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Transient Interfacial Pattern Formation in Block Copolymer Thin Films via Sequential Thermal and Solvent Immersion

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Highly nonequilibrium processing of block copolymers (BCP) creates novel transient structures. Reversing annealing order (thermal annealing then solvent immersion) generates unique wrinkling patterns not seen in equilibrium states.

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Area of Science:

  • Materials Science
  • Polymer Science
  • Soft Matter Physics

Background:

  • Naturally occurring structures often form under nonequilibrium conditions.
  • Block copolymer (BCP) self-assembly typically focuses on near-equilibrium processing.
  • Previous work explored direct solvent immersion annealing (DIA) followed by thermal annealing (TA).

Purpose of the Study:

  • To investigate nonequilibrium processing of BCP films by reversing the annealing sequence (TA then DIA).
  • To explore the creation of novel transient BCP morphologies.
  • To understand the formation and evolution of swelling-induced wrinkle patterns.

Main Methods:

  • Sequential processing of BCP films: initial thermal annealing (TA) to partial order, followed by direct solvent immersion annealing (DIA).
  • Observation of morphology evolution during DIA, including swelling-induced wrinkling.
  • Quenching of transient morphologies via solvent evaporation.
  • Comparison with equilibrium morphologies obtained by DIA alone or TA alone.

Main Results:

  • The TA + DIA sequence rapidly induces swelling-induced wrinkle patterns in BCP films.
  • These wrinkling "defect" patterns are transient and depend on DIA immersion time.
  • The wrinkling morphology can be quenched into a glassy state.
  • At long DIA times, the system evolves towards the equilibrium lamellar morphology.

Conclusions:

  • Switching the order of TA and DIA processing significantly alters intermediate transient morphologies.
  • While final equilibrium states are similar, transient states differ drastically between DIA + TA and TA + DIA sequences.
  • These unique transient BCP morphologies offer potential for novel applications.