A key feature of two-dimensional materials is that the sign and concentration of their carriers can be externally controlled with techniques such as electrostatic gating. However, conventional electrostatic gating has limitations, including a maximum carrier density set by the dielectric breakdown, and ionic liquid gating and direct chemical doping also suffer from drawbacks. Here, we show that an electron-beam-induced doping technique can be used to reversibly write high-resolution doping patterns in hexagonal boron nitride-encapsulated graphene and molybdenum disulfide (MoS2) van der Waals heterostructures. The doped MoS2 device exhibits an order of magnitude decrease of subthreshold swing compared with the device before doping, whereas the doped graphene devices demonstrate a previously inaccessible regime of high carrier concentration and high mobility, even at room temperature. We also show that the approach can be used to write high-quality p–n junctions and nanoscale doping patterns, illustrating that the technique can create nanoscale circuitry in van der Waals heterostructures.
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.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.
Hu, C. Modern Semiconductor Devices for Integrated Circuits (Pearson, 2010).
Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).
Lui, C. H., Li, Z., Mak, K. F., Cappelluti, E. & Heinz, T. F. Observation of an electrically tunable band gap in trilayer graphene. Nat. Phys. 7, 944–947 (2011).
Williams, J. R., DiCarlo, L. & Marcus, C. M. Quantum Hall effect in a graphene p–n junction. Science 317, 638–641 (2007).
Özyilmaz, B. et al. Electronic transport and quantum Hall effect in bipolar graphene p–n–p junctions. Phys. Rev. Lett. 99, 2–5 (2007).
Huard, B. et al. Transport measurements across a tunable potential barrier in graphene. Phys. Rev. Lett. 98, 8–11 (2007).
Liu, G., Velasco, J., Bao, W. & Lau, C. N. Fabrication of graphene p–n–p junctions with contactless top gates. Appl. Phys. Lett. 92, 1–4 (2008).
Dubey, S. et al. Tunable superlattice in graphene to control the number of Dirac points. Nano Lett. 13, 3990–3995 (2013).
Efetov, D. K. & Kim, P. Controlling electron–phonon interactions in graphene at ultrahigh carrier densities. Phys. Rev. Lett. 105, 2–5 (2010).
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).
Shi, W. et al. Superconductivity series in transition metal dichalcogenides by ionic gating. Sci. Rep. 5, 12534 (2015).
Zhao, S. Y. F. et al. Controlled electrochemical intercalation of graphene/h-BN van der Waals heterostructures. Nano Lett. 18, 460–466 (2018).
Xia, Y., Xie, W., Ruden, P. P. & Frisbie, C. D. Carrier localization on surfaces of organic semiconductors gated with electrolytes. Phys. Rev. Lett. 105, 36802 (2010).
Ovchinnikov, D. et al. Disorder engineering and conductivity dome in ReS2 with electrolyte gating. Nat. Commun. 7, 12391 (2016).
Lohmann, T., Von Klitzing, K. & Smet, J. H. Four-terminal magneto-transport in graphene p–n junctions created by spatially selective doping. Nano Lett. 9, 1973–1979 (2009).
Ojeda-Aristizabal, C. et al. Molecular arrangement and charge transfer in C60/graphene heterostructures. ACS Nano 11, 4686–4693 (2017).
Ju, L. et al. Photoinduced doping in heterostructures of graphene and boron nitride. Nat. Nanotechnol. 9, 348–352 (2014).
Velasco, J. et al. Nanoscale control of rewriteable doping patterns in pristine graphene/boron nitride heterostructures. Nano Lett. 16, 1620–1625 (2016).
Wong, D. et al. Characterization and manipulation of individual defects in insulating hexagonal boron nitride using scanning tunnelling microscopy. Nat. Nanotechnol. 10, 949–953 (2015).
Zhou, Y. et al. Programmable graphene doping via electron beam irradiation. Nanoscale 9, 8657–8664 (2017).
Childres, I. et al. Effect of electron-beam irradiation on graphene field effect devices. Appl. Phys. Lett. 97, 173109 (2010).
Yu, X., Shen, Y., Liu, T., Wu, T. & Jie Wang, Q. Photocurrent generation in lateral graphene p–n junction created by electron-beam irradiation. Sci. Rep. 5, 12014 (2015).
Iqbal, M. Z., Anwar, N., Siddique, S., Iqbal, M. W. & Hussain, T. Formation of p–n-junction with stable n-doping in graphene field effect transistors using e-beam irradiation. Opt. Mater. 69, 254–258 (2017).
Stará, V., Procházka, P., Mareček, D., Šikola, T. & Čechal, J. Ambipolar remote graphene doping by low-energy electron beam irradiation. Nanoscale 10, 17520–17524 (2018).
Teweldebrhan, D. & Balandin, A. A. Modification of graphene properties due to electron-beam irradiation. Appl. Phys. Lett. 94, 92–95 (2009).
Hwang, E. H. & Sarma, S. Das Acoustic phonon scattering limited carrier mobility in two-dimensional extrinsic graphene. Phys. Rev. Lett. 77, 1–6 (2008).
Katagiri, Y. et al. Gate-tunable atomically thin lateral MoS2 Schottky junction patterned by electron beam. Nano Lett. 16, 3788–3794 (2016).
Xie, X. et al. Designing artificial 2D crystals with site and size controlled quantum dots. Sci. Rep. 7, 9965 (2017).
Sule, N. & Knezevic, I. Phonon-limited electron mobility in graphene calculated using tight-binding Bloch waves. J. Appl. Phys. 112, 053702 (2012).
Wang, L. et al. One-dimensional electrical contact to a two-dimensional material. Science 342, 614–617 (2013).
Ausman, G. A. & McLean, F. B. Electron–hole pair creation energy in SiO2. Appl. Phys. Lett. 26, 173–175 (1975).
Curtis, O. L., Srour, J. R. & Chiu, K. Y. Hole and electron transport in SiO2 films. J. Appl. Phys. 45, 4506–4513 (1974).
We thank Y. Chen, W. Ruan, S. Zhao, and J. Jung for useful discussions. This work was supported in part by the Director, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, and Molecular Foundry of the US Department of Energy under contract no. DE-AC02-05-CH11231, primarily within the van der Waals Heterostructures Program (KCWF16), which provided for development of the concept and device fabrication, electron-beam doping and transport characterization, and within the sp2-Bonded Materials Program (KC2207), which provided for s-SNOM measurements, and by the National Science Foundation, under grant no.1542741, which provided for AFM topography and SdH measurements, and under grant no.1807233, which provided for EFM measurements.
The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Shi, W., Kahn, S., Jiang, L. 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). https://doi.org/10.1038/s41928-019-0351-x
Pressure tuned photoluminescence and band gap in two-dimensional layered g-C3N4: the effect of interlayer interactions
Nature Electronics (2020)
Nature Communications (2020)
Nano Research (2020)