Directed Block Copolymer Assembly Integrated with Conventional ArF or I-line lithography Kim, ang Ouk (sangouk.kim@kaist.ac.kr) oft Nanomaterials Laboratory (http://snml.kaist.ac.kr) Department of Materials cience and Engineering, Korea Advanced Institute of cience and Technology (KAIT), Daejeon, Republic of Korea
Graphoepitaxy vs. Epitaxial elf-assembly Low cost, arbitrary large area block copolymer lithography integrated with conventional photolithography?
Epitaxial elf-assembly upon Chemically Patterned urface Nanopatterned urface (Advanced Lithography) Deposition of Block Copolymer Film Registered Nanostructure Naturally assembled nanostructure with many defects Epitaxial assembly for defect-free nanostructure Nature, 424, 411, 2003 Device-oriented nanostructure cience, 308, 1442, 2005 Novel Complex Nanostructure Adv. Mater. 19, 3271, 2007
Block Copolymer Multiple Patterning for 193 nm Arf Lithography Conventional Double Patterning Lithography: Multiple Exposure and Etching 1st Exposure and Develop 1st Etch 2nd Exposure and Develop 2nd Etch Block Copolymer Multiple Patterning Lithography ingle Exposure and Develop Photoresist Thermal Flow to Narrow pacing Chemically Patterned urface Via Oxygen Plasma elf-assembled Multiple Patterning. H. Park, D. O. hin, B. H. Kim, D. K. Yoon,. Y. Lee,.-H. Oh,.-W. Choi,. C. Jeon, and. O. Kim* oft Matter 6, 120 (2010) (invited).
ubstrate Prepatterning by 193 nm ArF Photolithography
Block Copolymer Multiple Patterned Morphology A B C 60.6nm 46.2nm 36.3nm 200nm 200nm 200nm
Double Array of ub-20 nm cale Metal Nanodots 200nm 200nm
oft-graphoepitaxy of Block Copolymer Assembly with Disposable Photoresist Confinement -J. Jeong, J. E. Kim, H.-. Moon, B. H. Kim,. M. Kim, J. B. Kim,. O. Kim* Nano Letters 9, 2300 (2009).
Various Morphologies of oft-graphoepitaxy
Aluminum Nanowire Arrays from oft-graphoepitaxy ρ = R A/L = 17.6 µωcm (ρ Al-bulk = 2.65 µωcm at 293 K) J max = 4.69 10 8 A/cm 2
Ultralarge-Area Nanopatterning from oft Graphoepitaxy.-J. Jeong, H.-. Moon, B. H. Kim, J. Y. Kim, J. Yu,. Lee, M. G. Lee, H. Y. Choi,. O. Kim* AC Nano 4, 5181 (2010).
oft Graphopitaxy for Nanopatterned ubstrates
Ultralarge Area Lamellar Pattern
Pattern Perfection & Defect Formation
One-Dimensional Lamellar Assembly for Metal Nanowire Array.-J. Jeong, H.-. Moon, J. hin, B. H. Kim, D. O. hin, J. Y. Kim, Y.-H. Lee, J. U. Kim*,. O. Kim* Nano Lett. 10, 3500 (2010).
Grain Boundary Morphology vs. Lamellar Orientation
Hierarchical elf-assembly for Lithography-Free, Ultralarge-Area Nanopatterning ( 0.4 mm 0.05 mm ) - B. H. Kim, D. O. hin, -J. Jeong, C. M. Koo,. C. Jeon, W. J. Hwang,. Lee, M. G. Lee &. O. Kim* Adv. Mater. 20, 2303, (2008).
Plane View of the Thickest Part of Hierarchically Assembled Film 500 nm 5 µm
Cross-ectional View of the Thickest Part of Hierarchically Assembled Film 25 nm Extremely high aspect ratio 1: 56 1.4 µm 1 µm
pontanous Lamellar Alignment in Thickness-Gradiented Block Copolymer Films B. H. Kim, H. M. Lee, J.-H. Lee,.-W. on,.-j. Jeong,. Lee, D. I. Lee,. W. Kwak, H. Jeong, H. hin, J.-B. Yoon, O. D. Lavrentovich,. O. Kim* Adv. Funct. Mater. 19, 2584 (2009).
Energy Penalty From Lamellar Bending
Universal Block Copolymer Lithography for Metals, emiconductors, Ceramics, & Polymers -J. Jeong, G. Xia, B. H. Kim, D. O. hin,. H. Kwon,. W. Kang &. O. Kim* Adv. Mater. 20, 1898, (2008).
Universal urface Neutralization Process
urface Perpendicular Lamellae or Cylinders on Various Materials
Nanostructured Functional Thin Films of Various Materials Nanoporous TiO 2 Film Nanoporous Pt Film Pt Nanowires A B C L=43 nm L=43 nm D=20 nm Pt D=20 nm P=48 nm 100 nm i 35 nm Pt Ti i 150 nm L : Center to center distance of cylinders. D : Diameter of cylinder. P : Pitch of Nanowires.
ub-nanometer cale Metal Particle ize Tuning by Tilted Deposition 21 nm 42 nm t 35 cm t cos 4 θ θ 21 nm 35 nm θ E-beam 11 nm 20 nm 20 nm 12 Mean Diameter (nm) 10 8 6 4 12 15 18 21 24 27 30 21 nm 35 nm 20 nm 4.8 nm 20 nm Tilting Angle of Evaporation (degrees) D. H. Lee, W. J. Lee,*. O. Kim* Nano Lett. 9,1427 (2009).
ub-nanometer cale ize Tuning of Monodisperse Metal Particles with P-b-P4VP P4VP Block Copolymer Lithography (a) D. O. hin, D. H. Lee, H.-. Moon,.-J. Jeong, J. Y. Kim, J. H. Mun, H. Cho,. Park,*. O. Kim* Adv. Funct. Mater. (In press).
Monodisperse Nanoparticle Growth with Metal Ion Loading Time
Wall Number elective CNT Growth
Micropatterned Monodisperse Vertical CNT Growth
Reduced Graphene Film ubstrate for CNT Growth Chemical Oxidation Dialysis, onic., Centrifuge pin-coat with N 2 Blow Anneal Dip in NaOH (aq.) solution 1 cm x 1 cm ize (t:~10nm) Free-tanding rgo Film
Reduced Graphene Film for Neutral urface Modification B. H. Kim, J.-H. Kim,.-J. Jeong, J. O. Hwang, D. H. Lee,.-Y. Choi,. O. Kim* AC Nano 4, 5464 (2010).
urface Energy Tunability with Graphene Film Reduction
urface Perpendicular Nanodomains on Inert or Nonplanar urfaces
Hierarchical Patternability and Pattern Transfer with Graphene Film
CNT-Graphene Carbon Hybrid Films Graphene oxide film spin coating Block copolymer Template preparation Block copolymer nanoporous template 23 nm io 2 substrate Graphene oxide film CNTs Catalyst deposition & lift off Nanopatterned Fe catalysts 72 nm G 100 G 110, Fe 220 G 200 G 211, Fe 422 G 220, Fe 440 100 nm Reduced graphene film Raw carbon hybrid film (1) PDM infiltrated hybrid film (2) Floating on a diluted HF PDM PDM infiltration & Floating CNT growth & graphene oxide film reduction CNTs Catalyst 22 nm 50 nm CNT 13 nm Graphene film 7 nm CNT 8 nm Catalyst 12 nm Graphene film 7 nm 50 nm D. H. Lee, J. E. Kim, T. H. Han, J. W. Hwang,. W. Jeon,.-Y. Choi,. H. Hong, W. J. Lee, R.. Ruoff,. O. Kim* Adv. Mater. 22, 1247 (2010).
elf-upporting upporting Carbon Hybrid Films 1 37 μm CNT-PDM 2 Precipitated substrates 10 μm PDM CNT 200 nm 1 μm
Mechanically Flexible Carbon Hybrid Films Top ide Top ide 50 μm 10 μm
500 μm 10 μm
Flexible Field Emission under Mechanical Deformation Phosphor (Zn:Ag,Cl) PC (200?m) CNT/graphene Hybrid Film Au (15 nm) 0.9 V/um 2.27 cd /m 2 7.52 cd /m 2 31 cd /m 2 1.1 V/um 21.1 cd /m 2 77.5 cd /m 2 218 cd /m 2 1.3 V/um 81.7 cd /m 2 340 cd /m 2 469 cd /m 2 D. H. Lee, J. A. Lee, W. J. Lee*,. O. Kim* mall (accepted).
Directed Molecular Assembly of oft Materials for Nanofabrication Polymer, Peptide Assembly Carbon Assembly Functional Nanomaterials Nature 424, 411 (2003) cience 308, 1422 (2005) Macromolecules 39, 5466 (2006) Adv. Mater. 19, 3171 (2007) oft Matter 5, 2343 (2009) Nano Lett. 10, 3500 (2010) Macromol. Res. 16, 261 (2008) JAP 110, 2345 (2008) oft Matter 5, 2343 (2009) Adv. Mater. 20, 1898 (2008) Nano Lett. 9, 2300 (2009) J. Mater. Chem. 20, 7241 (2010) Adv. Funct. Mater. (accepted) Adv. Mater. 20, 2303 (2008) Adv. Funct. Mater. 19, 2584 (2009) ChemComm 46, 1911 (2010) AC Nano 4, 5181 (2010) JPC B 110, 13959 (2006) Adv. Funct. Mater. 17, 2315 (2007) Adv. Mater. 22. 2060 (2010) J. Mater. Chem. 19, 3512 (2009) AC Nano 4, 5464 (2010) Nano Lett. (online-published) Adv. Mater. 20, 2480 (2008) Chem. Mater. 21, 1368 (2009) Nano Lett. 9, 1427 (2009) Adv. Mater. (accepted) Adv. Mater. 22, 583 (2010) mall 6, 945 (2010) 500 nm Adv. Mater. 19, 3924 (2007) Adv. Mater. 22, 1247 (2010) Apply. Phys. Lett. 96, 213105 (2010) mall (accepted) AC Nano 3, 1085 (2009) J. Mater. Chem. 19, 3512 (2009) Nanotechnology 20, 225301 (2009) Angew. Chem. Int. Ed. 49, 5712 (2010) ChemComm 50nm (accepted)
Directed Assembly of CNTs & Graphene Immediate utilization of assembled morphology without pattern transfer Large polydispersity in size Bundling or stacking Functional 3D Architectures Extremely large surface area Mechanical flexibility & stretchability High environmental stability Tunable electrical properties Electrodes, substrates, etc.. H. Lee, D. H. Lee, W. J. Lee,. O. Kim* Tailored Assembly of CNTs and Graphene Adv. Funct. Mater. (invited Feature Article, submitted).
Acknowledgements Collaborators amsung Electronics Prof. Rodney Ruoff (ME, U Texas-Austin) Prof. Won Jong Lee (M&E, KAIT) Dr. eong-yool Choi (ETRI) Prof. oojin Park (UNIT) Prof. Jaeup E. Kim (UNIT) Group Members Dr. eong-jun Jeong Dr. Duck Hyun Lee Dr. Yoon, Je Moon Kim, Bong Hoon Lee, un Hwa hin, Dong Ok Park, Ji un Moon Hyoung-eok Hwang Jin Ok Lee, Won Jun Park, eokhan Lee, Ju Min hm, Jong Won Kim, Ji Eun Kim, Ju Young Lee, Jin Ah Kim, Hyun Wook Kwon, Jun Mun, Jung Ho Choi, Dong ung Haq, Atta UI