Polymer Field-effect Transistors Research Articles

Performance Improvements in Conjugated Polymer Devices by Removal of Water-Induced Traps.

The exploration of a wide range of molecular structures has led to the development of high-performance conjugated polymer semiconductors for flexible electronic applications including displays, sensors, and logic circuits. Nevertheless, many conjugated polymer field-effect transistors (OFETs) exhibit nonideal device characteristics and device instabilities rendering them unfit for industrial applications. These often do not originate in the material's intrinsic molecular structure, but rather in external trap states caused by chemical impurities or environmental species such as water. Here, a highly efficient mechanism is demonstrated for the removal of water-induced traps that are omnipresent in conjugated polymer devices even when processed in inert environments; the underlying mechanism is shown, by which small-molecular additives with water-binding nitrile groups or alternatively water-solvent azeotropes are capable of removing water-induced traps leading to a significant improvement in OFET performance. It is also shown how certain polymer structures containing strong hydrogen accepting groups will suffer from poor performances due to their high susceptibility to interact with water molecules; this allows the design guidelines for a next generation of stable, high-performing conjugated polymers to be set forth.

Facile and low-cost mechanical techniques for the fabrication of solution-processed polymer and perovskite thin film transistors

Low-temperature solution-processed polymer and perovskite thin film field effect transistors (FETs) are attractive, as they are compatible with flexible and printed electronics. Given that chemical treatment of the FET channel is expensive and tedious, and sometimes damages the underneath (dielectric) solution-processed layers, in this work, two facile and scalable mechanical treatment techniques are proposed. In the case of polymer FET, the wet spun film was excited by ultrasonic vibration imposed on the substrate. It is demonstrated that the micromixing effect induced by the ultrasonic radiation results in disentanglement, reorganization, and recrystallization of the polymer chains in the wet film. Ultrasonic vibration also improves the film leveling and uniformity and enhances the charge mobility of the channel of the polymer FET. In the case of the perovskite FET, we found that nitrogen blowing over the spun sample of the perovskite solution is a facile, yet effective substitution for the conventional anti-solvent treatment, commonly used to control the solvent evaporation rate. By nitrogen blowing, we achieved a uniform film of perovskite deposited on a solution-processed dielectric layer with domain sizes up to several hundreds of nanometers. By applying these techniques, the linear charge mobility of 0.041 cm2 Vs−1 and 0.055 cm2 Vs−1 were obtained for polymer and perovskite FETs under illumination, respectively. It is shown that while the performance of the polymer FET is only slightly sensitive to illumination, the perovskite FET performs well only under illumination.

Shellac Films as a Natural Dielectric Layer for Enhanced Electron Transport in Polymer Field-Effect Transistors.

Shellac, a natural polymer resin obtained from the secretions of lac bugs, was evaluated as a dielectric layer in organic field-effect transistors (OFETs) on the basis of donor (D)-acceptor (A)-type conjugated semiconducting copolymers. The measured dielectric constant and breakdown field of the shellac layer were ∼3.4 and 3.0 MV/cm, respectively, comparable with those of a poly(4-vinylphenol) (PVP) film, a commonly used dielectric material. Bottom-gate/top-contact OFETs were fabricated with shellac or PVP as the dielectric layer and one of three different D-A-type semiconducting copolymers as the active layer: poly(cyclopentadithiophene- alt-benzothiadiazole) with p-type characteristics, poly(naphthalene-bis(dicarboximide)- alt-bithiophene) [P(NDI2OD-T2)] with n-type characteristics, and poly(dithienyl-diketopyrrolopyrrole- alt-thienothiophene) [P(DPP2T-TT)] with ambipolar characteristics. The electrical characteristics of the fabricated OFETs were then measured. For all active layers, OFETs with a shellac film as the dielectric layer exhibited a better mobility than those with PVP. For example, the mobility of the OFET with a shellac dielectric and n-type P(NDI2OD-T2) active layer was approximately 2 orders of magnitude greater than that of the corresponding OFET with a PVP insulating layer. When P(DPP2T-TT) served as the active layer, the OFET with shellac as the dielectric exhibited ambipolar characteristics, whereas the corresponding OFET with the PVP dielectric operated only in hole-accumulation mode. The total density of states was analyzed using technology computer-aided design simulations. The results revealed that compared with the OFETs with PVP as the dielectric, the OFETs with shellac as the dielectric had a lower trap-site density at the polymer semiconductor/dielectric interface and much fewer acceptor-like trap sites acting as electron traps. These results demonstrate that shellac is a suitable dielectric material for D-A-type semiconducting copolymer-based OFETs, and the use of shellac as a dielectric layer facilitates electron transport at the interface with D-A-type copolymer channels.

Probing Device Degradation and Electric Fields in Polymeric Field-Effect Transistors by SFG Vibrational Spectroscopy

There is great interest on the study of the semiconductor/dielectric interface of organic field-effect transistors (OFETs), where a conducting channel is formed. Here, we use the interface selectivity, chemical sensitivity, and field-induced enhancement of sum-frequency generation (SFG) vibrational spectroscopy to probe interfacial molecular ordering and degradation processes in poly-3-hexylthiophene (P3HT) OFETs and also the electric field within their dielectric layer (poly(methyl methacrylate), PMMA). P3HT active layers fabricated by the Langmuir–Schaefer method are more orientationally ordered than spin-coated films. Upon electrical degradation of the device in ambient conditions, no noticeable changes were detected in the SFG spectra of the semiconductor/dielectric interface because the sensitivity of our experiment was not enough to detect degraded polymer chains due to loss of SFG electronic resonance enhancement. Perhaps for the same reason, we were also not able to detect any significant changes ...

Improved Electron Transport with Reduced Contact Resistance in N-Doped Polymer Field-Effect Transistors with a Dimeric Dopant.

Attaining control on charge injection properties is significant for meaningful applications of organic field-effect transistors (OFETs). Here, molecular electron-doping is applied with an air-stable dimer dopant for n-type OFETs based on (naphthalene diimide-diketopyrrolopyrrole) polymer hosts. Through investigating the doping effect on contact and transport properties, it is found that the electron transport increases in n-doped OFETs at low doping regime with remaining large on/off ratios. These favorable meliorations are reconciled by the mitigated impacts of contact resistance and interfacial traps, as well as the surface morphology exhibiting features of increased ordering. The occurrence of doping in the presence of dimer dopants is evidenced by the observed shift of Fermi level toward vacuum level coupled with compositional analysis. Without applying vacuum-deposition-based contact doping, charge injection efficiencies are gained without losing OFET characteristics using the solution-based methodology.

Well-Balanced Ambipolar Conjugated Polymers Featuring Mild Glass Transition Temperatures Toward High-Performance Flexible Field-Effect Transistors.

Conjugated polymers, which can be fabricated by simple processing techniques and possess excellent electrical performance, are key to the fabrication of flexible polymer field-effect transistors (PFETs) and integrated circuits. Herein, two ambipolar conjugated polymers based on (3E,7E)-3,7-bis(2-oxo-1H-pyrrolo[2,3-b]pyridin-3(2H)-ylidene)benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione and dithienylbenzothiadiazole units, namely PNBDOPV-DTBT and PNBDOPV-DTF2BT, are developed. Both copolymers possess almost planar conjugated backbone conformations and suitable highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) energy levels (-5.64/-4.38 eV for PNBDOPV-DTBT and -5.79/-4.48 eV for PNBDOPV-DTF2BT). Note that PNBDOPV-DTBT has a glass transition temperature (140 °C) lower than the deformation temperature of polyethylene terephthalate (PET), meaning well-ordered molecular packing can be obtained on PET substrate before its deformation in mild thermal annealing process. Flexible PFETs based on PNBDOPV-DTBT fabricated on PET substrates exhibit high and well-balanced hole/electron mobilities of 4.68/4.72 cm2 V-1 s-1 under ambient conditions. After the further modification of Au source/drain electrodes with 1-octanethiol self-assembled monolayers, impressively high and well-balanced hole/electron mobilities up to 5.97/7.07 cm2 V-1 s-1 are achieved in the flexible PFETs. Meanwhile, flexible complementary-like inverters based on PNBDOPV-DTBT on PET substrate also afford a much high gain of 148. The device performances of both the PFETs and inverters are among the highest values for ambipolar conjugated polymers reported to date.

Thionating iso-diketopyrrolopyrrole-based polymers: from p-type to ambipolar field effect transistors with enhanced charge mobility

Two polymers based on isoDPP and isoDTPP were designed and synthesized. Thionation reactions could transform p-type polymers into ambipolar polymers for field effect transistors with enhanced charge mobility.

Interface studies of well-controlled polymer bilayers and field-effect transistors prepared by a mixed-solvent method.

The properties of semiconductor/dielectric interfaces are crucial to the performance of polymer field-effect transistors. The key to fabricating high-performance polymer transistors by spin-coating is solving solvent corrosion issues, wherein the solvent of the top polymer produces a rough interface or damage on the underlying polymer layer during deposition. Herein, we propose a mixed-solvent method that employs a mixture of an orthogonal solvent of the underlying polymer and a good solvent of the top polymer as the solvent of the top polymer to prepare polymer bilayers and produce a comparative study of the trap density at the semiconductor/dielectric interface of the corresponding transistor. By changing the ratio of orthogonal solvent to good solvent, namely the degree of orthogonality of the mixed solvent with respect to the underlying polymer, the interface and film qualities of polymer bilayers can be well controlled. We applied this method to spin-coat poly(3-hexylthiophene) (P3HT) on poly(methylmethacrylate) (PMMA) with a mixture of cyclohexane (orthogonal solvent) and chloroform (good solvent). The results of morphology characterizations and electrical property studies indicate the optimal ratio of cyclohexane to chloroform for preparing high-quality P3HT/PMMA bilayers for field-effect conduction is 7 : 3. Transistors based on the optimal bilayers with a bottom-gate/top-contact configuration and a long channel length show good performance. The trap density at the P3HT/PMMA interface is evaluated to be 3.6 × 1012 cm−2 eV−1 from the subthreshold swing, characterizing the distribution of the interface trap levels across the bandgap in P3HT. Furthermore, based on deviations from ideality in the capacitance–voltage characteristics of the metal–insulator–semiconductor capacitor in the device, the traps at the interface are found to be acceptor-type, with the trap density determined to be 2.3 × 1011 cm−2. This value is in a good agreement with that estimated from the subthreshold swing.

Structure-Property Relationships of Semiconducting Polymers for Flexible and Durable Polymer Field-Effect Transistors.

We report high-performance top-gate bottom-contact flexible polymer field-effect transistors (FETs) fabricated by flow-coating diketopyrrolopyrrole (DPP)-based and naphthalene diimide (NDI)-based polymers (P(DPP2DT-T2), P(DPP2DT-TT), P(DPP2DT-DTT), P(NDI2OD-T2), P(NDI2OD-F2T2), and P(NDI2OD-Se2)) as semiconducting channel materials. All of the polymers displayed good FET characteristics with on/off current ratios exceeding 107. The highest hole mobility of 1.51 cm2 V-1 s-1 and the highest electron mobility of 0.85 cm2 V-1 s-1 were obtained from the P(DPP2DT-T2) and P(NDI2OD-Se2) polymer FETs, respectively. The impacts of the polymer structures on the FET performance are well-explained by the interplay between the crystallinity, the tendency of the polymer backbone to adopt an edge-on orientation, and the interconnectivity of polymer fibrils in the film state. Additionally, we demonstrated that all of the flexible polymer-based FETs were highly resistant to tensile stress, with negligible changes in their carrier mobilities and on/off ratios after a bending test. Conclusively, these high-performance, flexible, and durable FETs demonstrate the potential of semiconducting conjugated polymers for use in flexible electronic applications.

Directionally Aligned Amorphous Polymer Chains via Electrohydrodynamic-Jet Printing: Analysis of Morphology and Polymer Field-Effect Transistor Characteristics.

Electrohydrodynamic-jet (EHD-jet) printing provides an opportunity to directly assembled amorphous polymer chains in the printed pattern. Herein, an EHD-jet printed amorphous polymer was employed as the active layer for fabrication of organic field-effect transistors (OFETs). Under optimized conditions, the field-effect mobility (μFET) of the EHD-jet printed OFETs was 5 times higher than the highest μFET observed in the spin-coated OFETs, and this improvement was achieved without the use of complex surface templating or additional pre- or post-deposition processing. As the chain alignment can be affected by the surface energy of the dielectric layer in EHD-jet printed OFETs, dielectric layers with varying wettability were examined. Near-edge X-ray absorption fine structure measurements were performed to compare the amorphous chain alignment in OFET active layers prepared by EHD-jet printing and spin coating.

Thiophene-Thiazole-Based Semiconducting Copolymers for High-Performance Polymer Field-Effect Transistors.

We report a newly synthesized donor (D)-acceptor (A)type semiconducting copolymer, consisting of thiophene as an electron-donating unit and thiazole as an electron-accepting unit (PQTBTz-TT-C8) for the active layer of the organic field-effect transistors (OFETs). Specifically, this study investigates the structure and electrical property relationships of PQTBTz-TT-C8 with comprehensive analyses on the charge-transporting properties corresponding to the spin rate of the spin coater during the formation of the PQTBTz-TT-C8 film. The crystallinity of PQTBTz-TT-C8 films is examined with grazing incidence X-ray diffraction. Temperature-dependent transfer measurements of the OFETs are conducted to extract the density of states (DOS) and characterize the charge-transport properties. Comparative analyses on charge transports within the framework of the physical model, based on polaron hopping and Gaussian DOS, reveal that the prefactors of both physical charge-transport models are independent of the spin-coating condition for the films. For staggered structural transistors, however, the thickness of the PQTBTz-TT-C8 films, which strongly affect the series resistance along the charge-transfer path in a vertical direction, is changed in accordance with the spin-coating rate. In other words, the spin-coating rate of the PQTBTz-TT-C8 films influences the thickness of the polymer films, yet any significant changes in the crystallinity of the film or electronic coupling between the neighboring molecules upon the spin-coating condition were barely noticeable. Because the PQTBTz-TT-C8 backbone chains inside the thin film are stacked up with the edge-on, the series resistances are changed according to the thickness of the film and thus the performance of the device varies depending on the thickness.

A Nonchlorinated Solvent-Processable Fluorinated Planar Conjugated Polymer for Flexible Field-Effect Transistors.

High carrier mobilities have recently been achieved in polymer field effect transistors (FETs). However, many of these polymer FET devices require the use of chlorinated solvents such as chloroform (CF), chlorobenzene (CB), and o-dichlorobenzene (DCB) during fabrication. The use of these solvents is highly restricted in industry because of health and environmental issues. Here, we report the synthesis of a low band gap (1.43 eV, 870 nm) semiconducting polymer (PDPP2DT-F2T2) having a planar geometry, which can be readily processable with nonchlorinated solvents such as toluene (TOL), o-xylene (XY), and 1,2,4-trimethylbenzene (TMB). We performed structural characterization of PDPP2DT-F2T2 films prepared from different solvents, and the electrical properties of the films were measured in the context of FETs. The devices exhibited an ambipolar behavior with hole dominant transport. Hole mobilities increased with increasing boiling point (bp) of the nonchlorinated solvents: 0.03, 0.05, and 0.10 cm2 V-1 s-1 for devices processed using TOL, XY, and TMB, respectively. Thermal annealing further improved the FET performance. TMB-based polymer FETs annealed at 200 °C yielded a maximum hole mobility of 1.28 cm2 V-1 s-1, which is far higher than the 0.43 cm2 V-1 s-1 obtained from the CF-based device. This enhancement was attributed to increased interchain interactions as well as improved long-range interconnection between fibrous domains. Moreover, all of the nonchlorinated solutions generated purely edge-on orientations of the polymer chains, which is highly beneficial for carrier transport in FET devices. Furthermore, we fabricated an array of flexible TMB-processed PDPP2DT-F2T2 FETs on the plastic PEN substrates. These devices demonstrated excellent carrier mobilities and negligible degradation after 300 bending cycles. Overall, we demonstrated that the organized assembly of polymer chains can be achieved by slow drying using high bp nonchlorinated solvents and a post thermal treatment. Furthermore, we showed that polymer FETs processed using high bp nonhalogenated solvents may outperform those processed using halogenated solvents.

Fluorinated Dithienylethene–Naphthalenediimide Copolymers for High-Mobility n-Channel Field-Effect Transistors

We develop two donor–acceptor copolymers based on a fluorinated dithienylethene building block, namely PNFDTE1 and PNFDTE2, in which naphthalenediimide (NDI) acts as an acceptor unit. Thermogravimetric analysis displayed both copolymers having good thermal stability with high decomposition temperatures over 400 °C. Broad absorption spectra were observed in the UV–vis–NIR region, with the absorption maxima being 720 and 724 nm for PNFDTE1 and PNFDTE2, respectively. Cyclic voltammetry tests exhibited deep-lying lowest unoccupied molecular orbital energy levels of ca. −4.0 eV. Two-dimensional grazing incidence X-ray diffraction patterns showed that different packing modes for two polymers result in the variation in charge transport properties. Backbone fluorination effectively decreases electron injection barrier, thereby facilitating electron mobility. An impressive electron mobility of 3.20 cm2 V–1 s–1 was achieved in air for PNFDTE1-based polymer field-effect transistors fabricated on the poly(ethylene te...

Gradual Controlling the Work Function of Metal Electrodes by Water Dissolved Mixed Interlayers for Ambipolar Polymer Field-Effect Transistors

Gradual Controlling the Work Function of Metal Electrodes by Water Dissolved Mixed Interlayers for Ambipolar Polymer Field-Effect Transistors

Improvement charge injection in P-type polymer field-effect transistors with low-cost molybdenum electrodes through dodecanoic acid self assembled monolayer

ABSTRACTMost of the merit of organic thin film transistors (OTFTs) is that they can be manufactured using cost effective processes. However, expensive gold (Au) electrodes have usually been used as a source/drain (S/D), due to their benign energy level matching, high air stability, and easy patternability. In this article, we report a simple method for improving the charge injection from a low cost molybdenum (Mo) electrode to organic semiconductors in OTFTs by incorporating a dodecanoic acid (DA)–based self-assembled monolayer (SAM). The OTFT performance is remarkably improved when compared to the devices with a pristine Au electrode. The hole carrier mobilities (hole μFET) were ∼0.13 (rr-P3HT), ∼0.55 (PC12TV12T) and ∼0.72 (P2100) cm2/V·sec.

Manganese Oxide Nanoparticle as a New p-Type Dopant for High-Performance Polymer Field-Effect Transistors.

We report a new p-type dopant, manganese oxide (Mn3O4) nanoparticle, to enhance the performance of organic field-effect transistors (OFETs) with conjugated polymers, including poly(3-hexylthiophene-2,5-diyl), poly[[N,N 9-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,59-(2,29-bithiophene)], and 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(3,2b) thiophene]-5,5'-diyl]] (DPPT-TT). Incorporating a small amount of Mn3O4 nanoparticles in the semiconductor film significantly improved the hole mobility and decreased the threshold voltage for all OFETs, indicating efficient Mn3O4 nanoparticle p-type doping. The Mn3O4 nanoparticle showed a better doping efficiency than the widely used FeCl3 dopant due to better mixability with the host conjugated polymers. In particular, doped DPPT-TT OFETs showed significantly improved mobility up to 2.35 (±0.4) cm2/(V·s) with enhanced air and operational stability at 0.1 wt % doping concentration from 1.2 cm2/(V·s) for pristine devices.

Polarization effects from the ambient and the gate dielectric on charge transport in polymer field-effect transistors

Charge transport in polymer field-effect transistors is hugely affected by the polarization effects, which can be originated from polar molecules in the gate dielectric and ambient air. In this letter, we investigate the polarization induced trapping enhancement by dipoles in the gate dielectric layer and ambient air at the same time through the experiment with varying conditions of surface dielectric and polar analytes in the atmosphere. We demonstrate the result from diketopyrrolopyrrole based co-polymer transistors with high mobility. Polarization effects from dipoles in the atmosphere affect mostly the shallower trap states and are relatively less severe when the interface of the gate dielectric is very polar.

Dependence of electrical performance on structural organization in polymer field effect transistors

ABSTRACTOrganic semiconductors (OSCs) are strong contenders for use in printed, flexible electronics. Although organic electronic materials have been studied for many years, the physics of charge transport is still under investigation. This is in part due to variability resulting from the large variety of molecules that can be synthesized and inconsistency in electrical characterization due to device and processing conditions. Molecular ordering in OSCs is known to alter the charge transport characteristics and attention to long range and short range ordering provides clues as to the nature of transport pathways. Here, we study ordered regioregular poly(3‐hexylthiophene‐2,5‐diyl) films carefully prepared to obtain a set of three samples with incrementally increasing order on identical transistor architectures. Ordering was characterized using a variety of short and long range techniques to probe the coherence and number of crystallites formed during processing, and the correlation between these different measures of order are quantified. We observe three changes in transistor behavior that show a shift from non‐ideal to more textbook‐like characteristics with increasing order: reduction of the contact resistance, shift to field‐independent mobility, and a shift from a diode‐like (S‐shaped) to linear response at low lateral fields. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1063–1074

Threshold voltage modulation of polymer transistors by photoinduced charge–transfer between donor–acceptor dyads

In this work, the photoinduced optoelectronic properties of a conjugated polymer from device characterization and quantum calculations have been studied. It was demonstrated that the photosensitive conjugated polymer with electron donor–acceptor dyad (6) which contains a terthiophene unit, can modulate charge accumulation by photoirradiation resulting in a threshold voltage shift in the polymer field-effect transistors (PFETs) while this effect of the photoinactive polymer (5) containing a thienothiophene unit is negligible. These results suggest that the feasible molecular design strategies can provide an effective platform to achieve controllable threshold voltage modulation in PFETs.

High, Anisotropic, and Substrate-Independent Mobility in Polymer Field-Effect Transistors Based on Preassembled Semiconducting Nanofibrils.

Achieving nanoscale control over the crystalline structure and morphology of electroactive polymer films and the possibility to transfer them onto any solid substrate are important tasks for the fabrication of high-performance organic/polymeric field-effect transistors (FETs). In this work, we demonstrate that ultrathin active layers preassembled at the water/air interface can possess high, anisotropic, and substrate-independent mobility in polymer FETs. By exploiting a modified approach to the Langmuir-Schaeffer technique, we self-assemble conjugated polymers in fibrillar structures possessing controlled thickness, nanoscale structure, and morphology; these highly ordered nanofibrils can be transferred unaltered onto any arbitrary substrate. We show that FETs based on these films possess high and anisotropic hole mobility approaching 1 cm2 V-1 s-1 along the nanofibrils, being over 1 order of magnitude beyond the state-of-the-art for Langmuir-Schaefer polymer FETs. Significantly, we demonstrate that the FET performances are independent of the chemical nature and dielectric permittivity of the substrate, overcoming a critical limit in the field of polymer FETs. Our method allows the fabrication of ultrathin films for low-cost, high-performance, transparent, and flexible devices supported on any dielectric substrate.