Dual Mode Patterning of Fluorine-Containing Block Copolymers through Combined Top-down and Bottom-up Lithography

Integrated nanopatterns were successfully obtained from a combination of high lateral ordering of newly designed self-assembling fluorine-containing block copolymers and degradation of the fluorine-containing polymer nanodomains in e-beam irradiated areas. The fluorine-containing block copolymers of poly(styrene-block-2,2,2-trifluoroethyl methacrylate) (PS-b-PTFEMA) and poly[styrene-block-(methyl methacrylate-co-2,2,2-trifluoroethyl methacrylate)] (PS-b-(PMMA-co-PTFEMA)), which are capable of both top-down and bottom-up lithography, were developed. The reported block copolymers were synthesized by either anionic polymerization or atom transfer radical polymerization (ATRP). Characterization of bulk and thin films were carried out using differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS), and these studies revealed the formation of highly ordered self-assembled structures. Lateral ordering of arrays of PS dots was observed in the thin fil...

[1]  William F. Edmonds,et al.  Synthesis and self‐assembly of highly incompatible polybutadiene–poly(hexafluoropropylene oxide) diblock copolymers , 2005 .

[2]  Jongseung Yoon,et al.  Enabling nanotechnology with self assembled block copolymer patterns , 2003 .

[3]  T. Lodge,et al.  Mapping Large Regions of Diblock Copolymer Phase Space by Selective Chemical Modification , 2004 .

[4]  C. Ober,et al.  Selective area control of self-assembled pattern architecture using a lithographically patternable block copolymer. , 2009, ACS nano.

[5]  Joachim P. Spatz,et al.  Micro‐Nanostructured Interfaces Fabricated by the Use of Inorganic Block Copolymer Micellar Monolayers as Negative Resist for Electron‐Beam Lithography , 2003 .

[6]  Timothy P. Lodge,et al.  Synthesis, Characterization, and Interaction Strengths of Difluorocarbene-Modified Polystyrene−Polyisoprene Block Copolymers , 2000 .

[7]  F. Bates,et al.  Conformationally asymmetric block copolymers , 1997 .

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

[9]  S. Kutsumizu,et al.  Dielectric relaxations of poly(fluoroalkyl methacrylates) and poly(fluoroalkyl .alpha.-fluoroacrylates) , 1992 .

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

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

[12]  A. Plettl,et al.  A Combined Top–Down/Bottom–Up Approach to the Microscopic Localization of Metallic Nanodots , 2002 .

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

[14]  T. Lodge,et al.  Synthesis and self‐assembly of fluorinated block copolymers , 2002 .

[15]  Soojin Park,et al.  A simple top-down/bottom-up approach to sectored, ordered arrays of nanoscopic elements using block copolymers. , 2009, Small.

[16]  K. Sugiyama,et al.  Anionic Polymerizations of Perfluoroalkyl Methacrylates and Synthesis of Well-Defined ABC Triblock Copolymers of Methacrylates Containing Hydrophilic, Hydrophobic, and Perfluoroalkyl Groups , 1999 .

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

[18]  T. Lodge,et al.  Effect of Selective Perfluoroalkylation on the Segregation Strength of Polystyrene−1,2-Polybutadiene Block Copolymers , 2002 .

[19]  Ting Xu,et al.  The influence of molecular weight on nanoporous polymer films , 2001 .

[20]  M. Hillmyer,et al.  Templating Nanoporous Polymers with Ordered Block Copolymers , 2008 .

[21]  J. Chien,et al.  Radiolysis of resist polymers. III. Copolymers of methyl-α-chloroacrylate and trihaloethylmethacrylates , 1984 .

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

[23]  R. Jerome,et al.  Anionic polymerization of (meth)acrylic monomers. IV. Effect of lithium salts as ligands on the "living" polymerization of methyl methacrylate using monofunctional initiators , 1990 .

[24]  Craig J Hawker,et al.  Defect-free nanoporous thin films from ABC triblock copolymers. , 2006, Journal of the American Chemical Society.

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

[26]  Ying Zhang,et al.  Polymer self assembly in semiconductor microelectronics , 2006, 2006 International Electron Devices Meeting.

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

[28]  Jae‐Suk Lee,et al.  Polymerization of monomers containing functional silyl groups. 5. Synthesis of new porous membranes with functional groups , 1988 .

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

[30]  B. Boutevin,et al.  Control of free-radical polymerization of 2,2,2-trifluoroethyl methacrylate (TEMA) by a substituted fluorinated tetraphenylethane-type INITER , 2001 .

[31]  T. Russell,et al.  Nanofabrication of integrated magnetoelectronic devices using patterned self-assembled copolymer templates , 2002 .

[32]  J. Helbert,et al.  Synthesis and Radiation Degradation of Vinyl Polymers with Fluorine: Search for Improved Lithographic Resists, , 1980 .

[33]  Ricardo Ruiz,et al.  Control of self-assembly of lithographically patternable block copolymer films. , 2008, ACS nano.