Research ArticleMATERIALS SCIENCE

Ultrathin graphdiyne film on graphene through solution-phase van der Waals epitaxy

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Science Advances  06 Jul 2018:
Vol. 4, no. 7, eaat6378
DOI: 10.1126/sciadv.aat6378
  • Fig. 1 Synthetic process of single-crystalline GDY on graphene film.

    (A) Schematic illustration of the synthetic process. (B) Chemical structure of HEB, hexakis[(trimethylsilyl)ethynyl]benzene (TMS-HEB), and the Eglinton coupling reaction of HEB molecule for the growth of GDY. TMS = SiMe3. Typical OM image (C) and SEM image (D) of GDY film grown on graphene. (E) Typical AFM image of GDY/graphene film on SiO2/Si substrate, showing a thickness of ~1.74 nm (including a single-layer graphene).

  • Fig. 2 Aberration-corrected and monochromated HRTEM images of as-synthesized film.

    (A) TEM image of transferred GDY/graphene film on a holey elastic carbon matrix. (B) Electron diffraction pattern of as-synthesized film, which shows that GDY and graphene films are both single crystalline. (C) Corresponding FFT pattern of HRTEM image. Blue circle, GDY; red and green circles, graphene. (D) Aberration-corrected HRTEM imaging of GDY domain. (E) Enlarged image in the area highlighted by the red square of Fig. 3D. (F) Simulated HRTEM image of GDY with “ABC” stacking mode (amorphous noise included). (G) CTF-corrected, lattice-averaged (left) and p6m symmetry-imposed images (right). (H) Simulated projected potential map with a point spread function width of 2.6 Å. ABC stacking trilayer GDY model embedded. (I and J) Energetically preferred geometry of vdW heterostructure made of single-layer graphene and ABC-stacked trilayer GDY flake, optimized by self-consistent charge density functional tight-binding methods with dispersion. (K) Schematic illustration of GDY with ABC stacking mode.

  • Fig. 3 Spectroscopic characterization of as-grown GDY film.

    (A) High-resolution core-level XPS spectrum of C 1s. CPS, counts per second; a.u., arbitrary units. (B) Typical Raman spectrum (black) of GDY grown on graphene transferred to SiO2/Si substrate and polarization-dependent Raman spectra of GDY measured in XX (red) and XY (blue) polarization configurations by fixing the incident light and the scattered signal’s polarization directions in the parallel-polarized configuration and cross-polarized configuration (excitation at 514.5 nm). (C) PL spectrum of as-grown GDY on h-BN. (D) OM image of as-grown GDY on graphene with a mark indicating the mapping region. (E) Typical Raman spectra randomly collected across the corresponding sample in (D). (F) Integrated intensity ratio Raman maps of Y band (2189.2 cm−1) and 2D band (2696.5 cm−1) over the marked area in (D), confirming the uniformity of the GDY on the graphene surface in macroscopic scales.

  • Fig. 4 Proposed mechanism for synthesis of GDY film on graphene through a solution-phase vdW epitaxial strategy.

    (A) Raman spectra of GDY on different reaction areas (on graphene, in solution, and on SiO2/Si), synthesized under the same conditions. SEM images of as-grown GDY and corresponding selected-area electron diffraction (SAED) pattern in inset, synthesized in solution (B) and on graphene (C). (D) Proposed mechanism for the Eglinton reaction and computed free-energy profiles on graphene (blue) and in solution (red). (E) Optimized geometries from I to VI (see fig. S19 for details; Cu, blue; O, red; C, gray, and H, white).

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/4/7/eaat6378/DC1

    Supplementary Materials and Methods

    Fig. S1. Optical image and corresponding Raman spectrum of graphene film on SiO2/Si substrate.

    Fig. S2. HRTEM image of graphene substrate.

    Fig. S3. Thickness analysis of as-grown GDY on graphene through a solution-phase vdW epitaxial strategy.

    Fig. S4. The transfer process of the as-prepared GDY/graphene film from SiO2/Si substrate to copper grid.

    Fig. S5. Scanning TEM image and energy-dispersive x-ray spectroscopy elemental mapping images of C, O, and Si for GDY/graphene.

    Fig. S6. GDY models with AA, AB, and ABC stacking modes and corresponding simulated SAED patterns of the stacking models.

    Fig. S7. Calculated optimal binding energy of AA-, AB-, and ABC-stacked GDY structural models.

    Fig. S8. As-grown GDY/graphene vdW heterostructure at high resolution.

    Fig. S9. Monochromated core-loss EELS spectra of GDY/graphene film collected under the (low-loss and core-loss) dual EELS mode.

    Fig. S10. Raman spectrum of GDY grown on h-BN substrate.

    Fig. S11. Hybrid functional HSE06 predicted band structures and band gaps (Eg) for monolayer, bilayer, and trilayer GDY.

    Fig. S12. Typical Raman spectra of GDY grown on graphene (red) with a reference blank graphene on SiO2/Si substrate (black) and the calculated Raman spectra (29) of GDY (blue).

    Fig. S13. Raman spectrum and corresponding vibrational modes of GDY.

    Fig. S14. Raman spectra of HEB monomer (blue), TMS-HEB monomer (black), and GDY (red).

    Fig. S15. In situ Raman spectroscopy to detect the change of the Y′ peak in GDY, which is a Raman-active peak from the stretching of C≡C triple bonds.

    Fig. S16. The intensity of typical Y′ (2189.0 cm−1) peak as a function of reaction time, using the peak (520.7 cm−1) from Si substrate for intensity normalization.

    Fig. S17. Raman spectra taken from the same sample after being stored in air for several days.

    Fig. S18. Theoretical simulations of adsorption behavior of HEB on graphene.

    Fig. S19. Detailed structures and relative energy of I to VI and TS.

    Fig. S20. NH3 detection at room temperature and atmospheric pressure.

    Fig. S21. Evaluation of the electrical property of the as-synthesized GDY.

    Fig. S22. OM images of the device in fig. S20.

    Fig. S23. The optical layout of the polarized Raman measurement.

    References (3440)

  • Supplementary Materials

  • This PDF file includes:
    • Supplementary Materials and Methods
    • Fig. S1. Optical image and corresponding Raman spectrum of graphene film on SiO2/Si substrate.
    • Fig. S2. HRTEM image of graphene substrate.
    • Fig. S3. Thickness analysis of as-grown GDY on graphene through a solution-phase vdW epitaxial strategy.
    • Fig. S4. The transfer process of the as-prepared GDY/graphene film from SiO2/Si substrate to copper grid.
    • Fig. S5. Scanning TEM image and energy-dispersive x-ray spectroscopy elemental mapping images of C, O, and Si for GDY/graphene.
    • Fig. S6. GDY models with AA, AB, and ABC stacking modes and corresponding simulated SAED patterns of the stacking models.
    • Fig. S7. Calculated optimal binding energy of AA-, AB-, and ABC-stacked GDY structural models.
    • Fig. S8. As-grown GDY/graphene vdW heterostructure at high resolution.
    • Fig. S9. Monochromated core-loss EELS spectra of GDY/graphene film collected under the (low-loss and core-loss) dual EELS mode.
    • Fig. S10. Raman spectrum of GDY grown on h-BN substrate.
    • Fig. S11. Hybrid functional HSE06 predicted band structures and band gaps (Eg) for monolayer, bilayer, and trilayer GDY.
    • Fig. S12. Typical Raman spectra of GDY grown on graphene (red) with a reference blank graphene on SiO2/Si substrate (black) and the calculated Raman spectra ( 29) of GDY (blue).
    • Fig. S13. Raman spectrum and corresponding vibrational modes of GDY.
    • Fig. S14. Raman spectra of HEB monomer (blue), TMS-HEB monomer (black), and GDY (red).
    • Fig. S15. In situ Raman spectroscopy to detect the change of the Y′ peak in GDY, which is a Raman-active peak from the stretching of C≡C triple bonds.
    • Fig. S16. The intensity of typical Y′ (2189.0 cm−1) peak as a function of reaction time, using the peak (520.7 cm−1) from Si substrate for intensity normalization.
    • Fig. S17. Raman spectra taken from the same sample after being stored in air for several days.
    • Fig. S18. Theoretical simulations of adsorption behavior of HEB on graphene.
    • Fig. S19. Detailed structures and relative energy of I to VI and TS.
    • Fig. S20. NH3 detection at room temperature and atmospheric pressure.
    • Fig. S21. Evaluation of the electrical property of the as-synthesized GDY.
    • Fig. S22. OM images of the device in fig. S20.
    • Fig. S23. The optical layout of the polarized Raman measurement.
    • References (3440)

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