Low-resistance contacts of electroless-plated metals with high-mobility organic semiconductors: Novel organic field-effect transistors with solution-processed electrodes

The establishment of a reliable vacuum-free method for the formation of electrical contacts on high-performance organic semiconductors has become an urgent task due to rapid progress made in the development of solution-processable high-mobility organic field-effect transistors (OFETs). We have recently proposed that electroless plating, a standard technology to mass produce wirings in currently commercialized electronic devices, is suited for high-performance solution-crystallized OFETs. A low contact resistance at the source and drain electrodes is necessary with organic semiconductors for high-speed device operation; therefore, we have evaluated the contact resistance using the transfer line method. A top-contact geometry with sufficient contact area is employed to achieve stable carrier injection, which has enabled contact resistances as low as 1.4 kΩ cm on a polyethylene naphthalate substrate at a gate voltage of −10 V. This marks outstanding performance among the solution-processed metal electrodes reported for OFETs, particularly on plastic substrates. The result indicates that high-quality boundaries with minimized trap densities are realized due to the mild conditions of the electroless plating process at room temperature.     

Enhanced performance of room temperature ammonia sensors using morphology-controlled organic field-effect transistors

Developing electronic sensors for ammonia (NH₃) is very useful for environmental monitoring and diagnostic purposes. In this work, a highly sensitive, organic field-effect transistor (OFET) based, room temperature sensor for NH₃ has been fabricated using dinaphtho [2,3-b:2′,3′-f]thieno [3,2-b]thiophene (DNTT), which showed a fast response to low concentration of the analyte down to 100 ppb. A thin film of solution-processed polymethyl methacrylate (PMMA) has been used as the gate dielectric material and its hydrophobic surface promoted structured growth of organic semiconductor, DNTT, by inducing mass transfer. By controlling the thickness and thereby exploiting the growth dynamics of the semiconductor film, the sensor performance was improved. The sensitivity of the device towards 1 ppm of NH₃ was almost doubled with a thinner and porous film of DNTT as compared to that with a thick film. Morphological studies of the sensing layers, using atomic force microscopy (AFM), have established this structure-property relation. The variations in different transistor parameters have been studied with respect to different analyte concentrations. The p-channel devices in the enhancement mode showed depletion upon exposure to NH₃. The devices exhibited a fast response and good recovery to the initial state within 2 min.     

Downscaling of n-channel organic field-effect transistors with inkjet-printed electrodes

In this contribution we demonstrate for the first time a downscaled n-channel organic field-effect transistors based on N,N′-dialkylsubstituted-(1,7&1,6)-dicyanoperylene-3,4:9,10-bis(dicarboximide) with inkjet printed electrodes. First we demonstrate that the use of a high boiling point solvent is critical to achieve extended crystalline domains in spin-coated thin films and thus high electron mobility >0.1 cm² V⁻¹ s⁻¹ in top-gate devices. Then inkjet-printing is employed to realize sub-micrometer scale channels by dewetting of silver nanoparticles off a first patterned gold contact. By employing a 50 nm crosslinked fluoropolymer gate dielectric, ∼200 nm long channel transistors can achieve good current saturation when operated <5 V with good bias stress stability.     

Contactless charge carrier mobility measurement in organic field-effect transistors

With the increasing performance of organic semiconductors, contact resistances become an almost fundamental problem, obstructing the accurate measurement of charge carrier mobilities. Here, a generally applicable method is presented to determine the true charge carrier mobility in an organic field-effect transistor (OFET). The method uses two additional finger-shaped gates that capacitively generate and probe an alternating current in the OFET channel. The time lag between drive and probe can directly be related to the mobility, as is shown experimentally and numerically. As the scheme does not require the injection or uptake of charges it is fundamentally insensitive to contact resistances. Particularly for ambipolar materials the true mobilities are found to be substantially larger than determined by conventional (direct current) schemes.     

Potential of low-voltage organic transistors with high on-state drain current for temperature sensor development

Organic transistors with high on-state drain current at gate and drain voltages of −2 V fabricated on polyethylene naphthalate foils were investigated for sensor development. Two aspects were studied: (a) the ability of such transistors to raise the sensitivity of a temperature sensor and (b) the bias stress stability of the transistors subjected to square voltage pulses that turned them on and off repeatedly. To demonstrate the first aspect, the voltage-amplifying ability of the organic transistor was used to increase the response to the temperature, ordinarily achieved with a thermistor. To achieve voltage amplification, the transistor must have on-state drain current of at least 20 μA at gate and drain voltages of −2 V. Two transistors with on-state drain current of ~60 and ~120 μA were tested, leading to voltage gain of −2.8 and −4.9 V/V, respectively, thus increasing the sensitivity of the temperature sensor by a factor of up to 5. To study the second aspect, the same square voltage pulses were concurrently applied to the gate and drain electrodes, causing the transistor to turn on and off repeatedly. The turn-on and turn-off voltages were −2 and 0 V respectively and four different pulse periods were used: T of 5, 20, 40 and 60 s. For each T, 1000 pulses with turn-on time of 1 s and varying turn-off times were applied to the transistors, leading to the aggregate net stress time of 1000 s in all cases. The changes in the on-state drain current, threshold voltage, and field-effect mobility depended on T, in spite of the net stress time being the same. The reduction in the on-state drain current did not exceed 17%, stabilization was also observed after about 500 cycles in some cases, and the maximum drop occurred for medium T, thus making T = 60 s a favorable condition for sensor operation.     

The color change in polychromatic organic light-emitting field-effect transistors: Optical filtering versus reemission

In this contribution the color conversion process of a polychromatic organic light-emitting field-effect transistor (OLET) is revisited on the basis of an analytic device model. The device of interest consists of a color conversion layer out of rubrene on top of a monochromatic light-emitting transistor based on poly(9,9-di-n-octyl-fluorene-alt-benzothiadiazole) (F8BT). The model describes the relation of color coordinate and emission intensity – set by the applied drain and gate biases – linking the optoelectronic response of the employed monochromatic OLET to the optical processes occurring in the color conversion layer. The model shows that the color shift is rather due to partial absorption of the F8BT emission by rubrene than, as was claimed earlier, due to a color conversion process by absorption and reemission in the conversion layer. In addition to the earlier publication, it will be demonstrated that such a device allows for an independent electrical tunability of emission intensity and color coordinate within the color span of the F8BT and the rubrene spectrum being a unique feature of such a polychromatic light-emitting field-effect transistor.     

Effect of electron-donating unit on crystallinity and charge transport in organic field-effect transistors with thienoisoindigo-based small molecules

We report the effect of an electron-donating unit on solid-state crystal orientation and charge transport in organic field-effect transistors (OFETs) with thienoisoindigo (TIIG)-based small molecules. End-capping of different electron-donor moieties [benzene (Bz), naphthalene (Np), and benzofuran (Bf)] onto TIIG (giving TIIG-Bz, TIIG-Np, and TIIG-Bf) is resulted in different electronic energy levels, solid-state morphologies and performance in OFETs. The 80 °C post-annealed TIIG-Np OFETs show the best device performance with a best hole mobility of 0.019 cm² V⁻¹ s⁻¹ and threshold voltage of −8.6 ± 0.9 V using top gate/bottom contact geometry and a CYTOP gate dielectric. We further investigated the morphological microstructure of the TIIG-based small molecules by using grazing incidence wide angle X-ray scattering, atomic force microscopy and a polarized optical microscope. The electronic transport levels of the TIIG-based small molecules in thin-film states were investigated using ultraviolet photoelectron spectroscopy to examine the charge injection properties of the gold electrode.     

Modeling the gate bias dependence of contact resistance in staggered polycrystalline organic thin film transistors

We have modeled the dependence on the gate voltage of the bulk contact resistance and interface contact resistance in staggered polycrystalline organic thin film transistors. In the specific, we have investigated how traps, at the grain boundaries of an organic semiconductor thin film layer placed between the metal electrode and the active layer, can contribute to the bulk contact resistance. In order to the take into account this contribution, within the frame of the grain boundary trapping model (GBTM), a model of the energy barrier E_B, which emerges between the accumulation layer at the organic semiconductor/insulator interface and injecting contact, has been proposed. Moreover, the lowering of the energy barrier at the contacts interface region has been included by considering the influence of the electric field generated by the accumulation layer on the injection of carriers at the source and on the collection of charges from the accumulation layer to the drain contact. This work outlines both a Schottky barrier lowering, determined by the accumulation layer opposite the source electrode, as well as a Poole-Frenkel mechanism determined by the electric field of the accumulation layer active at the drain contact region. Finally it is provided and tested an analytical equation of our model for the contact resistance, summarizing the Poole-Frenkel and Schottky barrier lowering contribution with the grain boundary trapping model.     

Stable growth of large-area single crystalline thin films from an organic semiconductor/polymer blend solution for high-mobility organic field-effect transistors

We developed an effective and steady solution-processing technique for a small molecule–type semiconductor, C₁₀–DNBDT–NW, by adding an amorphous PMMA polymer to produce stable growth of a two-dimensional large-area single-crystalline thin film by effective phase separation at a crucially faster processing speed compared to the case without the addition of a polymer. By using this solution-processing technique, it is noteworthy that the single-crystalline films of C₁₀–DNBDT–NW/PMMA exhibit the highest and average mobilities of 17 and 10.6 cm²/Vs, respectively. Furthermore, we also show the limitations of two-dimensional continuous growth of a single-crystalline film in terms of the solution technique.     

Improved ambipolar charge injection in organic field-effect transistors with low cost metal electrode using polymer sorted semiconducting carbon nanotubes

Solution-processed thin film transistors can be implemented using simple and low cost fabrication, and are the best candidates for commercialization due to their application to a range of wearable electronics. We report an ambipolar charge injection interlayer that can improve both hole and electron injection in organic field-effect transistors (OFETs) with inexpensive source-drain electrodes. The solution processed ambipolar injection layer is fabricated by selective dispersion of semiconducting single walled carbon nanotubes using poly(9,9-dioctylfluorene). OFETs with molybdenum (Mo) contacts and interlayer (Mo/interlayer OFETs) exhibit superior performance, including higher hole and electron mobilities, device yield, lower threshold voltages, and lower trap densities than those of bare transistors. While OFETs with Mo contacts show unipolar p-type behaviour, Mo/interlayer OFETs display ambipolar transport due to significant enhancement of electron injection. In the p-type region, transistor performance is comparable to devices with gold (Au). Hole mobility is increased approximately ten-fold over devices with only Mo contacts. The electron mobility of Mo/interlayer OFETs is 0.05 cm²V⁻¹s⁻¹, which is higher than devices with Au electrodes. The p-type contact resistances of Mo/interlayer OFETs are half those of OFETs with Mo contacts. Trap density in Mo/interlayer OFETs is one order magnitude lower than that of pristine devices. We also demonstrate that this approach is extendible to other metals (nickel) and n-type semiconductors with different energy levels. Injection by tunnelling is suggested as the mechanism of ambipolar injection.     

Ionic self-assembled monolayer for low contact resistance in inkjet-printed coplanar structure organic thin-film transistors

To reduce the contact resistance in inkjet-printed organic thin-film transistors (OTFTs), the use of a newly synthesized ionic self-assembled monolayer (SAM) consisting of an anchoring group, a linker group, and an ionic functional group, is investigated. According to the gated transmission line method (TLM) measurements of a series of OTFT devices, where one type has no charge injection layer, another type having a pentafluorobenzenethiol (PFBT) injection layer, and a third type containing a (6-mercaptohexyl)trimethylammonium bromide (MTAB) ionic SAM, the latter exhibits the lowest contact resistance value of ∼3.1 K Ω cm. The OTFTs without charge injection layer and with the PFBT SAM have relatively higher contact resistance values of ∼6.4 K Ω cm and ∼5.0 K Ω cm, respectively. The reduced contact resistance in the OTFTs with ionic SAMs is attributed to the large charge carrier density induced by the ionic SAM, which allows sufficient tunneling-assisted injection of the carriers from the metal electrode to the polymer semiconductor. These results suggest that the use of appropriate ionic SAM injection layer is an effective way to reduce the contact resistance, hence improving the charge transport characteristics of inkjet-printed OTFTs.     

Fast detection of blood gases by solution gated organic field effect transistors

We characterize the electrochemical stability of the organic semiconductor Dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) in aqueous solutions. Electrochemical stability of DNTT in solution is validated by cyclic voltammetry and demonstrated by solution gating of DNTT organic field effect transistors (OFETs). Then, we investigate the response time of DNTT OFETs to ammonia, a common blood gas. For bare OFETs, the response time to ammonia is 1–2s only. The exact response time depends on the DNTT film morphology; the fastest response is obtained for pronounced 3D (Volmer-Weber) growth. By comparing OFETs with and without a semipermeable parylene-C encapsulation layer, the influence of the capping on the response time is investigated. An encapsulation layer of 86 nm prolongs the response time to 100s, indicating that parylene-C acts as an efficient diffusion barrier for ammonia.     

Relation between injection barrier and contact resistance in top-contact organic thin-film transistors

We theoretically investigate the carrier injection into top-contact bottom-gate organic thin film transistors. By means of a two-dimensional drift–diffusion model, we explicitly consider thermionic and tunneling injection in combination with subsequent carrier transport into the device. Based on numerical simulations with this model, we determine the contact resistance as a function of the nominal hole injection barrier height and temperature. Depending on the barrier height or the operating temperature, we find three distinct injection regimes. Our work reveals that in all three regimes self-regulating processes exist due to which the influx of current is adjusted according to the needs of the channel at the given point of operation.     

Non-functionalized soluble diketopyrrolopyrrole: Simplest p-channel core for organic field-effect transistors

We report the synthesis, characterization and behavior in field-effect transistors of non-functionalized soluble diketopyrrolopyrrole (DPP) core with only a solubilizing alkyl chain (i.e. –C₁₆H₃₃ or –C₁₈H₃₇) as the simplest p-channel semiconductor. The characteristics were evaluated by UV–vis and fluorescence spectroscopy, X-ray diffraction, cyclic voltammetry (CV), thermal analysis, atomic force microscopy (AFM) and density functional theory (DFT) calculation. For top-contact field-effect transistors, two types of active layers were prepared either by a solution process (as a 1D-microwire) or thermal vacuum deposition (as a thin-film) on a cross-linked poly(4-vinylphenol) gate dielectric. All the devices showed typical p-channel behavior with dominant hole transports. The device made with 1D-microwiress of DPP-R18 showed field-effect mobility in the saturation region of 1.42 × 10^?2 cm²/V s with I_ON/I_OFF of 1.82 × 10³. These findings suggest that the non-functionalized soluble DPP core itself without any further functionalization could also be used as a p-channel semiconductor for low-cost organic electronic devices.     

Directed self-assembly of organic semiconductors via confined evaporative capillary flows for use in organic field-effect transistors

We fabricated well-defined 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-PEN) crystal arrays for use in electronic applications via a simple but effective method, the confined evaporative capillary flow (CEC) method. This has been accomplished by systematically controlling the contact line pinning at the edge of glass stylus and the outward hydrodynamic flow within the drying droplet with various processing solvents and surface properties of the substrate during solidification. We found that after CEC coating of TIPS-PEN solution dissolved into toluene onto SiO₂ surface, ribbon-shaped TIPS-PEN crystals were well developed with a width of 20–100 μm and length of 300 μm – 2 mm, which is presumably owing to optimized capillary evaporation. Specifically, TIPS-PEN crystals present highly preferred crystal orientation along the (l 0 0) axis, which can lead to efficient charge transport in a lateral direction. Thus, TIPS-PEN field-effect transistors (FETs) exhibited a good hole mobility of 0.72 cm²/Vs.     

A high-yielding evaporation-based process for organic transistors based on the semiconductor DNTT

We report on the performance of organic thin film transistors manufactured in an all-evaporated vacuum roll-to-roll process. We show that dinaphtho [2,3-b:2′,3′-f] thieno[3,2-b]thiophene (DNTT) is a suitable semiconductor material for deposition onto a flash evaporated polymer insulator layer to make bottom-gate top-contact transistors. Significantly, in batches of 90 transistors, the process approached a 100% yield of high mobility transistors with high on/off ratios and low gate-leakage. By contrast, a solution-deposited insulator layer led to significant gate leakage in a high proportion of transistors leading to poor yield. The performance of DNTT devices is shown to be superior to that of previously reported pentacene devices. Transistor performance is further enhanced by inclusion of a low-polarity surface modification, such as polystyrene, to the acrylate. The devices show good environmental stability but we demonstrate also that they can be in-line encapsulated with an acrylate and a SiOx overlayer without damaging the underlying transistor. Finally, a first demonstration is made of organic vapour jet printing of the DNTT to manufacture transistors with a high semiconductor deposition rate.     

Field-effect transistors based on organic single crystals grown by an improved vapor phase method

High-quality organic single crystals are produced directly onto the substrates using an improved vapor phase method. Unlike the conventional vapor phase methods, the present method is characterized by forming a large-sized crystal to which semiconductor devices can readily be made. The relevant method requires small space of only a 10-cm cube in which a couple of plates are put in close proximity. The crystal growth is carried out nearly at the thermodynamic equilibrium within the narrow space surrounded with the two plates. Thin single crystals of several hundreds of micrometers in size are grown on one of those plates. For the organic materials to be crystallized, we have chosen 1,4-bis(5-phenylthiophen-2-yl)benzene (AC5) and 5,5-diphenyl-2,2′:5′,2″:5″,2:5,2-quinquethiophene (P5T) from among thiophene/phenylene co-oligomers. The resulting crystals are well-defined polygons, each side reflecting the specific crystallographic orientation. In particular, those grown on self-assembled monolayers are exceedingly flat and free from cracks. We have directly fabricated top-contact field-effect transistors on these crystals. The devices exhibit the excellent performance and keep it both in air and in vacuum for a maximum of a hundred days.     

Improved pentacene growth continuity for enhancing the performance of pentacene-based organic thin-film transistors

This study proposes an alternative planar bottom-contact (pBC) structure to enhance the electrical performance of pentacene-based organic thin-film transistors (OTFTs). This pBC structure uses a bilayer dielectric to control planarization with a precise etch depth and introduces a bilayer photoresist lift-off method to ensure that planarization produces an optimum flatness. Because of the improved growth continuity of pentacene near the edge of the source/drain electrodes, the contact resistance between the source/drain and the pentacene was reduced significantly, thereby enhancing the electrical performance of OTFTs. The mechanism for the enhanced performance was also verified by a physics-based numerical simulation.     

Inserting a Mn-doped TiO2 layer for improving performance of pentacene organic thin-film transistors

Device performance of pentacene organic thin-film transistors (OTFTs) was significantly improved via inserting a Mn-doped TiO₂ layer between pentacene semiconductor and the source–drain electrodes. In comparison with the OTFTs with only-Au electrodes, the introduction of a thin Mn-doped TiO₂ layer leads to saturation current increasing from 31.9 μA to 0.22 mA, effective field-effect mobility improving from 0.24 to 1.13 cm²/V s, and threshold voltage downshifting from −11 to −2 V. These performance enhancements are ascribed to the significant reduction of contact resistance and smoothed surface of pentacene layer. This work may provide an effective approach to improve the performance of the pentacene based OTFTs by inserting a Mn-doped TiO₂ layer.