High performance n-channel thin-film field-effect transistors based on angular-shaped naphthalene tetracarboxylic diimides

We report on the performance of organic field-effect transistors (OFETs) by using a series of angular-shaped naphthalene tetracarboxylic diimides as active layers. The fabricated OFET devices exhibit n-type semiconducting characteristics. The performance of OFETs can be substantially improved by modifying the surface of the gate dielectric chemically prior to the deposition of the organic semiconductors. An increased electron mobility of the OFETs was found owing to the improved crystallinity and enlarged grain sizes, which are attributed to the elevating substrate temperature during the semiconductor deposition. The highest mobility of 0.515 cm²/V s was achieved from a device fabricated at substrate temperature of 130 °C with octadecyltrichlorosilane (OTS) surface modification.     

Organic Field Effect Transistors Based on Graphene and Hexagonal Boron Nitride Heterostructures

Enhancing the device performance of single crystal organic field effect transistors (OFETs) requires both optimized engineering of efficient injection of the carriers through the contact and improvement of the dielectric interface for reduction of traps and scattering centers. Since the accumulation and flow of charge carriers in operating organic FETs takes place in the first few layers of the semiconductor next to the dielectric, the mobility can be easily degraded by surface roughness, charge traps, and foreign molecules at the interface. Here, a novel structure for high‐performance rubrene OFETs is demonstrated that uses graphene and hexagonal boron nitride (hBN) as the contacting electrodes and gate dielectric layer, respectively. These hetero‐stacked OFETs are fabricated by lithography‐free dry‐transfer method that allows the transfer of graphene and hBN on top of an organic single crystal, forming atomically sharp interfaces and efficient charge carrier‐injection electrodes without damage or contamination. The resulting heterostructured OFETs exhibit both high mobility and low operating gate voltage, opening up new strategy to make high‐performance OFETs and great potential for flexible electronics.     

Newly Synthesized Nonvacuum Processed High-k Polymeric Dielectrics with Carboxyl Functionality for Highly Stable Operating Printed Transistor Applications

Solution-processed polar hydroxyl containing polymers such as poly(4-vinylphenol) are widely utilized in organic filed-effect transistors (OFETs) due to their high dielectric constant (k) and excellent insulating properties owing to the crosslinking through their hydroxyl groups. However, hydroxyl functionalities can function as trapsites, and their crosslinking reactions decrease the k value of materials. Hence, in this study, new solution-processable copolymers containing both carboxyl and hydrophobic functionalities are synthesized. A fluorophenyl azide (FPA) based UV-assisted crosslinker is also employed to promote the movement of polar carboxyl groups toward the bulk region and the hydrophobic functionalities to the surface region, thereby maintaining the high-k characteristics and hydrophobic surface in thin film. Thus, the addition of an FPA crosslinker eliminates the trapsites on the surface, allowing a stable operation and efficient charge transport. Additionally, the solution-processability enables the production of uniform and thin films to yield OFETs with stable and low-voltage driving characteristics. The printed layers are also applied as gate dielectrics for floating gate memory devices and in integrated one-transistor-one-transistor based memory cells, displaying their excellent memory performance. The synthesis and fabrication strategies employed in this study can become useful guidelines for the production of high-k dielectrics for stable OFETs and other applications.     

Natural polyelectrolyte: Major ampullate spider silk for electrolyte organic field-effect transistors

The major ampullate (MA) silk collected from giant wood spiders Nephila pilipes consists of 12% glutamic acid (Glu) and 4% tyrosine (Tyr) acidic amino residues. The MA silk may act as a natural polyelectrolyte for organic field-effect transistors (OFETs). Pentacene and F₁₆CuPc OFETs were fabricated with the MA silk thin film as the gate dielectric. The MA silk thin film with surface roughness of 4 nm and surface energy of 36.1 mJ/m² was formed on glass using a hexafluoroisopropanol (HFIP) organic process. The MA silk gate dielectric in pentacene OFETs may improve the field-effect mobility (μ_FE,sat) value in the saturation regime from 0.11 in vacuum to 4.3 cm² V⁻¹ s⁻¹ in air ambient at ca. 70% RH. The corresponding threshold voltage (V_TH) value reduced from −6 V in vacuum to −0.5 V in air ambient. Similar to other polyelectrolytes, the changes of μ_FE,sat and V_TH may be explained by the generation of electric double layers (EDLs) in the MA silk thin film in air ambient due to water absorption.     

Hybrid Nanodielectrics for Low‐Voltage Organic Electronics

Nanoscale hybrid dielectrics composed of an ultra‐thin polymeric low‐κ bottom layer and an ultra‐thin high‐κ oxide top layer, with high dielectric strength and capacitances up to 0.25 μFcm^?2, compatible with low‐voltage, low‐power, organic electronic circuits are demonstrated. An efficient and reliable fabrication process, with 100% yield achieved on lab‐scale arrays, is demonstrated by means of pulsed laser deposition (PLD) for the fast growth of the oxide layer. With this strategy, high capacitance top gate (TG), n‐type and p‐type organic field effect transistors (OFETs) with high mobility, low leakage currents, and low subthreshold slopes are realized and employed in complementary‐like inverters, exhibiting ideal switching for supply voltages as low as 2 V. Importantly, the hybrid double‐layer allows for a neat decoupling between the need for a high capacitance, guaranteed by the nanoscale thickness of the double layer, and for an optimized semiconductor–dielectric interface, a crucial point in enabling high mobility OFETs, thanks to the low‐κ polymeric dielectric layer in direct contact with the polymer semiconductor. It is shown that such decoupling can be achieved already with a polymer dielectric as thin as 10 nm when the top oxide is deposited by PLD. This paves the way for a very versatile implementation of the proposed approach for the scaling of the operating voltages of TG OFETs with very low level of dielectric leakage currents to the fabrication of low‐voltage organic electronics with drastically reduced power consumption.     

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.     

The mutual influence of surface energy and substrate temperature on the saturation mobility in organic semiconductors

We report on a mutual correlation between the substrate temperature during semiconductor deposition and the surface energy of the gate dielectric on the charge carrier mobility in bottom gate top contact organic field effect transistors (OFETs) with N,N′-diphenyl-3,4,9,10-perylene tetracarboxylic diimide (DP-PDI) as organic semiconductor.     

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.     

Polarity Effects of Polymer Gate Electrets on Non‐Volatile Organic Field‐Effect Transistor Memory

Organic non‐volatile memory (ONVM) based on pentacene field‐effect transistors (FETs) has been fabricated using various chargeable thin polymer gate dielectrics—termed electrets—onto silicon oxide insulating layers. The overall transfer curve of organic FETs is significantly shifted in both positive and negative directions and the shifts in threshold voltage (V_Th) can be systemically and reversibly controlled via relatively brief application of the appropriate external gate bias. The shifted transfer curve is stable for a relatively long time—more than 10⁵ s. However, this significant reversible shift in V_Th is evident only in OFETs with non‐polar and hydrophobic polymer electret layers. Moreover, the magnitude of the memory window in this device is inversely proportional to the hydrophilicity (determined from the water contact angle) and dielectric polarity (determined from the dielectric constant), respectively. Memory behaviors of ONVM originate from charge storage in polymer gate electret layers. Therefore, the small shifts in V_Th in ONVM with hydrophilic and polar polymers may be due to very rapid dissipation of transferred charges through the conductive channels which form from dipoles, residual moisture, or ions in the polymer electret layers. It is verified that the surface or bulk conductivities of polymer gate electret layers played a critical role in determining the non‐volatile memory properties.     

Parylene based bilayer flexible gate dielectric layer for top-gated organic field-effect transistors

In this paper, we report on a bilayer insulating film based on parylene-c for gate dielectric layers in top-gate/bottom-contact inkjet-printed organic field-effect transistors (OFETs) with indacenodithiophene-co-benzothiadiazole (IDTBT) and poly([N,N’-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5’-(2,2’-bitthiophene)) (P(NDI2OD-T2)) as with p- and n-channel semiconductors. The thin parylene-c film (t = 210 nm) show large gate leakage density (2.52 nA/cm² at 25 V) and low breakdown voltage (2.2 MV/cm). In addition, a degraded field-effect mobility (μ) was observed in printed IDTBT and P(NDI2OD-T2) OFETs with the parylene-c single-layered dielectric. X-ray photoelectron spectroscopy (XPS) analysis reveals that the degradation of μ is due to unwanted chemical interaction between parylene-c and the conjugated polymer surface during the parylene-c deposition process. By inserting 50-nm thick poly(methyl-methacrylate) (PMMA) and polystyrene (PS) layer in-between the parylene-c and conjugated polymer film, highly improved gate leakage density and breakdown voltage are achieved. The printed IDTBT and P(NDI2OD-T2) OFETs with a bilayer dielectric compose of parylene-c and PMMA and PS show significantly improved hole and electron μ of 0.47 cm²/Vs and 0.13 cm²/Vs, respectively, and better operation stability. In addition, we demonstrate inkjet-printed polymer complementary inverter with a high voltage gain of 25.7 by applying a PS/parylene-c bilayer dielectric.     

Small-molecule vacuum processed melamine-C60, organic field-effect transistors

The transfer of benchtop knowledge into large scale industrial production processes represents a challenge in the field of organic electronics. Large scale industrial production of organic electronics is envisioned as roll to roll (R2R) processing which nowadays comprises usually solution-based large area printing steps. The search for a fast and reliable fabrication process able to accommodate the deposition of both insulator and semiconductor layers in a single step is still under way. Here we report on the fabrication of organic field effect transistors comprising only evaporable small molecules. Moreover, both the gate dielectric (melamine) and the semiconductor (C₆₀) are deposited in successive steps without breaking the vacuum in the evaporation chamber. The material characteristics of evaporated melamine thin films as well as their dielectric properties are investigated, suggesting the applicability of vacuum processed melamine for gate dielectric layer in OFETs. The transistor fabrication and its transfer and output characteristics are presented along with observations that lead to the fabrication of stable and virtually hysteresis-free transistors. The extremely low price of precursor materials and the ease of fabrication recommend the evaporation processes as alternative methods for a large scale, R2R production of organic field effect transistors.     

Porous Organic Field‐Effect Transistors for Enhanced Chemical Sensing Performances

The thin‐film structures of chemical sensors based on conventional organic field‐effect transistors (OFETs) can limit the sensitivity of the devices toward chemical vapors, because charge carriers in OFETs are usually concentrated within a few molecular layers at the bottom of the organic semiconductor (OSC) film near the dielectric/semiconductor interface. Chemical vapor molecules have to diffuse through the OSC films before they can interact with charge carriers in the OFET conduction channel. It has been demonstrated that OFET ammonia sensors with porous OSC films can be fabricated by a simple vacuum freeze‐drying template method. The resulted devices can have ammonia sensitivity not only much higher than the pristine OFETs with thin‐film structure but also better than any previously reported OFET sensors, to the best of our knowledge. The porous OFETs show a relative sensitivity as high as 340% ppm^?1 upon exposure to 10 parts per billion (ppb) NH₃. In addition, the devices also exhibit decent selectivity and stability. This general and simple strategy can be applied to a wide range of OFET chemical sensors to improve the device sensitivity.     

Engineering density of semiconductor-dielectric interface states to modulate threshold voltage in OFETs

Threshold-voltage control is critical to the further development of pentacene organic field-effect transistors (OFETs). In this paper, we demonstrate that the threshold voltage can be tuned through chemical treatment of the gate dielectric layer. We show that oxygen plasma treatment of an organic polymer gate dielectric, parylene, introduces traps at the semiconductor-dielectric interface that strongly affect the OFET performance. Atomic force microscopy, optical microscopy using crossed-polarizers, and current-voltage and capacitance-voltage characterization were performed on treated and untreated devices. A model is presented to account for the effects of trap-introduced charges, both 1) fixed charges (2.0/spl times/10/sup -6/ C/cm/sup 2/) that shift the threshold voltage from -17 to +116 V and 2) mobile charges (1.1/spl times/10/sup -6/ C/cm/sup 2/) that increase the parasitic bulk conductivity. This technique offers a potential method of tuning threshold voltage at the process level.     

Monitoring the Channel Formation in Organic Field‐Effect Transistors via Photoinduced Charge Transfer

Conducting channel formation in organic field‐effect transistors (OFETs) is considered to happen in the organic semiconductor layer very close to the interface with the gate dielectric. In the gradual channel approximation, the local density of accumulated charge carriers varies as a result of applied gate bias, with the majority of the charge carriers being localized in the first few semiconductor monolayers close to the dielectric interface. In this report, a new concept is employed which enables the accumulation of charge carriers in the channel by photoinduced charge transfer. An OFET employing C₆₀ as a semiconductor and divinyltetramethyldisiloxane‐bis(benzocyclobutene) as the gate dielectric is modified by a very thin noncontinuous layer of zinc‐phthalocyanine (ZnPc) at the semiconductor/dielectric interface. With this device geometry, it is possible to excite the phthalocyanine selectively and photogenerate charges directly at the semiconductor/dielectric interface via photoinduced electron transfer from ZnPc onto C₆₀. Thus the formation of a gate induced and a photoinduced channel in the same device can be correlated.     

Polymer dielectric layer functionality in organic field-effect transistor based ammonia gas sensor

Ammonia (NH₃) gas sensors based on pentacene organic field-effect transistors (OFETs) are fabricated using polymers as the dielectric. Compared with those incorporating poly(vinyl alcohol), poly(4-vinylphenol) or poly(methyl methacrylate) dielectric, a low detect limitation of 1 ppm and enhanced recovery property are obtained for OFETs with polystyrene (PS) as gate dielectric. By analyzing the morphologies of pentacene and electrical characteristics of the OFETs under various concentrations of NH₃, the variations of the sensing properties of different dielectrics based OFET-sensors are proved to be mainly caused by the diversities of dielectric/pentacene interfacial properties. Furthermore, low surface trap density and the absence of polar groups in PS dielectric are ascribed to be responsible for the high performance of NH₃ sensors.     

Organic Thin Film Transistors with Polymer Brush Gate Dielectrics Synthesized by Atom Transfer Radical Polymerization

Low operating voltage is an important requirement that must be met for industrial adoption of organic field‐effect transistors (OFETs). We report here solution fabricated polymer brush gate insulators with good uniformity, low surface roughness and high capacitance. These ultra thin polymer films, synthesized by atom transfer radical polymerization (ATRP), were used to fabricate low voltage OFETs with both evaporated pentacene and solution deposited poly(3‐hexylthiophene). The semiconductor‐dielectric interfaces in these systems were studied with a variety of methods including scanning force microscopy, grazing incidence X‐ray diffraction and neutron reflectometry. These studies highlighted key differences between the surfaces of brush and spun cast polymethyl methacrylate (PMMA) films.     

Photosensitivity of top gate C60 based OFETs: Potential applications for high efficiency organic photodetector

The comparison of light-induced effects in bottom-gate and top-gate organic field effect transistors (OFETs) provide a clear indication, that the nature of interface between the active layer and the gate dielectric plays a major role in the observed light-induced threshold voltage shift. The nature of interface was also analyzed by electron spin resonance (ESR) experiments, which provides a direct evidence for the creation of free radical species when parylene is deposited on the top of the C₆₀ semiconductor layer. The rate of change of light-induced threshold voltage shift strongly depends on the wavelength and intensity of the incident light, and transverse electric field at the interface. The observed effects provide a strong base for the realization of high efficiency organic photodetectors and optical memory devices. The responsivity of organic photodetector was measured up to 1047 A/W.     

Photo-patternable high-k ZrOx dielectrics prepared using zirconium acrylate for low-voltage-operating organic complementary inverters

Solution-processed dielectric materials with a high dielectric constant (k) have attracted considerable attention due to their potential applications in low-voltage-operating organic field-effect transistors (OFETs) for realizing large-area and low-power electronic devices. In terms of device commercialization, the patterning of each film component via a facile route is an important issue. In this study, we introduce a photo-patternable precursor, zirconium acrylate (ZrA), to fabricate photo-patterned high-k zirconium oxide (ZrO_x) dielectric layers with UV light. Solution-processed ZrA films were effectively micro-patterned with UV exposure and developing, and transitioned to ZrO_x through a sol-gel reaction during deep-UV annealing. The UV-assisted and ∼10 nm-thick ZrO_x dielectric films exhibited a high capacitance (917.13 nF/cm² at 1 KHz) and low leakage current density (10⁻⁷ A/cm² at 1.94 MV/cm). Those films could be utilized as gate dielectric layers of OFETs after surface modification with ultrathin cyclic olefin copolymer layers. Finally, we successfully fabricated organic complementary inverters exhibiting hysteresis-free operation and high voltage gains of over 42 at low voltages of ≤3 V.     

Ameliorating the bias stress stability of n-type OFETs

The bias stress effect on C₆₀ based n-type OFETs was studied comprehensively. The role of dielectric layers and the active layers on bias stress effect was quantified by choosing three different dielectric layers with three different morphologies of active layers. It was found, that the bias stress induced charges can be trapped in active layer as well as in dielectric layers. The charge trapping in active layers happened ten times faster as compared to the trapping of charges in dielectric layers. It was proved, that the use of appropriate dielectric layers increases the bias stress stability by decreasing bias stress effects up to 55%. It was experimentally proven that the fabrication of electrically stress stable devices is possible by using C₆₀ layers grown at higher substrate temperature or with large grain sizes. The OFETs fabricated with larger grain sizes also fulfil the criterion of Guard bands for modelling of electronic circuits, which is a first step of organic electronics towards the industrialization. On the basis of experimental evidences, the criterion of choosing appropriate dielectric layers for OFETs was also proposed.     

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.