Organic Transistors Research Articles

Distribution of Density of States in Organic Field–Effect Transistors Based on Polymer Dielectrics

AbstractThe distribution of density of states (DOS) holds fundamental importance in determining charge transport within organic field–effect transistors (OFETs). Herein, the modulation of DOS distribution in OFET devices is demonstrated by altering the chain conformation of the polymer dielectrics. A rapid film‐formation technique, specifically the spin‐casting method, is used to fabricate the dielectric layer using poly(methyl methacrylate) (PMMA). This method allows for the retention of some memory of the chain conformations from the solution to the resulting dry film. This memory effect is employed to prepare thin PMMA films with different local chain conformations by adjusting the quality of the solvent. Good solvent forms solidified films with a reduced amount of gauche conformer in the PMMA chain, resulting in a narrow DOS distribution width. Consequently, the device exhibited enhanced charge mobility and a reduced subthreshold swing. The observed change in the width of the DOS distribution can be attributed to the alteration of the local energy state of the semiconductor, induced by the local chain conformation of PMMA dielectrics through electrostatics and steric interactions.

Synergistic polarization engineering of dielectric towards low-voltage high-mobility solution-processed ultraflexible organic transistors

The emerging wearable skin-like electronics require the ultra-flexible organic transistor to operate at low voltage for electrical safety and energy efficiency and simultaneously enable high field-effect mobility to ensure the carrier migration ability and the switching speed of circuits. However, the currently reported low-voltage organic transistors generally present low mobility, originating from the trade-off between molecular polarity and surface polarity of the dielectrics. In this work, the orientation polarization of the dielectric is enhanced by introducing a flexible quaternary ammonium side chain, and the surface polarity is weakened by the shielding effect of the nonpolar methyl groups on the polar nitrogen atom. The resulting antisolvent QPSU dielectric enables the high-dielectric constant up to 18.8 and the low surface polarity with the polar component of surface energy only at 2.09 mJ/m2. Such a synergistic polarization engineering between orientation polarization and surface polarity makes the solution-processed ultraflexible transistors present the ultralow operational voltage down to −3 V, the ultrahigh charge-carrier mobility up to 8.28 cm2 V−1 s−1 at 1 Hz, excellent cyclic operational stability and long-term air stability. These results combined with the ultrathin thickness of transistor as low as 135 nm, the ultralight mass of 0.5 g/m2, the conformal adherence capability on human skin and 1-μm blade edge, and the strong mechanical robustness with stable electrical properties for 30,000 bending cycles, open up an available strategy to successfully realize low-voltage high-mobility solution-processed organic transistor, and presents the potential application of QPSU dielectric for the next-generation wearable imperceptible skin-like electronics.

Information Transmission through Biotic-Abiotic Interfaces to Restore or Enhance Human Function.

Advancements in reliable information transfer across biotic-abiotic interfaces have enabled the restoration of lost human function. For example, communication between neuronal cells and electrical devices restores the ability to walk to a tetraplegic patient and vision to patients blinded by retinal disease. These impactful medical achievements are aided by tailored biotic-abiotic interfaces that maximize information transfer fidelity by considering the physical properties of the underlying biological and synthetic components. This Review develops a modular framework to define and describe the engineering of biotic and abiotic components as well as the design of interfaces to facilitate biotic-abiotic information transfer using light or electricity. Delineating the properties of the biotic, interface, and abiotic components that enable communication can serve as a guide for future research in this highly interdisciplinary field. Application of synthetic biology to engineer light-sensitive proteins has facilitated the control of neural signaling and the restoration of rudimentary vision after retinal blindness. Electrophysiological methodologies that use brain-computer interfaces and stimulating implants to bypass spinal column injuries have led to the rehabilitation of limb movement and walking ability. Cellular interfacing methodologies and on-chip learning capability have been made possible by organic transistors that mimic the information processing capacity of neurons. The collaboration of molecular biologists, material scientists, and electrical engineers in the emerging field of biotic-abiotic interfacing will lead to the development of prosthetics capable of responding to thought and experiencing touch sensation via direct integration into the human nervous system. Further interdisciplinary research will improve electrical and optical interfacing technologies for the restoration of vision, offering greater visual acuity and potentially color vision in the near future.

Organic Synaptic Transistors with Environmentally Friendly Core/Shell Quantum Dots for Wavelength-Selective Memory and Neuromorphic Functions.

Organic transistors based on organic semiconductors together with quantum dots (QDs) are attracting more and more interest because both materials have excellent optoelectronic properties and solution processability. Electronics based on nontoxic QDs are highly desired considering the potential health risks but are limited by elevated surface defects, inadequate stability, and diminished luminescent efficiency. Herein, organic synaptic transistors based on environmentally friendly ZnSe/ZnS core/shell QDs with passivating surface defects are developed, exhibiting optically programmable and electrically erasable characteristics. The synaptic transistors feature linear multibit storage capability and wavelength-selective memory function with a retention time above 6000 s. Various neuromorphic applications, including memory enhancement, optical communication, and memory consolidation behaviors, are simulated. Utilizing an established neuromorphic model, accuracies of 92% and 91% are achieved in pattern recognition and complicated electrocardiogram signal processing, respectively. This research highlights the potential of environmentally friendly QDs in neuromorphic applications and health monitoring.

Boosting the performance of polymer field-effect transistors through fluorine atom substitutions and comparing the effect of various acceptor units and channel mobilities

Three conjugated copolymers, PDPP-2FTVT, PIID-2FTVT, and PNDI-2FTVT based on the 2,2′-(1E)-1,2-ethenediylbis[3-fluorothiophene] (2FTVT) core with varying acceptor units, diketopyrrolopyrrole (DPP), isoindigo (IID), and naphthalenediimide (NDI) were developed for organic field-effect transistors (OFETs). Combined electron-withdrawing fluorine atoms and vinyl linkage in the 2FTVT unit not only reduce the frontier molecular orbital energies but also extended the absorption profile and planarize the polymer backbone, manifesting synergetic effect on the strengthened molecular interactions and charge-carrier properties. The resulted copolymer, PDPP-2FTVT show highly reliable thin film transistor properties with highest hole mobility of 1.93 cm2 V−1 s−1 compared to PIID-2FTV and PNDI-2FTVT. PIID-2FTV copolymer show ambipolar characteristic with hole and electron mobilities of 0.71 and 0.03 cm2 V−1 s−1 respectively while PNDI-2FTVT exhibited the highest electron mobility of 0.20 cm2 V−1 s−1 among three copolymers. Thin film micro-structure characterization reveal that the three copolymers formed lamellar, edge-on molecular packing (for PDPP-2FTVT and PIID-2FTV), increased crystallinity with smaller π-π stacking distances, and strengthen the planarity after thermal annealing. These results contribute important progresses in solution-processed OFET and could provide a greater possibility of 2FTVT based copolymers for commercial application.

Interrogating Cocrystallization and Microphase Segregation in Meticulously Engineered Rod–Rod Poly(thieno)thiophene-Based Block Copolymers for Organic Field-Effect Transistors

Interrogating Cocrystallization and Microphase Segregation in Meticulously Engineered Rod–Rod Poly(thieno)thiophene-Based Block Copolymers for Organic Field-Effect Transistors

N-Type ion gel gated vertical organic electrochemical transistors based on benzodifurandione-based Oligo(p-phenylene vinylene)s

Organic electrochemical transistors (OECTs) using aqueous gate dielectrics have garnered significant interest for bioelectronic applications. However, their viability for long-term use in neuromorphic computing and synaptic devices is limited due to their short-term functionality. In this study, we synthesize two benzodifurandione-based oligo (p-phenylene vinylene) polymers, BDOPV-TCNVT and ClBDOPV-TCNVT, and investigate their electrochemical transistor properties using quasi-solid-state ion gel-gated vertical OECTs (v-OECTs). Compared to BDOPV-TCNVT, the chlorinated ClBDOPV-TCNVT demonstrates lower frontier molecular orbitals and easier electrochemical doping. The higher volumetric capacitance of as-spun ClBDOPV-TCNVT (1.94 F cm−3) compared to as-spun BDOPV-TCNVT films (1.49 F cm−3) is mainly attributed to the easier ion infiltration resulting from its lower crystallinity with mixed chain orientation. The quasi-solid-state v-OECTs based on both polymers (as-spun) exhibit transconductance (gm) of 0.06–0.08 mS. Following thermal treatments, the gm gradually decreases for both polymers due to enhanced edge-on ordering with tight interchain packing, hindering ion penetration. Despite the poor electrochemical doping by quasi-solid-state ion gel gated dielectrics, the enlarged area and decreased channel length in v-OECTs (compared to parallel OECTs) can enhance the gm. Further optimization of v-OECTs requires tailored material designs specifically suited for efficient vertical charge transport together with ion infiltration.

Towards sustainable, direct printed, organic transistors with biocompatible copolymer gate dielectrics

Towards sustainable, direct printed, organic transistors with biocompatible copolymer gate dielectrics

Accurate Description of Coulombic Interactions in Organic Field‐Effect Transistors Enabled by Efficient 3D Poisson's Equation Solver with Mixed Boundary Conditions

Accurate Description of Coulombic Interactions in Organic Field‐Effect Transistors Enabled by Efficient 3D Poisson's Equation Solver with Mixed Boundary Conditions

Anchoring groups for ordered and highly stable monomolecular films on naturally oxidized aluminum – phosphonate versus carboxylate

Modification of metal oxide surfaces by self-assembled monolayers (SAMs) is attracting growing attention. Carboxylic (CA) and phosphonic (PA) acids are most popular anchoring groups in this context, applied to create hydrophobic coatings, biosensors, and organic field-effect transistors. The efficiency of these devices is crucially affected by the structural quality and stability of the SAM. In this context, we studied the effect of the preparation procedure (solvent, incubation time, and temperature) on the quality of PA SAMs on naturally oxidized aluminum. We demonstrate formation of PA SAMs matching structural quality of archetypical alkanethiols on gold. Next, we compare their stability with analogue CA SAMs. Our data show that PA SAMs not only exhibit much higher hydrolytic stability but are also capable to protect aluminum substrate from oxidation and degradation. Importantly, even small improvement of the PA SAMs quality, translates into enormous increase of their hydrolytic stability crucial for majority of applications. Finally, we demonstrate that the thermal stability of PA on oxidized aluminum is by ∼250 K higher than CA SAMs, and by ∼200 K higher than for thiols on gold, which makes PA SAMs an excellent candidate for organic electronics, where overheating problems and high-temperature fabrication procedures are common issues.

Tunable Solid‐State Properties and Anisotropic Charge Mobility in Hydrogen‐Bonded Diketopyrolopyrrole Polymers via Automated Device Fabrication and Characterization

AbstractThe optoelectronic properties of semiconducting polymers and device performance rely on a delicate interplay of design and processing conditions. However, screening and optimizing the relationships between these parameters for reliably fabricating organic electronics can be an arduous task requiring significant time and resources. To overcome this challenge, Polybot is developed—a robotic platform within a self‐driving lab that can efficiently produce organic field‐effect transistors (OFETs) from various semiconducting polymers via high‐throughput blade coating deposition. Polybot not only handles the fabrication process but also can conduct characterization tests on the devices and autonomously analyze the data gathered, thus facilitating the rapid acquisition of data on a large scale. This work leverages the capabilities of this platform to investigate the fabrication of OFETs using hydrogen bonding‐containing semiconducting polymers. Through high‐throughput fabrication and characterization, various data trends are analyzed, and large extents of anisotropic charge mobility are observed in devices. The materials are thoroughly characterized to understand the role of processing conditions in solid state and electronic properties of these organic semiconductors. The findings demonstrate the effectiveness of automated fabrication and characterization platforms in uncovering novel structure–property relationships, facilitating refinement of rational chemical design, and processing conditions, ultimately leading to new semiconducting materials.

High Mobility Amorphous Polymer‐Based 3D Stacked Pseudo Logic Circuits through Precision Printing

AbstractDirect printing of conjugated polymer thin‐film transistors enables the fabrication of deformable devices with low cost, high throughput, and large area. However, a relatively poor device performance of printed devices remains a major obstacle to their application in high‐end display backplanes and integrated circuits. In this study, high‐performance and highly stackable printed organic transistors is developed, arrays, and circuits using a near‐amorphous polymer, indacenodithiophene‐co‐benzothiadiazole (IDT‐BT). The printed devices exhibited high saturation mobility (>1 cm2 V−1 s−1), high on/off ratio (>107), and low subthreshold slope (245 mV dec−1). In addition, 16 × 16 printed IDT‐BT arrays achieved 100% fabrication yield, with excellent device‐to‐device uniformity and low variations of mobility (9.55%) and threshold voltage (4.51%), and good operational and environmental stability (>365 days). Furthermore, five stacked 3D transistors are demonstrated with an excellent 3D uniformity without compromising device performance due to a low required thermal budget for processing amorphous IDT‐BT. Finally, a new concept of 3D universal logic gate with high voltage gain (33.91 V/V) and record density (100 printed transistors per cm2) is proposed and fabricated, which is relevant for the commercialization of low‐cost printed display backplanes and high‐density integrated circuits based on highly processable polymeric semiconductors.

Enhancing Sensitivity in Gas Detection: Porous Structures in Organic Field-Effect Transistor-Based Sensors.

Gas detection is crucial for detecting environmentally harmful gases. Organic field-effect transistor (OFET)-based gas sensors have attracted attention due to their promising performance and potential for integration into flexible and wearable devices. This review examines the operating mechanisms of OFET-based gas sensors and explores methods for improving sensitivity, with a focus on porous structures. Researchers have achieved significant enhancements in sensor performance by controlling the thickness and free volume of the organic semiconductor layer. Additionally, innovative fabrication techniques like self-assembly and etching have been used to create porous structures, facilitating the diffusion of target gas molecules, and improving sensor response and recovery. These advancements in porous structure fabrication suggest a promising future for OFET-based gas sensors, offering increased sensitivity and selectivity across various applications.

Highly Sensitive, Low-Energy-Consumption Biomimetic Olfactory Synaptic Transistors Based on the Aggregation of the Semiconductor Films.

Artificial olfactory synaptic devices with low energy consumption and low detection limits are important for the further development of neuromorphic computing and intelligent robotics. In this work, an ultralow energy consumption and low detection limit imitation olfactory synaptic device based on organic field-effect transistors (OFETs) was prepared. The aggregation state of poly(diketopyrrolopyrrole-selenophene) (PTDPP) semiconductor films is modulated by adding unfavorable solvents and annealing treatments to obtain excellent charge transfer and gas synaptic properties. The regulated OFET device can execute basic biological synaptic functions, including excitatory postsynaptic currents (EPSCs), paired-pulse facilitation (PPF), and the transition from short-term to long-term plasticity, at an ultralow operating voltage of -0.0005 V. The ultralow energy consumption during the biomimetic simulation is in the range of 8.94-88 fJ per spike. Noteworthily, the gas detection limit of the device is as low as 50 ppb, well below normal human NO2 gas perception limits (100-1000 ppb). Additionally, high-pass filtering, Pavlovian conditioned reflexes, and decoding of "Morse code" were simulated. Finally, a grid-free conformal device with outstanding flexibility and stability was fabricated. In conclusion, the control of semiconductor thin-film aggregation provides effective guidance for preparing low-energy-consumption, highly sensitive olfactory nerve-mimicking devices and promoting the development of wearable electronics.

Shape-Dependent Optical Waveguides and Low-Threshold Lasers from Polymorphic Two-Dimensional Organic Single Crystals.

Organic single crystals (OSCs) with uniform morphologies and highly ordered molecular aggregations are promising for high-performance optoelectronic devices, such as organic solid-state lasers (OSSLs), organic light-emitting transistors (OLETs), and organic light-emitting diodes (OLEDs). However, manipulating OSC morphologies and aggregation is challenging. In this study, we synthesized two-dimensional (2D) OSCs of 4,4'-bis[(N-carbazole)styryl]biphenyl (BSBCz) in hexagonal and parallelogram microplate (H-MP and P-MP) forms. Both types exhibit H-aggregation in the 2D plate plane but with different molecular transition dipole moment (TDM) orientations. This leads to different photon coupling modes with H-MP and P-MP microcavities. H-MPs enable isotropic 2D-waveguiding, forming whispering gallery mode (WGM) resonators, while P-MPs create unidirectional waveguiding, forming Fabry-Pérot mode (FP) resonators. These resonators can generate low-threshold laser emissions at 467 and 473 nm, respectively, and exhibit superior lasing stability with a half-life exceeding 2 h. Our BSBCz microplate OSCs are attractive candidates to combine controlled organic microcavities with photon transporting for realizing future integrated optoelectronic devices.

Metal-organic polymer enables efficient organic photoelectrochemical transistor biosensing

The field of organic photoelectrochemical transistor (OPECT) is newly emerged, with increasing efforts attempting to utilize its properties in biological sensing. Advanced materials with new physicochemical properties have proven important to this end. Herein, we report a metal-organic polymers-gated OPECT biosensing exemplified by CuⅠ-arylacetylide polymers (CuAs)-modulated poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) channel. Both the photoelectrochemical properties and gating capability of CuAs are explored and optimized for high-efficacy photogating. Morever, based on its inherent structure, the specific reaction between CuAs and sulfur ions (S2−) is revealed and S2−-mediated microRNA-21 detection is realized by linking with nucleic acid amplification and alkaline phosphatase catalytic chemistry. This work introduces metal-organic polymers as gating materials for OPECT biosensing.

N-Type semiconducting polymers based on an bithiophene imide-bridged isoindigo for organic field-effect transistors

n-Type polymer semiconductors are essential for enabling high-performance organic electronic devices; however, their development still remains a challenge. Herein, we reported a new electron-deficient building block, i.e. bithiophene imide (BTI)-bridged isoindigo (IID), BTIID, through a Knoevenagel condensation reaction between the bisaldehyde BTI and the alkylated indolinones. Three donor-acceptor (D-A) copolymers were then successfully synthesized via standard Stille coupling reaction based on this novel building block, which exhibit highly planar backbones and low-lying lowest unoccupied molecular orbitals (LUMO) energy levels. When integrated into organic field-effect transistors (OFETs), these polymers demonstrated unipolar n-type transport characteristics with a highest electron mobility of 5.79 × 10−4 cm2 V−1 s−1. Our research results indicate that the design of strong electron-withdrawing units via integrating two different electron-acceptor units into one single structure represents a promising strategy for developing n-type polymer semiconductors with low-lying LUMO energy levels.

Synthesis, Thermotropic Properties, and Applications of Porphyrin-based Liquid Crystals: A Comprehensive Review

Abstract: Research on novel discotic molecules, which consist of a rigid core with flexible peripheral chains, has gained much attention due to their crucial role as organic photovoltaic materials, organic field-effect transistors, and semiconductors for photocurrent generation, as well as the possibility of their other optoelectronic applications. This review article describes the developments in fundamental design ideas and synthetic approaches of porphyrin-based meso and beta-substituted liquid crystals. In addition, the current review highlights the various structural alterations made by the researchers in the field of porphyrin-based mesogens and changes in properties, both for materials intended for commercially successful liquid crystal displays, including other applications, and for more basic purposes of demonstrating structure-property relationships.

PNIPAM/PEDOT:PSS Hydrogels for Multifunctional Organic Electrochemical Transistors

AbstractThe development of multifunctional organic materials represents a vibrant area of research, with applications spanning from biosensing to drug delivery. This study shows the development of a multifunctional bioelectronic device suitable for prolonged temperature monitoring and drug delivery applications. The device relies on a conducting and thermo‐responsive hydrogel made of poly(3,4‐ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS) and poly(N‐isopropylacrylamide) (PNIPAM). This multifunctional hydrogel is 4D printable by Digital Light Processing (DLP) method and exhibits optimal biocompatibility. The hydrogel features a low critical solution temperature (LCST) ≈35 °C, above which its resistance changes dramatically due to the shrinkage it undergoes with temperature. The integration of PNIPAM/PEDOT hydrogel into an organic electrochemical transistor (OECT) as the gate electrode allows to generate a miniaturized bioelectronic device with a reversible response to temperature variations between 25 to 45 °C, along with high sensitivity of 0.05 °C−1. Furthermore, the PNIPAM/PEDOT hydrogel demonstrates its utility in drug delivery, achieving an Insulin‐FITC release rate of 82 ± 4% at 37 °C, mimicking human body conditions. The hydrogel's functionality to store and release the insulin does not compromise its thermo‐responsivity and the overall performance of the OECT. This multifunctional OECT opens new avenues for the development of customizable and personalized sensing and drug‐delivery systems.

Metal‐Organic Framework Nanozyme Enabling Dual‐Functional Photo‐Induced Charge Transfer and Biomimetic Precipitation for Advanced Organic Photoelectrochemical Transistor Bioanalysis

Comprehensive SummaryWe report herein the first observation of MOF nanozyme enabling dual‐functional photo‐induced charge transfer and biomimetic precipitation for advanced organic photoelectrochemical transistor (OPECT) bioanalysis. Specifically, Fe/Co‐MIL‐88, serving simultaneously as the semiconductor and nanozyme, was explored as a dual‐functional gating module in OPECT. Upon light illumination, it could accelerate the charge transfer of the photogate to produce enhanced photo‐induced voltage. Meanwhile, its catalytic property could efficiently produce biomimetic precipitation to block the nanopores in Fe/Co‐MIL‐88 and thus alter the device characteristics. The generic bioanalytical potential of such a rationale was then demonstrated with an aptasensing assisted by magnetic separation. This work represents the first exploration of biomimetic precipitation from MOF nanozymes for generic OPECT bioanalysis, it is expected to attract more interest in various nanozymes for novel optoelectronic bioanalytics.