Applications In Organic Field-effect Transistors Research Articles

A Review on the Synthetic Methods towards Benzothienobenzothiophenes.

Benzothienobenzothiophenes (BTBTs) are a class of heteroacenes for which two distinct isomers have been identified depending on the locations of the fused benzothiophene motifs. Benzothienobenzothiophenes represent a class of heteroacenes demonstrating remarkable electronic properties that make them prominent in the realm of organic semiconductors. The structure of BTBTs, incorporating two sulfur atoms, contributes to their unique electronic characteristics, including narrow bandgaps and effective charge transport pathways. These compounds have gained attention for their high charge carrier mobility, making them desirable candidates for application in organic field-effect transistors (OFETs) and other electronic devices. Researchers have explored various synthetic strategies to design and tailor the properties of BTBT derivatives, leading to advancements in the development of high-performance organic semiconductors. Various synthetic techniques for benzothienobenzothiophenes have been reported in the literature including multistep synthesis, tandem transformations, electrochemical synthesis, and annulations. This review investigates the generality of each synthetic methodology by highlighting its benefits and drawbacks, and it analyses all synthetic approaches described for the creation of the two isomers. For the advantage of the readers, we have delved upon every mechanism of the reactions that are known. Finally, we have also summarized the synthetic methodologies that are used for making benzothienobenzothiophene analogues for material applications.

Acetylene-extended triarylamines for solution-processable p-channel OFETs

New acetylene-extended molecules were developed as a semiconducting layer for application in solution-processable organic field-effect transistors through coupling reactions using substituted triphenylamines as wings and diacetylene as spacer units. The influence of donor ability and spacer strength on the electrical properties was explored by developing different acetylene-extended triarylamines with D–π and D–π–π–D architectures and their structure–properties analysis. Their optical studies revealed narrow Stoke's shift and optical bandgap values, especially for highly electron-rich systems. Encouraging results supported by their electrochemical studies that revealed high HOMO energy levels ranging from –5.1 to –5.3 eV suggested a low energy barrier and good hole-transporting ability, hence, their applicability as p-channel OFETs. Furthermore, the extended conjugation in D–π–π–D based molecules relative to their corresponding D–π system caused enhanced molecular orbital overlap along the triphenylamine and facilitated good charge transport characteristics. Upon fabrication as the semiconducting channel in top-gate/bottom-contact OFET devices, the acetylene-extended D–π–π–D system showed good p-channel properties with hole mobilities up to 1.2 cm2/Vs and the highest on/off ratio of 107.

Diselenophene-Dithioalkylthiophene Based Quinoidal Small Molecules for Ambipolar Organic Field Effect Transistors.

This work presents a series of novel quinoidal organic semiconductors based on diselenophene-dithioalkylthiophene (DSpDST) conjugated cores with various side-chain lengths (-thiohexyl, -thiodecyl, and -thiotetradecyl, designated DSpDSTQ-6, DSpDSTQ-10, and DSpDSTQ-14, respectively). The purpose of this research is to develop solution-processable organic semiconductors using dicyanomethylene end-capped organic small molecules for organic field effect transistors (OFETs) application. The physical, electrochemical, and electrical properties of these new DSpDSTQs are systematically studied, along with their performance in OFETs and thin film morphologies. Additionally, the molecular structures of DSpDSTQ are determined through density functional theory (DFT) calculations and single-crystal X-ray diffraction analysis. The results reveal the presence of intramolecular S (alkyl)···Se (selenophene) interactions, which result in a planar SR-containing DSpDSTQ core, thereby promoting extended π-orbital interactions and efficient charge transport in the OFETs. Moreover, the influence of thioalkyl side chain length on surface morphologies and microstructures is investigated. Remarkably, the compound with the shortest thioalkyl chain, DSpDSTQ-6, demonstrates ambipolar carrier transport with the highest electron and hole mobilities of 0.334 and 0.463 cm2 V-1 s-1 , respectively. These findings highlight the excellence of ambipolar characteristics of solution-processable OFETs based on DSpDSTQs even under ambient conditions.

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.

Donor-Acceptor-Based Organic Polymer Semiconductor Materials to Achieve High Hole Mobility in Organic Field-Effect Transistors.

Organic polymer semiconductor materials are conveniently tuned to energy levels because of their good chemically modifiable properties, thus enhancing their carrier transport capabilities. Here, we have designed and prepared a polymer with a donor-acceptor structure and tested its potential as a p-type material for organic field-effect transistor (OFET) applications using a solution-processing method. The conjugated polymers, obtained via the polymerization of the two monomers relying on the Stille coupling reaction, possess extremely high molecular weights and thermodynamic stability. Theoretical-based calculations show that PDPP-2S-Se has superior planarity, which is favorable for carrier transport within the main chain. Photophysical and electrochemical measurements systematically investigated the properties of the material and the energy levels with respect to the theoretical values. The maximum hole mobility of the PDPP-2S-Se-based OFET device is 0.59 cm2 V-1 s-1, which makes it a useful material for potential organic electronics applications.

Semiconducting Polymers Based on Simple Electron‐Deficient Cyanated trans‐1,3‐Butadienes for Organic Field‐Effect Transistors

AbstractDeveloping high‐performance but low‐cost n‐type polymers remains a significant challenge in the commercialization of organic field‐effect transistors (OFETs). To achieve this objective, it is essential to design the key electron‐deficient units with simple structures and facile preparation processes, which can facilitate the production of low‐cost n‐type polymers. Herein, by sequentially introducing fluorine and cyano functionalities onto trans‐1,3‐butadiene, we developed a series of structurally simple but highly electron‐deficient building blocks, namely 1,4‐dicyano‐butadiene (CNDE), 3‐fluoro‐1,4‐dicyano‐butadiene (CNFDE), and 2,3‐difluoro‐1,4‐dicyano‐butadiene (CNDFDE), featuring a highly coplanar backbone and deep‐positioned lowest unoccupied molecular orbital (LUMO) energy levels (−3.03–4.33 eV), which render them highly attractive for developing n‐type semiconducting polymers. Notably, all these electron‐deficient units can be easily accessed by a two‐step high‐yield synthetic procedure from low‐cost raw materials, thus rendering them highly promising candidates for commercial applications. Upon polymerization with diketopyrrolopyrrole (DPP), three copolymers were developed that demonstrated unipolar n‐type transport characteristics in OFETs with the highest electron mobility of >1 cm2 V−1 s−1. Hence, CNDE, CNFDE, and CNDFDE represent a class of novel, simple, and efficient electron‐deficient units for constructing low‐cost n‐type polymers, thereby providing valuable insight for OFET applications.

Semiconducting Polymers Based on Simple Electron-Deficient Cyanated trans-1, 3-Butadienes for Organic Field-Effect Transistors.

Developing high-performance but low-cost n-type polymers remains a significant challenge in the commercialization of organic field-effect transistors (OFETs). To achieve this objective, it is essential to design the key electron-deficient units with simple molecular structure and facile preparation process, which can directly facilitate the production of low-cost n-type polymers. Herein, by sequentially introducing fluorine and cyano functionalities onto trans-1,3-butadiene π-skeleton, we developed a series of structurally simple but highly electron-deficient building blocks, namely 1,4-dicyano-butadienes (CNDE), 3-fluoro-1,4-dicyano-butadienes (CNFDE), and 2,3-difluoro-1,4-dicyano-butadienes (CNDFDE), featuring highly coplanar backbone and deep-positioned lowest unoccupied molecular orbital (LUMO) energy levels (-3.03-4.33 eV), which render them highly attractive building blocks for developing n-type semiconducting polymers. Notably, all these electron-deficient units can be easily accessed via a two-step high-yield synthetic protocol from low-cost raw materials, thus rendering them highly promising candidates for commercial applications. Upon polymerized with diketopyrrolopyrrole (DPP) units, three copolymers are developed and demonstrated unipolar n-type transport characteristics in OFETs with the highest electron mobility > 1 cm2 V-1 s-1. Hence, CNDE, CNFDE, and CNDFDE represent a class of novel, simple, and efficient electron-deficient units for constructing low-cost n-type polymers, providing valuable insights for the OFET applications.

Structure-Property Relationship of Macrocycles in Organic Photoelectric Devices: A Comprehensive Review.

Macrocycles have attracted significant attention from academia due to their various applications in organic field-effect transistors, organic light-emitting diodes, organic photovoltaics, and dye-sensitized solar cells. Despite the existence of reports on the application of macrocycles in organic optoelectronic devices, these reports are mainly limited to analyzing the structure-property relationship of a particular type of macrocyclic structure, and a systematic discussion on the structure-property is still lacking. Herein, we conducted a comprehensive analysis of a series of macrocycle structures to identify the key factors that affect the structure-property relationship between macrocycles and their optoelectronic device properties, including energy level structure, structural stability, film-forming property, skeleton rigidity, inherent pore structure, spatial hindrance, exclusion of perturbing end-effects, macrocycle size-dependent effects, and fullerene-like charge transport characteristics. These macrocycles exhibit thin-film and single-crystal hole mobility up to 10 and 26.8 cm2 V-1 s-1, respectively, as well as a unique macrocyclization-induced emission enhancement property. A clear understanding of the structure-property relationship between macrocycles and optoelectronic device performance, as well as the creation of novel macrocycle structures such as organic nanogridarenes, may pave the way for high-performance organic optoelectronic devices.

Synthesis, Photophysical properties and OFET application of thienothiophene and benzothiadiazole based Donor-π-Acceptor-π (D-π -A-π) type conjugated polymers

Novel conjugated donor- π -acceptor- π (D- π -A- π) type polymers (P1-P3), possessing thieno[3,2-b]thiophene (TT) with different aromatic substituents as donors, benzo[1–3]thiadiazole (BT) as an acceptor and thiophene as a π -linker, were designed and synthesized via palladium-catalyzed Stille coupling reaction. Their electronic, optical and thermal properties were investigated using UV–vis and fluorescence spectroscopies, cylic voltammetry, and thermal gravimetric analysis. Photophysical characterizations of these novel polymers showed a remarkable mega Stokes shift, reaching up to 130 nm and optic/electronic band gaps between 1.70 and 2.00 eV, as well as good thermal stability of degradation temperature at around 260 °C. To study the effect of electron donating and withdrawing groups on the electronic properties of the π -extended polymers, their organic field-effect transistors (OFETs) were fabricated and charge transport characteristics were investigated. While all three polymers showed a p-type field-effect behaviour, dimethylamine substituted P3 exhibited the highest average saturated hole mobility, μsat, 0.04 cm2 V−1 s−1, on/off current ratio, Ion/Ioff = 3.0 × 103, and the smallest subthreshold swing, SS, 250 mV dec-1, outperforming similar p-type D- π -A- π semiconducting polymers reported in the literature. The results presented in this work corroborate that the three novel TT-BT polymers have promising potential for electronic and optoelectronic applications, in particular where the tunability of field-effect behaviour is essential for performance.

N-Type Doping of Naphthalenediimide-Based Random Donor–Acceptor Copolymers to Enhance Transistor Performance and Structural Crystallinity

An integrated strategy of molecular design and conjugated polymer doping is proposed to improve the electronic characteristics for organic field effect transistor (OFET) applications. Here, a series of soluble naphthalene diimide (NDI)-based random donor-acceptor copolymers with selenophene π-conjugated linkers and four acceptors with different electron-withdrawing strengths (named as rNDI-N/S/NN/SS) are synthesized, characterized, and used for OFETs. N-type doping of NDI-based random copolymers using (12a,18a)-5,6,12,12a,13,18,18a,19-octahydro-5,6-dimethyl-13,18[1',2']-benzenobisbenzimidazo[1,2-b:2',1'-d]benzo[i][2.5]benzodiazocine potassium triflate adduct (DMBI-BDZC) is successfully demonstrated. The undoped rNDI-N, rNDI-NN, and rNDI-SS samples exhibit ambipolar charge transport, while rNDI-S presents only a unipolar n-type characteristic. Doping with DMBI-BDZC significantly modulates the performance of rNDI-N/S OFETs, with a 3- to 6-fold increase in electron mobility (μe) for 1 wt % doped device due to simultaneous trap mitigation, lower contact resistance (RC), and activation energy (EA), and enhanced crystallinity and edge-on orientation for charge transport. However, the doping of intrinsic pro-quinoidal rNDI-NN/SS films exhibits unchanged or even reduced device performance. These findings allow us to manipulate the energy levels by developing conjugated copolymers based on various acceptors and quinoids and to optimize the dopant-polymer semiconductor interactions and their impacts on the film morphology and molecular orientation for enhanced charge transport.

Fluoro substitution effect on 2,1,3-benzothiadiazole-based hybridized local and charge transfer state fluorophores for high-performance organic light-emitting diodes

Fluoro substitution of organic semiconductors is an effective way to improve some related performance of the materials, such as the carrier mobility in organic photovoltaics (OPVs) and organic field-effect transistors (OFETs) applications. However, the influence of fluoro substitution for fluorophores in organic light-emitting diodes (OLEDs) applications is rarely reported. Here, with fluorinated electron-deficient 2,1,3-benzothiadiazole (BT) unit as the acceptor and triphenylamine (TPA) as the donor, we construct two new D-A-type fluorophores DTPA-fBT and DTPA-ffBT. Theoretical calculations and experimental results reveal that the lowest excited states (S1) of the materials are characterized by hybridized local and charge-transfer (HLCT) properties, in which the fluorine substitution will increase the proportion of the charge-transfer (CT) component. Due to the introduction of fluoro substitution, multiple fluorine hydrogen bonds are formed, which endow the molecules with more rigid conformation, leading to lower non-radiative rates and higher photoluminescence quantum yield (PLQY) in solution and doped film, as well as improved thermal stability in the solid state. As a result, the two fluorinated DTPA-ffBT demonstrate significantly improved performance in OLEDs with a maximum external quantum efficiency (EQE) of 7.25% (5.90% for fluorine-free counterpart) and very low-efficiency roll-off (roll-off <7% at 10,000 cd m−2).

π-Extended Pyrrole-Fused Heteropine: Synthesis, Properties, and Application in Organic Field-Effect Transistors.

Sulfur-embedded polycyclic aromatic compounds have been used as building blocks for numerous organic semiconductors over the past few decades. While the success is based on thiophene-containing compounds, aromatic compounds that contain thiepine, a sulfur-containing seven-membered-ring arene, has been less well investigated. Here we report the synthesis and properties of π-extended pyrrole-fused heteropine compounds such as thiepine and oxepine. A π-extended pyrrole-fused thiepine exhibited a "pitched π-stacking" structure in the crystal, and exhibited a high charge carrier mobility of up to 1.0 cm2 V-1 s-1 in single-crystal field-effect transistors.

Synthesis and characterization of naphthalenediimide-thienothiophene-conjugated polymers for OFET and OPT applications

Three new thienothiophene (TT) and naphthalenediimide (NDI)-based D–A-type conjugated polymers were designed, synthesized and fabricated for organic field effect transistor (OFET) and organic phototransistor (OPT) applications.

Theoretical Study of the Structural, Optoelectronic, and Reactivity Properties of N-[5′-Methyl-3′-Isoxasolyl]-N-[(E)-1-(-2-)]Methylidene] Amine and Some of Its Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ Complexes for OLED and OFET Applications

Herein, we report the structural, electronic, and charge transfer properties of N-[5′-methyl-3′-isoxasolyl]-N-[(E)-1-(-2-thiophene)] methylidene] amine (L) and its Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ complexes (dubbed A, B, C, D, and E, respectively) using the density functional theory (DFT). All molecules investigated were optimized at the BP86/def2-TZVP/RI level of theory. Single point energy calculations were carried out at the M06-D3ZERO/def2-TZVP/RIJCOSX level of theory. Reorganization energies of the hole and electron (λh and λe) and the charge transfer mobilities of the electron and hole (μe and μh) have been computed and reported. The λe and λh values vary in the order D &gt; E &gt; A &gt; B &gt; C &gt; L and E &gt; A &gt; D &gt; L &gt; C &gt; B, respectively, while μe and μh vary in the order B &gt; C &gt; L &gt; A &gt; E &gt; D and C &gt; B &gt; A &gt; L &gt; E &gt; D, respectively. μh of B (39.5401 cm2·V−1S−1) and C (366.4740 cm2·V−1s−1) is remarkably large, suggesting their application in organic light-emitting diode (OLED) and organic field-effect transistor (OFET) technologies. Electron excitation analysis based on time-dependent (TD)-DFT calculations revealed that charge transfer excitations may significantly affect charge transfer mobilities. Based on charge transfer mobility results, B and C are outstanding and are promising molecules for the manufacture of electron and hole-transport precursor materials for the construction of OLED and OFET devices as compared to L. The results also show that L and all its complexes interestingly have higher third-order NLO activity than those of para-nitroaniline, a prototypical NLO molecule.

Side-Chain Engineering of Polystyrene Dielectrics Toward High-Performance Photon Memories and Artificial Synapses

The emerging applications of organic field-effect transistors (OFETs), such as photon memories and artificial synapses, require polymer dielectrics with superior charge trapping properties. Despite the introduction of high-k and fluorinated polymers in the performance optimization of OFETs, there is still a lack of widely recognized acknowledgment between molecular structures and charge trapping characteristics, as well as no general principles in designing polymeric dielectrics for electronic memory devices. Here, we propose a series of fluorinated polystyrene isomers through side-chain engineering, namely, ortho-(o-), meta-(m-), and para-fluorinated polystyrene (p-FPS). The gradually enlarged intramolecular charge separation of o-, m-, and p-FPS enhances molecular electrostatic potential, which promotes polarization and charge trapping performances, resulting in an enlarged dielectric constant, as well as more deep traps toward stable electret. Subsequently, largely improved photon memory and artificial synapse performances of p-FPS-based OFETs further suggest the dominating role of dielectric side-chain structures on memory and synapse performances, leading to a recommendation of low-k (εr < 5) dielectric polymers with enhanced electrostatic potential for OFET-based memory devices and bionic nervous systems.

Microwave Irradiation as a Powerful Tool for the Preparation of n-Type Benzotriazole Semiconductors with Applications in Organic Field-Effect Transistors.

In this work, as an equivocal proof of the potential of microwave irradiation in organic synthesis, a complex pyrazine-decorated benzotriazole derivative that is challenging to prepare under conventional conditions has been obtained upon microwave irradiation, thus efficiently improving the process and yields, dramatically decreasing the reaction times and resulting in an environmentally friendly synthetic procedure. In addition, this useful derivative could be applied in organic electronics, specifically in organic field-effect transistors (OFETs), exhibiting the highest electron mobilities reported to date for benzotriazole discrete molecules, of around 10−2 cm2V−1s−1.

Chlorine‐Substituted N‐Heteroacene Analogues Acting as Organic Semiconductors for Solution‐Processed n‐type Organic Field‐Effect Transistors

High performance solution processable n-type organic semiconductor is an essential element to realize low-cost, all organic and flexible composite logic circuits. In the design of n-type semiconducting materials, tuning the LUMO level of compounds is a key point. As a strong electron withdrawing unit, the introduction of chlorine atom into the chemical structure can increase the electron affinity of the material and reduce the LUMO energy level. Here, a series chlorine substituted N-heteroacene analogues of 6,7,8,9-tetrachloro-4,11-bis(4-((2-ethylhexyl)oxy)phenyl)-[1,2,5]thiadiazolo[3,4-b]phenazine (O4Cl), 6,7,8,9-tetrachloro-4,11-bis(4-((2-ethylhexyl)thio)phenyl)-[1,2,5]thiadiazolo[3,4-b]phenazine (S4Cl), 1,2,3,4,8,9,10,11-octachloro-6,13-bis(4-((2-ethylhexyl)oxy)phenyl)quinoxalino[2,3-b]phenazine (8Cl) and 12Cl have been synthesized and characterized. Solution-processed organic field-effect transistors (OFETs) based on these four compounds exhibit good electron mobilities of 0.04 cm2 V-1 s-1 , 0.01 cm2 V-1 s-1 , 2×10-3 cm2 V-1 s-1 and 3×10-3 cm2 V-1 s-1 , respectively, under ambient conditions. The results suggest that these chlorine substituted π-conjugated N-heteroacene analogues are promising n-type semiconductors in OFET applications.

Recent Advances of Self-Healing Electronic Materials Applied in Organic Field-Effect Transistors.

Self-healing materials play an essential role in the field of organic electronics with numerous stunning applications such as novel integrated and wearable devices. With the development of stretchable, printable, and implantable electronics, organic field-effect transistors (OFETs) with a self-healable capability are becoming increasingly important both academically and industrially. However, the related research work is still in the initial stage due to the challenges in developing robust self-healing electronic materials with both electronic and mechanical properties. In this mini-review, we have summarized the recent research progress in self-healing materials used in OFETs from conductor, semiconductor, and insulator materials. Moreover, the relationship between the material design and device performance for self-healing properties is also further discussed. Finally, the primary challenges and outlook in this field are introduced. We believe that the review will shed light on the development of self-healing electronic materials for application in OFETs.

Air Stable Chalcogen-Doped Rubicenes with Diradical Character

Air Stable Chalcogen-Doped Rubicenes with Diradical Character

Electrohydrodynamic jet printing of small-molecule semiconductor crystals on chemically patterned surface for high-performance organic field-effect transistors

Direct writing of organic semiconducting crystals by electrohydrodynamic jet (EHD) printing has enabled the low-cost large-area fabrication of organic semiconducting crystal arrays without the need of complicated patterning procedures. However, morphological variations within a single printed pattern (e.g., variations in thickness, crystallinity, and local crystal orientation) caused by the “coffee-ring effect” can be an issue during their application in organic field-effect transistors (OFETs) since their charge-transport properties significantly affect the device characteristics. Herein, we report the EHD printing of small-molecule semiconducting crystals on a chemically patterned substrate to suppress the “coffee-ring effect” and produce uniform high-quality crystals oriented along the printing direction. The EHD printing of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-PEN) on hydrophobic polyurethane acrylate line patterns on a dielectric surface enables the selective and guided growth of the crystals. The OFETs with the TIPS-PEN crystals printed on the patterned surface exhibit an average field-effect mobility of 0.34 cm2/(V s), which is more than twice of that of the OFETs fabricated with crystals grown on unpatterned surfaces. Thus, the use of chemically patterned surface to improve the uniformity and crystallinity of organic semiconducting crystals is expected to promote the application of EHD printing for fabricating high-performance OFETs.