Macroscopically ordered hexagonal arrays by directed self-assembly of block copolymers with minimal topographic patterns.

A simple and robust method has been developed for the generation of macroscopically ordered hexagonal arrays from the directed self-assembly (DSA) of cylinder-forming block copolymers (BCPs) based on minimal trench patterns with solvent vapor annealing. The use of minimal trench patterns allows us to probe the guided hexagonal arrays of cylindrical microdomains using grazing incidence small angle X-ray scattering (GISAXS), where the sample stage is rotated on the basis of the six-fold symmetry of a hexagonal system. It is found that the (10) planes of hexagonal arrays of cylindrical microdomains are oriented parallel to the underlying trench direction over macroscopic length scales (∼1 × 1 cm2). However, there are misorientations of the hexagonal arrays with short-range ordering. GISAXS patterns show that the hexagonal arrays on the minimal trench pattern are distorted, deviating from a perfect hexagonal lattice. This distortion has been attributed to the absence of topographic constraints in the unconfined direction on the 1-D minimal trench pattern. Also, the frustration of BCP microdomains, arising from the incommensurability between the trench pitch and natural period of the BCP at the base of the trench, influences the distortion of the hexagonal arrays.

[1]  Aaas News,et al.  Book Reviews , 1893, Buffalo Medical and Surgical Journal.

[2]  T. Russell,et al.  Directed Self-Assembly of Block Copolymer Thin Films Using Minimal Topographic Patterns. , 2016, ACS nano.

[3]  P. Nealey,et al.  Directed self-assembly of block copolymers on chemical patterns: A platform for nanofabrication , 2016 .

[4]  Karl K. Berggren,et al.  Multilayer block copolymer meshes by orthogonal self-assembly , 2016, Nature Communications.

[5]  Christopher J. Ellison,et al.  Directed self assembly of block copolymers using chemical patterns with sidewall guiding lines, backfilled with random copolymer brushes. , 2015, Soft matter.

[6]  G. Hadziioannou,et al.  Laterally Ordered Sub-10 nm Features Obtained From Directed Self-Assembly of Si-Containing Block Copolymer Thin Films. , 2015, Small.

[7]  Rong Wang,et al.  Hierarchical nanostructures of diblock copolymer thin films directed by a saw-toothed substrate. , 2015, Soft matter.

[8]  Kim Y. Lee,et al.  Directed Self‐Assembly of Poly(2‐vinylpyridine)‐b‐polystyrene‐b‐poly(2‐vinylpyridine) Triblock Copolymer with Sub‐15 nm Spacing Line Patterns Using a Nanoimprinted Photoresist Template , 2015, Advanced materials.

[9]  Pawel W. Majewski,et al.  Latent Alignment in Pathway-Dependent Ordering of Block Copolymer Thin Films. , 2015, Nano letters.

[10]  Lei Wan,et al.  Double-Patterned Sidewall Directed Self-Assembly and Pattern Transfer of Sub-10 nm PTMSS-b-PMOST. , 2015, ACS applied materials & interfaces.

[11]  Shuaigang Xiao,et al.  Servo-integrated patterned media by hybrid directed self-assembly. , 2014, ACS nano.

[12]  Christophe Navarro,et al.  Probing Self-Assembly of Cylindrical Morphology Block Copolymer Using in Situ and ex Situ Grazing Incidence Small-Angle X-ray Scattering: The Attractive Case of Graphoepitaxy , 2014 .

[13]  Sungmin Park,et al.  Substrate-Independent Lamellar Orientation in High-Molecular-Weight Polystyrene-b-poly(methyl methacrylate) Films: Neutral Solvent Vapor and Thermal Annealing Effect , 2014 .

[14]  Hanqiong Hu,et al.  Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter. , 2014, Soft matter.

[15]  Chi-Chun Liu,et al.  Two-dimensional pattern formation using graphoepitaxy of PS-b-PMMA block copolymers for advanced FinFET device and circuit fabrication. , 2014, ACS nano.

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

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

[18]  M. Shaw,et al.  Fabrication of highly ordered sub-20 nm silicon nanopillars by block copolymer lithography combined with resist design , 2013 .

[19]  K. Carter,et al.  Patterned polymer films via reactive silane infusion-induced wrinkling. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[20]  Francesc Pérez-Murano,et al.  Grazing-incidence small-angle X-ray scattering of soft and hard nanofabricated gratings , 2012 .

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

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

[23]  Sarah Kim,et al.  Graphoepitaxy of block-copolymer self-assembly integrated with single-step ZnO nanoimprinting. , 2012, Small.

[24]  E. Kramer,et al.  Effect of film thickness and domain spacing on defect densities in directed self-assembly of cylindrical morphology block copolymers. , 2012, ACS nano.

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

[26]  W. Marsden.  I and J , 2012 .

[27]  X. Gu,et al.  Circular nanopatterns over large areas from the self-assembly of block copolymers guided by shallow trenches. , 2011, ACS nano.

[28]  T. Albrecht,et al.  Rectangular patterns using block copolymer directed assembly for high bit aspect ratio patterned media. , 2011, ACS nano.

[29]  Xavier Andre,et al.  Reversible Morphology Control in Block Copolymer Films via Solvent Vapor Processing: An In Situ GISAXS study. , 2010, Macromolecules.

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

[31]  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.

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

[33]  C. A. Ross,et al.  Patterned Magnetic Media Made by Self-Assembled Block-Copolymer Lithography , 2008 .

[34]  C. Rettner,et al.  Fabrication of 20 nm half-pitch gratings by corrugation-directed self-assembly , 2008, Nanotechnology.

[35]  Jinan Chai,et al.  Using cylindrical domains of block copolymers to self-assemble and align metallic nanowires. , 2008, ACS nano.

[36]  Minhao Yan,et al.  On the intersection of grating truncation rods with the Ewald sphere studied by grazing‐incidence small‐angle X‐ray scattering , 2007 .

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

[38]  Won Bo Lee,et al.  Thickness Dependent Ordering in Laterally Confined Monolayers of Spherical-Domain Block Copolymers , 2007 .

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

[40]  E. Kramer,et al.  Single-crystal diffraction from two-dimensional block copolymer arrays. , 2007, Physical review letters.

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

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

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

[44]  Kwang-Woo Kim,et al.  Structural Analysis of Block Copolymer Thin Films with Grazing Incidence Small-Angle X-ray Scattering , 2005 .

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

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

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

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

[49]  S. Darling,et al.  Hierarchical assembly and compliance of aligned nanoscale polymer cylinders in confinement. , 2004, Langmuir : the ACS journal of surfaces and colloids.

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

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

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

[53]  Stefan Luby,et al.  Coplanar and non-coplanar x-ray reflectivity characterization of lateral W/Si multilayer gratings , 2001 .

[54]  A. Mayes,et al.  Observed Substrate Topography-Mediated Lateral Patterning of Diblock Copolymer Films , 1997 .

[55]  R. Stephenson.  A and V , 1962, The British journal of ophthalmology.