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Title: Atomic-scale tuning of ultrathin memristors
Abstract

Continuous device downsizing and circuit complexity have motivated atomic-scale tuning of memristors. Herein, we report atomically tunable Pd/M1/M2/Al ultrathin (<2.5 nm M1/M2 bilayer oxide thickness) memristors using in vacuo atomic layer deposition by controlled insertion of MgO atomic layers into pristine Al2O3atomic layer stacks guided by theory predicted Fermi energy lowering leading to a higher high state resistance (HRS) and a reduction of oxygen vacancy formation energy. Excitingly, memristors with HRS and on/off ratio increasing exponentially with M1/M2 thickness in the range 1.2–2.4 nm have been obtained, illustrating tunneling mechanism and tunable on/off ratio in the range of 10–104. Further dynamic tunability of on/off ratio by electric field is possible by designing of the atomic M2 layer and M1/M2 interface. This result probes ways in the design of memristors with atomically tunable performance parameters.

 
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Award ID(s):
1809293 1909292
NSF-PAR ID:
10377043
Author(s) / Creator(s):
; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
Communications Physics
Volume:
5
Issue:
1
ISSN:
2399-3650
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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    Acknowledgment

    This work was partially supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.

    Figure 1

     

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    Acknowledgement

    This work was supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.

    References

    [1] Younget al.,IEEE Computational Intelligence Magazine,vol. 13, no. 3, pp. 55-75, 2018.

    [2] Hadsellet al.,Journal of Field Robotics,vol. 26, no. 2, pp. 120-144, 2009.

    [3] Najafabadiet al.,Journal of Big Data,vol. 2, no. 1, p. 1, 2015.

    [4] Zhaoet al.,Applied Physics Reviews,vol. 7, no. 1, 2020.

    [5] Zidanet al.,Nature Electronics,vol. 1, no. 1, pp. 22-29, 2018.

    [6] Wulfet al.,SIGARCH Comput. Archit. News,vol. 23, no. 1, pp. 20–24, 1995.

    [7] Wilkes,SIGARCH Comput. Archit. News,vol. 23, no. 4, pp. 4–6, 1995.

    [8] Ielminiet al.,Nature Electronics,vol. 1, no. 6, pp. 333-343, 2018.

    [9] Changet al.,Nano Letters,vol. 10, no. 4, pp. 1297-1301, 2010.

    [10] Qinet al., Physica Status Solidi (RRL) - Rapid Research Letters, pssr.202200075R1, In press, 2022.

     
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