Ultrathin films of poly(ethylene oxides) on oxidized silicon. 1: Spectroscopic characterization of film structure and crystallization kinetics

Macromolecules

Volumn 36, Issue 4, 2003, Pages 1188-1198

  Schönherr, Holger ^a,b   Frank, Curtis W ^a  

^a Stanford University   (United States)

^b UNIVERSITY OF TWENTE   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

ATOMIC FORCE MICROSCOPY; CRYSTALLIZATION; CRYSTALS; FLUORESCENCE; FOURIER TRANSFORM INFRARED SPECTROSCOPY; GLASS TRANSITION; ISOTHERMS; MICROSCOPIC EXAMINATION; MOLECULAR ORIENTATION; OXIDATION; REACTION KINETICS; SILICON; STRUCTURE (COMPOSITION); SUBSTRATES; ULTRATHIN FILMS;

INTERACTIVE SUBSTRATES;

POLYETHYLENE OXIDES;

EID: 0037465384     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma020685i     Document Type: Article

References (91)

1. Physics of Polymer Surfaces and Interfaces; Sanchez, I. C., Ed.; Butterworth-Heinemann: Boston, 1992.
2. Frank, C. W.; Rao, V.; Despotopoulou, M. M.; Pease, R. F. W.; Hinsberg, W. D.; Miller, R. D.; Rabolt, J. F. Science 1996, 273, 912 and references cited therein.
3. Hietpas, G. D.; Sands, J. M.; Allara, D. L. J. Phys. Chem. B 1998, 102, 10556 and references cited therein.
4. Pike, C.; Bell, S.; Lyons, C.; Plat, M.; Levinson, H.; Okoroanyanwu, U. J. Vac. Sci. Technol. B 2000, 18, 3360.
5. Johnson, K. E.; Mate, C. M.; Merz, J. A.; White, R. L.; Wu, A. W. IBM J. Res. Develop. 1996, 40, 511 and references cited therein.
6. Yang, X. G.; Shi, J. X.; Johnson, S.; Swanson, B. Langmuir 1998, 14, 1505.
7. Walheim, S.; Schaffer, E.; Mlynek, J.; Steiner, U. Science 1999, 283, 520.
8. Decher, G. Science 1997, 277, 1232.
9. Donath, E.; Sukhorukov, G. B.; Caruso, F.; Davis, S. A.; Möhwald, H. Angew. Chem., Int. Ed. 1998, 37, 2202.
10. Weimann, P. A.; Hajduk, D. A.; Chu, C.; Chaffin, K. A.; Brodil, J. C.; Bates, F. S. J. Polym. Sci., Part B: Polym. Phys. 1999, 37, 2053.
11. Zhu, L.; Cheng, S. Z. D.; Calhoun, B. H.; Ge, Q.; Quirk, R. P.; Thomas, E. L.; Hsiao, B. S.; Yeh, F.; Lotz, B. Polymer 2001, 42, 5829 and references cited therein.
12. Hong, S.; MacKnight, W. J.; Russell, T. P.; Gido, S. P. Macromolecules 2001, 34, 2876.
13. Anastasiadis, S. H.; Karatasos, K.; Vlachos, G.; Manias, E.; Giannelis, E. P. Phys. Rev. Lett. 2000, 84, 915.
14. Keddie, J. L.; Jones, R. A. L.; Cory, R. A. Europhys. Lett. 1994, 27, 59.
15. Keddie, J. L.; Jones, R. A. L.; Cory, R. A. Faraday Discuss. 1994, 98, 219.
16. Forrest, J. A.; Mattson, J. Phys. Rev. E 2000, 61, R53 and references cited therein.
17. Prucker, O.; Christian, S.; Bock, H.; Rühe, J.; Frank, C. W.; Knoll, W. Macromol. Chem. Phys. 1998, 199, 1435.
18. DeMaggio, G. B.; Frieze, W. E.; Gidley, D. W.; Zhu, M.; Hristov, H. A.; Yee, A. F. Phys. Rev. Lett. 1997, 78, 1524.
19. Jones, R. A. L. Curr. Opin. Colloid Interface Sci. 1999, 4, 153.
20. Kim, J. H.; Jang, J.; Zin, W. C. Langmuir 2001, 17, 2703.
21. Van Zanten, J. H.; Wallace, W. E.; Wu, W. L. Phys. Rev. E 1996, 53, R2053.
22. Despotopoulou, M. M.; Frank, C. W.; Miller, R. D.; Rabolt, J. F. Macromolecules 1996, 29, 5797.
23. Despotopoulou, M. M.; Frank, C. W.; Miller, R. D.; Rabolt, J. D. Macromolecules 1995, 28, 6687.
24. (b) Despotopoulou, M. M.; Miller, R. D.; Rabolt, J. D.; Frank, C. W. J. Polym. Sci., Part B: Polym. Phys. 1996, 34, 2335.
25. Sawamura, S.; Miyaji, H.; Izumi, K.; Sutton, S. J.; Miyamoto, Y. J. Phys. Soc. Jpn. 1998, 67, 3338.
26. (b) Sutton, S. J.; Izumi, K.; Miyaji, H.; Miyamoto, Y.; Miyatashi, S. J. Mater. Sci. 1997, 32, 5621.
27. Krausch, G.; Dai, C.-A.; Kramer, E. J.; Marko, J. F.; Bates, F. S. Macromolecules 1993, 26, 5566.
28. Meuse, C. W.; Yang, X.; Yang, D.; Hsu, S. L. Macromolecules 1992, 25, 925.
29. (b) Tao, H.-J.; Meuse, C. W.; Yang, X.; MacKnight, W. J.; Hsu, S. L. Macromolecules 1994, 27, 7146.
30. Fasolka, M. J.; Banerjee, P.; Mayes, A. M.; Pickett, G.; Balazs, A. C. Macromolecules 2000, 33, 5701.
31. Pfromm, P. H.; Koros, W. J. Polymer 1995, 36, 2379.
32. Liang, T.; Makita, Y.; Kimura, S. Polymer 2001, 42, 4867.
33. Beck Tan, N. C.; Wu, W. L.; Wallace, W. E.; Davis, G. T. J. Polym. Sci., Part B: Polym. Phys. 1998, 36, 155.
34. Reiter, G. Europhys. Lett. 1993, 23, 579.
35. Kraus, J.; Müller-Buschbaum, P.; Kuhlmann, T.; Schubert, D. W.; Stamm, M. Europhys. Lett. 2000, 49, 210.
36. Ten Brinke, G.; Ausserre, D.; Hadziioannou, G. J. Chem. Phys. 1988, 89, 4374.
37. (b) Kumar, S. K.; Vacatello, M.; Yoon, D. Y. J. Chem. Phys. 1988, 89, 5207.
38. (c) Bitsanis, I.; Hadziioannou, G. J. Chem. Phys. 1990, 92, 3827.
39. Jones, R. A. L.; Kumar, S. K.; Ho, D. L.; Briber, R. M.; Russell, T. P. Nature (London) 1999, 400, 146.
40. g depressions in ultrathin films, see: Tseng, K. C.; Turro, N. J.; Durning, C. J. Phys. Rev. E 2000, 61, 1800.
41. Fryer, D. S.; Nealey, P. F.; de Pablo, J. J. Macromolecules 2000, 33, 6439.
42. (b) Torres, J. A.; Nealey, P. F.; dePablo, J. J. Phys. Rev. Lett. 2000, 85, 3221.
43. Frank, B.; Gast, A. P.; Russell, T. P.; Brown, H. R.; Hawker, C. Macromolecules 1996, 29, 6531.
44. Zheng, X.; Rafailovich, M. H.; Sokolov, J.; Strzhemechny, Y.; Schwarz, S. A.; Sauer, B. B.; Rubinstein, M. Phys. Rev. Lett. 1997, 79, 241.
45. Zheng, X.; Sauer, B. B.; van Alsten, J. G.; Schwarz, S. A.; Rafailovich, M. H.; Sokolov, J.; Rubinstein, M. Phys. Rev. Lett. 1995, 74, 407.
46. Russell, T. P.; Kumar, S. K. Nature (London) 1997, 386, 771.
47. Lin, E. K.; Kolb, R.; Satija, S. K.; Wu, W.-L. Macromolecules 1999, 32, 3753.
48. Tseng, K. C.; Turro, N. J.; Durning, C. J. Polymer 2000, 41, 4751.
49. Hall, D. B.; Torkelson, J. M. Macromolecules 1998, 31, 8817.
50. Reiter, G.; Sommer, J.-U. Phys. Rev. Lett. 1998, 80, 3771.
51. (b) Reiter, G.; Sommer, J.-U. J. Chem. Phys. 2000, 112, 4376.
52. Bartczak, Z.; Argon, A. S.; Cohen, R. E.; Kowalewski, T. Polymer 1999, 40, 2367.
53. Srinivas, S.; Babu, J. R.; Riffle, J. S.; Wilkes, G. L. J. Macromol. Sci., Phys. 1997, B36, 455.
54. g is the glass transition temperature. For details, see: Hoffman, J. D.; Miller, R. L. Macromolecules 1989, 22, 3502 and cited references.
55. Vaia, R. A.; Sauer, B. B.; Tse, O. K.; Giannelis, E. P. J. Polym. Sci., Part B: Polym. Phys. 1997, 35, 59.
56. Avrami, M. J. Chem. Phys. 1939, 7, 1103.
57. Hoffman, C. L.; Rabolt, J. F. Macromolecules 1996, 29, 2543.
58. Muratoglu, O. K.; Argon, A. S.; Cohen, R. E. Polymer 1995, 36, 2143.
59. Hietpas, G. D.; Allara, D. L. J. Polym. Sci., Part B: Polym. Phys. 1998, 36, 1247.
60. Schönherr, H.; Waymouth, R. M.; Hawker, C. J.; Frank, C. W. ACS Polym. Mater.: Sci. Eng. 2001, 84, 453.
61. Schönherr, H.; Waymouth, R. M.; Frank, C. W., manuscript in preparation.
62. This paper. (b) Schönherr, H.; Bailey, L. E.; Frank, C. W. Langmuir 2002, 18, 490.
63. (c) Schönherr, H.; Frank, C. W. Macromolecules 2003, 36, 1199.
64. In the course of writing this manuscript a similar study has been published by Dalnoki-Veress et al., which describes the reduction of crystallization rates for PEO thin films on silicon and gold substrates as studied by quartz crystal microbalance and video optical microscopy (Dalnoki-Veress, N.; Forrest, J. A.; Massa, M. V.; Pratt, A.; Williams, A. J. Polym. Sci., Part B: Polym. Phys. 2001, 39, 2615). The complementary results reported by these authors are in good agreement with our data.
65. Kovacs, A. J.; Gonthier, A. Kolloid Z. Z. Polym. 1972, 250, 530.
66. (b) Marentette, J. M.; Brown, G. R. Polymer 1998, 39, 1405 and references cited therein.
67. Takahashi, Y.; Tadokoro, H. Macromolecules 1973, 6, 672.
68. Takahashi, Y.; Sumita, I.; Tadokoro, H. J. Polym. Sci., Part B: Polym. Phys. 1973, 11, 2113.
69. Pearce, R.; Vancso, G. J. Macromolecules 1997, 30, 5843
70. (b) Pearce, R.; Vancso, G. J. Polymer 1998, 39, 1237.
71. (c) Schultz, J. M.; Miles, M. J. J. Polym. Sci., Part B: Polym. Phys. 1998, 36, 2311.
72. The PEOpy materials were available from previous studies. GPC was measured relative to PS in chloroform at the Department of Materials Science and Technology of Polymers, University of Twente, Enschede, The Netherlands.
73. Gullerud, S. Ph.D. Thesis, Stanford University, 1999.
74. Because of heat generated by the AFM, this corresponds to a true sample temperature of ca. 34 °C.
75. In thick films there is a coexistence of edge-on and flat-on lamellae.
76. Bassett, D. C. Principles of Polymer Morphology; Cambridge University Press: Cambridge, 1981.
77. Yoshihara, T.; Tadokoro, H.; Murahashi, S. J. Chem. Phys. 1964, 41, 2902.
78. Allara, D. L. In Characterization of Organic Thin Films; Ulman, A., Ed.; Butterworth-Heinemann: Boston, 1994; Chapter 4.
79. Li, X.; Hsu, S. L. J. Polym. Sci., Polym. Phys. 1984, 22, 1331.
80. As shown in the Supporting Information (Figure S2), the transmission FT-IR spectra of PEO-100, PEOpy-49, PEOpy-29, and PEOpy-11 after isothermal crystallization at 44 °C were very similar.
81. For samples that are quenched to room temperature or below, the absorbance ratio does indeed indicate a more random orientation of the rapidly crystallized PEO helices.
82. Jing, S.; Qiao, C.; Tian, S.; Ji, X.; An, L.; Jiang, B. Polymer 2001, 42, 5755.
83. Lakowicz, J. R. Principles of Fluorescence Spectroscopy; Kluwer Academic/Plenum: New York, 1999.
84. Chen, S. H.; Frank, C. W. Langmuir 1991, 7, 1719 and references cited therein.
85. PEOpy-29 showed qualitatively similar behavior, while the strong excimer fluorescence dominated the spectra for PEOpy-11.
86. Frank, C. W. J. Chem. Phys. 1974, 61, 2015.
87. Gedde, U. Polymer Physics, 1st ed.; Kluwer Academic Publishers: Dordrecht, 1995.
88. Because of the limited time resolution of the experiment and the low probability to nucleate crystals at higher temperatures in unseeded melts, it is difficult to study a broad range of crystallization temperatures by FT-IR.
89. For these block copolymers the dimensionality of the growth was also a function of crystallization temperature; see ref 11.
90. g values of 10.8, 7.6, 5.8, and 3.5 nm, respectively.
91. Because of instrumental limitations we can follow the fluorescence intensity at a single emission wavelength only. Thus, it was impossible to acquire simultaneously the monomer and excimer emission intensities during crystallization. The data shown in Figure 11 represent the changes in excimer emission intensity during the crystallization of the PEO film. During crystallization the monomer emission intensity also decreases or increases depending on film thickness. Any of these changes in emission intensity must be related to the crystallization process since we crystallize under isothermal conditions. Hence, these changes may serve as an independent means to characterize the effect of confinement on the crystallization kinetics.