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Programmable devices based on reversible solid-state doping of two-dimensional semiconductors with superionic silver iodide

Abstract

Two-dimensional (2D) semiconductors are attractive for electronic devices with atomically thin channels. However, controlling the electronic properties of the 2D materials by incorporating impurity dopants is inherently difficult due to the limited physical space in the atomically thin lattices. Here we show that a solid-state ionic doping approach can be used to tailor the carrier type in 2D semiconductors and create programmable devices. Our strategy exploits a superionic phase transition in silver iodide to induce switchable ionic doping. We create few-layer tungsten diselenide (WSe2) devices that can be reversibly transformed into transistors with reconfigurable carrier types and into diodes with switchable polarities by controllably poling the van der Waals integrated silver iodide above the superionic phase transition temperature. We also construct complementary logic gates by integrating and programming identical transistors, and show that the programmed functions can be erased by an external trigger (temperature or ultraviolet irradiation) to create the temporary and delible electronics that are desirable for electronic security.

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Fig. 1: Illustrations of the WSe2 FET integrated with the AgI microplate.
Fig. 2: Type-switchable WSe2 FETs programmed by AgI.
Fig. 3: Polarity-switchable WSe2 diodes and photodiodes programmed by AgI.
Fig. 4: Reconfigurable logic gates and delible electronic functions.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding authors upon reasonable request.

References

  1. 1.

    Lundstrom, M. Moore’s law forever? Science 299, 210–211 (2003).

    Google Scholar 

  2. 2.

    Yu, W. J., Kang, B. R., Lee, I. H., Min, Y. S. & Lee, Y. H. Majority carrier type conversion with floating gates in carbon nanotube transistors. Adv. Mater. 21, 4821–4824 (2009).

    Google Scholar 

  3. 3.

    Huang, X. et al. Sub-50-nm P-channel FinFET. IEEE Trans. Electron Dev. 48, 880–886 (2001).

    Google Scholar 

  4. 4.

    Liu, H., Neal, A. T. & Ye, P. D. Channel length scaling of MoS2 MOSFETs. ACS Nano 6, 8563–8569 (2012).

    Google Scholar 

  5. 5.

    Vu, Q. A. et al. A high‐on/off‐ratio floating‐gate memristor array on a flexible substrate via CVD‐grown large‐area 2D layer stacking. Adv. Mater. 29, 1703363 (2017).

    Google Scholar 

  6. 6.

    Lee, C., Wei, X., Kysar, J. W. & Hone, J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321, 385–388 (2008).

    Google Scholar 

  7. 7.

    Li, X. et al. Transfer of large-area graphene films for high-performance transparent conductive electrodes. Nano Lett. 9, 4359–4363 (2009).

    Google Scholar 

  8. 8.

    Novoselov, K., Mishchenko, A., Carvalho, A. & Neto, A. C. 2D materials and van der Waals heterostructures. Science 353, aac9439 (2016).

    Google Scholar 

  9. 9.

    Mayer, J. W. Ion implantation in semiconductors. In Proc. 1973 Int. Electron Devices Meeting 3–5 (IEEE, 1973).

  10. 10.

    Zhang, K. et al. Manganese doping of monolayer MoS2: the substrate is critical. Nano Lett. 15, 6586–6591 (2015).

    Google Scholar 

  11. 11.

    Chen, C.-H. et al. Hole mobility enhancement and p-doping in monolayer WSe2 by gold decoration. 2D Mater. 1, 034001 (2014).

    Google Scholar 

  12. 12.

    Bayraktaroglu, B. Transient Electronics Categorization Report AFRL-RY-WP-TR-2017-0169 (US Air Force Research Laboratory, 2017).

  13. 13.

    Zhou, W. et al. Intrinsic structural defects in monolayer molybdenum disulfide. Nano Lett. 13, 2615–2622 (2013).

    Google Scholar 

  14. 14.

    Wang, F. et al. Tunable GaTe-MoS2 van der Waals p–n junctions with novel optoelectronic performance. Nano Lett. 15, 7558–7566 (2015).

    Google Scholar 

  15. 15.

    Cheng, R. et al. Electroluminescence and photocurrent generation from atomically sharp WSe2/MoS2 heterojunction p–n diodes. Nano Lett. 14, 5590–5597 (2014).

    Google Scholar 

  16. 16.

    Deng, Y. et al. Black phosphorus–monolayer MoS2 van der Waals heterojunction p–n diode. ACS Nano 8, 8292–8299 (2014).

    Google Scholar 

  17. 17.

    Jeon, P. J. et al. Low power consumption complementary inverters with n-MoS2 and p-WSe2 dichalcogenide nanosheets on glass for logic and light-emitting diode circuits. ACS Appl. Mater. Interfaces 7, 22333–22340 (2015).

    Google Scholar 

  18. 18.

    Resta, G. V. et al. Doping-free complementary logic gates enabled by two-dimensional polarity-controllable transistors. ACS Nano 12, 7039–7047 (2018).

    Google Scholar 

  19. 19.

    Baugher, B. W., Churchill, H. O., Yang, Y. & Jarillo-Herrero, P. Optoelectronic devices based on electrically tunable p–n diodes in a monolayer dichalcogenide. Nat. Nanotechnol. 9, 262–267 (2014).

    Google Scholar 

  20. 20.

    Li, D. et al. Two-dimensional non-volatile programmable p–n junctions. Nat. Nanotechnol. 12, 901–906 (2017).

    Google Scholar 

  21. 21.

    Pospischil, A., Furchi, M. M. & Mueller, T. Solar-energy conversion and light emission in an atomic monolayer pn diode. Nat. Nanotechnol. 9, 257–261 (2014).

    Google Scholar 

  22. 22.

    Perera, M. M. et al. Improved carrier mobility in few-layer MoS2 field-effect transistors with ionic-liquid gating. ACS Nano 7, 4449–4458 (2013).

    Google Scholar 

  23. 23.

    Zhang, Y., Ye, J., Matsuhashi, Y. & Iwasa, Y. Ambipolar MoS2 thin flake transistors. Nano Lett. 12, 1136–1140 (2012).

    Google Scholar 

  24. 24.

    Zhang, Y., Ye, J., Yomogida, Y., Takenobu, T. & Iwasa, Y. Formation of a stable p–n junction in a liquid-gated MoS2 ambipolar transistor. Nano Lett. 13, 3023–3028 (2013).

    Google Scholar 

  25. 25.

    Allain, A. & Kis, A. Electron and hole mobilities in single-layer WSe2. ACS Nano 8, 7180–7185 (2014).

    Google Scholar 

  26. 26.

    Seabaugh, A. et al. Steep subthreshold swing tunnel FETs: GaN/InN/GaN and transition metal dichalcogenide channels. In Proc. 2015 IEEE International Electron Devices Meeting (IEDM) 35.6.1–35.6.4 (IEEE, 2015).

  27. 27.

    Zhang, Y., Oka, T., Suzuki, R., Ye, J. & Iwasa, Y. Electrically switchable chiral light-emitting transistor. Science 344, 725–728 (2014).

    Google Scholar 

  28. 28.

    Salamon, M. B. Physics of Superionic Conductors Vol. 15 (Springer Science and Business Media, 2013).

  29. 29.

    Luryi, S., Xu, J. & Zaslavsky, A. Future Trends in Microelectronics (Wiley, 1999).

  30. 30.

    Li, L. et al. BEOL compatible graphene/Cu with improved electromigration lifetime for future interconnects. In 2016 IEEE International Electron Devices Meeting (IEDM) 9.5.1–9.5.4 (IEEE, 2016).

  31. 31.

    Saito, T. et al. High reliability packaging technologies for 175° C continuous operation in IGBT module. In Proc. 2015 Int. Conference on Electronics Packaging and iMAPS All Asia Conference (ICEP-IAAC) 791–794 (IEEE, 2015).

  32. 32.

    Intel Core Processors Technical Resources (Intel, 2019); https://www.intel.com/content/www/us/en/products/docs/processors/core/core-technical-resources.html

  33. 33.

    Dutta, A., Sinha, T., Jena, P. & Adak, S. A.c. conductivity and dielectric relaxation in ionically conducting soda–lime–silicate glasses. J. Non-Cryst. Solids 354, 3952–3957 (2008).

    Google Scholar 

  34. 34.

    Sinitsyn, V., Lips, O., Privalov, A., Fujara, F. & Murin, I. Transport properties of LaF3 fast ionic conductor studied by field gradient NMR and impedance spectroscopy. J. Phys. Chem. Solids 64, 1201–1205 (2003).

    Google Scholar 

  35. 35.

    Sato, T. et al. Novel solid‐state polymer electrolyte of colloidal crystal decorated with ionic‐liquid polymer brush. Adv. Mater. 23, 4868–4872 (2011).

    Google Scholar 

  36. 36.

    Wu, C.-L. et al. Gate-induced metal–insulator transition in MoS2 by solid superionic conductor LaF3. Nano Lett. 18, 2387–2392 (2018).

    Google Scholar 

  37. 37.

    Agrawal, R. & Gupta, R. Superionic solid: composite electrolyte phase—an overview. J. Mater. Sci. 34, 1131–1162 (1999).

    Google Scholar 

  38. 38.

    Chuang, H.-J. et al. High mobility WSe2 p- and n-type field-effect transistors contacted by highly doped graphene for low-resistance contacts. Nano Lett. 14, 3594–3601 (2014).

    Google Scholar 

  39. 39.

    Liu, Y. et al. Toward barrier free contact to molybdenum disulfide using graphene electrodes. Nano Lett. 15, 3030–3034 (2015).

    Google Scholar 

  40. 40.

    Cheng, R. et al. High-frequency self-aligned graphene transistors with transferred gate stacks. Proc. Natl Acad. Sci. USA 109, 11588–11592 (2012).

    Google Scholar 

  41. 41.

    Cha, J.-H. & Jung, D.-Y. Air-stable transparent silver iodide–copper iodide heterojunction diode. ACS Appl. Mater. Interfaces 9, 43807–43813 (2017).

    Google Scholar 

  42. 42.

    Wang, J. I.-J. et al. Electronic transport of encapsulated graphene and WSe2 devices fabricated by pick-up of prepatterned hBN. Nano Lett. 15, 1898–1903 (2015).

    Google Scholar 

  43. 43.

    Dean, C. R. et al. Boron nitride substrates for high-quality graphene electronics. Nat. Nanotechnol. 5, 722–726 (2010).

    Google Scholar 

  44. 44.

    Liu, Y. et al. Approaching the Schottky-Mott limit in van der Waals metal-semiconductor junctions. Nature 557, 696–700 (2018).

    Google Scholar 

  45. 45.

    Kharkats, Y. I. Fast ion transport in solids induced by an electric field. Solid State Ionics 2, 301–308 (1981).

    Google Scholar 

  46. 46.

    Shockley, W. Electrons and Holes in Semiconductors: with Applications to Transistor Electronics (van Nostrand, 1950).

  47. 47.

    Sze, S. M. & Ng, K. K. Physics of Semiconductor Devices (Wiley, 2006).

  48. 48.

    Reynolds, S., Hume, W. M., Vonnegut, B. & Schaefer, V. J. Effect of sunlight on the action of silver iodide particles as sublimation nuclei. Bull. Am. Meteorol. Soc. 32, 47–47 (1951).

    Google Scholar 

  49. 49.

    Debye, P. & Huckel, E. Phys. Z. 24, 185–305 (1923).

    Google Scholar 

  50. 50.

    Stegmaier, S., Voss, J., Reuter, K. & Luntz, A. C. Li+ defects in a solid-state Li ion battery: theoretical insights with a Li3OCl electrolyte. Chem. Mater. 29, 4330–4340 (2017).

    Google Scholar 

  51. 51.

    Kvist, A. & Tärneberg, R. Self-diffusion of silver ions in the cubic high temperature modification of silver iodide. Z. Naturforsch. A 25, 257–259 (1970).

    Google Scholar 

  52. 52.

    Samsung Completes Development of 5-nm EUV Process Technology (Anandtech, 2019); https://www.anandtech.com/show/14231/samsung-completes-development-of-5-nm-euv-process-technology

  53. 53.

    Fuller, E. J. et al. Parallel programming of an ionic floating-gate memory array for scalable neuromorphic computing. Science 364, 570–574 (2019).

    Google Scholar 

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Acknowledgements

X.D. acknowledges support from the Office of Naval Research through award no. N00014-18-1-2707. Y.H. acknowledges financial support from the Office of Naval Research through award no. N00014-18-1-2491. B.D. acknowledges support from the Office of Naval Research through award no. N00014-16-1-2164. I.S. acknowledges support from the International Scientific Partnership Program at King Saud University (ISPP-148). Y.Z. acknowledges support from the National Key Research and Development Program of China through grant no. 2018YFA0703503. We acknowledge the Electron Imaging Centre at UCLA for TEM technical support and the Nanoelectronics Research Facility at UCLA for device fabrication technical support. We thank H.-C. Cheng, Y.-C. Huang, H. Wu, C. Wang, C. Choi, Z. Zhao, Z. Huang, G. Zhong, P. Wang and J.-W. Lee for their help in the laboratory.

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X.D. and Y.H. designed and supervised the research. S.-J.L. conducted most of the experiments and analysed the data. J.H. conducted the XRD and TEM experiments, and C.S.C. and B.D. conducted the AgI ionic conductivity measurements. Z.L., P.C., Y.L., J.G., C.J., Y.W., L.W., Q.L., I.S., X.D.D. and Y.Z. contributed materials, material characterizations, device fabrications or data analysis. X.D. and S.-J.L. wrote the manuscript with input from all co-authors. All authors reviewed and commented on the manuscript.

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Correspondence to Yu Huang or Xiangfeng Duan.

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Supplementary Notes 1 and 2, Figs. 1–14 and Tables 1 and 2.

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Lee, SJ., Lin, Z., Huang, J. et al. Programmable devices based on reversible solid-state doping of two-dimensional semiconductors with superionic silver iodide. Nat Electron 3, 630–637 (2020). https://doi.org/10.1038/s41928-020-00472-x

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