Free Energy of Defects in Ordered Assemblies of Block Copolymer Domains.

We investigate commonly occurring defects in block copolymer thin films assembled on chemically nanopatterned substrates and predict their probability of occurrence by computing their free energies. A theoretically informed 3D coarse grain model is used to describe the system. These defects become increasingly unstable as the strength of interactions between the copolymer and the patterned substrate increases and when partial defects occur close to the top surface of the film. The results presented here reveal an extraordinarily large thermodynamic driving force for the elimination of defects. When the characteristics of the substrate are commensurate with the morphology of the block copolymer, the probability of creating a defect is extremely small and well below the specifications of the semiconductor industry for fabrication of features having characteristic dimensions on the scale of tens of nanometers. We also investigate how the occurrence of defect changes when imperfections arise in the underlying...

[1]  Marcus Müller,et al.  Calculating the free energy of self-assembled structures by thermodynamic integration. , 2008, The Journal of chemical physics.

[2]  A. Knoll,et al.  Rapid transitions between defect configurations in a block copolymer melt. , 2006, Nano letters.

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

[4]  H. Jaeger,et al.  Defect evolution in ultrathin films of polystyrene-block-polymethylmethacrylate diblock copolymers observed by atomic force microscopy , 1998 .

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

[6]  S. Sides,et al.  Defects and their removal in block copolymer thin film simulations , 2006 .

[7]  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.

[8]  P. Nealey,et al.  Theoretically informed coarse grain simulations of block copolymer melts: method and applications , 2009 .

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

[10]  Christopher Harrison,et al.  Block copolymer lithography: Periodic arrays of ~1011 holes in 1 square centimeter , 1997 .

[11]  William D. Hinsberg,et al.  Self-assembly patterning for sub-15nm half-pitch: a transition from lab to fab , 2011, Advanced Lithography.

[12]  Guojun Liu,et al.  Block copolymers in nanoscience , 2006 .

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

[14]  G. Sevink,et al.  Defect evolution in block copolymer thin films via temporal phase transitions. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[15]  Marcus Müller,et al.  Rapid Directed Assembly of Block Copolymer Films at Elevated Temperatures , 2008 .

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

[17]  Marcus Müller,et al.  Directed self-assembly of block copolymers for nanolithography: fabrication of isolated features and essential integrated circuit geometries. , 2007, ACS nano.

[18]  G. Fredrickson,et al.  Block Copolymers—Designer Soft Materials , 1999 .

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

[20]  S. Darling.  Directing the self-assembly of block copolymers , 2007 .

[21]  Soojin Park,et al.  Macroscopic 10-Terabit–per–Square-Inch Arrays from Block Copolymers with Lateral Order , 2009, Science.

[22]  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.

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

[24]  A. Krekhov,et al.  Specific features of defect structure and dynamics in the cylinder phase of block copolymers. , 2008, ACS nano.

[25]  E. Kramer,et al.  Topographic templating of islands and holes in highly Asymmetric block copolymer films , 2003 .