Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

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


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.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type



Prices may be subject to local taxes which are calculated during checkout

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


  1. Lv, R. et al. Ultrasensitive gas detection of large-area boron-doped graphene. Proc. Natl Acad. Sci. USA 112, 14527–14532 (2015).

    Article  Google Scholar 

  2. Wang, H., Maiyalagan, T. & Wang, X. Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catal. 2, 781–794 (2012).

    Article  Google Scholar 

  3. Chaban, V. V. & Prezhdo, O. V. Boron doping of graphene—pushing the limit. Nanoscale 8, 15521–15528 (2016).

    Article  Google Scholar 

  4. Zhang, K. et al. Tuning the electronic and photonic properties of monolayer MoS2 via in situ rhenium substitutional doping. Adv. Funct. Mater. 28, 1706950 (2018).

    Article  Google Scholar 

  5. Niyogi, S. et al. Spectroscopy of covalently functionalized graphene. Nano Lett. 10, 4061–4066 (2010).

    Article  Google Scholar 

  6. Makarova, M., Okawa, Y. & Aono, M. Selective adsorption of thiol molecules at sulfur vacancies on MoS2 (0001), followed by vacancy repair via S–C dissociation. J. Phys. Chem. C 116, 22411–22416 (2012).

    Article  Google Scholar 

  7. Sarkar, S., Bekyarova, E. & Haddon, R. C. Covalent chemistry in graphene electronics. Mater. Today 15, 276–285 (2012).

    Article  Google Scholar 

  8. Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).

    Article  Google Scholar 

  9. Gabor, N. M. et al. Hot carrier–assisted intrinsic photoresponse in graphene. Science 334, 648–652 (2011).

    Article  Google Scholar 

  10. Ju, L. et al. Photoinduced doping in heterostructures of graphene and boron nitride. Nat. Nanotechnol. 9, 348–352 (2014).

    Article  Google Scholar 

  11. Shi, W. et al. Reversible writing of high-mobility and high-carrier-density doping patterns in two-dimensional van der Waals heterostructures. Nat. Electron. 3, 99–105 (2020).

    Article  Google Scholar 

  12. Bediako, D. K. et al. Heterointerface effects in the electrointercalation of van der Waals heterostructures. Nature 558, 425–429 (2018).

    Article  Google Scholar 

  13. Zhao, S. F. et al. Controlled electrochemical intercalation of graphene/h-BN van der Waals heterostructures. Nano Lett. 18, 460–466 (2017).

    Article  Google Scholar 

  14. Efetov, D. K. & Kim, P. Controlling electron-phonon interactions in graphene at ultrahigh carrier densities. Phys. Rev. Lett. 105, 256805 (2010).

    Article  Google Scholar 

  15. Ovchinnikov, D. et al. Disorder engineering and conductivity dome in ReS2 with electrolyte gating. Nat. Commun. 7, 12391 (2016).

    Article  Google Scholar 

  16. Georgakilas, V. et al. Noncovalent functionalization of graphene and graphene oxide for energy materials, biosensing, catalytic, and biomedical applications. Chem. Rev. 116, 5464–5519 (2016).

    Article  Google Scholar 

  17. Baltazar, J. et al. Photochemical doping and tuning of the work function and Dirac point in graphene using photoacid and photobase generators. Adv. Funct. Mater. 24, 5147–5156 (2014).

    Article  Google Scholar 

  18. Yang, M., Zhou, L., Wang, J., Liu, Z. & Liu, Z. Evolutionary chlorination of graphene: from charge-transfer complex to covalent bonding and nonbonding. J. Phys. Chem. C 116, 844–850 (2012).

    Article  Google Scholar 

  19. Sahin, H. & Ciraci, S. Chlorine adsorption on graphene: chlorographene. J. Phys. Chem. C 116, 24075–24083 (2012).

    Article  Google Scholar 

  20. Robinson, J. T. et al. Properties of fluorinated graphene films. Nano Lett. 10, 3001–3005 (2010).

    Article  Google Scholar 

  21. Elias, D. C. et al. Control of graphene’s properties by reversible hydrogenation: evidence for graphane. Science 323, 610–613 (2009).

    Article  Google Scholar 

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

    Article  Google Scholar 

  23. Pham, V. P., Kim, K. N., Jeon, M. H., Kim, K. S. & Yeom, G. Y. Cyclic chlorine trap-doping for transparent, conductive, thermally stable and damage-free graphene. Nanoscale 6, 15301–15308 (2014).

    Article  Google Scholar 

  24. Copetti, G. et al. Reversibility of graphene photochlorination. J. Phys. Chem. C 122, 16333–16338 (2018).

    Article  Google Scholar 

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

    Article  Google Scholar 

  26. Zhang, X. et al. X-ray spectroscopic investigation of chlorinated graphene: surface structure and electronic effects. Adv. Funct. Mater. 25, 4163–4169 (2015).

    Article  Google Scholar 

  27. Pham, V. P. et al. Low damage pre-doping on CVD graphene/Cu using a chlorine inductively coupled plasma. Carbon 95, 664–671 (2015).

    Article  Google Scholar 

  28. Ye, J. et al. Accessing the transport properties of graphene and its multilayers at high carrier density. Proc. Natl Acad. Sci. USA 108, 13002–13006 (2011).

    Article  Google Scholar 

  29. Hwang, E. & Sarma, S. D. Acoustic phonon scattering limited carrier mobility in two-dimensional extrinsic graphene. Phys. Rev. B 77, 115449 (2008).

    Article  Google Scholar 

  30. Das, A. et al. Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. Nat. Nanotechnol. 3, 210–215 (2008).

    Article  Google Scholar 

  31. Ferrari, A. C. Raman spectroscopy of graphene and graphite: disorder, electron–phonon coupling, doping and nonadiabatic effects. Solid State Commun. 143, 47–57 (2007).

    Article  Google Scholar 

  32. Carey, V. P. Statistical Thermodynamics and Microscale Thermophysics (Cambridge Univ. Press, 1999).

  33. Heaven, M. C. & Clyne, M. A. A. Interpretation of the spontaneous predissociation of Cl2[B3Π(0+u)]. J. Chem. Soc., Faraday Trans. 2 78, 1339–1344 (1982).

    Article  Google Scholar 

  34. Bäuerle, D. W. Laser Processing and Chemistry (Springer, 2011).

  35. Moeini, B. et al. Definition of a new (Doniach‐Sunjic‐Shirley) peak shape for fitting asymmetric signals applied to reduced graphene oxide/graphene oxide XPS spectra. Surf. Interface Anal. 54, 67–77 (2021).

  36. Stöhr, J. NEXAFS Spectroscopy (Springer Science & Business Media, 1992).

  37. Grigoropoulos, C. P. Transport in Laser Microfabrication: Fundamentals and Applications (Cambridge Univ. Press, 2009).

  38. Mueller, T., Xia, F., Freitag, M., Tsang, J. & Avouris, P. Role of contacts in graphene transistors: a scanning photocurrent study. Phys. Rev. B 79, 245430 (2009).

    Article  Google Scholar 

  39. Xia, F. et al. Photocurrent imaging and efficient photon detection in a graphene transistor. Nano Lett. 9, 1039–1044 (2009).

    Article  Google Scholar 

  40. Hwang, E., Rossi, E. & Sarma, S. D. Theory of thermopower in two-dimensional graphene. Phys. Rev. B 80, 235415 (2009).

    Article  Google Scholar 

  41. De Sanctis, A. et al. Extraordinary linear dynamic range in laser-defined functionalized graphene photodetectors. Sci. Adv. 3, e1602617 (2017).

    Article  Google Scholar 

  42. Song, J. C., Rudner, M. S., Marcus, C. M. & Levitov, L. S. Hot carrier transport and photocurrent response in graphene. Nano Lett. 11, 4688–4692 (2011).

    Article  Google Scholar 

  43. Echtermeyer, T. J. et al. Photothermoelectric and photoelectric contributions to light detection in metal–graphene–metal photodetectors. Nano Lett. 14, 3733–3742 (2014).

    Article  Google Scholar 

  44. Park, J., Ahn, Y. H. & Ruiz-Vargas, C. Imaging of photocurrent generation and collection in single-layer graphene. Nano Lett. 9, 1742–1746 (2009).

    Article  Google Scholar 

  45. Kim, E. et al. Site selective doping of ultrathin metal dichalcogenides by laser-assisted reaction. Adv. Mater. 28, 341–346 (2016).

    Article  Google Scholar 

  46. Seo, B. H., Youn, J. & Shim, M. Direct laser writing of air-stable p–n junctions in graphene. ACS Nano 8, 8831–8836 (2014).

    Article  Google Scholar 

  47. Fairley, N. et al. Systematic and collaborative approach to problem solving using X-ray photoelectron spectroscopy. Appl. Surf. Sci. Adv. 5, 100112 2021).

    Article  Google Scholar 

Download references


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.

Author information

Authors and Affiliations



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.

Corresponding author

Correspondence to Costas P. Grigoropoulos.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

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

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

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

Supplementary Data

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

Rights and permissions

Reprints and Permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Rho, Y., Lee, K., Wang, L. et al. A laser-assisted chlorination process for reversible writing of doping patterns in graphene. Nat Electron 5, 505–510 (2022).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing