Kinetics of directed self-assembly of block copolymers on chemically patterned substrates

Chemically patterned surfaces have been successfully employed to direct the kinetics of self-assembly of block copolymers into dense, periodic morphologies ("chemoepitaxy"). Significant efforts have been directed towards understanding the kinetics of structure formation and, particularly, the formation and annihilation of defects. In the present manuscript we use computer simulations of a soft, coarse-grained polymer model to study the kinetics of structure formation of lamellar-forming block copolymer thin films on a chemical pattern of lines and spaces. The case where the copolymer material replicates the surface pattern and the more subtle scenario of sparse guiding patterns are considered. Our simulation results highlight (1) the importance of the early stages of pattern-directed self-assembly that template the subsequent morphology and (2) the dependence of the free-energy landscape on the incompatibility between the two blocks of the copolymer.

[1]  M. Peach,et al.  THE FORCES EXERTED ON DISLOCATIONS AND THE STRESS FIELDS PRODUCED BY THEM , 1950 .

[2]  P. Pershan.  Dislocation effects in smectic‐A liquid crystals , 1974 .

[3]  P. Hohenberg,et al.  Theory of Dynamic Critical Phenomena , 1977 .

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

[5]  P. Gennes.  Scaling Concepts in Polymer Physics , 1979 .

[6]  L. Leibler.  Theory of Microphase Separation in Block Copolymers , 1980 .

[7]  K. Binder.  Collective diffusion, nucleation, and spinodal decomposition in polymer mixtures , 1983 .

[8]  Mark E. Tuckerman,et al.  Reversible multiple time scale molecular dynamics , 1992 .

[9]  M. Cross,et al.  Pattern formation outside of equilibrium , 1993 .

[10]  Glenn H. Fredrickson,et al.  Dynamics of Block Copolymers: Theory and Experiment , 1996 .

[11]  Kurt Binder,et al.  Symmetric diblock copolymers in thin films. I. Phase stability in self-consistent field calculations and Monte Carlo simulations , 1999 .

[12]  D. Huse,et al.  Mechanisms of ordering in striped patterns. , 2000, Science.

[13]  K. Binder,et al.  Spinodal decomposition in a binary polymer mixture: dynamic self-consistent-field theory and Monte Carlo simulations. , 2001, Physical review. E, Statistical, nonlinear, and soft matter physics.

[14]  Steven J. Sibener,et al.  Time-resolved atomic force microscopy imaging studies of asymmetric PS-b-PMMA ultrathin films: Dislocation and disclination transformations, defect mobility, and evolution of nanoscale morphology , 2001 .

[15]  M. Matsen,et al.  Limitations of the dilution approximation for concentrated block copolymer/solvent mixtures , 2002 .

[16]  M. Schick,et al.  Theory of T junctions and symmetric tilt grain boundaries in pure and mixed polymer systems , 2002 .

[17]  D. A. Vega,et al.  Dynamics of pattern coarsening in a two-dimensional smectic system. , 2002, Physical review. E, Statistical, nonlinear, and soft matter physics.

[18]  E. Reister,et al.  Formation of enrichment layers in thin polymer films: The influence of single chain dynamics , 2003 .

[19]  P. Nealey,et al.  Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates , 2003, Nature.

[20]  E. W. Edwards,et al.  Mechanism and kinetics of ordering in diblock copolymer thin films on chemically nanopatterned substrates , 2005 .

[21]  Craig J. Hawker,et al.  Block Copolymer Lithography: Merging “Bottom-Up” with “Top-Down” Processes , 2005 .

[22]  P. Nealey,et al.  Block copolymers and conventional lithography , 2006 .

[23]  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.

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

[25]  Juan J. de Pablo,et al.  Dimensions and Shapes of Block Copolymer Domains Assembled on Lithographically Defined Chemically Patterned Substrates , 2007 .

[26]  Juan J de Pablo,et al.  Directed copolymer assembly on chemical substrate patterns: a phenomenological and single-chain-in-mean-field simulations study of the influence of roughness in the substrate pattern. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[27]  Joel K. W. Yang,et al.  Graphoepitaxy of Self-Assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates , 2008, Science.

[28]  C. Hawker,et al.  Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns , 2009, Advanced materials.

[29]  K. Daoulas,et al.  Computing free energies of interfaces in self-assembling systems. , 2009, Physical chemistry chemical physics : PCCP.

[30]  Marcus Müller,et al.  Monte carlo simulation of coarse grain polymeric systems. , 2009, Physical review letters.

[31]  Juan J. de Pablo,et al.  Remediation of Line Edge Roughness in Chemical Nanopatterns by the Directed Assembly of Overlying Block Copolymer Films , 2010 .

[32]  Juan J. de Pablo,et al.  Interpolation in the Directed Assembly of Block Copolymers on Nanopatterned Substrates: Simulation and Experiments , 2010 .

[33]  K. Daoulas,et al.  Polymer-solid contacts described by soft, coarse-grained models. , 2011, Physical chemistry chemical physics : PCCP.

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

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

[36]  Juan J. de Pablo,et al.  Free Energy of Defects in Ordered Assemblies of Block Copolymer Domains. , 2012, ACS macro letters.

[37]  M. Müller.  Geometry-controlled interface localization-delocalization transition in block copolymers. , 2012, Physical review letters.

[38]  Juan J. de Pablo,et al.  Chemical Patterns for Directed Self-Assembly of Lamellae-Forming Block Copolymers with Density Multiplication of Features , 2013 .

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

[40]  Bong Hoon Kim,et al.  Directed self-assembly of block copolymers for next generation nanolithography , 2013 .

[41]  J. Pablo,et al.  Theoretically informed entangled polymer simulations: linear and non-linear rheology of melts , 2013 .

[42]  P. Khalatur,et al.  Structural Changes in Lamellar Diblock Copolymer Thin Films upon Swelling in Nonselective Solvents , 2013 .

[43]  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.

[44]  C. Grant Willson,et al.  Block Copolymer Lithography , 2014 .

[45]  Marcus Müller,et al.  Defect removal in the course of directed self-assembly is facilitated in the vicinity of the order-disorder transition. , 2014, Physical review letters.