n‐Type Quinoidal Oligothiophene‐Based Semiconductors for Thin‐Film Transistors and Thermoelectrics

Organic electronic devices have gained immense popularity in the last 30 years owing to their increasing performance. Organic thin‐film transistors (OTFTs) are one of the basic organic electronic devices with potential industrial applications. Another class of devices called organic thermoelectric (OTE) materials can directly transform waste heat into usable electrical power without causing any pollution. p‐Type transistors outperform n‐type transistors because the latter requires a lower orbital energy level for efficient electron injection and stable electron transport under ambient conditions. Aromatic building blocks can be utilized in constructing n‐type semiconductors. Quinoidal compounds are another promising platform for optoelectronic applications because of their unique properties. Since their discovery in 1970s, quinoidal oligothiophene‐based n‐type semiconductors have drawn considerable attention as candidates for high‐performance n‐type semiconductors in OTFTs and OTEs. Herein, the development history of quinoidal oligothiophene‐based semiconductors is summarized, with a focus on the molecular design and the influence of structural modification on molecular packing and thus the device performance of the corresponding quinoidal oligothiophene‐based semiconductors. Insights on the potential of quinoidal oligothiophenes for high‐performance n‐type OTFTs and OTEs are also provided.     

Printed and Electrochemically Gated,High‐Mobility,Inorganic Oxide Nanoparticle FETs and Their Suitability for High‐Frequency Applications

Solution‐processed or printed n‐channel field‐effect transistors (FETs) with high performance are not reported very often in the literature due to the scarcity of high‐mobility n‐type organic semiconductors. On the other hand, low‐temperature processed n‐channel metal oxide semiconductor (NMOS) transistors from electron conducting inorganic‐oxide nanoparticles show reduced‐performance and low mobility because of large channel roughness at the channel‐dielectric interface. Here, a method to produce ink‐jet printed high performance NMOS transistor devices using inorganic‐oxide nanoparticles as the transistor channel in combination with a 3D electrochemical gating (EG) via printed composite solid polymer electrolytes is presented. The printed FETs produced show a device mobility value in excess of 5 cm² V^?1 s^?1, even though the root mean square (RMS) roughness of the nanoparticulate channel exceeds 15 nm. Extensive studies on the frequency dependent polarizability of composite polymer electrolyte capacitors show that the maximum attainable speed in such printed, long channel transistors is not limited by the ionic conductivity of the electrolytes. Therefore, the approach of combining printable, high‐quality oxide nanoparticles and the composite solid polymer electrolytes, offers the possibility to fully utilize the large mobility of oxide semiconductors to build all‐printed and high‐speed devices. The high polarizability of printable polymer electrolytes brings down the drive voltages to ≤1 V, making such FETs well‐suited for low‐power, battery compatible circuitry.     

Molecular Weight‐Induced Structural Transition of Liquid‐Crystalline Polymer Semiconductor for High‐Stability Organic Transistor

In order to fabricate polymer field‐effect transistors (PFETs) with high electrical stability under bias‐stress, it is crucial to minimize the density of charge trapping sites caused by the disordered regions. Here we report PFETs with excellent electrical stability comparable to that of single‐crystalline organic semiconductors by specifically controlling the molecular weight (MW) of the donor‐acceptor type copolymer semiconductors, poly (didodecylquaterthiophene‐alt‐didodecylbithiazole). We found that MW‐induced thermally structural transition from liquid‐crystalline to semi‐crystalline phases strongly affects the device performance (charge‐carrier mobility and electrical bias‐stability) as well as the nanostructures such as the molecular ordering and the morphological feature. In particular, for the polymer with a MW of 22 kDa, the transfer curves varied little (ΔV_th = 3～4 V) during a period of prolonged bias stress (about 50 000 s) under ambient conditions. This enhancement of the electrical bias‐stability can be attributed to highly ordered liquid‐crystalline nanostructure of copolymer semiconductors on dielectric surface via the optimization of molecular weights.     

Tuning Contact Resistance in Top‐Contact p‐Type and n‐Type Organic Field Effect Transistors by Self‐Generated Interlayers

Contact resistance significantly limits the performance of organic field‐effect transistors (OFETs). Positioning interlayers at the metal/organic interface can tune the effective work‐function and reduce contact resistance. Myriad techniques offer interlayer processing onto the metal pads in bottom‐contact OFETs. However, most methods are not suitable for deposition on organic films and incompatible with top‐contact OFET architectures. Here, a simple and versatile methodology is demonstrated for interlayer processing in both p‐ and n‐type devices that is also suitable for top‐contact OFETs. In this approach, judiciously selected interlayer molecules are co‐deposited as additives in the semiconducting polymer active layer. During top contact deposition, the additive molecules migrate from within the bulk film to the organic/metal interface due to additive‐metal interactions. Migration continues until a thin continuous interlayer is completed. Formation of the interlayer is confirmed by X‐ray photoelectron spectroscopy (XPS) and cross‐section scanning transmission electron microscopy (STEM), and its effect on contact resistance by device measurements and transfer line method (TLM) analysis. It is shown that self‐generated interlayers that reduce contact resistance in p‐type devices, increase that of n‐type devices, and vice versa, confirming the role of additives as interlayer materials that modulate the effective work‐function of the organic/metal interface.     

Systematic Study of Widely Applicable N‐Doping Strategy for High‐Performance Solution‐Processed Field‐Effect Transistors

A specific design for solution‐processed doping of active semiconducting materials would be a powerful strategy in order to improve device performance in flexible and/or printed electronics. Tetrabutylammonium fluoride and tetrabutylammonium hydroxide contain Lewis base anions, F^? and OH^?, respectively, which are considered as organic dopants for efficient and cost‐effective n‐doping processes both in n‐type organic and nanocarbon‐based semiconductors, such as poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)] (P(NDI2OD‐T2)) and selectively dispersed semiconducting single‐walled carbon nanotubes by π‐conjugated polymers. The dramatic enhancement of electron transport properties in field‐effect transistors is confirmed by the effective electron transfer from the dopants to the semiconductors as well as controllable onset and threshold voltages, convertible charge‐transport polarity, and simultaneously showing excellent device stabilities under ambient air and bias stress conditions. This simple solution‐processed chemical doping approach could facilitate the understanding of both intrinsic and extrinsic charge transport characteristics in organic semiconductors and nanocarbon‐based materials, and is thus widely applicable for developing high‐performance organic and printed electronics and optoelectronics devices.     

Simultaneous Tenfold Brightness Enhancement and Emitted‐Light Spectral Tunability in Transparent Ambipolar Organic Light‐Emitting Transistor by Integration of High‐k Photonic Crystal

In organic light‐emitting transistors, the structural properties such as the in‐plane geometry and the lateral charge injection are the key elements that enable the monolithic integration of multiple electronic, optoelectronic, and photonic functions within the same device. Here, the realization of highly integrated multifunctional optoelectronic organic device is reported by introducing a high‐capacitance photonic crystal as a gate dielectric into a transparent single‐layer ambipolar organic light‐emitting transistor (OLET). By engineering the photonic crystal multistack and bandgap, it is showed that the integration of the photonic structure has a twofold effect on the optoelectronic performance of the device, i.e., i) to modulate the spectral profile and outcoupling of the emitted light and ii) to enhance the transistor source–drain current by a 25‐fold factor. Consequently, the photonic‐crystal‐integrated OLET shows an order of magnitude higher emitted power and brightness with respect to the corresponding polymer‐dielectric device, while presenting as‐designed electroluminescence spectral and spatial distribution. The results validate the efficacy of the proposed approach that is expected to unravel the technological potential for the realization of highly integrated optoelectronic smart systems based on organic light‐emitting transistors.     

Hydrocarbons‐Driven Crystallization of Polymer Semiconductors for Low‐Temperature Fabrication of High‐Performance Organic Field‐Effect Transistors

While many high‐performance polymer semiconductors are reported for organic field‐effect transistors (OFETs), most require a high‐temperature postdeposition annealing of channel semiconductors to achieve high performance. This negates the fundamental attribute of OFETs being a low‐cost alternative to conventional high‐cost silicon technologies. A facile solution process is developed through which high‐performance OFETs can be fabricated without thermal annealing. The process involves incorporation of an incompatible hydrocarbon binder or wax into the channel semiconductor composition to drive rapid phase separation and instantaneous crystallization of polymer semiconductor at room temperature. The resulting composite channel semiconductor film manifests a nano/microporous surface morphology with a continuous semiconductor nanowire network. OFET mobility of up to about 5 cm² V^?1 s^?1 and on/off ratio ≥ 10⁶ are attained. These are hitherto benchmark performance characteristics for room‐temperature, solution‐processed polymer OFETs, which are functionally useful for many impactful applications.     

Recent Developments and Novel Applications of Thin Film,Light‐Emitting Transistors

Light‐emitting field‐effect transistors (LEFETs) combine switching and amplification with light emission and thus represent an interesting optoelectronic device. They are not limited anymore to a few examples and specific materials but are nearly universal for a wide range of semiconductors, from organic to inorganic and nanoscale. This review introduces the basic working principles of lateral unipolar and ambipolar LEFETs and discusses recent examples based on various solution‐processed semiconducting materials. Applications beyond simple light emission are presented and possible future directions for light‐emitting transistors with added functionalities are outlined.     

Strategies for Fast‐Switching in All‐Polymer Field Effect Transistors

Low‐cost printable field effect transistors (FETs) are typically associated with slow switching characteristics. Dynamic response of polymer field effect transistors (PFETs) is a manifestation of time scales involved in processes such as dielectric polarization, structural relaxation, and transport via disordered‐interfacial states. A range of dielectrics and semiconductors are studied to arrive at a parameter which serves as a figure of merit and quantifies the different processes contributing to the switching response. A cross‐over from transport limiting factors to dielectric limiting factors in the dynamics of PFETs is observed. The dielectric limited regime in the PFET dynamics is tapped in to explore high speed processes, and an enhancement of switching speed by three orders of magnitude (from 300 μs to 400 ns) is observed at channel lengths which can be accessed by low cost printing methods. The device structure utilizes polymer‐ferroelectrics (FE) as the dielectric layer and involves a fabrication‐procedure which assists in circumventing the slow dynamics within the bulk of FE. This method of enhancing the dynamic response of PFETs is universally applicable to all classes of disordered‐FE.     

Perovskite‐Based Phototransistors and Hybrid Photodetectors

In the past several years, organic–inorganic hybrid perovskites and all inorganic perovskites have attracted enormous research interest in a variety of optoelectronic applications including solar cells, light‐emitting diodes, semiconductor lasers, and photodetectors for their plenty of appealing electrical and optoelectrical properties. Benefiting from the inherent amplification function of transistors and the pronounced photogating effect, perovskite‐based phototransistors and hybrid photodetectors can provide very high photoresponsivity and gain, rendering them highly promising for some specific applications especially ultrasensitive light detection. A review on the recent progress of phototransistors and hybrid photodetectors using perovskites as light‐sensitive materials is presented. The efforts and development in 3D and 2D perovskite‐based phototransistors, and perovskite/functional material (e.g., graphene, 2D semiconductors, organic semiconductors, and other semiconductors) heterojunction‐based hybrid photodetectors are introduced and discussed systematically. Some processing techniques for optimizing device performance are also addressed. In the final section, a conclusion of the research achievements is presented and possible challenges as well as outlook are provided to guide future activity in this research field.     

Digital‐Inverter Amine Sensing via Synergistic Responses by n and p Organic Semiconductors

Chemiresistors and sensitive organic field‐effect transistors (OFETs) have been substantially developed as cheap, scalable, and versatile sensing platforms. While new materials are expanding OFET sensing capabilities, the device architectures have changed little. Higher order logic circuits utilizing OFETs sensitive to amine vapors are presented. The circuits depend on the synergistic responses of paired p‐ and n‐channel organic semiconductors, including a rare analyte‐induced current increase by the n‐channel semiconductor. This is the first step towards ‘intelligent sensors’ that utilize analog signal changes in sensitive OFETs to produce direct digital readouts suitable for further logic operations.     

Air Effect on the Ideality of p‐Type Organic Field‐Effect Transistors: A Double‐Edged Sword

Organic field‐effect transistors (OFETs) often deviate from ideal behaviors in air, which masks their intrinsic properties and thus significantly impedes their practical applications. A key issue of how the presence of air affects the ideality of OFETs has not yet been fully understood. It is revealed that air atmosphere may exert a double‐edged sword effect on the active semiconductor layer when determining the ideality of OFETs fabricated from p‐type crystalline organic semiconductors. Upon exposing the as‐fabricated device to air, water and oxygen mainly function as efficient p‐type dopants for the active layer in the contact regions, enhancing charge carrier injection and consequently improving device ideality. Nevertheless, as the exposure time increases, the trapping centers for the injected minority charge carriers appear in the channel region, leading to degradation of device ideality. Inspired by the double‐edged sword behavior of air, a near‐ideal OFET is achieved by ingeniously utilizing the doping/positive effect and eliminating the trapping/negative effect. The effect of air on the ideality of p‐type OFETs is clarified, which not only illuminates some common observations of OFETs in air but also offers useful guidance for the construction of high‐performance ideal OFETs.     

Anodization for Simplified Processing and Efficient Charge Transport in Vertical Organic Field‐Effect Transistors

Vertical organic transistors are an attractive alternative to realize short channel transistors, which are required for powerful electronic devices and flexible electronic circuits operating at high frequencies. Unfortunately, the vertical device architecture comes along with an increased device fabrication complexity, limiting the potential of this technology for application. A new design of vertical organic field‐effect transistors (VOFETs) with superior electrical performance and simplified processing is reported. By using electrochemical oxidized aluminum oxide (AlO_x) as a pseudo self‐aligned charge‐blocking structure in vertical organic transistors, direct leakage current between the source and drain can be effectively suppressed, enabling VOFETs with very low off‐current levels despite the short channel length. The anodization technique is easy to apply and can be surprisingly used on both n‐type and p‐type organic semiconductor thin films with significant signs of degradation. Hence, the anodization technique enables a simplified process of high‐performance p‐type and n‐type VOFETs, paving the road toward complementary circuits made of vertical transistors.     

Ultra‐Smooth and Ultra‐Strong Ion‐Exchanged Glass as Substrates for Organic Electronics

The introduction of new substrate materials into the world of electronics has previously opened up new possibilities for novel applications and device designs. Here, the use of ion‐exchanged sodium aluminosilicate (NAS) glass is presented as a new type of substrate that is not only highly damage resistant, but also allows the fabrication of high performance organic electronic devices. The smoothness of the NAS glass surface enables favorable growth of the semiconductor layer, enabling high charge carrier mobilities for typical organic semiconductors, such as pentacene or C60, and a polymer semiconductor. No degradation of the device performance is observed as a result of ion migration into the active device region, and no compromise in substrate strength due to the processing conditions is made. This work suggests the possibility of new, highly durable electronic devices on glass in large area format.     

Battery Drivable Organic Single‐Crystalline Transistors Based on Surface Grafting Ultrathin Polymer Dielectric

High‐performance and battery drivable organic single‐crystalline transistors with operational voltages ≤ 2.0 V are demonstrated using high‐quality copper phthalocyanine (CuPc) single‐crystalline nanoribbons and ultrathin polymer nanodielectrics. The ultrathin polymer nanodielectric is synthesized by grafting a ca. 10 nm poly(methyl methacrylate) (PMMA) brush on a silicon surface via surface‐initiated atom‐transfer radical polymerization (SI‐ATRP). This surface‐grafted nanodielectric exhibits a large capacitance, excellent insulating property, and good compatibility with organic semiconductors. The realization of a low operational voltage for battery driving at high performance, together with the merits of surface grafting of a nanodielectric, as well as the mechanical flexibility of the organic nanoribbon, suggests a bright future for use of these transistors in low‐cost and flexible circuits.     

Solution‐Processed Zinc Oxide as High‐Performance Air‐Stable Electron Injector in Organic Ambipolar Light‐Emitting Field‐Effect Transistors

Electron injection from the source–drain electrodes limits the performance of many n‐type organic field‐effect transistors (OFETs), particularly those based on organic semiconductors with electron affinities less than 3.5 eV. Here, it is shown that modification of gold source–drain electrodes with an overlying solution‐deposited, patterned layer of an n‐type metal oxide such as zinc oxide (ZnO) provides an efficient electron‐injecting contact, which avoids the use of unstable low‐work‐function metals and is compatible with high‐resolution patterning techniques such as photolithography. Ambipolar light‐emitting field‐effect transistors (LEFETs) based on green‐light‐emitting poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) and blue‐light‐emitting poly(9,9‐dioctylfluorene) (F8) with electron‐injecting gold/ZnO and hole‐injecting gold electrodes show significantly lower electron threshold voltages and several orders of magnitude higher ambipolar currents, and hence light emission intensities, than devices with bare gold electrodes. Moreover, different solution‐deposited metal oxide injection layers are compared. By spin‐coating ZnO from a low‐temperature precursor, processing temperatures could be reduced to 150 °C. Ultraviolet photoemission spectroscopy (UPS) shows that the improvement in transistor performance is due to reduction of the electron injection barrier at the interface between the organic semiconductor and ZnO/Au compared to bare gold electrodes.     

High‐Performance n‐ and p‐Type Field‐Effect Transistors Based on Hybridly Surface‐Passivated Colloidal PbS Nanosheets

Colloidally synthesized nanomaterials are among the promising candidates for future electronic devices due to their simplicity and the inexpensiveness of their production. Specifically, colloidal nanosheets are of great interest since they are conveniently producible through the colloidal approach while having the advantages of two‐dimensionality. In order to employ these materials, according transistor behavior should be adjustable and of high performance. It is shown that the transistor performance of colloidal lead sulfide nanosheets is tunable by altering the surface passivation, the contact metal, or by exposing them to air. It is found that adding halide ions to the synthesis leads to an improvement of the conductivity, the field‐effect mobility, and the on/off ratio of these transistors by passivating their surface defects. Superior n‐type behavior with a field‐effect mobility of 248 cm² V^?1 s^?1 and an on/off ratio of 4 × 10⁶ is achieved. The conductivity of these stripes can be changed from n‐type to p‐type by altering the contact metal and by adding oxygen to the working environment. As a possible solution for the post‐Moore era, realizing new high‐quality semiconductors such as colloidal materials is crucial. In this respect, the results can provide new insights which helps to accelerate their optimization for potential applications.     

Inkjet‐Printed Single‐Droplet Organic Transistors Based on Semiconductor Nanowires Embedded in Insulating Polymers

Fabrication of organic field‐effect transistors (OFETs) using a high‐throughput printing process has garnered tremendous interest for realizing low‐cost and large‐area flexible electronic devices. Printing of organic semiconductors for active layer of transistor is one of the most critical steps for achieving this goal. The charge carrier transport behavior in this layer, dictated by the crystalline microstructure and molecular orientations of the organic semiconductor, determines the transistor performance. Here, it is demonstrated that an inkjet‐printed single‐droplet of a semiconducting/insulating polymer blend holds substantial promise as a means for implementing direct‐write fabrication of organic transistors. Control of the solubility of the semiconducting component in a blend solution can yield an inkjet‐printed single‐droplet blend film characterized by a semiconductor nanowire network embedded in an insulating polymer matrix. The inkjet‐printed blend films having this unique structure provide effective pathways for charge carrier transport through semiconductor nanowires, as well as significantly improve the on‐off current ratio and the environmental stability of the printed transistors.     

A General Approach to Probe Dynamic Operation and Carrier Mobility in Field‐Effect Transistors with Nonuniform Accumulation

Revealing the intrinsic electrical properties is the basis of understanding new functional materials and developing their applications. However, in nonideal field‐effect transistors (FETs), conventional current–voltage characterizations do not accurately probe charge transport, particularly for newly developed semiconductors. Here, a generalized gated four‐probe (G‐GFP) technique is developed, which detects dynamic changes in carrier accumulation and transport. The technique is suitable for exploring the intrinsic properties of semiconductors in FETs with arbitrary contacts and in any operational regimes above the threshold. Application to simulated transistors confirms its accuracy in probing the evolution of channel potential, drift field, and gate‐dependent carrier mobility for devices with a contact‐limited operation and disordered semiconductors. Comparative experiments are performed based on FETs with various materials, device structures, and operational temperatures. The G‐GFP technique proves to exclude the various injection properties, to detect in situ how carriers are accumulated, and to clarify carrier mobility of the semiconductors. In particular, the well‐known “double‐slope” features in the current–voltage relations are controllably generated and their origins are identified. The approach could be used to explore electronic properties of newly developed materials such as organic, oxide, or 2D semiconductors.     

2D Single‐Crystalline Molecular Semiconductors with Precise Layer Definition Achieved by Floating‐Coffee‐Ring‐Driven Assembly

2D organic materials with in‐plane van der Waals forces among molecules have unique characteristics that ensure a brilliant future for multifunctional applications. Soluble organic semiconductors can be used to achieve low‐cost and high‐throughput manufacturing of electronic devices. However, achieving solution‐processed 2D single‐crystalline semiconductors with uniform morphology remains a substantial challenge. Here, the fabrication of 2D molecular single‐crystal semiconductors with precise layer definition by using a floating‐coffee‐ring‐driven assembly is presented. In particular, bilayer molecular films exhibit single‐crystalline features with atomic smoothness and high film uniformity over a large area; field‐effect transistors yield average and maximum carrier mobilities of 4.8 and 13.0 cm² V^?1 s^?1, respectively. This work demonstrates the strong potential of 2D molecular crystals for low‐cost, large‐area, and high‐performance electronics.