Molecular embroidering of graphene

Tao Wei; Malte Kohring; Heiko B. Weber; Frank Hauke; Andreas Hirsch

doi:10.1038/s41467-020-20651-w

journal article Open Access Jan 22, 2021

Molecular embroidering of graphene

Tao Wei

Malte Kohring Heiko B. Weber Frank Hauke Andreas Hirsch

Nature Communications Vol. 12 No. 1 · Springer Science and Business Media LLC

View at Publisher Save 10.1038/s41467-020-20651-w

Abstract

Abstract

Structured covalent two-dimensional patterning of graphene with different chemical functionalities constitutes a major challenge in nanotechnology. At the same time, it opens enormous opportunities towards tailoring of physical and chemical properties with limitless combinations of spatially defined surface functionalities. However, such highly integrated carbon-based architectures (graphene embroidery) are so far elusive. Here, we report a practical realization of molecular graphene embroidery by generating regular multiply functionalized patterns consisting of concentric regions of covalent addend binding. These spatially resolved hetero-architectures are generated by repetitive electron-beam lithography/reduction/covalent-binding sequences starting with polymethyl methacrylate covered graphene deposited on a Si/SiO
2
substrate. The corresponding functionalization zones carry bromobenzene-, deutero-, and chloro-addends. We employ statistical Raman spectroscopy together with scanning electron microscopy/energy dispersive X-ray spectroscopy for an unambiguous characterization. The exquisitely ordered nanoarchitectures of these covalently multi-patterned graphene sheets are clearly visualized.

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References

48

[1]

Bai, J. W., Zhong, X., Jiang, S., Huang, Y. & Duan, X. F. Graphene nanomesh. Nat. Nanotechnol. 5, 190–194 (2010). 10.1038/nnano.2010.8

[2]

Chemically Derived, Ultrasmooth Graphene Nanoribbon Semiconductors

Xiaolin Li, Xinran Wang, Li Zhang et al.

Science 2008 10.1126/science.1150878

[3]

Balog, R. et al. Bandgap opening in graphene induced by patterned hydrogen adsorption. Nat. Mater. 9, 315–319 (2010). 10.1038/nmat2710

[4]

Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane

D. C. Elias, R. R. Nair, T. M. G. Mohiuddin et al.

Science 2009 10.1126/science.1167130

[5]

Bai, J., Duan, X. & Huang, Y. Rational fabrication of graphene nanoribbons using a nanowire etch mask. Nano Lett. 9, 2083–2087 (2009). 10.1021/nl900531n

[6]

Wang, X. & Dai, H. Etching and narrowing of graphene from the edges. Nat. Chem. 2, 661–665 (2010). 10.1038/nchem.719

[7]

George, A. et al. Large area resist-free soft lithographic patterning of graphene. Small 9, 711–715 (2013). 10.1002/smll.201201889

[8]

Zhang, L. M. et al. Photocatalytic patterning and modification of graphene. J. Am. Chem. Soc. 133, 2706–2713 (2011). 10.1021/ja109934b

[9]

Abbas, A. N. et al. Patterning, characterization, and chemical sensing applications of graphene nanoribbon arrays down to 5 nm using helium ion beam lithography. ACS Nano 8, 1538–1546 (2014). 10.1021/nn405759v

[10]

Hyun, W. J., Secor, E. B., Hersam, M. C., Frisbie, C. D. & Francis, L. F. High-resolution patterning of graphene by screen printing with a silicon stencil for highly flexible printed electronics. Adv. Mater. 27, 109–115 (2015). 10.1002/adma.201404133

[11]

Cai, J. et al. Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 466, 470–473 (2010). 10.1038/nature09211

[12]

Narita, A. et al. Synthesis of structurally well-defined and liquid phase-processable graphene nanoribbons. Nat. Chem. 6, 126–132 (2014). 10.1038/nchem.1819

[13]

Dössel, L., Gherghel, L., Feng, X. & Müllen, K. Graphene nanoribbons by chemists: nanometer-sized, soluble, and defect-free. Angew. Chem. Int. Ed. 50, 2540–2543 (2011). 10.1002/anie.201006593

[14]

Schwab, M. G. et al. Structurally defined graphene nanoribbons with high lateral extension. J. Am. Chem. Soc. 134, 18169–18172 (2012). 10.1021/ja307697j

[15]

Bottom‐Up Synthesis of Chemically Precise Graphene Nanoribbons

Akimitsu Narita, Xinliang Feng, Klaus Müllen

The Chemical Record 2015 10.1002/tcr.201402082

[16]

Permanent Pattern‐Resolved Adjustment of the Surface Potential of Graphene‐Like Carbon through Chemical Functionalization

Fabian M. Koehler, Norman A. Luechinger, Dominik Ziegler et al.

Angewandte Chemie International Edition 2009 10.1002/anie.200804485

[17]

Sun, Z. Z. et al. Towards hybrid superlattices in graphene. Nat. Commun. 2, 559–564 (2011). 10.1038/ncomms1577

[18]

Liu, L. H. et al. A simple and scalable route to wafer-size patterned graphene. J. Mater. Chem. 20, 5041–5504 (2010). 10.1039/c0jm00509f

[19]

Bian, S. et al. Covalently patterned graphene surfaces by a force-accelerated Diels-Alder reaction. J. Am. Chem. Soc. 135, 9240–9243 (2013). 10.1021/ja4042077

[20]

Click and Patterned Functionalization of Graphene by Diels–Alder Reaction

Jing Li, Meng Li, Li-Li Zhou et al.

Journal of the American Chemical Society 2016 10.1021/jacs.6b02209

[21]

Patterned graphene functionalization via mask-free scanning of micro-plasma jet under ambient condition

Dong Ye, Shu-Qun Wu, Yao Yu et al.

Applied Physics Letters 2014 10.1063/1.4866788

[22]

Lee, W. K., Whitener, K. E., Robinson, J. J. T. & Sheehan, P. E. Patterning magnetic regions in hydrogenated graphene via e-beam irradiation. Adv. Mater. 27, 1774–1778 (2015). 10.1002/adma.201404144

[23]

Lee, W. H. et al. Selective-area fluorination of graphene with fluoropolymer and laser irradiation. Nano Lett. 12, 2374–2378 (2012). 10.1021/nl300346j

[24]

Highly Efficient and Reversible Covalent Patterning of Graphene: 2D‐Management of Chemical Information

Tao Wei, Malte Kohring, Shangfeng Yang et al.

Angewandte Chemie International Edition 2020 10.1002/anie.201914088

[25]

Bao, L. P. et al. Spatially resolved bottom-side fluorination of graphene by 2D-substrate patterning. Angew. Chem. Int. Ed. 59, 6766–6771 (2020). 10.1002/ange.202002508

[26]

Vecera, P. et al. Solvent-driven electron trapping and mass transport in reduced graphites to access perfect graphene. Nat. Commun. 7, 12411–12418 (2016). 10.1038/ncomms12411

[27]

Schäfer, R. A. et al. Substrate-modulated reductive graphene functionalization. Angew. Chem. Int. Ed. 55, 14858–14862 (2016). 10.1002/anie.201607427

[28]

Wang, Q. H. et al. Understanding and controlling the substrate effect on graphene electron-transfer chemistry via reactivity imprint lithography. Nat. Chem. 4, 724–732 (2012). 10.1038/nchem.1421

[29]

Amsharov, K. et al. Fractal-seaweeds type functionalization of graphene. Carbon 158, 435–448 (2020). 10.1016/j.carbon.2019.11.008

[30]

He, P. L. et al. Capillary electrophoresis of covalently functionalized single-chirality carbon nanotubes. Electrophoresis 38, 1669–1677 (2017). 10.1002/elps.201600570

[31]

Peng, Z. W. et al. Graphene as a functional layer for semiconducting carbon nanotube transistor sensors. Carbon 125, 49–55 (2017). 10.1016/j.carbon.2017.09.031

[32]

Mazza, A. R. Atomic deuteration of epitaxial many-layer graphene on 4H-SiC (0001−). J. Vac. Sci. Technol. B 37, 0418041–0418046 (2019). 10.1116/1.5095961

[33]

Schäfer, R. A. et al. On the way to graphane—pronounced fluorescence of polyhydrogenated graphene. Angew. Chem. Int. Ed. 52, 754–757 (2013). 10.1002/anie.201206799

[34]

Li, B. et al. Photochemical chlorination of graphene. ACS Nano 5, 5957–5961 (2011). 10.1021/nn201731t

[35]

Wu, J. et al. Controlled chlorine plasma reaction for noninvasive graphene doping. J. Am. Chem. Soc. 133, 19668–19671 (2011). 10.1021/ja2091068

[36]

Zhang, X. et al. Impact of chlorine functionalization high-mobility chemical vapor deposition grown graphene. ACS Nano 7, 7262–7270 (2013). 10.1021/nn4026756

[37]

Dong, X. C. et al. Doping single-layer graphene with aromatic molecules. Small 5, 1422–1426 (2009). 10.1002/smll.200801711

[38]

Das, B., Voggu, R., Rout, C. S. & Rao, C. N. R. Changes in the electronic structure and properties of graphene induced by molecular charge-transfer. Chem. Commun. 5155–5157 (2008). 10.1039/b808955h

[39]

Cançado, L. G. et al. Quantifying defects in graphene via Raman spectroscopy at different excitation energies. Nano Lett. 11, 3190–3196 (2011). 10.1021/nl201432g

[40]

Paris, A. et al. Kinetic isotope effect in the hydrogenation and deuteration of graphene. Adv. Funct. Mater. 23, 1628–1635 (2013). 10.1002/adfm.201202355

[41]

Sinitskii, A. et al. Kinetics of diazonium functionalization of chemically converted graphene nanoribbons. ACS Nano 4, 1949–1954 (2010). 10.1021/nn901899j

[42]

Ijäs, M. & Harju, A. Fracturing graphene by chlorination: a theoretical viewpoint. Phys. Rev. B 85, 035440–035450 (2012). 10.1103/physrevb.85.035440

[43]

Liu, X. Y., Zhang, J. M. & Xu, K. W. Chlorine molecule adsorbed on graphene and doped graphene: a first-principle study. Phys. B 436, 54–58 (2014). 10.1016/j.physb.2013.11.042

[44]

Pykal, M., Jurečka, P., Karlický, F. & Otyepka, M. Modelling of graphene functionalization. Phys. Chem. Chem. Phys. 18, 6351–6372 (2016). 10.1039/c5cp03599f

[45]

Syrgiannis, Z. et al. Reductive retrofunctionalization of single-walled carbon nanotubes. Angew. Chem. Int. Ed. 49, 3322–3325 (2010). 10.1002/anie.200906819

[46]

Knirsch, K. C. et al. Mono- and ditopic bisfunctionalization of graphene. Angew. Chem. Int. Ed. 55, 5861–5864 (2016). 10.1002/anie.201511807

[47]

Kessinger, R. et al. Preparation of enantiomerically pure C76 with a general electrochemical method for the removal of di(alkoxycarbonyl)methano bridges from methanofullerenes: the retro-Bingel reaction. Angew. Chem. Int. Ed. 37, 1919–1922 (1998). 10.1002/(sici)1521-3773(19980803)37:13/14<1919::aid-anie1919>3.0.co;2-x

[48]

Moonen, N.N.P. et al. The chemical retro-Bingel reaction: selective removal of bis(alkoxycarbonyl)methano addends from C60 and C70 with amalgamated magnesium.Chem. Commun. 36, 335–336 (2000). 10.1039/a909704j

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Citations

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References

Details

Published: Jan 22, 2021
Vol/Issue: 12(1)
License: View

Authors

T

Tao Wei

Department of Genetics, Harvard Medical School, and Department of Molecular Biology, Massachusetts General Hospital, Boston, MA 02114

M

Malte Kohring

Department of Applied Physics & Institute of Condensed Matter Physics Friedrich-Alexander University of Erlangen-Nürnberg Staudtstrsse 7/ Bau A3 91058 Erlangen Germany

H

Heiko B. Weber

Department of Applied Physics & Institute of Condensed Matter Physics Friedrich-Alexander University of Erlangen-Nürnberg Staudtstrsse 7/ Bau A3 91058 Erlangen Germany

F

Frank Hauke

Department of Chemistry and Pharmacy and Joint Institute of Advance Materials and Processes (ZMP) Friedrich‐Alexander University of Erlangen‐Nürnberg Nikolaus‐Fiebiger‐Strasse 10 91058 Erlangen Germany

A

Andreas Hirsch

Chair of Organic Chemistry II Friedrich-Alexander Universität Erlangen–Nürnberg Nikolaus-Fiebiger-Strasse 10 91058 Erlangen Germany

Funding

Deutsche Forschungsgemeinschaft Award: 182849149

Cite This Article

Tao Wei, Malte Kohring, Heiko B. Weber, et al. (2021). Molecular embroidering of graphene. Nature Communications, 12(1). https://doi.org/10.1038/s41467-020-20651-w

Molecular embroidering of graphene

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