Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter.

Self-assembly of soft materials is broadly considered an attractive means of generating nanoscale structures and patterns over large areas. However, the spontaneous formation of equilibrium nanostructures in response to temperature and concentration changes, for example, must be guided to yield the long-range order and orientation required for utility in a given scenario. In this review we examine directed self-assembly (DSA) of block copolymers (BCPs) as canonical examples of nanostructured soft matter systems which are additionally compelling for creating functional materials and devices. We survey well established and newly emerging DSA methods from a tutorial perspective. Special emphasis is given to exploring underlying physical phenomena, identifying prototypical BCPs that are compatible with different DSA techniques, describing experimental methods and highlighting the attractive functional properties of block copolymers overall. Finally we offer a brief perspective on some unresolved issues and future opportunities in this field.

[1]  Oriano Francescangeli,et al.  Phase and orientational behaviors in liquid crystalline main‐chain/side‐group block copolymers , 1998 .

[2]  Brian C. Berry,et al.  Orientational order in block copolymer films zone annealed below the order--disorder transition temperature. , 2007, Nano letters.

[3]  Pawel W. Majewski,et al.  Liquid crystalline order and magnetocrystalline anisotropy in magnetically doped semiconducting ZnO nanowires. , 2011, ACS nano.

[4]  Gurovich Why does an electric field align structures in copolymers? , 1995, Physical review letters.

[5]  G. Craig,et al.  Preparation of Neutral Wetting Brushes for Block Copolymer Films from Homopolymer Blends , 2008 .

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

[7]  Sergiy Minko,et al.  Ordered reactive nanomembranes/nanotemplates from thin films of block copolymer supramolecular assembly. , 2003, Journal of the American Chemical Society.

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

[9]  Jin Kon Kim,et al.  Enhancement in the Orientation of the Microdomain in Block Copolymer Thin Films upon the Addition of Homopolymer , 2004 .

[10]  Paul F. Nealey,et al.  Using Self-Assembled Monolayers Exposed to X-rays To Control the Wetting Behavior of Thin Films of Diblock Copolymers , 2000 .

[11]  Youngwoo Choo,et al.  Order-disorder transition and alignment dynamics of a block copolymer under high magnetic fields by in situ x-ray scattering. , 2012, Physical review letters.

[12]  Richard A. Register,et al.  Shear‐Induced Alignment in Thin Films of Spherical Nanodomains , 2005 .

[13]  Jongseung Yoon,et al.  Erratum to: ‘Enabling nanotechnology with self assembled block copolymer patterns’ [Polymer 44 (23) 6725–6760] , 2003 .

[14]  Peter Trefonas,et al.  Computational modeling of block‐copolymer directed self‐assembly , 2015 .

[15]  Yong Wang,et al.  Metal nanodot memory by self-assembled block copolymer lift-off. , 2010, Nano letters.

[16]  Joy Y. Cheng,et al.  Self-assembled one-dimensional nanostructure arrays. , 2006, Nano letters.

[17]  Martin E Vigild,et al.  Nanoporous materials with spherical and gyroid cavities created by quantitative etching of polydimethylsiloxane in polystyrene-polydimethylsiloxane block copolymers. , 2003, Journal of the American Chemical Society.

[18]  Jodie L. Lutkenhaus,et al.  Anisotropic ionic conductivity in block copolymer membranes by magnetic field alignment. , 2010, Journal of the American Chemical Society.

[19]  Bong Hoon Kim,et al.  Soft graphoepitaxy of block copolymer assembly with disposable photoresist confinement. , 2009, Nano letters.

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

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

[22]  Julia A. Kornfield,et al.  Pathways to Macroscale Order in Nanostructured Block Copolymers , 1997 .

[23]  Ramanan Krishnamoorti,et al.  Evolution of microstructure during shear alignment in a polystyrene-polyisoprene lamellar diblock copolymer , 1995 .

[24]  Matthew Libera,et al.  Kinetic Constraints on the Development of Surface Microstructure in SBS Thin Films , 1998 .

[25]  C. Hawker,et al.  Nanodomain control in copolymer thin films , 1998, Nature.

[26]  Soo-Jin Park,et al.  Lateral Ordering of Cylindrical Microdomains Under Solvent Vapor , 2009 .

[27]  Chinedum O Osuji,et al.  Controlled alignment of lamellar lyotropic mesophases by rotation in a magnetic field. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[28]  Lijia An,et al.  Study of the time evolution of the surface morphology of thin asymmetric diblock copolymer films under solvent vapor , 2005 .

[29]  Thomas P. Russell,et al.  Solvent annealing thin films of poly (isoprene- b-lactide) , 2005 .

[30]  Dorthe Posselt,et al.  Structural instabilities in lamellar diblock copolymer thin films during solvent vapor uptake. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[31]  Jin Kon Kim,et al.  Asymmetric Block Copolymers with Homopolymers: Routes to Multiple Length Scale Nanostructures , 2002 .

[32]  Steffen Trimper,et al.  Fluctuation effects in the theory of microphase separation of diblock copolymers in the presence of an electric field , 2007 .

[33]  Bongjin Moon,et al.  Synthesis of Photocleavable Poly(styrene-block-ethylene oxide) and Its Self-Assembly into Nanoporous Thin Films , 2009 .

[34]  Edwin L. Thomas,et al.  Microdomain patterns from directional eutectic solidification and epitaxy , 2000, Nature.

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

[36]  Christophe Navarro,et al.  Nanoscale Block Copolymer Ordering Induced by Visible Interferometric Micropatterning: A Route towards Large Scale Block Copolymer 2D Crystals , 2013, Advanced materials.

[37]  Eric W McFarland,et al.  Size- and support-dependent electronic and catalytic properties of Au0/Au3+ nanoparticles synthesized from block copolymer micelles. , 2003, Journal of the American Chemical Society.

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

[39]  Karl K. Berggren,et al.  Si-containing block copolymers for self-assembled nanolithography , 2008 .

[40]  Kenji Fukunaga,et al.  Observation of Perpendicular Orientation in Symmetric Diblock Copolymer Thin Films on Rough Substrates , 2003 .

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

[42]  Hiromichi Kawai,et al.  Deformation behavior of styrene-butadiene-styrene triblock copolymer with cylindrical morphology , 1985 .

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

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

[45]  Yu Xuan,et al.  Solvent vapor induced dewetting in diblock copolymer thin films , 2005 .

[46]  Ting Xu,et al.  Ion complexation: a route to enhanced block copolymer alignment with electric fields. , 2006, Physical review letters.

[47]  David Andelman,et al.  Thin film diblock copolymers in electric field: Transition from perpendicular to parallel lamellae , 2002 .

[48]  Evan S. Beach,et al.  Magnetic Field Alignment of a Diblock Copolymer Using a Supramolecular Route. , 2012, ACS macro letters.

[49]  Alexandru Vlad,et al.  Functionalized nanoporous thin films from photocleavable block copolymers. , 2012, Macromolecular rapid communications.

[50]  Rolf H. Berg,et al.  Nanoporous Crosslinked Polyisoprene from Polyisoprene—Polydimethylsiloxane Block Copolymer , 2004 .

[51]  Yong-Hee Lee,et al.  One-dimensional metal nanowire assembly via block copolymer soft graphoepitaxy. , 2010, Nano letters.

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

[53]  Bradley D. Olsen,et al.  Long-Range Ordering of Symmetric Block Copolymer Domains by Chaining of Superparamagnetic Nanoparticles in External Magnetic Fields , 2012 .

[54]  Hui Zhao,et al.  Highly Ordered Nanoporous Thin Films from Photocleavable Block Copolymers , 2011 .

[55]  F. E. Karasz,et al.  Shear-induced orientation transitions in triblock copolymer styrene-butadiene-styrene with cylindrical domain morphology , 1992 .

[56]  Soo-Jin Park,et al.  Sub‐Nanometer Level Size Tuning of a Monodisperse Nanoparticle Array Via Block Copolymer Lithography , 2011 .

[57]  R. Segalman Patterning with block copolymer thin films , 2005 .

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

[59]  Jianfu Ding,et al.  Potential Skin Layers for Membranes with Tunable Nanochannels , 1997 .

[60]  Nikos Hadjichristidis,et al.  Mechanical Properties and Deformation Behavior of the Double Gyroid Phase in Unoriented Thermoplastic Elastomers , 1999 .

[61]  Jillian M Buriak,et al.  Block copolymer-templated chemistry on Si, Ge, InP, and GaAs surfaces. , 2005, Journal of the American Chemical Society.

[62]  Juan Peng,et al.  Morphology change of asymmetric diblock copolymer micellar films during solvent annealing , 2007 .

[63]  Chi-Chun Liu,et al.  Plasma etch removal of poly(methyl methacrylate) in block copolymer lithography , 2008 .

[64]  Bradley D Olsen,et al.  Hierarchical nanostructure control in rod-coil block copolymers with magnetic fields. , 2007, Nano letters.

[65]  Leonidas E. Ocola,et al.  Enhanced Block Copolymer Lithography Using Sequential Infiltration Synthesis , 2011 .

[66]  Jonathan E. Seppala,et al.  Spatial and orientation control of cylindrical nanostructures in ABA triblock copolymer thin films by raster solvent vapor annealing. , 2012, ACS nano.

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

[68]  Kathryn L Beers,et al.  Gradient solvent vapor annealing of block copolymer thin films using a microfluidic mixing device. , 2011, Nano letters.

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

[70]  Armin Knoll,et al.  Phase behavior in thin films of cylinder-forming ABA block copolymers: experiments. , 2004, The Journal of chemical physics.

[71]  E. Han,et al.  Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions , 2009 .

[72]  Brian C. Berry,et al.  Dynamic thermal field-induced gradient soft-shear for highly oriented block copolymer thin films. , 2012, ACS nano.

[73]  M. Hillmyer,et al.  Perpendicular orientation of cylindrical domains upon solvent annealing thin films of polystyrene-b-polylactide , 2010 .

[74]  Jin Ok Hwang,et al.  Surface energy modification by spin-cast, large-area graphene film for block copolymer lithography. , 2010, ACS nano.

[75]  Alexander Hexemer,et al.  Ordering and Melting of Block Copolymer Spherical Domains in 2 and 3 Dimensions , 2003 .

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

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

[79]  W. Hinsberg,et al.  Block copolymer based nanostructures: materials, processes, and applications to electronics. , 2010, Chemical reviews.

[80]  Won Bo Lee,et al.  Controlling the orientation of block copolymer thin films using thermally-stable gold nanoparticles with tuned surface chemistry , 2011 .

[81]  Jillian M. Buriak,et al.  Assembly of aligned linear metallic patterns on silicon , 2007, Nature Nanotechnology.

[82]  Rui D M Travasso,et al.  Harnessing light to create defect-free, hierarchically structured polymeric materials. , 2005, Langmuir : the ACS journal of surfaces and colloids.

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

[84]  E. W. Edwards,et al.  Graphoepitaxy of cylinder-forming block copolymers for use as templates to pattern magnetic metal dot arrays , 2005, Nanotechnology.

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

[86]  Soo-Jin Park,et al.  Solvent-Induced Transition from Micelles in Solution to Cylindrical Microdomains in Diblock Copolymer Thin Films , 2007 .

[87]  Martin Brinkmann,et al.  Orientation of Regioregular Poly(3‐hexylthiophene) by Directional Solidification: A Simple Method to Reveal the Semicrystalline Structure of a Conjugated Polymer , 2006 .

[88]  Jillian M. Buriak,et al.  Block Copolymer Templated Chemistry for the Formation of Metallic Nanoparticle Arrays on Semiconductor Surfaces , 2007 .

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

[90]  K. W. Gotrik,et al.  Generalization of the Use of Random Copolymers To Control the Wetting Behavior of Block Copolymer Films , 2008 .

[91]  Craig J. Hawker,et al.  Interfacial Segregation in Disordered Block Copolymers: Effect of Tunable Surface Potentials , 1997 .

[92]  G. Krausch,et al.  Nanostructured Thin Films via Self‐Assembly of Block Copolymers , 2002 .

[93]  Ting Xu,et al.  Long-range ordering of diblock copolymers induced by droplet pinning , 2003 .

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

[95]  Alfredo Alexander-Katz,et al.  Morphology control in block copolymer films using mixed solvent vapors. , 2012, ACS nano.

[96]  Chinedum O. Osuji,et al.  Non-degenerate magnetic alignment of self-assembled mesophases , 2009 .

[97]  Shuaigang Xiao,et al.  Solvent‐Assisted Directed Self‐Assembly of Spherical Microdomain Block Copolymers to High Areal Density Arrays , 2013, Advanced materials.

[98]  Bong Hoon Kim,et al.  Mussel‐Inspired Block Copolymer Lithography for Low Surface Energy Materials of Teflon, Graphene, and Gold , 2011, Advanced materials.

[99]  Menachem Elimelech,et al.  Nanocomposites of vertically aligned single-walled carbon nanotubes by magnetic alignment and polymerization of a lyotropic precursor. , 2010, ACS nano.

[100]  Won-Ki Lee,et al.  Morphological reorientation by extensional flow deformation of a triblock copolymer styrene–isoprene–styrene , 2006 .

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

[102]  F. Bates,et al.  Unifying Weak- and Strong-Segregation Block Copolymer Theories , 1996 .

[103]  Edwin L. Thomas,et al.  Microphase separation of block copolymer solutions in a flow field , 1993 .

[104]  Timothy P. Lodge,et al.  Kinetics and Mechanisms for the Cylinder-to-Gyroid Transition in a Block Copolymer Solution , 2002 .

[105]  E. W. Edwards,et al.  Precise Control over Molecular Dimensions of Block‐Copolymer Domains Using the Interfacial Energy of Chemically Nanopatterned Substrates , 2004 .

[106]  Soo-Jin Park,et al.  Fabrication of Highly Ordered Silicon Oxide Dots and Stripes from Block Copolymer Thin Films , 2008 .

[107]  Selim Elhadj,et al.  Orientation of self-assembled block copolymer cylinders perpendicular to electric field in mesoscale film , 2003 .

[108]  Eugene Gurovich,et al.  On Microphase Separation of Block Copolymers In an Electric Field: Four Universal Classes , 1994 .

[109]  R. Ho,et al.  Long-range ordering of block copolymer cylinders driven by combining thermal annealing and substrate functionalization. , 2013, ACS nano.

[110]  Marc A. Hillmyer,et al.  Nanoporous materials from block copolymer precursors , 2005 .

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

[112]  A. Knoll,et al.  Phase behavior in thin films of cylinder-forming block copolymers. , 2002, Physical review letters.

[113]  Sang Woo Kim,et al.  Directed self-assembly of block copolymers in the extreme: guiding microdomains from the small to the large , 2013 .

[114]  Yu Xuan,et al.  Solvent-induced microphase separation in diblock copolymer thin films with reversibly switchable morphology. , 2004, The Journal of chemical physics.

[115]  Soojin Park,et al.  From nanorings to nanodots by patterning with block copolymers. , 2008, Nano letters.

[116]  Edwin L. Thomas,et al.  High‐strain tensile deformation of a sphere‐forming triblock copolymer/mineral oil blend , 1998 .

[117]  Julie N. L. Albert,et al.  Systematic study on the effect of solvent removal rate on the morphology of solvent vapor annealed ABA triblock copolymer thin films. , 2012, ACS nano.

[118]  Edwin L. Thomas,et al.  Hierarchical Ordering of Block Copolymer Nanostructures by Solvent Annealing Combined with Controlled Dewetting , 2008 .

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

[120]  Kookheon Char,et al.  Surfactant‐Assisted Orientation of Thin Diblock Copolymer Films , 2008 .

[121]  E. Thomas,et al.  Focused laser spike (FLaSk) annealing of photoactivated chemically amplified resists for rapid hierarchical patterning. , 2011, Nanoscale.

[122]  Chinedum O. Osuji,et al.  Understanding anisotropic transport in self-assembled membranes and maximizing ionic conductivity by microstructure alignment , 2013 .

[123]  Nan Yao,et al.  Nanolithographic templates from diblock copolymer thin films , 1996 .

[124]  Alexander Hexemer,et al.  Dynamics of Magnetic Alignment in Rod–Coil Block Copolymers , 2013 .

[125]  Ulrich Wiesner,et al.  Preparation of a liquid single-crystal triblock copolymer by shear , 1997 .

[126]  Ullrich Steiner,et al.  Freestanding nanowire arrays from soft-etch block copolymer templates. , 2006, Soft matter.

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

[128]  K. Matyjaszewski,et al.  Robust control of microdomain orientation in thin films of block copolymers by zone casting. , 2011, Journal of the American Chemical Society.

[129]  Julie N. L. Albert,et al.  Generation of monolayer gradients in surface energy and surface chemistry for block copolymer thin film studies. , 2009, ACS nano.

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

[131]  A. Keller,et al.  Macro-lattice from Segregated Amorphous Phases of a Three Block Copolymer , 1970, Nature.

[132]  David Andelman,et al.  Ionic effects on the electric field needed to orient dielectric lamellae. , 2010, The Journal of chemical physics.

[133]  Jan P. F. Lagerwall,et al.  Nanotube Alignment Using Lyotropic Liquid Crystals , 2007 .

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

[135]  T. Russell,et al.  Orienting block copolymer microdomains with block copolymer brushes. , 2012, ACS Nano.

[136]  I. Hamley Nanostructure fabrication using block copolymers , 2003 .

[137]  Clemens Liedel,et al.  Beyond Orientation: The Impact of Electric Fields on Block Copolymers , 2012 .

[138]  Angelika Niemz,et al.  Fabrication of nanoporous templates from diblock copolymer thin films on alkylchlorosilane-neutralized surfaces. , 2006, Langmuir : the ACS journal of surfaces and colloids.

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

[140]  Paul F. Nealey,et al.  Wetting Behavior of Block Copolymers on Self-Assembled Films of Alkylchlorosiloxanes: Effect of Grafting Density , 2000 .

[141]  Edwin L. Thomas,et al.  Roll‐Casting of block copolymers and of block copolymer‐homopolymer blends , 1994 .

[142]  Thomas P. Russell,et al.  Inorganic Nanodots from Thin Films of Block Copolymers , 2004 .

[143]  Ian W. Hamley,et al.  Transformations to and from the Gyroid Phase in a Diblock Copolymer , 1998 .

[144]  Eun Hye Kim,et al.  Lamellar microdomain orientation and phase transition of polystyrene-b-poly(methyl methacrylate) films by controlled interfacial interactions , 2012 .

[145]  Edwin L. Thomas,et al.  Spherical to cylindrical microdomain transformation by application of a flow field , 2000 .

[146]  Todd Emrick,et al.  Self‐Assembly of Nanoparticle–Copolymer Mixtures: A Kinetic Point of View , 2007 .

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

[148]  Bryan D. Vogt,et al.  Unidirectional Alignment of Block Copolymer Films Induced by Expansion of a Permeable Elastomer during Solvent Vapor Annealing , 2014 .

[149]  Nikos Hadjichristidis,et al.  Magnetic Field Induced Orientation in Diblock Copolymers with One Crystallizable Block , 2005 .

[150]  M. Hillmyer,et al.  Ordered nanoporous polymers from polystyrene-polylactide block copolymers. , 2002, Journal of the American Chemical Society.

[151]  Caroline A. Ross,et al.  Solvent‐Vapor‐Induced Tunability of Self‐Assembled Block Copolymer Patterns , 2009 .

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

[153]  Edwin L. Thomas,et al.  Nanostructured Thin Films of Organic–Organometallic Block Copolymers: One-Step Lithography with Poly(ferrocenylsilanes) by Reactive Ion Etching , 2000 .

[154]  F. Bates,et al.  Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition , 1995 .

[155]  H. Henning Winter,et al.  The effect of unidirectional shear on the structure of triblock copolymers. I. Polystyrene-polybutadiene-polystyrene , 1989 .

[156]  Helen Tran,et al.  Monoliths of semiconducting block copolymers by magnetic alignment. , 2013, ACS nano.

[157]  R. Register,et al.  Controlling order in block copolymer thin films for nanopatterning applications. , 2010, Annual review of chemical and biomolecular engineering.

[158]  Marco Pinna,et al.  Cubic phases of block copolymers under shear and electric fields by cell dynamics simulation. I. Spherical phase. , 2006, The Journal of chemical physics.

[159]  Wei-Han Huang,et al.  Effects of Annealing Solvents on the Morphology of Block Copolymer-Based Supramolecular Thin Films , 2012 .

[160]  Chinedum O. Osuji Alignment of Self-Assembled Structures in Block Copolymer Films by Solvent Vapor Permeation , 2010 .

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

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

[163]  Bao-Tsan Ko,et al.  Solvent-induced microdomain orientation in polystyrene-b-poly(l-lactide) diblock copolymer thin films for nanopatterning , 2005 .

[164]  Matthew Libera,et al.  Morphological Development in Solvent-Cast Polystyrene−Polybutadiene−Polystyrene (SBS) Triblock Copolymer Thin Films , 1998 .

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

[166]  K. W. Gotrik,et al.  Inverse Design of Topographical Templates for Directed Self-Assembly of Block Copolymers. , 2013, ACS macro letters.

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

[168]  Alexander Hexemer,et al.  Edge effects on the order and freezing of a 2D array of block copolymer spheres. , 2003, Physical review letters.

[169]  Bong Hoon Kim,et al.  Ultralarge-area block copolymer lithography enabled by disposable photoresist prepatterning. , 2010, ACS nano.

[170]  E. W. Edwards,et al.  Directed assembly of cylinder-forming block copolymer films and thermochemically induced cylinder to sphere transition: a hierarchical route to linear arrays of nanodots. , 2005, Nano letters.

[171]  Edward L Cussler,et al.  Core-shell gyroid morphology in a poly(isoprene-block-styrene-block- dimethylsiloxane) triblock copolymer , 1999 .

[172]  Edward L Cussler,et al.  Cylinder Orientation Mechanism in Block Copolymer Thin Films Upon Solvent Evaporation , 2010 .

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

[174]  Yoshinori Funaki,et al.  Nanoprocessing Based on Bicontinuous Microdomains of Block Copolymers: Nanochannels Coated with Metals , 1997 .

[175]  Ulrich Wiesner,et al.  Threshold strain value for perpendicular orientation in dynamically sheared diblock copolymers , 1997 .

[176]  Chinedum O. Osuji,et al.  Magnetic field alignment of block copolymers and polymer nanocomposites: Scalable microstructure control in functional soft materials , 2012 .

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

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

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

[180]  Christopher J. Ellison,et al.  Polarity-Switching Top Coats Enable Orientation of Sub–10-nm Block Copolymer Domains , 2012, Science.

[181]  A. Vijayaraghavan,et al.  Directed self-assembly of block copolymers for use in bit patterned media fabrication , 2013 .

[182]  Ian W. Hamley,et al.  Interplay between Smectic Ordering and Microphase Separation in a Series of Side-Group Liquid-Crystal Block Copolymers , 2004 .

[183]  Dae-Ho Park,et al.  The fabrication of thin films with nanopores and nanogrooves from block copolymer thin films on the neutral surface of self-assembled monolayers , 2007 .

[184]  Honglai Liu,et al.  A New Approach to Thick Films of a Block Copolymer with Ordered Surface Structures , 2005 .

[185]  C. Stafford,et al.  Nanoscopic Templates from Oriented Block Copolymer Films , 2000 .

[186]  Alexander Böker,et al.  Electric field alignment of a block copolymer nanopattern: direct observation of the microscopic mechanism. , 2009, ACS nano.

[187]  Juan Peng,et al.  Development of Nanodomain and Fractal Morphologies in Solvent Annealed Block Copolymer Thin Films , 2007 .

[188]  Ramanan Krishnamoorti,et al.  Dynamics of Shear Alignment in a Lamellar Diblock Copolymer: Interplay of Frequency, Strain Amplitude, and Temperature , 1996 .

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

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

[191]  Rui D M Travasso,et al.  Exploiting photoinduced reactions in polymer blends to create hierarchically ordered, defect-free materials. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[192]  Craig J. Hawker,et al.  Efficient Surface Neutralization and Enhanced Substrate Adhesion through Ketene Mediated Crosslinking and Functionalization , 2013 .

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

[194]  You Wang,et al.  Two-Dimensional Ordering in Block Copolymer Monolayer Thin Films upon Selective Solvent Annealing , 2008 .

[195]  B. Cuenya Synthesis and catalytic properties of metal nanoparticles: Size, shape, support, composition, and oxidation state effects , 2010 .

[196]  Sohrab Ismail-Beigi,et al.  Directed Self‐Assembly of Hybrid Oxide/Polymer Core/Shell Nanowires with Transport Optimized Morphology for Photovoltaics , 2012, Advanced materials.

[197]  Kristin Schmidt,et al.  Electric field induced selective disordering in lamellar block copolymers. , 2013, ACS nano.

[198]  E. Han,et al.  Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains , 2008 .

[199]  Todd Emrick,et al.  Self-directed self-assembly of nanoparticle/copolymer mixtures , 2005, Nature.

[200]  Shinichi Sakurai,et al.  Progress in control of microdomain orientation in block copolymers – Efficiencies of various external fields , 2008 .

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

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

[203]  Kenji Fukunaga,et al.  Symmetric diblock copolymer thin films on rough substrates. Kinetics and structure formation in pure block copolymer thin films , 2005 .

[204]  Bing Xu,et al.  Self-assembly of liquid crystal block copolymer PEG-b-smectic polymer in pure state and in dilute aqueous solution. , 2009, Faraday discussions.

[205]  Thomas P. Russell,et al.  Highly Ordered Nanoporous Thin Films from Cleavable Polystyrene‐block‐poly(ethylene oxide) , 2007 .

[206]  Eun Hye Kim,et al.  Cylindrical Microdomain Orientation of PS-b-PMMA on the Balanced Interfacial Interactions: Composition Effect of Block Copolymers , 2009 .

[207]  A. Mayes,et al.  Block copolymer thin films : Physics and applications , 2001 .

[208]  Thomas P. Russell,et al.  Nanoporous Membranes with Ultrahigh Selectivity and Flux for the Filtration of Viruses , 2006 .

[209]  Yoav Tsori,et al.  Colloquium: Phase transitions in polymers and liquids in electric fields , 2009, 0912.1736.

[210]  Kristin Schmidt,et al.  Influence of initial order on the microscopic mechanism of electric field induced alignment of block copolymer microdomains. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[211]  Edwin L. Thomas,et al.  Large area orientation of block copolymer microdomains in thin films via directional crystallization of a solvent , 2001 .

[212]  Guoping Mao,et al.  Transverse cylindrical microdomain orientation in an LC diblock copolymer under oscillatory shear , 1999 .

[213]  Padma Gopalan,et al.  Continuous equilibrated growth of ordered block copolymer thin films by electrospray deposition. , 2013, ACS nano.

[214]  D. Herr Directed block copolymer self-assembly for nanoelectronics fabrication , 2011 .

[215]  Yu Xuan,et al.  Morphology Development of Ultrathin Symmetric Diblock Copolymer Film via Solvent Vapor Treatment , 2004 .

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

[217]  Seth B Darling,et al.  A route to nanoscopic materials via sequential infiltration synthesis on block copolymer templates. , 2011, ACS nano.

[218]  Craig J. Hawker,et al.  Facile Routes to Patterned Surface Neutralization Layers for Block Copolymer Lithography , 2007 .

[219]  B. Sohn,et al.  Perpendicular lamellae induced at the interface of neutral self-assembled monolayers in thin diblock copolymer films , 2002 .

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

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

[222]  Hyo Seon Suh,et al.  Thickness Dependence of Neutral Parameter Windows for Perpendicularly Oriented Block Copolymer Thin Films , 2010 .

[223]  Feng Zhang,et al.  Pattern Registration Between Spherical Block‐Copolymer Domains and Topographical Templates , 2006 .

[224]  Kenji Fukunaga,et al.  Large-Scale Alignment of ABC Block Copolymer Microdomains via Solvent Vapor Treatment , 2000 .

[225]  Yu Xuan,et al.  Morphologies in solvent-annealed thin films of symmetric diblock copolymer. , 2006, The Journal of chemical physics.

[226]  Xiaobo Hu,et al.  In situ fabrication of ordered nanoring arrays via the reconstruction of patterned block copolymer thin films. , 2010, Chemical communications.

[227]  Clemens Liedel,et al.  Block Copolymer Nanocomposites in Electric Fields: Kinetics of Alignment. , 2013, ACS macro letters.

[228]  Soo-Jin Park,et al.  Phase transition behavior in thin films of block copolymers by use of immiscible solvent vapors , 2011 .

[229]  Detlef-M. Smilgies,et al.  Tuning Molecular Relaxation for Vertical Orientation in Cylindrical Block Copolymer Films via Sharp Dynamic Zone Annealing , 2012 .

[230]  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.

[231]  A. Knoll,et al.  Effect of confinement on the mesoscale and macroscopic swelling of thin block copolymer films. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[232]  Chi-Chun Liu,et al.  Orientation of Block Copolymer Resists on Interlayer Dielectrics with Tunable Surface Energy , 2010 .

[233]  Zhijun Hu,et al.  Lateral nanopatterns in thin diblock copolymer films induced by selective solvents. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[234]  D. Weller,et al.  Directed Block Copolymer Assembly versus Electron Beam Lithography for Bit-Patterned Media with Areal Density of 1 Terabit/inch(2) and Beyond. , 2009, ACS nano.

[235]  Chinedum O. Osuji,et al.  Facile Alignment of Amorphous Poly(ethylene oxide) Microdomains in a Liquid Crystalline Block Copolymer Using Magnetic Fields , 2010 .

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