Effect of film thickness on the phase behaviors of diblock copolymer thin film

ACS Nano

Volumn 4, Issue 6, 2010, Pages 3109-3116

  Jung, Jueun ^a   Park, Hae Woong ^a   Lee, Sekyung ^a   Lee, Hyojoon ^a   Chang, Taihyun ^a   Matsunaga, Kazuyuki ^b   Jinnai, Hiroshi ^b,c  

^a Pohang University of Science and Technology (POSTECH)   (South Korea)

^b KYOTO INSTITUTE OF TECHNOLOGY   (Japan)

^c TOHOKU UNIVERSITY   (Japan)

Author keywords

Block copolymer; Grazing incidence x ray scattering; Phase diagram; PS b PI; Thin film; Transmission electron microtomography

Indexed keywords

DG STRUCTURES; DIBLOCK COPOLYMER THIN FILMS; DOMAIN SPACING; FILMS THINNER; FREE SURFACES; GRAZING INCIDENCE; GRAZING INCIDENCE SMALL-ANGLE X-RAY SCATTERING; IN-SITU HEATING; INTERFACIAL TENSIONS; LAYER-LIKE STRUCTURES; ORDERED PHASIS; PACKED CYLINDERS; PERFORATED LAYERS; PHASE TRANSITION TEMPERATURES; PS-B-PI; SI WAFER; STABLE PHASE; STABLE REGION; TARGET TEMPERATURE; TEMPERATURE RANGE; TEMPERATURE WINDOW; TRANSMISSION ELECTRON MICROTOMOGRAPHY; VERY THIN FILMS;

BLOCK COPOLYMERS; COPOLYMERIZATION; ELECTRONS; GALERKIN METHODS; HEATING; MORPHOLOGY; ORGANIC POLYMERS; PHASE DIAGRAMS; PHASE TRANSITIONS; POLYSTYRENES; SCATTERING; SEMICONDUCTING SILICON COMPOUNDS; SILICON WAFERS; SURFACE STRUCTURE; THIN FILMS; TRANSMISSION ELECTRON MICROSCOPY; VAPOR DEPOSITION; X RAY SCATTERING; X RAYS;

FILM THICKNESS;

1,3 BUTADIENE DERIVATIVE; HEMITERPENE; ISOPRENE; NANOMATERIAL; PENTANE; POLYSTYRENE DERIVATIVE;

ARTICLE; ARTIFICIAL MEMBRANE; CHEMISTRY; CONFORMATION; HARDNESS; MACROMOLECULE; MATERIALS TESTING; PARTICLE SIZE; PHASE TRANSITION; SURFACE PROPERTY; ULTRASTRUCTURE;

BUTADIENES; HARDNESS; HEMITERPENES; MACROMOLECULAR SUBSTANCES; MATERIALS TESTING; MEMBRANES, ARTIFICIAL; MOLECULAR CONFORMATION; NANOSTRUCTURES; PARTICLE SIZE; PENTANES; PHASE TRANSITION; POLYSTYRENES; SURFACE PROPERTIES;

EID: 77955914907     PISSN: 19360851     EISSN: 1936086X     Source Type: Journal    
DOI: 10.1021/nn1003309     Document Type: Article

References (51)

1. Glass, R.; Moller, M.; Spatz, J. P. Block Copolymer Micelle Nanolithography. Nanotechnology 2003, 14, 1153-1160.
2. Hamley, I. W. Nanostructure Fabrication Using Block Copolymers. Nanotechnology 2003, 14, R39-R54.
3. Crossland, E. J. W.; Kamperman, M.; Nedelcu, M.; Ducati, C.; Wiesner, U.; Smilgies, D. M.; Toombes, G. E. S.; Hillmyer, M. A.; Ludwigs, S.; Steiner, U.; Snaith, H. J. A Bicontinuous Double Gyroid Hybrid Solar Cell. Nano Lett. 2009, 9, 2807-2812.
4. 2 Nanostructures Fabricated by Block Copolymer Template for Nanoimprint Lithography. ACS Nano 2009, 3, 2601-2608.
5. Zhao, Y.; Thorkelsson, K.; Mastroianni, A. J.; Schilling, T.; Luther, J. M.; Rancatore, B. J.; Matsunaga, K.; Jinnai, H.; Wu, Y.; Poulsen, D.; et al. Small-Molecule-Directed Nanoparticle Assembly Towards Stimuli-Responsive Nanocomposites. Nat. Mater. 2009, 8, 979-985.
6. Leibler, L. Theory of Microphase Separation in Block Copolymers. Macromolecules 1980, 13, 1602.
7. Bates, F. S.; Fredrickson, G. H. Block Copolymer Thermodynamics: Theory and Experiment Annu. Rev. Phy. Chem. 1990, 41, 525-557.
8. Matsen, M. W.; Bates, F. S. Unifying Weak-and Strong-Segregation Block Copolymer Theories. Macromolecules 1996, 29, 1091-1098.
9. Cochran, E. W.; Garcia-Cervera, C. J.; Fredrickson, G. H. Stability of the Gyroid Phase in Diblock Copolymers at Strong Segregation. Macromolecules 2006, 39, 2449-2451.
10. Khandpur, A. K.; Forster, S.; Bates, F. S.; Hamley, I. W.; Ryan, A. J.; Bras, W.; Almdal, K.; Mortensen, K. Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition. Macromolecules 1995, 28, 8796-8806.
11. Fischer, H.; Weidisch, R.; Stamm, M.; Budde, H.; Horing, S. The Phase Diagram of the System Poly (styrene-block-nbutyl methacrylate). Colloid Polym. Sci. 2000, 278, 1019-1031.
12. Floudas, G.; Vazaiou, B.; Schipper, F.; Ulrich, R.; Wiesner, U.; Iatrou, H.; Hadjichristidis, N. Poly (ethylene oxide-bisoprene) Diblock Copolymer Phase Diagram. Macromolecules 2001, 34, 2947-2957.
13. Park, S.; Kwon, K.; Cho, D.; Lee, B.; Ree, M.; Chang, T. Phase Diagram Constructed from the HPLC Fractions of a Polystyrene-b-polyisoprene Prepared by Anionic Polymerization. Macromolecules 2003, 36, 4662-4666.
14. Fasolka, M. J.; Mayes, A. M. Block Copolymer Thin Films: Physics and Applications. Annu. Rev. Mater. Res. 2001, 31, 323-355.
15. Kim, J. K.; Lee, J. I.; Lee, D. H. Self-Assembled Block Copolymers: Bulk to Thin Film. Macromol. Res. 2008, 16, 267-292.
16. Park, S.; Lee, D. H.; Xu, J.; Kim, B.; Hong, S. W.; Jeong, U.; Xu, T.; Russell, T. P. Macroscopic 10-Terabit-Per-Square-Inch Arrays from Block Copolymers with Lateral Order. Science 2009, 323, 1030-1033.
17. Hamley, I. W. Ordering in Thin Films of Block Copolymers: Fundamentals to Potential Applications. Prog. Polym. Sci. 2009, 34, 1161-1210.
18. Matsen, M. W. Thin films of Block Copolymer. J. Chem. Phys. 1997, 106, 7781-7791.
19. Lee, B.; Park, I.; Yoon, J.; Park, S.; Kim, J.; Kim, K. W.; Chang, T.; Ree, M. Structural Analysis of Block Copolymer Thin Films with Grazing Incidence Small-Angle X-ray Scattering. Macromolecules 2005, 38, 4311-4323.
20. Park, I.; Lee, B.; Ryu, J.; Im, K.; Yoon, J.; Ree, M.; Chang, T. Epitaxial Phase Transition of Polystyrene-b-polyisoprene from Hexagonally Perforated Layer to Gyroid Phase in Thin Film. Macromolecules 2005, 38, 10532-10536.
21. Park, H. W.; Im, K.; Chung, B.; Ree, M.; Chang, T.; Sawa, K.; Jinnai, H. Direct Observation of HPL and DG Structure in PS-b-PI Thin Film by Transmission Electron Microscopy. Macromolecules 2007, 40, 2603-2605.
22. Park, H. W.; Jung, J.; Chang, T. New Characterization Methods for Block Copolymers and Their Phase Behaviors. Macromol. Res. 2009, 17, 365-377.
23. Lyakhova, K. S.; Sevink, G. J. A.; Zvelindovsky, A. V.; Horvat, A.; Magerle, R. Role of Dissimilar Interfaces in Thin Films of Cylinder-Forming Block Copolymers. J. Chem. Phys. 2004, 120, 1127-1137.
24. Olszowka, V.; Tsarkova, L.; Boker, A. 3-Dimensional Control over Lamella Orientation and Order in Thick Block Copolymer Films. Soft Matter 2009, 5, 812-819.
25. Huang, E.; Russell, T. P.; Harrison, C.; Chaikin, P. M.; Register, R. A.; Hawker, C. J.; Mays, J. Using Surface Active Random Copolymers to Control the Domain Orientation in Diblock Copolymer Thin Films. Macromolecules 1998, 31, 7641-7650.
26. Xu, T.; Hawker, C. J.; Russell, T. P. Interfacial Interaction Dependence of Microdomain Orientation in Diblock Copolymer Thin Films. Macromolecules 2005, 38, 2802-2805.
27. Ryu, D. Y.; Wang, J. Y.; Lavery, K. A.; Drockenmuller, E.; Satija, S. K.; Hawker, C. J.; Russell, T. P. Surface Modification with Cross-Linked Random Copolymers: Minimum Effective Thickness. Macromolecules 2007, 40, 4296-4300.
28. Ham, S.; Shin, C.; Kim, E.; Ryu, D. Y.; Jeong, U.; Russell, T. P.; Hawker, C. J. Microdomain Orientation of PS-b-PMMA by Controlled Interfacial Interactions. Macromolecules 2008, 41, 6431-6437.
29. Albert, J. N. L.; Baney, M. J.; Stafford, C. M.; Kelly, J. Y.; Epps, T. H. Generation of Monolayer Gradients in Surface Energy and Surface Chemistry for Block Copolymer Thin Film Studies. ACS Nano 2009, 3, 3977-3986.
30. Ramanathan, M.; Nettleton, E.; Darling, S. B. Simple Orientational Control over Cylindrical Organic-Inorganic Block Copolymer Domains for Etch Mask Applications. Thin Solid Films 2009, 517, 4474-4478.
31. Arceo, A.; Green, P. F. Ordering Transition of Block Copolymer Films. J. Phys. Chem. B 2005, 109, 6958-6962.
32. Shin, C.; Ahn, H.; Kim, E.; Ryu, D. Y.; Huh, J.; Kim, K. W.; Russell, T. P. Transition Behavior of Block Copolymer Thin Films on Preferential Surfaces. Macromolecules 2008, 41, 9140-9145.
33. Knoll, A.; Horvat, A.; Lyakhova, K. S.; Krausch, G.; Sevink, G. J. A.; Zvelindovsky, A. V.; Magerle, R. Phase Behavior in Thin Films of Cylinder-Forming Block Copolymers. Phys. Rev. Lett. 2002, 89, 035501.
34. Park, I.; Park, S.; Park, H. W.; Chang, T.; Yang, H. C.; Ryu, C. Y. Unexpected Hexagonally Perforated Layer Morphology of PS-b-PMMA Block Copolymer in Supported Thin Film. Macromolecules 2006, 39, 315-318. (Pubitemid 43112752)
35. Tsarkova, L.; Knoll, A.; Krausch, G.; Magerle, R. Substrate-Induced Phase Transitions in Thin Films of Cylinder-Forming Diblock Copolymer Melts. Macromolecules 2006, 39, 3608-3615. (Pubitemid 43798239)
36. Heckmann, M.; Drossel, B. Cylindrical Phase of Block Copolymers in Thin Films. Macromolecules 2008, 41, 7679-7686.
37. Niihara, K. I.; Sugimori, H.; Matsuwaki, U.; Hirato, F.; Morita, H.; Doi, M.; Masunaga, H.; Sasaki, S.; Jinnai, H. A Transition from Cylindrical to Spherical Morphology in Diblock Copolymer Thin Films. Macromolecules 2008, 41, 9318-9325.
38. Zhang, X. H.; Berry, B. C.; Yager, K. G.; Kim, S.; Jones, R. L.; Satija, S.; Pickel, D. L.; Douglas, J. F.; Karim, A. Surface Morphology Diagram for Cylinder-Forming Block Copolymer Thin Films. ACS Nano 2008, 2, 2331-2341.
39. Shin, C.; Ryu, D. Y.; Huh, J.; Kim, J. H.; Kim, K. W. Order-to-Order Transitions of Block Copolymer in Film Geometry. Macromolecules 2009, 42, 2157-2160.
40. Jinnai, H.; Nishikawa, Y.; Spontak, R. J.; Smith, S. D.; Agard, D. A.; Hashimoto, T. Direct Measurement of Interfacial Curvature Distributions in a Bicontinuous Block Copolymer Morphology. Phys. Rev. Lett. 2000, 84, 518-521.
41. Park, H. W.; Jung, J.; Chang, T.; Matsunaga, K.; Jinnai, H. New Epitaxial Phase Transition between DG and HEX in PS-b-PI. J. Am. Chem. Soc. 2009, 131, 46-47.
42. Jinnai, H.; Spontak, R. J. Transmission Electron Microtomography in Polymer Research. Polymer 2009, 50, 1067-1087.
43. Jinnai, H.; Spontak, R. J.; Nishi, T. Transmission Electron Microtomography and Polymer Nanostructures. Macromolecules 2010, 43, 1675-1688.
44. Sohn, B. H.; Seo, B. W.; Yoo, S. I.; Zin, W. C. Sluggish Development of Parallel Lamellae at the Strongly Interacting Interface in Thin Films of Symmetric Diblock Copolymers. Langmuir 2002, 18, 10505-10508.
45. Heo, K. Y.; Yoon, J. W.; Jin, S. W.; Kim, J. H.; Kim, K. W.; Shin, T. J.; Chung, B. H.; Chang, T. Y.; Ree, M. H. Polystyrene-bpolyisoprene Thin Films with Hexagonally Perforated Layer Structure: Quantitative Grazing-Incidence X-ray Scattering Analysis. J. Appl. Crystallogr. 2008, 41, 281-291.
46. Hasegawa, H.; Hashimoto, T. Morphology of Block Polymers near a Free Surface. Macromolecules 1985, 18, 589-590.
47. Collins, S.; Hamley, I. W.; Mykhaylyk, T. An Atomic Force Microscopy Study of Ozone Etching of a Polystyrene/Polyisoprene Block Copolymer. Polymer 2003, 44, 2403-2410.
48. Mareau, V. H.; Akasaka, S.; Osaka, T.; Hasegawa, H. Direct Visualization of the Perforated Layer/Gyroid Grain Boundary in a Polystyrene-block- polyisoprene/Polystyrene Blend by Electron Tomography. Macromolecules 2007, 40, 9032-9039.
49. Kwon, K.; Lee, W.; Cho, D.; Chang, T. Apparatus for Anionic Polymerization under Inert Gas and Polymerization of Polystyrene. Korea Polym. J. 1999, 7, 321-324.
50. Lee, W.; Cho, D. Y.; Chang, T. Y.; Hanley, K. J.; Lodge, T. P. Characterization of Polystyrene-b-polyisoprene Diblock Copolymers by Liquid Chromatography at the Chromatographic Critical Condition. Macromolecules 2001, 34, 2353-2358.
51. Sugimori, H.; Nishi, T.; Jinnai, H. Dual-Axis Electron Tomography for Three-Dimensional Observations of Polymeric Nanostructures. Macromolecules 2005, 38, 10226-10233.