A printing technology combining screen-printing with a wet-etching process for the gate electrodes of organic thin film transistors on a plastic substrate

We have developed a practical printing technology for the gate electrode of organic thin film transistors (OTFTs) by combining screen-printing with a wet-etching process using nano-silver (Ag) ink as a conducting material. An Ag film was deposited onto a PVP (polyvinylphenol)-coated PC (polycarbonate) plastic substrate by screen-printing with nano-Ag ink, where Ag content of 20 wt.% was mixed using a terpineol solvent. Subsequently, the film was cured at 200 °C for 60 min, and then finally wet-etched through patterned positive photo-resist masks. The screen-printed Ag electrode exhibited a minimum line width of ∼5 μm, a thickness of ∼65 nm, and a resistivity of ∼10⁻⁶ Ω cm, producing good geometrical and electrical characteristics for a gate electrode. Additionally, it also provided good step coverage with the PVP dielectric layer, and consequently leakage current between the gate and source/drain electrodes was eliminated. Moreover, the electrical characteristic of the screen-printed Ag electrode was not significantly changed even after a bending test in which the Ag electrodes were bent with a bending radius of 6 mm and 2500 iterations of cyclic bending. OTFTs with the screen-printed Ag electrode produced a saturation mobility of 0.13 cm²/Vs and a current on/off ratio of 1.79 × 10⁶, being comparable to those of an OTFT with a thermally evaporated Al gate electrode.     

Effects of different electroplated gate electrodes on electrical performances of flexible organic thin film transistor and flexibility improvement

Various electroplated metal gate electrodes (Ni, Cu, and Au) on flexible polyimide (PI) substrates were applied to the fabrication of inverted staggered pentacene organic thin film transistors (OTFTs). The metal gate electrodes additively electroplated onto the patterned negative photoresist mask on the Cu(seed)/Cr(adhesion) layers sputter-deposited on the O₂-plasma-treated PI substrates were effective in obtaining good adhesion between the metal gate electrode and organic substrate. It was found that the reduction in the surface roughnesses of the electroplated metal gate and of the subsequently deposited PVP (poly-4-vinyl phenol) gate dielectric layers was a critical factor in improving the device performance. The Ni-gated OTFT exhibited the best electrical characteristics, with a field-effect mobility of ≅0.2 cm²/V-s and a current on/off ratio of ≅10³, due to the better chemical stability of the Ni electrode and the smoother surface of the PVP layer on the Ni electrode, as compared to the OTFTs with PVP/Cu or PVP/Au gates. The results of the flexibility test showed that the field-effect mobility and current on/off ratio were not changed significantly when the OTFTs were subjected to 10,000 cyclic bendings with a bending radius of 6 mm in tension mode (outward bending).     

Thermally curable polymers consisting of alcohol-functionalized cyclotetrasiloxane and melamine derivatives for use as insulators in OTFTs

New thermally curable organic/inorganic hybrid polymers were designed and synthesized as insulators for organic thin film transistors (OTFTs). Cyclotetrasiloxane (CTS) was reacted with allyl alcohols through a hydrosilylation reaction in the presence of a catalytic amount of Pt(0) to give the alcohol-functionalized cyclotetrasiloxane (CTS-OH). The synthesized CTS-OH was then thermally cured with hexamethoxymethylmelamine (HMMM) at 80 °C in the presence of a catalytic amount of p-toluenesulfonic acid to form a hard and smooth thin film composed of a highly cross-linked network polymers (CTS-MMs). Devices with indium-tin-oxide/CTS-MM/Au configuration were fabricated to investigate electrical properties of the polymers such as capacitance, dielectric constant, and leakage current. The CTS-MM showed lower leakage current level than the well-known curable insulator consisting of poly(vinylphenol) (PVP) and a melamine derivative. Pentacene-based OTFTs were fabricated using the synthesized insulators as the gate dielectric layers, and their performances were compared to those of the device fabricated using PVP. The OTFTs fabricated using CTS-MM showed higher field-effect mobility than that of the PVP. The hole mobility of the pentacene based-OTFTs fabricated using CTS-MM as gate dielectric was 0.36 cm²/V s and the on/off current ratio was >10⁷.     

Self-assembled monolayer modification of silver source-drain electrodes for high-performance pentacene organic field-effect transistors

We demonstrated excellent performance improvement of bottom-contact pentacene-based organic thin film transistors (OTFTs) fabricated at room-temperature with silver electrodes modified by self-assembled monolayers (SAMs) of binary mixtures of n-alkanethiol (n-decanethiol, HDT) and the fluorinated analog (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanethiol, FDT). The OTFTs with modified silver (Ag) electrodes exhibit carrier mobility of 0.21 cm²/V s, which is faster than most of bottom-contact pentacene-based OTFTs fabricated at room-temperature with gold (Au) electrodes. The threshold voltage is reduced from −30 V of the devices with Au electrodes to −5.4 V of the devices with modified Ag electrodes. The hole injection barrier is also reduced with modified Ag as indicated by ultraviolet photoemission spectroscopy. The enhancement of the saturation current and the mobility of the devices are due to both the reduction of hole injection barriers and the continuous grain size of pentacene on top of electrodes and dielectrics.     

Facile modification of Cu source–drain (S/D) electrodes for high-performance,low-voltage n-channel organic thin film transistors (OTFTs) based on C60

Exploring suitable electrode materials with sufficiently low work function, ambient stability and low-cost is of great technological importance to the development of n-channel OTFTs. Here, we show that the work function of Cu can be effectively reduced from 4.65 eV to 4.28 eV through surface modification via simply spin-coating a thin layer of branched polyethylenimine (PEI). By exploiting a high-capacitance density gate dielectric (200 nF/cm²), low-voltage (3 V) C₆₀ TFTs with electron mobility (μ_e) of 3.2 cm²/V s are demonstrated with PEI modified Cu as source–drain (S/D) electrodes. In contrast, the device with Cu S/D electrodes possesses μ_e of only 1.0 cm²/V s. The improvement in electrical performance of the PEI modified device is attributed to the efficient electron injection at the Cu/C₆₀ interface which resulted from the reduction in work function of Cu. Moreover, upon PEI modification, the bias stability of the device can be obviously enhanced as compared to the unmodified one, and the resultant device exhibits an excellent thermal stability up to 200 °C without appreciable degradation in mobility. The facile modification of low-cost Cu as S/D electrodes for high-performance n-channel OTFTs as well as the low-voltage operation will pave the way for large scale manufacturing of organic electronics.     

All-Inkjet-Printed Bottom-Gate Thin-Film Transistors Using UV Curable Dielectric for Well-Defined Source-Drain Electrodes

Technological restrictions of the inkjet printing technology for printed electronics can hinder its application potential, mainly due to the limited resolution and layer homogeneity in comparison to conventional manufacturing techniques for electronics. The manufacturing of active devices such as thin-film transistors with appropriate performance using printing technologies is still one of the current challenges towards industrial applications. This work demonstrates the application of an ultraviolet (UV) curable ink as insulating material for the gate dielectric. The advantage of the UV curable ink is its fast curing and the smooth surface enabling high resolution patterns on top of it. In this way, all-inkjet-printed organic thin-film transistors (OTFTs) were fabricated with silver electrodes, UV curable gate dielectric, and 6,13-bis(triisopropylsilylethynyl)pentacene for the active semiconductor layer. By fine tuning of processing parameters and pattern geometries, a stable channel length of about 10 μm was obtained in the bottom-gate configuration without the need of additional steps, suggesting a way to build low-cost all-inkjet-printed OTFTs with well-defined source-drain electrodes and fast UV curable dielectric without any additional steps. The inkjet-printed device is characterized by an electron mobility of 0.012 cm² V^?1 s^?1 and on/off ratio of 10³.     

Photocurable propyl-cinnamate-functionalized polyhedral oligomeric silsesquioxane as a gate dielectric for organic thin film transistors

A polyhedral oligomeric silsesquioxane (POSS)-based insulating material with photocurable propyl-cinnamate groups (POSS-CYNNAM) was designed and synthesized through simple single step reaction for use as a gate dielectric in organic thin-film transistors (OTFT). POSS-CYNNAM was soluble in common organic solvents and formed a smooth thin film after spin-casting. A thin film of POSS-CYNNAM was cross-linked and completely solidified under UV irradiation without the use of additives such as photoacid generators or photoradical initiators. ITO/insulator/Au devices were fabricated and characterized to measure the dielectric properties of POSS-CYNNAM thin films, such as leakage current and capacitance. A pentacene-based OTFT using the synthesized insulator as the gate dielectric layer was fabricated on the transparent indium tin oxide (ITO) electrode, and its performance was compared to OTFTs using thermally cross-linked poly(vinyl phenol) (PVP) as the insulator. The fabricated POSS-CYNNAM OTFT showed a comparable performance to devices based on the PVP insulator with 0.1 cm²/Vs of the field effect mobility and 4.2 × 10⁵ of an on/off ratio.     

TiO2-poly(4-vinylphenol) nanocomposite dielectrics for organic thin film transistors

We report on the fabrication of organic thin film transistors (OTFTs), which operate at low voltages, by incorporating a nanocomposite gate insulator material consisting of titania (TiO₂) nanoparticles used as fillers and poly(4-vinyl phenol) (PVP) used as matrix. The surface of the nanoparticles was modified by the ligands, 4-hydroxybenzoic acid, to enhance their compatibility with the polymer. The structure of the ligand is similar to that of the repeat units in the polymer. Once the nanoparticles were homogeneously dispersed in the polymer matrix, they were immobilized by cross-linking PVP with poly(melamine-co-formaldehyde) methylated/butylated (cross-linker). Consequently, no significant aggregation of the nanoparticles, even at a concentration of 31 wt%, was found in the nanocomposites, as observed by transmission electron microscopy (TEM). As a result, the nanocomposite exhibited a low leakage current density (∼10⁻⁸ A/cm⁻²). With an increase in the concentration of TiO₂ nanoparticles added, the dielectric constant of the nanocomposites also increased proportionately as compared to that of pristine PVP. The performance of the OTFTs in terms of the charge carrier mobility, on/off ratio, threshold voltages, and hysteresis was evaluated. In addition, the relationship between the concentration of TiO₂ nanoparticles and the device performance is discussed in detail.     

Fully solution-processed organic thin-film transistors by consecutive roll-to-roll gravure printing

A high-performance/flexible organic thin-film transistor (OTFT) is fabricated by using all-step solution processes, which are composed of roll-to-roll gravure, plate-to-roll gravure and inkjet printing with the least process number of 5. Roll-to-roll gravure printing is used to pattern source/drain electrodes on plastic substrate while semiconductor and dielectric layers are printed by consecutive plate-to-roll gravure printing. Finally, inkjet printing of Ag organometallic ink is used to pattern the gate electrode. The fabricated OTFT exhibits excellent electrical performance, field-effect mobility over 0.2 cm²/Vs, which is one of the best compared to the previous works. The deposition of a self-assembled monolayer on the source-drain electrodes results in a higher work function which is suitable for a p-type polymer semiconductor. Moreover, the formation of dense gate electrode line on hydrophobic dielectric is achieved by selecting suitable Ag ink.     

Enhanced electrical and photosensing properties of pentacene organic thin-film phototransistors by modifying the gate dielectric thickness

The effects of dielectric layer thickness on the electrical performance and photosensing properties of organic pentacene thin-film transistors have been investigated. To improve the electrical performance of pentacene thin-film transistors (TFTs), the poly-4-vinylphenol (PVP) polymer with various thicknesses was used in fabrication of the pentacene transistors. The pentacene thin-film transistor with the PVP dielectric layer of 70 nm exhibited a field-effect mobility of 4.46 cm²/Vs in the saturation region, a threshold voltage of −4.0 V, a gate voltage swing of 2.1 V/decade and an on/off current ratio of 5.1 × 10⁴. In the OFF-state, the photoresponse of the transistors increases linearly with illumination intensity. The pentacene transistor with the thinner dielectric layer thickness indicates the best photosensing behavior. It is evaluated that the electrical performance and photosensing properties of pentacene thin-film transistors can be improved by using various thickness dielectric layer.     

Silver nanowire-polymer composite electrode for high performance solution-processed thin-film transistors

Silver nanowires (AgNWs)/poly-(3,4-ethylenedioxythiophene/polystyrene sulphonate) (PEDOT:PSS) composite films as conductive electrode for OTFTs were prepared, and their optical and electrical properties were investigated. The conductive composite films used in this study afforded low sheet resistance of <140 Ω/sq and transmittance as high as 70% in the visible region. For the composite film with 0.1 wt.% of AgNWs, contact resistance as low as 2.7 × 10⁴ Ω cm was obtained, as examined by Transfer length model (TLM) analysis, and work function of the corresponding film was 5.0 eV. Furthermore, the composite films were employed as source and drain electrodes for top-gate/bottom-contact organic thin-film transistors (OTFTs) based on solution-processed 5,11-bistriethylsilylethynyl anthradithiophene (TES-ADT) as organic semiconductor, and the resulting device showed high electrical performance with carrier mobility as high as 0.21 cm²/V s.     

Crystallization of sexiphenyl induced by polyurethane containing terphenyl groups affording high-mobility organic thin-film transistor

Novel polyurethane containing terphenyl groups were designed and synthesized as gate insulators to induce the crystallization of p-sexiphenyl(p-6P) for organic thin-film transistors (OTFTs). Different sizes and shapes of p-6P grains were measured by atomic force microscopy (AFM), and results showed that the large size of p-6P grain can improve the performance of OTFTs. About 900 nm thick films can be easily fabricated by spin-coating under ambient conditions, followed by curing at UV irradiation for 10 min. OTFTs with this film as gate insulator were found to have good processability, a high charge-carrier mobility of 1.1 cm²/V s, a threshold voltage of −25 V, and an on/off current ratio >10⁵. The result indicated that this material is a promising candidate for the exploration of devices using OTFTs.     

High-resolution patterned nanoparticulate Ag electrodes toward all printed organic thin film transistors

High-resolution patterned nanoparticulate Ag electrode arrays and all printed organic thin film transistors (OTFTs) were demonstrated using a simple dip-casting and a photoresist-free, non-relief-pattern lithographic process. An octadecyltrichlorosilane self-assembled monolayer was deposited to provide low surface energy and patterned by deep ultraviolet light, resulting in reproducible periodic arrays of patterned hydrophilic domains separated from hydrophobic surroundings. Using a simple dip-casting with optimal withdrawal speed, viscosity, and solvent polarity, dot size and electrode width of less than 1 μm and 5 μm were obtained, respectively. All printed OTFTs were fabricated. Ink-jet printed 6,13-bis(triisopropyl-silylethynyl) pentacene OTFTs including high-resolution patterned nanoparticulate Ag source/drain electrodes (L < 10 μm) have shown similar performance to the OTFTs with photolithographically patterned electrodes.     

Thermal annealing effect on electrical properties of metal nitride gate electrodes with hafnium oxide gate dielectrics in nano-metric MOS devices

Electrical properties of hafnium oxide (HfO₂) gate dielectric with various metal nitride gate electrodes, i.e., tantalum nitride (TaN), molybdenum nitride (MoN), and tungsten nitride (WN), were studied over a range of HfO₂ thicknesses, e.g., 2.5-10 nm, and post-metal annealing (PMA) temperatures, e.g., 600 °C to 800 °C. The work function of the nitride gate electrode was dependent on the material and the post-metal annealing (PMA) temperature. The scanning transmission electron microscopy technique is used to observe the effect of PMA on the interfacial gate dielectric thickness. After high-temperature annealing, the metal nitride gates were suitable for NMOS. At the same PMA temperature, the oxide-trapped charges increased and the interface state densities decreased with the increase of the HfO₂ thickness for TaN and WN gate electrodes. However, for MoN gate electrode the interface state density is almost independent of film thickness. Therefore, dielectric properties of the HfO₂ high-k film depend not only on the metal nitride gate electrode material but also the post-metal annealing condition as well as the film thickness. During constant voltage stress of the MOS capacitors, an increase in the time-dependent gate leakage current is also observed.     

UV-directly patternable organic–inorganic hybrid composite dielectrics for organic thin-film transistors

A research on the design, synthesis, and characterization of novel cross-linked polymer organic–inorganic hybrid materials as gate insulators for organic thin-film transistors (OTFTs) with vanadyl-phthalocyanine as the organic semiconductor is presented. The hybrid films (0.5–1.2 μm thick) can be easily prepared by sol–gel technology and fabricated by spin-coating a mixture of zirconium n-butoxide sol with a side-chain triethoxysilane-capped polyurethane solution in ambient conditions, followed by curing at low temperatures (∼120 °C) and cross-linking under UV light. OTFTs with this film as gate insulator were achieved with good processability, high charge-carrier mobility of 0.56 cm²/Vs, surface roughness of around 0.49–0.59 nm, ultralow threshold of −6 V, and ultralow leakage of 0.24 mA. Hybrid films with various compositions were investigated, and the results showed that the field-effect mobility of the OTFTs was dominated by the high dielectric constant component ZrO₂. The result indicated that these hybrid materials are promising candidates for the exploration of devices using OTFTs.     

Direct writing of inkjet-printed short channel organic thin film transistors

A direct-writing fabrication process for fully inkjet-printed short-channel organic thin-film transistors (OTFTs) has been developed. Channels as narrow as 800 nm between two printed Ag electrodes were achieved by printing a special Ag ink on an SU-8 interlayer, which can be partially dissolved by the solvents used in the Ag ink. The ridge formed along the printed Ag line edges due to redistribution of the interlayer material during the drying process limits the ink spread, and separates neighboring printed lines, and is the key to defining an ultra-narrow channel for transistor fabrication. The short-channel OTFTs fabricated using this technique have demonstrated well-defined linear and saturation regimes. An extracted mobility of 0.27 cm²/Vs with an on/off ratio of 10⁵ was obtained at a driving voltage of −12 V. The excellent performance of these devices demonstrates the potential of this technique in fabrication of short-channel devices using standard printing technologies.     

UV-curable organic–inorganic hybrid gate dielectrics for organic thin film transistors

UV-curable hybrid thin films were prepared from ZrO₂ hybrid sols containing the acrylic monomer, DPHA, on substrates. The prepared ZrO₂ hybrid sols showed long-term storage stability. Hybrid dielectrics were prepared by sol–gel process and UV cross-linking below 160 °C. Leakage currents of dielectric layers remained below 10⁻⁶ A in 2 MV/cm and dielectric constants were measured to be 3.85–4 at 1 kHz. In addition, organic–inorganic hybrid thin films have smooth and hydrophobic surface. Pentacene OTFTs with thin hybrid dielectrics exhibit of mobility as large as 2.5 cm²/V s, subthreshold swing as low as 0.2 V/decade, an on–off ratio of 10⁵. These results demonstrated that UV-curable sol–gel hybrid systems are suitable for gate dielectrics in OTFTs.     

Effect of RuO2 electrode on laser-MBE prepared HfO2 gate dielectrics

In this paper, we report our recent study of the effect of RuO₂ as an alternative top electrode for pMOS devices to overcome the serious problems of polysilicon (poly-Si) gate depletion, high gate resistance and dopant penetration in the trend of down to 50 nm devices and beyond. The conductive oxide RuO₂, prepared by RF sputtering, was investigated as the gate electrode on the Laser MBE (LMBE) fabricated HfO₂ for pMOS devices. Structural, dielectric and electric properties were investigated. RuO₂/HfO₂/n-Si capacitors showed negligible flatband voltage shift (<10 mV), very strong breakdown strength (>10 MV cm⁻¹). Compared to the SiO₂ dielectric with the same EOT value, RuO₂/HfO₂/n-Si capacitors exhibited at least 4 orders of leakage current density reduction. The work function value of the RuO₂ top electrode was calculated to be about 5.0 eV by two methods, and the effective fixed oxide charge density was determined to be 3.3 × 10¹² cm⁻². All the results above indicate that RuO₂ is a promising alternative gate electrode for LMBE grown HfO₂ gate dielectrics.     

All-solution-processed foldable transparent electrodes of Ag nanowire mesh and metal matrix films for flexible electronics

In this study, we developed foldable transparent electrodes composed of Ag nanowire (AgNW) networks welded by Ag nanoparticles (AgNPs) reduced from commercial Ag ink. All the processes used were solution-based. Using the Meyer rod method, uniform AgNW networks were roll-to-roll coated on large-area polymer substrates, and the spin-coated AgNPs firmly welded the AgNWs together at junctions and to substrates. The hybrid films consisting of AgNWs and the Ag film matrix exhibited higher electrical conductivity (5.0–7.3 × 10⁵ S/m) than and equivalent transparency (90–95%) to the AgNW networks. Furthermore, the hybrid films showed significantly better bending stability than AgNW networks. During cyclic bending tests to 10,000 cycles at 5 mm bending radius and even when almost folded with r_b of 1 mm, the resistivity changes were negligible because AgNWs were tightly held and adhered to the substrate by Ag films covering wires, thereby hindering fracturing of AgNWs under tension. Because the films were fabricated at a low temperature, there was no oxidation on the surfaces of the films. Hence, flexible organic light-emitting diodes (f-OLEDs) were successfully fabricated on polyethylene terephthalates (PET) coated with the hybrid films. The f-OLED in the bent state was comparable to that in the flat state, validating the potential applications of these transparent hybrid films as electrodes in various flexible electronics.     

Growth of rubrene crystalline thin films using thermal annealing on DPPC LB monolayer

High crystalline thin films of 5,6,11,12-tetraphenylnaphthacene (rubrene) can be obtained after in situ thermal post annealing using SiO₂ gate dielectric modified with a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayer obtained via Langmuir–Blodgett transfer. Such formed rubrene crystalline films are interconnected and highly ordered with defined molecular orientation. Organic thin film transistors (OTFTs) with high performance are reproducibly demonstrated with the mobility of 0.98 cm²/V s, the threshold voltage of −8 V and the on–off current ratio of higher than 10⁷. The results indicate that our approach is a promising one for preparing high quality rubrene crystalline films.