Mobility Of Organic Field-effect Transistors Research Articles

Structure-Property Relationships for the Electronic Applications of Bis-Adduct Isomers of Phenyl-C61 Butyric Acid Methyl Ester.

Higher adducts of a fullerene, such as the bis-adduct of PCBM (bis-PCBM), can be used to achieve shallower molecular orbital energy levels than, for example, PCBM or C60. Substituting the bis-adduct for the parent fullerene is useful to increase the open-circuit voltage of organic solar cells or achieve better energy alignment as electron transport layers in, for example, perovskite solar cells. However, bis-PCBM is usually synthesized as a mixture of structural isomers, which can lead to both energetic and morphological disorder, negatively affecting device performance. Here, we present a comprehensive study on the molecular properties of 19 pure bis-isomers of PCBM using a variety of characterization methods, including ultraviolet photoelectron spectroscopy, thermal gravimetric analysis, differential scanning calorimetry, single crystal structure, and (time-dependent) density functional theory calculation. We find that the lowest unoccupied molecular orbital of such bis-isomers can be tuned to be up to 170 meV shallower than PCBM and up to 100 meV shallower than the mixture of unseparated isomers. The isolated bis-isomers also show an electron mobility in organic field-effect transistors of up to 4.5 × 10-2 cm2/(V s), which is an order of magnitude higher than that of the mixture of bis-isomers. These properties enable the fabrication of the highest performing bis-PCBM organic solar cell to date, with the best device showing a power conversion efficiency of 7.2%. Interestingly, we find that the crystallinity of bis-isomers correlates negatively with electron mobility and organic solar cell device performance, which we relate to their molecular symmetry, with a lower symmetry leading to more amorphous bis-isomers, less energetic disorder, and higher dimensional electron transport. This work demonstrates the potential of side chain engineering for optimizing the performance of fullerene-based organic electronic devices.

Large area polymer thin film towards high-sensitivity BGBC-OFET based phototransistor

With the expansion of organic electronics, organic field-effect transistors (OFETs) are broadly used in electronic devices and logic circuits. In these, OFET-based phototransistors were recently developed for detecting the light signal. Developing better field-effect mobility and sensitivity in bottom gate bottom contact (BGBC) OFET-based phototransistors, however, is still a difficulty. This is because the low mobility of most organic photoresponsive materials limits the efficiency of transporting and collecting charge carriers. In the current work, a poly (3-hexyl thiophene) based organic phototransistor was studied. For increasing the device performance, a thin layer of Self-assembled monolayer (SAM) is formed on the dielectric interface of SiO2. The ribbon-shaped floating film transfer method (FTM) is utilized in the fabrication of thin film. The prepared film shows the average OFETs mobility, Ion/Ioff ratio (μ) 2 × 10−2 Cm2/Vs, 104 respectively under air and dark conditions. This result is more than one order higher in the BGBC configuration reported by the conventional FTM. Further, illumination of light (λ = 550 nm, Pin = 1 mW/cm2) shows photosensitivity of ∼100 and responsivity of 22 AW1.

Molecular Design Concept for Enhancement Charge Carrier Mobility in OFETs: A Review.

In the last two decades, organic field-effect transistors (OFETs) have garnered increasing attention from the scientific and industrial communities. The performance of OFETs can be evaluated based on three factors: the charge transport mobility (μ), threshold voltage (Vth), and current on/off ratio (Ion/off). To enhance μ, numerous studies have concentrated on optimizing charge transport within the semiconductor layer. These efforts include: (i) extending π-conjugation, enhancing molecular planarity, and optimizing donor-acceptor structures to improve charge transport within individual molecules; and (ii) promoting strong aggregation, achieving well-ordered structures, and reducing molecular distances to enhance charge transport between molecules. In order to obtain a high charge transport mobility, the charge injection from the electrodes into the semiconductor layer is also important. Since a suitable frontier molecular orbitals' level could align with the work function of the electrodes, in turn forming an Ohmic contact at the interface. OFETs are classified into p-type (hole transport), n-type (electron transport), and ambipolar-type (both hole and electron transport) based on their charge transport characteristics. As of now, the majority of reported conjugated materials are of the p-type semiconductor category, with research on n-type or ambipolar conjugated materials lagging significantly behind. This review introduces the molecular design concept for enhancing charge carrier mobility, addressing both within the semiconductor layer and charge injection aspects. Additionally, the process of designing or converting the semiconductor type is summarized. Lastly, this review discusses potential trends in evolution and challenges and provides an outlook; the ultimate objective is to outline a theoretical framework for designing high-performance organic semiconductors that can advance the development of OFET applications.

Interfacial Interaction Enables Enhanced Mobility in Hybrid Perovskite-Conjugated Polymer Transistors with High-k Fluorinated Polymer Dielectrics.

The charge carrier mobility of organic field-effect transistors (OFETs) has been remarkably improved through several engineering approaches and techniques by targeting pivotal parts. Herein, an ultrathin perovskite channel layer that boosts the field-effect mobility of conjugated polymer OFETs by forming perovskite-conjugated polymer hybrid semiconducting channel is introduced. The optimized lead-iodide-based perovskite-conjugated polymer hybrid channel transistors show enhanced hole mobility of over 4cm2 V-1 s-1 (average=2.10cm2 V-1 s-1 ) with high reproducibility using a benchmark poly(3-hexylthiophene) (P3HT) polymer and employing high-k fluorinated polymer dielectrics. A significant hole carrier mobility enhancement of ≈200-400% in benzo[1,2-b:4,5:b']dithiophene (BDT)-based conjugated polymers is also demonstrated by exploring certain interactive groups with perovskite. This significant enhancement in the transistor performance is attributed to the increased charge carrier density in the hybrid semiconducting channel and the perovskite-polymer interactions. The findings of this paper demonstrate an exceptional engineering approach for carrier mobility enhancement in hybrid perovskite-conjugated-polymer-based electronic devices.

Recent Research Progress of Organic Small-Molecule Semiconductors with High Electron Mobilities.

Organic electronics has made great progress in the past decades, which is inseparable from the innovative development of organic electronic devices and the diversity of organic semiconductor materials. It is worth mentioning that both of these great advances are inextricably linked to the development of organic high-performance semiconductor materials, especially the representative n-type organic small-molecule semiconductor materials with high electron mobilities. The n-type organic small molecules have the advantages of simple synthesis process, strong intermolecular stacking, tunable molecular structure, and easy to functionalize structures. Furthermore, the n-type semiconductor is a remarkable and important component for constructing complementary logic circuits and p-n heterojunction structures. Therefore, n-type organic semiconductors play an extremely important role in the field of organic electronic materials and are the basis for the industrialization of organic electronic functional devices. This review focuses on the modification strategies of organic small molecules with high electron mobility at molecular level, and discusses in detail the applications of n-type small-molecule semiconductor materials with high mobility in organic field-effect transistors, organic light-emitting transistors, organic photodetectors, and gas sensors.

Solution-Processed Isoindigo- and Thienoisoindigo-Based Donor-Acceptor-Donor π-Conjugated Small Molecules: Synthesis, Morphology, Molecular Packing, and Field-Effect Transistor Characterization.

Molecular design and precise control of thin-film morphology and crystallinity of solution-processed small molecules are important for enhancing charge transport mobility of organic field-effect transistors and gaining more insight into the structure-property relationship. Here, two donor-acceptor-donor (D-A-D) architecture small molecules TRA-IID-TRA and TRA-TIID-TRA comprising an electron-donating triarylamine (TRA) and two different electron-withdrawing cores, isoindigo (IID) and thienoisoindigo (TIID), respectively, were synthesized and characterized. Replacing the phenylene rings of central IID A with thiophene gives a TIID core, which reduces the optical band gap and upshifts the energy levels of frontier molecular orbitals. The single-crystal structures and grazing-incidence wide-angle X-ray scattering (GIWAXS) analysis revealed that TRA-TIID-TRA exhibits the relatively tighter π-π stacking packing with preferential edge-on orientation, larger coherence length, and higher crystallinity due to the noncovalent S···O/S···π intermolecular interactions. The distinctly oriented and connected ribbon-like TRA-TIID-TRA crystalline film by the solution-shearing process achieved a superior hole mobility of 0.89 cm2 V-1 s-1 in the organic field-effect transistor (OFET) device, which is at least five times higher than that (0.17 cm2 V-1 s-1) of TRA-IID-TRA with clear cracks. Eventually, rational modulation of fused core in the π-conjugated D-A-D small molecule provides a new understanding of structural design for enhancing the performance of solution-processed organic semiconductors.

Impact of Narrowing Density of States in Semiconducting Polymers on Performance of Organic Field-Effect Transistors.

To improve the performance of organic field-effect transistors (OFETs) employing π-conjugated polymers, a basic understanding of the relationships between the material properties and device characteristics is crucial. Although the density of states (DOS) distribution is one of the essential material properties of semiconducting polymers, insights into how the DOS shape affects the mobility (µ), subthreshold swing (S), and contact resistance (RC ) in OFETs remain lacking. In this study, by combining sensitive DOS measurements and multilayered OFET structures, it is experimentally demonstrated that narrower DOS widths in the polymer channels lead to higher µ, smaller S, and lower RC . By contrast, variation of the DOS in the bulk layer does not affect the performance. These results demonstrate a direct relationship between the polymer properties and OFET performance and highlight the importance of controlling the DOS width in π-conjugated polymers.

Benzimidazolone-Dioxazine Pigments-Based Conjugated Polymers for Organic Field-Effect Transistor.

Molecules based on benzimidazolone-dioxazine are known as blue/violet pigments and have been commercialized for decades. However, unfavorable solubility limits the application of these structures as building blocks of conjugated polymers despite their low band gaps. Herein, a series of donor-acceptor conjugated polymers containing soluble benzimidazolone-dioxazine structures as the acceptors and oligothiophene as donors are synthesized and investigated. With increasing numbers of thiophene rings, the steric hindrance diminishes and high molecular weight polymers can be achieved, leading to an improved performance in organic field effect transistor devices. The hole mobility of polymers with three to six thiophene units is in the order of 10-1 cm2 V-1 s -1 . Among all the polymers, polymer P3 with three thiophene units between benzimidazolone-dioxazine structures shows the best hole mobility of 0.4 cm2 V-1 s -1 . Grazing-incidence wide-angle X-ray scattering results reveal that the high mobility of organic field-effect transistors (OFETs) can be accredited by matched donor-acceptor packing in the solid thin films.

TCNQ-based organic cocrystal integrated red emission and n-type charge transport

Simultaneously realizing the optical and electrical properties of organic materials is always challenging. Herein, a convenient and promising strategy for designing organic materials with integrated optoelectronic properties based on cocrystal engineering has been put forward. By selecting the fluorene (Flu) and the 7,7′,8,8′-tetracyanoquinodimethane (TCNQ) as functional constituents, the Flu-TCNQ cocrystal prepared shows deep red emission at 702 nm, which is comparable to the commercialized red quantum dot. The highest electron mobility of organic field-effect transistor (OFET) based on Flu-TCNQ is 0.32 cm2 V−1 s−1. Spectroscopic analysis indicates that the intermolecular driving force contributing to the co-assembly of Flu-TCNQ is mainly charge transfer (CT) interaction, which leads to its different optoelectronic properties from constituents.Graphical

High-Mobility Fungus-Triggered Biodegradable Ultraflexible Organic Transistors.

Biodegradable organic field‐effect transistors (OFETs) have drawn tremendous attention for potential applications such as green electronic skins, degradable flexible displays, and novel implantable devices. However, it remains a huge challenge to simultaneously achieve high mobility, stable operation and controllable biodegradation of OFETs, because most of the widely used biodegradable insulating materials contain large amounts of hydrophilic groups. Herein, it is firstly proposed fungal‐degradation ultraflexible OFETs based on the crosslinked dextran (C‐dextran) as dielectric layer. The crosslinking strategy effectively eliminates polar hydrophilic groups and improves water and solvent resistance of dextran dielectric layer. The device with spin‐coated 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT) semiconductor and C‐dextran dielectric exhibits the highest mobility up to 7.72 cm2 V−1 s−1, which is higher than all the reported degradable OFETs. Additionally, the device still maintains high performance regardless of in an environment humidity up to 80% or under the extreme bending radius of 0.0125 mm. After completion of their mission, the device can be controllably biodegraded by fungi without any adverse environmental effects, promoting the natural ecological cycles with the concepts of “From nature, for nature”. This work opens up a new avenue for realizing high‐performance biodegradable OFETs, and advances the process of the “green” electrical devices in practical applications.

Water-Soluble Reactive Polymer Blends for Stable Memory Layers in Low-Voltage Nonvolatile Organic Memory Transistors with High Mobility and Data-Retention Characteristics.

Here low-voltage nonvolatile organic memory transistors, featuring high charge-carrier mobility and outstanding data-retention characteristics, by employing water-soluble reactive polymer blends as a gate-insulating memory layer are demonstrated. Blend films of poly(vinyl alcohol) (PVA) and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA) (PVA:PAMPSA) are prepared from their aqueous solutions with various molar ratios of PAMPSA (0-18mol%) and thermally annealed at 70 and 110°C. Organic field-effect transistors (OFETs) are fabricated by depositing poly(3-hexylthiophene) (P3HT) channel layers on the thermally treated PVA:PAMPSA films. Results show that the hole mobility of OFETs is remarkably increased (≈294 times at 70°C and ≈42 times at 110°C) by adding only 2mol% PAMPSA to the PVA films and further improved at 10mol% PAMPSA (>11.7cm2 V-1 s-1 at 70°C and >3.8cm2 V-1 s-1 at 110°C). The hysteresis characteristics are rather strengthened for the PVA:PAMPSA layers by annealing at 110°C due to the formation of cross-linking sites, even though the OFETs with the pristine PVA layers do almost lose hysteresis characteristics at 110°C. The optimized OFETs with the PVA:PAMPSA layers (10mol%, 110°C) deliver excellent data retention characteristics during >10000 memory cycles at a voltage range of -5 to +5V.

Organic Field‐Effect Transistors Based on Ternary Blends Including a Fluorinated Polymer for Achieving Enhanced Device Stability

AbstractThe stability of organic semiconductors (OSCs) is strongly hampered by the presence of water molecules. One approach that has been proved to lead to organic field‐effect transistors with an enhanced performance is the use of blends of OSCs with insulating binding polymers. In this work, the fabrication of OSC thin films based on polymeric ternary blends including a hydrophobic fluorinated polymer is reported as a novel route to engineer long‐term reliable organic field‐effect transistors (OFET) devices. In particular, OFETs based on blends of bis(triisopropylsilylethynyl)pentacene (TIPS) with polystyrene (PS) and poly(pentafluorostyrene) (PFS) are explored. The PS:PFS ratio is tuned in order to find the optimum formulation. It is shown that films including 20% of PFS in the polymeric blend exhibit an improved device performance, which is reflected by a low bias stress and an exceptional environmental stability, without significantly hampering the OFET mobility. This work advocates that adding a small percentage of fluorinated polymers in OSC blends is a promising route to realize more reliable and stable devices without importantly compromising the device mobility.

Morphology and Charge Transport Properties of P(NDI2OD-T2)/Polystyrene Blends

While the strategy of blending commodity insulating polymers with conjugated polymers has been previously applied to modify the properties of organic field-effect transistors (OFETs), comprehensive studies on the evolution of morphology and OFET performance with film composition are scarce. In this contribution, films comprising the n-type semiconducting polymer P(NDI2OD-T2) and the insulating polymer polystyrene (PS) are explored in detail. In particular, the electrical properties and film morphology of blends with a P(NDI2OD-T2) concentration ranging from 0.125 to 100 wt % are studied. Two regimes characterized by distinct dependencies of device mobility as a function of P(NDI2OD-T2) content are observed: Above 12.5 wt % P(NDI2OD-T2), the OFET mobility exhibits a weak dependence on P(NDI2OD-T2) concentration despite the presence of strong lateral phase separation, while below 12.5%, the device mobility is observed to decrease strongly with decreasing P(NDI2OD-T2) concentration attributed to disrupted surface connectivity of the P(NDI2OD-T2) phase. UV–vis absorption spectroscopy and grazing incidence wide-angle X-ray scattering (GIWAXS) measurements indicate that the aggregation and crystalline packing are not strongly affected by the presence of PS. Atomic force microscopy and scanning transmission X-ray spectro-microscopy reveal lateral phase separation for blends with compositions of 87.5 to 25 wt % P(NDI2OD-T2). Enrichment of P(NDI2OD-T2) at the film surface is confirmed by near-edge X-ray absorption fine structure spectroscopy, with a high P(NDI2OD-T2) surface composition (>80 wt %) maintained down to an overall blend composition of 12.5 wt % P(NDI2OD-T2). The strong decrease in OFET mobility for P(NDI2OD-T2) concentration less than 25 wt % is attributed to a loss of P(NDI2OD-T2) surface connectivity at low P(NDI2OD-T2) loading. We also observe a transition from face-on to edge-on dominated configuration at low P(NDI2OD-T2) content with GIWAXS, consistent with an edge-on surface layer that persists down to monolayer surface coverage.

Toward Efficient Charge Transport of Polymer-Based Organic Field-Effect Transistors: Molecular Design, Processing, and Functional Utilization

ConspectusPolymer-based organic field-effect transistors (OFETs) have attracted great attention owing to their significantly improved performance and the recently emerged prospects for broad applications. The charge carrier mobility of polymer-based OFETs has been improved from 10–5 to more than 10 cm2 V–1 s–1 over the past three decades. With the carrier mobility close to or higher than that of amorphous silicon, the application fields of polymer-based OFETs have been extended from sensing to logic or drive circuits. During OFET operation, the charge carriers are successively injected in and then transferred across the semiconducting channel under an external electric field. The behavior of the charge carriers is determined by both charge injection and charge transport. Well-matched frontier molecular orbital (FMO) energy levels and optimized hierarchical structures of semiconducting polymers are essential for the realization of high-performance polymer-based OFETs.In this Account, we mainly demonstrate our recent progress in molecular design strategies and fabrication processing methods for high-performance semiconducting polymers. Moreover, we provide some examples of integrated applications of polymer-based OFETs. The convenient FMO energy level modulation and excellent molecular designability of donor–acceptor (D–A) conjugated polymers facilitate studies on their performance enhancement in OFETs. Proper molecular design of the D–A polymer backbone and side chain can significantly contribute to charge injection enhancement, transport pathway establishment, and trap reduction, thereby resulting in efficient charge transport. Moreover, special fabrication processes of OFET devices can further enhance the charge transport by optimizing the hierarchical structures of semiconducting polymers, thereby enhancing their carrier mobility and stability. By employing high-performance semiconducting polymers as the semiconducting channel of OFETs, various applications can be implemented. These applications range from small-scale logic signal processing and periodic signal generation to complex visual perception systems, indicating broad application prospects in human life. The works on performance improvement and functional utilization of the semiconducting polymers in OFETs might provide insights for molecular design strategies and applications for future plastic electronics.

Significant Performance Improvement in n-Channel Organic Field-Effect Transistors with C60 :C70 Co-Crystals Induced by Poly(2-ethyl-2-oxazoline) Nanodots.

Solution-processed organic field-effect transistors (OFETs) have attracted great interest due to their potential as logic devices for bendable and flexible electronics. In relation to n-channel structures, soluble fullerene semiconductors have been widely studied. However, they have not yet met the essential requirements for commercialization, primarily because of low charge carrier mobility, immature large-scale fabrication processes, and insufficient long-term operational stability. Interfacial engineering of the carrier-injecting source/drain (S/D) electrodes has been proposed as an effective approach to improve charge injection, leading also to overall improved device characteristics. Here, it is demonstrated that a non-conjugated neutral dipolar polymer, poly(2-ethyl-2-oxazoline) (PEOz), formed as a nanodot structure on the S/D electrodes, enhances electron mobility in n-channel OFETs using a range of soluble fullerenes. Overall performance is especially notable for (C60 -Ih )[5,6]fullerene (C60 ) and (C70 -D5h(6) )[5,6]fullerene (C70 ) blend films, with an increase from 0.1 to 2.1 cm2 V-1 s-1 . The high relative mobility and eighteen-fold improvement are attributed not only to the anticipated reduction in S/D electrode work function but also to the beneficial effects of PEOz on the formation of a face-centered-cubic C60 :C70 co-crystal structure within the blend films.

Alignment of linear polymeric grains for highly stable N-type thin-film transistors

Summary Temperature-insensitive properties are attractive for most electronics, including polymeric semiconducting devices. Especially, polymeric field-effect transistors (FETs) with high mobility have been important research targets due to their broad applications. However, polymeric FETs with stable charge transport operating at extremely cold or hot zones are faced with enormous challenges. In this study, the polyacrylonitrile was found to significantly tune the sizes of pre-aggregates of polymers in solutions and the crystallinity of the polymeric films. The orientation of 5–25 μm linear grains in the films were prepared through the bar-coating process with polyacrylonitrile as an additive, which stabilized the electron mobility over a wide range of temperatures. The linear-grain morphology of the film contributed to reducing the holes and grain boundaries in the transport paths of carriers. Typically, the top-gate FETs based on P(NDI2OD-T2) displayed a stable electron transporting behavior from 200 to 460 K, with mobility greater than 3.5 cm2V−1s−1.

Impact of Intermolecular Interactions Between a Diketopyrrolopyrrole-Based Conjugated Polymer and Bromobenzaldehyde on Field-Effect Transistors

In this study, intermolecular interactions were investigated for increasing the charge carrier mobility of organic field-effect transistors (OFETs) based on a conjugated polymer. A diketopyrrolopyrrole (DPP)-based conjugated polymer widely used in OFETs, i.e., poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno[3,2-b]thiophene)] (PDPP-DTT), was assembled using 2-bromobenzaldehyde (2-BBA) and used as an active layer for OFETs. Morphological characterization and analysis for non-covalent intermolecular interactions suggested that the halogen bonding between the bromide of 2-BBA and electron-donor group of PDPP-DTT and the association between the electron-acceptor group in 2-BBA and sulfur of PDPP-DTT improved the hole transfer in the PDPP-DTT-based OFETs. The intermolecular interactions resulting from the addition of 2-BBA contributed to the two-fold enhancement of the hole mobility, two-order increase in magnitude of the current on/off ratio, and 50% decrease in the threshold voltage of the OFETs based on PDPP-DPP.

Effect of Gaussian Disorder on Power-Law Contact Resistance and Mobility in Organic Field-Effect Transistors

We study the effect of Gaussian energetic disorder on the organic field-effect transistors (OFETs) with surprisingly high field-effect mobility and the low contact resistance. The numerical device simulation assumes the thermally assisted hopping transport and injection in disordered semiconductors. The results are analyzed with the power-law field-effect mobility and the asymptotic power-law contact resistance model. Transistor parameters extracted by the models reveal that a higher Gaussian disorder, which leads to a lower injection barrier and a larger mobility enhancement, is the origin of the high field-effect mobility and the low contact resistance.

Synthesis of dithieno[2,3-d:2′,3′-d']anthra[1,2-b:5,6-b']dithiophene (DTADT) units: Structure, polymerization, DFT study, and OFET application

In this study, we report the synthesis of dithieno[2,3-d:2′,3′-d']anthra[1,2-b:5,6-b']dithiophene (DTADT) unit and donor-acceptor (D-A) conjugated copolymers incorporated with the DTADT unit as the repeating unit. The novel oligoheteroacene unit––DTADT––was synthesized through the [2+2+2] annulation, which is the key reaction, and its reaction pathway was theoretically revealed using the density functional theory calculation. The D-A conjugated copolymers, synthesized through the transition metal-catalyzed polycondensation, could be applied as a solution-processable thin-film transistor. The our own n-layered integrated molecular orbital and molecular mechanics calculation in conjunction with the second order perturbation theory, analyzed based on the natural bond orbital analysis, unveiled that the steric repulsion among the side chains of DTADT and thiophene spacer kept away from the planarization of polymers; this affected the hole mobility of organic field-effect transistor.

Robust Unipolar Electron Conduction Using an Ambipolar Polymer Semiconductor with Solution-Processable Blends

Ambipolar polymer semiconductors are among the most ubiquitous semiconductors used for high mobility organic field-effect transistors. However, since ambipolar polymer semiconductors are capable of...