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.     

Cardanol-based polymeric gate dielectric for solution-processed organic field-effect transistors on flexible substrates

A cardanol-based polymer, poly(2-hydroxy-3-cardanylpropyl methacrylate) (PHCPM), was utilized as the gate dielectric of an organic field-effect transistor (OFET). PHCPM has good surface properties, appropriate gate dielectric characteristics, and good compatibility with solution-processed semiconducting polymers. The electrical properties of an FET that was prepared with natural resource-based PHCPM as a gate dielectric layer and solution-processed poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) as a semiconducting layer were investigated on flexible substrates. The flexible PBTTT-OFET device with the PCHPM gate dielectric exhibited high mobility and reliable performance, even in the bending state, without significant hysteresis.     

A new diketopyrrolopyrrole-based co-polymer for ambipolar field-effect transistors and solar cells

A new thieno[3,2-b]thiophenediketopyrrolopyrrole-benzo[1,2-b:4,5-b′]dithiophene based narrow optical gap co-polymer (PTTDPP-BDT) has been synthesized and characterized for field-effect transistors and solar cells. In field-effect transistors the polymer exhibited ambipolar charge transport behaviour with maximum hole and electron mobilities of 10⁻³ cm² V⁻¹ s⁻¹ and 10⁻⁵ cm² V⁻¹ s⁻¹, respectively. The respectable charge transporting properties of the polymer were consistent with X-ray diffraction measurements that showed close molecular packing in the solid state. The difference in hole and electron mobilities was explained by density functional theory calculations, which showed that the highest occupied molecular orbital was delocalized along the polymer backbone with the lowest unoccupied molecular orbital localized on the bis(thieno[3,2-b]thiophene)diketopyrrolopyrrole units. Bulk heterojunction photovoltaic devices with the fullerene acceptor PC₇₀BM were fabricated and delivered a maximum conversion efficiency of 3.3% under AM1.5G illumination.     

Low-resistance contacts of electroless-plated metals with high-mobility organic semiconductors: Novel organic field-effect transistors with solution-processed electrodes

The establishment of a reliable vacuum-free method for the formation of electrical contacts on high-performance organic semiconductors has become an urgent task due to rapid progress made in the development of solution-processable high-mobility organic field-effect transistors (OFETs). We have recently proposed that electroless plating, a standard technology to mass produce wirings in currently commercialized electronic devices, is suited for high-performance solution-crystallized OFETs. A low contact resistance at the source and drain electrodes is necessary with organic semiconductors for high-speed device operation; therefore, we have evaluated the contact resistance using the transfer line method. A top-contact geometry with sufficient contact area is employed to achieve stable carrier injection, which has enabled contact resistances as low as 1.4 kΩ cm on a polyethylene naphthalate substrate at a gate voltage of −10 V. This marks outstanding performance among the solution-processed metal electrodes reported for OFETs, particularly on plastic substrates. The result indicates that high-quality boundaries with minimized trap densities are realized due to the mild conditions of the electroless plating process at room temperature.     

High mobility organic field-effect transistors based on defect-free regioregular poly(3-hexylthiophene-2,5-diyl)

We report on organic field-effect transistors (OFETs) prepared using defect free (100% regioregular) poly(3-hexylthiophene-2,5-diyl) (DF-P3HT) as semiconductor and cross-linked poly(vinyl alcohol) (cr-PVA) as gate insulator. High field-effect mobility (μ_FET) of 1.2 cm² V⁻¹ s⁻¹ is obtained and attributed to the absence of regioregularity defects. These transistors have transconductance of 0.35 μS and the DF-P3HT film shows larger crystallites (∼80 Å) than a highly regioregular (>98%) material (∼32 Å). Devices with increased μ_FET (2.8 cm² V⁻¹ s⁻¹) could be obtained at the expense of the On-Off current ratio, which was reduced by one order of magnitude, when poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) treatment was applied to the dielectric surface. Our results suggest that the interaction of charged sites at the dielectric surface with regioregularity defects of the P3HT is an important factor degrading μ_FET even at very low concentration of regioregularity defects.     

Generalized enhancement of charge injection in bottom contact/top gate polymer field-effect transistors with single-walled carbon nanotubes

We investigate the influence of small amounts of dispersed single-walled carbon nanotubes (SWNTs) on the contact resistance and device characteristics of bottom contact/top gate polymer field-effect transistors (FETs). Five conjugated polymers representing different classes of polymer semiconductors with different HOMO/LUMO levels are employed, namely, polythiophenes (P3HT), polyphenylenevinylenes (MDMO-PPV), polyfluorenes (F8T2), naphthalene-bis(dicarboximide) bithiophene copolymers (P(NDI2OD-T2)), and diketopyrrolo-pyrrole-bithiophene copolymers (DPPT-TT). In all cases the presence of dispersed SWNTs reduces non-ohmic contact resistance and lowers threshold and onset voltages for charge transport. In some cases inherent ambipolar charge transport in conjugated polymers (F8T2 and P(NDI2OD-T2)) is revealed. The concentration of the SWNTs within the semiconducting layer remains below the percolation limit and thus the apparent mobilities and on/off ratios are still determined by the polymer and independent of the specific type of the carbon nanotubes (metallic or semiconducting). The degree of enhancement depends both on the energy level offset between the injecting gold electrode and the HOMO/LUMO level (i.e., Schottky barrier) and the charge carrier mobility of the respective polymer. The simplicity of this injection enhancement method and its broad applicability make it a step toward high performance polymer transistors without injection limitations.     

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.     

Enhancing the performance of solution-processed organic thin-film transistors by blending binary compatible small molecule semiconductors

Physical blending is a facile and effective way to improve the performance of solution processed organic thin-film transistors (OTFTs). Blending small molecule semiconductors with soluble polymers has been extensively studied in recent years. However, blending between binary small molecule semiconductors is rare due to the difficulty to obtain ideal thin films. Herein, we systematically investigate the blending effects on the morphologies of thin films and their field-effect performance by using two small molecule semiconductors, 2-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT) and 2-(4-dodecylphenyl) [1]benzothieno[3,2-b]benzothiophene, (C12-Ph-BTBT), which have the same aromatic skeleton. Molecular ordering and better crystallinity are observed in most of spin-coated blend thin films, thanks to the enhanced molecular interaction after blending. As a result, OTFTs based on blend thin films exhibit improved performance in most cases, with the highest average hole mobility about 1.5 cm² V⁻¹ s⁻¹ demonstrated. Further device performance improvements are demonstrated by blending polystyrene with Ph-BTBT and C12-Ph-BTBT blends. The results here indicate that blending between small molecule semiconductors with compatible fused ring structures may be a promising strategy to enhance the performance of organic transistors.     

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.     

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 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.     

Solution-processed natural gelatin was used as a gate dielectric for the fabrication of oxide field-effect transistors

Biocompatible and biodegradable materials are attractive for environmentally safe, flexible and biosustainable devices since they are nontoxic renewable materials with a low cost. Gelatin, a natural protein, is a promising biopolymer for photography, cosmetic manufacturing and food. In this paper, solution-processed natural gelatin was used as a gate dielectric for the fabrication of oxide field-effect transistors (FETs). Similarly to a polyelectrolyte, mobile ions can be generated in gelatin in air environment. A high gate specific capacitance larger than 0.93 μF/cm² was obtained in gelatin processed at low concentrations, due to the formation of electric-double-layers (EDLs). As gelatin films processed at a low concentration of 0.02 g/mL, the fabricated FETs showed excellent electrical performances. The average current on/off ratio and the mobility were estimated to be 1.36 × 10⁵ and 33.2 cm²/V, respectively. The proposed technique may be application in the bioelectronics field, including biosensors and synaptic devices.     

聚酰亚胺为栅绝缘层的并五苯场效应晶体管

以真空蒸发的有机半导体材料并五苯为有源层,以旋涂的聚酰亚胺作为栅绝缘层,以真空蒸发的Al为栅、源和漏电极,成功制作了顶接触式并五苯有机场效应晶体管(OFET).测试表明,在源漏电压为70 V时,器件的载流子迁移率μ为0.079 cm2/V·s,器件的开关电流比为1.7×104.     

Solution-processed organic crystals written directly with a rollerball pen for field-effect transistors

To deposit organic semiconducting crystals from solution, we propose the use of a rollerball pen as a simple and promising tool. These organic crystal grains of dioctylbenzothienobenzothiophene measured several hundred micrometers. The fabricated OFETs exhibited good device performance with a field-effect mobility (μ_FET) of 0.7 cm²/Vs and an on-off ratio of more than 10⁷. Simulation results reveal that the flow behavior of solution from the pen refill tube to the substrate intrinsically enhances the formation of large organic crystals.     

Ion-sensitive field-effect transistors with inorganic gate oxide for pH sensing

Ion-sensitive field-effect transistors (ISFET's) have been fabricated by using silicon films on sapphire substrates (SOS). Using this structure SiO2, ZrO2, and Ta2O5films are examined as hydrogenion-sensitive materials, and Ta2O5film has been found to have the highest pH sensitivity (56 mV/pH) among them. The measured pH sensitivity of this SOS-ISFET's is compared with the theoretical sensitivity based on the site-binding model of proton dissociation reaction on the metal oxide film and good agreement between them is obtained.     

Fabrication of single crystal field-effect transistors with phenacene-type molecules and their excellent transistor characteristics

Single crystal field-effect transistors (FETs) using [6]phenacene and [7]phenacene show p-channel FET characteristics. Field-effect mobilities, μs, as high as 5.6 × 10^?1 cm² V^?1 s^?1 in a [6]phenacene single crystal FET with an SiO₂ gate dielectric and 2.3 cm² V^?1 s^?1 in a [7]phenacene single crystal FET were recorded. In these FETs, 7,7,8,8-tetracyanoquinodimethane (TCNQ) was inserted between the Au source/drain electrodes and the single crystal to reduce hole-injection barrier heights. The μ reached 3.2 cm² V^?1 s^?1 in the [7]phenacene single crystal FET with a Ta₂O₅ gate dielectric, and a low absolute threshold voltage |V_TH| (6.3 V) was observed. Insertion of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F₄TCNQ) in the interface produced very a high μ value (4.7–6.7 cm² V^?1 s^?1) in the [7]phenacene single crystal FET, indicating that F₄TCNQ was better for interface modification than TCNQ. A single crystal electric double-layer FET provided μ as high as 3.8 × 10^?1 cm² V^?1 s^?1 and |V_TH| as low as 2.3 V. These results indicate that [6]phenacene and [7]phenacene are promising materials for future practical FET devices, and in addition we suggest that such devices might also provide a research tool to investigate a material’s potential as a superconductor and a possible new way to produce the superconducting state.     

SiC（0001）面衬底上自氧化栅介质和自对准形成石墨烯场效应晶体管

A scalable self-aligned approach is employed to fabricate monolayer graphene field-effect transistors on semi-insulated 4H-SiC （0001） substrates. The self-aligned process minimized access resistance and parasitic capacitance. Self-oxidized Al2O3, formed by deposition of 2 nm A1 followed by exposure in air to be oxidized, is used as gate dielectric and shows excellent insulation. An intrinsic cutoff frequency of 34 GHz and maximum oscillation frequency of 36.4 GHz are realized for the monolayer graphene field-effect transistor with a gate length of 0.2 μm. These studies show a pathway to fabricate graphene transistors for future applications in ultra-high frequency circuits.     

Submicron-meter tunneling field-effect poly-Si thin-film transistors with a thinned channel layer

Submicron-meter poly-Si tunneling-effect thin-film transistor (TFT) devices with a thinned channel layer have been investigated. With reducing the gate length to be shorter than 1 μm, the poly-Si TFT device with conventional MOSFET structure is considerably degraded. The tunneling field-effect transistor (TFET) structure can be employed to alleviate the short channel effect, thus largely suppressing the off-state leakage. However, for a poly-Si channel layer of 100 nm thickness, the TFET structure causes a small on-state current, which may not provide well sufficient driving current. By reducing the channel layer thickness to be 20 nm, the on-state current for the TFET structure can be largely increased, due to the enhanced bending of energy band for a thinned channel layer. As a result, for the TFET poly-Si TFTs at a gate bias of 5 V and a drain bias of 3 V, a 20-nm channel layer leads to an on-state current of about 1 order larger than that by a 100-nm channel layer, while still keeping an off-state leakage smaller than 0.1 pA/μm. Accordingly, the submicron-meter TFET poly-Si TFT devices with a thinned channel layer would show good feasibility for implementing high packing density of poly-Si TFT devices.