Process-directed self-assembly of block copolymers: a computer simulation study

The free-energy landscape of self-assembling block copolymer systems is characterized by a multitude of metastable minima and concomitant protracted relaxation times of the morphology. Tailoring rapid changes (quench) of thermodynamic conditions, one can reproducibly trap the ensuing kinetics of self-assembly in a specific metastable state. To this end, it is necessary to (1) control the generation of well-defined, highly unstable states and (2) design the unstable state such that the ensuing spontaneous kinetics of structure formation reaches the desired metastable morphology. This process-directed self-assembly provides an alternative to fine-tuning molecular architecture by synthesis or blending, for instance, in order to fabricate complex network structures. Comparing our simulation results to recently developed free-energy techniques, we highlight the importance of non-equilibrium molecular conformations in the starting state and motivate the significance of the local conservation of density.

[1]  Marcus Müller,et al.  Studying Amphiphilic Self-assembly with Soft Coarse-Grained Models , 2011 .

[2]  K. Daoulas,et al.  Comparison of Simulations of Lipid Membranes with Membranes of Block Copolymers , 2009 .

[3]  Linfa Peng,et al.  Micro hot embossing of thermoplastic polymers: a review , 2013 .

[4]  M. Mueller,et al.  Field theoretic study of bilayer membrane fusion: II. Mechanism of a stalk-hole complex. , 2005, Biophysical journal.

[5]  Wolfgang Meier,et al.  Polymer membranes/biomembranes , 2010 .

[6]  Zhen‐Gang Wang,et al.  Random isotropic structures and possible glass transitions in diblock copolymer melts. , 2005, Physical review. E, Statistical, nonlinear, and soft matter physics.

[7]  Pingwen Zhang,et al.  NUMERICAL STUDY FOR THE NUCLEATION OF ONE-DIMENSIONAL STOCHASTIC CAHN-HILLIARD DYNAMICS ∗ , 2012 .

[8]  Matsen.  Stabilizing new morphologies by blending homopolymer with block copolymer. , 1995, Physical review letters.

[9]  Marcus Müller,et al.  Morphology of multi-component polymer systems: single chain in mean field simulation studies. , 2006, Soft matter.

[10]  F. Bates,et al.  Spinodal decomposition of a symmetric critical mixture of deuterated and protonated polymer , 1989 .

[11]  Francisco J. Martinez-Veracoechea,et al.  Bicontinuous Phases in Diblock Copolymer/Homopolymer Blends : Simulation and Self-Consistent Field Theory , 2009 .

[12]  T. Dotera.  Tricontinuous cubic structures in ABC/A/C copolymer and homopolymer blends. , 2002, Physical review letters.

[13]  K. Kremer,et al.  Advanced Computer Simulation Approaches for Soft Matter Sciences III , 2005 .

[14]  Marcus Müller,et al.  Single chain in mean field simulations: quasi-instantaneous field approximation and quantitative comparison with Monte Carlo simulations. , 2006, The Journal of chemical physics.

[15]  De-Wen Sun,et al.  Directing the self-assembly of block copolymers into a metastable complex network phase via a deep and rapid quench. , 2013, Physical review letters.

[16]  G. Ciccotti,et al.  String method in collective variables: minimum free energy paths and isocommittor surfaces. , 2006, The Journal of chemical physics.

[17]  Howard G. Hatch,et al.  INFINITE PERIODIC MINIMAL SURFACES WITHOUT SELF-INTERSECTIONS , 2002 .

[18]  Marcus Mueller,et al.  Field theoretic study of bilayer membrane fusion , 2004 .

[19]  M. Matsen.  Polydispersity-induced macrophase separation in diblock copolymer melts. , 2007, Physical review letters.

[20]  K. Daoulas,et al.  Phase behaviour of quasi-block copolymers: A DFT-based Monte-Carlo study , 2009 .

[21]  Francisco J. Martinez-Veracoechea,et al.  The Plumber’s Nightmare Phase in Diblock Copolymer/Homopolymer Blends. A Self-Consistent Field Theory Study. , 2009 .

[22]  S. Edwards,et al.  The Theory of Polymer Dynamics , 1986 .

[23]  F. Schmid,et al.  Incorporating fluctuations and dynamics in self-consistent field theories for polymer blends , 2005, cond-mat/0501076.

[24]  Marcus Müller,et al.  Speeding up intrinsically slow collective processes in particle simulations by concurrent coupling to a continuum description. , 2011, Physical review letters.

[25]  Marcus Müller,et al.  Computational Approaches for the Dynamics of Structure Formation in Self-Assembling Polymeric Materials , 2013 .

[26]  E. Vanden-Eijnden,et al.  A temperature accelerated method for sampling free energy and determining reaction pathways in rare events simulations , 2006 .

[27]  M. Matsen.  The standard Gaussian model for block copolymer melts , 2002 .

[28]  Marcus Müller,et al.  Single-chain dynamics in a homogeneous melt and a lamellar microphase: a comparison between Smart Monte Carlo dynamics, slithering-snake dynamics, and slip-link dynamics. , 2008, The Journal of chemical physics.

[29]  J. D. Doll,et al.  Brownian dynamics as smart Monte Carlo simulation , 1978 .

[30]  A. Schoen.  Infinite periodic minimal surfaces without self-intersections , 1970 .