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A laser-assisted chlorination process for reversible writing of doping patterns in graphene

Abstract

Chemical doping can be used to control the charge-carrier polarity and concentration in two-dimensional van der Waals materials. However, conventional methods based on substitutional doping or surface functionalization result in the degradation of electrical mobility due to structural disorder, and the maximum doping density is set by the solubility limit of dopants. Here we show that a reversible laser-assisted chlorination process can be used to create high doping concentrations (above 3 × 1013 cm−2) in graphene monolayers with minimal drops in mobility. The approach uses two lasers—with distinct photon energies and geometric configurations—that are designed for chlorination and subsequent chlorine removal, allowing highly doped patterns to be written and erased without damaging the graphene. To illustrate the capabilities of our approach, we use it to create rewritable photoactive junctions for graphene-based photodetectors.

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Fig. 1: Schematic of laser-assisted surface functionalization by chlorine and demonstration of a high doping concentration and high mobility.
Fig. 2: Non-invasive and saturable characteristics of the chlorination process.
Fig. 3: Reversible chlorine removal process by CW green laser.
Fig. 4: Demonstration of rewritable photoactive junction using chlorination and local chlorine removal processes.

Data availability

The data supporting the plots within this paper are available via Zenodo at https://doi.org/10.5281/zenodo.6655757.

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Acknowledgements

We thank S. Khan, T. Zhu (Department of Physics, UC Berkeley) and J. Park (Department of Mechanical Engineering, Kumoh National Institute of Technology) for useful discussions. Financial support awarded to the University of California, Berkeley, by the US National Science Foundation (grant nos. CMMI-1662475 and CMMI-2024391 (C.P.G.)) is gratefully acknowledged. This work was also partially supported by the Samsung Research Global Outreach (C.P.G). Device fabrication was supported by the Director, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, US Department of Energy, under contract number DE-AC02-05CH11231 (van der Waals heterostructures program (KCWF16)) (A.Z.). The chlorination experiments were conducted at the Laser-Assisted Chemical Vapor Deposition (LACVD) apparatus at UC Berkeley’s Marvell Nanofabrication Laboratory.

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Contributions

C.P.G., J.W., Y.R. and K.L. conceived the experiments and idea. C.P.G., Y.R. and L.W. contributed to the development of the laser chemical doping process. A.Z., Y.R., K.L. and C.K. contributed to the device fabrication. Y.R. and K.L. conducted all the device fabrication and measurements. Y.R., Y.C., P.C. and J.P. contributed to the sample preparation and characterization. Y.R., K.L., J.W. and C.P.G. wrote the manuscript, with inputs and comments from all the authors.

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Correspondence to Costas P. Grigoropoulos.

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Nature Electronics thanks Nathaniel Gabor, Cláudio Radtke and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–17, Notes 1–18 and Table 1.

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Raw data for Supplementary Figs. 1, 3–12, 14 and 17.

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Rho, Y., Lee, K., Wang, L. et al. A laser-assisted chlorination process for reversible writing of doping patterns in graphene. Nat Electron (2022). https://doi.org/10.1038/s41928-022-00801-2

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