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.
Your institute does not have access to this article
Subscribe to Nature+
Get immediate online access to the entire Nature family of 50+ journals
Subscribe to Journal
Get full journal access for 1 year
only $8.25 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
The data supporting the plots within this paper are available via Zenodo at https://doi.org/10.5281/zenodo.6655757.
Lv, R. et al. Ultrasensitive gas detection of large-area boron-doped graphene. Proc. Natl Acad. Sci. USA 112, 14527–14532 (2015).
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).
Chaban, V. V. & Prezhdo, O. V. Boron doping of graphene—pushing the limit. Nanoscale 8, 15521–15528 (2016).
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).
Niyogi, S. et al. Spectroscopy of covalently functionalized graphene. Nano Lett. 10, 4061–4066 (2010).
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).
Sarkar, S., Bekyarova, E. & Haddon, R. C. Covalent chemistry in graphene electronics. Mater. Today 15, 276–285 (2012).
Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).
Gabor, N. M. et al. Hot carrier–assisted intrinsic photoresponse in graphene. Science 334, 648–652 (2011).
Ju, L. et al. Photoinduced doping in heterostructures of graphene and boron nitride. Nat. Nanotechnol. 9, 348–352 (2014).
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).
Bediako, D. K. et al. Heterointerface effects in the electrointercalation of van der Waals heterostructures. Nature 558, 425–429 (2018).
Zhao, S. F. et al. Controlled electrochemical intercalation of graphene/h-BN van der Waals heterostructures. Nano Lett. 18, 460–466 (2017).
Efetov, D. K. & Kim, P. Controlling electron-phonon interactions in graphene at ultrahigh carrier densities. Phys. Rev. Lett. 105, 256805 (2010).
Ovchinnikov, D. et al. Disorder engineering and conductivity dome in ReS2 with electrolyte gating. Nat. Commun. 7, 12391 (2016).
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).
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).
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).
Sahin, H. & Ciraci, S. Chlorine adsorption on graphene: chlorographene. J. Phys. Chem. C 116, 24075–24083 (2012).
Robinson, J. T. et al. Properties of fluorinated graphene films. Nano Lett. 10, 3001–3005 (2010).
Elias, D. C. et al. Control of graphene’s properties by reversible hydrogenation: evidence for graphane. Science 323, 610–613 (2009).
Zhang, X. et al. Impact of chlorine functionalization on high-mobility chemical vapor deposition grown graphene. ACS Nano 7, 7262–7270 (2013).
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).
Copetti, G. et al. Reversibility of graphene photochlorination. J. Phys. Chem. C 122, 16333–16338 (2018).
Li, B. et al. Photochemical chlorination of graphene. ACS Nano 5, 5957–5961 (2011).
Zhang, X. et al. X-ray spectroscopic investigation of chlorinated graphene: surface structure and electronic effects. Adv. Funct. Mater. 25, 4163–4169 (2015).
Pham, V. P. et al. Low damage pre-doping on CVD graphene/Cu using a chlorine inductively coupled plasma. Carbon 95, 664–671 (2015).
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).
Hwang, E. & Sarma, S. D. Acoustic phonon scattering limited carrier mobility in two-dimensional extrinsic graphene. Phys. Rev. B 77, 115449 (2008).
Das, A. et al. Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. Nat. Nanotechnol. 3, 210–215 (2008).
Ferrari, A. C. Raman spectroscopy of graphene and graphite: disorder, electron–phonon coupling, doping and nonadiabatic effects. Solid State Commun. 143, 47–57 (2007).
Carey, V. P. Statistical Thermodynamics and Microscale Thermophysics (Cambridge Univ. Press, 1999).
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).
Bäuerle, D. W. Laser Processing and Chemistry (Springer, 2011).
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).
Stöhr, J. NEXAFS Spectroscopy (Springer Science & Business Media, 1992).
Grigoropoulos, C. P. Transport in Laser Microfabrication: Fundamentals and Applications (Cambridge Univ. Press, 2009).
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).
Xia, F. et al. Photocurrent imaging and efficient photon detection in a graphene transistor. Nano Lett. 9, 1039–1044 (2009).
Hwang, E., Rossi, E. & Sarma, S. D. Theory of thermopower in two-dimensional graphene. Phys. Rev. B 80, 235415 (2009).
De Sanctis, A. et al. Extraordinary linear dynamic range in laser-defined functionalized graphene photodetectors. Sci. Adv. 3, e1602617 (2017).
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).
Echtermeyer, T. J. et al. Photothermoelectric and photoelectric contributions to light detection in metal–graphene–metal photodetectors. Nano Lett. 14, 3733–3742 (2014).
Park, J., Ahn, Y. H. & Ruiz-Vargas, C. Imaging of photocurrent generation and collection in single-layer graphene. Nano Lett. 9, 1742–1746 (2009).
Kim, E. et al. Site selective doping of ultrathin metal dichalcogenides by laser-assisted reaction. Adv. Mater. 28, 341–346 (2016).
Seo, B. H., Youn, J. & Shim, M. Direct laser writing of air-stable p–n junctions in graphene. ACS Nano 8, 8831–8836 (2014).
Fairley, N. et al. Systematic and collaborative approach to problem solving using X-ray photoelectron spectroscopy. Appl. Surf. Sci. Adv. 5, 100112 2021).
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.
The authors declare no competing interests.
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.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
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 (2022). https://doi.org/10.1038/s41928-022-00801-2