Complex macrophase-separated nanostructure induced by microphase separation in binary blends of lamellar diblock copolymer thin films.

The nanostructures of thin films spin-coated from binary blends of compositionally symmetric polystyrene-b-polybutadiene (PS-b-PB) diblock copolymer having different molar masses are investigated by means of atomic force microscopy (AFM) and grazing-incidence small-angle X-ray scattering (GISAXS) after spin-coating and after subsequent solvent vapor annealing (SVA). In thin films of the pure diblock copolymers having high or low molar mass, the lamellae are perpendicular or parallel to the substrate, respectively. The as-prepared binary blend thin films feature mainly perpendicular lamellae in a one-phase state, indicating that the higher molar mass diblock copolymer dominates the lamellar orientation. The lamellar thickness decreases linearly with increasing volume fraction of the low molar mass diblock copolymer. After SVA, well-defined macrophase-separated nanostructures appear, which feature parallel lamellae near the film surface and perpendicular ones in the bulk.

[1]  Thomas H. Epps,et al.  Directed Block Copolymer Thin Film Self-Assembly: Emerging Trends in Nanopattern Fabrication , 2013 .

[2]  Detlef-Matthias Smilgies,et al.  Structural evolution of perpendicular lamellae in diblock copolymer thin films during solvent vapor treatment investigated by grazing-incidence small-angle X-ray scattering. , 2013, Macromolecular rapid communications.

[3]  M. Morris,et al.  Solvent Vapor Annealing of Block Polymer Thin Films , 2013 .

[4]  Ruipeng Li,et al.  Stepwise Swelling of a Thin Film of Lamellae-Forming Poly(styrene-b-butadiene) in Cyclohexane Vapor , 2012 .

[5]  Detlef-Matthias Smilgies,et al.  The effect of heat treatment on the internal structure of nanostructured block copolymer films , 2011 .

[6]  P. Müller‐Buschbaum,et al.  Debye–Scherrer rings from block copolymer films with powder-like order , 2011 .

[7]  Baohui Li,et al.  Microphase and Macrophase Separations in Binary Blends of Diblock Copolymers , 2011 .

[8]  Baohui Li,et al.  Phase behavior of binary blends of diblock copolymers. , 2010, The journal of physical chemistry. B.

[9]  Dorthe Posselt,et al.  Structural rearrangements in a lamellar diblock copolymer thin film during treatment with saturated solvent vapor. , 2010, Macromolecules.

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

[11]  C. A. Ross,et al.  Nanowire conductive polymer gas sensor patterned using self-assembled block copolymer lithography. , 2008, Nano letters.

[12]  E. Thomas,et al.  Phase Behavior of Binary Blends of High Molecular Weight Diblock Copolymers with a Low Molecular Weight Triblock , 2008 .

[13]  Soojin Park,et al.  A simple route to highly oriented and ordered nanoporous block copolymer templates. , 2008, ACS nano.

[14]  D. Smilgies,et al.  Inner Structure of Thin Films of Lamellar Poly(styrene- b -butadiene) Diblock Copolymers As Revealed by Grazing-Incidence Small-Angle Scattering , 2007 .

[15]  M. Kuhlmann,et al.  Small-angle options of the upgraded ultrasmall-angle x-ray scattering beamline BW4 at HASYLAB , 2006 .

[16]  Detlef-M. Smilgies,et al.  Grazing‐incidence small‐angle X‐ray scattering from thin polymer films with lamellar structures – the scattering cross section in the distorted‐wave Born approximation , 2006 .

[17]  Stephen Y. Chou,et al.  Macroscopic Orientation of Block Copolymer Cylinders in Single‐Layer Films by Shearing , 2004 .

[18]  D. Smilgies,et al.  Lamellar Diblock Copolymer Thin Films Investigated by Tapping Mode Atomic Force Microscopy: Molar-Mass Dependence of Surface Ordering , 2003 .

[19]  Koji Asakawa,et al.  2.5-inch disk patterned media prepared by an artificially assisted self-assembling method , 2002 .

[20]  T. Hashimoto,et al.  A Phase Diagram for the Binary Blends of Nearly Symmetric Diblock Copolymers. 2. Parameter Space of Temperature and Blend Composition , 2001 .

[21]  Daisuke Yamaguchi,et al.  A Phase Diagram for the Binary Blends of Nearly Symmetric Diblock Copolymers. 1. Parameter Space of Molecular Weight Ratio and Blend Composition , 2001 .

[22]  T. Hashimoto,et al.  Morphological studies of binary mixtures of block copolymers. 1. Cosurfactant effects and composition dependence of morphology , 2001 .

[23]  K. Guarini,et al.  Ultrahigh-density nanowire arrays grown in self-assembled diblock copolymer templates. , 2000, Science.

[24]  Y. Fink,et al.  One-dimensionally periodic dielectric reflectors from self-assembled block copolymer-homopolymer blends , 1999 .

[25]  K. Mortensen,et al.  Phase behavior of binary blends of symmetric polystyrene-polybutadiene diblock copolymers studied using SANS , 1998 .

[26]  K. Mortensen,et al.  A Small-Angle Scattering Study of the Bulk Structure of a Symmetric Diblock Copolymer System , 1997 .

[27]  R. Spontak,et al.  Phase Behavior and Morphological Characteristics of Compositionally Symmetric Diblock Copolymer Blends , 1996 .

[28]  M. Matsen,et al.  Immiscibility of large and small symmetric diblock copolymers , 1995 .

[29]  M. Matsen.  Phase Behavior of Block Copolymer/Homopolymer Blends , 1995 .

[30]  T. Hashimoto,et al.  Ordered Structure in Blends of Block Copolymers.2.Self-Assembly for Immiscible Lamella-Forming Copolymers , 1994 .

[31]  T. Hashimoto,et al.  Ordered structure in blends of block copolymers. 1. Miscibility criterion for lamellar block copolymers , 1993 .

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

[33]  E. Helfand,et al.  Theory of the Interface between Immiscible Polymers. II , 1972 .

[34]  A. Hexemer,et al.  An In Situ Grazing Incidence X‐Ray Scattering Study of Block Copolymer Thin Films During Solvent Vapor Annealing , 2014, Advanced materials.

[35]  L. Leibler,et al.  Block copolymers in tomorrow's plastics , 2005, Nature materials.

[36]  P. Vacca,et al.  Free surface morphology of block copolymers: 1. Styrene-butadiene diblock copolymers , 1995 .