Block Copolymer Micelle Nanolithography
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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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Erika parra ee235 4 18 2007

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)