Research ArticleMATERIALS SCIENCE

Shear-solvo defect annihilation of diblock copolymer thin films over a large area

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Science Advances  14 Jun 2019:
Vol. 5, no. 6, eaaw3974
DOI: 10.1126/sciadv.aaw3974
  • Fig. 1 Schematic illustration of the SS annealing process of BCP thin films.

    1D, one-dimensional.

  • Fig. 2 Long-range structural order control of SS-annealed cylinder patterns.

    SEM and grazing incidence small-angle x-ray scattering (GISAXS) 2D images after (A) shear-only and SS annealing with (B) toluene, (C) THF, and (D) their mixture for 15 min. The insets show fast Fourier transform (FFT) patterns obtained from each SEM images, and the arrows indicate the orientation direction, which is determined from the azimuthal angle distribution of each FFT image. (E) GISAXS 1D profiles, (F) integral breadth of first-order peaks, and (G) normalized d-spacing variation with that of shear-only films were obtained from GISAXS 2D data. 1D profiles were vertically shifted for clarity, and each error bar represents the range from average value. Scale bar in SEM image in (D), 300 nm. All SEM images have the same magnification. a.u., arbitrary units.

  • Fig. 3 Microscopic structural order analysis of SS-annealed cylinder patterns.

    The representative analysis results (SEM image, colored orientation of pixels, marked defect number, marked defect area, and colored orientation of stripes) of (A) shear-only, SS annealing with (B) toluene (Toln), (C) THF, and (D) their mixture (Mix) for 10 min are shown in each row from left to right. (E) Plot of Hermans parameter, P2. The inset shows the scaled persistence length (Lp/L0). (F) Plot of correlation function, g(r). The inset shows the correlation length, Lc. (G) Plot of areal defect density, ρA. The inset shows the defect number density, ρN. Bif, bifurcation; Ter, termination. (H) Plot of stripe pattern uniformity (SPU). (I) Plot of P2 of stripes. (J) Plot of scaled degree of matching with ideal patterns using Gabor filter. Each error bar represents the range from average value. Scale bars in (A), 500 nm.

  • Fig. 4 MFEP calculation.

    (A) MFEPs between defective (dislocation dipole) and defect-free lamellar structures in symmetric BCP thin film at χN = 20. The x axis represents the reaction coordinate α along the pathway, while the y axis shows the free energy difference from the starting defective morphology, in units of kBT. Morphologies of the initial defective (α = 0), transition, and final defect-free (α = 1) states are shown in insets. Periodicity, L, of lamellae varies from 1.655, 1.728, 1.8, 1.9, 2.0, to 2.1 Re (end to end distance of polymer chain). The system size in lateral direction varies accordingly to Lx = 6 L, while Ly and Lz are fixed at 8.275 and 1.655 Re, respectively. (B) Defect formation energy, ΔFd (free energy difference between states at α = 0 and α = 1, blue), and kinetic energy barrier, ΔFb (free energy difference between states at α = 0 and the transition state, black), in units of kBT, as a function of periodicity of lamellae. Each error bar shows the range from the average values.

  • Fig. 5 Investigation of global uniformity of pattern quality in a large area.

    (A) Real image of a BCP thin film (1.2 cm by 1.2 cm) and a scheme showing nine-divided regions. (B) Hermans parameter, P2, (C) areal defect density (ρA), (D) SPU, and (E) scaled magnitude after Gabor filtering (M/Mi) obtained from each of the nine regions. (F) SEM image of fabricated Au 1D array after SS annealing with mixture for 7 min. Left bottom insets show enlarged and tilted view SEM image of Au 1D array. The right top inset shows the FFT image obtained from the SEM image. (G) Semilog plots for the rocking curves of Au nanowires [shear-only and SS annealing with different times (5, 7, and 8.5 min)] obtained by x-ray double crystal Bragg diffraction. For the sample with SS for 8.5 min, we marked several peaks corresponding to sequential diffraction order with arrows. (H) Ultraviolet–visible–near-infrared spectrometral behaviors of Au nanowires [shear-only and SS annealing with different times (5, 7, and 8.5 min)]. The behaviors were obtained from reflectance difference between transverse electric– and transverse magnetic–polarized incident light from the sample. The blue dashed line indicates RTERTM of 1D infinite parallel nanolines of Au on Si substrate calculated by rigorous coupled wave approximation.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/5/6/eaaw3974/DC1

    Section S1. A temporal evolution of the structural order in SS-annealed BCP thin films

    Section S2. Effects of initial shearing temperature for SS annealing on BCP thin films

    Section S3. Analysis of peak broadening of a small-angle scattering peak as a function of fluctuations in the domain spacing and line width of 1D line-and-space patterns

    Section S4. Calculation of the orientational order and correlation of self-assembled BCP thin films

    Section S5. Detection and quantification of areal and number density of topological defects in self-assembled BCP thin films

    Section S6. Calculation of the SPU of self-assembled patterns

    Section S7. Gabor filtering and convolution for the measurement of the uniformity of self-assembled patterns in BCP thin films

    Section S8. Measurement of the LER and LWR of self-assembled patterns

    Section S9. Experimental details of SVA and swelling of BCP thin films

    Section S10. Long-time SS annealing effects on the morphological stability and orientational order of BCP thin films

    Section S11. Comparison of the domain spacing of BCP thin films with different film thicknesses under thermal annealing

    Section S12. Effects of ST annealing on the self-assembled patterns in BCP thin films

    Section S13. Comparison of morphological stability and structural order of BCP thin films annealed by different methods

    Section S14. Large-area uniformity of self-assembled pattern of shear-only and SS-annealed BCP thin films

    Section S15. UV-Vis-NIR reflectance of TE- and TM-polarized incident light from 1D metal nanowire array on the substrate

    Fig. S1. A temporal evolution of the structural order in SS-annealed BCP thin films.

    Fig. S2. Effects of initial shearing temperature and solvent vapor exposure time.

    Fig. S3. Numerical calculation of broadening behavior of the primary scattering peak.

    Fig. S4. Effects of the periodicity fluctuation of lamellae patterns on the small-angle scattering behavior.

    Fig. S5. Procedure of orientation calculation and color mapping.

    Fig. S6. Calculation of orientational correlation function, g(r).

    Fig. S7. Procedure for original raw SEM image to precisely detect topological defects and measure their areal densities in the self-assembled pattern of BCP thin films.

    Fig. S8. Procedure for the calculation of number density of the topological defects in the BCP thin films using the fingerprint analysis algorithm.

    Fig. S9. Calculation of SPU.

    Fig. S10. A measurement of a line-and-space pattern uniformity using a Gabor filter.

    Fig. S11. Measurement of the LER and LWR of self-assembled BCP thin films using a commercially available software (SuMMIT).

    Fig. S12. Swelling experiments of BCP and homopolymer thin films.

    Fig. S13. Effects of SS annealing on the film stability and pattern uniformity of BCP thin films after long-time exposure to solvent.

    Fig. S14. Calculation of domain d-spacing of thermally annealed BCP thin films with different film thicknesses.

    Fig. S15. Experimental results for the self-assembled pattern quality of BCP thin films after ST annealing.

    Fig. S16. Effects of different combinations of annealing methods on the structural order and film stability of BCP thin films.

    Fig. S17. Comparison of large-area uniformity of self-assembled patterns of shear-only and SS-annealed BCP thin films.

    Fig. S18. UV-Vis-NIR reflectance spectra from a 1D parallelly aligned array of gold nanowires.

    Table S1. An algorithm for the calculation of SPU.

    Table S2. Comparison of optimized condition and long-time SS annealing.

    References (5361)

  • Supplementary Materials

    This PDF file includes:

    • Section S1. A temporal evolution of the structural order in SS-annealed BCP thin films
    • Section S2. Effects of initial shearing temperature for SS annealing on BCP thin films
    • Section S3. Analysis of peak broadening of a small-angle scattering peak as a function of fluctuations in the domain spacing and line width of 1D line-and-space patterns
    • Section S4. Calculation of the orientational order and correlation of self-assembled BCP thin films
    • Section S5. Detection and quantification of areal and number density of topological defects in self-assembled BCP thin films
    • Section S6. Calculation of the SPU of self-assembled patterns
    • Section S7. Gabor filtering and convolution for the measurement of the uniformity of self-assembled patterns in BCP thin films
    • Section S8. Measurement of the LER and LWR of self-assembled patterns
    • Section S9. Experimental details of SVA and swelling of BCP thin films
    • Section S10. Long-time SS annealing effects on the morphological stability and orientational order of BCP thin films
    • Section S11. Comparison of the domain spacing of BCP thin films with different film thicknesses under thermal annealing
    • Section S12. Effects of ST annealing on the self-assembled patterns in BCP thin films
    • Section S13. Comparison of morphological stability and structural order of BCP thin films annealed by different methods
    • Section S14. Large-area uniformity of self-assembled pattern of shear-only and SS-annealed BCP thin films
    • Section S15. UV-Vis-NIR reflectance of TE- and TM-polarized incident light from 1D metal nanowire array on the substrate
    • Fig. S1. A temporal evolution of the structural order in SS-annealed BCP thin films.
    • Fig. S2. Effects of initial shearing temperature and solvent vapor exposure time.
    • Fig. S3. Numerical calculation of broadening behavior of the primary scattering peak.
    • Fig. S4. Effects of the periodicity fluctuation of lamellae patterns on the small-angle scattering behavior.
    • Fig. S5. Procedure of orientation calculation and color mapping.
    • Fig. S6. Calculation of orientational correlation function, g(r).
    • Fig. S7. Procedure for original raw SEM image to precisely detect topological defects and measure their areal densities in the self-assembled pattern of BCP thin films.
    • Fig. S8. Procedure for the calculation of number density of the topological defects in the BCP thin films using the fingerprint analysis algorithm.
    • Fig. S9. Calculation of SPU.
    • Fig. S10. A measurement of a line-and-space pattern uniformity using a Gabor filter.
    • Fig. S11. Measurement of the LER and LWR of self-assembled BCP thin films using a commercially available software (SuMMIT).
    • Fig. S12. Swelling experiments of BCP and homopolymer thin films.
    • Fig. S13. Effects of SS annealing on the film stability and pattern uniformity of BCP thin films after long-time exposure to solvent.
    • Fig. S14. Calculation of domain d-spacing of thermally annealed BCP thin films with different film thicknesses.
    • Fig. S15. Experimental results for the self-assembled pattern quality of BCP thin films after ST annealing.
    • Fig. S16. Effects of different combinations of annealing methods on the structural order and film stability of BCP thin films.
    • Fig. S17. Comparison of large-area uniformity of self-assembled patterns of shear-only and SS-annealed BCP thin films.
    • Fig. S18. UV-Vis-NIR reflectance spectra from a 1D parallelly aligned array of gold nanowires.
    • Table S1. An algorithm for the calculation of SPU.
    • Table S2. Comparison of optimized condition and long-time SS annealing.
    • References (5361)

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