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.

Organic field-effect transistors (OFETs) have the advantages of low-cost, large-area processing and could be utilized in a variety of emerging applications. However, the generally large contact resistance (Rc) limits the integration and miniaturization of OFETs. The Rc is difficult to reduce due to an incompatibility between obtaining strong orbit coupling and the barrier height reduction. In this study, we developed an oxygen-induced barrier lowering strategy by introducing oxygen (O2) into the nanointerface between the electrodes and organic semiconductors layer and achieved an ultralow channel width-normalized Rc (Rc·W) of 89.8 Ω·cm and a high mobility of 11.32 cm2 V-1 s-1. This work demonstrates that O2 adsorbed at the nanointerface of metal-semiconductor contact can significantly reduce the Rc from both experiments and theoretical simulations and provides guidance for the construction of high-performance OFETs, which is conducive to the integration and miniaturization of OFETs.

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.

Semiconductors are widely used in electron devices. With the development of wearable soft-electron devices, conventional inorganic semiconductors are unable to meet the demand because of their high rigidity and high cost. Thus, scientists construct organic semiconductors with high charge mobility, low cost, eco-friendly, stretchable, etc. Due to the excellent performance of stretchable organic semiconductors, they can be widely used as wearable soft-electron devices, such as stretchable organic field-effect transistors (OFETs), organic solar cells (OSCs), etc. Contains flexible display devices and flexible power sources, which are of great interest for applications of future electron devices. However, there are still some challenges that need to be solved. Commonly, enhancing the stretchability may cause the degradation of charge mobility, because of the destruction of the conjugated system. Currently, scientists find that hydrogen bonding can enhance the stretchability of organic semiconductors with high charge mobility. Thus in this review, based on the structure and design strategies of hydrogen bonding, various hydrogen bonding induced stretchable organic semiconductors are introduced. In addition, the applications of the hydrogen bonding induced stretchable organic semiconductors are reviewed. Finally, the stretchable organic semiconductors design concept and potential evolution trends are discussed. The final goal is to outline a theoretical scaffold for the design of high-performance wearable soft-electron devices, which can also further advance the development of stretchable organic semiconductors for applications.

This review highlights selected examples, published in the last three to four years, of recent advance in the design, synthesis, properties, and device performance of quinoidal π-conjugated materials. A particular emphasis is placed on emerging materials, such as indophenine dyes that have the potential to enable high-performance devices. We specifically discuss the recent advances and design guidelines of π-conjugated quinoidal molecules from a chemical standpoint. To the best of the authors\' knowledge, this review is the first compilation of literature on indophenine-based semiconducting materials covering their scope, limitations, and applications. In the first section, we briefly introduce some of the organic electronic devices that are the basic building blocks for certain applications involving organic semiconductors (OSCs). We introduce the definition of key performance parameters of three organic devices: organic field effect transistors (OFET), organic photovoltaics (OPV), and organic thermoelectric generators (TE). In section two, we review recent progress towards the synthesis of quinoidal semiconducting materials. Our focus will be on indophenine family that has never been reviewed. We discuss the relationship between structural properties and energy levels in this family of molecules. The last section reports the effect of structural modifications on the performance of devices: OFET, OPV and TE. In this review, we provide a general insight into the association between the molecular structure and electronic properties in quinoidal materials, encompassing both small molecules and polymers. We also believe that this review offers benefits to the organic electronics and photovoltaic communities, by shedding light on current trends in the synthesis and progression of promising novel building blocks. This can provide guidance for synthesizing new generations of quinoidal or diradical materials with tunable optoelectronic properties and more outstanding charge carrier mobility.

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.

Diketopyrrolopyrrole (DPP) and its derivatives have been widely studied in the past few years due to its intrinsic physical and chemical properties, such as strong electron-withdrawing, deep color, high charge carrier mobility, strong aggregation, good thermal-/photo-stability. In the 1970s, DPP was developed and used only in inks, paints, and plastics. Later, DPP containing materials were found to have potential other applications, typically in electronic devices, which attracted the attention of scientists. In this feature article, the synthesis pathway of DPP-based materials and their applications in organic field-effect transistors, photovoltaic devices, sensors, two photo-absorption materials, and others are reviewed, and possible future applications are discussed. The review outlines a theoretical scaffold for the development of conjugated DPP-based materials, which have multiple potential applications.

Altering the charge carrier transport polarities of organic semiconductors by molecular orbital distribution has gained great interest. Herein, we report two isomeric azulene-decorated naphthodithiophene diimide (NDTI)-based triads (e.g., NDTI-B2Az and NDTI-B6Az), in which two azulene units were connected with NDTI at the 2-position of the azulene ring in NDTI-B2Az, whereas two azulene units were incorporated with NDTI at the 6-position of the azulene ring in NDTI-B6Az. The two isomeric triads were excellently soluble in common organic solvents. Density functional theory calculations on the molecular orbital distributions of the triads reveal that the lowest unoccupied molecular orbitals are completely delocalized over the entire molecule for both NDTI-B2Az and NDTI-B6Az, indicating great potential for n-type transport behavior, whereas the highest occupied molecular orbitals are mainly delocalized over the entire molecule for NDTI-B2Az or only localized at the two terminal azulene units for NDTI-B6Az, implying great potential for p-type transport behavior for the former and a disadvantage of hole carrier transport for the latter. Under ambient conditions, solution-processed bottom-gate top-contact transistors based on NDTI-B2Az showed ambipolar field-effect transistor (FET) characteristics with high electron and hole mobilities of 0.32 (effective electron mobility ≈0.14 cm2 V-1 s-1 according to a reliability factor of 43%) and 0.03 cm2 V-1 s-1 (effective hole mobility ≈0.01 cm2 V-1 s-1 according to a reliability factor of 33%), respectively, whereas a typically unipolar n-channel behavior is found for a film of NDTI-B6Az with a high electron mobility up to 0.13 cm2 V-1 s-1 (effective electron mobility ≈0.06 cm2 V-1 s-1 according to a reliability factor of 43%). The results indicate that the polarity change of organic FETs based on the two isomeric triads could be controlled by the molecular orbital distributions through the connection position between the azulene unit and NDTI.

Organic field-effect transistors (OFETs) have acquired increasing attention because of their wide range of potential applications in electronics; nevertheless, high operating voltage and low carrier mobility are considered as major bottlenecks in their commercialization. In this work, we demonstrate low-voltage, flexible OFETs based on ultrathin single-crystal microribbons. Flexible OFETs fabricated with 2,7-dioctylbenzothieno[3,2-b]benzothiophene (C8-BTBT) based solution-processed ultrathin single-crystal microribbon as the semiconductor layer and high-k polymer, polysiloxane-poly(vinyl alcohol) composite as an insulator layer manifest a significantly low operating voltage of -4 V, and several devices showed a high mobility of >30 cm2 V-1 s-1. Besides, the carrier mobility of the fabricated devices exhibits a slight degradation in static bending condition, which can be retained by 83.3% compared with its original value under a bending radius of 9 mm. As compared to the bulk C8-BTBT single-crystal-based OFET, which showed a large crack only after 50 dynamic bending cycles, our ultrathin single-crystal-based counterpart demonstrates a much better dynamic force stability. Moreover, under a 20 mm bending radius, the mobility of the device decreased by only 11.7% even after 500 bending cycles and no further decrease was observed until 1000 bending cycles. Our findings reveal that ultrathin C8-BTBT single-crystal-based flexible OFETs are promising candidates for various high-performance flexible electronic devices.

N-Heterocyclic carbenes (NHCs), which react with the surface of Au electrodes, have been successfully applied in pentacene transistors. With the application of NHCs, the charge-carrier mobility of pentacene transistors increased by five times, while the contact resistance at the pentacene-Au interface was reduced by 85 %. Even after annealing the NHC-Au electrodes at 200 °C for 2 h before pentacene deposition, the charge-carrier mobility of the pentacene transistors did not decrease. The distinguished performance makes NHCs as excellent alternatives to thiols as metal modifiers for the application in organic field-effect transistors (OFETs).