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Nov 24, 2017 - (c) Hysteretic drain current as a function of gate voltage clockwise sweeping for OFeFET on rigid substrate in dark with the channel le...
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Cite This: ACS Appl. Mater. Interfaces 2017, 9, 43880−43885

Solution-Processed Flexible Organic Ferroelectric Phototransistor Qiang Zhao,†,§,⊥ Hanlin Wang,†,§,⊥ Lang Jiang,*,† Yonggang Zhen,† Huanli Dong,*,† and Wenping Hu*,†,‡ †

Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University and Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China § School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China ‡

S Supporting Information *

ABSTRACT: In this article, we demonstrate ferroelectric insulator, P(VDF-TrFE), can be integrated with red light sensitive polymeric semiconductor, P(DPP-TzBT), toward ferroelectric organic phototransistors (OPTs). This ferroelectricity-modulated phototransistor possesses different nonvolatile and tunable dark current states due to P(VDF-TrFE)’s remnant polarization. As a result, the OPT is endowed with a tunable dark current level ranging from 1 nA to 100 nA. Once the OPT is programmed or electrically polarized, its photo-to-dark (signal-to-noise) ratio can be “flexible” during photodetection process, without gate bias application. This kind of organic ferroelectric phototransistor has great potential in detecting wide ranges of light signals with good linearity. Moreover, its tuning mechanism discussed in this work can be helpful to understand the operation mechanism of organic phototransistor (OPT). It can be promising for novel photodetection application in plastic electronic devices. KEYWORDS: P(VDF-TrFE), nonvolatile memory (NVM), organic ferroelectric field-effect transistor (OFeFET), organic phototransistor (OPT), organic field-effect transistor (OFET)



voltage.3,16 Remarkably, there are also some groups exploring organic nonvolatile memory by integration of OFeFET with drive OFET to form memory cell matrixes.21−24 Photoelectric 2D material (MoS2) has recently been combined with ferroelectric polymer to fabricate a highly sensitive photodetector, exhibiting a maximum photoresponsivity of 2570 A/W.25 Compared with conventional MoS2 photodetector, it shows a much lower dark current to give a high signal-to-noise (photo-todark) ratio. To date, large quantities of organic semiconductors have demonstrated both high mobility and excellent photo sensitivity within ultraviolet (UV) to near-infrared (NIR) spectrum.26 However, incorporation of ferroelectric polymer into organic phototransistors (OPTs) has not been investigated, and its ferroelectricity can be potentially utilized to tune OPT’s photosensing characteristics, other than nonvolatile memory. Organic ferroelectric phototransistors with ferroelectric-modulated dark current and different photoresponse intensity can be promising for novel photodetection application in plastic electronic devices. With P(VDF-TrFE) as ferroelectric insulator (with no responsivity under 730 nm red light as Figure S1 shown), here we demonstrate a solution-processed, photosensitive copolymer with an alternative unit of diketopyrrolopyrrole (DPP) and

INTRODUCTION Organic ferroelectric field-effect transistors (OFeFETs) have aroused profound interests in nonvolatile memory application. The utilization of ferroelectric polymer gate insulator in organic field-effect transistors (OFETs) offers convenient and low-cost strategies of solution processability, flexible memory modules, and simplified device manufacturing over floating-gate memory. For OFeFETs, figures of merit such as memory window, retention characteristics, and multistate nonvolatile conductance have developed rapidly to fulfill the needs for low power dissipation and nondestructive read-out.1−10 By virtue of their data storage capability and manufacturing compatibility with organic complementary circuit technology, OFeFETs are promising memory modules to be incorporated in the nextgeneration radio frequency identification (RFID) tags and NAND-like flash memory.11,12 Poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) with VDF/TrFE mole ratio of 7:3 can show ferroelectricity with a saturated polarization (Ps) of 8 μC/cm2 above its coercive field (Ec) (50 MV/m). Because of its reversible remnant polarization, a hysteretic transfer curve for memory operation is available when the OFET is undergoing a back-and-forth gate bias sweeping.13 In most cases, researchers almost pay major efforts to improve their memory retention and dynamic range by optimizing electrode materials14 or modulating insulator/semiconductor (I/S) interface.15 Other attempts focus on its applications on flexible electronics,16−18 multilevel memory,18−20 and memory devices with low operation © 2017 American Chemical Society

Received: September 9, 2017 Accepted: November 24, 2017 Published: November 24, 2017 43880

DOI: 10.1021/acsami.7b13709 ACS Appl. Mater. Interfaces 2017, 9, 43880−43885

Research Article

ACS Applied Materials & Interfaces

Figure 1. (a) Molecular structure of P(VDF-TrFE) with VDF/TrFE mole ratio of 7:3; D−E hysteresis loop of P(VDF-TrFE) thin film (1050 μm). (b) Schematic structure of photoresponse organic flexible ferroelectric FET employing TGBC configuration on polyimide (PI) substrate in a bottom-to-top view sight. (c) Hysteretic drain current as a function of gate voltage clockwise sweeping for OFeFET on rigid substrate in dark with the channel length of 40 μm and W/L of 10. (d) Cross-sectional scanning electron microscopic image of OFeFET device with substrate (PI) and dielectric layer (P(VDFTrFE)), where semiconductor layer is covered by insulator. (e) AFM height image of P(VDF-TrFE) thin film annealed at 140 °C for 2 h. (f) X-ray diffraction pattern of P(VDF-TrFE) annealed thin film and scanning electron microscopic (SEM) morphology of its crystalline grains with a width range of 20−40 nm. bottom electrode, which was deposited through ULVAC vacuum thermos-evaporation system. The unfinished capacitor device with P(VDF-TrFE) thin film was annealed at 140 °C for 2 h and then cooled to room temperature gradually. A 20 nm-thick gold top electrode was subsequently thermally evaporated to form a sandwiched structure (Al/ P(VDF-TrFE)/Au). The capacitor was characterized with Radiant Ferroelectric Material Tester Premier II-100 V in ambient atmosphere. Ferroelectric Phototransistor Device Fabrication and Characterization. P(VDF-TrFE) powder was dissolved in butanone solvent with concentration of 65 mg/mL and the solution was filtered with 0.45 μm PTFE syringe filter before use. P(DPP-TzBT) was dissolved in dichlorobenzene via heating and stirring. To construct the transistor devices, the following procedures were carried out: (1) the substrate was successively rinsed with detergent, deionized water, and isopropyl alcohol, and it was finally dried with high-pressure nitrogen; (2) Au source/drain electrode (18 nm) was thermally evaporated on both rigid (glass) and flexible (PI) substrate; (3) substrate with gold electrode was cleaned by UVO for 20 min prior to OTS treatment in a mixed solvent of OTS/cyclohexane (v/v = 1:1000); (4) P(DPP-TzBT) solution was spin-coated on the OTS modified substrate and then annealed at 120 °C for 5 min; (5) P(VDF-TrFE) solution was subsequently spin-coated on the polymeric semiconductor layer and then the sample was annealed at 140 °C for 2 h in vacuum oven; and (6) Au top gate electrode was finally evaporated cautiously. The transistor devices were characterized with a Keithley 4200 semiconductor characterization system. The light source was a red LED bulb with a wavelength of 730 nm driven by a DC voltage source. The illumination intensity was measured with an irradiatometer.

thiophene-thiazolothiazole-thiophene (TzBT) (P(DPP-TzBT) (its absorption spectrum is shown in Figure S2), of which detailed synthesis route is shown in Figure S3, as OFeFET’s active layer.27,28 Ferroelectricity-modulated, tunable, and multilevel dark current states can be obtained in this organic ferroelectric phototransistor. Unlike conventional organic phototransistor (OPT), the organic ferroelectric phototransistor possesses more than two nonvolatile and tunable dark current states due to P(VDF-TrFE)’s remnant polarization. In detail, OPT’s dark current can be further reduced by a simple poling process when using P(VDF-TrFE) dielectric, leading to a “flexible” photo-to-dark current ratio. Furthermore, tuned dark current can be “nonvolatile” or sustained in the absence of gate bias, corresponding to a permanently changed dark current. As a result of reduced dark current, our photosensitive OFeFETs are beneficial for photodetection with high sensitivity. Moreover, we fabricate OFeFETs on flexible substrates and examine the stability and reliability under cumulative operation cycles and continuous mechanical deformation cycles.



EXPERIMENTAL SECTION

Materials. P(VDF-TrFE) powder (VDF/TrFE mole ratio of 7:3) was purchased from Piezotech Co., Ltd. France. Butanone (AR) and dichlorobenzene were purchased from Beijing Chemical Co. China. P(DPP-TzBT) polymer was synthesized via Suzuki-coupling polymerization in our lab. All of the chemicals were directly used without further purifications except polymeric semiconductor material. Deionized water (18.2 ΩM/cm) was made by a Milli-Q (Millipore) water purification system. Capacitor Device Fabrication and Characterization. P(VDFTrFE) powder was dissolved in butanone solvent at the concentration of 80 mg/mL and the solution was filtered with 0.45 μm PTFE syringe filter before use. Then it was spin-coated on glass substrate with Al



RESULTS AND DISCUSSION Short-range ordered semicrystalline ferroelectric copolymer plays a key role in our fabricated OFeFETs. All-trans β-phase segment in P(VDF-TrFE) is responsible for its ferroelectricity. Figure 1a shows its displacement-electric field (D−E) loop of P(VDF-TrFE) thin film sandwiched between gold and aluminum electrode. At room temperature (298 K), its Pr 43881

DOI: 10.1021/acsami.7b13709 ACS Appl. Mater. Interfaces 2017, 9, 43880−43885

Research Article

ACS Applied Materials & Interfaces

Figure 2. (a) Hysteretic drain current as a function of gate voltage clockwise sweeping for this OFeFET in dark (purple line) and when being exposed to 730 nm broadband illumination from red LED bulb at 80 mW/cm2 (pink line). (b) Data retention behavior of “1” state and “0” states recorded under Vread = −10 V, Vgate= 0 V after a short Vwrite pulse (±100 V for 1−2 s). (c) Dynamic erasing and writing process of this OFeFET device. (d) Photoresponse current as a function of diverse intensity of light. (e) Photoresponse behavior of this OFeFET under three different resistance states (“1” state, “0” state, and “Vgate = 60 V state) when light pulses for 10 s with intensity of 80 mW/cm2 were carried out every 60 s. (f) Photocurrent as a function of photo intensity diagram in this organic ferroelectric phototransistor at the gate bias of +60 V.

∼24.6° suggesting a π−π stacking distance of 3.62 Å in this P(DPP-TzBT) thin film (Figure S4b). The transistor (channel width-to-length ratio = 45 μm/450 μm) is measured at a source−drain voltage bias of −10 V within a clockwise gate voltage sweeping of ±50 V. Polarization reversal of ferroelectric occurs and the associated drain current ascends or declines as sharp features at its coercive voltage of around ±25 V in this OFeFET device (Figures 1c and 2a). In this case, two resistance states (“0” and “1” state) are obtained at zero gate bias and the largest ratio of 1/0 is above 103. Its estimated power consumption of every transistor unit is between 10 nW (“0” state) and 10 μW (“1” state). A slight decrease of drain current when gate voltage value approached −60 V in the hysteretic transfer curve (Figure 1c) is likely to be attributed to the nonlinearity and “butterfly-shaped” capacitance−voltage (C−V) characteristic of MIM-structured capacitor with P(VDF-TrFE) dielectric. In detail, a peak in C−V curve is due to polarization reversal at around coercive electric field and a capacitance decline happens when electric field reaches above Ec. Figure 2a and 2b show transfer and data retention characteristic of this OFeFET device. The “1” state (low resistance state) (LRS) is obtained after a short gate voltage (Vwrite) pulse of −100 V, whereas the “0” state (high resistance state) (HRS) is obtained after a gate voltage (Verase) pulse of +100 V. The two resistance states are maintained up to 103 seconds without significant decay indicating its long data retention capability. The dynamic nonvolatile memory properties of this OFeFET are displayed in Figure 2c. The device exhibits good writing and erasing operation repeatability when a gate voltage pulse of −60 V (Vwrite) for around 450 ms and a pulse of +100 V (Verase) are carried out alternately.

reaches up to 5.57 μC/cm2. The observed Ps is as high as 6.77 μC/cm2 and Ec is about 50 MV/m, indicating polarization switching voltage bias reaches up to 50 V for 1 μm-thick P(VDFTrFE) thin film. It is noteworthy that such an ordered ferroelectric phase can be easily obtained via postannealing process. As depicted by schematics in Figure 1b and d, a top gate, bottom contact device configuration was employed to build this photoresponsive OFeFET. Thickness of dielectric and polymeric semiconductor layer is around 600 and 15 nm for P(VDF-TrFE) and P(DPP-TzBT), respectively. A clockwise sweeping in the gate terminal causes a hysteretic transfer curve, which indicates an electrically configurable polarization for this photoresponsive OFeFET (rigid device) as shown in Figure 1c. Then a relatively smooth surface with RMS roughness of 2.24 nm can be confirmed by atomic force microscopy (AFM) height image of P(VDF-TrFE) thin film in Figure 1e. X-ray diffraction (XRD) (Figure 1f) analysis for such a thin film exhibits the (110) and (200) ferroelectric β-phase peak at ∼19.8° indicating a high degree of crystallinity of this ferroelectric polymer. Large amounts of crystalline grains with rod-like morphology are observed on the surface of P(VDF-TrFE) thin film according to its scanning electron microscopic (SEM) image (Figure 1f), and these grains (length ranges from 20 to 40 nm) embedded in the thin film may cause defects of dielectric layer in OFET devices. In Figure S4a, small crystalline grains of P(DPP-TzBT) annealed thin film can be seen in its AFM height (left) and phase (right) image. According to its out-of-plane grazing incidence X-ray (GIXRD) scattering pattern, we can see a strong primary peak at ∼3.7° (100) and a weak one at ∼7.3° (200) indicating a good degree of crystallinity. In-plane scattering pattern shows a peak at 43882

DOI: 10.1021/acsami.7b13709 ACS Appl. Mater. Interfaces 2017, 9, 43880−43885

Research Article

ACS Applied Materials & Interfaces

Figure 3. (a) Photographs of these solution-processed flexible OFeFET devices array on PI substrate. (b) Hysteretic drain current as a function of gate voltage clockwise sweeping for this OFeFET on PI substrate in dark with the channel length of 45 μm and W/L of 10. (c) Data retention behavior of “1” state and “0” states recorded under Vread = −10 V, Vgate = 0 V after a short Vwrite pulse (±100 V for 1−2 s). (d) Photographs of these solution-processed flexible nonvolatile OFeFET devices array withstanding bend fatigue test with the smallest bending radius of 2.5 mm. (e) Hysteretic drain current as a function of gate voltage clockwise sweeping for this OFeFET as bending cycles accumulate from zero to 5000. (f) Dynamic erasing, writing, and reading process of this flexible nonvolatile memory OFeFET array after bend fatigue test undergoing 400 cycles.

Figure 4. Schematic illustration of the energy band diagram of metal/semiconductor junction (Au/P(DPP-TzBT)) under optical illumination (under) and in dark (upper) at three different resistance states ((a) “0” state; (b) “1” state; (c) “VG= 60 V” state) of this device.

measured by using commercially available red LED bulb. Figure 2d shows the transient photocurrent as a function of incident intensity of light. When a positive gate bias exists, the dark current maintains around 0.1 nA, whereas the photo current under gradually increased intensity of light ascends by several

The photoresponse characteristic of this OFeFET is also studied when operated at a source−drain voltage bias of −10 V and a gate voltage bias of +60 V. Its transfer characteristic under both light and dark is investigated as shown in Figure 2a. The photocurrent in response to diverse intensity of a 730 nm light is 43883

DOI: 10.1021/acsami.7b13709 ACS Appl. Mater. Interfaces 2017, 9, 43880−43885

Research Article

ACS Applied Materials & Interfaces

TrFE) interface and the drain current can be quite remarkable once motivated by a small source/drain voltage bias. We confirm that both of these two modes are responsible for drain current increasing under source/drain bias. As shown in Figure 4a, when this OFeFET maintains high resistance state (“0” state), mode (i) is dominant. Because of the positive remnant polarization of ferroelectric dielectric, free hole density in the channel is suppressed and hence contributes little to drain current. Under illumination, photogenerated excitons dissociate into free e/h pairs gradually encounter radiative decay, exciton diffusion, and exciton quenching, resulting in an increase of free hole carrier density in OFeFET’s channel and evident photocurrent can be detected. On the contrary, mode (ii) governs free charge carrier formation in low resistance state (“1” state). Because of the negative remnant polarization of ferroelectric, a high density of hole carriers has already been induced in the bulk P(DPP-TzBT). Though illumination is provided, no more photogenerated free charge carriers (from mode (i) form and change in drain current is negligible (Figure 4b). To further demonstrate these two competing modes in its photoresponse process, a large positive gate bias of +60 V is applied to enhance the dominance of mode (i) as shown in Figure 4c and a relatively higher photoresponse intensity was observed in Figure 2e. In this case, the photogenerated charge carriers (free hole carriers) effectively increase channel conductance. The activated bound e/ h pair density in P(DPP-TzBT)’s HOMO level under Vg of +60 V are considered to be higher than those in “0” state, so these photogenerated excitons are easily formed under a 730 nm light and separate into free e/h pairs and then free charge carriers (hole carriers) contribute to drain current.

multiples in sequence. Then different photo-to-dark current ratios are observed under three different resistance states (“1” state, “0” state, and “Vgate = 60 V” state) when light pulses for 10 s with intensity of 80 mW/cm2 are carried out every 1 min according to Figure 2e. Here we can change the memory states to control the dark noise and photo-to-dark current ratio in this device. The largest ratio was obtained when a positive gate bias is applied due to a suppression of hole transport. Moreover, positive gate bias facilitates a recombination of photogenerated holes and electrons, which leads to a remarkably faster photo current response speed, as observed in both Figure 2d and e. The diagram of photocurrent as a function of photo intensity shows a good linearity, which indicates an excellent photodetection ability for strong red light (Figure 2f). Besides devices on rigid substrates, we also investigated the bending stability of this flexible OFeFET devices on polyimide (PI) substrates. In this circumstance, semitransparent PI thin film instead of glasses serves as substrates (Figure 3a), and similar hysteretic drain current as a function of gate voltage clockwise sweeping is observed in Figure 3b. Though these flexible devices have a slightly higher drain current compared to rigid ones, almost the same value of 1/0 ratio is observed in data retention measurement of these flexible devices (Figure 3c). The “1” state and the “0” state of this flexible device are maintained with long duration time up to 103 seconds, indicating highly stable data retention capability. To evaluate the mechanical stability of these flexible devices, bending fatigue test was carried out via thousands of bending cycles with bending radius of 2.5 mm, as shown in Figure 3d. As a result, a clockwise gate voltage sweeping reveals a slight change of hysteretic transfer curve even after 5000 bending cycles (Figure 3e). Dynamic erasing, writing, and reading process of this flexible OFeFET array after 400 bending cycles is investigated and its capability of repeatable erasing and writing process is reproducible. The dynamic 1/0 ratio is kept above 102 in general (Figure 3f). To understand the OFeFET’s photoresponse behavior, we attribute the operation mechanism to a Schottky junction model.29,30 As shown in Figure 4, the energy band diagram of metal/semiconductor (Au/P(DPP-TzBT), M/S) junction structure is simulated by this theory. The thermo-evaporated bottom gold electrode has a lower Fermi level (4.7 eV) than P(DPP-TzBT)’s HOMO level (5.28 eV) in this M/S junction structure in air. Because of internal electric field in semiconductor layer, a Schottky barrier of 0.58 eV is present in the range of several micrometers in this layer next to M/S interface. It leads to P(DPP-TzBT)’s HOMO energy band bending and a barrier may influence the efficiency of hole injection. In the case of p-type semiconductor, here P(DPP-TzBT), this barrier can be overcome by an external electric field applied across the source and drain electrode. First, two competing modes are responsible for the formation of free charge carriers in the channel (these photoresponse OFeFETs perform as the rule of traditional OPTs in general), where large amounts of charge carriers induced by (i) photogeneration and (ii) gate bias. For mode (i), either photodiode or phototransistor is basicly applicable to this operation mechanism. Excitons (bound e/h pairs) are formed upon illumination and dissociate into free hole and electron carriers or limited space charge with the assistance of barrier potential and vertical electric field (gate field-effect). For mode (ii), when a negative gate potential (Vg > Vth) is applied, the concentration of free holes (p-type OPT) substantially increases in semiconductor layer next to the P(DPP-TzBT)/ P(VDF-



CONCLUSION In conclusion, we have developed a novel optoelectronic device, organic ferroelectric phototransistor. Because of P(VDF-TrFE) dielectric, without continuous gate bias, dark current level can be modulated by ferroelectric. Combined with a narrow bandgap polymer semiconductor, P(DPP-TzBT), the device’s potential application lies in photosensing. We also show the flexible OFeFET array are endurable after bending fatigue test with high stability and efficiency in data storage performance. Because of OFeFET’s memory and photoresponse characteristic, possible mechanisms of their correlation with the source/drain current are given. Existing imperfection lies in yet unsatisfactory photoresponse intensity and response speed, which need to be improved in further. This type of photoresponsive OFeFET will have broad utilization in flexible electronics, information storage, and novel photo detectors.



ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.7b13709. Contact angle change of modified substrate; morphology and GI-XRD pattern of semiconductor layer; absorption spectrum and synthesis route of semiconductor material; memory performance stats of OFeFETs (PDF)



AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. *E-mail: [email protected]. 43884

DOI: 10.1021/acsami.7b13709 ACS Appl. Mater. Interfaces 2017, 9, 43880−43885

Research Article

ACS Applied Materials & Interfaces ORCID

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Wenping Hu: 0000-0001-5686-2740 Author Contributions ⊥

These authors contributed equally to this work.

Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS W.P.H., L.J. and H.L.D. appreciate the financial support by Ministry of Science and Technology of China (2016YFB04001100, 2013CB933403, 2013CB933504), National Natural Science Foundation of China (51633006, 91222203, 91233205, 91433115), and Chinese Academy of Sciences (Hundred Talents Plan and XDB12030300).



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DOI: 10.1021/acsami.7b13709 ACS Appl. Mater. Interfaces 2017, 9, 43880−43885