Small‐Molecule‐Based Organic Field‐Effect Transistor for Nonvolatile Memory and Artificial Synapse

With the incorporation of tailorable organic electronic materials as channel and storage materials, organic field‐effect transistor (OFET)‐based memory has become one of the most promising data storage technologies for hosting a variety of emerging memory applications, such as sensory memory, storage memory, and neuromorphic computing. Here, the recent state‐of‐the‐art progresses in the use of small molecules for OFET nonvolatile memory and artificial synapses are comprehensively reviewed, focusing on the characteristic features of small molecules in versatile functional roles (channel, storage, modifier, and dopant). Techniques for optimizing the storage capacity, speed, and reliability of nonvolatile memory devices are addressed in detail. Insight into the use of small molecules in artificial synapses constructed on OFET memory is also obtained in this emerging field. Finally, the strategies of molecular design for improving memory performance in view of small molecules as storage mediums are discussed systematically, and challenges are addressed to shed light on the future development of this vital research field.     

Organic Junction Field‐Effect Transistor

The realization and performance of a novel organic field‐effect transistor—the organic junction field‐effect transistor (JFET)—is discussed. The transistors are based on the modulation of the thickness of a depletion layer in an organic pin junction with varying gate potential. Based on numerical modeling, suitable layer thicknesses and doping concentrations are identified. Experimentally, organic JFETs are realized and it is shown that the devices clearly exhibit amplification. Changes in the electrical characteristics due to a variation of the intrinsic and the p‐doped layer thickness are rationalized by the numerical model, giving further proof to the proposed operational mechanism.     

Organic Field Effect Transistor-Based Photonic Synapses: Materials,Devices, and Applications

Photonic artificial synapses-based neuromorphic computing systems have been regarded as promising candidates for replacing von Neumann-based computing systems due to the high bandwidth, ultrafast signal transmission, low energy consumption, and wireless communication. Although significant progress has been made in developing varied device structures for synaptic emulation, organic field-effect transistors (OFETs) hold the compelling advantages of facile preparation, liable integration, and versatile structures. As a powerful and effective platform for photonic synapses, OFETs can fulfill not only the simulation of simple synaptic functions, but also complex photoelectric dual modulation and simulation of the visual system. Herein, an overview of OFET-based photonic synapses, including functional materials, device configurations, and innovative applications is provided. Meanwhile, rules for selecting materials, mechanism of photoelectric conversion, and fabrication techniques of devices are also highlighted. Finally, challenges and opportunities are all discussed, providing solid guidance for multilevel memory, multi-functional tandem artificial neural system, and artificial intelligence.     

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.     

Photo‐Stable Organic Thin‐Film Transistor Utilizing a New Indolocarbazole Derivative for Image Pixel and Logic Applications

Small molecule pentacene layer has been a representative among many organic thin‐film transistor (OTFT) channels with decent p‐type mobilities, but it is certainly light‐sensitive due to its relatively small highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) gap (1.85 eV). Although a few other small molecule‐based layers have been reported later, their photo‐stabilities or related device applications have hardly been addressed. Here, a new photostable organic layer is reported, heptazole (C₂₆H₁₆N₂), which has almost the same HOMO level as that of pentacene but with a higher HOMO‐LUMO gap (≈2.95 eV). This heptazole OTFT displays a decent mobility comparable to that of conventional amorphous Si TFTs, showing good photostability unlike pentacene OTFTs. An image pixel driving the photostable heptazole OTFT connected to a pentacene/Al Schottky photodiode is demonstrated. This heptazole OTFT also conveniently forms a logic inverter coupled with a pentacene OTFT, sharing Au for source/drain.     

A Memristive Nanoparticle/Organic Hybrid Synapstor for Neuroinspired Computing

A large effort is devoted to the research of new computing paradigms associated with innovative nanotechnologies that should complement and/or propose alternative solutions to the classical Von Neumann/CMOS (complementary metal oxide semiconductor) association. Among various propositions, spiking neural network (SNN) seems a valid candidate. i) In terms of functions, SNN using relative spike timing for information coding are deemed to be the most effective at taking inspiration from the brain to allow fast and efficient processing of information for complex tasks in recognition or classification. ii) In terms of technology, SNN may be able to benefit the most from nanodevices because SNN architectures are intrinsically tolerant to defective devices and performance variability. Here, spike‐timing‐dependent plasticity (STDP), a basic and primordial learning function in the brain, is demonstrated with a new class of synapstor (synapse‐transistor), called nanoparticle organic memory field‐effect transistor (NOMFET). This learning function is obtained with a simple hybrid material made of the self‐assembly of gold nanoparticles and organic semiconductor thin films. Beyond mimicking biological synapses, it is also demonstrated how the shape of the applied spikes can tailor the STDP learning function. Moreover, the experiments and modeling show that this synapstor is a memristive device. Finally, these synapstors are successfully coupled with a CMOS platform emulating the pre‐ and postsynaptic neurons, and a behavioral macromodel is developed on usual device simulator.     

Core‐Brominated Tetraazaperopyrenes as n‐Channel Semiconductors for Organic Complementary Circuits on Flexible Substrates

Organic thin‐film transistors (TFTs) are prepared by vacuum deposition and solution shearing of 2,9‐bis(perfluoroalkyl)‐substituted tetraazaperopyrenes (TAPPs) with bromine substituents at the aromatic core. The TAPP derivatives are synthesized by reacting known unsubstituted TAPPs with bromine in fuming sulphuric acid, and their electrochemical properties are studied in detail by cyclic voltammetry and modelled with density functional theory (DFT) methods. Lowest unoccupied molecular orbital (LUMO) energies and electron affinities indicate that the core‐brominated TAPPs should exhibit n‐channel semiconducting properties. Current‐voltage characteristics of the TFTs established electron mobilities of up to μ_n = 0.032 cm² V^?1 s^?1 for a derivative which was subsequently processed in the fabrication of a complementary ring oscillator on a flexible plastic substrate (PEN).     

High‐Performance Organic Transistor Memory Elements with Steep Flanks of Hysteresis

High‐performance organic transistor memory elements with donor‐polymer blends as buffer layers are presented. These organic memory transistors have steep flanks of hysteresis with an ON/OFF memory ratio of up to 2 × 10⁴, and a retention time in excess of 24 h. Inexpensive materials such as poly(methyl methacrylate), ferrocene and copper phthalocyanine are used for the device fabrication, providing a convenient approach of producing organic memory transistors at low cost and high efficiency.     

Control of the Morphology and Structural Development of Solution‐Processed Functionalized Acenes for High‐Performance Organic Transistors

Solution‐processable functionalized acenes have received special attention as promising organic semiconductors in recent years because of their superior intermolecular interactions and solution‐processability, and provide useful benchmarks for organic field‐effect transistors (OFETs). Charge‐carrier transport in organic semiconductor thin films is governed by their morphologies and molecular orientation, so self‐assembly of these functionalized acenes during solution processing is an important challenge. This article discusses the charge‐carrier transport characteristics of solution‐processed functionalized acene transistors and, in particular, focuses on the fine control of the films' morphologies and structural evolution during film‐deposition processes such as inkjet printing and post‐deposition annealing. We discuss strategies for controlling morphologies and crystalline microstructure of soluble acenes with a view to fabricating high‐performance OFETs.     

Very Low Degree of Energetic Disorder as the Origin of High Mobility in an n‐channel Polymer Semiconductor

Charge transport is investigated in high‐mobility n‐channel organic field‐effect transistors (OFETs) based on poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (P(NDI2OD‐T2), Polyera ActivInk? N2200) with variable‐temperature electrical measurements and charge‐modulation spectroscopy. Results indicate an unusually uniform energetic landscape of sites for charge‐carrier transport along the channel of the transistor as the main reason for the observed high‐electron mobility. Consistent with a lateral field‐independent transport at temperatures down to 10 K, the reorganization energy is proposed to play an important role in determining the activation energy for the mobility. Quantum chemical calculations, which show an efficient electronic coupling between adjacent units and a reorganization energy of a few hundred meV, are consistent with these findings.     

Fabrication of Organic Thin‐Film Transistors on Three‐Dimensional Substrates Using Free‐Standing Polymeric Masks Based on Soft Lithography

Here, a novel fabrication technique for integrated organic devices on substrates with complex structure is presented. For this work, free‐standing polymeric masks with stencil‐patterns are fabricated using an ultra‐violet (UV) curable polyurethaneacrylate (PUA) mixture, and used as shadow masks for thermal evaporation. High flexibility and adhesive properties of the free‐standing PUA masks ensure conformal contact with various materials such as glass, silicon (Si), and polymer, and thus can also be utilized as patterning masks for solution‐based deposition methods, such as spin‐coating and drop‐casting. Based on this technique, a number of integrated organic transistors are fabricated simultaneously on a cylindrical glass bottle with high curvature, as well as on a flat silicon wafer. It is anticipated that these results will be applied to the development of various integrated organic devices on complex‐structured substrates, which can lead to further applications.     

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.     

Biocompatible and Biodegradable Materials for Organic Field‐Effect Transistors

Biocompatible‐ingestible electronic circuits and capsules for medical diagnosis and monitoring are currently based on traditional silicon technology. Organic electronics has huge potential for developing biodegradable, biocompatible, bioresorbable, or even metabolizable products. An ideal pathway for such electronic devices involves fabrication with materials from nature, or materials found in common commodity products. Transistors with an operational voltage as low as 4–5 V, a source drain current of up to 0.5 μA and an on‐off ratio of 3–5 orders of magnitude have been fabricated with such materials. This work comprises steps towards environmentally safe devices in low‐cost, large volume, disposable or throwaway electronic applications, such as in food packaging, plastic bags, and disposable dishware. In addition, there is significant potential to use such electronic items in biomedical implants.     

High‐Performance,Air‐Stable,Top‐Gate,p‐Channel WSe2 Field‐Effect Transistor with Fluoropolymer Buffer Layer

High‐performance, air‐stable, p‐channel WSe₂ top‐gate field‐effect transistors (FETs) using a bilayer gate dielectric composed of high‐ and low‐k dielectrics are reported. Using only a high‐k Al₂O₃ as the top‐gate dielectric generally degrades the electrical properties of p‐channel WSe₂, therefore, a thin fluoropolymer (Cytop) as a buffer layer to protect the 2D channel from high‐k oxide forming is deposited. As a result, a top‐gate‐patterned 2D WSe₂ FET is realized. The top‐gate p‐channel WSe₂ FET demonstrates a high hole mobility of 100 cm²_­ V^?1 s^?1 and a I_ON/I_OFF ratio > 10⁷ at low gate voltages (V_GS ca. ?4 V) and a drain voltage (V_DS) of ?1 V on a glass substrate. Furthermore, the top‐gate FET shows a very good stability in ambient air with a relative humidity of 45% for 7 days after device fabrication. Our approach of creating a high‐k oxide/low‐k organic bilayer dielectric is advantageous over single‐layer high‐k dielectrics for top‐gate p‐channel WSe₂ FETs, which will lead the way toward future electronic nanodevices and their integration.     

Highly Efficient Inverted Organic Solar Cells Through Material and Interfacial Engineering of Indacenodithieno[3,2‐b]thiophene‐Based Polymers and Devices

A synergistic approach combining new material design and interfacial engineering of devices is adopted to produce high efficiency inverted solar cells. Two new polymers, based on an indacenodithieno[3,2‐b]thiophene‐difluorobenzothiadiazole (PIDTT‐DFBT) donor–acceptor (D–A) polymer, are produced by incorporating either an alkyl thiophene (PIDTT‐DFBT‐T) or alkyl thieno[3,2‐b]thiophene (PIDTT‐DFBT‐TT) π‐bridge as spacer. Although the PIDTT‐DFBT‐TT polymer exhibits decreased absorption at longer wavelengths and increased absorption at higher energy wavelengths, it shows higher power conversion efficiencies in devices. In contrast, the thiophene bridged PIDTT‐DFBT‐T shows a similar change in its absorption spectrum, but its low molecular weight leads to reduced hole mobilities and performance in photovoltaic cells. Inverted solar cells based on PIDTT‐DFBT‐TT are explored by modifying the electron‐transporting ZnO layer with a fullerene self‐assembled monolayer and the MoO₃ hole‐transporting layer with graphene oxide. This leads to power conversion efficiencies as high as 7.3% in inverted cells. PIDTT‐DFBT‐TT's characteristic strong short wavelength absorption and high efficiency suggests it is a good candidate as a wide band gap material for tandem solar cells.     

Silsesquioxane Resins as High‐Performance Solution Processible Dielectric Materials for Organic Transistor Applications

Silsesquioxane polymers have been successfully used as the dielectric layer in organic field‐effect transistors (FETs) deposited on robust, plastic substrates. Performance comparable to that found with silicon substrates having SiO₂ as the active dielectric layer was observed with six p‐ and n‐ channel organic semiconductors. These organopolysiloxane materials can be deposited using conventional liquid coating technologies and are compatible with non‐photolithographic microcontact printing. Their low curing temperature permits the use of a variety of low‐cost plastic materials as substrates in FET devices. These findings have facilitated the realization of low‐cost, large area plastic electronics.     

An Organic Thin‐Film Transistor with a Photoinitiator‐Free Photosensitive Polyimide as Gate Insulator

This investigation deals with the synthesis and detailed study of a photoinitiator‐free photosensitive polyimide gate insulator for organic thin‐film transistors (OTFTs), one of the most important components of active‐matrix displays on plastic substrates. The photosensitive polyimide precursor poly(amic acid) is prepared from the aromatic dianhydride 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) and the novel aromatic diamine 7‐(3,5‐diaminobenzoyloxy)coumarine (DACM). The photosensitivity of the poly(amic acid) film is investigated using a high‐pressure mercury lamp at 280–310 nm. The pattern resolution of the photocured film was about 50 μm. The surface morphology of the films before and after the photopatterning process is also investigated. In addition, we have fabricated pentacene OTFTs with the photoinitiator‐free photosensitive polyimide as gate insulator. The OTFT characteristics are discussed in more detail with respect to the electrical properties of the photosensitive polyimide thin film.     

High‐Performance Top‐Gated Organic Field‐Effect Transistor Memory using Electrets for Monolithic Printed Flexible NAND Flash Memory

High‐performance top‐gated organic field‐effect transistor (OFET) memory devices using electrets and their applications to flexible printed organic NAND flash are reported. The OFETs based on an inkjet‐printed p‐type polymer semiconductor with efficiently chargeable dielectric poly(2‐vinylnaphthalene) (PVN) and high‐k blocking gate dielectric poly(vinylidenefluoride‐trifluoroethylene) (P(VDF‐TrFE)) shows excellent non‐volatile memory characteristics. The superior memory characteristics originate mainly from reversible charge trapping and detrapping in the PVN electret layer efficiently in low‐k/high‐k bilayered dielectrics. A strategy is devised for the successful development of monolithically inkjet‐printed flexible organic NAND flash memory through the proper selection of the polymer electrets (PVN or PS), where PVN/‐ and PS/P(VDF‐TrFE) devices are used as non‐volatile memory cells and ground‐ and bit‐line select transistors, respectively. Electrical simulations reveal that the flexible printed organic NAND flash can be possible to program, read, and erase all memory cells in the memory array repeatedly without affecting the non‐selected memory cells.     

Effects of Confinement on Microstructure and Charge Transport in High Performance Semicrystalline Polymer Semiconductors

The film thickness of one of the most crystalline and highest performing polymer semiconductors, poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT), is varied in order to determine the effects of interfaces and confinement on the microstructure and performance in organic field effect transistors (OFETs). Crystalline texture and overall film crystallinity are found to depend strongly on film thickness and thermal processing. The angular distribution of crystallites narrows upon both a decrease in film thickness and thermal annealing. These changes in the film microstructure are paired with thin‐film transistor characterization and shown to be directly correlated with variations in charge carrier mobility. Charge transport is shown to be governed by film crystallinity in films below 20 nm and by crystalline orientation for thicker films. An optimal thickness is found for PBTTT at which the mobility is maximized in unannealed films and where mobility reaches a plateau at its highest value for annealed films.