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.     

Interface optimization using diindenoperylene for C60 thin film transistors with high electron mobility and stability

C₆₀-based organic thin film transistors (OTFTs) with high electron mobility and high operational stability are achieved with (1 1 1) oriented C₆₀ films grown by using template effects of diindenoperylene (DIP) under layer on the SiO₂ gate insulator. The electron mobility of the C₆₀ transistor is significantly increased from 0.21 cm² V⁻¹ s⁻¹ to 2.92 cm² V⁻¹ s⁻¹ by inserting the template-DIP layer. Moreover much higher operational stability is also observed for the DIP-template C₆₀ OTFTs. A grazing incidence X-ray diffraction and ultrahigh-sensitivity photoelectron spectroscopy measurements indicate that the improved electron mobility and stability arise from the decreased density of trap states in the C₆₀ film due to increased (1 1 1) orientation of C₆₀-grains and their crystallinity on the DIP template.     

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.     

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.     

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.     

Morphology transformations of pentacene on an UV-patternable polymer insulator and their effect on performance of flexible organic thin-film transistors

This work presents a low temperature with high resolution capability UV-patternable polymer, i.e. mr-UVCur06, for use as a gate insulator in OTFTs, by investigating the morphology transformation of pentacene deposited on the mr-UVCur06. The device structure is polyethylene terephthalate (PET)/indium-tin oxide (ITO)/mr-UVCur06/pentacene/Au (source/drain). In addition to its solution-processable capability, mr-UVCur06 is directly patterned by UV light in a low-temperature process. UV/ozone post-treatment of the patternable mr-UVCur06 can illuminate organic contaminants from its surface and increases surface energy. Experimental results indicate that a high surface energy existing at the mr-UVCur06 surface has produced in a larger ratio of I_{thin film phase}/I_{triclinic bulk phase} in pentacene. Then, the distance of pentacene molecular crystal structure, which is arranged in the thin film phase, is shorter than that in triclinic bulk phase. The performance of pentacene-based OTFTs can be enhanced with few contaminants and a high surface energy on the UV-patternable gate insulator. By performing UV/ozone post-treatment on the mr-UVCur06 insulator surface for 60 s, the OTFTs demonstrate a mobility, on/off drain current ratio, and V_T of 0.34 cm²/V s, 5.5 × 10⁴, and 2.5 V, respectively. Furthermore, the low-temperature photopatternable polymer dielectric paves the way for a relatively easy and low-cost fabrication of an OTFT array without expensive and complicated photolithography and dry etching.     

Solvent-vapor induced self-assembly of a conjugated polymer: A correlation between solvent nature and transistor performance

A systematical investigation on solvent-vapor annealing in polymer thin film transistors is performed using a thiazolothiazole-bithiazole conjugated polymer as the active layer. Film morphology, packing order and device performance are closely related to polarity and solubility parameter of the annealing solvent and annealing time. The formation of highly ordered and closely connected fibrillar domains is realized by using a solvent with similar solubility parameter and polarity to the conjugated polymer. Field-effect transistors based on pristine polymer films exhibit a highest charge carrier mobility of 0.0067 cm² V⁻¹ s⁻¹. After solvent vapor annealing with THF for 48 h, the mobility boosts up to 0.075 cm² V⁻¹ s⁻¹. This correlation between solvent polarity, solubility parameter and film morphology, packing order and mobility provides a useful guideline towards high performance polymer thin film transistors with solvent-vapor annealing method.     

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.     

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 the Ag content on the geometrical and electrical characteristics of the screen-printed etched gate electrodes of OTFTs using Ag ink

During the fabrication of gate electrodes by Ag ink screen-printing combined with a wet-etching process, the effects of the Ag content on the geometrical and electrical characteristics such as the thickness and surface roughness of gate electrode, step coverage with the gate dielectric, leakage current associated with the step coverage, and the electrical performance of organic thin film transistors (OTFTs) were investigated. An increase of Ag content resulted in the thick and densely-packed Ag electrode, which had a stable and excellent conductivity. But, the large thickness of Ag electrode caused the worse step coverage of PVP (polyvinylphenol) dielectric layer on the edge of the Ag gate electrode, therefore, for Ag contents more than 40 wt.%, MIM (metal-insulator-metal) devices and OTFTs with the Ag gate electrodes had very large leakage current (>10⁻⁴ A/cm²) and off-state current (>∼19 pA/μm) due to the poor step coverage of PVP dielectric layers, respectively. Finally, we found that an Ag content of 20-30 wt.% was suitable for the screen-printed etched gate electrode of OTFTs using Ag ink. This range generated a mobility of 0.18 cm²/V s, an on/off current of 5 × 10⁶, and an off-state current of 0.002 pA/μm, which are suitable to drive e-paper.     

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.     

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.     

Mobility enhancement by using silk fibroin in F16CuPc organic thin film transistors

High performance n-type F₁₆CuPc organic thin-film transistors (OTFTs) were fabricated on polyethylene terephthalate (PET) using silk fibroin as the gate dielectric. The average field-effect mobility (μ_FE) value in the saturation regime is 0.39 cm² V⁻¹ s⁻¹ approximately one order of magnitude higher than the reported values in the literature. A typical F₁₆CuPc OTFT exhibits an on/off current ratio of 9.3 × 10², a low threshold voltage of 0.65 V, and a subthreshold swing value of 730 mV/decade. The enhancement of μ_FE results from very good crystal quality of F₁₆CuPc on silk fibroin, supported by grazing incidence X-ray diffraction (GIXD) data.     

Modulation of surface solubility and wettability for high-performance inkjet-printed organic transistors

The surface solubility and wettability of photosensitive layers of polystyrene (PS) were engineered to evaluate its effect on the crystalline microstructure and film morphology of inkjet-printed 6,13-bis(triisopropylsiylethynyl) pentacene (TIPS-pentacene). UV exposure proved to be a simple and effective method for modulating the solubility of PS films with controllable crosslinking. As compared with the untreated PS film, the film morphology of the printed semiconductor on the UV-irradiated crosslinked PS films was significantly optimized. The optimal degree of crosslinking and solubility of the PS film were achieved by UV irradiation at a dose of 0.417 J cm⁻². Field-effect transistors fabricated using well-organized crystals on the optimal crosslinked PS film exhibited a maximum mobility of 0.48 cm² V⁻¹ s⁻¹ and an average value of 0.19 cm² V⁻¹ s⁻¹. The performance is clearly superior to that of devices prepared on a pristine PS film (0.02 cm² V⁻¹ s⁻¹).     

Transfer printing approach to all-carbon nanoelectronics

Transfer printing methods are used to pattern and assemble monolithic carbon nanotube (CNT) thin-film transistors on large-area transparent, flexible substrates. Airbrushed CNT thin-films with sheet resistance 1 kΩ sq⁻¹ at 80% transparency were used as electrodes, and high quality chemical vapor deposition (CVD)-grown CNT networks were used as the semiconductor component. Transfer printing was used to pre-pattern and assemble thin film transistors on polyethylene terephthalate (PET) substrates which incorporated Al₂O₃/poly-methylmethacrylate (PMMA) dielectric bi-layer. CNT-based ambipolar devices exhibit field-effect mobility in range 1-33 cm²/V s and on/off ratio ∼10³, comparable to the control devices fabricated using Au as the electrode material.     

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.     

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.     

Laser-assisted patterning of solution-processed oxide semiconductor thin film using a metal absorption layer

We present a method to pattern solution-processed oxide semiconductor thin films by all laser process. A metal thin film is first photoetched by a spatially-modulated pulsed Nd-YAG laser beam and this layer is then covered with a semiconductor film. Uniform irradiation by the same laser generates a thermo-elastic force on the underlying metal layer and this force serves to detach it from the substrate, leaving only a patterned semiconductor structure. Sharp-edged zinc-tin oxide (ZTO) patterns at the micrometer scales could be fabricated over a few square centimeters by a single pulse of 850 mJ. A mobility of 7.6 × 10⁻² cm² V⁻¹ s⁻¹, an on/off ratio higher than 10⁶, and an off-current of 1.91 × 10⁻¹¹ A were achieved from a thin film transistor (TFT) with the patterned ZTO channel. These values were similar to those from a reference TFT, demonstrating the feasibility of this patterning process for electronic devices.     

Phospholipid film in electrolyte-gated organic field-effect transistors

A totally innovative electrolyte-gated field effect transistor, embedding a phospholipid film at the interface between the organic semiconductor and the gating solution, is described. The electronic properties of OFETs including a phospholipid film are studied in both pure water and in an electrolyte solution and compared to those of an OFET with the organic semiconductor directly in contact with the gating solution. In addition, to investigate the role of the lipid layers in the charge polarization process and quantify the field-effect mobility, impedance spectroscopy was employed. The results indicate that the integration of the biological film minimizes the penetration of ions into the organic semiconductor thus leading to a capacitive operational mode as opposed to an electrochemical one. The OFETs operate at low voltages with a field-effect mobility in the 10⁻³ cm² V⁻¹ s⁻¹ range and an on/off current ratio of 10³. This achievement opens perspectives to the development of FET biosensors potentially capable to operate in direct contact with physiological fluids.     

Pentacene thin-film transistors with sol-gel derived amorphous Ba0.6Sr0.4TiO3 gate dielectric

An amorphous Ba_0.6Sr_0.4TiO₃ (BST) film with the thickness of 200 nm was deposited on indium-tin-oxide (ITO)-coated glass substrate through sol-gel route and post-annealing at 500 °C. The dielectric constant of the BST film was determined to be 20.6 at 100 kHz by measuring the Ag/BST/ITO parallel plate capacitor, and no dielectric tunability was observed with the bias voltage varying from −5 to 5 V. The BST film shows a dense and uniform microstructure as well as a smooth surface with the root-mean-square (RMS) roughness of about 1.4 nm. The leakage current density was found to be 3.5 × 10⁻⁸ A/cm² at an applied voltage of −5 V. The transmittance of the BST/ITO/glass structure is more than 70% in the visible region. Pentacene based transistor using the as-prepared BST film as gate insulator exhibits a low threshold voltage of −1.3 V, the saturation field-effect mobility of 0.68 cm²/Vs, and the current on/off ratio of 3.6 × 10⁵. The results indicate that the sol-gel derived BST film is a promising high-k gate dielectric for large-area transparent organic transistor arrays on glass substrate.