N‐Type Self‐Assembled Monolayer Field‐Effect Transistors and Complementary Inverters

This work describes n‐type self‐assembled monolayer field‐effect transistors (SAMFETs) based on a perylene derivative which is covalently fixed to an aluminum oxide dielectric via a phosphonic acid linker. N‐type SAMFETs spontaneously formed by a single layer of active molecules are demonstrated for transistor channel length up to 100 μm. Highly reproducible transistors with electron mobilities of 1.5 × 10^?3 cm² V^?1 s^?1 and on/off current ratios up to 10⁵ are obtained. By implementing n‐type and p‐type transistors in one device, a complimentary inverter based solely on SAMFETs is demonstrated for the first time.     

Vertical Organic Field‐Effect Transistors

Field‐effect transistors are the fundamental building blocks for electronic circuits and processors. Compared with inorganic transistors, organic field‐effect transistors (OFETs), featuring low cost, low weight, and easy fabrication, are attractive for large‐area flexible electronic devices. At present, OFETs with planar structures are widely investigated device structures in organic electronics and optoelectronics; however, they face enormous challenges in realizing large current density, fast operation speed, and outstanding mechanical flexibility for advancing their potential commercialized applications. In this context, vertical organic field‐effect transistors (VOFETs), composed of vertically stacked source/drain electrodes, could provide an effective approach for solving these questions due to their inherent small channel length and unique working principles. Since the first report of VOFETs in 2004, impressive progress has been witnessed in this field with the improvement of device performance. The aim of this review is to give a systematical summary of VOFETs with a special focus on device structure optimization for improved performance and potential applications demonstrated by VOFETs. An overview of the development of VOFETs along with current challenges and perspectives is also discussed. It is hoped that this review is timely and valuable for the next step in the rapid development of VOFETs and their related research fields.     

Metal Based Nonvolatile Field‐Effect Transistors

The reduction of metals from their oxides through solid electrochemical reactions usually requires a high temperature above 800 °C and a specially designed electrochemical structure. It is demonstrated that, in a simple field‐effect transistor (FET) structure, the redox reaction between Co metal and CoO_x is reversible under a small electric field and can be achieved at a moderate temperature below 200 °C. The FETs functioning through the reversible redox reaction show nonvolatile behavior and a high on/off ratio of about 10⁵. Moreover, the FETs show a threshold resistance switching behavior at high resistance states, but with opposite switching directions compared to normal metal/oxide/metal structures. The electric field induced metal–oxide transition may also be used for other energy storage applications.     

Controlling Electron and Hole Charge Injection in Ambipolar Organic Field‐Effect Transistors by Self‐Assembled Monolayers

Controlling contact resistance in organic field‐effect transistors (OFETs) is one of the major hurdles to achieve transistor scaling and dimensional reduction. In particular in the context of ambipolar and/or light‐emitting OFETs it is a difficult challenge to obtain efficient injection of both electrons and holes from one injecting electrode such as gold since organic semiconductors have intrinsically large band gaps resulting in significant injection barrier heights for at least one type of carrier. Here, systematic control of electron and hole contact resistance in poly(9,9‐di‐n‐octylfluorene‐alt‐benzothiadiazole) ambipolar OFETs using thiol‐based self‐assembled monolayers (SAMs) is demonstrated. In contrast to common believe, it is found that for a certain SAM the injection of both electrons and holes can be improved. This simultaneous enhancement of electron and hole injection cannot be explained by SAM‐induced work‐function modifications because the surface dipole induced by the SAM on the metal surface lowers the injection barrier only for one type of carrier, but increases it for the other. These investigations reveal that other key factors also affect contact resistance, including i) interfacial tunneling through the SAM, ii) SAM‐induced modifications of interface morphology, and iii) the interface electronic structure. Of particular importance for top‐gate OFET geometry is iv) the active polymer layer thickness that dominates the electrode/polymer contact resistance. Therefore, a consistent explanation of how SAM electrode modification is able to improve both electron and hole injection in ambipolar OFETs requires considering all mentioned factors.     

Extracting Parameters from the Current–Voltage Characteristics of Organic Field‐Effect Transistors

Organic field‐effect transistors were fabricated with vapor‐deposited pentacene on aluminum oxide insulating layers. Several methods are used in order to extract the mobility and threshold voltage from the transfer characteristic of the devices. In all cases, the mobility is found to depend on the gate voltage. The first method consists of deriving the drain current as a function of gate voltage (transconductance), leading to the so‐called field‐effect mobility. In the second method, we assume a power‐law dependence of the mobility with gate voltage together with a constant contact resistance. The third method is the so‐called transfer line method, in which several devices with various channel length are used. It is shown that the mobility is significantly enhanced by modifying the aluminum oxide layer with carboxylic acid self‐assembled monolayers prior to pentacene deposition. The methods used to extract parameters yield threshold voltages with an absolute value of less than 2 V. It is also shown that there is a shift of the threshold voltage after modification of the aluminum oxide layer. These features seem to confirm the validity of the parameter‐extraction methods.     

Contact Doping for Vertical Organic Field‐Effect Transistors

Doping is a powerful tool to overcome contact limitations in short‐channel organic field‐effect transistors (OFETs) and has been successfully used in the past to improve the charge carrier injection in OFETs. The present study applies this familiar concept to the architecture of vertical organic field‐effect transistors (VOFETs), which are often severely limited by injection due to their very short channel lengths. The present study shows that the performance of p‐type VOFETs with pentacene as an active material can be significantly enhanced by the addition of the common p‐dopant C₆₀F₃₆ as a thin injection layer underneath the VOFET source electrode, resulting in an increase of On‐state current and On/Off ratio by one order of magnitude. The present study further investigates mixed injection layers of pentacene and the p‐dopant and finds that the improvement is less pronounced than for the pure dopant layers and depends on the concentration of dopant molecules in the injection layer. Through application of the transfer length method to equivalent OFET geometries, the present study is finally able to link the observed improvement to a decrease in transfer length and can thus conclude that this length is a crucial parameter onto which further improvement efforts have to be concentrated to realize true short‐channel VOFETs.     

ReS2‐Based Field‐Effect Transistors and Photodetectors

Atomically thin 2D layered transition metal dichalcogenides (TMDs) have been extensively studied in recent years because of their appealing electrical and optical properties. Here, the fabrication of ReS₂ field‐effect transistors is reported via the encapsulation of ReS₂ nanosheets in a high‐κ Al₂O₃ dielectric environment. Low‐temperature transport measurements allow to observe a direct metal‐to‐insulator transition originating from strong electron–electron interactions. Remarkably, the photodetectors based on ReS₂ exhibit gate‐tunable photoresponsivity up to 16.14 A W^?1 and external quantum efficiency reaching 3168%, showing a competitive device performance to those reported in graphene, MoSe₂, GaS, and GaSe‐based photodetectors. This study unambiguously distinguishes ReS₂ as a new candidate for future applications in electronics and optoelectronics.     

Electrical Double‐Slope Nonideality in Organic Field‐Effect Transistors

The field effect transistor (FET) is arguably one of the most important circuit elements in modern electronics. Recently, a need has developed for flexible electronics in a variety of emerging applications. Examples include form‐fitting healthcare‐monitoring devices, flexible displays, and flexible radio frequency identification tags. Organic FETs (OFETs) are viable candidates for producing such flexible devices because they incorporate semiconducting π‐conjugated materials, including small molecules and conjugated polymers, which are intrinsically soft and mechanically compatible with flexible substrates. For OFETs to be industrially viable, however, they must achieve not only high charge carrier mobility, but also ideal and comprehensible electrical characteristics. Most recently, nonideal double‐slope characteristics in the transfer curves of OFETs (i.e., high slope at low gate voltage and low slope at high gate voltage), have stirred debate, which has led to different mechanistic rationales in the literature. This review focuses on the general observations, mechanistic understanding, and possible solutions associated with phenomena that result in FETs with double‐slope characteristics. By surveying and systematically summarizing in a single source relevant literature that deals with the issue of double slope, the experimental framework and theoretical basis for interpreting and avoiding this electrical nonideality in OFETs is provided.     

Sensing of Alkylating Agents Using Organic Field‐Effect Transistors

Alkylating agents are simple and reactive molecules that are commonly used in many and diverse fields, such as organic synthesis, medicine, and agriculture. Some highly reactive alkylating species are also being used as blister chemical warfare agents. The detection and identification of alkylating agent is not a trivial issue because of their high reactivity and simple structure. Here, a novel polythiophene derivative that is capable of reacting with alkylating agents is reported, along with its application in direct electrical sensing of alkylators using an organic field‐effect transistor, OFET, device. Upon reacting with alkylators, the OFET containing the new polythiophene analogue as its channel becomes conductive, and the gate effect is lost; this is in marked contrast to the response of the OFET to “innocent” vapors, such as alcohols and acetone. By following the drain–source current under gate bias, one can easily follow the processes of absorption of the analyte to the polythiophene channel and their subsequent reaction.     

Highly Crystalline Soluble Acene Crystal Arrays for Organic Transistors: Mechanism of Crystal Growth During Dip‐Coating

The preparation of uniform large‐area highly crystalline organic semiconductor thin films that show outstanding carrier mobilities remains a challenge in the field of organic electronics, including organic field‐effect transistors. Quantitative control over the drying speed during dip‐coating permits optimization of the organic semiconductor film formation, although the kinetics of crystallization at the air–solution–substrate contact line are still not well understood. Here, we report the facile one‐step growth of self‐aligning, highly crystalline soluble acene crystal arrays that exhibit excellent field‐effect mobilities (up to 1.5 cm V^?1 s^?1) via an optimized dip‐coating process. We discover that optimized acene crystals grew at a particular substrate lifting‐rate in the presence of low boiling point solvents, such as dichloromethane (b.p. of 40.0 °C) or chloroform (b.p. of 60.4 °C). Variable‐temperature dip‐coating experiments using various solvents and lift rates are performed to elucidate the crystallization behavior. This bottom‐up study of soluble acene crystal growth during dip‐coating provides conditions under which one may obtain uniform organic semiconductor crystal arrays with high crystallinity and mobilities over large substrate areas, regardless of the substrate geometry (wafer substrates or cylinder‐shaped substrates).     

Biocompatible and Biodegradable Materials for Organic Field‐Effect Transistors

Biocompatible‐ingestible electronic circuits and capsules for medical diagnosis and monitoring are currently based on traditional silicon technology. Organic electronics has huge potential for developing biodegradable, biocompatible, bioresorbable, or even metabolizable products. An ideal pathway for such electronic devices involves fabrication with materials from nature, or materials found in common commodity products. Transistors with an operational voltage as low as 4–5 V, a source drain current of up to 0.5 μA and an on‐off ratio of 3–5 orders of magnitude have been fabricated with such materials. This work comprises steps towards environmentally safe devices in low‐cost, large volume, disposable or throwaway electronic applications, such as in food packaging, plastic bags, and disposable dishware. In addition, there is significant potential to use such electronic items in biomedical implants.     

Ionic‐Liquid Gating of InAs Nanowire‐Based Field‐Effect Transistors

Here, the operation of a field‐effect transistor based on a single InAs nanowire gated by an ionic liquid is reported. Liquid gating yields very efficient carrier modulation with a transconductance value 30 times larger than standard back gating with the SiO₂/Si₊₊ substrate. Thanks to this wide modulation, the controlled evolution from semiconductor to metallic‐like behavior in the nanowire is shown. This work provides the first systematic study of ionic‐liquid gating in electronic devices based on individual III–V semiconductor nanowires: this architecture opens the way to a wide range of fundamental and applied studies from the phase transitions to bioelectronics.     

Temperature Performance of Doping‐Free Top‐Gate CNT Field‐Effect Transistors: Potential for Low‐ and High‐Temperature Electronics

High‐performance top‐gate carbon nanotube (CNT) field‐effect transistors (FETs) have been fabricated via a doping‐free fabrication process in which the polarity of the CNT FET is controlled by the injection of carriers from the electrodes, instead of using dopants. The performance of the doping‐free CNT FETs is systemically investigated over a wide temperature range, from very low temperatures of down to 4.3 K up to 573 K, and analyzed using several temperature‐dependent key device parameters including the ON/OFF state current and ratio, carrier mobility, and subthreshold swing. It is demonstrated that for ballistic and quasi‐ballistic CNT FETs, the operation of the CNT FETs is largely independent of the presence of dopant, thus avoiding detrimental effects due to dopant freeze‐out at low temperature and dopant diffusion at high temperature, and making it possible to use doping‐free CNT FETs in both low‐ and high‐temperature electronics. A new method is also proposed for extracting the band‐gap and diameter of a semiconducting CNT from the temperature dependent OFF‐state current and shown to yield results that are consistent with AFM measurements.     

Insulator Polarization Mechanisms in Polyelectrolyte‐Gated Organic Field‐Effect Transistors

Electrolyte‐gated organic field‐effect transistors (OFETs) hold promise for robust printed electronics operating at low voltages. The polarization mechanism of thin solid electrolyte films, the gate insulator in such OFETs, is still unclear and appears to limit the transient current characteristics of the transistors. Here, the polarization response of a thin proton membrane, a poly(styrenesulfonic acid) film, is controlled by varying the relative humidity. The formation of the conducting transistor channel follows the polarization of the polyelectrolyte, such that the drain transient current characteristics versus the time are rationalized by three different polarization mechanisms: the dipolar relaxation at high frequencies, the ionic relaxation (migration) at intermediate frequencies, and the electric double‐layer formation at the polyelectrolyte interfaces at low frequencies. The electric double layers of polyelectrolyte capacitors are formed in ～1 µs at humid conditions and an effective capacitance per area of 10 µF cm^?2 is obtained at 1 MHz, thus suggesting that this class of OFETs might operate at up to 1 MHz at 1 V.     

Star‐Shaped Oligothiophenes for Solution‐Processible Organic Field‐Effect Transistors

We have designed and successfully synthesized star‐shaped oligothiophenes, which could be used as semiconducting materials for solution‐processible organic field‐effect transistors (FETs). By systematically changing the chemical structure of the star‐shaped oligothiophenes we obtained the structural requirements needed for making working FETs from them. UV‐vis fluorescence measurements showed that a molecule of the star‐shaped compounds under consideration is not a fully conjugated molecule, but it has three independently conjugated oligothienyl‐phenylene blocks. A possible scheme of molecular packing of the star‐shaped oligothiophenes in a lamellar structure was proposed and confirmed by atomic force microscopy (AFM) and X‐ray diffraction (XRD) measurements. Although the star‐shaped semiconductors show a somewhat lower mobility than their linear analogs, they possess better solubility and film‐forming properties, leading to improved spin‐coating processing. The best FETs were made by spin‐coating 1,3,5‐tris(5″‐decyl‐2,2′:5′,2″‐terthien‐5‐yl)benzene from a chloroform solution, which resulted in a mobility of 2 × 10^–4 cm² V ^–1s^–1, a 10² on/off ratio at gate voltages of 0 V and –20 V, and a threshold voltage close to 0 V.     

Self‐Protective Room‐Temperature Phosphorescence of Fluorine and Nitrogen Codoped Carbon Dots

The unstable triplet excited state is a core problem when developing self‐protective room temperature phosphorescence (RTP) in carbon dots (CDs). Here, fluorine and nitrogen codoped carbon dots (FNCDs) with long‐lived triplet excited states, emitting pH‐stabilized blue fluorescence and pH‐responsive green self‐protective RTP, are reported for the first time. The self‐protective RTP of FNCDs arises from n–π * electron transitions for C? N/C?N bonds with a small energy gap between singlet and triplet states at room temperature. Moreover, the interdot/intradot hydrogen bonds and steric protection of C? F bonds reduce quenching of RTP by oxygen at room temperature. The RTP emission of FNCDs shows outstanding reversibility, while the blue fluorescence emission has good pH stability. Based on these FNCDs, a data encoding/reading strategy for advanced anticounterfeiting is proposed via time‐resolved luminescence imaging techniques, as well as steganography of complex patterns.     

Variable Temperature Mobility Analysis of n‐Channel,p‐Channel,and Ambipolar Organic Field‐Effect Transistors

The temperature dependence of field‐effect transistor (FET) mobility is analyzed for a series of n‐channel, p‐channel, and ambipolar organic semiconductor‐based FETs selected for varied semiconductor structural and device characteristics. The materials (and dominant carrier type) studied are 5,5′′′‐bis(perfluorophenacyl)‐2,2′:5′,2″:5″,2′′′‐quaterthiophene ( 1 , n‐channel), 5,5′′′‐bis(perfluorohexyl carbonyl)‐2,2′:5′,2″:5″,2′′′‐quaterthiophene ( 2 , n‐channel), pentacene ( 3 , p‐channel); 5,5′′′‐bis(hexylcarbonyl)‐2,2′:5′,2″:5″,2′′′‐quaterthiophene ( 4 , ambipolar), 5,5′′′‐bis‐(phenacyl)‐2,2′: 5′,2″:5″,2′′′‐quaterthiophene ( 5 , p‐channel), 2,7‐bis((5‐perfluorophenacyl)thiophen‐2‐yl)‐9,10‐phenanthrenequinone ( 6 , n‐channel), and poly(N‐(2‐octyldodecyl)‐2,2′‐bithiophene‐3,3′‐dicarboximide) ( 7 , n‐channel). Fits of the effective field‐effect mobility (µ_eff) data assuming a discrete trap energy within a multiple trapping and release (MTR) model reveal low activation energies (E_As) for high‐mobility semiconductors 1 – 3 of 21, 22, and 30 meV, respectively. Higher E_A values of 40–70 meV are exhibited by 4 – 7 ‐derived FETs having lower mobilities (µ_eff). Analysis of these data reveals little correlation between the conduction state energy level and E_A, while there is an inverse relationship between E_A and µ_eff. The first variable‐temperature study of an ambipolar organic FET reveals that although n‐channel behavior exhibits E_A = 27 meV, the p‐channel regime exhibits significantly more trapping with E_A = 250 meV. Interestingly, calculated free carrier mobilities (µ₀) are in the range of ～0.2–0.8 cm² V^?1 s^?1 in this materials set, largely independent of µ_eff. This indicates that in the absence of charge traps, the inherent magnitude of carrier mobility is comparable for each of these materials. Finally, the effect of temperature on threshold voltage (V_T) reveals two distinct trapping regimes, with the change in trapped charge exhibiting a striking correlation with room temperature µ_eff. The observation that E_A is independent of conduction state energy, and that changes in trapped charge with temperature correlate with room temperature µ_eff, support the applicability of trap‐limited mobility models such as a MTR mechanism to this materials set.     

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.     

Effect of Doping Concentration on Microstructure of Conjugated Polymers and Characteristics in N‐Type Polymer Field‐Effect Transistors

Despite extensive progress in organic field‐effect transistors, there are still far fewer reliable, high‐mobility n‐type polymers than p‐type polymers. It is demonstrated that by using dopants at a critical doping molar ratio (MR), performance of n‐type polymer poly[[N,N9‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,59‐(2,29‐bithiophene)] (P(NDI2DO‐T2)) field‐effect transistors (FETs) can be significantly improved and simultaneously optimized in mobility, on–off ratio, crystallinity, injection, and reliability. In particular, when using the organic dopant bis(cyclopentadienyl)–cobalt(II) (cobaltocene, CoCp₂) at a low concentration (0.05 wt%), the FET mobility is increased from 0.34 to 0.72 cm² V^–1 s^–1, and the threshold voltage was decreased from 32.7 to 8.8 V. The relationship between the MR of dopants and electrical characteristics as well as the evolution in polymer crystallinity revealed by synchrotron X‐ray diffractions are systematically investigated. Deviating from previous discoveries, it is found that mobility increases first and then decreases drastically beyond a critical value of MR. Meanwhile, the intensity and width of the main peak of in‐plane X‐ray diffraction start to decrease at the same critical MR. Thus, the mobility decrease is correlated with the disturbed in‐plane crystallinity of the conjugated polymer, for both organic and inorganic dopants. The method provides a simple and efficient approach to employing dopants to optimize the electrical performance and microstructure of P(NDI2DO‐T2).     

Modulated Thermoelectric Properties of Organic Semiconductors Using Field‐Effect Transistors

Organic thermoelectric materials, which can transform heat flow into electricity, have great potential for flexible, ultra‐low‐cost and large‐area thermoelectric applications. Despite rapid developments of organic thermoelectric materials, exploration and investigation of promising organic thermoelectric semiconductors still remain as a challenge. Here, the thermoelectric properties of several p‐ and n‐type organic semiconductors are investigated and studied, in particular, how the electric field modulations of the Seebeck coefficient in organic field‐effect transistors (OFETs) compare with the Seebeck coefficient in chemically doped films. The extracted relationship between the Seebeck coefficient (S) and electrical conductivity (σ) from the field‐effect transistor (FET) geometry is in good agreement with that of chemically doped films, enabling the investigation of the trade‐off relationship among σ, S, carrier concentration, and charging level. The results make OFETs an effective candidate for the thermoelectric studies of organic semiconductors.