Introducing pinMOS Memory: A Novel,Nonvolatile Organic Memory Device

In recent decades, organic memory devices have been researched intensely and they can, among other application scenarios, play an important role in the vision of an internet of things. Most studies concentrate on storing charges in electronic traps or nanoparticles while memory types where the information is stored in the local charge up of an integrated capacitance and presented by capacitance received far less attention. Here, a new type of programmable organic capacitive memory called p‐i‐n‐metal‐oxide‐semiconductor (pinMOS) memory is demonstrated with the possibility to store multiple states. Another attractive property is that this simple, diode‐based pinMOS memory can be written as well as read electrically and optically. The pinMOS memory device shows excellent repeatability, an endurance of more than 10⁴ write‐read‐erase‐read cycles, and currently already over 24 h retention time. The working mechanism of the pinMOS memory under dynamic and steady‐state operations is investigated to identify further optimization steps. The results reveal that the pinMOS memory principle is promising as a reliable capacitive memory device for future applications in electronic and photonic circuits like in neuromorphic computing or visual memory systems.     

Self‐Assembled Nanowires of Organic n‐Type Semiconductor for Nonvolatile Transistor Memory Devices

Organic nonvolatile transistor‐type memory (ONVM) devices are developed using self‐assembled nanowires of n‐type semiconductor, N,N′‐bis(2‐phenylethyl)‐perylene‐3,4:9,10‐tetracarboxylic diimide (BPE‐PTCDI). The effects of nanowire dimension and silane surface treatment on the memory characteristics are explored. The diameter of the nanowires is reduced by increasing the non‐solvent methanol composition, which led to the enhanced crystallinity and high field‐effect mobility. The BPE‐PTCDI nanowires with small diameters induce high electrical fields and result in a large memory window (the shifting of the threshold voltage, ΔV_th). The ΔV_th value of BPE‐PTCDI nanowire based ONVM device on the bare substrate can reach 51 V, which is significantly larger than that of thin film. The memory window is further enhanced to 78 V with the on/off ratio of 2.1 × 10⁴ and the long retention time (10⁴ s), using a hydrophobic surface (such as trichloro(phenyl)silane‐treated surface). The above results demonstrate that the n‐type semiconducting nanowires have potential applications in high performance non‐volatile transistor memory devices.     

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.     

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.     

Investigation of Time–Dependent Resistive Switching Behaviors of Unipolar Nonvolatile Organic Memory Devices

Organic resistive memory devices are one of the promising next‐generation data storage technologies which can potentially enable low‐cost printable and flexible memory devices. Despite a substantial development of the field, the mechanism of the resistive switching phenomenon in organic resistive memory devices has not been clearly understood. Here, the time–dependent current behavior of unipolar organic resistive memory devices under a constant voltage stress to investigate the turn‐on process is studied. The turn‐on process is discovered to occur probabilistically through a series of abrupt increases in the current, each of which can be associated with new conducting paths formation. The measured turn‐on time values can be collectively described with the Weibull distribution which reveals the properties of the percolated conducting paths. Both the shape of the network and the current path formation rate are significantly affected by the stress voltage. A general probabilistic nature of the percolated conducting path formation during the turn‐on process is demonstrated among unipolar memory devices made of various materials. The results of this study are also highly relevant for practical operations of the resistive memory devices since the guidelines for time‐widths and magnitudes of voltage pulses required for writing and reading operation can be potentially set.     

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.     

Highly Reliable Charge Trap-Type Organic Non-Volatile Memory Device Using Advanced Band-Engineered Organic-Inorganic Hybrid Dielectric Stacks

With the recent interest in data storage in flexible electronics, highly reliable charge trap-type organic-based non-volatile memory (CT-ONVM) has attracted much attention. CT-ONVM should have a wide memory window, good endurance, and long-term retention characteristics, as well as mechanical flexibility. This paper proposed CT-ONVM devices consisting of band-engineered organic–inorganic hybrid films synthesized via an initiated chemical vapor deposition process. The synthesized poly(1,3,5-trimethyl-1,3,5,-trivinyl cyclotrisiloxane) and Al hybrid films are used as a tunneling dielectric layer and a blocking dielectric layer, respectively. For the charge trapping layer, different Hf, Zr, and Ti hybrids are examined, and their memory performances are systematically compared. The best combination of hybrid dielectric stacks showed a wide memory window of 6.77 V, good endurance of up to 10⁴ cycles, and charge retention of up to 71% after 10⁸ s even under the 2% strained condition. The CT-ONVM device using the hybrid dielectric stacks outperforms other organic-based charge trap memory devices and is even comparable in performance to conventional inorganic-based poly-silicon/oxide/nitride/oxide/silicon structures devices. The CT-ONVM using hybrid dielectrics can overcome the inherent low reliability and process complexity limitations of organic electronics and expedite the realization of wearable organic electronics.     

A 4 V Operation,Flexible Braille Display Using Organic Transistors,Carbon Nanotube Actuators,and Organic Static Random‐Access Memory

A sheet‐type Braille display operating at 4 V has been successfully fabricated by integrating organic an static random‐access memory (SRAM) array with carbon nanotube (CNT)‐based actuators that are driven by organic thin‐film transistors (control‐TFTs). The on current of organic control‐TFTs that drive CNT actuators exceeds 3 mA, the mobility exceeds 1 cm² V^?1s^?1, and the on/off ratio exceeds 10⁵ at an operational voltage of 3 V. By adjusting the process time for the formation of the aluminum oxide dielectrics, the threshold voltage of the organic TFTs can be systematically controlled. This technique leads to an improved static noise margin of the SRAM and enables its stable operation with a short programming time of 2 ms at a programming voltage of 2 V. As a demonstration of the operation of one actuator with one control‐TFT and SRAM: the displacement of actuator exceeds 300 μm at an operation voltage of 4 V, which is large enough for a blind person to recognize the pop‐up of braille dots. Integrating the SRAM array reduces the frame rate of a 12 dot × 12 dot display from 1/21.6 s to 1/2.9 s.     

Nonvolatile Ferroelectric P(VDF‐TrFE) Memory Transistors Based on Inkjet‐Printed Organic Semiconductor

Nonvolatile ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) memory based on an organic thin‐film transistor with inkjet‐printed dodecyl‐substituted thienylenevinylene‐thiophene copolymer (PC12TV12T) as the active layer is developed. The memory window is 4.5 V with a gate voltage sweep of ?12.5 V to 12.5 V. The field effect mobility, on/off ratio, and gate leakage current are 0.1 cm²/Vs, 10⁵, and 10^?10 A, respectively. Although the retention behaviors should be improved and optimized, the obtained characteristics are very promising for future flexible electronics.     

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.     

Low‐Power Nonvolatile Charge Storage Memory Based on MoS2 and an Ultrathin Polymer Tunneling Dielectric

Low‐power, nonvolatile memory is an essential electronic component to store and process the unprecedented data flood arising from the oncoming Internet of Things era. Molybdenum disulfide (MoS₂) is a 2D material that is increasingly regarded as a promising semiconductor material in electronic device applications because of its unique physical characteristics. However, dielectric formation of an ultrathin low‐k tunneling on the dangling bond‐free surface of MoS₂ is a challenging task. Here, MoS₂‐based low‐power nonvolatile charge storage memory devices are reported with a poly(1,3,5‐trimethyl‐1,3,5‐trivinyl cyclotrisiloxane) (pV3D3) tunneling dielectric layer formed via a solvent‐free initiated chemical vapor deposition (iCVD) process. The surface‐growing polymerization and low‐temperature nature of the iCVD process enable the conformal growing of low‐k (≈2.2) pV3D3 insulating films on MoS₂. The fabricated memory devices exhibit a tunable memory window with high on/off ratio (≈10⁶), excellent retention times of 10⁵ s with an extrapolated time of possibly years, and an excellent cycling endurance of more than 10³ cycles, which are much higher than those reported previously for MoS₂‐based memory devices. By leveraging the inherent flexibility of both MoS₂ and polymer dielectric films, this research presents an important milestone in the development of low‐power flexible nonvolatile memory devices.     

Organic Materials and Thin‐Film Structures for Cross‐Point Memory Cells Based on Trapping in Metallic Nanoparticles

Non‐volatile solid‐state memory cells based on composites of metal nanoparticles and polymers are embedded in organic semiconducting host materials. This paper presents data from a wide range of materials and device structures and shows that the switching phenomenon is commonly observed.     

A Catalytic and Shape‐Memory Polymer Reactor

An originally designed catalytic and shape‐memory polymer reactor is reported. This reactor is made of a unique shape‐switchable polymer composed of a thermosensitive control layer and an inert substrate layer. With the inert substrate layer made of poly(acrylamide), the thermosensitive control layer consists of nickel nanoparticles and a smart polymer composite of poly(1‐vinylimidazole) (PVIm) and poly(acrylic acid) (PAAc) that exhibit switchable domains. The self‐healing and dissociation between PVIm and PAAc induce convex/concave‐switchable shapes in the resulting reactor, which cause tunable access to the encapsulated metal nanoparticles. In this way, this reactor demonstrates tunable catalytic ability. Unlike reported smart polymer reactors exhibiting tunable catalysis usually due to the thermal phase transition of poly(N‐isopropylacrylamide) (PNIPAm), this novel reactor adopts the shape‐switchable strategy for tunable catalysis. This novel design suggests a new protocol for the development of smart catalytic reactors, which opens new opportunities for controlled chemical processes.     

Non‐Volatile Organic Memory Elements Based on Carbon‐Nanotube‐Enabled Vertical Field‐Effect Transistors

High‐performance non‐volatile memory elements based on carbon‐nanotube‐enabled vertical field‐effect transistors (CN‐VFETs) are demonstrated. A thin crosslinking polymer layer, benzocyclobutene (BCB), on top of the gate dielectric acts as the charge storage layer. This results in a large, fully gate sweep programmable, hysteresis in the cyclic transfer curves exhibiting on/off ratios >4 orders of magnitude. The carbon nanotube random network source electrode facilitates charge injection into the charge storage layer, realizing the strong memory effect without sacrificing mobility in the vertical channel. Given their intrinsically simple fabrication and compact size CN‐VFETs could provide a path to cost‐effective, high‐density organic memory devices.     

Flexible Nonvolatile Transistor Memory Devices Based on One‐Dimensional Electrospun P3HT:Au Hybrid Nanofibers

A novel flexible nonvolatile flash transistor memory devices on polyethylene naphthalate (PEN) substrate using 1D electrospun nanofiber of poly(3‐hexylthiophene) (P3HT):gold nanoparticles (Au NPs) hybrid as the channel is presented. The Au NPs are functionalized with self‐assembled monolayer (SAM) of para‐substituted amino (Au‐NH₂), methyl (Au‐CH₃) or trifluoromethyl (Au‐CF₃) tail groups on the benzenethiol moiety. They are employed as localized charge traps across the nanofiber channel and program/erase the device towards low conductance (OFF)/high conductance (ON) states under the applied electrical field. With the low operation voltage of ±5 V, the hybrid nanofiber transistor memories exhibit a 3.5–10.6 V threshold voltage shifting and at least 10⁴ s data retention, with a minimum effect on ≈100 programmed/erased stress endurances. The dipoles of the SAM probably modify the work function of the Au NPs associated with the P3HT nanofiber channel and manifest the degree of negative threshold voltage shifting in an order of Au‐NH₂ > Au‐CH₃ > Au‐CF₃. The devices remain reliable and stable even under the bending conditions (radius: 5–30 mm) or 1000 repetitive bending cycles. The hybrid nanofiber can be used to obtain high‐performance digital nanoscale memories for flexible high density data storage devices.     

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.