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Advancements in Block Copolymer Micelle Nanolithography for Sub-10nm Patterning

This paper presents a novel approach to nanolithography utilizing block copolymer micelles to create sub-10nm clusters and patterns. By dip-coating silicon wafers in micelle solutions, we demonstrate a method that enhances throughput and reduces production costs compared to traditional lithography. The resulting patterns range from 50nm to 250nm, leveraging precisely controlled micelle structures. We explore the fabrication process, the uniformity of patterns, and the robustness of nano-clusters, highlighting the method's potential for applications in electronics and nanotechnology.

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Advancements in Block Copolymer Micelle Nanolithography for Sub-10nm Patterning

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  1. Block Copolymer Micelle NanolithographyRoman Glass, Martin Mollerand Joachim P SpatzUniversity of HeidelbergIOP Nanotechnology (2003) Erika Parra EE235 4/18/2007

  2. Motivation • 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

  3. Process Overview • Dip wafer (Si) into micelle solution • Retrieve at 12mm/min • Air-evaporate solvent • Plasma (H2, Ar, or O2) removes polymer shell Results: • Uniform • Hexagonal • 2, 5, 6, or 8nm • Spherical PS(190)-b-P[2VP(Au0.2)](190) PS(500)-b-P[2VP(Au0.5)](270) PS(990)-b-P[2VP(Au0.5)](385) PS(1350)-b-P[2VP(Au0.5)](400) Side view TEM – treated wafer Au ~ HAuCl4

  4. 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 PS P2VP Au • 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)

  5. 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) Low PDI

  6. 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) PS(1350)-b-P[2VP(Au0.5)](400) D = 8nm, L = 85nm

  7. Cluster Aggregation • Vary PR thickness • Feature height (volume) defines cluster diameter • Figure: e-beam 200nm features on 2um square lattice 800nm 500nm 75nm

  8. 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

  9. 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

  10. Micelles on Electrically Insulating Films • Glass substrate desired in biology • E-beam requires conductive substrate • Evaporate 5nm carbon layer

  11. 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

  12. Conclusions • 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)

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