Phase behavior in thin films of cylinder-forming ABA block copolymers: mesoscale modeling.

The phase behavior of cylinder-forming ABA block copolymers in thin films is modeled in detail using dynamic density functional theory and compared with recent experiments on polystyrene-block-polybutadiene-block-polystyrene triblock copolymers. Deviations from the bulk structure, such as wetting layer, perforated lamella, and lamella, are identified as surface reconstructions. Their stability regions are determined by an interplay between surface fields and confinement effects. Our results give evidence for a general mechanism governing the phase behavior in thin films of modulated phases.

[1]  A. Mayes,et al.  Block copolymer thin films : Physics and applications , 2001 .

[2]  Armin Knoll,et al.  Phase behavior in thin films of cylinder-forming ABA block copolymers: experiments. , 2004, The Journal of chemical physics.

[3]  A. Karim,et al.  Ordering in asymmetric poly (ethylene–propylene)–poly (ethylethylene) diblock copolymer thin films , 1994 .

[4]  G. Fredrickson,et al.  Field-Theoretic Computer Simulation Methods for Polymers and Complex Fluids , 2002 .

[5]  M. S. Turner,et al.  Surface-Induced Lamellar Ordering in a Hexagonal Phase of Diblock Copolymers , 1994 .

[6]  Marcus Müller,et al.  Thin films of asymmetric triblock copolymers: A Monte Carlo study , 2003 .

[7]  J. Fraaije,et al.  Dynamic density functional theory for microphase separation kinetics of block copolymer melts , 1993 .

[8]  A. Knoll,et al.  Volume Imaging of an Ultrathin SBS Triblock Copolymer Film , 2000 .

[9]  Ian W. Hamley,et al.  The physics of block copolymers , 1998 .

[10]  Russell,et al.  Neutron reflectivity studies of the surface-induced ordering of diblock copolymer films. , 1989, Physical review letters.

[11]  Galen T. Pickett,et al.  Morphology of Ultrathin Supported Diblock Copolymer Films: Theory and Experiment , 2000 .

[12]  Matthew Libera,et al.  Kinetic Constraints on the Development of Surface Microstructure in SBS Thin Films , 1998 .

[13]  Thomas El,et al.  Morphology of steps in terraced block copolymer films. , 1994 .

[14]  A. Mayes,et al.  A Free Energy Model for Confined Diblock Copolymers , 1994 .

[15]  Juan J. de Pablo,et al.  Monte Carlo Simulations of Asymmetric Diblock Copolymer Thin Films Confined between Two Homogeneous Surfaces , 2001 .

[16]  E. Thomas,et al.  The effect of surface constraints on the ordering of block copolymer domains , 1988 .

[17]  Gallagher,et al.  Observed surface energy effects in confined diblock copolymers. , 1996, Physical review letters.

[18]  Natasha Maurits,et al.  Dynamics of surface directed mesophase formation in block copolymer melts , 1999 .

[19]  G. Sevink,et al.  Surface-Induced Transitions in Thin Films of Asymmetric Diblock Copolymers , 2001 .

[20]  A. Knoll,et al.  Phase behavior in thin films of cylinder-forming block copolymers. , 2002, Physical review letters.

[21]  E. Ruckenstein,et al.  Monte Carlo simulation of triblock copolymer thin films , 2002 .

[22]  D. Agard,et al.  Three-dimensional study of cylindrical morphology in a styrene-butadiene-styrene block copolymer , 1988 .

[23]  Edwin L. Thomas,et al.  Monolayer films of diblock copolymer microdomains for nanolithographic applications , 1995, Journal of Materials Science.

[24]  M. Matsen Self-assembly of block copolymers in thin films , 1998 .

[25]  M. V. Dijk,et al.  Ordering Phenomena in Thin Block Copolymer Films Studied Using Atomic Force Microscopy , 1995 .

[26]  Russell B. Thompson,et al.  Equilibrium behavior of symmetric ABA triblock copolymer melts , 1999 .

[27]  N. Maurits,et al.  The dynamic mean-field density functional method and its application to the mesoscopic dynamics of quenched block copolymer melts , 1997 .

[28]  Qinglin Zhang,et al.  Observation of Inverted Phases in Poly(styrene-b-butadiene-b-styrene) Triblock Copolymer by Solvent-Induced Order−Disorder Phase Transition , 2000 .

[29]  G. Pereira Cylindrical phase of block copolymers: stability of circular configuration to elliptical distortions and thin film morphologies. , 2001, Physical review. E, Statistical, nonlinear, and soft matter physics.

[30]  E. Thomas,et al.  Structure of minimum thickness and terraced free‐standing films of block copolymers , 1996 .

[31]  G. Fredrickson,et al.  Block copolymer thermodynamics: theory and experiment. , 1990, Annual review of physical chemistry.

[32]  P. Chaikin,et al.  Layer by layer imaging of diblock copolymer films with a scanning electron microscope , 1998 .

[33]  K. Binder Phase Transitions of Polymer Blends and Block Copolymer Melts in Thin Films , 1999 .

[34]  A. Knoll,et al.  Surface reconstruction of an ordered fluid: an analogy with crystal surfaces. , 2001, Physical review letters.

[35]  G. Sevink,et al.  Asymmetric block copolymers confined in a thin film , 2000 .

[36]  A. Chakrabarti,et al.  Ordering of block copolymer melts in confined geometry , 1995 .