Automated Defect and Correlation Length Analysis of Block Copolymer Thin Film Nanopatterns

Line patterns produced by lamellae- and cylinder-forming block copolymer (BCP) thin films are of widespread interest for their potential to enable nanoscale patterning over large areas. In order for such patterning methods to effectively integrate with current technologies, the resulting patterns need to have low defect densities, and be produced in a short timescale. To understand whether a given polymer or annealing method might potentially meet such challenges, it is necessary to examine the evolution of defects. Unfortunately, few tools are readily available to researchers, particularly those engaged in the synthesis and design of new polymeric systems with the potential for patterning, to measure defects in such line patterns. To this end, we present an image analysis tool, which we have developed and made available, to measure the characteristics of such patterns in an automated fashion. Additionally we apply the tool to six cylinder-forming polystyrene-block-poly(2-vinylpyridine) polymers thermally annealed to explore the relationship between the size of each polymer and measured characteristics including line period, line-width, defect density, line-edge roughness (LER), line-width roughness (LWR), and correlation length. Finally, we explore the line-edge roughness, line-width roughness, defect density, and correlation length as a function of the image area sampled to determine each in a more rigorous fashion.

[1]  C. Hawker,et al.  The dramatic effect of architecture on the self-assembly of block copolymers at interfaces. , 2005, Langmuir : the ACS journal of surfaces and colloids.

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

[3]  Jonathan W. Choi,et al.  Rational Design of a Block Copolymer with a High Interaction Parameter , 2014 .

[4]  Kevin G Yager,et al.  Millisecond Ordering of Block Copolymer Films via Photothermal Gradients. , 2015, ACS nano.

[5]  Manfred Engelhardt,et al.  Impact of line edge roughness on the resistivity of nanometer-scale interconnects , 2004 .

[6]  Juan J. de Pablo,et al.  Free Energy of Defects in Ordered Assemblies of Block Copolymer Domains. , 2012, ACS macro letters.

[7]  Sandra J Shefelbine,et al.  BoneJ: Free and extensible bone image analysis in ImageJ. , 2010, Bone.

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

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

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

[11]  R. Magerle,et al.  Visualizing the dynamics of complex spatial networks in structured fluids. , 2007, The Journal of chemical physics.

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

[13]  Nasser Mohieddin Abukhdeir,et al.  Defect kinetics and dynamics of pattern coarsening in a two-dimensional smectic-A system , 2008, 0805.3651.

[14]  H. Kessler,et al.  Stimulation of Cell Adhesion at Nanostructured Teflon Interfaces , 2010, Advanced materials.

[15]  D. Huse,et al.  Mechanisms of ordering in striped patterns. , 2000, Science.

[16]  Mark P. Stoykovich,et al.  Processing Approaches for the Defect Engineering of Lamellar-Forming Block Copolymers in Thin Films , 2013 .

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

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

[19]  Jeffrey N. Murphy,et al.  Density doubling of block copolymer templated features. , 2012, Nano letters.

[20]  Abraham J. Koster,et al.  Virtual nanoscopy: Generation of ultra-large high resolution electron microscopy maps , 2012, The Journal of cell biology.

[21]  S. Darling,et al.  Block Copolymer Nanostructures for Technology , 2010 .

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

[23]  Jeffrey N. Murphy,et al.  Deconvoluting the mechanism of microwave annealing of block copolymer thin films. , 2014, ACS nano.

[24]  H. Jagodzinski Points, lines and walls in liquid crystals, magnetic systems and various ordered media by M. Kléman , 1984 .

[25]  Kevin W Eliceiri,et al.  NIH Image to ImageJ: 25 years of image analysis , 2012, Nature Methods.

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

[27]  Kevin A. Cavicchi,et al.  A generalized method for alignment of block copolymer films: solvent vapor annealing with soft shear. , 2014, Soft matter.

[28]  T. Aida,et al.  Cyclic block copolymers for controlling feature sizes in block copolymer lithography. , 2012, ACS nano.

[29]  Marc A. Hillmyer,et al.  Influence of Polydispersity on the Self-Assembly of Diblock Copolymers , 2005 .

[30]  M. Matsen,et al.  Monte Carlo Phase Diagram for a Polydisperse Diblock Copolymer Melt , 2011 .

[31]  G. Fredrickson,et al.  Defectivity in Laterally Confined Lamella-Forming Diblock Copolymers: Thermodynamic and Kinetic Aspects , 2012 .

[32]  Clifford L. Henderson,et al.  Effects of block copolymer polydispersity and χN on pattern line edge roughness and line width roughness from directed self-assembly of diblock copolymers , 2013, Advanced Lithography.

[33]  Marc A. Hillmyer,et al.  Effects of Polydispersity on the Order-Disorder Transition in Block Copolymer Melts , 2007 .

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

[35]  K. Mecke,et al.  Characterization of the dynamics of block copolymer microdomains with local morphological measures. , 2008, Physical review. E, Statistical, nonlinear, and soft matter physics.

[36]  P. Mistark,et al.  Block-copolymer-based plasmonic nanostructures. , 2009, ACS nano.

[37]  Christopher J. Ellison,et al.  Oligosaccharide/silicon-containing block copolymers with 5 nm features for lithographic applications. , 2012, ACS nano.

[38]  N. Otsu A threshold selection method from gray level histograms , 1979 .

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

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

[41]  B. A. Garetz,et al.  Orientation correlations in lamellar block copolymers , 1996 .

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

[43]  Tom Misteli,et al.  The JCB DataViewer scales up , 2012, The Journal of cell biology.

[44]  Gregg M. Gallatin,et al.  Modeling Line Edge Roughness in Templated, Lamellar Block Copolymer Systems , 2012 .

[45]  Xiaochuan Hu,et al.  The effect of molecular architecture on the grain growth kinetics of AnBn star block copolymers. , 2005, Faraday discussions.

[46]  N. Friedman,et al.  Engineering of synthetic cellular microenvironments: implications for immunity. , 2014, Journal of autoimmunity.

[47]  Ofir Montal,et al.  Directed self-assembly defectivity assessment. Part II , 2012, Advanced Lithography.

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

[49]  A. Krekhov,et al.  Specific features of defect structure and dynamics in the cylinder phase of block copolymers. , 2008, ACS nano.

[50]  Darrel C. Ince,et al.  The case for open computer programs , 2012, Nature.

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

[52]  R. Ruiz,et al.  Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly , 2008, Science.

[53]  Nathaniel Beck,et al.  International Encyclopedia of Political Science , 2011 .

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

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

[56]  Joachim P Spatz,et al.  Impact of local versus global ligand density on cellular adhesion. , 2011, Nano letters.

[57]  C. Grant Willson,et al.  Block Copolymer Lithography , 2014 .

[58]  N. David Mermin,et al.  Points, Lines and Walls: In Liquid Crystals, Magnetic Systems and Various Ordered Media. , 1982 .

[59]  Hiroshi Yoshida,et al.  Line edge roughness measurement technique for fingerprint pattern in block copolymer thin film , 2013, Advanced Lithography.

[60]  Karen Maex,et al.  Impact of line-edge roughness on resistance and capacitance of scaled interconnects , 2007 .

[61]  Jeffrey N. Murphy,et al.  Fast assembly of ordered block copolymer nanostructures through microwave annealing. , 2010, ACS nano.

[62]  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.

[63]  Gregg M. Gallatin,et al.  Modeling line-edge roughness in lamellar block copolymer systems , 2012, Advanced Lithography.

[64]  Lei Zhu,et al.  Synthesis and characterization of silicon-containing block copolymers from nitroxide-mediated living free radical polymerization , 2005 .

[65]  M. P. Stoykovich,et al.  Topologically Distinct Lamellar Block Copolymer Morphologies Formed by Solvent and Thermal Annealing. , 2013, ACS macro letters.

[66]  K. Harris,et al.  Conversion of bilayers of PS-b-PDMS block copolymer into closely packed, aligned silica nanopatterns. , 2013, ACS nano.

[67]  Eunhye Kim,et al.  Directed assembly of high molecular weight block copolymers: highly ordered line patterns of perpendicularly oriented lamellae with large periods. , 2013, ACS nano.

[68]  Ching Y. Suen,et al.  A fast parallel algorithm for thinning digital patterns , 1984, CACM.

[69]  Simiao Niu,et al.  Topographically-designed triboelectric nanogenerator via block copolymer self-assembly. , 2014, Nano letters.

[70]  Jillian M. Buriak,et al.  Rapid Assembly of Nanolines with Precisely Controlled Spacing from Binary Blends of Block Copolymers , 2011 .

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

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

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

[74]  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.

[75]  A. Asenov,et al.  Intrinsic parameter fluctuations in decananometer MOSFETs introduced by gate line edge roughness , 2003 .

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

[77]  R. Grubbs,et al.  On the self-assembly of brush block copolymers in thin films. , 2013, ACS nano.

[78]  Hyun-Woo Kim,et al.  Experimental investigation of the impact of LWR on sub-100-nm device performance , 2004, IEEE Transactions on Electron Devices.