Mussel‐Inspired Polydopamine Coating for Flexible Ternary Resistive Memory

In recent years, numerous organic molecules and polymers carrying various functional groups were synthesized and used in fabrication of wearable electronic devices. Compared to previous materials that suffer from poisonousness, stiffness and complex film fabrication, we circumvent above matters by taking advantage of mussel‐inspired polydopamine as our active material to realize resistive random access memories (RRAMs). Polydopamine thin films were grown on indium tin oxide glass catalyzed by Cu₂SO₄/H₂O₂ and characterized by Fourier infrared spectroscopy (FT‐IR), UV/Vis spectroscopy and scanning electron microscopy. The Al/Polydopamine film/ITO devices possess ternary memory behavior with good ternary device yield with two threshold voltages around 1.50 V and 3.50 V, long data retention over 10⁴ s of continuous reading or 10⁴ pulse reading. The two resistance switchings are attributed to defects functioning as charge traps and the formation of conductive filaments. A flexible device based on Al/polydopamine film/ITO/polyethylene terephthalate retains its ternary memory behavior after being bent with a bending radius of 1.54 cm and bending cycles up to 5000, demonstrating good compatibility and flexibility of polydopamine.     

A Solution‐Processable Donor–Acceptor Compound Containing Boron(III) Centers for Small‐Molecule‐Based High‐Performance Ternary Electronic Memory Devices

A novel small‐molecule boron(III)‐containing donor–acceptor compound has been synthesized and employed in the fabrication of solution‐processable electronic resistive memory devices. High ternary memory performances with low turn‐on (V_Th1=2.0 V) and distinct threshold voltages (V_Th2=3.3 V), small reading bias (1.0 V), and long retention time (>10⁴ seconds) with a large ON/OFF ratio of each state (current ratio of “OFF”, “ON1”, and “ON2”=1:10³:10⁶) have been demonstrated, suggestive of its potential application in high‐density data storage. The present design strategy provides new insight in the future design of memory devices with multi‐level transition states.     

One-Step Fabrication of Bio-Compatible Coordination Complex Film on Diverse Substrates for Ternary Flexible Memory

Recently, resistance random access memories (RRAMs) have been studied extensively, because the demand for information storage is increasing. However, it remains challenging to obtain a flexible device because the active materials involved need to be nontoxic, nonpolluting, distortion-tolerable, and biodegradable as well adhesive to diverse flexible substrates. In this paper, tannic acid (TA) and an iron ion (Fe^III) coordination complex were employed as the active layer in a sandwich-like (Al/active layer/substrate) device to achieve memory performance. A nontoxic, biocompatible TA-Fe^III coordination complex was synthesized by a one-step self-assembly solution method. The retention time of the TA-Fe^III memory performance was up to 15 000 s, the yield up to 53 %. Furthermore, the TA-Fe^III coordination complex can form a high-quality film and shows stable ternary memory behavior on various flexible substrates, such as polyethylene terephthalate (PET), polyimide (PI), printer paper, and leaf. The device can be degraded by immersing it in vinegar solution. Our work will broaden the application of organic coordination complexes in flexible memory devices with diverse substrates.     

Novel Conjugated Side Chain Fluorinated Polymers Based on Fluorene for Light-Emitting and Ternary Flash Memory Devices

Three novel conjugated polymers based on 9,9′-dioctylfluorene unit and isoindolo[2,1-a]benzimidazol-11-one with different fluorine substituents (0, 2 and 4) were synthesized. PLED and resistive memory devices based on these polymers were prepared consequently. PLED based on four-fluorinated polymer showed the highest maximum brightness of 3192 cd m⁻² with almost 5-fold increase of current efficiency 8-fold increase of external quantum efficiency compared to that of the other two, and all the PLEDs exhibited good emission stability with no noticeable change of electroluminescence even under high voltage of 10 V. The memory device of doubly-fluorinated polymer exhibited ternary flash behavior with threshold voltages below −2.5 V, while device of four-fluorinated polymer possessed ON/OFF current ratio above 10⁴. Impact of fluorine substitutions on the performance of devices were briefly investigated. The results revealed that the improvement of device performance might not scale with the increasing number of fluorine substitutions, and the four-fluorine-substituted polymer and doubly-fluorinated polymer could be encouraging materials for applications of PLED and resistive memory device and worth of further design of other new polymer systems.     

A Molecular Platform for Multistate Near‐Infrared Electrochromism and Flip‐Flop,Flip‐Flap‐Flop,and Ternary Memory

A diruthenium complex with a redox‐active amine bridge has been designed, synthesized, and studied by single‐crystal X‐ray analysis and DFT and TDDFT calculations. It shows three well‐separated redox processes with exclusive near‐infrared (NIR) absorbance at each redox state. The electropolymerized film of a related vinyl‐functionalized complex displays multistate NIR electrochromism with low operational potential, good contrast ratio, and long retention time. Flip‐flop, flip‐flap‐flop, and ternary memories have been realized by using the obtained film (ca. 15–20 nm thick) with three electrochemical inputs and three NIR optical outputs that each displays three levels of signal intensity.     

The Effect of Random and Block Copolymerization with Pendent Carbozole Donors and Naphthalimide Acceptors on Multilevel Memory Performance

Polymeric materials have been widely used in the fabrication of data‐storage devices, owing to their unique advantages and defined conduction mechanisms. To date, the most‐functional polymers that have been reported for memory devices were synthesized through random copolymerization, whilst there have been no reports regarding the memory effect of block polymers. Herein, we synthesized a random copolymer (PMCz₈‐co‐PMBNa₂) and its corresponding block copolymer (PMCz₈‐b‐PMBNa₂) to study the effect of the method of polymerization on the memory properties of the corresponding devices. Interestingly, both devices (ITO/PMCz₈‐co‐PMBNa₂/Al and ITO/PMCz₈‐b‐PMBNa₂/Al) exhibited ternary memory performance, with threshold voltages of ?1.7 V/?3.3 V and ?2.7 V/?3.8 V, respectively. However, based on comprehensive measurements, the memory properties of PMCz₈‐co‐PMBNa₂ and PMCz₈‐b‐PMBNa₂ were found to be owing to the operation of different conduction mechanisms, which resulted from different molecular stacking in the film state. Therefore, we expect that this work will be helpful for improving our understanding of the conduction mechanisms in polymer‐based data‐storage devices.     

Amplified Self‐Immolative Release of Small Molecules by Spatial Isolation of Reactive Groups on DNA‐Minimal Architectures

Triggering the release of small molecules in response to unique biomarkers is important for applications in drug delivery and biodetection. Due to low quantities of biomarker, amplifying release is necessary to gain appreciable responses. Nucleic acids have been used for both their biomarker‐recognition properties and as stimuli, notably in amplified small‐molecule release by nucleic‐acid‐templated catalysis (NATC). The multiple components and reversibility of NATC, however, make it difficult to apply in vivo. Herein, we report the use of the hybridization chain reaction (HCR) for the amplified, conditional release of small molecules from standalone nanodevices. We couple HCR with a DNA‐templated reaction resulting in the amplified, immolative release of small molecules. We integrate the HCR components into single nanodevices as DNA tracks and spherical nucleic acids, spatially isolating reactive groups until triggering. This could be applied to biosensing, imaging, and drug delivery.     

Nonvolatile resistive memory devices based on ferrocene‐terminated hyperbranched polyimide derived from different dianhydrides

A series of ferrocene‐terminated hyperbranched polyimides (HBPI‐Fcs) were synthesized from a tetra‐amine, bis(4‐(3,5‐bis (4‐amino‐2‐(trifluoromethyl) phenoxy) phenoxy) phenyl) methanon, and various dianhydrides, followed by termination with (4‐amino) phenyl ferrocene. All the HBPI‐Fcs possessed good organo‐solubility and high thermal stability. The devices based on HBPI‐Fcs exhibited bipolar and nonvolatile write‐once‐read‐many times (WORM) memory performance with various threshold voltages and the same ON/OFF current ratio of 10⁴. Moreover, the devices possessed excellent bistability under a constant bias of −1.00 V during a test period of 10⁴ s. The different charge trapping ability of the electron‐accepting moiety endowed the devices with different the threshold voltages. Mechanism analysis showed that the switching behavior was dominated by the charge trapping effect and the charge transfer was well fitted with the space‐current‐limited‐current (SCLC) and ohmic model. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 505–513     

Improving Memory Performances by Adjusting the Symmetry and Polarity of O‐Fluoroazobenzene‐Based Molecules

Three O‐fluoroazobenzene‐based molecules were chosen as memory‐active molecules: FAZO‐1 with a D–A2–D symmetric structure, FAZO‐2 with an A1–A2–A1 symmetric structure, and FAZO‐3 with a D–A2–A1 asymmetric structure. Both FAZO‐1 and FAZO‐2 had a lower molecular polarity, whereas FAZO‐3 had a higher polarity. The fabricated indium–tin oxide (ITO)/ FAZO‐1 /Al (Au) and ITO/ FAZO‐2 /Al (Au) memory devices both exhibited volatile static random access memory (SRAM) behavior, whereas the ITO/ FAZO‐3 /Al (Au) device showed nonvolatile ternary write‐once‐read‐many‐times (WORM) behavior. It should be noted that the reproducibility of these devices was considerably high, which is significant for practical application in memory devices. In addition, the different memory performances of the three active materials were determined to be attributable to the stability of electric‐field‐induced charge‐transfer complexes. Therefore, the switching memory behavior could be tuned by adjusting the molecular polarity.     

Superior Electrical Conductivity in Hydrogenated Layered Ternary Chalcogenide Nanosheets for Flexible All‐Solid‐State Supercapacitors

As the properties of ultrathin two‐dimensional (2D) crystals are strongly related to their electronic structures, more and more attempts were carried out to tune their electronic structures to meet the high standards for the construction of next‐generation smart electronics. Herein, for the first time, we show that the conductive nature of layered ternary chalcogenide with formula of Cu₂WS₄ can be switched from semiconducting to metallic by hydrogen incorporation, accompanied by a high increase in electrical conductivity. In detail, the room‐temperature electrical conductivity of hydrogenated‐Cu₂WS₄ nanosheet film was almost 10¹⁰ times higher than that of pristine bulk sample with a value of about 2.9×10⁴ S m^?1, which is among the best values for conductive 2D nanosheets. In addition, the metallicity in the hydrogenated‐Cu₂WS₄ is robust and can be retained under high‐temperature treatment. The fabricated all‐solid‐state flexible supercapacitor based on the hydrogenated‐Cu₂WS₄ nanosheet film shows promising electrochemical performances with capacitance of 583.3 F cm^?3 at a current density of 0.31 A cm^?3. This work not only offers a prototype material for the study of electronic structure regulation in 2D crystals, but also paves the way in searching for highly conductive electrodes.     

Organic Memory Device Based on Carbazole‐Substituted Cellulose

A novel functionalized cellulose derivative, 6‐O‐[4‐(9H‐carbazol‐9‐yl)butyl]‐2,3‐di‐O‐methyl cellulose, has been synthesized and characterized. The photoluminescence spectrum of the as‐cast film of the cellulose derivative exhibits sharp peaks with a well‐defined vibronic structure, which indicates that the interaction between carbazole groups is rather weak. This is in contrast to the broad spectrum of a poly(N‐vinylcarbazole) thin film. A thin‐film device, where the cellulose derivative is sandwiched by two different metals, shows a drastic transition between low‐ and high‐conductivity states upon the forward and backward sweeping of an external electric field. This reversible current density transition behavior demonstrates a typical memory characteristic, with the ON/OFF (high‐ and low‐conductivity) states exhibiting a current ratio of about four orders of magnitude. The cellulose derivative with a functional group such as a carbazole moiety will be a candidate for organic electronic materials.

     

Decreasing the Energy Consumption of Memory Devices by Enhancing the Conjugation Extent of the Terminal Electron‐Donating Moieties within Molecules

Three small organic molecules that contained a phenothiazine backbone and triphenylamine (TPA), carbazole (CZ), or anthracene (AN) as a terminal electron donor were synthesized and fabricated in ITO/organic film/Al sandwiched memory devices. The influence of the extent of conjugation in the three molecules on the performance of their corresponding devices was investigated and the results showed that all of the fabricated devices exhibited nonvolatile ternary WORM character, whilst the switch threshold voltages decreased on moving from TPA to CZ and AN, which is promising for low‐power‐consumption data storage. These results revealed that tailoring the extent of conjugation in the terminal electron donor in the D–A molecules could effectively optimize the device performance, in particular the switch‐threshold voltage, which could be instructive for the design of low‐energy‐consumption memory materials.     

Effect of the Side‐Chain‐Distribution Density on the Single‐Conjugated‐Polymer‐Chain Conformation

The spatial arrangement of the side chains of conjugated polymer backbones has critical effects on the morphology and electronic and photophysical properties of the corresponding bulk films. The effect of the side‐chain‐distribution density on the conformation at the isolated single‐polymer‐chain level was investigated with regiorandom (rra‐) poly(3‐hexylthiophene) (P3HT) and poly(3‐hexyl‐2,5‐thienylene vinylene) (P3HTV). Although pure P3HTV films are known to have low fluorescence quantum efficiencies, we observed a considerable increase in fluorescence intensity by dispersing P3HTV in poly(methyl methacrylate) (PMMA), which enabled a single‐molecule spectroscopy investigation. With single‐molecule fluorescence excitation polarization spectroscopy, we found that rra‐P3HTV single molecules form highly ordered conformations. In contrast, rra‐P3HT single molecules, display a wide variety of different conformations from isotropic to highly ordered, were observed. The experimental results are supported by extensive molecular dynamics simulations, which reveal that the reduced side‐chain‐distribution density, that is, the spaced‐out side‐chain substitution pattern, in rra‐P3HTV favors more ordered conformations compared to rra‐P3HT. Our results demonstrate that the distribution of side chains strongly affects the polymer‐chain conformation, even at the single‐molecule level, an aspect that has important implications when interpreting the macroscopic interchain packing structure exhibited by bulk polymer films.     

Amplified Self-Immolative Release of Small Molecules by Spatial Isolation of Reactive Groups on DNA-Minimal Architectures

Triggering the release of small molecules in response to unique biomarkers is important for applications in drug delivery and biodetection. Due to low quantities of biomarker, amplifying release is necessary to gain appreciable responses. Nucleic acids have been used for both their biomarker-recognition properties and as stimuli, notably in amplified small-molecule release by nucleic-acid-templated catalysis (NATC). The multiple components and reversibility of NATC, however, make it difficult to apply in vivo. Herein, we report the use of the hybridization chain reaction (HCR) for the amplified, conditional release of small molecules from standalone nanodevices. We couple HCR with a DNA-templated reaction resulting in the amplified, immolative release of small molecules. We integrate the HCR components into single nanodevices as DNA tracks and spherical nucleic acids, spatially isolating reactive groups until triggering. This could be applied to biosensing, imaging, and drug delivery.     

Solvents Effects on Film Morphologies and Memory Behavior of a Perylenediimide‐Containing Pendent Polymer

The large polydispersity index of functional pendant polymers has hindered their application in semiconductors. Herein, a novel pendant polymer with perylenediimide (PDI) in the side chains was successfully synthesized through ring‐opening metathesis polymerization (ROMP) with a very low polydispersity index. The synthesized polymers were spin‐coated on indium tin oxide (ITO) substrate by using a mixture of 1,2‐dichlorobenzene (o‐DCB) and methanol (MeOH) solvents. The surface morphologies and intermolecular π–π stacking of the fabricated film could be adjusted through tuning of the ratio of o‐DCB and MeOH, and thus, the sandwich‐structured device of ITO/polymer/aluminum exhibited different electrical behavior. The threshold voltages of the devices decreased as the MeOH content was increased from 0 to 30 % (v/v); however, the device changed from being unrewritable to rewritable if the MeOH content was increased to 40 %; a probable mechanism for this process is discussed. It is hoped that this new idea of synthesizing narrow polydispersity index pendant polymers, and the fabrication of high‐quality films through the use of a mixture of solvents could allow high‐performance memory devices to be prepared in the future.     

Resistance Controllability in Alkynylgold(III) Complex‐Based Resistive Memory for Flash‐Type Storage Applications

Owing to the demands of state‐of‐the‐art information technologies that are suitable for vast data storage, the necessity for organic memory device (OMD) materials is highlighted. However, OMDs based on metal complexes are limited to several types of transition‐metal complex systems containing nitrogen‐donor ligands. Herein, attempts are made to introduce novel alkynylgold(III) materials into memory devices with superior performance. In this respect, an alkynyl‐containing coumarin gold(III) complex, [(C₁₉N₅H₁₁)Au−C≡C−C₉H₅O], has been synthesized and integrated into a sandwiched Al/[(C₁₉N₅H₁₁)Au−C≡C−C₉H₅O]/indium tin oxide device. By precisely controlling the compliance current (I _cc), the devices show different switching characteristics from flash‐type binary resistance switching (I _cc≤10⁻³ A) to WORM‐type (WORM=write once read many times) ternary resistance switching (I _cc=10⁻² A). This work explores electrical gold(III) complex based memories for potential use in organic electronics.