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Monolithically integrated high-density vertical organic electrochemical transistor arrays and complementary circuits

Nature Electronics volume 7, pages 234–243 (2024)Cite this article

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Abstract

Organic electrochemical transistors (OECTs) can be used to create biosensors, wearable devices and neuromorphic systems. However, restrictions in the micro- and nanopatterning of organic semiconductors, as well as topological irregularities, often limit their use in monolithically integrated circuits. Here we show that the micropatterning of organic semiconductors by electron-beam exposure can be used to create high-density (up to around 7.2 million OECTs per cm2) and mechanically flexible vertical OECT arrays and circuits. The energetic electrons convert the semiconductor exposed area to an electronic insulator while retaining ionic conductivity and topological continuity with the redox-active unexposed areas essential for monolithic integration. The resulting p- and n-type vertical OECT active-matrix arrays exhibit transconductances of 0.08–1.7 S, transient times of less than 100 μs and stable switching properties of more than 100,000 cycles. We also fabricate vertically stacked complementary logic circuits, including NOT, NAND and NOR gates.

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Fig. 1: Fabrication and monolithic integration of vOECTs using e-beam patterning.
Fig. 2: vOECT ionic and electronic transport characterization and transient response stability.
Fig. 3: Characterization of e-beam unexposed and exposed OSC films.
Fig. 4: High-density monolithically integrated vOECT arrays fabricated by e-beam exposure.
Fig. 5: 2D areal mapping and flexible vOECT arrays.
Fig. 6: High-resolution vertically stacked complementary circuits.

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Source data are provided with this paper. Additional data related to this work are available from the corresponding authors upon request.

References

  1. Chen, J. et al. Highly stretchable organic electrochemical transistors with strain-resistant performance. Nat. Mater. 21, 564–571 (2022).

    Google Scholar 

  2. Andersson Ersman, P. et al. All-printed large-scale integrated circuits based on organic electrochemical transistors. Nat. Commun. 10, 5053 (2019).

    Google Scholar 

  3. Park, S. et al. Self-powered ultra-flexible electronics via nano-grating-patterned organic photovoltaics. Nature 561, 516–521 (2018).

    Google Scholar 

  4. Stein, E. et al. Ambipolar blend-based organic electrochemical transistors and inverters. Nat. Commun. 13, 5548 (2022).

    Google Scholar 

  5. Rashid, R. B. et al. Ambipolar inverters based on cofacial vertical organic electrochemical transistor pairs for biosignal amplification. Sci. Adv. 7, eabh1055 (2021).

    Google Scholar 

  6. Picca, R. A. et al. Ultimately sensitive organic bioelectronic transistor sensors by materials and device structure design. Adv. Funct. Mater. 30, 1904513 (2020).

    Google Scholar 

  7. Torricelli, F. et al. Electrolyte-gated transistors for enhanced performance bioelectronics. Nat. Rev. Meth. Primers 1, 66 (2021).

    Google Scholar 

  8. Abarkan, M. et al. Vertical organic electrochemical transistors and electronics for low amplitude micro-organ signals. Adv. Sci. 9, 2105211 (2022).

    Google Scholar 

  9. Spyropoulos, G. D., Gelinas, J. N. & Khodagholy, D. Internal ion-gated organic electrochemical transistor: a building block for integrated bioelectronics. Sci. Adv. 5, eaau7378 (2020).

    Google Scholar 

  10. Harikesh, P. C. et al. Ion-tunable antiambipolarity in mixed ion–electron conducting polymers enables biorealistic organic electrochemical neurons. Nat. Mater. 22, 242–248 (2023).

    Google Scholar 

  11. Song, J. et al. 2D metal-organic frameworks for ultraflexible electrochemical transistors with high transconductance and fast response speeds. Sci. Adv. 9, eadd9627 (2023).

    Google Scholar 

  12. Wang, Y. et al. n-type organic electrochemical transistors with high transconductance and stability. Chem. Mater. 35, 405–415 (2023).

    Google Scholar 

  13. Rivnay, J. et al. Organic electrochemical transistors. Nat. Rev. Mater. 3, 17086 (2018).

    Google Scholar 

  14. Wu, X. et al. High performing solid-state organic electrochemical transistors enabled by glycolated polythiophene and ion-gel electrolyte with a wide operation temperature range from −50 to 110°C. Adv. Funct. Mater. 33, 2209354 (2023).

    Google Scholar 

  15. Cea, C. et al. Enhancement-mode ion-based transistor as a comprehensive interface and real-time processing unit for in vivo electrophysiology. Nat. Mater. 19, 679–686 (2020).

    Google Scholar 

  16. Khodagholy, D. et al. High transconductance organic electrochemical transistors. Nat. Commun. 4, 2133 (2013).

    Google Scholar 

  17. Schmatz, B., Lang, A. W. & Reynolds, J. R. Fully printed organic electrochemical transistors from green solvents. Adv. Funct. Mater. 29, 1905266 (2019).

    Google Scholar 

  18. Jiang, C., De Rijk, S. R., Malliaras, G. G. & Bance, M. L. Electrochemical impedance spectroscopy of human cochleas for modeling cochlear implant electrical stimulus spread. APL Mater. 8, 091102 (2020).

    Google Scholar 

  19. Koutsouras, D. A., Torricelli, F. & Blom, P. W. M. Submicron vertical channel organic electrochemical transistors with ultrahigh transconductance. Adv. Electron. Mater. 9, 2200868 (2023).

    Google Scholar 

  20. Kleemann, H., Krechan, K., Fischer, A. & Leo, K. A review of vertical organic transistors. Adv. Funct. Mater. 30, 1907113 (2020).

    Google Scholar 

  21. Huang, W. et al. Vertical organic electrochemical transistors for complementary circuits. Nature 613, 496–502 (2023).

    Google Scholar 

  22. Kim, J. et al. Scalable sub-micron patterning of organic materials toward high density soft electronics. Sci. Rep. 5, 14520 (2015).

    Google Scholar 

  23. Zheng, Y. Q. et al. Monolithic optical microlithography of high-density elastic circuits. Science 373, 88–94 (2021).

    Google Scholar 

  24. Wang, S. et al. Skin electronics from scalable fabrication of an intrinsically stretchable transistor array. Nature 555, 83–88 (2018).

    Google Scholar 

  25. Chortos, A. et al. Mechanically durable and highly stretchable transistors employing carbon nanotube semiconductor and electrodes. Adv. Mater. 28, 4441–4448 (2016).

    Google Scholar 

  26. Malinowski, P. E. et al. Photolithographic patterning of organic photodetectors with a non-fluorinated photoresist system. Org. Electron. 15, 2355–2359 (2014).

    Google Scholar 

  27. Chang, J. F., Gwinner, M. C., Caironi, M., Sakanoue, T. & Sirringhaus, H. Conjugated-polymer-based lateral heterostructures defined by high-resolution photolithography. Adv. Funct. Mater. 20, 2825–2832 (2010).

    Google Scholar 

  28. Gangnaik, A. S., Georgiev, Y. M. & Holmes, J. D. New generation electron beam resists: a review. Chem. Mater. 29, 1898–1917 (2017).

    Google Scholar 

  29. Qin, N. et al. Nanoscale probing of electron-regulated structural transitions in silk proteins by near-field IR imaging and nano-spectroscopy. Nat. Commun. 7, 13079 (2016).

    Google Scholar 

  30. Blanksby, S. J. & Ellison, G. B. Bond dissociation energies of organic molecules. Acc. Chem. Res. 36, 255–263 (2003).

    Google Scholar 

  31. Bässler, H. & Köhler, A. Charge transport in organic semiconductors. Top. Curr. Chem. 312, 1–65 (2012).

    Google Scholar 

  32. Liu, G. et al. Ultralow-power and multisensory artificial synapse based on electrolyte-gated vertical organic transistors. Adv. Funct. Mater. 32, 2200959 (2022).

    Google Scholar 

  33. Lenz, J., del Giudice, F., Geisenhof, F. R., Winterer, F. & Weitz, R. T. Vertical, electrolyte-gated organic transistors show continuous operation in the MA cm−2 regime and artificial synaptic behaviour. Nat. Nanotechnol. 14, 579–585 (2019).

    Google Scholar 

  34. Xie, Z. et al. All-solid-state vertical three-terminal N-type organic synaptic devices for neuromorphic computing. Adv. Funct. Mater. 32, 2107314 (2022).

    Google Scholar 

  35. Guo, E. et al. Vertical organic permeable dual-base transistors for logic circuits. Nat. Commun. 11, 4725 (2020).

    Google Scholar 

  36. Huggins, R. A. Simple method to determine electronic conductivity and ionic components of the conductors in mixed a review. Ionics 8, 300–313 (2002).

    Google Scholar 

  37. Wang, Y. et al. Hybrid alkyl-ethylene glycol side chains enhance substrate adhesion and operational stability in accumulation mode organic electrochemical transistors. Chem. Mater. 31, 9797–9806 (2019).

    Google Scholar 

  38. Wu, H. Y. et al. Influence of molecular weight on the organic electrochemical transistor performance of ladder-type conjugated polymers. Adv. Mater. 34, 2106235 (2022).

    Google Scholar 

  39. Ohayon, D. et al. Influence of side chains on the n-type organic electrochemical transistor performance. ACS Appl. Mater. Interfaces 13, 4253–4266 (2021).

    Google Scholar 

  40. Giovannitti, A. et al. N-type organic electrochemical transistors with stability in water. Nat. Commun. 7, 13066 (2016).

    Google Scholar 

  41. Yan, Y. et al. High-performance organic electrochemical transistors with nanoscale channel length and their application to artificial synapse. ACS Appl. Mater. Interfaces 12, 49915–49925 (2020).

    Google Scholar 

  42. Savva, A. et al. Solvent engineering for high-performance n-type organic electrochemical transistors. Adv. Electron. Mater. 5, 1900249 (2019).

    Google Scholar 

  43. Wu, X. et al. Universal spray-deposition process for scalable, high-performance, and stable organic electrochemical transistors. ACS Appl. Mater. Interfaces 12, 20757–20764 (2020).

    Google Scholar 

  44. Moser, M. et al. Side chain redistribution as a strategy to boost organic electrochemical transistor performance and stability. Adv. Mater. 32, 2002748 (2020).

    Google Scholar 

  45. Chércoles Asensio, R., San Andrés Moya, M., De La Roja, J. M. & Gómez, M. Analytical characterization of polymers used in conservation and restoration by ATR-FTIR spectroscopy. Anal. Bioanal. Chem. 395, 2081–2096 (2009).

    Google Scholar 

  46. Kim, J. et al. Vertically stacked full color quantum dots phototransistor arrays for high-resolution and enhanced color-selective imaging. Adv. Mater. 34, 2106215 (2022).

    Google Scholar 

  47. Lee, W. et al. Transparent, conformable, active multielectrode array using organic electrochemical transistors. Proc. Natl Acad. Sci. USA 114, 10554–10559 (2017).

    Google Scholar 

  48. Lee, W. et al. Nonthrombogenic, stretchable, active multielectrode array for electroanatomical mapping. Sci. Adv. 4, eaau2426 (2018).

    Google Scholar 

  49. Weissbach, A. et al. Photopatternable solid electrolyte for integrable organic electrochemical transistors: Operation and hysteresis. J. Mater. Chem. C. 10, 2656–2662 (2022).

    Google Scholar 

  50. Kang, J. et al. Symmetrically ion-gated in-plane metal-oxide transistors for highly sensitive and low-voltage driven bioelectronics. Adv. Sci. 9, 2103275 (2022).

    Google Scholar 

  51. Koutsouras, D. A., Torricelli, F., Gkoupidenis, P. & Blom, P. W. M. Efficient gating of organic electrochemical transistors with in-plane gate electrodes. Adv. Mater. Technol. 6, 2100732 (2021).

    Google Scholar 

  52. Rivnay, J. et al. Organic electrochemical transistors with maximum transconductance at zero gate bias. Adv. Mater. 25, 7010–7014 (2013).

    Google Scholar 

  53. Song, C. K., Eckstein, B. J., Tam, T. L. D., Trahey, L. & Marks, T. J. Conjugated polymer energy level shifts in lithium-ion battery electrolytes. ACS Appl. Mater. Interfaces 6, 19347–19354 (2014).

    Google Scholar 

  54. Wang, Z. et al. Cinnamate-functionalized natural carbohydrates as photopatternable gate dielectrics for organic transistors. Chem. Mater. 31, 7608–7617 (2019).

    Google Scholar 

  55. Kostianovskii, V., Sanyoto, B. & Noh, Y. Y. A facile way to pattern PEDOT:PSS film as an electrode for organic devices. Org. Electron. 44, 99–105 (2017).

    Google Scholar 

Download references

Acknowledgements

This work was supported by the AFOSR (contract no. FA9550-22-1-0423), the US Office of Naval Research Contract no. N00014-20-1-2116, by the US Department of Commerce, National Institute of Standards and Technology as part of the Centre for Hierarchical Materials Design Award no. 70NANB10H005, BSF (award no. 2020384), NSF (DMR-2223922) and the Northwestern University Materials Research Science and Engineering Center Awards NSF DMR-1720139 and DMR-2308691. J.R. gratefully acknowledges support from the Alfred P. Sloan Foundation (FG-2019-12046). This work acknowledges the US Department of Energy under contract no. DE-AC02-05CH11231 at beamline 8-ID-E of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This work made use of the NUFAB facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN and Northwestern’s MRSEC programme (NSF DMR-1720139).

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Authors and Affiliations

  1. Department of Chemistry and Materials Research Center, Northwestern University, Evanston, IL, USA

    Jaehyun Kim, Robert M. Pankow, Yongjoon Cho, Isaiah D. Duplessis, Fei Qin, Ding Zheng, Wei Huang, Tobin J. Marks & Antonio Facchetti

  2. Department of Semiconductor Science, Dongguk University, Seoul, Republic of Korea

    Jaehyun Kim

  3. Department of Materials Science and Engineering, Northwestern University, Evanston, IL, USA

    Dilara Meli, Jonathan Rivnay & Tobin J. Marks

  4. Department of Biomedical Engineering, Northwestern University, Evanston, IL, USA

    Rachel Daso & Jonathan Rivnay

  5. Laboratory of Organic Electronics, Department of Science and Technology, Linköping University, SE-601 74, Norrköping, Sweden

    Antonio Facchetti

  6. School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA, USA

    Antonio Facchetti

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Contributions

J.K., T.J.M. and A.F. conceived and designed the research. J.K. carried out the device fabrication, characterizations and demonstrations. R.M.P. and Y.C. synthesized the polymer semiconductors. J.K., R.M.P., I.D.D., F.Q., D.Z. and W.H. analysed the data. D.M., R.D. and J.R. conducted the bandwidth and EIS measurements. R.M.P. and I.D.D. measured and analysed the GIWAXS. All the authors discussed the results and commented on the manuscript. J.K., J.R., T.J.M. and A.F. wrote the manuscript.

Corresponding authors

Correspondence to Jonathan Rivnay, Tobin J. Marks or Antonio Facchetti.

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A patent application has been filed by Northwestern with inventors J.K., T.J.M. and A.F. The remaining authors declare no competing interests.

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Nature Electronics thanks Wei Lin Leong and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Kim, J., Pankow, R.M., Cho, Y. et al. Monolithically integrated high-density vertical organic electrochemical transistor arrays and complementary circuits. Nat Electron 7, 234–243 (2024). https://doi.org/10.1038/s41928-024-01127-x

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