High-response organic thin-film memory transistors based on dipole-functional polymer electret layers

A molecular design for the electret material of n-operating organic field-effect transistor-based (OFET) memories is introduced. A large memory window and high operating speed were achieved while the polar groups are connected to the polymer chain of polyimide, which plays the role of electret of a transistor memory device. The phase variation of electrical force microscopy images showed that polarization field induces charge trapping states on the surface of electret layer and accumulates charged carriers within the conducting channel of OFET to achieve high-performance memory and transistor simultaneously. An extra-large memory window was also obtained by introducing photo-induced charge transfer effect.     

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.     

Effect of thickness of polymer electret on charge trapping properties of pentacene-based nonvolatile field-effect transistor memory

In this report, a set of pentacene-based organic field-effect transistor (OFET) memory devices using different thicknesses (ranged from 17.8 to 100.4 nm) of Poly (N-vinylcarbazole) (PVK) as charge trapping layers were fabricated, and the dependences of thickness on charge trapping behaviors were systematically investigated. As the thickness increased, the charge trapping capacity shows a Gaussian distributed growth behavior while the surface tunneling distance demonstrates the property of exponential decrease, which is ascribed to the synergistic effects of potential redistribution of trapped charge carriers and the co-existence of direct tunneling and Fowler–Nordheim (FN) tunneling. The optimum thickness (d_ot) to possess the most efficient charge trapping properties, which means a reasonably low programming voltage and high charge trapping capacity with good bias stress stability, is approximately 40 ± 5 nm. By calculating the threshold thickness (d_th) of PVK for an ultrathin memory, we proposed a model of superficial tunneling distance to deconstruct the continuous chargeable polymer electret-based OFET memory. Our work provided a quantitative evaluation method and can improve the understanding of charge trapping process from the aspect of electret thickness.     

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.     

Programmable memory in organic field-effect transistor based on lead phthalocyanine

A nonvolatile organic field-effect transistor (OFET) with a polymeric electret as gate insulator and spun cast film of lead phthalocyanine (PbPc) as semiconductor channel is reported. Hysteresis induced by gate–bias stress was exploited to study nonvolatile memory effects. The observation of the hysteresis and memory window is proposed to originate from charge storage in the polymeric electret. The on state retention time for the OFET memory device is more than 5 h and the device can reproduce continuous write–read–erase–read switching cycles.     

Novel Authentic and Ultrafast Organic Photorecorders Enhanced by AIE-Active Polymer Electrets via Interlayer Charge Recombination

Organic photonic memory, featuring a variety of glamorously light-driven characteristics, is rapidly growing into an indispensable building block for next-generation optical communication systems. However, the ambiguity of their operating mechanism associated with the limitation of photoadaptive materials as an electronics promoter results in the slow development of photonic transistor-based devices. In this study, the conjugated polymers composed of donor–acceptor motifs with typical aggregation-induced emission (AIE) behaviors are designed and successfully discover high-performance photoprogrammable memory. Moreover, the mechanism of photoboosted recording behavior, attributed to the recombination of the formed interlayer excitons right after simultaneous excitation without applying vertical and parallel electric-field at the interface in-between active semiconductor and AIE polymers, is cautiously corroborated by steady-state PL and pulse PL measurements. The AIE-polymer memory devices perform ultrafast photoresponse time of 0.1 ms, an outstanding current switch ratio up to 10⁶, and retention stability over 40 000 s without significant dissipation. Furthermore, photoresponsive AIE-polymer electrets not only modulate the memory performance through the emission wavelength but easily switch storage behavior of nonvolatile memory from flash to WORM by adjusting the torsion-angle through the motif of the donor and acceptor moieties. These findings open an avenue for designing conjugated polymer electret for ultrafast optical storage devices.     

Organic Field‐Effect Transistors and Unipolar Logic Gates on Charged Electrets from Spin‐On Organosilsesquioxane Resins

Controllable shifting of threshold voltage and modulation of current in organic field‐effect transistors (OFETs) is demonstrated, resulting in the formation of unipolar inverters by making use of space‐charge electrets. Prior to the deposition of the organic semiconductor (OSC), negative corona charges are injected and trapped in the bulk of the organosilsesquioxane glass resin gate dielectrics. The effective surface potential is controlled by the corona‐charging and subsequent annealing process. It is found that the shift of the transfer characteristics is governed by the electrostatic induction effects of the charged gate electrets, and this observed shift can be related to the surface potential of the layer next to the transistor channel. The process control, efficiency, and long‐term stability of charge storage in spin‐on organosilsesquioxane glass resins are sufficient to enable the construction of simple unipolar inverters and to allow for circuit tuning. New OFET unipolar inverters with an enhancement‐mode driver and a depletion‐mode load are presented, composed of only two simple OFETs with the same channel dimensions and the same p‐type OSC on charged electrets. This design allows the implementation of full‐swing organic logic circuits and illustrates a potential process simplification for organic electronics.     

High‐Performance Nonvolatile Transistor Memories of Pentacence Using the Green Electrets of Sugar‐based Block Copolymers and Their Supramolecules

Reported here are the nonvolatile electrical characteristics of pentacene‐based organic field‐effect transistor (OFET) memory devices created from the green electrets of sugar‐based block copolymer maltoheptaose‐block‐polystyrene (MH‐b‐PS), and their supramolecules with 1‐aminopyrene (APy). The very hydrophilic and abundant‐hydroxyl MH block is employed as a charge‐trapping site, while the hydrophobic PS block serves as a matrix as well as a tunneling layer. The orientation of the MH nanodomains could be well controlled in the PS matrix with random spheres, vertical cylinders, and ordered horizontal cylinders via increasing solvent annealing time, leading to different electrical switching characteristics. The electron‐trapping ability induced by the horizontal‐cylinder MH is stronger than those of the random‐sphere and vertical‐cylinder structures, attributed to the effective contact area. The electrical memory window of the device is further improved via the supramolecules of hydrogen‐bonding 1‐aminopyrene to the MH moieties of MH‐b‐PS for enhancing the hole‐trapping ability. The optimized device using the horizontal cylinders of the supramolecule electret exhibits the excellent memory characteristics of a wide memory window (52.7 V), retention time longer than 10⁴ s with a high ON/OFF ratio of >10⁵, and stable reversibility over 200 cycles. This study reveals a new approach to achieve a high‐performance flash memory through the morphology control of sugar‐based block copolymers and their supramolecules.     

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.     

Polarity Effects of Polymer Gate Electrets on Non‐Volatile Organic Field‐Effect Transistor Memory

Organic non‐volatile memory (ONVM) based on pentacene field‐effect transistors (FETs) has been fabricated using various chargeable thin polymer gate dielectrics—termed electrets—onto silicon oxide insulating layers. The overall transfer curve of organic FETs is significantly shifted in both positive and negative directions and the shifts in threshold voltage (V_Th) can be systemically and reversibly controlled via relatively brief application of the appropriate external gate bias. The shifted transfer curve is stable for a relatively long time—more than 10⁵ s. However, this significant reversible shift in V_Th is evident only in OFETs with non‐polar and hydrophobic polymer electret layers. Moreover, the magnitude of the memory window in this device is inversely proportional to the hydrophilicity (determined from the water contact angle) and dielectric polarity (determined from the dielectric constant), respectively. Memory behaviors of ONVM originate from charge storage in polymer gate electret layers. Therefore, the small shifts in V_Th in ONVM with hydrophilic and polar polymers may be due to very rapid dissipation of transferred charges through the conductive channels which form from dipoles, residual moisture, or ions in the polymer electret layers. It is verified that the surface or bulk conductivities of polymer gate electret layers played a critical role in determining the non‐volatile memory properties.     

UV assisted non-volatile memory behaviour using Copper (II) phthalocyanine based organic field-effect transistors

In this report, we have demonstrated the optical non-volatile memory characteristics using CuPc OFET. The memory operation was comprehensively demonstrated with different programming conditions. It was found that the programming of CuPc OFET with an electric pulse at the gate terminal under UV-light photo-illumination compared to other programming conditions, could substantially increase the memory window due to massive charge trapping in the polymer electret layer, which causes shift in the device transfer characteristics from low-conduction state (“OFF state”, or logic 0) to high conduction state (“ON state”, or logic 1) at V_GS = 0V. From device operation at −50V, a memory window of greater than 45V could be achieved by applying a programming voltage of +70 V at the gate terminal under UV-light photo-illumination. Moreover, it was completely erased by applying −100 V at the gate terminal in dark.     

结晶聚合物驻极体中的跳跃电流和电荷储存

推导了聚合物和聚合物驻极体中的跳跃电流公式。依据这些公式导出了聚合物驻极体等温放电的理论公式，用驻极体等温衰减的数据估算出电子跳跃的步距约为10^-8m，用X光衍射实验测得的聚合物中结晶区的线度也是10^-8m量极。这从实验上支持上述公式的成立。理论和实验都证明稳态地储存的电荷几乎都被驻极体中的结晶区的能带所俘获。     

Conjugated Polymer Nanoparticles as Nano Floating Gate Electrets for High Performance Nonvolatile Organic Transistor Memory Devices

A molecular nano‐floating gate (NFG) of pentacene‐based transistor memory devices is developed using conjugated polymer nanoparticles (CPN) as the discrete trapping sites embedded in an insulating polymer, poly (methacrylic acid) (PMAA). The nanoparticles of polyfluorene (PF) and poly(fluorene‐alt‐benzo[2,1,3]thiadiazole (PFBT) with average diameters of around 50–70 nm are used as charge‐trapping sites, while hydrophilic PMAA serves as a matrix and a tunneling layer. By inserting PF nanoparticles as the floating gate, the transistor memory device reveals a controllable threshold voltage shift, indicating effectively electron‐trapping by the PF CPN. The electron‐storage capability can be further improved using the PFBT‐based NFG since their lower unoccupied molecular orbital level is beneficial for stabilization of the trapped charges, leading a large memory window (35 V), retention time longer than 10⁴ s with a high ON/OFF ratio of >10⁴. In addition, the memory device performance using conjugated polymer nanoparticle NFG is much higher than that of the corresponding polymer blend thin films of PF/polystyrene. It suggests that the discrete polymer nanoparticles can be effectively covered by the tunneling layer, PMAA, to achieve the superior memory characteristics.     

陷阱俘获存储器中电荷积累过程对保持特性的影响

本文通过数值模拟的方法对陷阱俘获存储器单元在多次擦写过程中的电荷积累过程进行了分析。由于多次擦写后陷阱电荷的积累,电荷之间的复合过程成为一个重要的问题。分析结果显示擦写过程中积累的空穴会对存储器的保持特性产生影响,同时在分析器件保持特性的时候电荷之间的复合机制必须加以考虑。     

Electret Molecular Configuration Induced Programmable Photonic Memory for Advanced Logic Operation and Data Encryption

Nonvolatile organic photonic transistor (OPT) memories have attracted widespread attention due to their nondestructive readout, remote controllability, and robust tunability. Developing electrets with similar molecular structures but different memory behaviors and light-responsive features is crucial for light-wavelength-modulated data encryption. However, reported OPT memories have yet to meet this challenge. Here a new electret molecule (“H-PDI”) is developed via reconfiguring the linear perylene diimide molecule (“L-PDI”) to a helical shape. Respectively incorporating H-PDI and L-PDI into the floating gate layer results to H-PDI OPT and L-PDI OPT. Attributing to their remarkably different electronic structures and energy bandgaps, H-PDI OPT and L-PDI OPT preferably respond to 405 and 532 nm light irradiation, respectively. Upon electrical programming, data can be written and stored in both memories with good retention features and a high “1”/“0” state current ratio over 10⁵, though the data can only be erased by light with correct wavelengths, rather than the electrical field. Moreover, data stored in a memory array consisting of both H-PDI OPT and L-PDI OPT can only be read out by correct inputs, and wrong inputs will lead to highly deceptive outputs. This study provides a general design strategy of OPT for advanced data encryption and protection.     

Device characteristics of polymer dual-gate field-effect transistors

Dual-gate organic field-effect transistors (OFETs) were fabricated by solution processing using different p-type polymer semiconductors and polymer top-dielectric materials on prefabricated substrates with gold source-drain contacts defined by photolithography. The semiconductors and top dielectrics films were processed from solution by spin-coating and the silver top gate was applied by shadow mask evaporation. The dual-gate OFETs were characterized in double gate mode by sweeping the bottom gate bias from 40 to −50 V while fixing the top gate potentials, and vice versa. We demonstrate that the change in the threshold voltage of the bottom gate depends on the top gate bias with two linear relationships for two different regimes. The interpretations of the results, assuming that the mobilities of the top and bottom channels have similar magnitudes, and that the capacitance of the semiconductor layer is not negligible, indicated two distinct regimes for a dual-gate p-type OFET.1. When one gate is positive, hence the respective channel is in depletion and no gate screening will occur, while the other gate is in accumulation regime, the field of the positive gate will penetrate to such a large extend that the channel in accumulation will be affected by both gates.2. When both channels are in accumulation, the charges present in the channels will screen the respective gate potentials, hence both channels will operate individually and no mutual influences are observed.For a dual-gate OFET with its top channel in accumulation, we demonstrate a drop in the transconductance when the bottom gate potential becomes negative. This transition regime between both linear regimes is marked by a drop in the transconductance, where the bottom channel depends on the bottom gate only and the top channel will depend on both gates. The transition regime results from the fact that the charges accumulated in the bottom channel will start to screen the influence of the bottom gate potential on the top channel and the change in overall drain current will depend only on the change of the current of the bottom channel.     

用存储器映射的方法实现片外FLASH的擦写

提出一种通过存储器地址映射的方式实现对DSP嵌入式系统片外FLASH擦写的方法。文中介绍的程序有一定参考价值。     

Influence of Electric Field on Microstructures of Pentacene Thin‐Films in Field‐Effect Transistors

We report on electric‐field‐induced irreversible structural modifications in pentacene thin films after long‐term operation of organic field‐effect transistor (OFET) devices. Micro‐Raman spectroscopy allows for the analysis of the microstructural modifications of pentacene in the small active channel of OFET during device operation. The results suggest that the herringbone packing of pentacene molecules in a solid film is affected by an external electric field, particularly the source‐to‐drain field that parallels the a–b lattice plane. The analysis of vibrational frequency and Davydov splitting in the Raman spectra reveals a singular behavior suggesting a reduced separation distance between pentacene molecules after long‐term operations and, thus, large intermolecular interactions. These results provide evidence for improved OFET performance after long‐term operation, related to the microstructures of organic semiconductors. It is known that the application of large electric fields alters the semiconductor properties of the material owing to the generation of defects and the trapping of charges. However, we first suggest that large electric fields may alter the molecular geometry and further induce structural phase transitions in the pentacene films. These results provide a basis for understanding the improved electronic properties in test devices after long‐term operations, including enhanced field‐effect mobility, improved on/off current ratio, sharp sub‐threshold swing, and a slower decay rate in the output drain current. In addition, the effects of source‐to‐drain electric field, gate electric field, current and charge carriers, and thermal annealing on the pentacene films during OFET operations are discussed.     

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

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

A FinFET memory with remote carrier trapping in ONO buried insulator

Advanced FinFETs fabricated on SiO₂-Si₃N₄-SiO₂ (ONO) buried insulator are investigated for flash memory applications. Systematic measurements reveal that the Si₃N₄ layer can easily trap charges by applying appropriate drain bias. The amount of trapped/detrapped charges in the buried nitride is sensed remotely by gate coupling through the variation of the drain current flowing at the front-gate interface. The front-channel threshold voltage variation, ΔV_THF, resulting from the charge trapping, induces a hysteresis “window” proper to non-volatile memory devices. Finally, our measurements highlight the geometrical parameter effects on the memory window size.