skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Robust resistive memory devices using solution-processable metal-coordinated azo aromatics

Abstract

Non-volatile memories will play a decisive role in the next generation of digital technology. Flash memories are currently the key player in the field, yet they fail to meet the commercial demands of scalability and endurance. Resistive memory devices, and in particular memories based on low-cost, solution-processable and chemically tunable organic materials, are promising alternatives explored by the industry. However, to date, they have been lacking the performance and mechanistic understanding required for commercial translation. Here we report a resistive memory device based on a spin-coated active layer of a transition-metal complex, which shows high reproducibility (~350 devices), fast switching (≤30 ns), excellent endurance (~10 12 cycles), stability (>10 6 s) and scalability (down to ~60 nm 2). In situ Raman and ultraviolet–visible spectroscopy alongside spectroelectrochemistry and quantum chemical calculations demonstrate that the redox state of the ligands determines the switching states of the device whereas the counterions control the hysteresis. This insight may accelerate the technological deployment of organic resistive memories.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2];  [4];  [4]; ORCiD logo [3];  [1];  [4];  [1];  [1];  [4];  [5];  [6]; ORCiD logo [3];  [2]; ORCiD logo [7]
  1. National Univ. of Singapore (Singapore). NUSNNI-NanoCore and NUS Graduate School for Integrative Science and Engineering
  2. Yale Univ., New Haven, CT (United States). Dept. of Chemistry
  3. Indian Association for the Cultivation of Science (IACS), Kolkata (India). Dept. of Inorganic Chemistry
  4. National Univ. of Singapore (Singapore). NUSNNI-NanoCore
  5. National Univ. of Singapore (Singapore). Dept. of Chemistry and Centre for Advanced 2D Materials
  6. National Univ. of Singapore (Singapore). Centre for Advanced 2D Materials and Dept. of Physics
  7. National Univ. of Singapore (Singapore). NUSNNI-NanoCore, NUS Graduate School for Integrative Science and Engineering, Dept. of Physics, Dept. of Electrical and Computer Engineering and Materials Science and Engineering Dept.
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE
OSTI Identifier:
1489156
Resource Type:
Journal Article
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 16; Journal Issue: 12; Journal ID: ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing Group
Country of Publication:
United States
Language:
English

Citation Formats

Goswami, Sreetosh, Matula, Adam J., Rath, Santi P., Hedström, Svante, Saha, Surajit, Annamalai, Meenakshi, Sengupta, Debabrata, Patra, Abhijeet, Ghosh, Siddhartha, Jani, Hariom, Sarkar, Soumya, Motapothula, Mallikarjuna Rao, Nijhuis, Christian A., Martin, Jens, Goswami, Sreebrata, Batista, Victor S., and Venkatesan, T. Robust resistive memory devices using solution-processable metal-coordinated azo aromatics. United States: N. p., 2017. Web. doi:10.1038/NMAT5009.
Goswami, Sreetosh, Matula, Adam J., Rath, Santi P., Hedström, Svante, Saha, Surajit, Annamalai, Meenakshi, Sengupta, Debabrata, Patra, Abhijeet, Ghosh, Siddhartha, Jani, Hariom, Sarkar, Soumya, Motapothula, Mallikarjuna Rao, Nijhuis, Christian A., Martin, Jens, Goswami, Sreebrata, Batista, Victor S., & Venkatesan, T. Robust resistive memory devices using solution-processable metal-coordinated azo aromatics. United States. doi:10.1038/NMAT5009.
Goswami, Sreetosh, Matula, Adam J., Rath, Santi P., Hedström, Svante, Saha, Surajit, Annamalai, Meenakshi, Sengupta, Debabrata, Patra, Abhijeet, Ghosh, Siddhartha, Jani, Hariom, Sarkar, Soumya, Motapothula, Mallikarjuna Rao, Nijhuis, Christian A., Martin, Jens, Goswami, Sreebrata, Batista, Victor S., and Venkatesan, T. Mon . "Robust resistive memory devices using solution-processable metal-coordinated azo aromatics". United States. doi:10.1038/NMAT5009.
@article{osti_1489156,
title = {Robust resistive memory devices using solution-processable metal-coordinated azo aromatics},
author = {Goswami, Sreetosh and Matula, Adam J. and Rath, Santi P. and Hedström, Svante and Saha, Surajit and Annamalai, Meenakshi and Sengupta, Debabrata and Patra, Abhijeet and Ghosh, Siddhartha and Jani, Hariom and Sarkar, Soumya and Motapothula, Mallikarjuna Rao and Nijhuis, Christian A. and Martin, Jens and Goswami, Sreebrata and Batista, Victor S. and Venkatesan, T.},
abstractNote = {Non-volatile memories will play a decisive role in the next generation of digital technology. Flash memories are currently the key player in the field, yet they fail to meet the commercial demands of scalability and endurance. Resistive memory devices, and in particular memories based on low-cost, solution-processable and chemically tunable organic materials, are promising alternatives explored by the industry. However, to date, they have been lacking the performance and mechanistic understanding required for commercial translation. Here we report a resistive memory device based on a spin-coated active layer of a transition-metal complex, which shows high reproducibility (~350 devices), fast switching (≤30 ns), excellent endurance (~1012 cycles), stability (>106 s) and scalability (down to ~60 nm2). In situ Raman and ultraviolet–visible spectroscopy alongside spectroelectrochemistry and quantum chemical calculations demonstrate that the redox state of the ligands determines the switching states of the device whereas the counterions control the hysteresis. This insight may accelerate the technological deployment of organic resistive memories.},
doi = {10.1038/NMAT5009},
journal = {Nature Materials},
issn = {1476-1122},
number = 12,
volume = 16,
place = {United States},
year = {2017},
month = {10}
}

Works referenced in this record:

The missing memristor found
journal, May 2008

  • Strukov, Dmitri B.; Snider, Gregory S.; Stewart, Duncan R.
  • Nature, Vol. 453, Issue 7191
  • DOI: 10.1038/nature06932

Molecular-Scale Electronics: From Concept to Function
journal, March 2016


Recent advances on the chemistry of transition metal complexes of 2-(arylazo)pyridines and its arylamino derivatives
journal, January 2012

  • Samanta, Subhas; Ghosh, Pradip; Goswami, Sreebrata
  • Dalton Transactions, Vol. 41, Issue 8
  • DOI: 10.1039/c2dt10986g

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

The path to ubiquitous and low-cost organic electronic appliances on plastic
journal, April 2004


Molecules for Charge-Based Information Storage
journal, August 2011

  • Lindsey, Jonathan S.; Bocian, David F.
  • Accounts of Chemical Research, Vol. 44, Issue 8
  • DOI: 10.1021/ar200107x

Molecular Conductance Switch-On of Single Ruthenium Complex Molecules
journal, February 2008

  • Seo, Kyoungja; Konchenko, Alexander V.; Lee, Junghyun
  • Journal of the American Chemical Society, Vol. 130, Issue 8
  • DOI: 10.1021/ja077089u

Review on Non-Volatile Memory with High-k Dielectrics: Flash for Generation Beyond 32 nm
journal, July 2014

  • Zhao, Chun; Zhao, Ce; Taylor, Stephen
  • Materials, Vol. 7, Issue 7
  • DOI: 10.3390/ma7075117

In Situ Raman Spectroscopy of Sulfur Speciation in Lithium–Sulfur Batteries
journal, January 2015

  • Wu, Heng-Liang; Huff, Laura A.; Gewirth, Andrew A.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 3
  • DOI: 10.1021/am5072942

Inorganic–organic hybrid polymer with multiple redox for high-density data storage
journal, January 2014

  • Hu, Benlin; Wang, Chengyuan; Wang, Jiangxin
  • Chem. Sci., Vol. 5, Issue 9
  • DOI: 10.1039/C4SC00823E

Introducing a New Azoaromatic Pincer Ligand. Isolation and Characterization of Redox Events in Its Ferrous Complexes
journal, April 2014

  • Ghosh, Pradip; Samanta, Subhas; Roy, Suman K.
  • Inorganic Chemistry, Vol. 53, Issue 9
  • DOI: 10.1021/ic500355f

Memristive phase switching in two-dimensional 1T-TaS 2 crystals
journal, October 2015


A Phosphole Oxide-Containing Organogold(III) Complex for Solution-Processable Resistive Memory Devices with Ternary Memory Performances
journal, May 2016

  • Hong, Eugene Yau-Hin; Poon, Chun-Ting; Yam, Vivian Wing-Wah
  • Journal of the American Chemical Society, Vol. 138, Issue 20
  • DOI: 10.1021/jacs.6b02629

Molecular length adjustment for organic azo-based nonvolatile ternary memory devices
journal, January 2012

  • Miao, Shifeng; Li, Hua; Xu, Qingfeng
  • Journal of Materials Chemistry, Vol. 22, Issue 32
  • DOI: 10.1039/c2jm32992a

Training and operation of an integrated neuromorphic network based on metal-oxide memristors
journal, May 2015

  • Prezioso, M.; Merrikh-Bayat, F.; Hoskins, B. D.
  • Nature, Vol. 521, Issue 7550
  • DOI: 10.1038/nature14441

Control of the Metal-Insulator Transition at Complex Oxide Heterointerfaces through Visible Light
journal, November 2015

  • Lin, Jheng-Cyuan; Tra, Vu Thanh; Tsai, Dung-Sheng
  • Advanced Materials, Vol. 28, Issue 4
  • DOI: 10.1002/adma.201503499

Gate-tunable memristive phenomena mediated by grain boundaries in single-layer MoS2
journal, April 2015

  • Sangwan, Vinod K.; Jariwala, Deep; Kim, In Soo
  • Nature Nanotechnology, Vol. 10, Issue 5
  • DOI: 10.1038/nnano.2015.56

Nanostructured Ferroelectrics: Fabrication and Structure-Property Relations
journal, September 2011


Nitronyl Nitroxide Radicals as Organic Memory Elements with Both n- and p-Type Properties
journal, April 2011

  • Lee, Junghyun; Lee, Eunkyo; Kim, Sangkwan
  • Angewandte Chemie International Edition, Vol. 50, Issue 19
  • DOI: 10.1002/anie.201004899

Modeling Anomalous Hysteresis in Perovskite Solar Cells
journal, September 2015

  • van Reenen, Stephan; Kemerink, Martijn; Snaith, Henry J.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 19
  • DOI: 10.1021/acs.jpclett.5b01645

Polymer-Based Resistive Memory Materials and Devices
journal, December 2013


Charge trapping-detrapping induced resistive switching in Ba 0.7 Sr 0.3 TiO 3
journal, September 2012

  • Zou, Xi; Ong, Hock Guan; You, Lu
  • AIP Advances, Vol. 2, Issue 3
  • DOI: 10.1063/1.4754150

Organic Memory Devices Based on a Bis-Cyclometalated Alkynylgold(III) Complex
journal, April 2015

  • Au, Vonika Ka-Man; Wu, Di; Yam, Vivian Wing-Wah
  • Journal of the American Chemical Society, Vol. 137, Issue 14
  • DOI: 10.1021/jacs.5b02113

Azo Anion Radical Complex of Rhodium as a Molecular Memory Switching Device: Isolation, Characterization, and Evaluation of Current–Voltage Characteristics
journal, April 2012

  • Paul, Nanda D.; Rana, Utpal; Goswami, Sreetosh
  • Journal of the American Chemical Society, Vol. 134, Issue 15
  • DOI: 10.1021/ja212197s

Organic Resistive Memory Devices: Performance Enhancement, Integration, and Advanced Architectures
journal, July 2011

  • Cho, Byungjin; Song, Sunghun; Ji, Yongsung
  • Advanced Functional Materials, Vol. 21, Issue 15
  • DOI: 10.1002/adfm.201100686

Size dependence of vacancy migration energy in ionic nano particles: A potential energy landscape perspective
journal, June 2016


Tunable Switching Characteristics of Low Operating Voltage Organic Bistable Memory Devices Based on Gold Nanoparticles and Copper Phthalocyanine Thin Films
journal, March 2017

  • Padma, Narayanan; Betty, Chirayath A.; Samanta, Soumen
  • The Journal of Physical Chemistry C, Vol. 121, Issue 10
  • DOI: 10.1021/acs.jpcc.6b09404

Measuring the switching dynamics and energy efficiency of tantalum oxide memristors
journal, November 2011


Nanoscale cation motion in TaOx, HfOx and TiOx memristive systems
journal, September 2015

  • Wedig, Anja; Luebben, Michael; Cho, Deok-Yong
  • Nature Nanotechnology, Vol. 11, Issue 1
  • DOI: 10.1038/nnano.2015.221

Revealing the role of defects in ferroelectric switching with atomic resolution
journal, September 2011

  • Gao, Peng; Nelson, Christopher T.; Jokisaari, Jacob R.
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1600

Layer-by-layer grown scalable redox-active ruthenium-based molecular multilayer thin films for electrochemical applications and beyond
journal, January 2015

  • Kaliginedi, Veerabhadrarao; Ozawa, Hiroaki; Kuzume, Akiyoshi
  • Nanoscale, Vol. 7, Issue 42
  • DOI: 10.1039/C5NR04087F

A fast, high-endurance and scalable non-volatile memory device made from asymmetric Ta2O5−x/TaO2−x bilayer structures
journal, July 2011

  • Lee, Myoung-Jae; Lee, Chang Bum; Lee, Dongsoo
  • Nature Materials, Vol. 10, Issue 8, p. 625-630
  • DOI: 10.1038/nmat3070

257. Geometrical isomerism of azo-compounds
journal, January 1953

  • Campbell, Neil; Henderson, Andrew W.; Taylor, Duncan
  • Journal of the Chemical Society (Resumed)
  • DOI: 10.1039/jr9530001281

Molecular Memories That Survive Silicon Device Processing and Real-World Operation
journal, November 2003


Memristive devices for computing
journal, January 2013

  • Yang, J. Joshua; Strukov, Dmitri B.; Stewart, Duncan R.
  • Nature Nanotechnology, Vol. 8, Issue 1, p. 13-24
  • DOI: 10.1038/nnano.2012.240

Tuning of Nonvolatile Bipolar Memristive Switching in Co(III) Polymer with an Extended Azo Aromatic Ligand
journal, February 2011

  • Bandyopadhyay, Anasuya; Sahu, Satyajit; Higuchi, Masayoshi
  • Journal of the American Chemical Society, Vol. 133, Issue 5
  • DOI: 10.1021/ja106945v

Molecular Rectification in Metal−SAM−Metal Oxide−Metal Junctions
journal, December 2009

  • Nijhuis, Christian A.; Reus, William F.; Whitesides, George M.
  • Journal of the American Chemical Society, Vol. 131, Issue 49
  • DOI: 10.1021/ja9048898

Synthesis, Characterization, and Nonvolatile Ternary Memory Behavior of a Larger Heteroacene with Nine Linearly Fused Rings and Two Different Heteroatoms
journal, September 2013

  • Gu, Pei-Yang; Zhou, Feng; Gao, Junkuo
  • Journal of the American Chemical Society, Vol. 135, Issue 38
  • DOI: 10.1021/ja408208c

In situ cyclic voltammetry-surface-enhanced Raman spectroscopy: studies on the doping–undoping of polypyrrole film
journal, October 2000


Voltage divider effect for the improvement of variability and endurance of TaOx memristor
journal, February 2016

  • Kim, Kyung Min; Yang, J. Joshua; Strachan, John Paul
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep20085