Block Copolymer Lithography: Merging “Bottom-Up” with “Top-Down” Processes

As the size scale of device features becomes ever smaller, conventional lithographic processes become increasingly more difficult and expensive, especially at a minimum feature size of less than 45 nm. Consequently, to achieve higher-density circuits, storage devices, or displays, it is evident that alternative routes need to be developed to circumvent both cost and manufacturing issues. An ideal process would be compatible with existing technological processes and manufacturing techniques; these strategies, together with novel materials, could allow significant advances to be made in meeting both short-term and long-term demands for higher-density, faster devices. The self-assembly of block copolymers (BCPs), two polymer chains covalently linked together at one end, provides a robust solution to these challenges. As thin films, immiscible BCPs self-assemble into a range of highly ordered morphologies where the size scale of the features is only limited by the size of the polymer chains and are, therefore, nanoscopic. While self-assembly alone is sufficient for a number of applications in fabricating advanced microelectronics, directed, self-orienting, self-assembly processes are also required to produce complex devices with the required density and addressability of elements to meet future demands. Both strategies require the design and synthesis of polymers that have well-defined characteristics such that the necessary fine control over the morphology, interfacial properties, and simplicity of processes can be realized. By combining tailored self-assembly processes (a “bottom-up” approach) with microfabrication processes (a “top-down” approach), the ever-present thirst of the consumer for faster, better, and cheaper devices can be met in very simple, yet robust, ways. The integration of novel chemistries with the manipulation of self-assembly will be treated in this article.

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

[2]  D. Haddleton,et al.  Effect of DMSO used as solvent in copper mediated living radical polymerization , 2004 .

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

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

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

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

[7]  D. A. Vega,et al.  Dynamics of pattern coarsening in a two-dimensional smectic system. , 2002, Physical review. E, Statistical, nonlinear, and soft matter physics.

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

[9]  Sol M Gruner,et al.  The plumber's nightmare: a new morphology in block copolymer-ceramic nanocomposites and mesoporous aluminosilicates. , 2003, Journal of the American Chemical Society.

[10]  M. Monteiro Design strategies for controlling the molecular weight and rate using reversible addition–fragmentation chain transfer mediated living radical polymerization , 2005 .

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

[12]  Turner,et al.  Equilibrium properties of a diblock copolymer lamellar phase confined between flat plates. , 1992, Physical review letters.

[13]  E. Kramer,et al.  Topographic templating of islands and holes in highly Asymmetric block copolymer films , 2003 .

[14]  E. Harth,et al.  Production of crosslinked, hollow nanoparticles by surface‐initiated living free‐radical polymerization , 2002 .

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

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

[17]  U. Wiesner,et al.  The synthesis of spherical mesoporous molecular sieves MCM-48 with heteroatoms incorporated into the silica framework , 1999 .

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

[19]  Ulrich B Wiesner,et al.  Mesoporous aluminosilicate materials with superparamagnetic gamma-Fe2O3 particles embedded in the walls. , 2003, Angewandte Chemie.

[20]  G. Whitesides,et al.  Monolayer Films Prepared by the Spontaneous Self-Assembly of Symmetrical and Unsymmetrical Dialkyl Sulfides from Solution onto Gold Substrates: Structure, Properties, and Reactivity of Constituent Functional Groups , 1988 .

[21]  C. Solans,et al.  Meso/Macroporous Inorganic Oxide Monoliths from Polymer Foams , 2003 .

[22]  Andrew G. Glen,et al.  APPL , 2001 .

[23]  C. Ober,et al.  Spatially Controlled Fabrication of Nanoporous Block Copolymers , 2004 .

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

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

[26]  Archita Sengupta,et al.  Mesoporous Silicates Prepared Using Preorganized Templates in Supercritical Fluids , 2004, Science.

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

[28]  Craig J. Hawker,et al.  The Convergence of Synthetic Organic and Polymer Chemistries , 2005, Science.

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

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

[31]  S. Mochrie,et al.  Propagation of nanopatterned substrate templated ordering of block copolymers in thick films , 2001 .

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

[33]  D. A. Vega,et al.  Ordering mechanisms in two-dimensional sphere-forming block copolymers. , 2005, Physical review. E, Statistical, nonlinear, and soft matter physics.

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

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

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

[37]  B. Bauer,et al.  Characterization of Ordered Mesoporous Silica Films Using Small-Angle Neutron Scattering and X Ray Porosimetry , 2005 .

[38]  Dong Ha Kim,et al.  High-temperature resistant, ordered gold nanoparticle arrays , 2006 .

[39]  George M. Whitesides,et al.  Comparison of the Structures and Wetting Properties of Self-Assembled Monolayers of n- Alkanethiols on the Coinage Metal Surfaces, Cu, Ag, Au' , 1991 .

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

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

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

[43]  K.H.J. Buschow,et al.  Encyclopedia of Materials: Science and Technology , 2004 .

[44]  Koji Asakawa,et al.  Nanopatterning with Microdomains of Block Copolymers using Reactive-Ion Etching Selectivity , 2002 .

[45]  T. J. McCarthy,et al.  Self-Assembly Is Not the Only Reaction Possible between Alkyltrichlorosilanes and Surfaces: Monomolecular and Oligomeric Covalently Attached Layers of Dichloro- and Trichloroalkylsilanes on Silicon , 2000 .

[46]  I. Manners,et al.  Spontaneous Vertical Ordering and Pyrolytic Formation of Nanoscopic Ceramic Patterns from Poly(styrene‐b‐ferrocenylsilane) , 2003 .

[47]  K. Matyjaszewski,et al.  Effect of variation of [PMDETA]0/[Cu(I)Br]0 ratio on atom transfer radical polymerization of n‐butyl acrylate , 2004 .

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

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

[50]  B. Jacobson,et al.  Fibroblast adhesion to micro- and nano-heterogeneous topography using diblock copolymers and homopolymers. , 2004, Journal of biomedical materials research. Part A.

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

[52]  Guojun Liu NANOSTRUCTURES OF FUNCTIONAL BLOCK COPOLYMERS , 1998 .

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

[54]  Deng,et al.  Hierarchically ordered oxides , 1998, Science.

[55]  U. Krappe,et al.  Evolution of the “knitting pattern” morphology in ABC triblock copolymers , 1996 .

[56]  K. Guarini,et al.  Growth of Silicon Oxide in Thin Film Block Copolymer Scaffolds , 2004 .

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

[58]  Makinen,et al.  Switching supramolecular polymeric materials with multiple length scales , 1998, Science.

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

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

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

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

[63]  O. Ikkala,et al.  Functional Materials Based on Self-Assembly of Polymeric Supramolecules , 2002, Science.

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

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

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

[67]  C. Ober,et al.  Additive‐Driven Phase‐Selective Chemistry in Block Copolymer Thin Films: The Convergence of Top–Down and Bottom–Up Approaches , 2004 .

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

[69]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[70]  G. Sauer,et al.  Microdomain Morphology of Thin ABC Triblock Copolymer Films , 1999 .

[71]  Stucky,et al.  Mirrorless lasing from mesostructured waveguides patterned by soft lithography , 2000, Science.

[72]  K. Matyjaszewski,et al.  Atom transfer radical polymerization. , 2001, Chemical reviews.

[73]  Guojun Liu,et al.  Hairy, Semi-shaved, and Fully Shaved Hollow Nanospheres from Polyisoprene-block-poly(2-cinnamoylethyl methacrylate) , 1998 .

[74]  K. Guarini,et al.  Integration of self-assembled diblock copolymers for semiconductor capacitor fabrication , 2001 .

[75]  M. Torkkeli,et al.  Amphiphiles coordinated to block copolymers as a template for mesoporous materials , 2003 .

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

[77]  Charles T. Black,et al.  Nanoscale patterning using self-assembled polymers for semiconductor applications , 2001 .

[78]  S. Ludwigs,et al.  Self-assembly of functional nanostructures from ABC triblock copolymers , 2003, Nature materials.

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

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

[81]  J. Sagiv,et al.  A NEW APPROACH TO CONSTRUCTION OF ARTIFICIAL MONOLAYER ASSEMBLIES , 1983 .

[82]  Ho-Cheol Kim,et al.  Ordering in thin films of asymmetric diblock copolymers , 2001 .

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

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

[85]  Guojun Liu,et al.  WATER-SOLUBLE HOLLOW NANOSPHERES AS POTENTIAL DRUG CARRIERS , 1998 .

[86]  H. Fan,et al.  Evaporation-induced self-assembly to functional nanostructures , 2004 .

[87]  E. Kramer,et al.  Thin diblock copolymer films on chemically heterogeneous surfaces , 1997 .

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

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

[90]  Jin Kon Kim,et al.  An optical waveguide study on the nanopore formation in block copolymer/homopolymer thin films by selective solvent swelling. , 2006, The journal of physical chemistry. B.

[91]  Miss A.O. Penney (b) , 1974, The New Yale Book of Quotations.

[92]  E. Harth,et al.  New polymer synthesis by nitroxide mediated living radical polymerizations. , 2001, Chemical reviews.

[93]  M. Hillmyer,et al.  Nanoporous Polystyrene by Chemical Etching of Poly(ethylene oxide) from Ordered Block Copolymers , 2005 .

[94]  R. Stadler,et al.  Polymer alloys based on poly(2,6-dimethyl-1,4-phenylene ether) and poly(styrene-co-acrylonitrile) using poly(styrene-b-(ethylene-co-butylene)-b-methyl methacrylate) triblock copolymers as compatibilizers , 1993 .

[95]  David A. Huse,et al.  Pattern coarsening in a 2D hexagonal system , 2004 .

[96]  K. Guarini,et al.  SCATTERING STUDY ON THE SELECTIVE SOLVENT SWELLING INDUCED SURFACE RECONSTRUCTION , 2004 .

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

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

[99]  M. Hillmyer,et al.  Nanoporous Polystyrene Containing Hydrophilic Pores from an ABC Triblock Copolymer Precursor , 2005 .

[100]  J. Spatz,et al.  Noble metal loaded block ionomers: micelle organization, adsorption of free chains and formation of thin films , 1995 .

[101]  S. Gruner,et al.  Nanostructure and Shape Control in Polymer-Ceramic Hybrids from Poly(ethylene oxide)-block-Poly(hexyl methacrylate) and Aluminosilicates Derived from Them , 2004 .

[102]  Didier Benoit,et al.  Development of a Universal Alkoxyamine for “Living” Free Radical Polymerizations , 1999 .

[103]  Ho-Cheol Kim,et al.  Covalent stabilization of nanostructures: Robust block copolymer templates from novel thermoreactive systems , 2005 .

[104]  C. Hawker,et al.  A Thermal and Manufacturable Approach to Stabilized Diblock Copolymer Templates , 2005 .

[105]  Ian W. Hamley,et al.  The physics of block copolymers , 1998 .

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