Abstract
Novel two-dimensional semiconductor crystals can exhibit diverse physical properties beyond their inherent semiconducting attributes, making their pursuit paramount. Memristive properties, as exemplars of these attributes, are predominantly manifested in wide-bandgap materials. However, simultaneously harnessing semiconductor properties alongside memristive characteristics to produce memtransistors is challenging. Herein we prepared a class of semiconducting III–V-derived van der Waals crystals, specifically the HxA1–xBX form, exhibiting memristive characteristics. To identify candidates for the material synthesis, we conducted a systematic high-throughput screening, leading us to 44 prospective III–V candidates; of these, we successfully synthesized ten, including nitrides, phosphides, arsenides and antimonides. These materials exhibited intriguing characteristics such as electrochemical polarization and memristive phenomena while retaining their semiconductive attributes. We demonstrated the gate-tunable synaptic and logic functions within single-gate memtransistors, capitalizing on the synergistic interplay between the semiconducting and memristive properties of our two-dimensional crystals. Our approach guides the discovery of van der Waals materials with unique properties from unconventional crystal symmetries.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on SpringerLink
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
The data that support the other findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper. Other relevant information in this study is included in the Supplementary Information.
References
Xiao, X., Wang, H., Urbankowski, P. & Gogotsi, Y. Topochemical synthesis of 2D materials. Chem. Soc. Rev. 47, 8744–8765 (2018).
Uppuluri, R., Gupta, A. S., Rosas, A. S. & Mallouk, T. E. Soft chemistry of ion-exchangeable layered metal oxides. Chem. Soc. Rev. 47, 2401–2430 (2018).
Xia, Q. & Yang, J. J. Memristive crossbar arrays for brain-inspired computing. Nat. Mater. 18, 309–323 (2019).
Yan, X., Qian, J. H., Sangwan, V. K. & Hersam, M. C. Progress and challenges for memtransistors in neuromorphic circuits and systems. Adv. Mater. 34, 2108025 (2022).
Chen, S. et al. Wafer-scale integration of two-dimensional materials in high-density memristive crossbar arrays for artificial neural networks. Nat. Electron. 3, 638–645 (2020).
Pi, S. et al. Memristor crossbar arrays with 6-nm half-pitch and 2-nm critical dimension. Nat. Nanotechnol. 14, 35–39 (2019).
Li, M. et al. Imperfection-enabled memristive switching in van der Waals materials. Nat. Electron. 6, 491–505 (2023).
Geselbracht, M. J., Richardson, T. J. & Stacy, A. M. Superconductivity in the layered compound LixNbO2. Nature 345, 324–326 (1990).
Peng, J. et al. Stoichiometric two-dimensional non-van der Waals AgCrS2 with superionic behaviour at room temperature. Nat. Chem. 13, 1235–1240 (2021).
Hantanasirisakul, K. & Gogotsi, Y. Electronic and optical properties of 2D transition metal carbides and nitrides (MXenes). Adv. Mater. 30, 1804779 (2018).
Belsky, A., Hellenbrandt, M., Karen, V. L. & Luksch, P. New developments in the Inorganic Crystal Structure Database (ICSD): accessibility in support of materials research and design. Acta Crystallogr. B Struct. Sci. 58, 364–369 (2002).
Jain, A. et al. Commentary: the Materials Project: a materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013).
Ong, S. P. et al. Python Materials Genomics (pymatgen): a robust, open-source python library for materials analysis. Comput. Mater. Sci. 68, 314–319 (2013).
Hautier, G., Fischer, C., Ehrlacher, V., Jain, A. & Ceder, G. Data mined ionic substitutions for the discovery of new compounds. Inorg. Chem. 50, 656–663 (2011).
Rohrer, G. S. Structure and Bonding in Crystalline Materials (Cambridege Univ. Press, 2001).
Kang, K., Meng, Y. S., Bréger, J., Grey, C. P. & Ceder, G. Electrodes with high power and high capacity for rechargeable lithium batteries. Science 311, 977–980 (2006).
Schroeder, U., Park, M. H., Mikolajick, T. & Hwang, C. S. The fundamentals and applications of ferroelectric HfO2. Nat. Rev. Mater. 7, 653–669 (2022).
Balke, N. et al. Nanoscale mapping of ion diffusion in a lithium-ion battery cathode. Nat. Nanotechnol. 5, 749–754 (2010).
Lide, D. R. (ed.) CRC Handbook of Chemistry and Physics 77th edn (CRC Press, 1996).
Streetman, B. G. Solid State Electronic Devices 3rd edn (Prentice Hall, 1990).
Liu, K. et al. An optoelectronic synapse based on α-In2Se3 with controllable temporal dynamics for multimode and multiscale reservoir computing. Nat. Electron. 5, 761–773 (2022).
Xue, F. et al. Gate-tunable and multidirection-switchable memristive phenomena in a van der Waals ferroelectric. Adv. Mater. 31, 1901300 (2019).
Kwon, G. et al. Interaction- and defect-free van der Waals contacts between metals and two-dimensional semiconductors. Nat. Electron. 5, 241–247 (2022).
Bessonov, A. A. et al. Layered memristive and memcapacitive switches for printable electronics. Nat. Mater. 14, 199–204 (2015).
Sangwan, V. K. et al. Multi-terminal memtransistors from polycrystalline monolayer molybdenum disulfide. Nature 554, 500–504 (2018).
Zhu, X., Li, D., Liang, X. & Lu, W. D. Ionic modulation and ionic coupling effects in MoS2 devices for neuromorphic computing. Nat. Mater. 18, 141–148 (2019).
Li, Y. et al. Anomalous resistive switching in memristors based on two-dimensional palladium diselenide using heterophase grain boundaries. Nat. Electron. 4, 348–356 (2021).
Gerstner, W., Kistler, W. M., Naud, R. & Paninski, L. Neuronal Dynamics: from Single Neurons to Networks and Models of Cognition (Cambridge Univ. Press, 2014).
Khan, A. I., Keshavarzi, A. & Datta, S. The future of ferroelectric field-effect transistor technology. Nat. Electron. 3, 588–597 (2020).
Si, M. et al. A ferroelectric semiconductor field-effect transistor. Nat. Electron. 2, 580–586 (2019).
Bae, J. et al. Kinetic 2D crystals via topochemical approach. Adv. Mater. 33, 2006043 (2021).
Mao, L., Stoumpos, C. C. & Kanatzidis, M. G. Two-dimensional hybrid halide perovskites: principles and promises. J. Am. Chem. Soc. 141, 1171–1190 (2019).
Pauling, L. The principles determining the structure of complex ionic crystals. J. Am. Chem. Soc. 51, 1010–1026 (1929).
Sun, W. et al. Thermodynamic routes to novel metastable nitrogen-rich nitrides. Chem. Mater. 29, 6936–6946 (2017).
Ganose, A. M. & Jain, A. Robocrystallographer: automated crystal structure text descriptions and analysis. MRS Commun. 9, 874–881 (2019).
Acknowledgements
This work was supported by the National Research Foundation (NRF) of Korea through a grant funded by the Korean government (2018M3D1A1058793) and a grant from the Institute for Basic Science (IBS-R026-D1). We are grateful to the UK Materials and Molecular Modelling Hub for providing computational resources, which were partially funded by the Engineering and Physical Sciences Research Council (EPSRC; EP/T022213/1).
Author information
Authors and Affiliations
Contributions
J.B., J.W., Taeyoung Kim, S.C., Hyesoo Kim, J.C., Cheolmin Park, J.-Y.K. and W.S. designed the experiments. J.B., J.W., Taeyoung Kim, S.C., Hyesoo Kim, E.L., S.J., Minjung Kim, S. Kim, Y.C., B.K., Hong Choi and J.H. synthesized the materials. J.B., Minjung Kim, H.W.D., D.S., H. Kang, Taehoon Kim, N.N., H.M., Jeongmin Kim, Dohyun Kim, W.L. and Heonjin Choi developed the devices and performed the measurements. S.-H.V.O., G.L., H.L., H.-J.S., M.-C.J., K.J.C., M.J.H. and A.S. performed the first-principles calculations and analyses, while D.W.D. and A.W. developed the data-driven models. Chanho Park, K.L., S. Kang, Jungkil Kim, I.C., Hyunyong Choi, Dohun Kim, H.Y., Y.K., H.-G.P., Miso Kim and Cheolmin Park analysed the characteristics. J.B., J.W., S.C., H. Kim, E.L., B.-K.Y., Jaegyeom Kim, M.K.C., J.-H.B., S.P., H.B., J.-H.L., D.W.C., J.-Y.K. and W.S. performed the structural analysis. All authors wrote the manuscript and contributed to the overall scientific interpretation.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Materials thanks Gerbrand Ceder 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. 1–24, Tables 8 and 9, Discussions 1 and 2, Methods and references.
Supplementary Tables
Supplementary Tables 1–7.
Source data
Source Data Fig. 2
Fig. 2 source data.
Source Data Fig. 3
Fig. 3 source data.
Source Data Fig. 4
Fig. 4 source data.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Bae, J., Won, J., Kim, T. et al. Cation-eutaxy-enabled III–V-derived van der Waals crystals as memristive semiconductors. Nat. Mater. 23, 1402–1410 (2024). https://doi.org/10.1038/s41563-024-01986-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41563-024-01986-x
