The color change in polychromatic organic light-emitting field-effect transistors: Optical filtering versus reemission

In this contribution the color conversion process of a polychromatic organic light-emitting field-effect transistor (OLET) is revisited on the basis of an analytic device model. The device of interest consists of a color conversion layer out of rubrene on top of a monochromatic light-emitting transistor based on poly(9,9-di-n-octyl-fluorene-alt-benzothiadiazole) (F8BT). The model describes the relation of color coordinate and emission intensity – set by the applied drain and gate biases – linking the optoelectronic response of the employed monochromatic OLET to the optical processes occurring in the color conversion layer. The model shows that the color shift is rather due to partial absorption of the F8BT emission by rubrene than, as was claimed earlier, due to a color conversion process by absorption and reemission in the conversion layer. In addition to the earlier publication, it will be demonstrated that such a device allows for an independent electrical tunability of emission intensity and color coordinate within the color span of the F8BT and the rubrene spectrum being a unique feature of such a polychromatic light-emitting field-effect transistor.     

Contactless charge carrier mobility measurement in organic field-effect transistors

With the increasing performance of organic semiconductors, contact resistances become an almost fundamental problem, obstructing the accurate measurement of charge carrier mobilities. Here, a generally applicable method is presented to determine the true charge carrier mobility in an organic field-effect transistor (OFET). The method uses two additional finger-shaped gates that capacitively generate and probe an alternating current in the OFET channel. The time lag between drive and probe can directly be related to the mobility, as is shown experimentally and numerically. As the scheme does not require the injection or uptake of charges it is fundamentally insensitive to contact resistances. Particularly for ambipolar materials the true mobilities are found to be substantially larger than determined by conventional (direct current) schemes.     

Directed self-assembly of organic semiconductors via confined evaporative capillary flows for use in organic field-effect transistors

We fabricated well-defined 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-PEN) crystal arrays for use in electronic applications via a simple but effective method, the confined evaporative capillary flow (CEC) method. This has been accomplished by systematically controlling the contact line pinning at the edge of glass stylus and the outward hydrodynamic flow within the drying droplet with various processing solvents and surface properties of the substrate during solidification. We found that after CEC coating of TIPS-PEN solution dissolved into toluene onto SiO₂ surface, ribbon-shaped TIPS-PEN crystals were well developed with a width of 20–100 μm and length of 300 μm – 2 mm, which is presumably owing to optimized capillary evaporation. Specifically, TIPS-PEN crystals present highly preferred crystal orientation along the (l 0 0) axis, which can lead to efficient charge transport in a lateral direction. Thus, TIPS-PEN field-effect transistors (FETs) exhibited a good hole mobility of 0.72 cm²/Vs.     

Electrical characterization of mica as an insulator for organic field-effect transistors

Electrical properties of conjugated polymer films, including poly(3-hexylthiophene)-2,5-diyl (P3HT), poly(3,3-didodecylquarterthiophene) (PQT-12), and poly(triarylamine) (PTAA), on mica substrates have been studied. The test structure was similar to a standard organic field-effect transistor but with a 150-μm-thick commercially available mica gate insulator/substrate, which allowed to obtain a field-effect mobility of P3HT as high as 0.08 cm²/Vs in the linear regime in ambient air. The influence of interface treatment, thermal annealing, and measurement conditions on the electrical properties of the P3HT films has been characterized and analyzed. We also studied the time dependence of the carrier concentration and mobility before and after a thermal annealing process. The results indicate that mica is a promising insulator for organic field-effect transistors, apart from already being one of the common thin-film materials widely used in electric capacitors.     

Stable growth of large-area single crystalline thin films from an organic semiconductor/polymer blend solution for high-mobility organic field-effect transistors

We developed an effective and steady solution-processing technique for a small molecule–type semiconductor, C₁₀–DNBDT–NW, by adding an amorphous PMMA polymer to produce stable growth of a two-dimensional large-area single-crystalline thin film by effective phase separation at a crucially faster processing speed compared to the case without the addition of a polymer. By using this solution-processing technique, it is noteworthy that the single-crystalline films of C₁₀–DNBDT–NW/PMMA exhibit the highest and average mobilities of 17 and 10.6 cm²/Vs, respectively. Furthermore, we also show the limitations of two-dimensional continuous growth of a single-crystalline film in terms of the solution technique.     

Alternating dithienobenzoxadiazole-based conjugated polymers for field-effect transistors and polymer solar cells

Three new alternating copolymers derived from dithienobenzoxadizole (DTfBO) and different thiophene-based π-spacers, including terthiophene, quarterthiophene, and dithienyl flanked thienothiophene, were successfully synthesized. The DTfBO-based polymers possess optical band-gaps in the range of 1.84–1.89 eV and exhibit relatively deep HOMO levels between −5.36 eV and −5.50 eV. Due to strong interchain aggregation, DTfBO-based polymers could not be well dissolved in chlorobenzene at room temperature, but they could be processed with hot chlorobenzene solutions of ∼100 °C. Evolutions of UV absorption spectra of polymer solutions during heating process could differentiate their different aggregation ability, among which a repeating unit based on a DTfBO and a terthiophene could supply the strongest inter-chain interaction. Notably, the three DTfBO-based polymers displayed high field-effect hole mobilities between 0.21 and 0.54 cm²/(V s). In polymer solar cells (PSCs) with the three polymers as the donors, high open-circuit voltages between 0.87 and 0.93 V could be realized. For active layer thickness of 80 nm, the PSCs displayed power conversion efficiency (PCE) between 2.85% and 5.07%. A very high fill factor of 75.4% was achieved for the polymer comprising dithienyl flanked thienothiophene. With thicker ative layers of 250 nm, the three DTfBO-based polymers exhibited comparable PCEs of ∼5.61% due to obviously increased short-circuit currents. Our results suggest that DTfBO, a big coplanar heterocycle, is a promising building block to construct high mobility conjugated polymers for efficient thick-film PSCs.     

Hydrogen-bonded diketopyrrolopyrrole (DPP) pigments as organic semiconductors

Diketopyrrolopyrroles (DPPs) have recently gained attention as building-blocks for organic semiconducting polymers and small molecules, however the semiconducting properties of their hydrogen-bonded (H-bonded) pigment forms have not been explored. Herein we report on the performance of three archetypical H-bonded DPP pigments, which show ambipolar carrier mobilities in the range 0.01–0.06 cm²/V s in organic field-effect transistors. Their semiconducting properties are correlated with crystal structure, where an H-bonded crystal lattice supports close and relatively cofacial π–π stacking. To better understand transport in these systems, density functional theory calculations were carried out, indicating theoretical maximum ambipolar mobility values of ∼0.3 cm²/V s. Based on these experimental and theoretical results, H-bonded DPPs represent a viable alternative to more established DPP-containing polymers and small molecules where H-bonding is blocked by N-alkylation.     

Parylene based bilayer flexible gate dielectric layer for top-gated organic field-effect transistors

In this paper, we report on a bilayer insulating film based on parylene-c for gate dielectric layers in top-gate/bottom-contact inkjet-printed organic field-effect transistors (OFETs) with indacenodithiophene-co-benzothiadiazole (IDTBT) and poly([N,N’-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5’-(2,2’-bitthiophene)) (P(NDI2OD-T2)) as with p- and n-channel semiconductors. The thin parylene-c film (t = 210 nm) show large gate leakage density (2.52 nA/cm² at 25 V) and low breakdown voltage (2.2 MV/cm). In addition, a degraded field-effect mobility (μ) was observed in printed IDTBT and P(NDI2OD-T2) OFETs with the parylene-c single-layered dielectric. X-ray photoelectron spectroscopy (XPS) analysis reveals that the degradation of μ is due to unwanted chemical interaction between parylene-c and the conjugated polymer surface during the parylene-c deposition process. By inserting 50-nm thick poly(methyl-methacrylate) (PMMA) and polystyrene (PS) layer in-between the parylene-c and conjugated polymer film, highly improved gate leakage density and breakdown voltage are achieved. The printed IDTBT and P(NDI2OD-T2) OFETs with a bilayer dielectric compose of parylene-c and PMMA and PS show significantly improved hole and electron μ of 0.47 cm²/Vs and 0.13 cm²/Vs, respectively, and better operation stability. In addition, we demonstrate inkjet-printed polymer complementary inverter with a high voltage gain of 25.7 by applying a PS/parylene-c bilayer dielectric.     

High operational stability of solution-processed organic field-effect transistors with top-gate configuration

Electrical characteristics of top-gate field-effect transistors based on a wide range of solution-processed organic semiconductors are systematically investigated. The top-gate field-effect transistors based on different organic semiconductors—from an amorphous polymer semiconductor to a polycrystalline molecular semiconductor—exhibit higher operational stability compared with bottom-gate organic field-effect transistors reported in literature, in spite of significant difference in field-effect mobility. The correlation between charge transport and operational stability is discussed to gain insight into high operational stability of top-gate organic field-effect transistors.     

Downscaling of n-channel organic field-effect transistors with inkjet-printed electrodes

In this contribution we demonstrate for the first time a downscaled n-channel organic field-effect transistors based on N,N′-dialkylsubstituted-(1,7&1,6)-dicyanoperylene-3,4:9,10-bis(dicarboximide) with inkjet printed electrodes. First we demonstrate that the use of a high boiling point solvent is critical to achieve extended crystalline domains in spin-coated thin films and thus high electron mobility >0.1 cm² V⁻¹ s⁻¹ in top-gate devices. Then inkjet-printing is employed to realize sub-micrometer scale channels by dewetting of silver nanoparticles off a first patterned gold contact. By employing a 50 nm crosslinked fluoropolymer gate dielectric, ∼200 nm long channel transistors can achieve good current saturation when operated <5 V with good bias stress stability.     

Non-conventional metallic electrodes for organic field-effect transistors

We study micrometer-sized organic field-effect transistors with either Pd or NiFe metallic electrodes. Neither of these materials is commonly used in organic electronics applications, but they could prove to be particularly advantageous in certain niche applications such as organic spintronics. Using organic semiconductors with different carrier transport characteristics as active layer, namely n-type C60 fullerene and p-type Pentacene, we prove that Pd (NiFe) is a very suitable electrode for p- (n-) type semiconductors. In particular, we characterized devices with channel lengths in the order of the micrometer, a distance which has allowed us to evaluate the electronic behavior in a regime where the interfacial problems become predominant and it is possible to reach elevated longitudinal electric fields. Our experimental results agree well with a simple model based on rigid energy levels.     

Enhanced performance of room temperature ammonia sensors using morphology-controlled organic field-effect transistors

Developing electronic sensors for ammonia (NH₃) is very useful for environmental monitoring and diagnostic purposes. In this work, a highly sensitive, organic field-effect transistor (OFET) based, room temperature sensor for NH₃ has been fabricated using dinaphtho [2,3-b:2′,3′-f]thieno [3,2-b]thiophene (DNTT), which showed a fast response to low concentration of the analyte down to 100 ppb. A thin film of solution-processed polymethyl methacrylate (PMMA) has been used as the gate dielectric material and its hydrophobic surface promoted structured growth of organic semiconductor, DNTT, by inducing mass transfer. By controlling the thickness and thereby exploiting the growth dynamics of the semiconductor film, the sensor performance was improved. The sensitivity of the device towards 1 ppm of NH₃ was almost doubled with a thinner and porous film of DNTT as compared to that with a thick film. Morphological studies of the sensing layers, using atomic force microscopy (AFM), have established this structure-property relation. The variations in different transistor parameters have been studied with respect to different analyte concentrations. The p-channel devices in the enhancement mode showed depletion upon exposure to NH₃. The devices exhibited a fast response and good recovery to the initial state within 2 min.     

Direct investigations of the interface impedance of organic field-effect transistors with self-assembled-monolayer-modified electrodes

It has been demonstrated that the modification of electrodes with self-assembled monolayers (SAMs) reduces the contact resistance and improves the device performances of organic field-effect transistors (OFETs). However, it has been difficult to judge if the contact resistance was reduced by the change in the electronic properties or by the change in the morphology of the metal–organic interface caused by the SAM modification because they have been difficult to be separately assessed. We have directly investigated the local impedance and the potential difference at the electrode–channel interfaces of the OFETs with and without modification of the electrodes by a pentafluorobenzenethiol SAM using frequency-modulation scanning impedance microscopy (FM-SIM). The potential profile measurement and the FM-SIM measurement at the interface showed that the improvement of the field-effect mobility in the SAM-modified OFET was caused by the reduction of the energy level mismatch, namely, the hole injection barrier at the source–channel interface, presumably with the reduction of the hole trap sites at the source–channel interface.     

Using d-limonene as the non-aromatic and non-chlorinated solvent for the fabrications of high performance polymer light-emitting diodes and field-effect transistors

Aiming to environment protection, green solvents are crucial for commercialization of solution-processed optoelectronic devices. In this work, d-limonene, a natural product, was introduced as the non-aromatic and non-chlorinated solvent for processing of polymer light-emitting diodes (PLEDs) and organic field effect transistors (OFETs). It was found that d-limonene could be a good solvent for a blue-emitting polyfluorene-based random copolymer for PLEDs and an alternating copolymer FBT-Th₄(1,4) with high hole mobility (μ_h) for OFETs. In comparisons to routine solvent-casted films of the two conjugated polymers, the resulting d-limonene-deposited films could show comparable film qualities, based on UV–vis absorption spectra and observations by atomic force microscopy (AFM). With d-limonene as the processing solvent, efficient blue PLEDs with CIE coordinates of (0.16, 0.16), maximum external quantum efficiency of 3.57%, and luminous efficiency of 3.66 cd/A, and OFETs with outstanding μ_h of 1.06 cm² (V s)⁻¹ were demonstrated. Our results suggest that d-limonene would be a promising non-aromatic and non-chlorinated solvent for solution processing of conjugated polymers and molecules for optoelectronic device applications.     

Solution-processed flexible nonvolatile organic field-effect transistor memory using polymer electret

Flexible organic field-effect-transistor (OFET) memory is one of the promising candidates for next-generation wearable nonvolatile data storage due to its low price, solution-processability, light-weight, mechanically flexibility, and tunable energy level via molecular tailoring. In this paper, we report flexible nonvolatile OFET memory devices fabricated with solution-processed polystyrene-brush electret and organic semiconductor blends of p-channel 6, 13-bis-(triisopropylsilylethynyl)pentacene (TIPS-PEN) and n-channel poly-{[N,N′-bis(2- octyldodecyl)-naphthalene-1,4,5,8-bis-(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} (P-(NDI2OD-2T); N2200). Fabricated flexible OFET memory devices exhibited high memory window (30 V) and ON/OFF current ratio (memory ratio) over 10³. Furthermore, we obtained reliable memory ratio (~10³) over retention time of 10⁸ s, 100 times of repeated programming/erasing cycles, and 1000 times of bending tests at a radius of 3 mm.     

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.     

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.     

Electrical responses of short-channel organic transistor prepared by solution-processed organic crystal wire mask

We report a formation of a solution-grown single crystal wire mask for the fabrication of short-channel organic field-effect transistor with enhanced dynamic response time. The various channel length, ranging from submicrometer to a few micrometers, were obtained by controlling the concentration of solution and processing conditions. We fabricated p- and n-channel bottom-contact organic field-effect transistors using pentacene and PTCDI-C₁₃, respectively, and static and dynamic electrical characteristics of the devices were investigated. The highest and average field-effect hole mobility values were found to be 0.892 cm²/V s and 0.192 cm²/V s, respectively. The load type inverter based on the short-channel transistor connected with a 2 MΩ resistor showed a clear switching response when square wave input signals up to 1 kHz were applied at V_DD = −60 V.     

Methylated conjugated polymers based on diketopyrrolopyrrole and dithienothiophene for high performance field-effect transistors

In this work, a series of conjugated polymers based on diketopyrrolopyrrole (DPP) and dithienothiophene were designed for application in field-effect transistors (FETs). Owing to the synthetic nature of DPP units, the DPP polymers here contain different aromatic linkers with thiophene and methylthiophene, resulting in non-methylated and methylated DPP polymers. Methylated DPP polymers were found to show good crystalline properties and provide high hole mobilties up to 5.32 cm² V⁻¹ s⁻¹ in FETs, while non-methylated polymer exhibits a hole mobility of 3.16 cm² V⁻¹ s⁻¹. Especially, the polymer containing asymmetric linkers presents “face-on” orientation in thin films but provides the highest mobility. Our results reveal that the polymers incorporating methyl units as side chains can be used to realize high carrier mobility in FETs.     

Spray-coated contacts from an organic charge transfer complex solution for organic field-effect transistors

We demonstrate the deposition of films of the conducting charge transfer complex TTF-TCNQ from solution by spray-coating. The benefit of spray-coating is the ability to process large volumes of solution, therefore allowing the utilisation of compounds with very low solubility. The sheet resistance in the TTF-TCNQ film is similar to that of the commonly used organic PEDOT:PSS electrodes, with the added benefit of room temperature deposition and no additional thermal treatments. Spray-coated TTF-TCNQ is used as source and drain electrodes for transistors based on the organic semiconductor C8-BTBT, achieving similar performances in terms of mobility and turn-on voltage than when conventional contacts of MoO_x/Au are used, whilst exhibiting a slight improvement in the linearity of the output characteristics.