Organic nanomaterials are attracting a great deal of interest for use in flexible electronic applications such as logic circuits, displays and solar cells. These technologies have already demonstrated good performances, but flexible organic memories are yet to deliver on all their promise in terms of volatility, operational voltage, write/erase speed, as well as the number of distinct attainable levels. Here, we report a multilevel non-volatile flexible optical memory thin-film transistor based on a blend of a reference polymer semiconductor, namely poly(3-hexylthiophene), and a photochromic diarylethene, switched with ultraviolet and green light irradiation. A three-terminal device featuring over 256 (8 bit storage) distinct current levels was fabricated, the memory states of which could be switched with 3 ns laser pulses. We also report robustness over 70 write–erase cycles and non-volatility exceeding 500 days. The device was implemented on a flexible polyethylene terephthalate substrate, validating the concept for integration into wearable electronics and smart nanodevices.
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.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Kelley, T. W. et al. Recent progress in organic electronics: materials, devices, and processes. Chem. Mater. 16, 4413–4422 (2004).
Braga, D. & Horowitz, G. High-performance organic field-effect transistors. Adv. Mater. 21, 1473–1486 (2009).
Han, S. T., Zhou, Y. & Roy, V. A. L. Towards the development of flexible non-volatile memories. Adv. Mater. 25, 5425–5449 (2013).
Benight, S. J., Wang, C., Tok, J. B. H. & Bao, Z. A. Stretchable and self-healing polymers and devices for electronic skin. Prog. Polym. Sci. 38, 1961–1977 (2013).
Pang, C., Lee, C. & Suh, K. Y. Recent advances in flexible sensors for wearable and implantable devices. J. Appl. Polym. Sci. 130, 1429–1441 (2013).
Baeg, K. J., Caironi, M. & Noh, Y. Y. Toward printed integrated circuits based on unipolar or ambipolar polymer semiconductors. Adv. Mater. 25, 4210–4244 (2013).
Ahmad, S. Organic semiconductors for device applications: current trends and future prospects. J. Polym. Eng. 34, 279–338 (2014).
Chiu, Y. C. et al. High-performance nonvolatile organic transistor memory devices using the electrets of semiconducting blends. ACS Appl. Mater. Inter. 6, 12780–12788 (2014).
Smithson, C. S., Wu, Y., Wigglesworth, T. & Zhu, S. A more than six orders of magnitude UV-responsive organic field-effect transistor utilizing a benzothiophene semiconductor and Disperse Red 1 for enhanced charge separation. Adv. Mater. 27, 228–233 (2015).
Yoon, S. M. et al. Fully transparent non-volatile memory thin-film transistors using an organic ferroelectric and oxide semiconductor below 200 °C. Adv. Funct. Mater. 20, 921–926 (2010).
Radha, B., Sagade, A. A. & Kulkarni, G. U. Metal–organic molecular device for non-volatile memory storage. Appl. Phys. Lett. 105, 083103 (2014).
Liu, X. H. et al. The effect of oxygen content on the performance of low-voltage organic phototransistor memory. Org. Electron. 15, 1664–1671 (2014).
Nougaret, L. et al. Nanoscale design of multifunctional organic layers for low-power high-density memory devices. ACS Nano 8, 3498–3505 (2014).
Lee, S. et al. Overcoming the ‘retention vs. voltage’ trade-off in nonvolatile organic memory: Ag nanoparticles covered with dipolar self-assembled monolayers as robust charge storage nodes. Org. Electron. 14, 3260–3266 (2013).
Kim, S. J. & Lee, J. S. Flexible organic transistor memory devices. Nano Lett. 10, 2884–2890 (2010).
Cosseddu, P., Lai, S., Casula, G., Raffo, L. & Bonfiglio, A. High performance, foldable, organic memories based on ultra-low voltage, thin film transistors. Org. Electron. 15, 3595–3600 (2014).
Kim, R. H. et al. Non-volatile organic memory with sub-millimetre bending radius. Nature Commun. 5, 3583 (2014).
Sekitani, T. et al. Organic nonvolatile memory transistors for flexible sensor arrays. Science 326, 1516–1519 (2009).
Liu, X. et al. Advancements in organic nonvolatile memory devices. Chin. Sci. Bull. 56, 3178–3190 (2011).
Bez, R., Camerlenghi, E., Modelli, A. & Visconti, A. Introduction to flash memory. Proc. IEEE 91, 489–502 (2003).
Sala, F., Gabrys, R. & Dolecek, L. Dynamic threshold schemes for multi-level non-volatile memories. IEEE Trans. Commun. 61, 2624–2634 (2013).
Pirovano, A. et al. Reliability study of phase-change nonvolatile memories. IEEE Trans. Dev. Mater. Res. 4, 422–427 (2004).
Nili, H. et al. Nanoscale resistive switching in amorphous perovskite oxide (a-SrTiO3) memristors. Adv. Funct. Mater. 24, 6741–6750 (2014).
Han, Y., Cho, K., Park, S. & Kim, S. Resistive switching characteristics of HfO2-based memory devices on flexible plastics. J. Nanosci. Nanotechnol. 14, 8191–8195 (2014).
Zhang, W. B. et al. Thermally-stable resistive switching with a large ON/OFF ratio achieved in poly(triphenylamine). Chem. Commun. 50, 11856–11858 (2014).
Heremans, P. et al. Polymer and organic nonvolatile memory devices. Chem. Mater. 23, 341–358 (2011).
Chiu, Y. C. et al. High performance nonvolatile transistor memories of pentacene using the electrets of star-branched p-type polymers and their donor–acceptor blends. J. Mater. Chem. C 2, 1436–1446 (2014).
Baeg, K. J. et al. High-performance top-gated organic field-effect transistor memory using electrets for monolithic printed flexible NAND flash memory. Adv. Funct. Mater. 22, 2915–2926 (2012).
Das, B. C., Pillai, R. G., Wu, Y. L. & McCreery, R. L. Redox-gated three-terminal organic memory devices: effect of composition and environment on performance. ACS Appl. Mater. Inter. 5, 11052–11058 (2013).
Kumar, R., Pillai, R. G., Pekas, N., Wu, Y. L. & McCreery, R. L. Spatially resolved Raman spectroelectrochemistry of solid-state polythiophene/viologen memory devices. J. Am. Chem. Soc. 134, 14869–14876 (2012).
Chiu, Y. C. et al. Multilevel nonvolatile transistor memories using a star-shaped poly((4-diphenylamino)benzyl methacrylate) gate electret. NPG Asia Mater. 5, e35 (2013).
Chou, Y.-H., Chang, H.-C., Liu, C.-L. & Chen, W.-C. Polymeric charge storage electrets for non-volatile organic field effect transistor memory devices. Polym. Chem. 6, 341–352 (2015).
Zhou, Y., Han, S. T., Sonar, P. & Roy, V. A. L. Nonvolatile multilevel data storage memory device from controlled ambipolar charge trapping mechanism. Sci. Rep. 3, 2319 (2013).
Orgiu, E. & Samori, P. Organic electronics marries photochromism: generation of multifunctional interfaces, materials, and devices. Adv. Mater. 26, 1827–1845 (2014).
Hayakawa, R., Higashiguchi, K., Matsuda, K., Chikyow, T. & Wakayama, Y. Optically and electrically driven organic thin film transistors with diarylethene photochromic channel layers. ACS Appl. Mater. Inter. 5, 3625–3630 (2013).
Matsui, N. & Tsujioka, T. Carrier mobility of photochromic diarylethene amorphous films. Org. Electron. 15, 2264–2269 (2014).
Tsujioka, T., Hamada, Y., Shibata, K., Taniguchi, A. & Fuyuki, T. Nondestructive readout of photochromic optical memory using photocurrent detection. Appl. Phys. Lett. 78, 2282–2284 (2001).
Andersson, P., Robinson, N. D. & Berggren, M. Switchable charge traps in polymer diodes. Adv. Mater. 17, 1798–1803 (2005).
Raimondo, C. et al. Optically switchable organic field-effect transistors based on photoresponsive gold nanoparticles blended with poly(3-hexylthiophene). Proc. Natl Acad. Sci. USA 109, 12375–12380 (2012).
Taguchi, M., Nakagawa, T., Nakashima, T., Adachi, C. & Kawai, T. Photo-patternable electroluminescence based on one-way photoisomerization reaction of tetraoxidized triangle terarylenes. Chem. Commun. 49, 6373–6375 (2013).
Russew, M. M. & Hecht, S. Photoswitches: from molecules to materials. Adv. Mater. 22, 3348–3360 (2010).
Irie, M., Fukaminato, T., Matsuda, K. & Kobatake, S. Photochromism of diarylethene molecules and crystals: memories, switches, and actuators. Chem. Rev. 114, 12174–12277 (2014).
Shallcross, R. C., Korner, P. O., Maibach, E., Kohnen, A. & Meerholz, K. Photochromic diode with a continuum of intermediate states: towards high density multilevel storage. Adv. Mater. 25, 4807–4813 (2013).
Korner, P. O., Shallcross, R. C., Maibach, E., Kohnen, A. & Meerholz, K. Optical and electrical multilevel storage in organic memory passive matrix arrays. Org. Electron. 15, 3688–3693 (2014).
El Gemayel, M. et al. Optically switchable transistors by simple incorporation of photochromic systems into small-molecule semiconducting matrices. Nature Commun. 6, 6330 (2015).
Borjesson, K. et al. Optically switchable transistors comprising a hybrid photochromic molecule/n-type organic active layer. J. Mater. Chem. C 3, 4156–4161 (2015).
Orgiu, E. et al. Optically switchable transistor via energy-level phototuning in a bicomponent organic semiconductor. Nature Chem. 4, 675–679 (2012).
Chua, L. L. et al. General observation of n-type field-effect behaviour in organic semiconductors. Nature 434, 194–199 (2005).
This work was supported financially by the EC through the MSCA-ITN project iSwitch (GA no. 642196) as well as ERC projects SUPRAFUNCTION (GA-257305) and LIGHT4FUNCTION (GA-308117), the Agence Nationale de la Recherche through the LabEx CSC (ANR-10-LABX-0026_CSC), the International Center for Frontier Research in Chemistry (icFRC) and the German Research Foundation (via SFB 658).
The authors declare no competing financial interests.
About this article
Cite this article
Leydecker, T., Herder, M., Pavlica, E. et al. Flexible non-volatile optical memory thin-film transistor device with over 256 distinct levels based on an organic bicomponent blend. Nature Nanotech 11, 769–775 (2016). https://doi.org/10.1038/nnano.2016.87
Nanoscale Research Letters (2021)
Ultrafast processes in photochromic material YHxOy studied by excited-state density functional theory simulation
Science China Materials (2020)
A Universal Strategy for Stretchable Polymer Nonvolatile Memory via Tailoring Nanostructured Surfaces
Scientific Reports (2019)
Nature Nanotechnology (2019)
Nature Nanotechnology (2019)