Directed self-assembly of block copolymers in the extreme: guiding microdomains from the small to the large

The self-assembly of block copolymers (BCPs) is emerging as a promising route for numerous applications to generate templates and scaffolds for the fabrication of nanostructured materials. Here, we present an overview of recent progress in the directed self-assembly of BCPs with a focus on guiding the assemblies of extreme (small and large) features over large areas. We introduce inorganic-containing hybrid BCPs that enable access to ultra-small feature sizes. To achieve the desired orientation and lateral ordering of the BCP microdomains, we discuss routes that combine top-down (lithographic) processes with the bottom-up self-assembly of BCPs. On the extreme large size scale, high-molecular-weight BCPs and brush-type copolymers are discussed, covering the other extreme of this promising strategy.

[1]  T. Nose Coexistence curves of polystyrene/poly(dimethylsiloxane) blends , 1995 .

[2]  Zhiqun Lin,et al.  A Rapid Route to Arrays of Nanostructures in Thin Films , 2002 .

[3]  Karl R. Amundson,et al.  Effect of an electric field on block copolymer microstructure , 1991 .

[4]  K. Berggren,et al.  A path to ultranarrow patterns using self-assembled lithography. , 2010, Nano letters.

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

[6]  Heinrich M. Jaeger,et al.  Large-Area Domain Alignment in Block Copolymer Thin Films Using Electric Fields , 1998 .

[7]  Jeffrey N. Murphy,et al.  Density doubling of block copolymer templated features. , 2012, Nano letters.

[8]  Ting Xu,et al.  Highly Oriented and Ordered Arrays from Block Copolymers via Solvent Evaporation , 2004 .

[9]  T. Russell,et al.  Free Structure Confinement of Diblock Copolymer Multilayers , 1995 .

[10]  Craig J. Hawker,et al.  Surface Modification with Cross-Linked Random Copolymers: Minimum Effective Thickness , 2007 .

[11]  X. Gu,et al.  Unidirectionally aligned line patterns driven by entropic effects on faceted surfaces , 2012, Proceedings of the National Academy of Sciences.

[12]  Eun Hye Kim,et al.  Microdomain Orientation of PS-b-PMMA by Controlled Interfacial Interactions , 2008 .

[13]  Yoshinori Funaki,et al.  The Effect of Temperature Gradient on the Microdomain Orientation of Diblock Copolymers Undergoing an Order−Disorder Transition , 1999 .

[14]  Y. Gallot,et al.  Microphases and macrophases in polymer blends with a diblock copolymer , 1994 .

[15]  Padma Gopalan,et al.  Side-chain-grafted random copolymer brushes as neutral surfaces for controlling the orientation of block copolymer microdomains in thin films. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[16]  Timothy P. Lodge,et al.  Block Copolymers: Past Successes and Future Challenges , 2003 .

[17]  Craig J Hawker,et al.  A Generalized Approach to the Modification of Solid Surfaces , 2005, Science.

[18]  Craig J. Hawker,et al.  Using Surface Active Random Copolymers To Control the Domain Orientation in Diblock Copolymer Thin Films , 1998 .

[19]  Edwin L. Thomas,et al.  Competing Interactions and Levels of Ordering in Self-Organizing Polymeric Materials , 1997 .

[20]  N. Bowden,et al.  Investigation of the Assembly of Comb Block Copolymers in the Solid State , 2008 .

[21]  Soojin Park,et al.  Interaction-controlled HPLC for block copolymer analysis and separation. , 2004, Journal of the American Chemical Society.

[22]  S. Mochrie,et al.  Polymers on Nanoperiodic, Heterogeneous Surfaces , 1999 .

[23]  B. Ocko,et al.  Block copolymer self-assembly in chemically patterned squares , 2011 .

[24]  Jin Kon Kim,et al.  Property of diblock copolymer having extremely narrow molecular weight distribution , 2008 .

[25]  Sang-Won Kang,et al.  Universal Block Copolymer Lithography for Metals, Semiconductors, Ceramics, and Polymers , 2008 .

[26]  Y. Zhang,et al.  Local Defectivity Control of 2D Self‐Assembled Block Copolymer Patterns , 2007 .

[27]  Padma Gopalan,et al.  Hierarchical Nanostructures of Organosilicate Nanosheets within Self-Organized Block Copolymer Films , 2008 .

[28]  A. Knoll,et al.  Large Scale Domain Alignment of a Block Copolymer from Solution Using Electric Fields , 2002 .

[29]  Karl R. Amundson,et al.  Alignment of lamellar block copolymer microstructure in an electric field. 1. Alignment kinetics , 1993 .

[30]  S. Darling,et al.  Guiding Polymers to Perfection: Macroscopic Alignment of Nanoscale Domains , 2004 .

[31]  Joy Y. Cheng,et al.  Dense Self‐Assembly on Sparse Chemical Patterns: Rectifying and Multiplying Lithographic Patterns Using Block Copolymers , 2008 .

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

[33]  Joy Cheng,et al.  Formation of a Cobalt Magnetic Dot Array via Block Copolymer Lithography , 2001 .

[34]  V. Deline,et al.  Surface-induced orientation of symmetric, diblock copolymers: a secondary ion mass spectrometry study , 1989 .

[35]  V. Deline,et al.  Characteristics of the surface-induced orientation for symmetric diblock PS/PMMA copolymers , 1989 .

[36]  N. Bowden,et al.  Synthesis of Comb Block Copolymers by ROMP, ATRP, and ROP and Their Assembly in the Solid State , 2006 .

[37]  T. Hashimoto,et al.  Order–disorder transition of starblock copolymers , 1988 .

[38]  A. Blumen,et al.  Block copolymer films between neutral walls: A Monte Carlo study , 1999 .

[39]  Henry I. Smith,et al.  Fabrication of nanostructures with long-range order using block copolymer lithography , 2002 .

[40]  Charles F. Majkrzak,et al.  The morphology of symmetric diblock copolymers as revealed by neutron reflectivity , 1990 .

[41]  Joy Y. Cheng,et al.  Nanostructure engineering by templated self-assembly of block copolymers , 2004, Nature materials.

[42]  E. Kramer,et al.  Graphoepitaxy of Spherical Domain Block Copolymer Films , 2001 .

[43]  E. W. Edwards,et al.  Directed Assembly of Block Copolymer Blends into Nonregular Device-Oriented Structures , 2005, Science.

[44]  E. Thomas,et al.  Swelling of lamellar diblock copolymer by homopolymer: influences of homopolymer concentration and molecular weight , 1991 .

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

[46]  Rachel A. Segalman,et al.  Effects of lateral confinement on order in spherical domain block copolymer thin films , 2003 .

[47]  C. Ross,et al.  Templated Self‐Assembly of Block Copolymers: Effect of Substrate Topography , 2003 .

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

[49]  Ian W. Hamley,et al.  Small-angle scattering of block copolymers: in the melt, solution and crystal states , 2004 .

[50]  R. Roe,et al.  Solubilization of a Homopolymer in a Block Copolymer , 1994 .

[51]  S. Fort,et al.  Nano-organization of amylose-b-polystyrene block copolymer films doped with bipyridine. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[52]  D. Muller,et al.  Block Copolymer Self-Assembly–Directed Single-Crystal Homo- and Heteroepitaxial Nanostructures , 2010, Science.

[53]  Craig J. Hawker,et al.  Neutrality conditions for block copolymer systems on random copolymer brush surfaces , 1999 .

[54]  Craig J. Hawker,et al.  Ordered diblock copolymer films on random copolymer brushes , 1997 .

[55]  C. Grant Willson,et al.  Thin Film Self-Assembly of Poly(trimethylsilylstyrene-b-D,L-lactide) with Sub-10 nm Domains , 2012 .

[56]  A. Knoll,et al.  Microscopic mechanisms of electric-field-induced alignment of block copolymer microdomains. , 2002, Physical review letters.

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

[58]  J. Rzayev Synthesis of Polystyrene−Polylactide Bottlebrush Block Copolymers and Their Melt Self-Assembly into Large Domain Nanostructures , 2009 .

[59]  A. Knoll,et al.  Electric Field Induced Alignment of Concentrated Block Copolymer Solutions , 2003 .

[60]  S. Fort,et al.  Control of 10 nm scale cylinder orientation in self-organized sugar-based block copolymer thin films. , 2013, Nanoscale.

[61]  Heinrich M. Jaeger,et al.  Overcoming Interfacial Interactions with Electric Fields , 2000 .

[62]  I. Potemkin Lamellar Orientation in Thin, Supported Diblock Copolymer Films: Strong Segregation Theory , 2004 .

[63]  Galen T. Pickett,et al.  Equilibrium surface orientation of lamellae , 1993 .

[64]  Wonjoon Jung,et al.  Nanofabricated concentric ring structures by templated self-assembly of a diblock copolymer. , 2008, Nano letters.

[65]  T. Hashimoto,et al.  Ordered structure in mixtures of a block copolymer and homopolymers. 1. Solubilization of low molecular weight homopolymers , 1991 .

[66]  Franco Cerrina,et al.  Guided Self-Assembly of Symmetric Diblock Copolymer Films on Chemically Nanopatterned Substrates , 2000 .

[67]  T. P. Russell,et al.  Solvent‐Induced Ordering in Thin Film Diblock Copolymer/Homopolymer Mixtures , 2004 .

[68]  Augustine Urbas,et al.  Tunable Block Copolymer/Homopolymer Photonic Crystals , 2000 .

[69]  G. Fredrickson,et al.  Can a single function for χ account for block copolymer and homopolymer blend phase behavior , 1998 .

[70]  Soojin Park,et al.  Directed Self‐Assembly of Block Copolymers on Two‐Dimensional Chemical Patterns Fabricated by Electro‐Oxidation Nanolithography , 2010, Advanced materials.

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

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

[73]  Eungnak Han,et al.  Graphoepitaxial Assembly of Symmetric Block Copolymers on Weakly Preferential Substrates , 2010, Advanced materials.

[74]  S. Fort,et al.  Thermoresponsive vesicular morphologies obtained by self-assemblies of hybrid oligosaccharide-block-poly(N-isopropylacrylamide) copolymer systems. , 2010, Langmuir : the ACS journal of surfaces and colloids.

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

[76]  E. Thomas,et al.  Broad-wavelength-range chemically tunable block-copolymer photonic gels. , 2007, Nature materials.

[77]  Krzysztof Matyjaszewski,et al.  Long-range ordered thin films of block copolymers prepared by zone-casting and their thermal conversion into ordered nanostructured carbon. , 2005, Journal of the American Chemical Society.

[78]  N. Bowden,et al.  Synthesis of high molecular weight comb block copolymers and their assembly into ordered morphologies in the solid state. , 2007, Journal of the American Chemical Society.

[79]  Erin M. Lennon,et al.  Evolution of Block Copolymer Lithography to Highly Ordered Square Arrays , 2008, Science.

[80]  Jongseung Yoon,et al.  Highly Oriented Thin‐Film Microdomain Patterns of Ultrahigh Molecular Weight Block Copolymers via Directional Solidification of a Solvent , 2006 .

[81]  B. Ocko,et al.  Electric Field Induced Sphere-to-Cylinder Transition in Diblock Copolymer Thin Films , 2004 .

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

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

[84]  A. Hexemer,et al.  Controlled Orientation of Block Copolymers on Defect‐Free Faceted Surfaces , 2012, Advanced materials.

[85]  Joel K. W. Yang,et al.  Complex self-assembled patterns using sparse commensurate templates with locally varying motifs. , 2010, Nature nanotechnology.

[86]  Y. Zhang,et al.  Directed Assembly of Lamellae‐ Forming Block Copolymers by Using Chemically and Topographically Patterned Substrates , 2007 .

[87]  Yan Xia,et al.  Efficient synthesis of narrowly dispersed brush copolymers and study of their assemblies: the importance of side chain arrangement. , 2009, Journal of the American Chemical Society.

[88]  C. Hawker,et al.  Controlling Polymer-Surface Interactions with Random Copolymer Brushes , 1997, Science.

[89]  Massimo Lazzari,et al.  Block Copolymers as a Tool for Nanomaterial Fabrication , 2003 .

[90]  J. Rzayev,et al.  Large pore size nanoporous materials from the self-assembly of asymmetric bottlebrush block copolymers. , 2011, Nano letters.

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

[92]  Eungnak Han,et al.  One‐Step Direct‐Patterning Template Utilizing Self‐Assembly of POSS‐Containing Block Copolymers , 2009, Advanced materials.

[93]  Y. Jung,et al.  Orientation-controlled self-assembled nanolithography using a polystyrene-polydimethylsiloxane block copolymer. , 2007, Nano letters.

[94]  Karl Amundson,et al.  Alignment of Lamellar Block Copolymer Microstructure in an Electric Field. 2. Mechanisms of Alignment , 1994 .

[95]  Gallagher,et al.  Observed frustration in confined block copolymers. , 1994, Physical review letters.

[96]  H. Jaeger,et al.  Local Control of Microdomain Orientation in Diblock Copolymer Thin Films with Electric Fields , 1996, Science.

[97]  P. Gopalan,et al.  Hierarchical Self-Assembled Structures from POSS-Containing Block Copolymers Synthesized by Living Anionic Polymerization , 2009 .

[98]  T. Satoh,et al.  10 nm Scale Cylinder-Cubic Phase Transition Induced by Caramelization in Sugar-Based Block Copolymers. , 2012, ACS macro letters.

[99]  Eunhye Kim,et al.  Directed assembly of high molecular weight block copolymers: highly ordered line patterns of perpendicularly oriented lamellae with large periods. , 2013, ACS nano.

[100]  Yoshinori Funaki,et al.  Single-Grain Lamellar Microdomain from a Diblock Copolymer , 1999 .

[101]  Eric W. Cochran,et al.  Stability of the Gyroid Phase in Diblock Copolymers at Strong Segregation , 2006 .

[102]  Soojin Park,et al.  Fractionation of Block Copolymers Prepared by Anionic Polymerization into Fractions Exhibiting Three Different Morphologies , 2002 .

[103]  A. Khokhlov,et al.  Polymers with Strongly Interacting Groups: Theory for Nonspherical Multiplets , 1995 .

[104]  Jae Won Jeong,et al.  Highly tunable self-assembled nanostructures from a poly(2-vinylpyridine-b-dimethylsiloxane) block copolymer. , 2011, Nano letters.

[105]  Hirokazu Hasegawa,et al.  Ordered structure in mixtures of a block copolymer and homopolymers. 2. Effects of molecular weights of homopolymers , 1990 .

[106]  T. Satoh,et al.  Sub-10 nm Nano-Organization in AB2- and AB3-Type Miktoarm Star Copolymers Consisting of Maltoheptaose and Polycaprolactone , 2013 .

[107]  R. Grubbs,et al.  Self-assembly of symmetric brush diblock copolymers. , 2013, ACS nano.

[108]  Jumi Lee,et al.  Phase Behavior of Polystyrene-b-poly(methyl methacrylate) Diblock Copolymer , 2009 .

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

[110]  Christopher J. Ellison,et al.  Oligosaccharide/silicon-containing block copolymers with 5 nm features for lithographic applications. , 2012, ACS nano.

[111]  K. W. Gotrik,et al.  Templating Three-Dimensional Self-Assembled Structures in Bilayer Block Copolymer Films , 2012, Science.