Two-in-One Device with Versatile Compatible Electrical Switching or

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Research Article Cite This: ACS Appl. Mater. Interfaces 2019, 11, 25358−25368

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Two-in-One Device with Versatile Compatible Electrical Switching or Data Storage Functions Controlled by the Ferroelectricity of P(VDFTrFE) via Photocrosslinking Sunbin Hwang,† Sukjae Jang,† Minji Kang,† Sukang Bae,† Seoung-Ki Lee,† Jae-Min Hong,† Sang Hyun Lee,‡ Gunuk Wang,§ Simone Fabiano,∥ Magnus Berggren,∥ and Tae-Wook Kim*,†

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Functional Composite Materials Research Center, Korea Institute of Science and Technology (KIST), 92 Chudong-ro, Bongdong-eup, Wanju-gun, Jeollabuk-Do 55324, Republic of Korea ‡ School of Chemical Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwangju 61186, Republic of Korea § KU-KIST Graduate School of Converging Science and Technology, Korea University, Seoul 136-701, Republic of Korea ∥ Laboratory of Organic Electronics, Department of Science and Technology, Linköping University, SE-601 74 Norrköping, Sweden S Supporting Information *

ABSTRACT: Organic electronics demand new platforms that can make integrated circuits and undergo mass production while maintaining diverse functions with high performance. The field-effect transistor has great potential to be a multifunctional device capable of sensing, data processing, data storage, and display. Currently, transistor-based devices cannot be considered intrinsic multifunctional devices because all installed functions are mutually coupled. Such incompatibilities are a crucial barrier to developing an all-in-one multifunctional device capable of driving each function individually. In this study, we focus on the decoupling of electric switching and data storage functions in an organic ferroelectric memory transistor. To overcome the incompatibility of each function, the high permittivity needed for electrical switching and the ferroelectricity needed for data storage become compatible by restricting the motion of poly(vinylidene fluoride-trifluoroethylene) via photocrosslinking with bis-perfluorobenzoazide. The two-in-one device consisting of a photocrosslinked ferroelectric layer exhibits reversible and individual dual-functional operation as a typical transistor with nonvolatile memory. Moreover, a p-MOS depletion load inverter composed of the two transistors with different threshold voltages is also demonstrated by simply changing only one of the threshold voltages by polarization switching. We believe that the two-in-one device will be considered a potential component of integrated organic logic circuits, including memory, in the future. KEYWORDS: organic ferroelectric memory, organic field-effect transistor, bis-FB-N3, inverter, switchable functions

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INTRODUCTION

to switch the source−drain current by gate bias, while multifunctional OFETs possess controllable functions in addition to electrical switching. The previous concept of multifunctional OFETs simply borrowed the transistor platform for detection, data storage, or light illumination. However, previously reported transistor-based multifunctional devices are not able to be considered intrinsic multifunctional devices because all functions installed in the multifunctional device are mutually coupled. Therefore, one function affects another function, making the extraction of the optimum characteristics for each function difficult.13−18 An organic ferroelectric transistor is a multifunctional OFET device, which utilizes π-conjugated organic molecules and

Recent organic electronics require a new device platform that can participate in roll-to-roll mass production, integrate circuit modules, and reduce costs while maintaining their diverse functions and high performances.1−7 Accordingly, organic electronic devices (light-emitting diodes, photovoltaic cells, sensors, field-effect transistors, nonvolatile memory devices, etc.) capable of versatile functionalization have been extensively studied. Because the electrical properties of organic semiconductors can be modulated, various functions of organic electronic devices can be achieved simultaneously by tailoring their functional groups.8,9 Among these devices, organic field-effect transistors (OFETs) have been considered a promising platform to develop multifunctional devices, such as OFET-based sensors, phototransistors, light-emitting transistors, and memory transistors.10−12 A typical OFET only has a simple function, © 2019 American Chemical Society

Received: April 29, 2019 Accepted: June 20, 2019 Published: June 20, 2019 25358

DOI: 10.1021/acsami.9b07462 ACS Appl. Mater. Interfaces 2019, 11, 25358−25368

Research Article

ACS Applied Materials & Interfaces

crystallinity. Because of the large PR of the β-phase crystalline structure, a β-phase P(VDF-TrFE) ferroelectric layer is suitable as the dielectric layer of a nonvolatile memory transistor but is not suitable for typical switching transistor applications. In terms of the dielectric material for typical transistor applications, the high permittivity of the α- and γ-phase P(VDF-TrFE) copolymer is an attractive and precious property for achieving low-voltage operation. A highpermittivity dielectric allows more charge accumulation at the interface with an organic semiconductor than do lowpermittivity dielectrics under the same gate bias conditions. A few approaches have been utilized to reduce the ferroelectric properties of a β-phase P(VDF-TrFE) layer while keeping its high permittivity for use as the dielectric layer in OFETs.25 Thermal annealing at a relatively low temperature below TC (104 s), and stable endurance performance (> 400 cycles) with a ±50 V writing/erasing gate bias. In addition, the ferroelectric properties of P(VDF-TrFE) were systematically controlled by the photocrosslinker content and gate bias of the device independently. For example, the threshold voltage could be shifted by a strong gate field (±50 V) independently and retained during the transistor operation. The p-MOS depletion load inverter, which connected the same two devices in series but with different threshold voltages, was successfully demonstrated by switching the polarization of the photocrosslinked P(VDF-TrFE) and controlling the threshold voltage (gain value of 5.6 at VDD of −30 V). As described above, we decoupled the electrical switching and data storage functions and introduced a new device that can drive each function independently. We believe that this two-in-one device can contribute to realizing intrinsic all-in-one-type multifunctional devices.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.9b07462. Morphologies of P(VDF-TrFE) thin films photocrosslinked with various concentrations of bis-FB-N3 (0.0, 6.7, 12.5, 17.6, and 22.2 wt %) on SiO2/p-Si++ substrates (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Jae-Min Hong: 0000-0001-9238-5451 Gunuk Wang: 0000-0001-6059-0530 Simone Fabiano: 0000-0001-7016-6514 Tae-Wook Kim: 0000-0003-2157-732X Author Contributions

T.-W.K. developed the idea. S.H. and S.J. designed, conducted the experiments, and wrote the text of the paper. S.H., S.J., M.K., S.B., S.-K.L., J.-M.H., S.H.L., G.W., S.F., M.B., and T.W.K. investigated the obtained results. Notes

The authors declare no competing financial interest.

EXPERIMENTAL SECTION

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Heavily doped p-type Si wafers (Namkang Hi-Tech Co., Ltd.), dehydrated dimethylformamide (DMF, Aldrich), and P(VDF-TrFE) (Solvay, 70:30 by moles, Mw: 400 K) were purchased commercially and used without further purification. bis-FB-N3, a photocrosslinker, was synthesized, and the details of the method are described in our previous reports.41,42 Heavily doped p-type Si wafers were cleaned by ultrasonication in acetone and isopropanol for 10 min, which was followed by drying with nitrogen gas. For the fabrication of the dielectric layer on Si substrates, a P(VDF-TrFE) solution was prepared by dissolving 70 mg of P(VDF-TrFE) in 1 mL of dehydrated DMF. Various amounts of the photoactive crosslinker, 5, 10, 15, and 20 mg of bis-FB-N3, were then added to the prepared P(VDF-TrFE) solution. The mixed solutions were stirred in a nitrogen-filled glovebox at 50 °C for 30 min. The prepared solutions were spincoated on the cleaned Si substrate at 1500 rpm for 2 min. To photoactivate bis-FB-N3 in the P(VDF-TrFE) matrix, the thin films were irradiated by UV light (λ, ∼254 nm) for 5 min and annealed at 140 °C for 2 h. To fabricate the multifunctional organic ferroelectric memory transistor (channel length L = 50 μm and width W = 1000 μm), a 50 nm-thick pentacene (a p-type organic semiconductor) layer and gold

ACKNOWLEDGMENTS This work was supported by the Korea Institute of Science and Technology (KIST) Young Fellow Program, and also partially supported by the National Research Foundation of Korea (NRF-2016R1C1B2007330) and the Ministry of Trade, Industry, and Energy (MOTIE, Korea) under the Industrial Technology Innovation Program “Development of 3DDeformable Multilayered FPCB Devices” (Grant no. 10051162).

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ABBREVIATIONS OFET, organic field-effect transistor PVDF, poly(vinylidene fluoride) P(VDF-TrFE), poly(vinylidene fluoride-co-trifluoroethylene) P, polarization V, voltage PR, remanent polarization

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DOI: 10.1021/acsami.9b07462 ACS Appl. Mater. Interfaces 2019, 11, 25358−25368

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VC, coercive voltage TC, Curie transition temperature Tm, melting temperature bis-FB-N3, bis-perfluorobenzoazide XPS, X-ray photoelectron spectroscopy GIXRD, glancing incidence X-ray diffraction θ, Bragg’s angle FWHM, full width at half-maximum τ, size of the ordered crystalline domains κ, dimensionless shape factor with a value close to unity λ, X-ray wavelength ε, dielectric constant C, capacitance A, surface of a capacitor f , frequency MFM, metal−ferroelectric−metal THDA, 2,4,4-trimethyl-1,6-hexanediamine L, length W, width VD, drain voltage VG, gate sweep voltage ID, drain current W−R−E−R, write/read/erase/read VOUT, output voltage VIN, Input voltage DMF, dimethylformamide

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