High‐Performance Solution‐Processed Organo‐Metal Halide Perovskite Unipolar Resistive Memory Devices in a Cross‐Bar Array Structure

Resistive random access memories can potentially open a niche area in memory technology applications by combining the advantages of the long endurance of dynamic random‐access memory and the long retention time of flash memories. Recently, resistive memory devices based on organo‐metal halide perovskite materials have demonstrated outstanding memory properties, such as a low‐voltage operation and a high ON/OFF ratio; such properties are essential requirements for low power consumption in developing practical memory devices. In this study, a nonhalide lead source is employed to deposit perovskite films via a simple single‐step spin‐coating method for fabricating unipolar resistive memory devices in a cross‐bar array architecture. These unipolar perovskite memory devices achieve a high ON/OFF ratio up to 10⁸ with a relatively low operation voltage, a large endurance, and long retention times. The high‐yield device fabrication based on the solution‐process demonstrated here will be a step toward achieving low‐cost and high‐density practical perovskite memory devices.     

Polymer‐Based Resistive Memory Materials and Devices

Due to the advantages of good scalability, flexibility, low cost, ease of processing, 3D‐stacking capability, and large capacity for data storage, polymer‐based resistive memories have been a promising alternative or supplementary devices to conventional inorganic semiconductor‐based memory technology, and attracted significant scientific interest as a new and promising research field. In this review, we first introduced the general characteristics of the device structures and fabrication, memory effects, switching mechanisms, and effects of electrodes on memory properties associated with polymer‐based resistive memory devices. Subsequently, the research progress concerning the use of single polymers or polymer composites as active materials for resistive memory devices has been summarized and discussed. In particular, we consider a rational approach to their design and discuss how to realize the excellent memory devices and understand the memory mechanisms. Finally, the current challenges and several possible future research directions in this field have also been discussed.     

Recent Advances of Flexible Data Storage Devices Based on Organic Nanoscaled Materials

Following the trend of miniaturization as per Moore's law, and facing the strong demand of next‐generation electronic devices that should be highly portable, wearable, transplantable, and lightweight, growing endeavors have been made to develop novel flexible data storage devices possessing nonvolatile ability, high‐density storage, high‐switching speed, and reliable endurance properties. Nonvolatile organic data storage devices including memory devices on the basis of floating‐gate, charge‐trapping, and ferroelectric architectures, as well as organic resistive memory are believed to be favorable candidates for future data storage applications. In this Review, typical information on device structure, memory characteristics, device operation mechanisms, mechanical properties, challenges, and recent progress of the above categories of flexible data storage devices based on organic nanoscaled materials is summarized.     

Nonvolatile Memories Based on Graphene and Related 2D Materials

The pervasiveness of information technologies is generating an impressive amount of data, which need to be accessed very quickly. Nonvolatile memories (NVMs) are making inroads into high‐capacity storage to replace hard disk drives, fuelling the expansion of the global storage memory market. As silicon‐based flash memories are approaching their fundamental limit, vertical stacking of multiple memory cell layers, innovative device concepts, and novel materials are being investigated. In this context, emerging 2D materials, such as graphene, transition metal dichalcogenides, and black phosphorous, offer a host of physical and chemical properties, which could both improve existing memory technologies and enable the next generation of low‐cost, flexible, and wearable storage devices. Herein, an overview of graphene and related 2D materials (GRMs) in different types of NVM cells is provided, including resistive random‐access, flash, magnetic and phase‐change memories. The physical and chemical mechanisms underlying the switching of GRM‐based memory devices studied in the last decade are discussed. Although at this stage most of the proof‐of‐concept devices investigated do not compete with state‐of‐the‐art devices, a number of promising technological advancements have emerged. Here, the most relevant material properties and device structures are analyzed, emphasizing opportunities and challenges toward the realization of practical NVM devices.     

A Strategy to Design High‐Density Nanoscale Devices utilizing Vapor Deposition of Metal Halide Perovskite Materials

The demand for high memory density has increased due to increasing needs of information storage, such as big data processing and the Internet of Things. Organic–inorganic perovskite materials that show nonvolatile resistive switching memory properties have potential applications as the resistive switching layer for next‐generation memory devices, but, for practical applications, these materials should be utilized in high‐density data‐storage devices. Here, nanoscale memory devices are fabricated by sequential vapor deposition of organolead halide perovskite (OHP) CH₃NH₃PbI₃ layers on wafers perforated with 250 nm via‐holes. These devices have bipolar resistive switching properties, and show low‐voltage operation, fast switching speed (200 ns), good endurance, and data‐retention time >10⁵ s. Moreover, the use of sequential vapor deposition is extended to deposit CH₃NH₃PbI₃ as the memory element in a cross‐point array structure. This method to fabricate high‐density memory devices could be used for memory cells that occupy large areas, and to overcome the scaling limit of existing methods; it also presents a way to use OHPs to increase memory storage capacity.     

A High‐On/Off‐Ratio Floating‐Gate Memristor Array on a Flexible Substrate via CVD‐Grown Large‐Area 2D Layer Stacking

Memristors such as phase‐change memory and resistive memory have been proposed to emulate the synaptic activities in neuromorphic systems. However, the low reliability of these types of memories is their biggest challenge for commercialization. Here, a highly reliable memristor array using floating‐gate memory operated by two terminals (source and drain) using van der Waals layered materials is demonstrated. Centimeter‐scale samples (1.5 cm × 1.5 cm) of MoS₂ as a channel and graphene as a trap layer grown by chemical vapor deposition (CVD) are used for array fabrication with Al₂O₃ as the tunneling barrier. With regard to the memory characteristics, 93% of the devices exhibit an on/off ratio of over 10³ with an average ratio of 10⁴. The high on/off ratio and reliable endurance in the devices allow stable 6‐level memory applications. The devices also exhibit excellent memory durability over 8000 cycles with a negligible shift in the threshold voltage and on‐current, which is a significant improvement over other types of memristors. In addition, the devices can be strained up to 1% by fabricating on a flexible substrate. This demonstration opens a practical route for next‐generation electronics with CVD‐grown van der Waals layered materials.     

3D Printed Photoresponsive Devices Based on Shape Memory Composites

Compared with traditional stimuli‐responsive devices with simple planar or tubular geometries, 3D printed stimuli‐responsive devices not only intimately meet the requirement of complicated shapes at macrolevel but also satisfy various conformation changes triggered by external stimuli at the microscopic scale. However, their development is limited by the lack of 3D printing functional materials. This paper demonstrates the 3D printing of photoresponsive shape memory devices through combining fused deposition modeling printing technology and photoresponsive shape memory composites based on shape memory polymers and carbon black with high photothermal conversion efficiency. External illumination triggers the shape recovery of 3D printed devices from the temporary shape to the original shape. The effect of materials thickness and light density on the shape memory behavior of 3D printed devices is quantified and calculated. Remarkably, sunlight also triggers the shape memory behavior of these 3D printed devices. This facile printing strategy would provide tremendous opportunities for the design and fabrication of biomimetic smart devices and soft robotics.     

Organic Field‐Effect Transistor Memory Devices Using Discrete Ferritin Nanoparticle‐Based Gate Dielectrics

Organic field‐effect transistor (OFET) memory devices made using highly stable iron‐storage protein nanoparticle (NP) multilayers and pentacene semiconductor materials are introduced. These transistor memory devices have nonvolatile memory properties that cause reversible shifts in the threshold voltage (V_th) as a result of charge trapping and detrapping in the protein NP (i.e., the ferritin NP with a ferrihydrite phosphate core) gate dielectric layers rather than the metallic NP layers employed in conventional OFET memory devices. The protein NP‐based OFET memory devices exhibit good programmable memory properties, namely, large memory window ΔV_th (greater than 20 V), a fast switching speed (10 μs), high ON/OFF current ratio (above 10⁴), and good electrical reliability. The memory performance of the devices is significantly enhanced by molecular‐level manipulation of the protein NP layers, and various biomaterials with heme Fe^III/Fe^II redox couples similar to a ferrihydrite phosphate core are also employed as charge storage dielectrics. Furthermore, when these protein NP multilayers are deposited onto poly(ethylene naphthalate) substrates coated with an indium tin oxide gate electrode and a 50‐nm‐thick high‐k Al₂O₃ gate dielectric layer, the approach is effectively extended to flexible protein transistor memory devices that have good electrical performance within a range of low operating voltages (<10 V) and reliable mechanical bending stability.     

A Centimeter‐Scale Inorganic Nanoparticle Superlattice Monolayer with Non‐Close‐Packing and its High Performance in Memory Devices

Due to the near‐field coupling effect, non‐close‐packed nanoparticle (NP) assemblies with tunable interparticle distance (d) attract great attention and show huge potential applications in various functional devices, e.g., organic nano‐floating‐gate memory (NFGM) devices. Unfortunately, the fabrication of device‐scale non‐close‐packed 2D NPs material still remains a challenge, limiting its practical applications. Here, a facile yet robust “rapid liquid–liquid interface assembly” strategy is reported to generate a non‐close‐packed AuNP superlattice monolayer (SM) on a centimeter scale for high‐performance pentacene‐based NFGM. The d and hence the surface plasmon resonance spectra of SM can be tailored by adjusting the molecular weight of tethered polymers. Precise control over the d value allows the successful fabrication of photosensitive NFGM devices with highly tunable performances from short‐term memory to nonvolatile data storage. The best performing nonvolatile memory device shows remarkable 8‐level (3‐bit) storage and a memory ratio over 10⁵ even after 10 years compared with traditional devices with a AuNP amorphous monolayer. This work provides a new opportunity to obtain large area 2D NPs materials with non‐close‐packed structure, which is significantly meaningful to microelectronic, photovoltaics devices, and biochemical sensors.     

High‐Performance Flexible Organic Nano‐Floating Gate Memory Devices Functionalized with Cobalt Ferrite Nanoparticles

Nano‐floating gate memory (NFGM) devices are transistor‐type memory devices that use nanostructured materials as charge trap sites. They have recently attracted a great deal of attention due to their excellent performance, capability for multilevel programming, and suitability as platforms for integrated circuits. Herein, novel NFGM devices have been fabricated using semiconducting cobalt ferrite (CoFe₂O₄) nanoparticles (NPs) as charge trap sites and pentacene as a p‐type semiconductor. Monodisperse CoFe₂O₄ NPs with different diameters have been synthesized by thermal decomposition and embedded in NFGM devices. The particle size effects on the memory performance have been investigated in terms of energy levels and particle–particle interactions. CoFe₂O₄ NP‐based memory devices exhibit a large memory window (≈73.84 V), a high read current on/off ratio (read I_on/I_off) of ≈2.98 × 10³_, and excellent data retention. Fast switching behaviors are observed due to the exceptional charge trapping/release capability of CoFe₂O₄ NPs surrounded by the oleate layer, which acts as an alternative tunneling dielectric layer and simplifies the device fabrication process. Furthermore, the NFGM devices show excellent thermal stability, and flexible memory devices fabricated on plastic substrates exhibit remarkable mechanical and electrical stability. This study demonstrates a viable means of fabricating highly flexible, high‐performance organic memory devices.     

Einfluss thermomechanischer Behandlung auf eine NiTiNb‐Formgedächtnislegierung für den Einsatz in Kopplungsmechanismen

Influence of thermomechanical treatment on a NiTiNb shape memory alloy for coupling devices The application of shape memory alloys in coupling devices depends considerably on the phase transition temperatures of the material. On the one hand it is important to achieve a high austenite start temperature. On the other hand the difference between martensitic and austenitic transition start‐temperatures should be as large as possible. The present work investigates the influence of thermomechanical treatments on the phase transition temperatures of a NiTiNb alloy. The aim is to optimize the properties of the semi‐product for later applications in coupling devices.     

An Artificial Flexible Visual Memory System Based on an UV‐Motivated Memristor

For the mimicry of human visual memory, a prominent challenge is how to detect and store the image information by electronic devices, which demands a multifunctional integration to sense light like eyes and to memorize image information like the brain by transforming optical signals to electrical signals that can be recognized by electronic devices. Although current image sensors can perceive simple images in real time, the image information fades away when the external image stimuli are removed. The deficiency between the state‐of‐the‐art image sensors and visual memory system inspires the logical integration of image sensors and memory devices to realize the sensing and memory process toward light information for the bionic design of human visual memory. Hence, a facile architecture is designed to construct artificial flexible visual memory system by employing an UV‐motivated memristor. The visual memory arrays can realize the detection and memory process of UV light distribution with a patterned image for a long‐term retention and the stored image information can be reset by a negative voltage sweep and reprogrammed to the same or an other image distribution, which proves the effective reusability. These results provide new opportunities for the mimicry of human visual memory and enable the flexible visual memory device to be applied in future wearable electronics, electronic eyes, multifunctional robotics, and auxiliary equipment for visual handicapped.     

A High‐Performance Optical Memory Array Based on Inhomogeneity of Organic Semiconductors

Organic optical memory devices keep attracting intensive interests for diverse optoelectronic applications including optical sensors and memories. Here, flexible nonvolatile optical memory devices are developed based on the bis[1]benzothieno[2,3‐d;2′,3′‐d′]naphtho[2,3‐b;6,7‐b′]dithiophene (BBTNDT) organic field‐effect transistors with charge trapping centers induced by the inhomogeneity (nanosprouts) of the organic thin film. The devices exhibit average mobility as high as 7.7 cm² V^?1 s^?1, photoresponsivity of 433 A W^?1, and long retention time for more than 6 h with a current ratio larger than 10⁶. Compared with the standard floating gate memory transistors, the BBTNDT devices can reduce the fabrication complexity, cost, and time. Based on the reasonable performance of the single device on a rigid substrate, the optical memory transistor is further scaled up to a 16 × 16 active matrix array on a flexible substrate with operating voltage less than 3 V, and it is used to map out 2D optical images. The findings reveal the potentials of utilizing [1]benzothieno[3,2‐b][1]benzothiophene (BTBT) derivatives as organic semiconductors for high‐performance optical memory transistors with a facile structure. A detailed study on the charge trapping mechanism in the derivatives of BTBT materials is also provided, which is closely related to the nanosprouts formed inside the organic active layer.     

Breaking the Current‐Retention Dilemma in Cation‐Based Resistive Switching Devices Utilizing Graphene with Controlled Defects

Cation‐based resistive switching (RS) devices, dominated by conductive filaments (CF) formation/dissolution, are widely considered for the ultrahigh density nonvolatile memory application. However, the current‐retention dilemma that the CF stability deteriorates greatly with decreasing compliance current makes it hard to decrease operating current for memory application and increase driving current for selector application. By centralizing/decentralizing the CF distribution, this current‐retention dilemma of cation‐based RS devices is broken for the first time. Utilizing the graphene impermeability, the cation injecting path to the RS layer can be well modulated by structure‐defective graphene, leading to control of the CF quantity and size. By graphene defect engineering, a low operating current (≈1 µA) memory and a high driving current (≈1 mA) selector are successfully realized in the same material system. Based on systematically materials analysis, the diameter of CF, modulated by graphene defect size, is the major factor for CF stability. Breakthrough in addressing the current‐retention dilemma will instruct the future implementation of high‐density 3D integration of RS memory immune to crosstalk issues.     

Solution‐Processed Wide‐Bandgap Organic Semiconductor Nanostructures Arrays for Nonvolatile Organic Field‐Effect Transistor Memory

In this paper, the development of organic field‐effect transistor (OFET) memory device based on isolated and ordered nanostructures (NSs) arrays of wide‐bandgap (WBG) small‐molecule organic semiconductor material [2‐(9‐(4‐(octyloxy)phenyl)‐9H‐fluoren‐2‐yl)thiophene]3 (WG₃) is reported. The WG₃ NSs are prepared from phase separation by spin‐coating blend solutions of WG₃/trimethylolpropane (TMP), and then introduced as charge storage elements for nonvolatile OFET memory devices. Compared to the OFET memory device with smooth WG₃ film, the device based on WG₃ NSs arrays exhibits significant improvements in memory performance including larger memory window (≈45 V), faster switching speed (≈1 s), stable retention capability (>10⁴ s), and reliable switching properties. A quantitative study of the WG₃ NSs morphology reveals that enhanced memory performance is attributed to the improved charge trapping/charge‐exciton annihilation efficiency induced by increased contact area between the WG₃ NSs and pentacene layer. This versatile solution‐processing approach to preparing WG₃ NSs arrays as charge trapping sites allows for fabrication of high‐performance nonvolatile OFET memory devices, which could be applicable to a wide range of WBG organic semiconductor materials.     

Single Nanoparticle Magnetic Spin Memristor

There is an increasing demand for the development of a simple Si‐based universal memory device at the nanoscale that operates at high frequencies. Spin‐electronics (spintronics) can, in principle, increase the efficiency of devices and allow them to operate at high frequencies. A primary challenge for reducing the dimensions of spintronic devices is the requirement for high spin currents. To overcome this problem, a new approach is presented that uses helical chiral molecules exhibiting spin‐selective electron transport, which is called the chiral‐induced spin selectivity (CISS) effect. Using the CISS effect, the active memory device is miniaturized for the first time from the micrometer scale to 30 nm in size, and this device presents memristor‐like nonlinear logic operation at low voltages under ambient conditions and room temperature. A single nanoparticle, along with Au contacts and chiral molecules, is sufficient to function as a memory device. A single ferromagnetic nanoplatelet is used as a fixed hard magnet combined with Au contacts in which the gold contacts act as soft magnets due to the adsorbed chiral molecules.     

Topotactic Phase Transition Driving Memristive Behavior

Redox‐based memristive devices are one of the most attractive candidates for future nonvolatile memory applications and neuromorphic circuits, and their performance is determined by redox processes and the corresponding oxygen‐ion dynamics. In this regard, brownmillerite SrFeO_2.5 has been recently introduced as a novel material platform due to its exceptional oxygen‐ion transport properties for resistive‐switching memory devices. However, the underlying redox processes that give rise to resistive switching remain poorly understood. By using X‐ray absorption spectromicroscopy, it is demonstrated that the reversible redox‐based topotactic phase transition between the insulating brownmillerite phase, SrFeO_2.5, and the conductive perovskite phase, SrFeO₃, gives rise to the resistive‐switching properties of SrFeO_x memristive devices. Furthermore, it is found that the electric‐field‐induced phase transition spreads over a large area in (001) oriented SrFeO_2.5 devices, where oxygen vacancy channels are ordered along the in‐plane direction of the device. In contrast, (111)‐grown SrFeO_2.5 devices with out‐of‐plane oriented oxygen vacancy channels, reaching from the bottom to the top electrode, show a localized phase transition. These findings provide detailed insight into the resistive‐switching mechanism in SrFeO_x‐based memristive devices within the framework of metal–insulator topotactic phase transitions.     

Brain‐Inspired Photonic Neuromorphic Devices using Photodynamic Amorphous Oxide Semiconductors and their Persistent Photoconductivity

The combination of a neuromorphic architecture and photonic computing may open up a new era for computational systems owing to the possibility of attaining high bandwidths and the low‐computation‐power requirements. Here, the demonstration of photonic neuromorphic devices based on amorphous oxide semiconductors (AOSs) that mimic major synaptic functions, such as short‐term memory/long‐term memory, spike‐timing‐dependent plasticity, and neural facilitation, is reported. The synaptic functions are successfully emulated using the inherent persistent photoconductivity (PPC) characteristic of AOSs. Systematic analysis of the dynamics of photogenerated carriers for various AOSs is carried out to understand the fundamental mechanisms underlying the photoinduced carrier‐generation and relaxation behaviors, and to search for a proper channel material for photonic neuromorphic devices. It is found that the activation energy for the neutralization of ionized oxygen vacancies has a significant influence on the photocarrier‐generation and time‐variant recovery behaviors of AOSs, affecting the PPC behavior.     

Structural Phase Transition Effect on Resistive Switching Behavior of MoS2‐Polyvinylpyrrolidone Nanocomposites Films for Flexible Memory Devices

The 2H phase and 1T phase coexisting in the same molybdenum disulfide (MoS₂) nanosheets can influence the electronic properties of the materials. The 1T phase of MoS₂ is introduced into the 2H‐MoS₂ nanosheets by two‐step hydrothermal synthetic methods. Two types of nonvolatile memory effects, namely write‐once read‐many times memory and rewritable memory effect, are observed in the flexible memory devices with the configuration of Al/1T@2H‐MoS₂‐polyvinylpyrrolidone (PVP)/indium tin oxide (ITO)/polyethylene terephthalate (PET) and Al/2H‐MoS₂‐PVP/ITO/PET, respectively. It is observed that structural phase transition in MoS₂ nanosheets plays an important role on the resistive switching behaviors of the MoS₂‐based device. It is hoped that our results can offer a general route for the preparation of various promising nanocomposites based on 2D nanosheets of layered transition metal dichalcogenides for fabricating the high performance and flexible nonvolatile memory devices through regulating the phase structure in the 2D nanosheets.     

Charge‐Storage Aromatic Amino Compounds for Nonvolatile Organic Transistor Memory Devices

Here, charge‐storage nonvolatile organic field‐effect transistor (OFET) memory devices based on interfacial self‐assembled molecules are proposed. The functional molecules contain various aromatic amino moieties (N‐phenyl‐N‐pyridyl amino‐ (PyPN), N‐phenyl amino‐ (PN), and N,N‐diphenyl amino‐ (DPN)) which are linked by a propyl chain to a triethoxysilyl anchor group and act as the interface modifiers and the charge‐storage elements. The PyPN‐containing pentacene‐based memory device (denoted as PyPN device) presents the memory window of 48.43 V, while PN and DPN devices show the memory windows of 24.88 and 8.34 V, respectively. The memory characteristic of the PyPN device can remain stable along with 150 continuous write‐read‐erase‐read cycles. The morphology analysis confirms that three interfacial layers show aggregation due to the N atomic self‐catalysis and hydrogen bonding effects. The large aggregate‐covered PyPN layer has the full contact area with the pentacene molecules, leading to the high memory performance. In addition, the energy level matching between PyPN molecules and pentacene creates the smallest tunneling barrier and facilitates the injection of the hole carriers from pentacene to the PyPN layer. The experimental memory characteristics are well in agreement with the computational calculation.