Ultrathin,Organic, Semiconductor/Polymer Blends by Scanning Corona‐Discharge Coating for High‐Performance Organic Thin‐Film Transistors

A new thin‐film coating process, scanning corona‐discharge coating (SCDC), to fabricate ultrathin tri‐isopropylsilylethynyl pentacene (TIPS‐PEN)/amorphous‐polymer blend layers suitable for high‐performance, bottom‐gate, organic thin‐film transistors (OTFTs) is described. The method is based on utilizing the electrodynamic flow of gas molecules that are corona‐discharged at a sharp metallic tip under a high voltage and subsequently directed towards a bottom electrode. With the static movement of the bottom electrode, on which a blend solution of TIPS‐PEN and an amorphous polymer is deposited, SCDC provides an efficient route to produce uniform blend films with thicknesses of less than one hundred nanometers, in which the TIPS‐PEN and the amorphous polymer are vertically phase‐separated into a bilayered structure with a single‐crystalline nature of the TIPS‐PEN. A bottom‐gate field‐effect transistor with a blend layer of TIPS‐PEN/polystyrene (PS) (90/10 wt%) operated at ambient conditions, for example, indeed exhibits a highly reliable device performance with a field‐effect mobility of approximately 0.23 cm² V^?1 s^?1: two orders of magnitude greater than that of a spin‐coated blend film. SCDC also turns out to be applicable to other amorphous polymers, such as poly(α‐methyl styrene) and poly(methyl methacrylate) and, readily combined with the conventional transfer‐printing technique, gives rise to micropatterned arrays of TIPS‐PEN/polymer films.     

Printable Ferroelectric PVDF/PMMA Blend Films with Ultralow Roughness for Low Voltage Non‐Volatile Polymer Memory

Here, a facile route to fabricate thin ferroelectric poly(vinylidene fluoride) (PVDF)/poly(methylmethacrylate) (PMMA) blend films with very low surface roughness based on spin‐coating and subsequent melt‐quenching is described. Amorphous PMMA in a blend film effectively retards the rapid crystallization of PVDF upon quenching, giving rise to a thin and flat ferroelectric film with nanometer scale β‐type PVDF crystals. The still, flat interfaces of the blend film with metal electrode and/or an organic semi‐conducting channel layer enable fabrication of a highly reliable ferroelectric capacitor and transistor memory unit operating at voltages as low as 15 V. For instance, with a TIPS‐pentacene single crystal as an active semi‐conducting layer, a flexible ferroelectric field effect transistor shows a clockwise I–V hysteresis with a drain current bistability of 10³ and data retention time of more than 15 h at ±15 V gate voltage. Furthermore, the robust interfacial homogeneity of the ferroelectric film is highly beneficial for transfer printing in which arrays of metal/ferroelectric/metal micro‐capacitors are developed over a large area with well defined edge sharpness.     

High Performance Multi‐Level Non‐Volatile Polymer Memory with Solution‐Blended Ferroelectric Polymer/High‐k Insulators for Low Voltage Operation

Polymer ferroelectric‐gate field effect transistors (Fe‐FETs) employing ferroelectric polymer thin films as gate insulators are highly attractive as a next‐generation non‐volatile memory. Furthermore, polymer Fe‐FETs have been recently of interest owing to their capability of storing data in more than 2 states in a single device, that is, they have multi‐level cell (MLC) operation potential for high density data storage. However, among a variety of technological issues of MLC polymer Fe‐FETs, the requirement of high voltage for cell operation is one of the most urgent problems. Here, a low voltage operating MLC polymer Fe‐FET memory with a high dielectric constant (k) ferroelectric polymer insulator is presented. Effective enhancement of capacitance of the ferroelectric gate insulator layer is achieved by a simple binary solution‐blend of a ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) (PVDF‐TrFE) (k ≈ 8) with a relaxer high‐k poly(vinylidene‐fluoride–trifluoroethylene–chlorotrifluoroethylene) (PVDF‐TrFE‐CTFE) (k ≈ 18). At optimized conditions, a ferroelectric insulator with a PVDF‐TrFE/PVDF‐TrFE‐CTFE (10/5) blend composition enables the discrete six‐level multi‐state operation of a MLC Fe‐FET at a gate voltage sweep of ±18 V with excellent data retention and endurance of each state of more than 10⁴ s and 120 cycles, respectively.     

Control of Current Hysteresis of Networked Single‐Walled Carbon Nanotube Transistors by a Ferroelectric Polymer Gate Insulator

Films made of 2D networks of single‐walled carbon nanotubes (SWNTs) are one of the most promising active‐channel materials for field‐effect transistors (FETs) and have a variety of flexible electronic applications, ranging from biological and chemical sensors to high‐speed switching devices. Challenges, however, still remain due to the current hysteresis of SWNT‐containing FETs, which has hindered further development. A new and robust method to control the current hysteresis of a SWNT‐network FET is presented, which involves the non‐volatile polarization of a ferroelectric poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) gate insulator. A top‐gate FET with a solution‐processed SWNT‐network exhibits significant suppression of the hysteresis when the gate‐voltage sweep is greater than the coercive field of the ferroelectric polymer layer (≈50 MV m^?1). These near‐hysteresis‐free characteristics are believed to be due to the characteristic hysteresis of the P(VDF‐TrFE), resulting from its non‐volatile polarization, which makes effective compensation for the current hysteresis of the SWNT‐network FETs. The onset voltage for hysteresis‐minimized operation is able to be tuned simply by controlling the thickness of the ferroelectric film, which opens the possibility of operating hysteresis‐free devices with gate voltages down to a few volts.     

Fully Transparent Non‐volatile Memory Thin‐Film Transistors Using an Organic Ferroelectric and Oxide Semiconductor Below 200 °C

A fully transparent non‐volatile memory thin‐film transistor (T‐MTFT) is demonstrated. The gate stack is composed of organic ferroelectric poly(vinylidene fluoride‐trifluoroethylene) [P(VDF‐TrFE)] and oxide semiconducting Al‐Zn‐Sn‐O (AZTO) layers, in which thin Al₂O₃ is introduced between two layers. All the fabrication processes are performed below 200 °C on the glass substrate. The transmittance of the fabricated device was more than 90% at the wavelength of 550 nm. The memory window obtained in the T‐MTFT was 7.5 V with a gate voltage sweep of ?10 to 10 V, and it was still 1.8 V even with a lower voltage sweep of ?6 to 6 V. The field‐effect mobility, subthreshold swing, on/off ratio, and gate leakage currents were obtained to be 32.2 cm² V^?1 s^?1, 0.45 V decade^?1, 10⁸, and 10^?13 A, respectively. All these characteristics correspond to the best performances among all types of non‐volatile memory transistors reported so far, although the programming speed and retention time should be more improved.     

Semitransparent,Flexible, and Self‐Powered Photodetectors Based on Ferroelectricity‐Assisted Perovskite Nanowire Arrays

Transparent and flexible photodetectors hold great promise in next‐generation portable and wearable optoelectronic devices. However, most of the previously reported devices need an external energy power source to drive its operation or require complex fabrication processes. Herein, designed is a semitransparent, flexible, and self‐powered photodetector based on the integrated ferroelectric poly(vinylidene‐fluoride‐trifluoroethylene) (P(VDF‐TrFE)) and perovskite nanowire arrays on the flexible polyethylene naphthalate substrate via a facile imprinting method. Through optimizing the treatment conditions, including polarization voltage, polarization time, and the concentration of P(VDF‐TrFE), the resulting device exhibits remarkable detectivity (7.3 × 10¹² Jones), fast response time (88/154 µs) at zero bias, as well as outstanding mechanical stability. The excellent performance is attributed to the efficient charge separation and transport originating from the highly oriented 1D transport pathway and the polarization‐induced internal electric field within P(VDF‐TrFE)/perovskite hybrid nanowire arrays.     

Enhanced Performance Consistency in Nanoparticle/TIPS Pentacene‐Based Organic Thin Film Transistors

In this study, inorganic silica nanoparticles are used to manipulate the morphology of 6,13‐bis(triisopropylsilylethynyl)‐pentacene (TIPS pentacene) thin films and the performance of solution‐processed organic thin‐film transistors (OTFTs). This approach is taken to control crystal anisotropy, which is the origin of poor consistency in TIPS pentacene based OTFT devices. Thin film active layers are produced by drop‐casting mixtures of SiO₂ nanoparticles and TIPS pentacene. The resultant drop‐cast films yield improved morphological uniformity at ～10% SiO₂ loading, which also leads to a 3‐fold increase in average mobility and nearly 4 times reduction in the ratio of measured mobility standard deviation (μ_Stdev) to average mobility (μ_Avg). Grazing‐incidence X‐ray diffraction, scanning and transmission electron microscopy as well as polarized optical microscopy are used to investigate the nanoparticle‐mediated TIPS pentacene crystallization. The experimental results suggest that the SiO₂ nanoparticles mostly aggregate at TIPS pentacene grain boundaries, and 10% nanoparticle concentration effectively reduces the undesirable crystal misorientation without considerably compromising TIPS pentacene crystallinity.     

Ultrahigh‐Performance Flexible and Self‐Powered Photodetectors with Ferroelectric P(VDF‐TrFE)/Perovskite Bulk Heterojunction

Flexible and self‐powered perovskite photodetectors attract widespread research interests due to their potential applications in portable and wearable optoelectronic devices. However, the reported devices mainly adopt an independent layered structure with complex fabrication processes and high carrier recombination. Herein, an integrated ferroelectric poly(vinylidene‐fluoride‐trifluoroethylene) (P(VDF‐TrFE)) and perovskite bulk heterojunction film photodetector on the polyethylene naphthalate substrate is demonstrated. Under the optimum treatment conditions (the polarization voltage and time, and the concentration of P(VDF‐TrFE)), the photodetector exhibits a largely enhanced performance compared to the pristine perovskite device. The resulting device exhibits ultrahigh performance with a large detectivity (1.4 × 10¹³ Jones) and fast response time (92/193 µs) at the wavelength of 650 nm. The improved performance is attributed to the fact that the polarized P(VDF‐TrFE)/perovskite hybrid film provides a stronger built‐in electric field to facilitate the separation and transportation of photogenerated carriers. These findings provide a new route to design self‐powered photodetectors from the aspect of device structure and carrier transport.     

All‐Polymer Bistable Resistive Memory Device Based on Nanoscale Phase‐Separated PCBM‐Ferroelectric Blends

All polymer nonvolatile bistable memory devices are fabricated from blends of ferroelectric poly(vinylidenefluoride–trifluoroethylene (P(VDF‐TrFE)) and n‐type semiconducting [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM). The nanoscale phase separated films consist of PCBM domains that extend from bottom to top electrode, surrounded by a ferroelectric P(VDF‐TrFE) matrix. Highly conducting poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) polymer electrodes are used to engineer band offsets at the interfaces. The devices display resistive switching behavior due to modulation of this injection barrier. With careful optimization of the solvent and processing conditions, it is possible to spin cast very smooth blend films (R_rms ≈ 7.94 nm) and with good reproducibility. The devices exhibit high I_on/I_off ratios (≈3 × 10³), low read voltages (≈5 V), excellent dielectric response at high frequencies (?_r ≈ 8.3 at 1 MHz), and excellent retention characteristics up to 10 000 s.     

A High‐k Fluorinated P(VDF‐TrFE)‐g‐PMMA Gate Dielectric for High‐Performance Flexible Field‐Effect Transistors

A newly synthesized high‐k polymeric insulator for use as gate dielectric layer for organic field‐effect transistors (OFETs) obtained by grafting poly(methyl methacrylate) (PMMA) in poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) via atom transfer radical polymerization transfer is reported. This material design concept intents to tune the electrical properties of the gate insulating layer (capacitance, leakage current, breakdown voltage, and operational stability) of the high‐k fluorinated polymer dielectric without a large increase in operating voltage by incorporating an amorphous PMMA as an insulator. By controlling the grafted PMMA percentage, an optimized P(VDF‐TrFE)‐g‐PMMA with 7 mol% grafted PMMA showing reasonably high capacitance (23–30 nF cm^?2) with low voltage operation and negligible current hysteresis is achieved. High‐performance low‐voltage‐operated top‐gate/bottom‐contact OFETs with widely used high mobility polymer semiconductors, poly[[2,5‐bis(2‐octyldodecyl)‐2,3,5,6‐tetrahydro‐3,6‐dioxopyrrolo [3,4‐c]pyrrole‐1,4‐diyl]‐alt‐[[2,2′‐(2,5‐thiophene)bis‐thieno(3,2‐b)thiophene]‐5,5′‐diyl]] (DPPT‐TT), and poly([N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)) are demonstrated here. DPPT‐TT OFETs with P(VDF‐TrFE)‐g‐PMMA gate dielectrics exhibit a reasonably high field‐effect mobility of over 1 cm² V^?1 s^?1 with excellent operational stability.     

High‐Performance Ferroelectric Memory Based on Phase‐Separated Films of Polymer Blends

High‐performance polymer memory is fabricated using blends of ferroelectric poly(vinylidene‐fluoride‐trifluoroethylene) (P(VDF‐TrFE)) and highly insulating poly(p‐phenylene oxide) (PPO). The blend films spontaneously phase separate into amorphous PPO nanospheres embedded in a semicrystalline P(VDF‐TrFE) matrix. Using low molecular weight PPO with high miscibility in a common solvent, i.e., methyl ethyl ketone, blend films are spin cast with extremely low roughness (R_rms ≈ 4.92 nm) and achieve nanoscale phase seperation (PPO domain size < 200 nm). These blend devices display highly improved ferroelectric and dielectric performance with low dielectric losses (<0.2 up to 1 MHz), enhanced thermal stability (up to ≈353 K), excellent fatigue endurance (80% retention after 10⁶ cycles at 1 KHz) and high dielectric breakdown fields (≈360 MV/m).     

Micropatterned P(VDF‐TrFE) Film‐Based Piezoelectric Nanogenerators for Highly Sensitive Self‐Powered Pressure Sensors

Here micropatterned poly(vinylidenefluoride‐co‐trifluoroethylene) (P(VDF‐TrFE)) films‐based piezoelectric nanogenerators (PNGs) with high power‐generating performance for highly sensitive self‐powered pressure sensors are demonstrated. The microstructured P(VDF‐TrFE)‐based PNGs reveal nearly five times larger power output compared to a flat film‐based PNG. The micropatterning of P(VDF‐TrFE) polymer makes itself ultrasensitive in response to mechanical deformation. The application is demonstrated successfully as self‐powered pressure sensors in which mechanical energy comes from water droplet and wind. The mechanism of the high performance is intensively discussed and illustrated in terms of strain developed in the flat and micropatterned P(VDF‐TrFE) films. The impact derived from the patterning on the output performance is studied in term of effective pressure using COMSOL multiphysics software.     

Photo‐Stable Organic Thin‐Film Transistor Utilizing a New Indolocarbazole Derivative for Image Pixel and Logic Applications

Small molecule pentacene layer has been a representative among many organic thin‐film transistor (OTFT) channels with decent p‐type mobilities, but it is certainly light‐sensitive due to its relatively small highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) gap (1.85 eV). Although a few other small molecule‐based layers have been reported later, their photo‐stabilities or related device applications have hardly been addressed. Here, a new photostable organic layer is reported, heptazole (C₂₆H₁₆N₂), which has almost the same HOMO level as that of pentacene but with a higher HOMO‐LUMO gap (≈2.95 eV). This heptazole OTFT displays a decent mobility comparable to that of conventional amorphous Si TFTs, showing good photostability unlike pentacene OTFTs. An image pixel driving the photostable heptazole OTFT connected to a pentacene/Al Schottky photodiode is demonstrated. This heptazole OTFT also conveniently forms a logic inverter coupled with a pentacene OTFT, sharing Au for source/drain.     

Nano‐Imprinted Ferroelectric Polymer Nanodot Arrays for High Density Data Storage

Ferroelectric vinylidene fluoride‐trifluoroethylene copolymer [P(VDF‐TrFE)] free‐standing ultrahigh density (≈75 Gb inch^?2) nanodot arrays are successfully fabricated through a facile, high‐throughput, and cost‐effective nano‐imprinting method using disposable anodic aluminum oxide with orderly arranged nanometer‐scale pores as molds. The nanodots show a large‐area smooth surface morphology, and the piezoresponse in each nanodot is strong and uniform. The preferred orientation of the copolymer chains in the nanodot arrays is favorable for polarization switching of single nanodots. The ferroelectric polymer memory prototype can be operated by a few volts with high writing/erasing speed, which comply with the requirements of integrated circuit. This approach provides a way of directly writing nanometer electronic features in two dimensions by piezoresponse force microscopy probe based technology, which is attractive for high density data storage.     

Self‐Assembled,Millimeter‐Sized TIPS‐Pentacene Spherulites Grown on Partially Crosslinked Polymer Gate Dielectric

Here, a highly crystalline and self‐assembled 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐Pentacene) thin films formed by simple spin‐coating for the fabrication of high‐performance solution‐processed organic field‐effect transistors (OFETs) are reported. Rather than using semiconducting organic small‐molecule–insulating polymer blends for an active layer of an organic transistor, TIPS‐Pentacene organic semiconductor is separately self‐assembled on partially crosslinked poly‐4‐vinylphenol:poly(melamine‐co‐formaldehyde) (PVP:PMF) gate dielectric, which results in a vertically segregated semiconductor‐dielectric film with millimeter‐sized spherulite‐crystalline morphology of TIPS‐Pentacene. The structural and electrical properties of TIPS‐Pentacene/PVP:PMF films have been studied using a combination of polarized optical microscopy, atomic force microscopy, 2D‐grazing incidence wide‐angle X‐ray scattering, and secondary ion mass spectrometry. It is finally demonstrated a high‐performance OFETs with a maximum hole mobility of 3.40 cm² V^?1 s^?1 which is, to the best of our knowledge, one of the highest mobility values for TIPS‐Pentacene OFETs fabricated using a conventional solution process. It is expected that this new deposition method would be applicable to other small molecular semiconductor–curable polymer gate dielectric systems for high‐performance organic electronic applications.     

Electrode Dependence of Tunneling Electroresistance and Switching Stability in Organic Ferroelectric P(VDF‐TrFE)‐Based Tunnel Junctions

Ferroelectric tunnel junctions (FTJs) are promising candidates for nonvolatile memories and memristor‐based computing circuits. Thus far, most research has focused on FTJs with a perovskite oxide ferroelectric tunnel barrier. As the need for high‐temperature epitaxial film growth challenges the technological application of such inorganic junctions, more easily processable organic ferroelectrics can serve as alternative if large tunneling electroresistance (TER) and good switching durability would persist. This study reports on the performance of FTJs with a spin‐coated ferroelectric P(VDF‐TrFE) copolymer tunnel barrier. The use of three different bottom electrodes, indium tin oxide (ITO), La_0.67Sr_0.33MnO₃, (LSMO), and Nb‐doped SrTiO₃ (STO) are compared and it is shown that the polarity and magnitude of the TER effect depend on their conductivity. The largest TER of up to 10⁷% at room temperature is measured on FTJs with a semiconducting Nb‐doped STO electrode. This large switching effect is attributed to the formation of an extra barrier over the space charge region in the substrate. The organic FTJs exhibit good resistance retention and switching endurance up to 380 K, which is just below the ferroelectric Curie temperature of the P(VDF‐TrFE) barrier.     

Processing and Low Voltage Switching of Organic Ferroelectric Phase‐Separated Bistable Diodes

The processing of solution‐based binary blends of the ferroelectric random copolymer poly(vinylidene fluoride‐trifluoroethylene) P(VDF‐TrFE) and the semiconducting polymer poly(9,9‐dioctylfluorenyl‐2,7‐diyl) (PFO) applied by spin‐coating and wire‐bar coating is investigated. By systematic variation of blend composition, solvent, and deposition temperature it is shown that much smoother blend films can be obtained than reported thus far. At a low PFO:P(VDF‐TrFE) ratio the blend film consists of disk‐shaped PFO domains embedded in a P(VDF‐TrFE) matrix, while an inverted structure is obtained in case the P(VDF‐TrFE) is the minority component. The microstructure of the phase separated blend films is self‐affine. From this observation and from the domain size distribution it is concluded that the phase separation occurs via spinodal decomposition, irrespectively of blend ratio. This is explained by the strong incompatibility of the two polymers expressed by the binary phase diagram, as constructed from thermal analysis data. Time resolved numerical simulation of the microstructure evolution during de‐mixing qualitatively shows how an elevated deposition temperature has a smoothening effect as a result of the reduction of the repulsion between the blend components. The small roughness allowed the realization of bistable rectifying diodes that switch at low voltages with a yield of 100%. This indicates that memory characteristics can be tailored from the outset while processing parameters can be adjusted according to the phase behavior of the active components.     

Effect of active layer thickness on environmental stability of printed thin-film transistor

We have studied the effect of active layer thickness on the performance and environmental stability of the 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) thin-film transistor. The organic thin-film transistors (OTFTs) were fabricated by inkjet printing using a solution based TIPS pentacene. To get thick organic semiconductor, the surface of gate insulator was treated with n-octyltrichlorosilane (OTS-C₈) before jetting. The on-currents of the OTFT with ～1 μm active layer decreases a little in air, but the OTFT with 0.05 μm TIPS pentacene shows a significant degradation in drain currents.     

High‐Performance Piezoelectric,Pyroelectric, and Triboelectric Nanogenerators Based on P(VDF‐TrFE) with Controlled Crystallinity and Dipole Alignment

Poly(vinylidenefluoride‐co‐trifluoroethylene) (P(VDF‐TrFE)), as a ferroelectric polymer, offers great promise for energy harvesting for flexible and wearable applications. Here, this paper shows that the choice of solvent used to dissolve the polymer significantly influences its properties in terms of energy harvesting. Indeed, the P(VDF‐TrFE) prepared using a high dipole moment solvent has higher piezoelectric and pyroelectric coefficients and triboelectric property. Such improvements are the result of higher crystallinity and better dipole alignment of the polymer prepared using a higher dipole moment solvent. Finite element method simulations confirm that the higher dipole moment results in higher piezoelectric, pyroelectric, and triboelectric potential distributions. Furthermore, P(VDF‐TrFE)‐based piezoelectric, pyroelectric, and triboelectric nanogenerators (NGs) experimentally validate that the higher dipole moment solvent significantly enhances the power output performance of the NGs; the improvement is about 24% and 82% in output voltage and current, respectively, for piezoelectric NG; about 40% and 35% in output voltage and current, respectively, for pyroelectric NG; and about 65% and 75% in output voltage and current for triboelectric NG. In brief, the approach of using a high dipole moment solvent is very promising for high output P(VDF‐TrFE)‐based wearable NGs.     

Surface Directed Phase Separation of Semiconductor Ferroelectric Polymer Blends and their Use in Non‐Volatile Memories

The polymer phase separation of P(VDF‐TrFE):F8BT blends is studied in detail. Its morphology is key to the operation and performance of memory diodes. In this study, it is demonstrated that it is possible to direct the semiconducting domains of a phase‐separating mixture of P(VDF‐TrFE) and F8BT in a thin film into a highly ordered 2D lattice by means of surface directed phase separation. Numerical simulation of the surface‐controlled de‐mixing process provides insight in the ability of the substrate pattern to direct the phase separation, and hence the regularity of the domain pattern in the final dry blend layer. By optimizing the ratio of the blend components, the number of electrically active semiconductor domains is maximized. Pattern replication on a cm‐scale is achieved, and improved functional device performance is demonstrated in the form of a 10‐fold increase of the ON‐current and a sixfold increase in current modulation. This approach therefore provides a simple and scalable means to higher density integration, the ultimate target being a single semiconducting domain per memory cell.