Organic field-effect transistors based on low-temperature processable transparent polymer dielectrics with low leakage current

A solution-based transparent polymer was investigated as the gate dielectric for organic field-effect transistors (OFETs). Organic thin films (400 nm) are readily fabricated by spin-coating a polyhydrazide solution under ambient conditions on the ITO substrates, followed by annealing at a low temperature (120 °C). The smooth transparent dielectrics exhibited excellent insulating properties with very low leakage current densities of ～10^?8 A/cm². High performance OFETs with evaporated pentacene as organic semiconductor function at a low operate voltage (?15 V). The mobility could reach as high as 0.7 cm²/Vs and on/off current ratio up to 10⁴. Solution-processed TIPS-pentacene OFETs also work well with this polymer dielectric.     

D–A copolymer with high ambipolar mobilities based on dithienothiophene and diketopyrrolopyrrole for polymer solar cells and organic field-effect transistors

Donor–acceptor (D–A) type conjugated polymers have been developed to absorb longer wavelength light in polymer solar cells (PSCs) and to achieve a high charge carrier mobility in organic field-effect transistors (OFETs). PDTDP, containing dithienothiophene (DTT) as the electron donor and diketopyrrolopyrrole (DPP) as the electron acceptor, was synthesized by stille polycondensation in order to achieve the advantages of D–A type conjugated polymers. The polymer showed optical band gaps of 1.44 and 1.42 eV in solution and in film, respectively, and a HOMO level of 5.09 eV. PDTDP and PC₇₁BM blends with 1,8-diiodooctane (DIO) exhibited improved performance in PSCs with a power conversion efficiency (PCE) of 4.45% under AM 1.5G irradiation. By investigating transmission electron microscopy (TEM), atomic force microscopy (AFM), and the light intensity dependence of J_SC and V_OC, we conclude that DIO acts as a processing additive that helps to form a nanoscale phase separation between donor and acceptor, resulting in an enhancement of μ_h and μ_e, which affects the J_SC, EQE, and PCE of PSCs. The charge carrier mobilities of PDTDP in OFETs were also investigated at various annealing temperatures and the polymer exhibited the highest hole and electron mobilities of 2.53 cm² V⁻¹ s⁻¹ at 250 °C and 0.36 cm² V⁻¹ s⁻¹ at 310 °C, respectively. XRD and AFM results demonstrated that the thermal annealing temperature had a critical effect on the changes in the crystallinity and morphology of the polymer. The low-voltage device was fabricated using high-k dielectric, P(VDF-TrFE) and P(VDF-TrFE-CTFE), and the carrier mobility of PDTDP was reached 0.1 cm² V⁻¹ s⁻¹ at V_d = −5 V. PDTDP complementary inverters were fabricated, and the high ambipolar characteristics of the polymer resulted in an output voltage gain of more than 25.     

Low-voltage,high speed inkjet-printed flexible complementary polymer electronic circuits

We report the development of high-performance inkjet-printed organic field-effect transistors (OFETs) and complementary circuits using high-k polymer dielectric blends comprising poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) and poly(methyl methacrylate) (PMMA) for high-speed and low-voltage operation. Inkjet-printed p-type polymer semiconductors containing alkyl-substituted thienylenevinylene (TV) and dodecylthiophene (PC12TV12T) and n-type P(NDI2OD-T2) OFETs showed high field-effect mobilities of 0.1–0.4 cm² V^?1 s^?1 and low threshold voltages down to 5 V. These OFET properties were modified by changing the blend ratio of P(VDF-TrFE) and PMMA. The optimum blend – a 7:3 wt% mixture of P(VDF-TrFE) and PMMA – was successfully used to realize high-performance complementary inverters and ring oscillators (ROs). The complementary ROs operated at a supplied bias (V_DD) of 5 V and showed an oscillation frequency (f_osc) as high as ～80 kHz at V_DD = 30 V. Furthermore, the f_osc of the complementary ROs was significantly affected by a variety of fundamental parameters such as the electron and hole mobilities, channel width and length, capacitance of the gate dielectrics, V_DD, and the overlap capacitance in the circuit configuration.     

Polymer nanocomposite dielectric based on P(VDF-TrFE)/PMMA/BaTiO3 for TIPs-pentacene OFETs

TIPs-pentacene OFETs were fabricated on a plastic substrate using polymer nanocomposite dielectric. The blend polymer P(VDF-TrFE)/PMMA (30 wt%) was used as polymer matrix and BaTiO₃ nanoparticles modified by 3-glycidoxypropyltrimethoxysilane (GPTMS) were dispersed as ceramic fillers. The effects of different loadings of BaTiO₃ on the surface morphology and electrical properties of dielectric films were investigated. The formulation of screen-printable dielectric ink of P(VDF-TrFE)/PMMA/BaTiO₃/Silica (SII) was achieved by adding fumed silica as the viscosity modifier. TIPs-pentacene OFETs using SII as the gate dielectric features a mobility of 0.01 cm²/V s, and having a threshold voltage of −6 V. This screen-printable dielectric ink is promising for low operating-voltage fully-printed OFETs.     

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

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

1 Volt organic transistors with mixed self-assembled monolayer/Al2O3 gate dielectrics

Control of the threshold voltage and the subthreshold swing is critical for low voltage transistor operation. In this contribution, organic field-effect transistors (OFETs) operating at 1 V using ultra-thin (∼4 nm), self-assembled monolayer (SAM) modified aluminium oxide layers as the gate dielectric are demonstrated. A solution-processed donor–acceptor semiconducting polymer poly(3,6-di(2-thien-5-yl)-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione)thieno[3,2-b]thiophene) (PDPP2TTT) is used as the active layer. It is shown that the threshold voltage of the fabricated transistors can be simply tuned by carefully controlling the composition of the applied SAM. The optimised OFETs display threshold voltages around 0 V, low subthreshold slopes (150 ± 5 mV/dec), operate with negligible hysteresis and show average saturated field-effect mobilities in excess of 0.1 cm²/V s at 1 V.     

Development of a new diindenopyrazine–benzotriazole copolymer for multifunctional application in organic field-effect transistors,polymer solar cells and light-emitting diodes

A new donor–acceptor (D?A) copolymer (PIPY–DTBTA) containing 6,12-dihydro-diindeno[1,2-b;1′,2′-e]pyrazine donor and benzotriazole acceptor was synthesized and characterized for multifunctional applications in organic field-effect transistors (OFETs), polymer solar cells (PSCs) and polymer light-emitting diodes (PLEDs). The polymer exhibits high molecular weights, excellent film-forming ability, a deep HOMO energy level, and good solution processability. Solution-processed thin film OFETs based on this polymer revealed good p-type characteristic with a high hole mobility up to 0.0521 cm² V^?1 s^?1. Bulk-heterojunction PSCs comprising this polymer and PC₆₁BM gave a power conversion efficiency (PCE) of 0.77%. The single-layer PLEDs based on PIPY–DTBTA emitted a yellow–red light with a maximum brightness of 385 cd m^?2 at the turn-on voltage of 6 V.     

The role of water in the device performance of n-type PTCDI-C8 organic field-effect transistors with solution-based gelatin dielectric

Gelatin is a natural protein, which works well as the gate dielectric for N,N-dioctyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C₈) organic field-effect transistors (OFETs). An aqueous solution process was applied to form the gelatin gate dielectric on poly(ethylene terephthalate) (PET) by spin-coating and subsequent casting. The field-effect mobility in the saturation regime (μ_FE,sat) and the threshold voltage (V_T) values of a typical 40 nm PTCDI-C₈ OFET are (0.22 cm² V⁻¹ s⁻¹, 55 V) in vacuum and (0.74 cm² V⁻¹ s⁻¹, 2.6 V) in air ambient. The maximum voltage shift in hysteresis is also reduced from 10 V to 2 V when the operation environment for PTCDI-C₈ OFETs is changed from vacuum to air ambient. Nevertheless, a slight reduction of electron mobility was found when the device was stressed in the air ambient. The change in the device performance has been attributed to the charged ions generation owing to water absorption in gelatin in air ambient.     

Solution-processable ambipolar organic field-effect transistor based on Co-planar bisphthalocyaninato copper

A soluble binuclear phthalocyaninato copper (II) complex, Cu₂[Pc(COOC₈H₁₇)₆]₂ (1), with planar molecular structure and extended conjugation system, has been designed and synthesized. By fusing two phthalocyanine rings side by side and introducing electron withdrawing groups at periphery positions, the energy levels of HOMO and LUMO have been tuned successfully into the range of an air-stable ambipolar organic semiconductor required as revealed by the electrochemical studies. With the help of a solution-based quasi-Langmuir–Shäfer (QLS) method, thin solid films of this compound were fabricated and organic field effect transistors (OFETs) based on these QLS thin solid films were constructed. Because of the promising electrochemical properties as well as the high ordered packing structure of the molecules in the thin solid films, the OFETs performed excellent ambipolar operating properties, with the electron and hole mobility in air as high as 1.7 × 10⁻¹ and 2.3 × 10⁻⁴ cm² V⁻¹ s⁻¹, respectively. For comparison purpose, mononuclear compound Cu[Pc(COOC₈H₁₇)₈] (2) was comparatively studied. The QLS thin solid films of this compound possess similar ordered structure with that of Cu₂[Pc(COOC₈H₁₇)₆]₂ (1), but the OFETs based on the thin solid films of this compound can only show n-type properties under nitrogen atmosphere with an extremely small electron mobility of 1.6 × 10⁻⁴ cm² V⁻¹ s⁻¹. This result suggests that extension on the conjugation system of an aromatic compound with multiple electron withdrawing groups can tune the molecule into an air stable ambipolar organic semiconductor.     

Organic field-effect transistor and its photoresponse using a benzo[1,2-b:4,5-b′]difuran-based donor–acceptor conjugated polymer

Organic field-effect transistors (OFETs) were fabricated through a solution process with a donor–acceptor (D–A) conjugated polymer poly{4,8-bis(2′-ethylhexylthiophene)benzo [1,2-b;3,4-b′]difuran-alt-5,5-(4′,7′-di-2-thienyl-5′,6′-dioctyloxy-2′,1′,3′-benzothiadiazole)} (PBDFTDTBT) as the active layer, which is a highly efficient D–A conjugated polymer as a donor in polymer solar cells with a power conversion efficiency (PCE) over 6.0%. The OFET devices showed a hole mobility of 0.05 cm²/Vs and an on/off ratio of 4.6 × 10⁵. Those are one of the best performance parameters for OFETs based on D–A conjugated polymers including benzo[1,2-b:4,5-b′]dithiophene (BDT) or benzo[1,2-b:4,5-b′]difuran (BDF) unit. The photoresponse of OFETs was investigated by modulating light with various intensities. The devices produced a photosensitivity (I_light/I_dark) of 1.2 × 10⁵ and a photoresponsivity of 360 mA W⁻¹ under white light illumination. The drain current in saturation region increases gradually with increasing illumination intensity. The threshold voltage exhibited a positive shift from −15.6 V in darkness to 27.8 V under illumination, which can be attributed to the well-known photovoltaic effect resulting from the transport of photogenerated holes and trapping of photogenerated electrons near the source electrode in organic phototransistors. Meanwhile, the devices showed good stability and with no obvious degeneration for 3 months in air. The study suggests that D–A conjugated polymers including BDF unit can be potentially applied in OFETs and organic phototransistors in addition to highly efficient polymer solar cells.     

High-performance diketopyrrolopyrrole-based organic field-effect transistors for flexible gas sensors

We demonstrate high-performance flexible polymer OFETs with P-29-DPP-SVS in various geometries. The mobilities of TG/BC OFETs are approximately 3.48 ± 0.93 cm²/V s on a glass substrate and 2.98 ± 0.19 cm²/V s on a PEN substrate. The flexible P-29-DPP-SVS OFETs exhibit excellent ambient and mechanical stabilities under a continuous bending stress of 1200 times at an R = 8.3 mm. In particular, the variation of μ_FET, V_Th and leakage current was very negligible (below 10%) after continuous bending stress. The BG/TC P-29-DPP-SVS OFETs on a PEN substrate applies to flexible NH₃ gas sensors. As the concentration of NH₃ increased, the channel resistance of P-29-DPP-SVS OFETs increased approximately 100 times from ∼10⁷ to ∼10⁹ Ω at V_SD = −5 V and V_GS = −5 V.     

High-speed organic single-crystal transistors gated with short-channel air gaps: Efficient hole and electron injection in organic semiconductor crystals

Short-channel, high-mobility organic filed-effect transistors (OFETs) are developed based on single crystals gated with short-channel air gaps. The high hole mobility of 10 cm²/Vs for rubrene, and high electron mobility of 4 cm²/Vs for PDIF-CN₂ crystals are demonstrated even with a short channel length of 6 μm. Such performance is due to low contact resistance in these devices estimated to be as low as ～0.5 kΩ cm at gate voltage of ?4 V for rubrene. With the benefit of the short channel length of 4.5 μm in a new device architecture with less parasitic capacitance, the cutoff frequency of the rubrene air–gap device was estimated to be as high as 25 MHz for drain voltage of ?15 V, which is the fastest reported for p-type OFETs, operating in ambient conditions.     

Ambipolar field-effect transistors with bilayered thiophene/phenylene co-oligomers

Bilayered organic field-effect transistors were fabricated by successive vapor-depositions of 1,4-bis{5-[4-(trifluoromethyl)phenyl]thiophene-2-yl}benzene (AC5-CF₃) and 5,5″-bis(4-biphenylyl)-2,2′:5′,2″-terthiophene (BP3T). With decreasing thickness of the n-type AC5-CF₃ film in contact with the dielectric layer, ambipolar characteristics were improved under both positive and negative gate biases. Two types of asymmetric source/drain electrodes were prepared by either obliquely shadowed lamination or mask-shifted depositions of AlLi and Au. The latter method in which the device was characterized without exposure to air after the electrode deposition of AlLi resulted in remarkable improvement of ambipolarity and reduction of leak currents. Finally, optimized ambipolar mobilities of μ_e = 5.00 × 10^?2 and μ_h = 1.56 × 10^?2 cm² V^?1 s^?1) were obtained with 5-nm-thick AC5-CF₃ and 30-nm-thick BP3T.     

High performance inkjet-printed C60 fullerene thin-film transistors: Toward a low-cost and reproducible solution process

We have demonstrated high performance inkjet-printed n-channel thin-film transistors (TFTs) using C₆₀ fullerene as a channel material. Highly uniform amorphous C₆₀ thin-film patterns were fabricated on a solution-wettable polymer gate dielectric layer by inkjet-printing and vacuum drying process. Fabricated C₆₀ TFTs shows great reproducibility and high performance; field-effect mobilities of 2.2–2.4 cm² V^?1 s^?1, threshold voltages of 0.4–0.6 V, subthreshold slopes of 0.11–0.16 V dec^?1 and current on/off ratio of 10⁷–10⁸ in a driving voltage of 5 V. This is due to the efficient annealing process that extracting the solvent residue and the formation of low trap-density gate dielectric surface.     

Dielectric surface-polarity tuning and enhanced operation stability of solution-processed organic field-effect transistors

The electrical performance of triethylsilylethynyl anthradithiophene (TES-ADT) organic field-effect transistors (OFETs) was significantly affected by dielectric surface polarity controlled by grafting hexamethyldisilazane and dimethyl chlorosilane-terminated polystyrene (PS-Si(CH₃)₂Cl) to 300-nm-thick SiO₂ dielectrics. On the untreated and treated SiO₂ dielectrics, solvent–vapor annealed TES-ADT films contained millimeter-sized crystals with low grain boundaries (GBs). The operation and bias stability of OFETs containing similar crystalline structures of TES-ADT could be significantly increased with a decrease in dielectric surface polarity. Among dielectrics with similar capacitances (10.5–11 nF cm⁻²) and surface roughnesses (0.40–0.44 nm), the TES-ADT/PS-grafted dielectric interface contained the fewest trap sites and therefore the OFET produced using it had low-voltage operation and a charge-carrier mobility ∼1.32 cm² V⁻¹ s⁻¹, on–off current ratio >10⁶, threshold voltage ∼0 V, and long-term operation stability under negative bias stress.     

Solution processable poly(2,5-dialkyl-2,5-dihydro-3,6-di-2-thienyl-pyrrolo[3,4-c]pyrrole-1,4-dione) for ambipolar organic thin film transistors

Solution processable diketopyrrolopyrrole (DPP)-bithiophene polymers (PDBT) with long branched alkyl side chains on the DPP unit are synthesized. These polymers have favourable highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels for the injection and transport of both holes and electrons. Organic thin film transistors (OTFTs) using these polymers as semiconductors and gold as source/drain electrodes show typical ambipolar characteristics with very well balanced high hole and electron mobilities (μ_h = 0.024 cm² V^?1 s^?1 and μ_e = 0.056 cm² V^?1 s^?1). These simple and high-performing polymers are promising materials for ambipolar organic thin film transistors for low-cost CMOS-like logic circuits.     

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.     

AlGaN/GaN Schottky barrier diodes on silicon substrates with various Fe doping concentrations in the buffer layers

This study demonstrated AlGaN/GaN Schottky barrier diodes (SBDs) for use in high-frequency, high-power, and high-temperature electronics applications. Four structures with various Fe doping concentrations in the buffer layers were investigated to suppress the leakage current and improve the breakdown voltage. The fabricated SBD with an Fe-doped AlGaN buffer layer of 8 × 10¹⁷ cm^− 3 realized the highest on-resistance (R_ON) and turn-on voltage (V_ON) because of the memory effect of Fe diffusion. The optimal device was the SBD with an Fe-doped buffer layer of 7 × 10¹⁷ cm^− 3, which exhibited a R_ON of 31.6 mΩ-cm², a V_ON of 1.2 V, a breakdown voltage of 803 V, and a buffer breakdown voltage of 758 V. Additionally, the low-frequency noise decreased when the Fe doping concentration in the buffer layer was increased. This was because the electron density in the channel exhibited the same trend as that of the Fe doping concentration in the buffer layer.     

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.     

Light-emitting field-effect transistors with π-conjugated liquid crystalline polymer driven by AC-gate voltages

Light-emitting field-effect transistors with a liquid crystalline polymer of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-bithiophene] (F8T2) were investigated under alternating current (AC) gate operations. Bottom-contact/top-gate devices were fabricated with indium-tin-oxide (ITO) source/drain electrodes, a poly(methyl methacrylate) dielectric and a gold gate electrode. The crystalline F8T2 film exhibited ambipolar characteristics with electron and hole mobilities of 1.8 × 10^?3 and 2.5 × 10^?3 cm²/V s, respectively, although the threshold voltage was considerably higher for electron injection. By applying square-wave voltages to the gate, light emission was obtained at the both edges of the source and drain electrodes by alternating injection of opposite carriers even when the source and drain were grounded. The light intensity was enhanced in the channel region by biasing the source negative while biasing the drain positive where the holes injected from the drain were transported to recombine with the electrons injected at the source edge.