N-type Organic Field-effect Transistors Research Articles

Impact of Packing Geometry on Excimer Characteristics and Mobility in Perylene Bisimide Polycrystalline Films.

Efficient exciton transport is essential for high-performance optoelectronics. Considerable efforts have been focused on improving the exciton mobility in organic materials. While it is feasible to improve mobility in organic systems by forming well-ordered stacks, the formation of trap states, particularly the lower-lying states referred to as excimers, remains a significant challenge to enhancing mobility. The mobility of excimer excitons intricately depends on the strength of excitonic coupling in terms of Förster-type diffusive exciton transfer processes. Given that the formation and mobility of excimer excitons are highly sensitive to molecular arrangements (packing geometries), conducting comprehensive investigations into the structure-property relationship in organic systems is crucial. In this study, we prepared three types of polycrystalline films of perylene bisimide (PBI) by varying substituents at the imide and bay positions, which allowed us to tailor the properties of excimer excitons and their mobility based on packing geometries and excitonic coupling strengths. By utilizing femtosecond transient absorption spectroscopy, we observed ultrafast excimer formation in the higher coupling regime, while in the lower coupling regime, the transition from Frenkel to excimer excitons occurs with a time constant of 500 fs. Under high pump-fluence, exciton-exciton annihilation processes occur, indicating the diffusion of excimer excitons. Intriguingly, employing a three-dimensional diffusion model, we derived a diffusion constant that is 3000 times greater in the high coupling regime than in the low coupling regime. To investigate the optoelectronic properties in the form of a bulk system, we fabricated n-type organic field effect transistors and obtained 8000 times higher mobility in the high coupling regime. Furthermore, photocurrent measurements enable us to investigate the charge carrier transport by mobile excimer excitons, suggesting a 230-fold improvement in external quantum efficiency with tightly packing PBI molecules compared to the low coupling regime. These findings not only offer valuable insights into optimizing organic materials for optoelectronic devices but also unveil the intriguing potential of exciton migration within excimers.

A Novel N-Type Molecular Dopant With a Closed-Shell Electronic Structure Applicable to the Vacuum-Deposition Process.

Rational design, synthesis, and characterization of a new efficient versatile n-type dopant with a closed-shell electronic structure are described. By employing the tetraphenyl-dipyranylidene (DP0) framework with two 7π-electron systems modified with N,N-dimethylamino groups as the strong electron-donating substituent, 2,2',6,6'-tetrakis[4-(dimethylamino)phenyl]-4,4'-dipyranylidene (DP7), a closed-shell molecule with an extremely high-lying energy level of the highest occupied molecular orbital, close to 4.0eV below the vacuum level, is successfully developed. Thanks to its thermal stability, DP7 is applicable to vacuum deposition, which allows utilization of DP7 in bulk doping for the development of n-type organic thermoelectric materials and contact doping for reducing contact resistance in n-type organic field-effect transistors. As vacuum-deposition processable n-type dopants are very limited, DP7 stands out as a useful n-type dopant, particularly for the latter purpose.

Ambient stable solution-processed organic field effect transistors from electron deficient planar aromatics: effect of end-groups on ambient stability.

Ambient stable solution processed n-channel organic field effect transistors (OFETs) are essential for next-generation low-cost organic electronic devices. Several molecular features, such as suitable orbital energy levels, easy synthetic steps, etc., must be considered while designing efficient active layer materials. Here, we report a case of improved ambient stability of solution-processed n-type OFETs upon suitable end-groups substitution of the active layer materials. A pair of core-substituted napthalenediimide (NDIFCN2 and EHNDICN2) derivatives with alkyl and perfluorinated end groups are considered. The transistor devices made out of these two derivatives exhibited largely different ambient stability behavior. The superior device stability (more than 25 days under ambient conditions) of one of the derivatives (NDIFCN2) was ascribed to the presence of fluorinated end groups that function as hydrophobic guard units inhibiting moisture infiltration into the active layer, thereby achieving ambient stability under humid conditions (>65% relative atmospheric humidity). Molecular level optical and electrochemical properties, thermal stability, and the solution-processed (spin coat and drop cast active layers) device characteristics are described in detail. Our findings highlight the requirement of hydrophobic end groups or sidechains for ambient stability of active layer materials, along with deep LUMO levels for ambient stability.

Solution-processable quinoidal compounds containing heterocycle for air-stable n‑type organic field-effect transistors and gas sensors

Organic field effect transistors (OFETs) have potential applications in gas sensing area, but the performance and diversity of n-type OFETs are still far behind that of p-type OFETs due to the poor stability in air atmosphere. Herein, a series of novel dicyanomethylene-terminated quinoids compounds were synthesized and characterized by using electron withdrawing aromatic heterocycles as the core structural units. The introduction of alkyl branch chain greatly improves the solubility, which is helpful to the preparation of thin film OFETs devices by low-cost solution method. These OFETs show typical n-channel FET characteristics with mobility ranging from 10−3∼10−1 cm2V−1s−1. Among them, the 3-T-TZCN based OFETs exhibit the best stability, in which the mobility decreased no more than 18 % after 90 days stored in air atmosphere, this is an outstanding performance compared with the previous researches. We further investigated the dimethyl methylphosphonate (DMMP, which is a substitute for detecting sarin) gas sensing performance of each material, the experimental results indicated that the sensitivity, recovery and stability of 3-T-TZCN are better than other materials, and the limit of detection can be lower to 10 ppb level. This general approach could offer new solution for constructing n-type OFET-based gas sensors with good stability in air atmosphere.

Aldol Condensation for the Construction of Organic Functional Materials.

Aldol condensation is a cost-effective and sustainable synthetic method, offering the advantages of low complexity, substrate universality, and high efficiency. Over the past decade, it has become popular for creating next-generation organic functional materials, particularly rigid-rod conjugated (semi)conductors. This review focuses on conjugated small molecules, oligomers, and polymeric (semi)conductors synthesized through aldol condensation, with emphasis on their remarkable features in advancing n-type organic field-effect transistors (OFETs), organic electrochemical transistors (OECTs), organic photovoltaics (OPVs), and organic thermoelectrics (OTEs) as well as NIR-II photothermal conversion. Coherence character, optical properties, microstructure, and chain conformation are investigated to understand material-property relationships. Future applications and challenges in this area are also discussed.

Efficient N-Type Organic Electrochemical Transistors and Field-Effect Transistors Based on PNDI-Copolymers Bearing Fluorinated Selenophene-Vinylene-Selenophenes.

n-Type organic electrochemical transistors (OECTs) and organic field-effect transistors (OFETs) are less developed than their p-type counterparts. Herein, polynaphthalenediimide (PNDI)-based copolymers bearing novel fluorinated selenophene-vinylene-selenophene (FSVS) units as efficient materials for both n-type OECTs and n-type OFETs are reported. The PNDI polymers with oligo(ethylene glycol) (EG7) side chains P(NDIEG7-FSVS), affords a high µC* of > 0.2Fcm-1 V-1 s-1 , outperforming the benchmark n-type Pg4NDI-T2 and Pg4NDI-gT2 by two orders of magnitude. The deep-lying LUMO of -4.63eV endows P(NDIEG7-FSVS) with an ultra-low threshold voltage of 0.16V. Moreover, the conjugated polymer with octyldodecyl (OD) side chains P(NDIOD-FSVS) exhibits a surprisingly low energetic disorder with an Urbach energy of 36meV and an ultra-low activation energy of 39meV, resulting in high electron mobility of up to 0.32cm2 V-1 s-1 in n-type OFETs. These results demonstrate the great potential for simultaneously achieving a lower LUMO and a tighter intermolecular packing for the next-generation efficient n-type organic electronics.

Remarkable Electrical Conductivity Increase and Pure Metallic Properties from Semiconducting Colloidal Nanocrystals by Cation Exchange for Solution-Processable Optoelectronic Applications.

The authors report a strategic approach to achieve metallic properties from semiconducting CuFeS colloidal nanocrystal (NC) solids through cation exchange method. An unprecedentedly high electrical conductivity is realized by the efficient generation of charge carriers onto a semiconducting CuS NC template via minimal Fe exchange. An electrical conductivity exceeding 10 500 S cm-1 (13 400 S cm-1 at 2 K) and a sheet resistance of 17 Ω/sq at room temperature, which are among the highest values for solution-processable semiconducting NCs, are achieved successfully from bornite-phase CuFeS NC films possessing 10% Fe atom. The temperature dependence of the corresponding films exhibits pure metallic characteristics. Highly conducting NCs are demonstrated for a thermoelectric layer exhibiting a high power factor over 1.2mW m-1 K-2 at room temperature, electrical wires for switching on light emitting diods (LEDs), and source-drain electrodes for p- and n-type organic field-effect transistors. Ambient stability, eco-friendly composition, and solution-processability further validate their sustainable and practical applicability. The present study provides a simple but very effective method for significantly increasing charge carrier concentrations in semiconducting colloidal NCs to achieve metallic properties, which is applicable to various optoelectronic devices.

Modular Modeling of Analog Organic Neuromorphic Circuits: Toward Prototyping of Hardware-Level Spiking Neural Networks

This work proposes a novel modeling approach for analog organic circuits using very simple to customize circuit topology and parameters of individual p- and n-type organic field effect transistors (OFETs). Aided with the combination of primitive elements (OFETs, capacitors, resistors), the convoluted behavior of analog organic neuromorphic circuits (ONCs) and even other general analog organic circuits, can be predicted. The organic log-domain integrator (oLDI) synaptic circuit, the organic differential-pair integrator (oDPI) synaptic circuit, and the organic Axon-Hillock (oAH) somatic circuit are designed and serve as the modular circuit primitives of more complicated ONCs. We first validate our modeling approach by comparing the simulated oDPI and oAH circuit responses to their experimental measurements. Thereafter, the summation effects of the excitatory and inhibitory oDPI circuits in prototyped ONCs are investigated. We also predict the dynamic power dissipation of modular ONCs and show an average power consumption of <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$2.1 \mu \text {J}$ </tex-math></inline-formula> per spike for the oAH soma at a ~1 Hz spiking frequency. Furthermore, we compare our modeling approach with other two representative organic circuit models and prove that our approach outperforms the other two in terms of accuracy and convergence speed.

Difluorobenzimidazole-decorated helical perylene diimide dimers for high-performance n-type organic field-effect transistors

N-type benzimidazole and difluorobenzimidazole fused perylene diimide dimer semiconductors were synthesized and a remarkable electronic mobility of 0.13 cm2 V−1 s−1 was obtained for a FMBI-PDI2-based organic field-effect transistor (OFET).

Enhanced environmental stability of n-type polymer transistors with nickel contacts

N-type organic field-effect transistors have suffered from poor environmental instability. Here, we report that, by using nickel (Ni) instead of the commonly used gold (Au) as contact electrodes, n-type polymer transistors showed much improved stability upon annealing in nitrogen and exposure to air. In particular, Au-contacted devices exhibited pronounced ambipolar conduction whereas Ni-contacted devices retained fairly good unipolar properties. The results are important to build stable n-type polymer transistors at low cost.

Naphthodipyrrolopyrrole-based Aza-BODIPY dye for N-type organic field-effect transistors

To date, n-type semiconductor designs are less investigated than their p-type counterparts, due to the fact that the charge transport mobility and the stability of the n-type materials are generally lower than those of the p-type ones. Well-defined n-type semiconductors often require low lowest unoccupied molecular orbital (LUMO) levels that facilitate the electron injection from the electrode into the semiconductors. Therefore, it is of significance to explore novel chromophores with strong electron-deficient properties, yet it is still challenging. Herein, a naphthodipyrrolopyrrole-based dimeric aza-boron dipyrromethene (Aza-BODIPY) dye (NDP-AB) is designed and synthesized. The optical studies indicate that NDP-AB presents a blue spectral shift (111 nm) in solution phase compared to the thin film state, while exhibiting a photoluminescence emission quenching. The NDP-AB semiconductor demonstrates strong acceptor properties with a low LUMO energy level of only −4.25 eV, owing to the multi-fluorine atoms, unsaturated nitrogen atoms, as well as the amide functional groups. Moreover, the large conjugation system, highly planar core, along with the large transition dipole on the line that links 2-position with 6-position of the BODIPY core, result in NDP-AB with a strong H-aggregation. As a consequence, the NDP-AB-based semiconductors show a good n-type behavior with an average electron mobility of 0.16 cm2 V−1 s−1. Our work, proposes a strong electron-deficient chromophore that is a promising candidate as building block of organic field-effect transistors. Our design strategy paves the way for the identification of more n-type semiconductor materials with high-performance.

Isoindigo-based aza-BODIPY small molecule for N-type organic field-effect transistors

To date, most of the reported conjugated materials are p-type semiconductors, while the advances in n-type or ambipolar conjugated materials greatly fall behind those in p-type counterparts. Well-defined n-type semiconductors should possess suitable electron-deficient groups and relatively low lowest unoccupied molecular orbitals (LUMO) levels that facilitate the electron injection and stabilize the electron transport. Thus, developing novel n-type semiconductor materials with strong electron-deficient property, high electron mobility, and competitive stability is still highly desirable, though challenging. Herein, a new isoindigo-based dimeric aza-boron dipyrromethene (aza-BODIPY) chromophore (IIDG-AB) is designed and synthesized. IIDG-AB contains multiple fluorine and unsaturated nitrogen atoms, which endow it with strong electron-deficient property as well as an ultra-low LUMO level of only −4.24 eV. In addition, IIDG-AB features a large conjugation system and a high degree of coplanarity, which are beneficial for effective intermolecular charge transfer. The UV/visible absorption spectra, X-ray diffraction analysis, and morphological studies via atomic force microscopy imaging indicate that the IIDG-AB thin film presents strong aggregation, good π-π stacking, and long-range order packing, all of which are favorable for the electron transfer between neighboring molecules. Furthermore, IIDG-AB-based organic field-effect transistors exhibit a moderate stable n-type behavior with the highest electron mobility of 1.1 × 10−1 cm2 V−1 s−1. This work provides a simple and effective strategy to synthesize highly functional n-type chromophores via a Schiff base reaction between bislactams and heteroaromatic amines, and also paves the way for future design to fabricate high-performance n-type semiconductor materials for a wide range of applications.

Solution processable dithioalkylated methylidenyl cyclopentadithiophene based quinoidal small molecules for n-type organic field-effect transistors

A series of dithioalkylated methylidenyl cyclopentadithiophene-based quinoidal small molecules (CDTSQs) with different side chain lengths were designed for n-type OFETs, reaching electron mobility of 0.14 cm2 V−1 s−1 with good ambient stability.

Tailored Polymer Gate Dielectric Engineering to Optimize Flexible Organic Field-Effect Transistors and Complementary Integrated Circuits.

The increasing demand for solution-processed and flexible organic electronics has promoted the fabrication of integrated logic circuits using organic field-effect transistors (OFETs) instead of fundamental unit devices. This has been made possible through the rapid development of materials and processes in the past few decades. It is important for the p- and n-type OFETs using different organic semiconductors (OSCs) to have complementarily matched electrical characteristics, which significantly improve the performance of organic logic circuits. In this study, an efficient strategy to optimize the performance of flexible organic electronics, such as OFETs and complementary inverters, is proposed using a combination of polymer insulators tailored to each OSC type. Photopatternable soluble copolyimides (ScoPIs), which exhibit excellent insulating properties and chemical resistance, are synthesized and applied as gate dielectric layers in the OFETs. The material and electrical properties are systematically investigated by varying the molecular ratio of ScoPIs to determine the optimal conditions for each OFET type. As a result, complementary inverters report 1.67 times higher integration density compared to the conventional ones while maintaining gain, switching threshold, and static noise margin of 23.7 V/V, 22.1 V, and 12.1 V, respectively, at a supply voltage of 40 V. The flexible complementary inverters are successfully demonstrated by fully exploiting the advantages of ScoPIs.

Directly Patterning Conductive Polymer Electrodes on Organic Semiconductor via In Situ Polymerization in Microchannels for High-Performance Organic Transistors.

Conductive polymers are considered promising electrode materials for organic transistors, but the reported devices with conductive polymer electrodes generally suffer from considerable contact resistance. Currently, it is still highly challenging to pattern conductive polymer electrodes on organic semiconductor surfaces with good structure and interface quality. Herein, we develop an in situ polymerization strategy to directly pattern the top-contacted polypyrrole (PPy) electrodes on hydrophobic surfaces of organic semiconductors by microchannel templates, which is also applicable on diverse hydrophobic and hydrophilic surfaces. Remarkably, a width-normalized contact resistance as low as 1.01 kΩ·cm is achieved in the PPy-contacted transistors. Both p-type and n-type organic field-effect transistors (OFETs) exhibit ideal electrical characteristics, including almost hysteresis-free, low threshold voltage, and good stability under long-term test. The facile patterning method and high device performance indicate that the in situ polymerization strategy in confined microchannels has application prospects in all-organic, transparent, and flexible electronics.

Electron Injection Improvement of n-Type Organic Field-Effect Transistors With Indium Contact Interlayer

The organic field-effect transistors (OFETs) have developed rapidly in recent years. However, compared with the p-type OFETs, the n-type devices always show poorer performance due to their hard electron injection and low stability. It is necessary to further improve the charge injection properties of n-type OFETs. In this work, indium (In) layers, as an interlayer above contacts, were adopted for electron injection improvement in the n-type poly((N, $\text{N}^{\prime }$ -bis(2-octyldodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl)-alt-5, $5^{\prime }$ -(2, $2^{\prime }$ -bithiophene)) (N2200) OFETs. The injection barrier, such as Schottky barrier, at the metal/semiconductor interface was effectively weakened with the In interlayers thickness ( ${T}_{In}$ ) increasing from 0 to 6 nm. The mechanism of electron injection changed from thermionic emission to tunneling, as the ${T}_{In}$ reaching 6 nm. It results in a marked improvement in electrical properties for N2200 OFETs. The mobility increased from 0.09 to 0.29 cm ${}^{2}\cdot \text{V}^{-1}\cdot \text{s}^{-1}$ while the subthreshold swing decreased from 2.7 to 0.8 $\text{V}\cdot $ dec−1 with the ${T}_{In}$ . This work provides an efficient approach for the electron injection improvement in n-type OFETs.

One-Step Sixfold Cyanation of Benzothiadiazole Acceptor Units for Air-Stable High-Performance n-Type Organic Field-Effect Transistors.

Reported here is a new high electron affinity acceptor end group for organic semiconductors, 2,1,3‐benzothiadiazole‐4,5,6‐tricarbonitrile (TCNBT). An n‐type organic semiconductor with an indacenodithiophene (IDT) core and TCNBT end groups was synthesized by a sixfold nucleophilic substitution with cyanide on a fluorinated precursor, itself prepared by a direct arylation approach. This one‐step chemical modification significantly impacted the molecular properties: the fluorinated precursor, TFBT IDT, a poor ambipolar semiconductor, was converted into TCNBT IDT, a good n‐type semiconductor. The electron‐deficient end group TCNBT dramatically decreased the energy of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO) compared to the fluorinated analogue and improved the molecular orientation when utilized in n‐type organic field‐effect transistors (OFETs). Solution‐processed OFETs based on TCNBT IDT exhibited a charge‐carrier mobility of up to μ e≈0.15 cm2 V−1 s−1 with excellent ambient stability for 100 hours, highlighting the benefits of the cyanated end group and the synthetic approach.

Effect of selenophene in naphthalene-diimide-vinylene-based small molecules on n-type organic field-effect transistors

Abstract Two naphthalene diimide (NDI)-based small molecules, one with a thiophene-vinylene-thiophene linker donor unit (N-TVT-N) and the other with a selenophene-vinylene-selenophene linker donor unit (N-SVS-N), were newly synthesized for the purpose of serving as the active materials of n-type organic field-effect transistors (OFETs). We investigated the various characteristics of the synthesized small molecules to study how the type of donor unit would affect the charge transport of the resulting thin film. The monomeric molecular structure of N-SVS-N, i.e., that with selenium (Se) substituted for sulfur, was found to be tilted about twice as much as that of N-TVT-N, and to display lower backbone planarity. Unexpectedly, the thin films of N-SVS-N each showed a smoother and more uniform surface morphology and predominantly edge-on orientation in comparison with those of N-TVT-N. As the result, the optimally annealed OFETs containing N-SVS-N and N-TVT-N exhibited electron mobilities of up to 0.016 cm2 V−1 s−1 and 6.6 × 10−3 cm2 V−1 s−1, respectively. These results could be explained by the structural features of N-SVS-N facilitating interactions between the electron-rich selenophenes.

High performance n-type organic field-effect transistors based on halogenated derivatives of naphthalene tetracarboxylic diimides

We synthesized three kinds of naphthalene tetracarboxylic diimides (NDIs) containing halogenated phenyl groups by one-step reaction, and they were used as organic semiconductor layers in top-contact Organic field-effect transistors (OFETs). Besides, we adopted SiO2/Si substrates that treated by N-octadecylphosphonic acid (ODPA). In addition, a layer of 4, 4′, 4″-triphenylamine (n-3-methylphenyl-n-phenylamine) triphenylamine (m-MTDATA) was deposited by vacuum between the organic semiconductor layer and the gold electrode as the modification material. It was found through experiments that all the organic materials synthesized by us showed n-type organic semiconductor characteristics. Happily, the device made of NDI-FAN attained the highest electron mobility of 2.2 × 10−1 cm2v−1s−1 at room temperature and in air. The crystallinity and morphology of the films were characterized by x-ray diffraction (XRD) and atomic force microscope (AFM). The results expose that introducing electron withdrawing substituents into naphthalene tetracarboxylic diimides besides inserting ODPA and m-MTDATA are effective ways to achieve high electron mobility.

Direct Printing of Asymmetric Electrodes for Improving Charge Injection/Extraction in Organic Electronics.

Engineering the energy levels of organic conducting materials can be useful for developing high-performance organic field-effect transistors (OFETs), whose electrodes must be well controlled to facilitate easy charge carrier transport from the source to drain through an active channel. However, symmetric source and drain electrodes that have the same energy levels are inevitably unfavorable for either charge injection or charge extraction. In this study, asymmetric source and drain electrodes are simply prepared using the electrohydrodynamic (EHD)-jet printing technique after the careful work function engineering of organic conducting material composites. Two types of additives effectively tune the energy levels of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate-based composites. These solutions are alternately patterned using the EHD-jet printing process, where the use of an electric field makes fine jet control that enables to directly print asymmetric electrodes. The asymmetric combination of EHD-printed electrodes helps in obtaining advanced charge transport properties in p-type and n-type OFETs, as well as their organic complementary inverters. This strategy is believed to provide useful guidelines for the facile patterning of asymmetric electrodes, enabling the desirable properties of charge injection and extraction to be achieved in organic electronic devices.