Preparation of Self-Assembled Monolayers in scCO2 and Their Application to Fabrication and Patterning of Polymer Thin Films

Ji Young Kim; Young Hwan Park; Jong Su Kim; Kwon Taek Lim; Yeon Tae Jeong

Journal of Industrial and Engineering Chemistry, Vol.13, No.6, 1023-1028, November, 2007

Ji Young Kim, Young Hwan Park, Jong Su Kim, Kwon Taek Lim , and Yeon Tae Jeong^†

Division of Image and Information Engineering, Pukyong National University, Busan 608-739, Korea

E-mail:

A thin film of polymer was fabricated on functionalized silicon wafer through self-assembled monolayers (SAMs) of perfluorophenyl azide derivatives (PFPA-silane) with covalent bonds by photochemical reaction. The SAMs were formed in supercritical carbon dioxide (scCO2), and the immobilization of polymers was performed by UV irradiation. The results indicate that scCO2 is a good solvent for silylation reactions, better than common organic solvent such as toluene. Compared with the optimum conditions for silylation, reactions are faster and optimum concentration of PFPA-silane is lower in scCO2. The SAMs formed in scCO2 are more uniform than SAMs formed in toluene. The immobilization of polymers is based on photoreactive azido groups of PFPA-silane which is bound to SiO2 surface via silane anchor. Furthermore, the combination of immobilization chemistry with photolithography, which generated patterned polymer films and hybrid arrays with unique surface topographies is also reported.

Keywords:self-assembled monolayers;supercritical carbon dioxide;perfluorophenyl azide derivatives;photochemical reaction;photolithography;immobilization

[References]

Stenger DA, Georger JH, Dulcey CS, Hickman JJ, Rudolph AS, Nielsen TB, McCort SM, Calvert JM, J. Am. Chem. Soc., 114, 8435 (1992)
Jeon NL, Finnie K, Branshaw K, Nuzzo RG, Langmuir, 13(13), 3382 (1997)
Xia Y, Zhao XM, Whitesides GM, Microelectron. Eng., 32, 255 (1996)
Kim HY, Kim H, J. Ind. Eng. Chem., 4(2), 78 (1998)
Keefe MH, Slone RV, Hupp JT, Czaplewski KF, Snurr RQ, Stern CL, Langmuir, 16(8), 3964 (2000)
Wen WK, Jou JH, Wu HS, Cheng CL, Macromolecules, 31(19), 6515 (1998)
Santini JT, Cima MJ, Langer R, Nature, 397(6717), 335 (1999)
Sofia SJ, Premnath V, Merrill EW, Macromolecules, 31(15), 5059 (1998)
Zamborini FP, Crooks RM, Langmuir, 14(12), 3279 (1998)
Kim JY, Park YH, Kim JS, Lim KT, Yan M, Jeong YT, J. Ind. Eng. Chem., 13(5), 781 (2007)
Kendall JL, Canelas DA, Young JL, DeSimone JM, Chem. Rev., 99(2), 543 (1999)
Cason JP, Roberts CB, J. Phys. Chem. B, 104(6), 1217 (2000)
Lee JY, Lee KN, Lee HJ, Kim JH, J. Ind. Eng. Chem., 8(6), 546 (2002)
Weinstein RD, Yan D, Jennings GK, Ind. Eng. Chem. Res., 40(9), 2046 (2001)
Gallyamov MO, Vinokur RA, Nikitin LN, Said-Galiyev EE, Khokhlov AR, Yaminsky IV, Schaumburg K, Langmuir, 18(18), 6928 (2002)
Muratov G, Seo KW, Kim C, J. Ind. Eng. Chem., 11(1), 42 (2005)
Gross T, Buchhauser J, Ludemann HD, J. Chem. Phys., 109(11), 4518 (1998)
Cooper AI, J. Mater. Chem., 10, 207 (2000)
van der Gulik PS, Physica A, 238, 81 (1997)
Keana JFW, Cai SX, J. Org. Chem., 55, 3640 (1990)
Zhuravlev LT, Langmuir, 3, 316 (1987)
Poe R, Schnapp K, Young MJT, Grayzar J, Platz MS, J. Am. Chem. Soc., 114, 5054 (1992)
Gritsan NP, Gudmundsdottir AD, Tigelaar D, Zhu ZD, Karney WL, Hadad CM, Platz MS, J. Am. Chem. Soc., 123(9), 1951 (2001)
Yan M, Cai SX, Keana JFW, J. Org. Chem., 59, 5951 (1994)
Yan M, Cai SX, Wybourne MN, Keana JFW, J. Am. Chem. Soc., 115, 814 (1993)
Chang JH, Exarhos GJ, Shin YK, J. Ind. Eng. Chem., 11(3), 375 (2005)
Ballard DGH, Wignall GD, Schelten J, Eur. Polym. J., 9, 965 (1973)

[Referenced By]

[Related Articles]

[1] Stenger DA, Georger JH, Dulcey CS, Hickman JJ, Rudolph AS, Nielsen TB, McCort SM, Calvert JM, J. Am. Chem. Soc., 114, 8435 (1992)

[2] Jeon NL, Finnie K, Branshaw K, Nuzzo RG, Langmuir, 13(13), 3382 (1997)

[3] Xia Y, Zhao XM, Whitesides GM, Microelectron. Eng., 32, 255 (1996)

[4] Kim HY, Kim H, J. Ind. Eng. Chem., 4(2), 78 (1998)

[5] Keefe MH, Slone RV, Hupp JT, Czaplewski KF, Snurr RQ, Stern CL, Langmuir, 16(8), 3964 (2000)

[6] Wen WK, Jou JH, Wu HS, Cheng CL, Macromolecules, 31(19), 6515 (1998)

[7] Santini JT, Cima MJ, Langer R, Nature, 397(6717), 335 (1999)

[8] Sofia SJ, Premnath V, Merrill EW, Macromolecules, 31(15), 5059 (1998)

[9] Zamborini FP, Crooks RM, Langmuir, 14(12), 3279 (1998)

[10] Kim JY, Park YH, Kim JS, Lim KT, Yan M, Jeong YT, J. Ind. Eng. Chem., 13(5), 781 (2007)

[11] Kendall JL, Canelas DA, Young JL, DeSimone JM, Chem. Rev., 99(2), 543 (1999)

[12] Cason JP, Roberts CB, J. Phys. Chem. B, 104(6), 1217 (2000)

[13] Lee JY, Lee KN, Lee HJ, Kim JH, J. Ind. Eng. Chem., 8(6), 546 (2002)

[14] Weinstein RD, Yan D, Jennings GK, Ind. Eng. Chem. Res., 40(9), 2046 (2001)

[15] Gallyamov MO, Vinokur RA, Nikitin LN, Said-Galiyev EE, Khokhlov AR, Yaminsky IV, Schaumburg K, Langmuir, 18(18), 6928 (2002)

[16] Muratov G, Seo KW, Kim C, J. Ind. Eng. Chem., 11(1), 42 (2005)

[17] Gross T, Buchhauser J, Ludemann HD, J. Chem. Phys., 109(11), 4518 (1998)

[18] Cooper AI, J. Mater. Chem., 10, 207 (2000)

[19] van der Gulik PS, Physica A, 238, 81 (1997)

[20] Keana JFW, Cai SX, J. Org. Chem., 55, 3640 (1990)

[21] Zhuravlev LT, Langmuir, 3, 316 (1987)

[22] Poe R, Schnapp K, Young MJT, Grayzar J, Platz MS, J. Am. Chem. Soc., 114, 5054 (1992)

[23] Gritsan NP, Gudmundsdottir AD, Tigelaar D, Zhu ZD, Karney WL, Hadad CM, Platz MS, J. Am. Chem. Soc., 123(9), 1951 (2001)

[24] Yan M, Cai SX, Keana JFW, J. Org. Chem., 59, 5951 (1994)

[25] Yan M, Cai SX, Wybourne MN, Keana JFW, J. Am. Chem. Soc., 115, 814 (1993)

[26] Chang JH, Exarhos GJ, Shin YK, J. Ind. Eng. Chem., 11(3), 375 (2005)

[27] Ballard DGH, Wignall GD, Schelten J, Eur. Polym. J., 9, 965 (1973)