SiLK® Surfaces Functionalized by Viologen, J. Electrochem. Soc., 150, pp.F156-F163. 2003. 4. Yu, W.H., E.T. Kang, K.G. Neoh and S. Zhu. Controlled Grafting of WellDefined Polymers on Hydrogen-Terminated Silicon Substrates by SurfaceInitiated Atom Transfer Radical Polymerization, J. Phys. Chem. B, 107, pp.10198-10205. 2003. 5. W.H. Yu, E.T. Kang and K.G. Neoh. Controlled Grafting of Well-Defined Functional Polymers on Hydrogen-Terminated Silicon Substrates-Relevance to Adhesion of Electroless Deposited Copper. In Polymer Surface Modification: Relevance to Adhesion, Vol.3. Mittal K. L.(editor), pp. 435-455 (Book Chapter). VSP, 2004. 6. Yu, W.H., E.T. Kang and K.G. Neoh. Functionalization of HydrogenTerminated Si(100) Substrate by Surface-Initiated RAFT of 4-Vinyl Chloride and Subsequent Derivatization for Photo-induced Metallization. Ind. Eng. Chem. Res. 43, pp.5194-5202, 2004. 7. Yu, W.H., E.T. Kang and K.G. Neoh. Controlled Grafting of Well-Defined Epoxide Polymers on Hydrogen-Terminated Silicon Substrates by SurfaceInitiated ATRP at Ambient Temperature. Langmuir. 20, 8294-8300. 2004. 8. Zhai, G.Q., W.H. Yu, E. T. Kang, K.G. Neoh, C.C. Huang, and D.J. Liaw. Functionalization of Hydrogen-Terminated Silicon with Polybetaine Brushes via Surface-Initiated Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization, Ind. Eng. Chem. Res. 43, pp.1673-1680. 2004. 9. Ying, L. W.H. Yu, E.T. Kang and K.G. Neoh. ‘Smart’ and ‘Living’ Membranes from RAFT-mediated Graft Copolymers, Langmuir. 20, pp. 60326040. 2004. 10. Xu, D., W.H. Yu, E.T. Kang, and K.G. Neoh. Functionalization of HydrogenTerminated Silicon via Surface-Initiated Atom Transfer Radical Polymerization and Derivatization of the Polymer Brushes. J. Colloid Interf. Sci. 279, pp. 7887, 2004. 206 [...]... on the solid surface The purpose of this thesis is to functionalize the silicon surface via the graft polymerization techniques, such as surface- initiated living free radical polymerization, UV-induced graft polymerization and plasma graft polymerization The applications of the graft- modified silicon surface in simplifying the electroless plating process and in promoting the adhesion of the electrolessly... ratio, of the SiLK surface Figure 6.5 XPS C 1s and N 1s core-level spectra of the graft- modified SiLK-Si surfaces prepared at UV graft copolymerization time of 60 min x Figure 6.6 The dependence of the graft concentration of the VIDz polymer and the resulting 180º-peel adhesion strength of the electrolessly deposited copper on (a) the concentration of the VIDz monomer and (b) the UV graft copolymerization... strength of the electrolessly deposited copper with the Si-g-viologen surface was evaluated 8 Chapter 5 is concerned with the functionalization of silicon surface by plasma graft polymerization of 4-vinylpyridine (4VP) and its application in electroless plating of copper The effect of plasma graft polymerization parameters, such as plasma power, monomer temperature, carrier gas flow rate, on the graft. .. understanding and control of silicon surface is of great importance in the production of silicon- based devices for applications ranging from advanced microelectronics to biomaterials (Nalwa, 2001) Recently, there has been growing interest in the functionalization of silicon and other semiconductor surfaces with organic molecules to modify the surface and interfacial properties of these substrates The motivation... Figure 6.7 The dependence of the surface graft concentration of the 4VP polymer and the resulting 180º-peel adhesion strength of the electrolessly deposited copper on (a) the concentration of the 4VP monomer and (b) the UV graft copolymerization time Figure 6.8 The AFM images of (a) the pristine SiLK-Si surface, (b) the VIDz-g-SiLKSi surface ([N]/[C*] = 1.0), (c) the 2VP-g-SiLK-Si surface ([N]/[C*] = 1.5),... strength of 226 kJ/mol (Waltenburg and Yates, 1995) When the crystal is cut or cleaved, bond is broken, creating dangling bonds at the surface The dangling bonds are the sources of the chemical activity of silicon surfaces The number and direction of these dangling bonds will depend on the macroscopic direction of the surface normal Reducing the number of the dangling bonds via rebonding can lower the surface. .. uniform Si(100)–H surfaces Using this approach, the surface has undergone a reconstruction to form rows of Si–Si dimmers The reconstruction of the surface to this 2×1 structure is driven by the formation of Si=Si bonds which reduced the number of the dangling bonds on the surface atoms from two per silicon to only one (Waltenburg and Yates, 1995) 12 Hydrogen terminated silicon surfaces (Si-H surfaces) are... Hydrogen-Terminated Silicon Surface Covalent attachment of organic monolayer to the oriented single crystal silicon surface via Si-C bond allows a direct coupling between organic materials and semiconductors One of the most efficient Si-C bond forming reactions is hydrosilylation which involves insertion of an unsaturated bond into a silicon- hydride group via the use of a radical initiator, as well as via thermal... ascertain the “living” character of the PVBC-grafted silicon surface The benzyl chloride groups of the PVBC brushes were derivatized into the viologen moieties (the Si-g-viologen surface) The redoxresponsive property of the viologen polymer brushes was demonstrated by photoreduction of the surface- adsorbed Pd(II) and Au(III) ions Electroless plating of copper on the Si-g-viologen surfaces with the photo-reduced... removal of silicon from the surface (etching) in the form of SiF3OH and the capping of the surface silicon atom by hydrogen Treatment of commercial, native oxide-capped flat crystal Si(100) wafers with diluent aqueous HF solution yields hydrogen terminated Si(100) (Si(100)-H) surface, which contains some SiH and SiH3 groups, but predominantly SiH2 (Chabal et al., 1989) Roughening of the Si(100) surface . 10 2.1 Surface Functionalization of Silicon Substrates via Self- Assembled Monolayers 11 2.2 Surface Functionalization via Layer-By-Layer Approach 22 2.3 Surface Functionalization via Grafted. diagram illustrating the processes of RAFT-mediated graft polymerization of VBC on the Si-H surface and functionalization of the VBC graft- polymerized Si surface with viologen. Figure 4.3. ii Chapter 4 Functionalization of Hydrogen-Terminated Silicon via Surface- Initiated Reversible Addition-Fragmentation Chain Transfer Polymerization of 4-Vinylbenzyl Chloride and Coupling of Viologen