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.     

High rectifier output voltages with printed organic charge pump circuit

It is known that in many wireless organic electronic applications the required supply voltage is higher than the accessible signal amplitude. Therefore, voltage multiplier circuits are needed in many cases. We report a gravure printed organic charge pump circuit operating at 13.56 MHz suitable for rectified voltage amplification in printed electronic devices. The circuit, consisting of four diodes and four capacitors, has been monolithically printed using only high volume production compatible manufacturing methods. With 10 V AC input the output of the circuit at 13.56 MHz is 8.4 V and 11.8 V using 1 MΩ and 10 MΩ output loads, respectively. At 13.56 MHz the output voltage of the charge pump is three times higher than the output of a half-wave rectifier. The results demonstrate the possibility to print efficient high frequency (HF) charge pump circuits to meet the supply voltage requirements of the printed electronic applications.     

All solution-processed organic single-crystal transistors with high mobility and low-voltage operation

High-mobility organic single-crystal field-effect transistors of 3,11-didecyldinaphtho[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]-dithiophene (C₁₀-DNBDT) operating at low driving voltage are fabricated by an all-solution process. A field-effect mobility as high as 6.9 cm²/V s is achieved at a driving voltage below 5 V, a voltage as low as in battery-operated devices, for example. A low density of trap states is realized at the surface of the solution-processed organic single-crystal films, so that the typical subthreshold swing is less than 0.4 V/decade even on a reasonably thick amorphous polymer gate dielectrics with reliable insulation. The high carrier mobility and low interface trap density at the surface of the C₁₀-DNBDT crystals are both responsible for the development of the high-performance all-solution processed transistors.     

Megahertz operation of flexible low-voltage organic thin-film transistors

Bottom-gate, top-contact (inverted staggered) organic thin-film transistors with a channel length of 1 μm have been fabricated on flexible plastic substrates using the vacuum-deposited small-molecule semiconductor 2,9-didecyl-dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (C₁₀-DNTT). The transistors have an effective field-effect mobility of 1.2 cm²/V s, an on/off ratio of 10⁷, a width-normalized transconductance of 1.2 S/m (with a standard deviation of 6%), and a signal propagation delay (measured in 11-stage ring oscillators) of 420 ns per stage at a supply voltage of 3 V. To our knowledge, this is the first time that megahertz operation has been achieved in flexible organic transistors at supply voltages of less than 10 V.     

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.     

Improving the performance of organic thin-film transistor with a doped interlayer

Top contact organic thin-film transistors (TC OTFTs) based on pentacene are fabricated. For improving the contact characteristics between the organic semiconductor thin-film and gold electrodes, we doped the starburst molecular 4,4′,4″-tris{N,(3-methylpheny)-N-phenylamino}-triphenylamine) (m-MTDATA), which is an excellent hole injection material for the organic light-emitting devices (OLEDs), into the interlayer contact with the electrodes. Compared with conventional TC OTFT, the performances of the organic transistor with the doped interlayer are improved. The field-effect mobility increases from 0.16 to 0.51 cm²/V s, and threshold voltage downshifts from –11 to –2.8 V for the linear region. The on/off current ratio is more than 10⁴ when the gate voltage varies from 0 to –20 V. We ascribe the improvements to the doped interlayer for which the contact resistance is reduced and the hole injection is enhanced.     

Flexible nonvolatile organic ferroelectric memory transistors fabricated on polydimethylsiloxane elastomer

The flexible organic ferroelectric nonvolatile memory thin film transistors (OFMTs) were fabricated on polydimethylsiloxane (PDMS) elastomer substrates, in which an organic ferroelectric poly(vinylidene-trifluoroethylene) and an organic semiconducting poly(9,9-dioctylfluorene-co-bithiophene) layers were used as gate insulator and active channel, respectively. The carrier mobility, on/off ratio, and subthreshold swing of the OFMTs fabricated on PDMS showed 5 × 10⁻² cm² V⁻¹ s⁻¹, 7.5 × 10³, and 2.5 V/decade, respectively. These obtained values did not markedly change when the substrate was bent with a radius of curvature of 0.6 cm. The memory on/off ratio was initially obtained to be 1.5 × 10³ and maintained to be 20 even after a lapse of 2000 s. The fabricated OFMTs exhibited sufficiently encouraging device characteristics even on the PDMS elastomer to realize mechanically stretchable nonvolatile memory devices.     

Gravure printed organic rectifying diodes operating at high frequencies

Organic rectifier diodes operating at 10 MHz made using roll-to-roll compatible mass printing processes to define patterns and deposit inks are reported. The diodes consist of a layer of poly(triarylamine) sandwiched between layers of silver and copper. No high resolution prepatterning of any surfaces was performed, thus the entire process could be carried out on large-scale roll-to-roll production lines. The organic diode based rectifier circuit generates a DC output voltage of approximately 2.7 V at 10 MHz, using an input signal with zero-to-peak voltage amplitude of 10 V. The result demonstrates the possibility of printed organic diodes for RFID applications.     

All-inkjet printed organic transistors: Dielectric surface passivation techniques for improved operational stability and lifetime

We report about the use of a printed pentafluorothiophenol layer on top of the dielectric surface as a passivation coating to improve the operational stability of all-ink-jet printed transistors. Transistors with bottom-gate structure were fabricated using cross-linked poly-4-vinylphenol (c-PVP) as dielectric layer and an ink formulation of an amorphous triarylamine polymer as semiconductor. The resulting TFTs had low turn-on voltage (V_th < |5 V|) and a mobility ≈0.1 cm²/(V s). A comparison of identically fabricated transistors shows that devices with coated dielectric have a higher operational stability than those using bare c-PVP. This conclusion is supported by a quantitative study of the threshold voltage shift with time under continuous operation. Long exposure to the ambient atmosphere causes an increase in the threshold voltage strongly dependent on the used semiconducting ink formulation.     

A high-yield vacuum-evaporation-based R2R-compatible fabrication route for organic electronic circuits

Advances are described in a vacuum-evaporation-based approach for the roll-to-roll (R2R) production of organic thin film transistors (TFTs) and circuits. Results from 90-transistor arrays formed directly onto a plasma-polymerised diacrylate gate dielectric are compared with those formed on polystyrene-buffered diacrylate. The latter approach resulted in stable, reproducible transistors with yields in excess of 90%. The resulting TFTs had low turn-on voltage, on–off ratios ∼10⁶ and mobility ∼1 cm²/V s in the linear regime, as expected for dinaphtho[2,3-b:2′,3′-f] thieno[3,2-b]thiophene the air stable small molecule used as the active semiconductor. We show that when device design is constrained by the generally poor registration ability of R2R processes, parasitic source–drain currents can lead to a >50% increase in the mobility extracted from the resulting TFTs, the increases being especially marked in low channel width devices. Batches of 27 saturated-load inverters were fabricated with 100% yield and their behaviour successfully reproduced using TFT parameters extracted with Silvaco’s UOTFT Model. 5- and 7-stage ring oscillator (RO) outputs ranged from ∼120 Hz to >2 kHz with rail voltages, V_DD, increasing from −15 V to −90 V. From simulations an order of magnitude increase in frequency could be expected by reducing parasitic gate capacitances. During 8 h of continuous operation at V_DD = −60 V, the frequency of a 7-stage RO remained almost constant at ∼1.4 kHz albeit that the output signal amplitude decreased from ∼22 V to ∼10 V. Over the next 30 days of intermittent operation further degradation in performance occurred although an unused RO showed no deterioration over the same period.     

Self-aligned flexible organic thin-film transistors with gates patterned by nano-imprint lithography

Many applications that rely on organic electronic circuits still suffer from the limited switching speed of their basic elements – the organic thin film transistor (OTFT). For a given set of materials the OTFT speed scales inversely with the square of the channel length, the parasitic gate overlap capacitance, and the contact resistance. For maximising speed we pattern transistor channels with lengths from 10 μm down to the sub-micrometre regime by industrially scalable UV-nanoimprint lithography. The reduction of the overlap capacitance is achieved by minimising the source–drain to gate overlap lengths to values as low as 0.2 μm by self-aligned electrode definition using substrate reverse side exposure. Pentacene based organic thin film transistors with an exceptionally low line edge roughness <20 nm of the channels, a mobility of 0.1 cm²/Vs, and an on–off ratio of 10⁴, are fabricated on 4″ × 4″ flexible substrates in a carrier-free process scheme. The stability and spatial distribution of the transistor channel lengths are assessed in detail with standard deviations of L ranging from 185 to 28 nm. Such high-performing self-aligned organic thin film transistors enabled a ring-oscillator circuit with an average stage delay below 4 μs at an operation voltage of 7.5 V.     

Scaling down of organic complementary logic gates for compact logic on foil

In this work, we realize complementary circuits with organic p-type and n-type transistor integrated on polyethylene naphthalate (PEN) foil. We employ evaporated p-type and n-type organic semiconductors spaced side by side in bottom-contact bottom-gate coplanar structures with channel lengths of 5 μm. The area density is 0.08 mm² per complementary logic gate. Both p-type and n-type transistors show mobilities >0.1 cm²/V s with V_on close to zero volt. Small circuits like inverters and 19-stage ring oscillators (RO) are fabricated to study the static and the dynamic performance of the logic inverter gate. The circuits operate at V_dd as low as 2.5 V and the inverter stage delay at V_dd = 10 V is as low as 2 μs. Finally, an 8 bit organic complementary transponder chip with data rate up to 2.7 k bits/s is fabricated on foil by successfully integrating 358 transistors.     

Fast,simple ZnO/organic CMOS integrated circuits

Hybrid organic–inorganic CMOS thin-film circuits are a simple, potentially low-cost, approach for large-area, low-power microelectronic applications. We have used atmospheric pressure processes to deposit inorganic ZnO and organic diF TES-ADT semiconductor layers and an Al₂O₃ gate dielectric. The organic semiconductor uses a contact-treatment-related microstructure that allows circuits to operate without directly patterning the organic layer. Using a simple 4-mask process with bifunctional Ti/Au contacts for both ZnO and organic transistors, 7-stage ring oscillators were fabricated and operated at >500 kHz corresponding to a propagation delay of <150 ns/stage at a supply bias of 35 V. These are the fastest organic–inorganic CMOS circuits reported to date.     

High mobility and low operation voltage organic field effect transistors by using polymer-gel dielectric and molecular doping

In this work, we present a method to increase the performance in solution processed organic field effect transistors (OFET) by using gel as dielectric and molecular doping to the active organic semiconductor. In order to compare the performance improvement, Poly (methylmethacrylate) (PMMA) and Poly (3-hexylthiophene-2,5-diyl) P3HT material system were used as a reference. Propylene carbonate (PC) is introduced into PMMA to form the gel for using as gate dielectric. The mobility increases from 5.72×10⁻³ to 0.26 cm² V s^–1 and operation voltage decreases from −60 to −0.8 with gel dielectric. Then, the molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) is introduced into P3HT via co-solution. The mobility increases up to 1.1 cm² V s^–1 and the threshold voltage downs to −0.09 V with doping. The increase in performance is discussed in terms of better charge inducing by high dielectric properties of gel and trap filling due to the increased carrier density in active semiconductor by molecular doping.     

Large magnetoresistance at high bias voltage in double-layer organic spin valves

We report studies of magnetoresistance (MR) in double-layer organic spin valves (DOSV) using tris (8-hydroxyquinolinato) aluminum (Alq₃) spacers. The device exhibits three distinct resistance levels depending on the relative magnetizations of the ferromagnetic electrodes. We observed a much weaker bias voltage dependence of MR in the device compared to that in the conventional organic spin valve (OSV). The MR magnitude reduces by the factor of two at 0.7 V bias voltage in the DOSV compared to 0.02 V in the conventional OSV. Remarkably, the MR magnitude reaches 0.3% at 6 V bias in the DOSVs, the largest MR response ever reported in OSVs at this bias. Our finding may have a significant impact on achieving high efficient bipolar OSVs strictly performed at high voltages.     

An inverted,organic WORM device based on PEDOT:PSS with very low turn-on voltage

An organic Write-Once-Read-Many (WORM) device based on poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) as the active layer was fabricated with an inverted architecture. Insertion of an ultrathin layer of poly(methylmethacrylate) (PMMA) between the bottom electrode and the PEDOT:PSS resulted in a systematic and substantial decrease in turn-on voltage, from 7.0 V to less than 1.0 V. An optimal thickness of the PMMA layer was found to yield the lowest consistent turn-on voltage of ∼0.8 V, with 0.5 V being the lowest value of all fabricated devices. The switching mechanism was attributed to filamentary doping of the PEDOT:PSS. Insertion of the PMMA acted to protect the underlying ZnO from being etched by the acidic PEDOT:PSS as well as to improve its wetting properties. Devices were demonstrated on both ITO and aluminum bottom electrodes, with aluminum yielding the highest ON/OFF ratios in the study. Owing to their inverted architecture, the devices demonstrated good stability, and the retention time of the ON-state was determined to be greater than twenty months while stored in air for devices with ITO bottom electrodes. In addition to deposition via spin-coating, blade-coating was demonstrated as a viable processing technique for applications requiring rapid or large-area manufacturing.     

Very facile fabrication of aligned organic nanowires based high-performance top-gate transistors on flexible,transparent substrate

Aligned single-crystalline organic nanowires (NWs) show promising applications in flexible and stretchable electronics, while the use of pre-existing aligned techniques and well-developed photolithography techniques are impeded by the large incompatibility with organic materials and flexible substrates. In this work, aligned copper phthalocyanine (CuPc) organic NWs were grown on flexible and transparent poly(dimethylsiloxane) (PDMS) substrate via a grating-assisted growth approach. Furthermore, a simple yet efficient etching-assisted transfer printing (ETP) method was used to achieve CuPc NW array-based flexible top-gate organic field-effect transistors (OFETs) with a high mobility up to 2.0 cm² V⁻¹ s⁻¹, a small operating voltage within ±10 V, a high on/off ratio >10⁴, and excellent bend stability with bending radius down to 3 mm. It is expected that the high-performance organic NW array-based top-gate OFETs with exceeding bend stability will have important applications in future flexible electronics.     

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.     

Low-voltage organic thin film transistors with hydrophobic aluminum nitride film as gate insulator

This paper reports on the low-voltage (<5 V) pentacene-based organic thin film transistors (OTFTs) with a hydrophobic aluminum nitride (AlN) gate-dielectric. In this work, a thin (about 50 nm), smooth (roughness about 0.18 nm) and low-leakage AlN gate dielectric is obtained and characterized. The AlN film is hydrophobic and the surface free energy is similar to the organic or the polymer films. The demonstrated AlN–OTFTs were operated at a low-voltage (3–5 V). A low-threshold voltage (−2 V) and an extremely low-subthreshold swing (∼170 mV/dec) were also obtained. Under low-voltage operating conditions, the on/off current ratio exceeded 10⁶, and the field effect mobility was mobility was 1.67 cm²/V s.     

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

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