Oriented growth of rubrene thin films on aligned pentacene buffer layer and its anisotropic thin-film transistor characteristics

Oriented growth of polycrystalline rubrene thin film on oriented pentacene buffer layer was investigated. The oriented pentacene buffer layer was created by thermal evaporation of pentacene on a rubbed polyvinylalcohol (PVA) surface. The pentacene layer in turn induced the oriented growth of rubrene crystals upon thermal deposition. The structures of successive layers were characterized by using grazing incidence X-ray diffraction (GIXD) and atomic force microscopy. Highly oriented rubrene crystallites with the a-axis aligning along the surface normal and the (0 0 2) plane preferentially oriented 45° away from the rubbing direction were found. In contrast, the rubrene thin film deposited on PVA or rubbed-PVA substrate without a pentacene buffer layer only gave amorphous phases. With the aligned pentacene/rubrene film as the active layer of organic field-effect transistor, anisotropic mobilities were observed. The highest field-effect mobility (0.105 cm²/V s) was observed along the direction 45° away from the rubbing direction and is ∼4 times higher than that for similar device prepared on unrubbed PVA. The direction was consistent with the GIXD observation that a large number of rubrene crystallites are having their [0 0 2] direction aligning in this direction. A favourable C–H⋯π interaction between an oriented pentacene layer and the rubrene layer on the control of molecular orientation in the conduction channel of the OFET is suggested.     

Addressable growth of oriented organic semiconductor ultra-thin films on hydrophobic surface by direct dip-coating

Oriented organic field-effect transistor (OFET) stripe arrays on hydrophobic substrates were fabricated by fast dip-coating technique. The addressable growth was achieved by decreasing surface energy of the channel areas with respect to the electrodes via hydrophobic treatment. The higher surface energy of the electrodes allows solution to adhere and then organic semiconductors nucleate and bridge the channels after evaporation of the solvent. Area-selective behaviour can be controlled by adjusting surface property of transistor channel, geometry features of the gold electrodes, pulling speed and evaporation atmosphere. The mechanism behind is the competition between receding of the solution and evaporating of the solvent that generate the organic semiconductor films on the substrate. The patterned bottom-contact transistor arrays exhibit carrier mobility of 2.0 × 10⁻³ cm² V⁻¹ s⁻¹, while no field-effect characteristics can be detected for bottom-contact arrays without hydrophobic treatment. Such reliable, fast and solution-based patterned OFET arrays are highly desirable for large-scale and low-cost production.     

Hybridization of a low-temperature processable polyimide gate insulator for high performance pentacene thin-film transistors

We have synthesized a novel fully soluble and low-temperature processable polyimide gate insulator (KSPI) through the one-step condensation polymerization of the monomers 5-(2,5-dioxytetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride and 4,4-diaminodiphenylmethane. Fully imidized KSPI was found to be completely soluble in organic solvents such as N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), γ-butyrolactone, dimethylsulfoxide (DMSO), and 2-butoxyethanol. Thin films of KSPI can be fabricated at only 150 °C and a pentacene OTFT with KSPI as a gate dielectric was found to exhibit a field effect mobility of 0.22 cm²/V s. To obtain a high performance organic thin-film transistor (OTFT), the KSPI surface was modified in our new technique by hybridization with a non-polar side chain containing a polyimide insulator (PI). The carrier mobility of a pentacene OTFT with a hybridized polyimide gate insulator (BPI-3) was found to be 0.92 cm²/V s. Our new low-temperature processable polyimides show promise as gate dielectrics for OTFTs.     

Pentacene organic thin-film transistors with solution-based gelatin dielectric

Gelatin is a natural protein in the field of food, pharmaceutical and tissue engineering, which works very well as the gate dielectric for pentacene organic thin-film transistors (OTFTs). An aqueous solution process has been applied to form a gelatin thin film on poly(ethylene terephthalate) (PET) or glass by spin-coating and subsequent casting. The device performance of pentacene OTFTs depend on the bloom number (molecular weight) of gelatin. The pentacene OTFT with 300 bloom gelatin as the gate dielectric in air ambient exhibits the best performance with an average field-effect mobility (μ_FE) value of ca. 16 cm² V^?1 s^?1 in the saturation regime and a low threshold voltage of ?1 V. The high performance of the pentacene OTFT in air ambient is attributed to the water resided in gelatin. The crystal quality of pentacene is not the key factor for the high performance.     

High-performance pentacene field-effect transistors using Al2O3 gate dielectrics prepared by atomic layer deposition (ALD)

High-performance pentacene field-effect transistors have been fabricated using Al₂O₃ as a gate dielectric material grown by atomic layer deposition (ALD). Hole mobility values of 1.5 ± 0.2 cm²/V s and 0.9 ± 0.1 cm²/V s were obtained when using heavily n-doped silicon (n⁺-Si) and ITO-coated glass as gate electrodes, respectively. These transistors were operated in enhancement mode with a zero turn-on voltage and exhibited a low threshold voltage (< −10 V) as well as a low sub-threshold slope (<1 V/decade) and an on/off current ratio larger than 10⁶. Atomic force microscopy (AFM) images of pentacene films on Al₂O₃ treated with octadecyltrichlorosilane (OTS) revealed well-ordered island formation, and X-ray diffraction patterns showed characteristics of a “thin film” phase. Low surface trap density and high capacitance density of Al₂O₃ gate insulators also contributed to the high performance of pentacene field-effect transistors.     

High-performance thin-film transistor with 6,13-bis(triisopropylsilylethynyl) pentacene by inkjet printing

We have studied the performance improvement of organic thin-film transistor (OTFT) with a solution based TIPS pentacene (6,13-bis(triisopropylsilylethynyl)pentacene) by inkjet printing. The TIPS pentacene with 1.0 wt.% solution in 1,2-dichlorobenzene was used for printing of an active layer of OTFT. The OTFT printed at room temperature shows a shoulder-like behavior but it disappears for the OTFT printed at the substrate temperature of 60 °C. The OTFT on plastic exhibited an on/off current ratio of ∼10⁷, a threshold voltage of −2.0 V, a gate voltage swing of 0.6 V/decade and a field-effect mobility of 0.24 cm²/Vs in the saturation region.     

Charge carrier mobility study of a mesogenic thienothiophene derivative in bulk and thin films

A novel mesogenic 2,5-bis-(5-octylthiophene)-thieno[3,2b]thiophene (TT) derivative has been synthesized. The fused-ring thiophene, end-capped with two octylthiophenes, exhibits ordered lamellar mesophases which were characterized by polarizing optical microscopy, differential scanning calorimetry and small-angle X-ray diffraction at various temperatures. The charge transport properties were investigated by time-of-flight technique as a function of temperature. On cooling from isotropic phase, a maximum hole mobility value of 0.07 cm² V⁻¹ s⁻¹ was measured in the highly ordered mesophase of the bulk films. Field-effect transistor experiments on both solution and vacuum deposited thin films have also been performed. The solution-processed films exhibit charge carrier mobilities several orders of magnitude lower than values extracted from bulk time-of-flight curves and from vacuum deposited thin film transistors. This work provides evidence that the melt-processing route is an efficient alternative to commonly used solution-processing for fabrication of charge transporting layers from liquid crystalline semiconductors, with performances comparable to evaporation techniques.     

Inkjet-printed copper electrodes using photonic sintering and their application to organic thin-film transistors

We report on copper (Cu) electrodes fabricated with inkjet-printed nanoparticle inks that are photonic sintered on a polymer dielectric layer and their application to source and drain electrodes in organic thin-film transistor (TFT). By using photonic sintering with a radiant energy density of 9 J/cm², printed Cu nanoparticle layers on a glass substrate showed very low electrical resistivity levels of 7 μΩ cm. By optimizing the sintering conditions on polymer dielectric, the pentacene-based TFT using these printed Cu electrodes showed good mobility levels of 0.13 cm²/Vs and high on/off current ratios of about 10⁶. In addition, we revealed that the crystal grain growth of pentacene near the printed Cu electrodes was inhibited by the thermal damage of polymer underlayer due to the high radiant energy density of the intense light.     

Increased photooxidation stability of pentacene derivatives linked with aromatic groups for OTFTs

Pentacene derivatives linked with aromatic groups at the 6,13-positions have been synthesized and characterized for their photooxidation properties. They exhibit high solubility which provides low-cost solution deposition methods. However, most of them are highly susceptible to photooxidation in solution determined with a few minutes of their half-life time under ambient conditions, practically precluding them from solution fabrication applications. Interestingly, their photooxidation stability can be significantly increased by blocking out light. The thin film transistor device for 3,4,5-trifluorophenyl-substituted pentacene (2c) showed the highest mobility of 1.1 × 10⁻² cm² V⁻¹ s⁻¹ with the threshold voltage of 20 V when it was prepared in the dark condition.     

Effect of the substrate temperature on the electrical and structural properties of spray-deposited SnO2:F thin films

SnO₂:F thin films were prepared by the spray pyrolysis (SP) technique at substrate temperature in the range 360–480 °C. The effect of varying the substrate temperature on the electrical and structural properties of the films was investigated by studying the I–V characteristics, the X-ray diffraction patterns (XRD), and the scanning electron microscope images (SEM). The I–V characteristics of the films were improved by increasing the substrate temperature, i.e. the resistivity of the films had decreased from 98 to 0.22 Ω cm. The X-ray diffraction patterns taken at 400 and 480 °C showed that the films are polycrystalline and two directions of crystal growth appeared in the difractogram of the film deposited at the lower substrate temperature, which correspond to the reflections from the (1 1 0) and (2 0 0) planes. With the increase in the substrate temperature a new direction of crystal growth appeared, which corresponds to the reflection from the (1 0 1) plane. Also the (1 1 0) and (2 0 0) lines were slightly grown at the higher substrate temperature, which means the crystal growth was enhanced and the grain size had increased. The SEM images confirmed these results and showed larger grains and more crystallization for the higher substrate temperature too.     

In situ modification of low-cost Cu electrodes for high-performance low-voltage pentacene thin film transistors (TFTs)

We demonstrate low-voltage pentacene thin film transistors (TFTs) using in situ modified low-cost Cu (M-Cu) as source–drain (S/D) electrodes and solution-processed high capacitance (200 nF/cm²) gate dielectrics. Under a gate voltage of ?3 V, the device with M-Cu electrodes shows a much higher apparent mobility (1.0 cm²/V s), a positively shifted threshold voltage (?0.62 V), a lower contact resistance (0.11 MΩ) and a larger transconductance (12 μS) as compared to the device with conventional Au electrodes (corresponding parameters are 0.71 cm²/V s, ?1.44 V, 0.41 MΩ, and 5.7 μS, respectively). The enhancement in the device performance is attributed to the optimized interface properties between S/D electrodes and pentacene. Moreover, after encapsulation the M-Cu electrodes with a thin layer of Au in the aim of suppressing unfavorable surface oxidation, the electronic characteristics of the device are further improved, and highly enhanced apparent mobility (2.3 cm²/V s) and transconductance (19 μS) can be achieved arising from the increased conductivity of the electrode itself. Our study provides a simple and feasible approach to achieve high performance low-voltage OTFTs with low-cost S/D electrodes, which is desirable for large area applications.     

Effect of active layer thickness on environmental stability of printed thin-film transistor

We have studied the effect of active layer thickness on the performance and environmental stability of the 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) thin-film transistor. The organic thin-film transistors (OTFTs) were fabricated by inkjet printing using a solution based TIPS pentacene. To get thick organic semiconductor, the surface of gate insulator was treated with n-octyltrichlorosilane (OTS-C₈) before jetting. The on-currents of the OTFT with ～1 μm active layer decreases a little in air, but the OTFT with 0.05 μm TIPS pentacene shows a significant degradation in drain currents.     

Low power flexible organic thin film transistors with amorphous Ba0.7Sr0.3TiO3 gate dielectric grown by pulsed laser deposition at low temperature

We deposited amorphous Ba_0.7Sr_0.3TiO₃ (BST) on silicon and plastic substrate under 110 °C by pulsed laser deposition (PLD) and use it as the dielectric of the organic transistor. Depends on the thickness of BST layer, the highest mobility of the devices can achieve 1.24 cm² V^?1 s^?1 and 1.01 cm² V^?1 s^?1 on the silicon and polyethylene naphthalate (PEN) substrate, respectively. We also studied the upward and downward bending tests on the transistors and the dielectric thin films. We found that the BST dielectric pentacene transistor can maintain the mobility at 0.5 cm² V^?1 s^?1 or higher while the bending radius is around 3 mm in both upward and downward bending. Our finding demonstrates the potential application of PLD growth high-k dielectric in the large area organic electronics devices.     

The effects of the surface morphology of poly(3,4-ethylenedioxythiophene) electrodes on the growth of pentacene,and the electrical performance of the bottom contact pentacene transistor

An investigation is presented of the effect of the surface roughness of poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes on the growth of pentacene and the electrical performance of PEDOT electrode bottom contact pentacene transistor. Smooth PEDOT films contained well-oriented and small sized pentacene islands whilst rough PEDOT films exhibited randomly oriented islands with non-uniformly sized islands. In addition, PEDOT electrodes provided morphological continuity at the electrode–channel interface, making the accumulation channel of the pentacene formed on the electrodes a main contributor to the contact resistance. Accordingly, the smooth PEDOT surface yielded the low contact resistance (5.7 kΩ cm), approximately half of that obtained with the rough surface.     

Functionalized terfluorene for solution-processed high efficiency blue fluorescence OLED and electrophosphorescent devices

A new multifunctional blue-emitting terfluorene derivative (TFDPA) featured with triphenylamine groups for hole-transportation and long alkyl chains for solution processability on the conjugation inert bridge centers was reported. TFDPA can give homogeneous thin film by solution process and exhibits high hole mobility (μ_h ≈ 10^?3 cm² V^?1 s^?1) and suitable HOMO for hole injection. Particularly, TFDPA performs efficient deep-blue emission with high quantum yield (～100% in solution, 43% in thin film) and suitable triplet energy (E_T = 2.28 eV), making solution-processed OLED devices of using TFDPA as blue emitter and as host for iridium-containing phosphorescent dopants feasible. The solution-processed nondoped blue OLED device gives saturated deep-blue electroluminescence [CIE = (0.17, 0.07)] with EQE of 2.7%. TFDPA-hosted electrophosphorescent devices performed with EQE of 6.5% for yellow [(Bt)₂Ir(acac)], 9.3% of orange [Ir(2–phq)₃], and 6.9% of red [(Mpq)₂Ir(acac)], respectively. In addition, with careful control on the doping concentration of [(Bt)₂Ir(acac)], a solution-processed fluorescence–phosphorescence hybrided two-color-based WOLED with EQE of 3.6% and CIE coordinate of (0.38, 0.33) was successfully achieved.     

Improving solution-processed n-type organic field-effect transistors by transfer-printed metal/semiconductor and semiconductor/semiconductor heterojunctions

Solution-processed n-type organic field effect transistors (OFETs) are in need of proper metal contact for improving injection and mobility, as well as balanced hole mobility for building logic circuit units. We address the two distinct problems by a simple technique of transfer-printing. Transfer-printed Au contacts on a terrylene-based semiconductor (TDI) significantly reduced the inverse subthreshold slope by 5.6 V/dec and enhanced the linear mobility by over 5 times compared to evaporated Au contacts. Hence, devices with a high-work-function metal (Au) are comparable with those with low-work-function metals (Al and Ca), indicating a fundamental advantage of transfer-printed electrodes in electron injection. We also transfer-printed a poly(3-hexylthiophene) (P3HT) layer onto TDI to construct a double-channel ambipolar transistor by a solution process for the first time. The transistor exhibits balanced hole and electron mobility (3.0 × 10⁻³ and 2.8 × 10⁻³ cm² V⁻¹ s⁻¹) even in a coplanar structure with symmetric Au electrodes. The technique is especially useful for reaching intrinsic mobility of new materials, and enables significant enlargement of the material tanks for solution-processed functional heterojunction OFETs.     

Enhanced organic ferroelectric field effect transistor characteristics with strained poly(vinylidene fluoride-trifluoroethylene) dielectric

Poly(vinylidene fluoride-trifluoroethylene) (70–30 mol%) was used as the functional dielectric layer in organic ferroelectric field effect transistors (FeFET) for non-volatile memory applications. Thin P(VDF-TrFE) film samples spin-coated on metallized plastic substrates were stretch-annealed to attain a topographically flat-grain structure and greatly reduce the surface roughness and current leakage of semi-crystalline copolymer film, while enhancing the preferred β-phase of the ferroelectric films. Resultant ferroelectric properties (P_R = |10| μC/cm², E_C = |50| MV/m) for samples simultaneously stretched (50–70% strain) and heated below the Curie transition (70 ^oC) were comparable to those resulting from high temperature annealing (>140 ^oC). The observed enhancements by heating and stretching were studied by vibration spectroscopy and showed mutual complementary effects of both processes. Organic FeFET fabricated by thermal evaporating pentacene on the smooth P(VDF-TrFE) films showed substantial improvement of semiconductor grain growth and enhanced electrical characteristics with promising non-volatile memory functionality.     

Defect modification in ZnInSnO transistor with solution-processed Al2O3 dielectric by annealing

The properties of solution-processed Al₂O₃ thin films annealed at different temperatures were thoroughly studied through thermogravimetry–differential thermal analysis, UV–vis-NIR spectrophotometer measurements, scanning electron microscopy, X-ray diffraction, atomic force microscopy and a series of electrical measurements. The solution-processed ZnInSnO thin films transistors (TFTs) with the prepared Al₂O₃ dielectric were annealed at different temperatures. The TFTs annealed at 600 °C have displayed excellent electrical performance such as the field-effect mobility of 116.9 cm² V⁻¹ s⁻¹ and a subthreshold slope of 93.3 mV/dec. The performance of TFT device could be controlled by adjusting the annealing temperature. The results of two-dimensional device simulations demonstrate that the improvement of device performance are closely related with the reduction of interface defects between channel and dielectric and subgap density of stats (DOS) in the channel layer.     

Solution-processed organic field-effect transistors composed of poly(4-styrene sulfonate) wrapped multiwalled carbon nanotube source/drain electrodes

Multiwalled carbon nanotubes (MWNTs) were solubilized in water by wrapping them noncovalently with poly(4-styrene sulfonate) (PSS). The PSS-wrapped MWNTs exhibited a high conductivity (2.0 × 10² S/cm) when compared to other solution-processed electrodes. Ultraviolet photoelectron spectroscopy results show the PSS-wrapped nanotubes have a work function of 4.83 eV, which is 0.36 eV higher than that of untreated MWNTs. We fabricated triisopropylsilylethynyl pentacene field-effect transistors (FETs) using the PSS-wrapped MWNTs as source/drain electrodes and found that the field-effect mobility of the thus obtained devices was 0.043 cm² V^?1 s^?2. This mobility is four times higher than that of similar FETs containing gold electrodes (0.011 cm² V^?1 s^?2).     

Multihydroxylated aryl amine as a novel alcohol-processable hole-transport molecular glass exhibiting remarkable resistance to weakly polar solvents

Multihydroxylation of a small-molecule aryl amine leads to a contrasting solubility in polar and weakly polar solvents. The resulting compound shows an intrinsic amorphous morphology with a high T_g of 190 °C and is capable of affording uniform smooth and transparent films, spin-cast from 2-propanol. The fitting of the space-charge-limited current characteristics reveals a hole mobility of ～4.6 × 10^?6 cm² V^?1 s^?1 at low-voltages. Incorporating this new compound as a hole-transport layer into conventional bottom-anode organic light-emitting diodes that consisted of a solution-processed emitter provides promising performance.