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Block Copolymer Micelle Nanolithography Roman Glass, Martin Moller and Joachim P Spatz University of Heidelberg IOP Nanotechnology (2003). Erika Parra EE235 4/18/2007. Motivation. Market Trends Small features Sub-10nm clusters deposited Patterns 50nm to 250nm and greater

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Block Copolymer Micelle NanolithographyRoman Glass, Martin Mollerand Joachim P SpatzUniversity of HeidelbergIOP Nanotechnology (2003)

Erika Parra



  • Market Trends
  • Small features
    • Sub-10nm clusters deposited
    • Patterns 50nm to 250nm and greater
  • Lower cost of tedious fabrication processes for conventional lithography
  • Increase throughput (from e-beam) – parallel process
  • Bottom line: bridge gap between traditional self-assembly and lithography
process overview
Process Overview
  • Dip wafer (Si) into micelle solution
  • Retrieve at 12mm/min
  • Air-evaporate solvent
  • Plasma (H2, Ar, or O2) removes polymer shell


  • Uniform
  • Hexagonal
  • 2, 5, 6, or 8nm
  • Spherical





Side view TEM – treated wafer

Au ~ HAuCl4

diblock copolymer micelles
Diblock Copolymer Micelles
  • Dendrite shaped macromolecule
  • Corona is amphiphilic
  • Micelle MW and shape controlled by initial monomer concentration
  • Polymer corona with “neutralized” core (Au, Ag, AgOx, Pt, Pd, ZnOx, TiOx, Co, Ni, and FeOx)
  • Nanodot “core” size is controlled by the amount of metal precursor salt




  • In this paper:
    • Water-in-oil micelle (toulene solvent)
    • Polystyrene(x)-b-poly(2-vinylpyridine)(y) (PS(x)-b-P2VP(y))
    • Au core from chloroauric precursor (HAuCl4)
cluster pattern characterization
Cluster Pattern Characterization
  • MW tunes nanodot distance (max of 200 nm micelle)
  • Low polydispersity permits regularity
  • Higher MW decreased pattern quality and position precision (softness in shell)



guided self assembly 250nm
Guided Self-Assembly (>250nm)
  • Predefine topographies using photo or e-beam
  • Spin-on concentrated micelle solution (capillary forces of evaporating solvent adheres them to sides)
  • Micelles are pinned to the substrate by plasma (100W, 0.4mbar, 3min)
  • Lift-off removes PR and micelles
  • 2nd plasma treatment removes micelle polymer (100W, 0.4mbar, 20min)


D = 8nm, L = 85nm

cluster aggregation
Cluster Aggregation
  • Vary PR thickness
  • Feature height (volume) defines cluster diameter
  • Figure: e-beam 200nm features on 2um square lattice




line patterning
Line Patterning
  • Cylindrical micelle
  • Formed if corona volume fraction < core
  • PS(80)-b-P2VP(330)
  • Length of several microns
  • Substrate patterned with grooves & dipped in micelle solution

4nm line

negative patterning with e beam
Negative Patterning with E-beam
  • Spin-on micelles
  • Expose with e-beam (1KeV, 400-50,000 μC/cm2), 200um width
  • Ultrasound bath + 30min plasma
  • Electrons stabilize micelle on Si due to carbon species formed during exposure
micelles on electrically insulating films
Micelles on Electrically Insulating Films
  • Glass substrate desired in biology
  • E-beam requires conductive substrate
  • Evaporate 5nm carbon layer
mechanical stability of nano clusters
Mechanical Stability of Nano-Clusters
  • Treated and unaffected by:
    • Pirahna, acids, many bases, alcohols, ultrasonic water bath
  • Hypothesis: edge formed by the substrate-cluster borderline is partly wetted by surface atoms during plasma treatment
  • Thermal
    • 800 C evaporated clusters but no migration occured
  • Simple process for sub-10nm clusters and lines
  • Block copolymer micelle size controls nano-cluster interspacing
  • Micelle size controlled by monometer concentrations

Micelles as masks for diamond field emitters

F. Weigl et al. / Diamond & Related Materials 15 (2006)