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All-polymeric control of nanoferronics

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Science Advances  18 Dec 2015:
Vol. 1, no. 11, e1501264
DOI: 10.1126/sciadv.1501264
  • Fig. 1 Schematic representations of the crystal growth method and structure of the CTCCs.

    (A) Modified antisolvent crystallization growth scheme combined with solvent vapor evaporation. 1,2-DCB was used as the good solvent and acetonitrile as the antisolvent. Acetonitrile was added to induce localized supersaturation and precipitation of cocrystals at the interface of good solvent and antisolvent. (B) Photograph of the as-grown CTCCs. (C) XRD spectrum of CTCCs. (D) TEM image and SAED pattern of the CTCC. (E) Segregated stacking pattern of the CTCCs. (F) Schematic structural schemes of the CTCC. Blue denotes the polythiophene backbones and side chains, yellow denotes the S atoms on the backbone of polythiophene, and cyan-green denotes the C60 clusters.

  • Fig. 2 Morphology, phase separation, and polythiophene/C60 interface configuration of the CTCCs.

    (A) Typical side-view SEM image of the CTCCs. The inset is the carbon and sulfur chemical analysis mapping from energy-dispersive x-ray spectroscopy. (B) TEM image of the center region in the CTCCs. The inset is the high-resolution TEM image. (C) Current (top) and topography (bottom) images from the conducting AFM (c-AFM) of the CTCCs. (D to G) Polythiophene/C60 interface configurations obtained by classical MD simulation for configuration 1 with rough surface at t = 0 and 1 ns, respectively (D and E), and configuration 2 with flat surface at t = 0 and 1 ns, respectively (F and G). (H and I) Highest occupied molecular orbital of polythiophene molecules at each layer of configuration 1 (H) and configuration 2 (I).

  • Fig. 3 The RR of polythiophene-dependent CTCC growth and corresponding optical properties.

    (A) Molecular structures of 91% (LRR) and 96.3% (HRR) polythiophene. (B) Confocal fluorescence microscopy images of CTCC synthesized with LRR (above) and HRR (below) polythiophene. Scale bars, 50 μm. (C and D) Dimensions in the length and width directions of the time-dependent LRR and HRR CTCC growth. Error bars are attributed to ~20 crystals present on the surface of the substrates. (E) Confocal fluorescence spectra of LRR and HRR CTCCs. The excitation wavelength is 488 nm. The inset is the absorption spectra of LRR and HRR CTCCs. a.u., arbitrary units.

  • Fig. 4 Anisotropic electrical and MC properties of the HRR CTCCs.

    (A) Current density–electric field curves, oriented parallel and perpendicular to the long axis (b axis) of the CTCC, respectively. The inset shows the photograph of CTCC between two silver electrodes for the parallel measurements. (B) Temperature-dependent permittivity for the selected frequencies of CTCCs. (C) Dark MC under different electric fields. The left and right insets are the parallel and perpendicular direction measurement schemes, respectively. (D) Dark/light-controlled MC under different magnetic fields in the perpendicular direction. The applied electric field is 13 kV/cm. The light intensity is 70 mW/cm2.

  • Fig. 5 Ferroelectric properties of the HRR CTCCs.

    (A) Electric field–dependent saturation polarization value in the parallel and perpendicular directions. The insets are the PUND polarization measurement of the CTCCs in the parallel (left) and perpendicular (right) directions, respectively. The electric fields of PUND measurement in the parallel and perpendicular directions are 9 and 520 V/cm, respectively. (B) Hysteresis loops of the piezoelectric response versus tip bias. (C) Light intensity–induced saturation polarization change in the parallel and perpendicular directions.

  • Fig. 6 Magnetic properties of the HRR CTCCs.

    (A) M-H loops of the CTCCs in the in-plane and out-of-plane directions. ΔMs shows the difference in the saturation magnetization in the two directions. (B) Angle-dependent saturation magnetization (top), experimental (middle left) and calculated spin susceptibility (middle right), and saturation polarization (bottom). The electric field is loaded parallel to the CTCC long axis. The external magnetic field for the polarization measurement is 200 Oe. (C) Spin cone distribution along the long axis (b axis) of the CTCC and the polarization induced by charge ordering and CT at the interface. The direction and width of the spin cone depend on the spin direction and the charge-lattice coupling extent. The positive and negative charges in polythiophene and C60 are used for the illustration of CT and dipoles, which do not represent the real charge distribution in the cocrystals.

  • Fig. 7 ME coupling of HRR CTCCs.

    (A) ME coupling effect (electric field–dependent magnetization) with a bias magnetic field of 60 Oe. (B) Light intensity–dependent ME coupling of CTCCs.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/1/11/e1501264/DC1

    Mass transport–induced crystallization of CTCCs

    Fig. S1. Photograph of the crystals.

    Fig. S2. Optical microscopy image of the initial growth stage of the crystals.

    Fig. S3. Dark-field optical microscopy image of the CTCC.

    Fig. S4. High resolution TEM images of CTCCs, and AFM image near the center of the cocrystals.

    Classical molecule dynamics (MD) simulations on the interface configuration of polythiophene/C60 CTCCs

    Fig. S5. Polythiophene/C60 interface configuration while polythiophene structure starts from free surface in the x direction.

    Fig. S6. Polythiophene/C60 interface configuration with monolayer or single-molecule polythiophene.

    Table S1. Energy-level distribution of polythiophene layer close to the polythiophene/C60 interface with multilayer polythiophene crystal and single molecule, respectively.

    Time- and RR-dependent crystallization

    Fig. S7. Time-dependent crystal growing for 91% RR CTCC.

    Fig. S8. Time-dependent crystal growing for 95.7% RR CTCC.

    Absorption spectra

    Fig. S9. Absorption spectra of CTCCs measured by a microscope in the range of 600 to 1200 nm.

    RR-dependent electrical and magnetic properties

    Fig. S10. Magnetoconductance.

    Fig. S11. ME coupling effect with different loading electric field.

    Electrical properties

    Fig. S12. Electrical properties as a function of temperature and frequency.

    Anisotropic MC effect

    Fig. S13. MC of CTCC under different electric fields.

    Fig. S14. MC of CTCC under different magnetic fields.

    Fig. S15. Light-illuminated MC of CTCC under different magnetic fields.

    Fig. S16. Light intensity–dependent MC of vertical.

    Piezoelectric response

    Fig. S17. Amplitude of the piezoelectric response versus tip bias.

    Electron spin resonance

    Fig. S18. ESR of CTCC at 80 K and room temperature.

    Angle-dependent magnetism

    Fig. S19. Angle-dependent M-H loops of CTCC.

    M-H loop of CTCC powder

    Fig. S20. M-H loop of the free-standing CTCC powder.

    Dark and light-illuminated magnetism

    Fig. S21. Magnetic and spin resonance properties of the cocrystal.

    Magnetoelectric coupling

    Fig. S22. Tunability of magnetization by electric field when the electric field is oriented perpendicular (A and C) and parallel (B and D) to the cocrystal long axis without (A and B) and with (C and D) light illumination.

    References (4355)

  • Supplementary Materials

    This PDF file includes:

    • Mass transport–induced crystallization of CTCCs
    • Fig. S1. Photograph of the crystals.
    • Fig. S2. Optical microscopy image of the initial growth stage of the crystals.
    • Fig. S3. Dark-field optical microscopy image of the CTCC.
    • Fig. S4. AFM image near the center of the cocrystals.
    • Classical molecule dynamics (MD) simulations on the interface configuration of polythiophene/C60 CTCCs
    • Fig. S5. Polythiophene/C60 interface configuration while polythiophene structure starts from free surface at x direction.
    • Fig. S6. Polythiophene/C60 interface configuration with monolayer or single-molecule polythiophene.
    • Table S1. Energy-level distribution of polythiophene layer close to the polythiophene/C60 interface with multilayer polythiophene crystal and single molecule, respectively.
    • Time- and RR-dependent crystallization
    • Fig. S7. Time-dependent crystal growing for 91% RR CTCC.
    • Fig. S8. Time-dependent crystal growing for 95.7% RR CTCC.
    • Absorption spectra
    • Fig. S9. Absorption spectra of CTCCs measured by microscope in the range of 600 to 1200 nm.
      RR-dependent electrical and magnetic properties
    • Fig. S10. Magnetoconductance.
    • Fig. S11. ME coupling effect with different loading electric field.
    • Electrical properties
    • Fig. S12. Electrical properties as a function of temperature and frequency.
    • Anisotropic MC effect
    • Fig. S13. MC of CTCC under different electric field.
    • Fig. S14. MC of CTCC under different magnetic field.
    • Fig. S15. Light-illuminated MC of CTCC under different magnetic field.
    • Fig. S16. Light intensity–dependent MC of vertical.
    • Piezoelectric response
    • Fig. S17. Amplitude of the piezoelectric response versus tip bias.
    • Electron spin resonance
    • Fig. S18. ESR of CTCC at 80 K and room temperature.
    • Angle-dependent magnetism
    • Fig. S19. Angle-dependent M-H loops of CTCC.
    • M-H loop of CTCC powder
    • Fig. S20. M-H loop of the free-standing CTCC powder.
    • Dark and light-illuminated magnetism
    • Fig. S21
    • Magnetoelectric coupling
    • Fig. S22. Tunability of magnetization by electric field when the electric field is oriented perpendicular (A and C) and parallel (B and D) to the cocrystal long axis without (A and B) and with (C and D) light illumination.
    • References (43–55)

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