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.     

Performance of pentacene-based organic field effect transistors using different polymer gate dielectrics

Pentacene-based organic field effect transistors（OFETs） are fabricated using poly（methyl methacrylate）（PMMA） and polyimide（PI） as gate dielectrics,respectively.The fabricated OFETs exhibit reasonable device characteristics.The field-effect mobility,threshold voltage,and on/off current radio are determined to be 3.214 ×10^-2 cm^2 /Vs,-28 V,and 1 ×10^3 respectively for OFETs with PMMA as gate dielectrics,and 7.306×10^-3cm^2 /Vs,-21 V,and 2 ×10^2 for OFETs with PI.Furthermore,the dielectric properties of gate insulator layer are tested and the dipole effect at the semiconductor/dielectrics interface is also analyzed by a model of energy level diagram.     

High Tg Cyclic Olefin Copolymer Gate Dielectrics for N,N′‐Ditridecyl Perylene Diimide Based Field‐Effect Transistors: Improving Performance and Stability with Thermal Treatment

A novel application of ethylene‐norbornene cyclic olefin copolymers (COC) as gate dielectric layers in organic field‐effect transistors (OFETs) that require thermal annealing as a strategy for improving the OFET performance and stability is reported. The thermally‐treated N,N′‐ditridecyl perylene diimide (PTCDI‐C13)‐based n‐type FETs using a COC/SiO₂ gate dielectric show remarkably enhanced atmospheric performance and stability. The COC gate dielectric layer displays a hydrophobic surface (water contact angle = 95° ± 1°) and high thermal stability (glass transition temperature = 181 °C) without producing crosslinking. After thermal annealing, the crystallinity improves and the grain size of PTCDI‐C13 domains grown on the COC/SiO₂ gate dielectric increases significantly. The resulting n‐type FETs exhibit high atmospheric field‐effect mobilities, up to 0.90 cm² V^?1 s^?1 in the 20 V saturation regime and long‐term stability with respect to H₂O/O₂ degradation, hysteresis, or sweep‐stress over 110 days. By integrating the n‐type FETs with p‐type pentacene‐based FETs in a single device, high performance organic complementary inverters that exhibit high gain (exceeding 45 in ambient air) are realized.     

Organic Electronics: High Tg Cyclic Olefin Copolymer Gate Dielectrics for N,N′‐Ditridecyl Perylene Diimide Based Field‐Effect Transistors: Improving Performance and Stability with Thermal Treatment (Adv. Funct. Mater. 16/2010)

A novel application of ethylene‐norbornene cyclic olefin copolymers (COC) as gate dielectric layers in organic field‐effect transistors (OFETs) that require thermal annealing as a strategy for improving the OFET performance and stability is reported. The thermally‐treated N,N′‐ditridecyl perylene diimide (PTCDI‐C13)‐based n‐type FETs using a COC/SiO₂ gate dielectric show remarkably enhanced atmospheric performance and stability. The COC gate dielectric layer displays a hydrophobic surface (water contact angle = 95° ± 1°) and high thermal stability (glass transition temperature = 181 °C) without producing crosslinking. After thermal annealing, the crystallinity improves and the grain size of PTCDI‐C13 domains grown on the COC/SiO₂ gate dielectric increases significantly. The resulting n‐type FETs exhibit high atmospheric field‐effect mobilities, up to 0.90 cm² V^?1 s^?1 in the 20 V saturation regime and long‐term stability with respect to H₂O/O₂ degradation, hysteresis, or sweep‐stress over 110 days. By integrating the n‐type FETs with p‐type pentacene‐based FETs in a single device, high performance organic complementary inverters that exhibit high gain (exceeding 45 in ambient air) are realized.     

A High‐k Fluorinated P(VDF‐TrFE)‐g‐PMMA Gate Dielectric for High‐Performance Flexible Field‐Effect Transistors

A newly synthesized high‐k polymeric insulator for use as gate dielectric layer for organic field‐effect transistors (OFETs) obtained by grafting poly(methyl methacrylate) (PMMA) in poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) via atom transfer radical polymerization transfer is reported. This material design concept intents to tune the electrical properties of the gate insulating layer (capacitance, leakage current, breakdown voltage, and operational stability) of the high‐k fluorinated polymer dielectric without a large increase in operating voltage by incorporating an amorphous PMMA as an insulator. By controlling the grafted PMMA percentage, an optimized P(VDF‐TrFE)‐g‐PMMA with 7 mol% grafted PMMA showing reasonably high capacitance (23–30 nF cm^?2) with low voltage operation and negligible current hysteresis is achieved. High‐performance low‐voltage‐operated top‐gate/bottom‐contact OFETs with widely used high mobility polymer semiconductors, poly[[2,5‐bis(2‐octyldodecyl)‐2,3,5,6‐tetrahydro‐3,6‐dioxopyrrolo [3,4‐c]pyrrole‐1,4‐diyl]‐alt‐[[2,2′‐(2,5‐thiophene)bis‐thieno(3,2‐b)thiophene]‐5,5′‐diyl]] (DPPT‐TT), and poly([N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)) are demonstrated here. DPPT‐TT OFETs with P(VDF‐TrFE)‐g‐PMMA gate dielectrics exhibit a reasonably high field‐effect mobility of over 1 cm² V^?1 s^?1 with excellent operational stability.     

Self‐Assembled,Millimeter‐Sized TIPS‐Pentacene Spherulites Grown on Partially Crosslinked Polymer Gate Dielectric

Here, a highly crystalline and self‐assembled 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐Pentacene) thin films formed by simple spin‐coating for the fabrication of high‐performance solution‐processed organic field‐effect transistors (OFETs) are reported. Rather than using semiconducting organic small‐molecule–insulating polymer blends for an active layer of an organic transistor, TIPS‐Pentacene organic semiconductor is separately self‐assembled on partially crosslinked poly‐4‐vinylphenol:poly(melamine‐co‐formaldehyde) (PVP:PMF) gate dielectric, which results in a vertically segregated semiconductor‐dielectric film with millimeter‐sized spherulite‐crystalline morphology of TIPS‐Pentacene. The structural and electrical properties of TIPS‐Pentacene/PVP:PMF films have been studied using a combination of polarized optical microscopy, atomic force microscopy, 2D‐grazing incidence wide‐angle X‐ray scattering, and secondary ion mass spectrometry. It is finally demonstrated a high‐performance OFETs with a maximum hole mobility of 3.40 cm² V^?1 s^?1 which is, to the best of our knowledge, one of the highest mobility values for TIPS‐Pentacene OFETs fabricated using a conventional solution process. It is expected that this new deposition method would be applicable to other small molecular semiconductor–curable polymer gate dielectric systems for high‐performance organic electronic applications.     

Understanding the Meniscus‐Guided Coating Parameters in Organic Field‐Effect‐Transistor Fabrications

Meniscus‐guided coating (MGC) is mainly applicable on the soluble organic semiconductors with strong π–π overlap for achieving single‐crystalline organic thin films and high‐performance organic field‐effect‐transistors (OFETs). In this work, four elementary factors including shearing speed (v), solute concentration (c), deposition temperature (T), and solvent boiling point (T_b) are unified to analyze crystal growth behavior in the meniscus‐guided coating. By carefully varying and studying these four key factors, it is confirmed that v is the thickness regulation factor, while c is proportional to crystal growth rate. The MGC crystal growth rate is also correlated to latent heat (L) of solvents and deposition temperature in an Arrhenius form. The latent heat of solvents is proportional to T_b. The OFET channels grown by the optimized MGC parameters show uniform crystal morphology (Roughness R_q < 0.25 nm) with decent carrier mobilities (average µ = 5.88 cm² V^?1 s^?1 and highest µ = 7.68 cm² V^?1 s^?1). The studies provide a generalized formula to estimate the effects of these fabrication parameters, which can serve as crystal growth guidelines for the MGC approach. It is also an important cornerstone towards scaling up the OFETs for the sophisticated organic circuits or mass production.     

Low‐Voltage,High‐Performance Organic Field‐Effect Transistors with an Ultra‐Thin TiO2 Layer as Gate Insulator

We report on our latest improvements in organic field‐effect transistors (OFETs) using ultra‐thin anodized gate insulators. Anodization of titanium (Ti) is an extremely cheap and simple technique to obtain high‐quality, very thin (～ 7.5 nm), pinhole‐free, and robust gate insulators for OFETs. The anodized insulators have been tested in transistors using pentacene and poly(triarylamine) (PTAA) as active layers. The fabricated devices display low‐threshold, normally “off” OFETs with negligible hysteresis, good carrier mobility, high gate capacitance, and exceptionally low inverse subthreshold slope. Device performance is improved via chemical modification of TiO₂ with an octadecyltrichlorosilane (OTS) self‐assembled monolayer (SAM). As the result of this combination of favorable properties, we have demonstrated OFETs that can be operated with voltages well below 1 V.     

High‐Performance,Low‐Operating‐Voltage Organic Field‐Effect Transistors with Low Pinch‐Off Voltages

Organic field‐effect transistors suffer from ultra‐high operating voltages in addition to their relative low mobility. A general approach to low‐operating‐voltage organic field‐effect transistors (OFETs) using donor/acceptor buffer layers is demonstrated. P‐type OFETs with acceptor molecule buffer layers show reduced operating voltages (from 60–100 V to 10–20 V), with mobility up to 0.19 cm² V^?1 s^?1 and an on/off ratio of 3 × 10⁶. The subthreshold slopes of the devices are greatly reduced from 5–12 V/decade to 1.68–3 V/decade. This favorable combination of properties means that such OFETs can be operated successfully at voltages below 20 V (|V_DS| ≤ 20 V, |V_GS| ≤ 20 V). This method also works for n‐type semiconductors. The reduced operating voltage and low pinch‐off voltage contribute to the improved ordering of the polycrystalline films, reduced grain boundary resistance, and steeper subthreshold slopes.     

Polymer‐Based Organic Field‐Effect Transistors with Active Layers Aligned by Highly Hydrophobic Nanogrooved Surfaces

In this study, polymer‐based organic field‐effect transistors (OFETs) that exhibit alignment‐induced mobility enhancement, very small device‐to‐device variation, and high operational stability are successfully fabricated by a simple coating method of semiconductor solutions on highly hydrophobic nanogrooved surfaces. The highly hydrophobic nanogrooved surfaces (water contact angle >110°) are effective at inducing unidirectional alignment of polymer backbone structures with edge‐on orientation and are advantageous for realizing high operational stability because of their water‐repellent nature. The dewetting of the semiconductor solution is a critical problem in the thin film formation on highly hydrophobic surfaces. Dewetting during spin coating is suppressed by surrounding the hydrophobic regions with hydrophilic ones under appropriate designs. For the OFET array with an aligned terrace‐phase active layer of poly(2,5‐bis(3‐hexadecylthiophene‐2‐yl)thieno[3,2‐b]thiophene), the hole mobility in the saturation regime of 30 OFETs with channel current direction parallel to the nanogrooves is 0.513 ± 0.018 cm² V^?1 s^?1, which is approximately double that of the OFETs without nanogrooves, and the intrinsic operational stability is comparable to the operational stability of amorphous‐silicon field‐effect transistors. In other words, alignment‐induced mobility enhancement and high operational stability are successfully achieved with very small device‐to‐device variation. This coating method should be a promising means of fabricating high‐performance OFETs.     

Manipulating the Hysteresis in Poly(vinyl alcohol)‐Dielectric Organic Field‐Effect Transistors Toward Memory Elements

The origins of hysteresis in organic field‐effect transistors (OFETs) and its applications in organic memory devices is investigated. It is found that the orientations of the hydroxyl groups in poly(vinyl alcohol) (PVA) gate dielectrics are correlated with the hysteresis of transfer characteristics in pentacene‐based OFETs under the forward and backward scan. The applied gate bias partially aligns the orientations of the hydroxyl groups perpendicular to the substrate as characterized by reflective absorption Fourier transform infrared spectroscopy (RA‐FTIR), in which the field‐induced surface dipoles at the pentacene/PVA interface trap charges and cause the hysteresis. Treating PVA with an anhydrous solvent eliminates the residual moisture in the dielectrics layer, allowing for more effective control of the induced dipoles by the applied gate bias. OFETs of dehydrated‐PVA dielectrics present a pronounced shift of the threshold voltage (ΔV_Th) of 35.7 V in transfer characteristics, higher than that of 18.5 V for untreated devices and results in sufficient dynamic response for applications in memory elements. This work highlights the usage of non‐ferroelectric gate dielectrics to fabricate OFET memory elements by manipulating the molecular orientations in the dielectrics layer.     

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.     

Highly Sensitive Chemical‐Vapor Sensor Based on Thin‐Film Organic Field‐Effect Transistors with Benzothiadiazole‐Fused‐Tetrathiafulvalene

The synthesis of a new tetrathiafulvalene derivative with an electron‐withdrawing benzothiadiazole moiety and its use in thin‐film organic field‐effect transistors (OFETs) are reported. Compared to reported OFETs with other TTF derivatives, a high hole mobility up to 0.73 cm² V^?1 s^?1, low off‐current and high on/off ratio up to 10⁵ are demonstrated. In addition, the developed OFETs show fast responsiveness toward chemical vapors of DECP (diethyl chlorophosphate) or POCl₃ which are simulants of phosphate‐based nerve agents. In contrast to previously reported OFET‐based sensors, off‐current is used as the output signal, which increases quickly upon exposure to either DECP or POCl₃ vapors. High sensitivity is demonstrated toward DECP and POCl₃ vapors, with concentrations as low as 10 ppb being detected. These OFETs are also responsive to TNT vapor. The sensing mechanisms for the new type of OFET are discussed.     

Polymer Dielectrics and Orthogonal Solvent Effects for High‐Performance Inkjet‐Printed Top‐Gated P‐Channel Polymer Field‐Effect Transistors

We investigated the effects of a gate dielectric and its solvent on the characteristics of top‐gated organic field‐effect transistors (OFETs). Despite the rough top surface of the inkjet‐printed active features, the charge transport in an OFET is still favorable, with no significant degradation in performance. Moreover, the characteristics of the OFETs showed a strong dependency on the gate dielectrics used and its orthogonal solvents. Poly(3‐hexylthiophene) OFETs with a poly(methyl methacrylate) dielectric showed typical p‐type OFET characteristics. The selection of gate dielectric and solvent is very important to achieve high‐performance organic electronic circuits.     

Oligothiophene‐Functionalized Truxene: Star‐Shaped Compounds for Organic Field‐Effect Transistors

Organic field‐effect transistors (OFETs) based on oligothiophene‐functionalized truxene derivatives have been fabricated for use as novel star‐shaped organic semiconductors in solution‐processible organic electronics. The electronic and optical properties of compounds 1 – 3 , with increasing numbers of thiophene rings at each of the three branches, have been investigated using scanning electron microscopy (SEM), X‐ray diffraction measurements, and ultraviolet–visible (UV‐vis) and photoluminescence spectroscopies. The results show that with a stepwise increase of the thiophene rings at every branch, a transition from a polycrystalline to an amorphous state is observed. The characteristics of compounds 1 , 2 , and 3 used for OFETs exhibit a significant difference. The mobility depends greatly on the morphology in the solid state, and decreases in going from 1 to 3 . Mobilities up to 1.03 × 10^–3 cm² V^–1 s^–1 and an on/off ratio of about 10³ for compound 1 have been achieved; these are the highest values for star‐shaped organic semiconductors used for OFETs so far. All the results demonstrate that the truxene core of the oligothiophene‐functionalized truxene derivatives not only extends the π‐delocalized system, but also leads to high mobilities for the compounds.     

The Effects of Moisture in Low‐Voltage Organic Field‐Effect Transistors Gated with a Hydrous Solid Electrolyte

The concept of using ion conducting membranes (50–150 μm thick) for gating low‐voltage (1 V) organic field‐effect transistors (OFETs) is attractive due to its low‐cost and large‐area manufacturing capabilities. Furthermore, the membranes can be tailor‐made to be ion conducting in any desired way or pattern. For the electrolyte gated OFETs in general, the key to low‐voltage operation is the electrolyte “insulator” (the membrane) that provides a high effective capacitance due to ionic polarization within the insulator. Hydrous ion conducting membranes are easy to process and readily available. However, the role of the water in combination with the polymeric semiconductor has not yet been fully clarified. In this work electrical and optical techniques are utilized to carefully monitor the electrolyte/semiconductor interface in an ion conducting membrane based OFET. The main findings are that 1) moisture plays a major part in the transistor operation and careful control of both the ambient atmosphere and the potential differences between the electrodes are required for stable and consistent device behavior, 2) the obtained maximum effective capacitance (5 μF cm^?2) of the membrane suggests that the electric double layer is distributed over a broad region within the polyelectrolyte, and 3) electromodulation spectroscopy combined with current–voltage characteristics provide a method to determine the threshold gate voltage from an electrostatic field‐effect doping to a region of (irreversible) electrochemical perturbation of the polymeric semiconductor.     

Printed Sub‐2 V Gel‐Electrolyte‐Gated Polymer Transistors and Circuits

The fabrication and characterization of printed ion‐gel‐gated poly(3‐hexylthiophene) (P3HT) transistors and integrated circuits is reported, with emphasis on demonstrating both function and performance at supply voltages below 2 V. The key to achieving fast sub‐2 V operation is an unusual gel electrolyte based on an ionic liquid and a gelating block copolymer. This gel electrolyte serves as the gate dielectric and has both a short polarization response time (<1 ms) and a large specific capacitance (>10 µF cm^?2), which leads simultaneously to high output conductance (>2 mS mm^?1), low threshold voltage (<1 V) and high inverter switching frequencies (1–10 kHz). Aerosol‐jet‐printed inverters, ring oscillators, NAND gates, and flip‐flop circuits are demonstrated. The five‐stage ring oscillator operates at frequencies up to 150 Hz, corresponding to a propagation delay of 0.7 ms per stage. These printed gel electrolyte gated circuits compare favorably with other reported printed circuits that often require much larger operating voltages. Materials factors influencing the performance of the devices are discussed.     

Enhanced Photorefractivity of Poly(N‐vinylcarbazole)‐Based Composites through Electric‐Field Treatments and Ionic Liquid Doping

It is shown that the photorefractive (PR) performance of polymer composites based on poly(N‐vinylcarbazole) can be improved when samples are subjected to an electric field for a certain time, i.e. conditioned, previous to the PR characterization. It is also found that for conditioned samples the addition of an organic ionic liquid to the PR composition allows to obtain PR effect without the need of using a sensitizer. The typical electric field treatment time at room temperature and at a field of 20 V µm^?1 is 20 min. This procedure leads to a decrease of dark conductivity and an increase of photoconductivity, and consequently an increase of conductivity contrast. This results in higher PR two‐beam‐coupling gain coefficients and shorter response times, particularly at low fields. Dependencies of the process dynamics on impurities, applied field strength, temperature and the presence of an organic ionic liquid are examined in detail. It is remarkable the significant increase of the PR gain coefficients, and more drastically of the net gain coefficients, observed at low fields (<55 V µm^?1), when an ionic organic liquid such as benzalkonium chloride is added to unsensitized conditioned PR composites. These findings open a new route to improve the PR performance, not only of PVK‐based composites, but also of other types of organic materials, the main advantage being that no sensitizer is needed.     

Control of Ambipolar and Unipolar Transport in Organic Transistors by Selective Inkjet‐Printed Chemical Doping for High Performance Complementary Circuits

The selective tuning of the operational mode from ambipolar to unipolar transport in organic field‐effect transistors (OFETs) by printing molecular dopants is reported. The field‐effect mobility (μ_FET) and onset voltage (V_on) of both for electrons and holes in initially ambipolar methanofullerene [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) OFETs are precisely modulated by incorporating a small amount of cesium fluoride (CsF) n‐type dopant or tetrafluoro‐tetracyanoquinodimethane (F4‐TCNQ) p‐type dopant for n‐channel or p‐channel OFETs either by blending or inkjet printing of the dopant on the pre‐deposited semiconductor. Excess carriers introduced by the chemical doping compensate traps by shifting the Fermi level (E_F) toward respective transport energy levels and therefore increase the number of mobile charges electrostatically accumulated in channel at the same gate bias voltage. In particular, n‐doped OFETs with CsF show gate‐voltage independent Ohmic injection. Interestingly, n‐ or p‐doped OFETs show a lower sensitivity to gate‐bias stress and an improved ambient stability with respect to pristine devices. Finally, complementary inverters composed of n‐ and p‐type PCBM OFETs are demonstrated by selective doping of the pre‐deposited semiconductor via inkjet printing of the dopants.     

High‐Mobility Air‐Stable Naphthalene Diimide‐Based Copolymer Containing Extended π‐Conjugation for n‐Channel Organic Field Effect Transistors

A high‐performance naphthalene diimide (NDI)‐based conjugated polymer for use as the active layer of n‐channel organic field‐effect transistors (OFETs) is reported. The solution‐processable n‐channel polymer is systematically designed and synthesized with an alternating structure of long alkyl substituted‐NDI and thienylene–vinylene–thienylene units (PNDI‐TVT). The material has a well‐controlled molecular structure with an extended π‐conjugated backbone, with no increase in the LUMO level, achieving a high mobility and highly ambient stable n‐type OFET. The top‐gate, bottom‐contact device shows remarkably high electron charge‐carrier mobility of up to 1.8 cm² V^?1 s^?1 (I_on/I_off = 10⁶) with the commonly used polymer dielectric, poly(methyl methacrylate) (PMMA). Moreover, PNDI‐TVT OFETs exhibit excellent air and operation stability. Such high device performance is attributed to improved π–π intermolecular interactions owing to the extended π‐conjugation, apart from the improved crystallinity and highly interdigitated lamellar structure caused by the extended π–π backbone and long alkyl groups.