High‐Speed Organic Single‐Crystal Transistor Responding to Very High Frequency Band

Although high carrier mobility organic field‐effect transistors (OFETs) are required for high‐speed device applications, improving the carrier mobility alone does not lead to high‐speed operation. Because the cut‐off frequency is determined predominantly by the total resistance and parasitic capacitance of a transistor, it is necessary to miniaturize OFETs while reducing these factors. Depositing a dopant layer only at the metal/semiconductor interface is an effective technique to reduce the contact resistance. However, fine‐patterning techniques for a dopant layer are still challenging especially for a top‐contact solution‐processed OFET geometry because organic semiconductors are vulnerable to chemical damage by solvents. In this work, high‐resolution, damage‐free patterning of a dopant layer is developed to fabricate short‐channel OFETs with a dopant interlayer inserted at the contacts. The fabricated OFETs exhibit high mobility exceeding 10 cm² V^?1 s^?1 together with a reasonably low contact resistance, allowing for high frequency operation at 38 MHz. In addition, a diode‐connected OFET shows a rectifying capability of up to 78 MHz at an applied voltage of 5 V. This shows that an OFET can respond to the very high frequency band, which is beneficial for long‐distance wireless communication.     

High‐Mobility n‐Type Organic Transistors Based on a Crystallized Diketopyrrolopyrrole Derivative

A new high‐performing small molecule n‐channel semiconductor based on diketopyrrolopyrrole (DPP), 2,2′‐(5,5′‐(2,5‐bis(2‐ethylhexyl)‐3,6‐dioxo‐2,3,5,6‐tetrahydropyrrolo[3,4‐c]pyrrole‐1,4‐diyl)bis(thiophene‐5,2‐diyl))bis(methan‐1‐yl‐1‐ylidene)dimalononitrile (DPP‐T‐DCV), is successfully synthesized. The frontier molecular orbitals in this designed structure are elaborately tuned by introducing a strong electron‐accepting functionality (dicyanovinyl). The well‐defined lamellar structures of the crystals display a uniform terrace step height corresponding to a molecular monolayer in the solid‐state. As a result of this tuning and the remarkable crystallinity derived from the conformational planarity, organic field‐effect transistors (OFETs) based on dense‐packed solution‐processed single‐crystals of DPP‐T‐DCV exhibit an electron mobility (μ_e) up to 0.96 cm² V^?1 s^?1, one of the highest values yet obtained for DPP derivative‐based n‐channel OFETs. Polycrystalline OFETs show promise (with an μ_e up to 0.64 cm² V^?1 s^?1) for practical utility in organic device applications.     

Hydrocarbons‐Driven Crystallization of Polymer Semiconductors for Low‐Temperature Fabrication of High‐Performance Organic Field‐Effect Transistors

While many high‐performance polymer semiconductors are reported for organic field‐effect transistors (OFETs), most require a high‐temperature postdeposition annealing of channel semiconductors to achieve high performance. This negates the fundamental attribute of OFETs being a low‐cost alternative to conventional high‐cost silicon technologies. A facile solution process is developed through which high‐performance OFETs can be fabricated without thermal annealing. The process involves incorporation of an incompatible hydrocarbon binder or wax into the channel semiconductor composition to drive rapid phase separation and instantaneous crystallization of polymer semiconductor at room temperature. The resulting composite channel semiconductor film manifests a nano/microporous surface morphology with a continuous semiconductor nanowire network. OFET mobility of up to about 5 cm² V^?1 s^?1 and on/off ratio ≥ 10⁶ are attained. These are hitherto benchmark performance characteristics for room‐temperature, solution‐processed polymer OFETs, which are functionally useful for many impactful applications.     

Self‐Assembled,Millimeter‐Sized TIPS‐Pentacene Spherulites Grown on Partially Crosslinked Polymer Gate Dielectric

Here, a highly crystalline and self‐assembled 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐Pentacene) thin films formed by simple spin‐coating for the fabrication of high‐performance solution‐processed organic field‐effect transistors (OFETs) are reported. Rather than using semiconducting organic small‐molecule–insulating polymer blends for an active layer of an organic transistor, TIPS‐Pentacene organic semiconductor is separately self‐assembled on partially crosslinked poly‐4‐vinylphenol:poly(melamine‐co‐formaldehyde) (PVP:PMF) gate dielectric, which results in a vertically segregated semiconductor‐dielectric film with millimeter‐sized spherulite‐crystalline morphology of TIPS‐Pentacene. The structural and electrical properties of TIPS‐Pentacene/PVP:PMF films have been studied using a combination of polarized optical microscopy, atomic force microscopy, 2D‐grazing incidence wide‐angle X‐ray scattering, and secondary ion mass spectrometry. It is finally demonstrated a high‐performance OFETs with a maximum hole mobility of 3.40 cm² V^?1 s^?1 which is, to the best of our knowledge, one of the highest mobility values for TIPS‐Pentacene OFETs fabricated using a conventional solution process. It is expected that this new deposition method would be applicable to other small molecular semiconductor–curable polymer gate dielectric systems for high‐performance organic electronic applications.     

Highly Efficient Charge Transport in a Quasi‐Monolayer Semiconductor on Pure Polymer Dielectric

The study of monolayer organic field‐effect transistors (MOFETs) provides an effective way to investigate the intrinsic charge transport of semiconductors. To date, the research based on organic monolayers on polymeric dielectrics lays far behind that on inorganic dielectrics and the realization of a bulk‐like carrier mobility on pure polymer dielectrics is still a formidable challenge for MOFETs. Herein, a quasi‐monolayer coverage of pentacene film with orthorhombic phase is grown on the poly (amic acid) (PAA) dielectric layer. More significantly, charge density redistribution occurs at the interface between the pentacene and PAA caused by electron transfer from pentacene to the PAA dielectric layer, which is verified by theoretical simulations and experiments. As a consequence, an enhanced hole accumulation layer is formed and pentacene‐based MOFETs on pure polymer dielectrics exhibit bulk‐like carrier mobilities of up to 13.7 cm² V^?1 s^?1 from the saturation region at low V_GS, 9.1 cm² V^?1 s^?1 at high V_GS and 7.6 cm² V^?1 s^?1 from the linear region, which presents one of the best results of previously reported MOFETs so far and indicates that the monolayer semiconductor growing on pure polymer dielectric could produce highly efficient charge transport.     

Highly Efficient Three Primary Color Organic Single‐Crystal Light‐Emitting Devices with Balanced Carrier Injection and Transport

Organic single crystals have a great potential in the field of organic optoelectronics because of their advantages of high carrier mobility and high thermal stability. However, the application of the organic single crystals in light‐emitting devices (OLEDs) has been limited by single‐layered structure with unbalanced carrier injection and transport. Here, fabrication of a multilayered‐structure crystal‐based OLED constitutes a major step toward balanced carrier injection and transport by introducing an anodic buffer layer and electron transport layer into the device structure. Three primary color single‐crystal‐based OLEDs based on the multilayered structure and molecular doping exhibit a maximum luminance and current efficiency of 820 cd cm^?2 and 0.9 cd A^?1, respectively, which are the highest performance to date for organic single‐crystal‐based OLEDs. This work paves the way toward high‐performance organic optoelectronic devices based on the organic single crystals.     

Polymer‐Based Organic Field‐Effect Transistors with Active Layers Aligned by Highly Hydrophobic Nanogrooved Surfaces

In this study, polymer‐based organic field‐effect transistors (OFETs) that exhibit alignment‐induced mobility enhancement, very small device‐to‐device variation, and high operational stability are successfully fabricated by a simple coating method of semiconductor solutions on highly hydrophobic nanogrooved surfaces. The highly hydrophobic nanogrooved surfaces (water contact angle >110°) are effective at inducing unidirectional alignment of polymer backbone structures with edge‐on orientation and are advantageous for realizing high operational stability because of their water‐repellent nature. The dewetting of the semiconductor solution is a critical problem in the thin film formation on highly hydrophobic surfaces. Dewetting during spin coating is suppressed by surrounding the hydrophobic regions with hydrophilic ones under appropriate designs. For the OFET array with an aligned terrace‐phase active layer of poly(2,5‐bis(3‐hexadecylthiophene‐2‐yl)thieno[3,2‐b]thiophene), the hole mobility in the saturation regime of 30 OFETs with channel current direction parallel to the nanogrooves is 0.513 ± 0.018 cm² V^?1 s^?1, which is approximately double that of the OFETs without nanogrooves, and the intrinsic operational stability is comparable to the operational stability of amorphous‐silicon field‐effect transistors. In other words, alignment‐induced mobility enhancement and high operational stability are successfully achieved with very small device‐to‐device variation. This coating method should be a promising means of fabricating high‐performance OFETs.     

Solution‐Processable Dithienothiophenoquinoid (DTTQ) Structures for Ambient‐Stable n‐Channel Organic Field Effect Transistors

A series of dialkylated dithienothiophenoquinoids ( DTTQ s), end‐functionalized with dicyanomethylene units and substituted with different alkyl chains, are synthesized and characterized. Facile one‐pot synthesis of the dialkylated DTT core is achieved, which enables the efficient realization of DTTQ s as n‐type active semiconductors for solution‐processable organic field effect transistors (OFETs). The molecular structure of hexyl substituted DTTQ‐6 is determined via single‐crystal X‐ray diffraction, revealing DTTQ is a very planar core. The DTTQ cores form a “zig‐zag” linking layer and the layers stack in a “face‐to‐face” arrangement. The very planar core structure, short core stacking distance (3.30 Å), short intermolecular S? N distance (2.84 Å), and very low lying lowest unoccupied molecular orbital energy level of ?4.2 eV suggest that DTTQ s should be excellent electron transport candidates. The physical and electrochemical properties as well as OFETs performance and thin film morphologies of these new DTTQ s are systematically studied. Using a solution‐shearing method, DTTQ‐11 exhibits n‐channel transport with the highest mobility of up to 0.45 cm² V^?1 s^?1 and a current ON/OFF ratio (I _ON/I _OFF) greater than 10⁵. As such, DTTQ‐11 has the highest electron mobility of any DTT‐based small molecule semiconductors yet discovered combined with excellent ambient stability. Within this family, carrier mobility magnitudes are correlated with the alkyl chain length of the side chain substituents of DTTQ s.     

Boosting the Charge Transport Property of Indeno[1,2‐b]fluorene‐6,12‐dione though Incorporation of Sulfur‐ or Nitrogen‐Linked Side Chains

Alkyl chains are basic units in the design of organic semiconductors for purposes of enhancing solubility, tuning electronic energy levels, and tailoring molecular packing. This work demonstrates that the carrier mobilities of indeno[1,2‐b ]fluorene‐6,12‐dione ( IFD )‐based semiconductors can be dramatically enhanced by the incorporation of sulfur‐ or nitrogen‐linked side chains. Three IFD derivatives possessing butyl, butylthio, and dibutylamino substituents are synthesized, and their organic field‐effect transistors (OFET) are fabricated and characterized. The IFD possessing butyl substituents exhibits a very poor charge transport property with mobility lower than 10^?7 cm² V^?1 s^?1. In contrast, the hole mobility is dramatically increased to 1.03 cm² V^?1 s^?1 by replacing the butyl units with dibutylamino groups ( DBA‐IFD ), while the butylthio‐modified IFD ( BT‐IFD ) derivative exhibits a high and balanced ambipolar charge transport property with the maximum hole and electron mobilities up to 0.71 and 0.65 cm² V^?1 s^?1, respectively. Moreover, the complementary metal–oxide–semiconductor‐like inverters incorporated with the ambipolar OFETs shows sharp inversions with a maximum gain value up to 173. This work reveals that modification of the aromatic core with heteroatom‐linked side chains, such as alkylthio or dialkylamino, can be an efficient strategy for the design of high‐performance organic semiconductors.     

Molecular Packing‐Induced Transition between Ambipolar and Unipolar Behavior in Dithiophene‐4,9‐dione‐Containing Organic Semiconductors

By changing the packing motif of the conjugated cores and the thin‐film microstructures, unipolar organic semiconductors may be converted into ambipolar materials. A combined experimental and theoretical investigation is conducted on the thin‐film organic field‐effect transistors (OFETs) of three organic semiconductors that have the same conjugated core structure of s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐4,9‐dione but with different n‐alkyl groups. The optical and electrochemical measurements suggest that the three organic semiconductors have very similar energy levels; however, their OFETs exhibit dramatically different transport characteristics. Transistors based on compound 1a or 1c show ambipolar transport properties, while those based on compound 1b show p‐type unipolar behavior. Specifically, compound 1c is characterized as a good ambipolar semiconductor with the highest electron mobility of 0.22 cm² V^?1 s^?1 and the highest hole mobility of 0.03 cm² V^?1 s^?1. Complementary metal oxide semiconductor (CMOS) inverters incorporated with compound 1c show sharp inversions with high gains above 50. Theoretical investigations reveal that the drastic difference in the transport properties of the three materials is due to the difference in their molecular packing and film microstructures.     

Effect of Donor Molecular Structure and Gate Dielectric on Charge‐Transporting Characteristics for Isoindigo‐Based Donor–Acceptor Conjugated Polymers

This study investigates the effect of the molecular structure of three different donor units, naphthalene (Np), bithiophene (BT), and thiophene–vinylene–thiophene (TVT), in isoindigo (IIG)‐based donor –acceptor conjugated polymers (PIIG‐Np, PIIG‐BT and PIIG‐TVT) on the charge carrier mobility of organic field‐effect transistors (OFETs). The charge transport properties of three different IIG‐based polymers strongly depend on donor units. PIIG–BT OFETs showed 50 times higher hole mobility (0.63 cm² V^?1 s^?1) than PIIG–TVT and PIIG–Np ones of ≈ 0.01 cm² V^?1 s^?1 with CYTOP dielectric though the BT units have less planarity than the TVT and Np units. The reasons for the different mobility in IIG‐based polymers are studied by analyzing the energy structure by absorption spectra, calculating transport levels by density functional theory, investigating the in‐ and out‐of‐plane crystallinity of thin film by grazing‐incidence wide‐angle X‐ray scattering, and extracting key transport parameters via low‐temperature measurements. By combining theoretical, optical, electrical, and structural analyses, this study finds that the large difference in OFET mobility mainly originates from the transport disorders determined by the different microcrystal structure, rather than the intrinsic transport properties in isolated chains for different polymers.     

Stable Delocalized Singlet Biradical Hydrocarbon for Organic Field‐Effect Transistors

Delocalized singlet biradical hydrocarbons hold promise as new semiconducting materials for high‐performance organic devices. However, to date biradical organic molecules have attracted little attention as a material for organic electronic devices. Here, this work shows that films of a crystallized diphenyl derivative of s‐indacenodiphenalene (Ph₂‐IDPL) exhibit high ambipolar mobilities in organic field‐effect transistors (OFETs). Furthermore, OFETs fabricated using Ph₂‐IDPL single crystals show high hole mobility (μ_h = 7.2 × 10^?1 cm² V^?1 s^?1) comparable to that of amorphous Si. Additionally, high on/off ratios are achieved for Ph₂‐IDPL by inserting self‐assembled mono­layer of alkanethiol between the semiconducting layer and the Au electrodes. These findings open a door to the application of ambipolar OFETs to organic electronics such as complementary metal oxide semiconductor logic circuits.     

Inkjet‐Printed Organic Electrodes for Bottom‐Contact Organic Field‐Effect Transistors

A graphite thin film was investigated as the drain and source electrodes for bottom‐contact organic field‐effect transistors (BC OFETs). Highly conducting electrodes (10² S cm^?1) at room temperature were obtained from pyrolyzed poly(l,3,4‐oxadiazole) (PPOD) thin films that were prepatterned with a low‐cost inkjet printing method. Compared to the devices with traditional Au electrodes, the BC OFETs showed rather high performances when using these source/drain electrodes without any further modification. Being based on a graphite‐like material these electrodes possess excellent compatibility and proper energy matching with both p‐ and n‐type organic semiconductors, which results in an improved electrode/organic‐layer contact and homogeneous morphology of the organic semiconductors in the conducting channel, and finally a significant reduction of the contact resistance and enhancement of the charge‐carrier mobility of the devices is displayed. This work demonstrates that with the advantages of low‐cost, high‐performance, and printability, PPOD could serve as an excellent electrode material for BC OFETs.     

Electroless‐Plated Gold Contacts for High‐Performance,Low Contact Resistance Organic Thin Film Transistors

Deposition of metallic electrodes on a semiconductor medium is an indispensable factor in governing carrier injection, and a metal/semiconductor contact that can be formed via solution process is highly desired in printed electronics. However, fine‐patterning the solution processes of metallic electrodes without damaging the excellent electronic properties of organic semiconductors (OSCs) is still a challenge. In this work, electroless plating, a metal coating technique that involves auto‐catalytic reaction in an aqueous solution, is used to fabricate top‐contact organic thin‐film transistors (OTFTs). An electroless‐plated gold pattern with a spatial resolution of 10 micrometers is transferred and laminated on a monolayer of OSCs to serve as a hole‐injection electrode. The fabricated OTFTs exhibit reasonably high field‐effect mobility of up to 13 cm² V^?1 s^?1 and decent contact resistance as low as 120 Ω · cm, which implies that an ideal metal/semiconductor contact can be realized. This electroless plating technique can provide possibilities for practical mass production of organic integrated circuits because it is in principle cost‐effective, capable of covering large areas, high‐vacuum free, and environmentally friendly.     

Accurate Extraction of Charge Carrier Mobility in 4‐Probe Field‐Effect Transistors

Charge carrier mobility is an important characteristic of organic field‐effect transistors (OFETs) and other semiconductor devices. However, accurate mobility determination in FETs is frequently compromised by issues related to Schottky‐barrier contact resistance, that can be efficiently addressed by measurements in 4‐probe/Hall‐bar contact geometry. Here, it is shown that this technique, widely used in materials science, can still lead to significant mobility overestimation due to longitudinal channel shunting caused by voltage probes in 4‐probe structures. This effect is investigated numerically and experimentally in specially designed multiterminal OFETs based on optimized novel organic‐semiconductor blends and bulk single crystals. Numerical simulations reveal that 4‐probe FETs with long but narrow channels and wide voltage probes are especially prone to channel shunting, that can lead to mobilities overestimated by as much as 350%. In addition, the first Hall effect measurements in blended OFETs are reported and how Hall mobility can be affected by channel shunting is shown. As a solution to this problem, a numerical correction factor is introduced that can be used to obtain much more accurate experimental mobilities. This methodology is relevant to characterization of a variety of materials, including organic semiconductors, inorganic oxides, monolayer materials, as well as carbon nanotube and semiconductor nanocrystal arrays.     

High‐Mobility Air‐Stable Naphthalene Diimide‐Based Copolymer Containing Extended π‐Conjugation for n‐Channel Organic Field Effect Transistors

A high‐performance naphthalene diimide (NDI)‐based conjugated polymer for use as the active layer of n‐channel organic field‐effect transistors (OFETs) is reported. The solution‐processable n‐channel polymer is systematically designed and synthesized with an alternating structure of long alkyl substituted‐NDI and thienylene–vinylene–thienylene units (PNDI‐TVT). The material has a well‐controlled molecular structure with an extended π‐conjugated backbone, with no increase in the LUMO level, achieving a high mobility and highly ambient stable n‐type OFET. The top‐gate, bottom‐contact device shows remarkably high electron charge‐carrier mobility of up to 1.8 cm² V^?1 s^?1 (I_on/I_off = 10⁶) with the commonly used polymer dielectric, poly(methyl methacrylate) (PMMA). Moreover, PNDI‐TVT OFETs exhibit excellent air and operation stability. Such high device performance is attributed to improved π–π intermolecular interactions owing to the extended π‐conjugation, apart from the improved crystallinity and highly interdigitated lamellar structure caused by the extended π–π backbone and long alkyl groups.     

A Densely and Uniformly Packed Organic Semiconductor Based on Annelated β‐Trithiophenes for High‐Performance Thin Film Transistors

A novel semiconductor based on annelated β‐trithiophenes is presented, possessing an extraordinary compressed packing mode combining edge‐to‐face π–π interactions and S…S interactions in single crystals, which is favorable for more effective charge transporting. Accordingly, the device incorporating this semiconductor shows remarkably high charge carrier mobility, as high as 0.89 cm² V^?1 s^?1, and an on/off ratio of 4.6 × 10⁷ for vacuum‐deposited thin films.     

High Hole Mobility in Long‐Range Ordered 2D Lead Sulfide Nanocrystal Monolayer Films

Coupling between colloidal semiconductor nanocrystals (NCs) with long‐range order is critical for designing advanced nanostructures with controlled energy flow and charge carrier transport. Herein, under the premise of keeping long‐range order in 2D NC monolayer, its native organic ligands are exchanged with halogen ions in situ at the liquid–air interface to enhance the coupling between NCs. Further treatments on the films with dimethyl sulfoxide, methanol, or their mixture effectively improve carrier mobility of the devices. The devices show repeatable enhanced p‐type transport behavior with hole mobility of up to 0.224 ± 0.069 cm² V^?1 s^?1, the highest value reported for lead sulfide NC solids without annealing treatment. Thanks to accurate control over the surface of NCs as well as the structure of NC film, the ordered NC monolayer film of high hole mobility suggests great potentials for making reliable high performance devices.     

A Facile Method for the Growth of Organic Semiconductor Single Crystal Arrays on Polymer Dielectric toward Flexible Field‐Effect Transistors

Polymer dielectrics with intrinsic mechanical flexibility are considered as a key component for flexible organic field‐effect transistors (OFETs). However, it remains a challenge to fabricate highly aligned organic semiconductor single crystal (OSSC) arrays on the polymer dielectrics. Herein, for the first time, a facile and universal strategy, polar surface‐confined crystallization (PSCC), is proposed to grow highly aligned OSSC arrays on poly(4‐vinylphenol) (PVP) dielectric layer. The surface polarity of PVP is altered periodically with oxygen‐plasma treatment, enabling the preferential nucleation of organic crystals on the strong‐polarity regions. Moreover, a geometrical confinement effect of the patterned regions can also prevent multiple nucleation and misaligned molecular packing, enabling the highly aligned growth of OSSC arrays with uniform morphology and unitary crystallographic orientation. Using 2,7‐dioctyl[1]benzothieno[3,2‐b]benzothiophene (C8‐BTBT) as an example, highly aligned C8‐BTBT single crystal arrays with uniform molecular packing and crystal orientation are successfully fabricated on the PVP layer, which can guarantee their uniform electrical properties. OFETs made from the C8‐BTBT single crystal arrays on flexible substrates exhibit a mobility as high as 2.25 cm² V^?1 s^?1, which has surpassed the C8‐BTBT polycrystalline film‐based flexible devices. This work paves the way toward the fabrication of highly aligned OSSCs on polymer dielectrics for high‐performance, flexible organic devices.     

Hybrid Nanodielectrics for Low‐Voltage Organic Electronics

Nanoscale hybrid dielectrics composed of an ultra‐thin polymeric low‐κ bottom layer and an ultra‐thin high‐κ oxide top layer, with high dielectric strength and capacitances up to 0.25 μFcm^?2, compatible with low‐voltage, low‐power, organic electronic circuits are demonstrated. An efficient and reliable fabrication process, with 100% yield achieved on lab‐scale arrays, is demonstrated by means of pulsed laser deposition (PLD) for the fast growth of the oxide layer. With this strategy, high capacitance top gate (TG), n‐type and p‐type organic field effect transistors (OFETs) with high mobility, low leakage currents, and low subthreshold slopes are realized and employed in complementary‐like inverters, exhibiting ideal switching for supply voltages as low as 2 V. Importantly, the hybrid double‐layer allows for a neat decoupling between the need for a high capacitance, guaranteed by the nanoscale thickness of the double layer, and for an optimized semiconductor–dielectric interface, a crucial point in enabling high mobility OFETs, thanks to the low‐κ polymeric dielectric layer in direct contact with the polymer semiconductor. It is shown that such decoupling can be achieved already with a polymer dielectric as thin as 10 nm when the top oxide is deposited by PLD. This paves the way for a very versatile implementation of the proposed approach for the scaling of the operating voltages of TG OFETs with very low level of dielectric leakage currents to the fabrication of low‐voltage organic electronics with drastically reduced power consumption.