Multilayer block copolymer meshes by orthogonal self-assembly

Continued scaling-down of lithographic-pattern feature sizes has brought templated self-assembly of block copolymers (BCPs) into the forefront of nanofabrication research. Technologies now exist that facilitate significant control over otherwise unorganized assembly of BCP microdomains to form both long-range and locally complex monolayer patterns. In contrast, the extension of this control into multilayers or 3D structures of BCP microdomains remains limited, despite the possible technological applications in next-generation devices. Here, we develop and analyse an orthogonal self-assembly method in which multiple layers of distinct-molecular-weight BCPs naturally produce nanomesh structures of cylindrical microdomains without requiring layer-by-layer alignment or high-resolution lithographic templating. The mechanisms for orthogonal self-assembly are investigated with both experiment and simulation, and we determine that the control over height and chemical preference of templates are critical process parameters. The method is employed to produce nanomeshes with the shapes of circles and Y-intersections, and is extended to produce three layers of orthogonally oriented cylinders.

[1]  Joy Y. Cheng,et al.  Three‐Dimensional Nanofabrication by Block Copolymer Self‐Assembly , 2014, Advanced materials.

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

[3]  K. W. Gotrik,et al.  Rectangular Symmetry Morphologies in a Topographically Templated Block Copolymer , 2012, Advanced materials.

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

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

[6]  H. Yabu,et al.  Three-dimensional observation of confined phase-separated structures in block copolymer nanoparticles , 2012 .

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

[8]  K. Berggren,et al.  Assembly of sub-10-nm block copolymer patterns with mixed morphology and period using electron irradiation and solvent annealing. , 2011, Nano letters.

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

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

[11]  Glenn H. Fredrickson,et al.  Parallel algorithm for numerical self-consistent field theory simulations of block copolymer structure , 2003 .

[12]  Jae Won Jeong,et al.  High-resolution nanotransfer printing applicable to diverse surfaces via interface-targeted adhesion switching , 2014, Nature Communications.

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

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

[15]  George C Schatz,et al.  Nanoscale Form Dictates Mesoscale Function in Plasmonic DNA-Nanoparticle Superlattices* , 2020, Spherical Nucleic Acids.

[16]  Y. Jung,et al.  Fabrication of diverse metallic nanowire arrays based on block copolymer self-assembly. , 2010, Nano letters.

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

[18]  M. Matsen Thin films of block copolymer , 1997 .

[19]  Caroline A. Ross,et al.  Hierarchical Nanostructures by Sequential Self‐Assembly of Styrene‐Dimethylsiloxane Block Copolymers of Different Periods , 2011, Advanced materials.

[20]  Liquan Wang,et al.  Harnessing Anisotropic Nanoposts to Enhance Long-Range Orientation Order of Directed Self-Assembly Nanostructures via Large Cell Simulations. , 2014, ACS macro letters.

[21]  A. Mulchandani,et al.  Graphene nanomesh as highly sensitive chemiresistor gas sensor. , 2012, Analytical chemistry.

[22]  Lili Jiang,et al.  Design of advanced porous graphene materials: from graphene nanomesh to 3D architectures. , 2014, Nanoscale.

[23]  Alfredo Alexander-Katz,et al.  Sacrificial-post templating method for block copolymer self-assembly. , 2014, Small.

[24]  X. Duan,et al.  Graphene nanomesh , 2010, Nature nanotechnology.

[25]  D. A. Vega,et al.  Smectic block copolymer thin films on corrugated substrates. , 2015, Soft matter.

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

[27]  Karl K. Berggren,et al.  Using high-contrast salty development of hydrogen silsesquioxane for sub-10‐nm half-pitch lithography , 2007 .

[28]  Charles T. Rettner,et al.  Enabling complex nanoscale pattern customization using directed self-assembly , 2014, Nature Communications.

[29]  Eric W. Cochran,et al.  Effect of Chain Architecture and Surface Energies on the Ordering Behavior of Lamellar and Cylinder Forming Block Copolymers , 2006 .

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

[31]  Bong Hoon Kim,et al.  Large-area, highly oriented lamellar block copolymer nanopatterning directed by graphoepitaxially assembled cylinder nanopatterns , 2012 .

[32]  H. Wong,et al.  Flexible Control of Block Copolymer Directed Self‐Assembly using Small, Topographical Templates: Potential Lithography Solution for Integrated Circuit Contact Hole Patterning , 2012, Advanced materials.

[33]  Charles T. Black,et al.  Arbitrary lattice symmetries via block copolymer nanomeshes , 2015, Nature Communications.

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

[35]  C. T. Black,et al.  Nanometer-scale pattern registration and alignment by directed diblock copolymer self-assembly , 2004, IEEE Transactions on Nanotechnology.

[36]  Jillian M. Buriak,et al.  Automated Defect and Correlation Length Analysis of Block Copolymer Thin Film Nanopatterns , 2015, PloS one.

[37]  C. Rettner,et al.  Directed Self-Assembly of Lamellar Microdomains of Block Copolymers Using Topographic Guiding Patterns , 2009 .

[38]  Jae Won Jeong,et al.  Nanotransfer printing with sub-10 nm resolution realized using directed self-assembly. , 2012, Advanced materials.

[39]  Joel K. W. Yang,et al.  Sub-10-nm half-pitch electron-beam lithography by using poly(methyl methacrylate) as a negative resist , 2010 .

[40]  Héctor D. Ceniceros,et al.  Block Copolymer Self Assembly during Rapid Solvent Evaporation: Insights into Cylinder Growth and Stability. , 2014, ACS macro letters.

[41]  C. Ross,et al.  A Top Coat with Solvent Annealing Enables Perpendicular Orientation of Sub‐10 nm Microdomains in Si‐Containing Block Copolymer Thin Films , 2014 .

[42]  Yiying Wu,et al.  Composite mesostructures by nano-confinement , 2004, Nature materials.

[43]  Ricardo Ruiz,et al.  Induced Orientational Order in Symmetric Diblock Copolymer Thin Films , 2007 .

[44]  Won Bo Lee,et al.  Three-dimensional multilayered nanostructures with controlled orientation of microdomains from cross-linkable block copolymers. , 2011, ACS nano.

[45]  C. Rettner,et al.  Bending of Lamellar Microdomains of Block Copolymers on Nonselective Surfaces , 2010 .

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

[47]  Xiaodan Gu,et al.  High Aspect Ratio Sub‐15 nm Silicon Trenches From Block Copolymer Templates , 2012, Advanced materials.

[48]  Sungmin Park,et al.  Combined epitaxial self-assembly of block copolymer lamellae on a hexagonal pre-pattern within microgrooves. , 2015, Soft matter.

[49]  A. Saxena,et al.  Efficient computation of the structural phase behavior of block copolymers. , 2002, Physical review. E, Statistical, nonlinear, and soft matter physics.

[50]  Ilarion V. Melnikov,et al.  Reducing substrate pinning of block copolymer microdomains with a buffer layer of polymer brushes , 2000 .

[51]  Joy Y. Cheng,et al.  Patterning sub-10 nm line patterns from a block copolymer hybrid , 2008, Nanotechnology.

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

[53]  E. Dobisz,et al.  Three-dimensional mesoporous structures fabricated by independent stacking of self-assembled films on suspended membranes , 2011, Nanotechnology.

[54]  Kurt Binder,et al.  Symmetric diblock copolymers in thin films. I. Phase stability in self-consistent field calculations and Monte Carlo simulations , 1999 .

[55]  H. Yokoyama,et al.  Aligning Single‐Layer Cylinders of Block Copolymer Nanodomains using Soft Molding , 2005, Advanced materials.

[56]  Diblock copolymer thin films: Parallel and perpendicular lamellar phases in the weak segregation limit , 2001, cond-mat/0105213.

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

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

[59]  So Youn Kim,et al.  Large-area nanosquare arrays from shear-aligned block copolymer thin films. , 2014, Nano letters.

[60]  T. Russell,et al.  Cylindrically Confined Diblock Copolymers , 2009 .

[61]  K. W. Gotrik,et al.  3D TEM Tomography of Templated Bilayer Films of Block Copolymers , 2014 .

[62]  M. Hillmyer,et al.  Non-lift-off block copolymer lithography of 25 nm magnetic nanodot arrays. , 2011, ACS applied materials & interfaces.

[63]  Marcus Müller,et al.  Fabrication of complex three-dimensional nanostructures from self-assembling block copolymer materials on two-dimensional chemically patterned templates with mismatched symmetry. , 2006, Physical review letters.

[64]  Bong Hoon Kim,et al.  Flexible and Transferrable Self‐Assembled Nanopatterning on Chemically Modified Graphene , 2013, Advanced materials.

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

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

[67]  S. Kim,et al.  Atomic Layer Deposition Assisted Pattern Multiplication of Block Copolymer Lithography for 5 nm Scale Nanopatterning , 2014 .

[68]  Brian C. Berry,et al.  Observation of surface corrugation-induced alignment of lamellar microdomains in PS-b-PMMA thin films , 2009 .

[69]  D. A. Vega,et al.  Mixed-morphology and mixed-orientation block copolymer bilayers , 2014 .