Write-once-read-many-times Research Articles

Observation of irreversible current path in polymer dielectric using conductive atomic force microscope

During the measurement of the electrical properties of a metal-polymer-metal capacitor, it was found that the capacitor exhibited write-once-read-many-times (WORM) memory behavior, even though it was made of the dielectric polymer, polystyrene. The initial low conductance state changed to a high conductance state when a threshold voltage was applied, but this final state never reverted to the initial state. This phenomenon only appeared in sub-100-nm-thick films. To understand this phenomenon, conductive atomic force microscopy (CAFM) was used. The current distribution measured with CAFM showed an irreversible current path had formed near particles in the polymer film. For reproducibility, particles were intentionally inserted into the polymer film during the fabrication of metal-polymer-metal capacitors, and the same current mechanism was found. From these results, it is concluded that the purification and cleaning process of organic devices severely affects the device characteristics. In addition, particle-insertion appears to be a promising method for fabrication low-cost and air-stable WORM type memory for various applications.

Resistive switching memory devices based on electrical conductance tuning in poly(4-vinyl phenol)-oxadiazole composites.

Nonvolatile memory devices, based on electrical conductance tuning in thin films of poly(4-vinyl phenol) (PVP) and 2-(4-tert-butylphenyl)-5-(4-biphenylyl)-1,3,4-oxadiazole (PBD) composites, are fabricated. The current-voltage characteristics of the fabricated devices show different electrical conductance behaviors, such as the write-once read-many-times (WORM) memory effect, the rewritable flash memory effect and insulator behavior, which depend on the content of PBD in the PVP + PBD composites. The OFF and ON states of the WORM and rewritable flash memory devices are stable under a constant voltage stress or a continuous pulse voltage stress at a read voltage. The memory mechanism is deduced from the modeling of the nature of currents in both states in the devices.

Polymer memory devices with widely tunable memory characteristics based on functional copolynaphthalimides bearing varied fluorene and triphenylamine moieties

For producing flexible memory materials with controlled memory characteristics, functional copolynaphthalimides (co-PNIs), with varied composition of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA), 4,4′-(9-fluorenylidene) dianiline (BAPF) and 4,4′-diaminotriphenylamine (DATPA), were designed and synthesized in this work. Optical and electrochemical measurements on the synthesized co-PNIs, denoted as co-PNI-TPAx (where x=0, 1, 2, 5, 10 for the molar ratio of the DATPA-containing unit in the co-PNIs), indicate gradually enhanced HOMO and continually degraded band gap with increasing DATPA unit, as further approved by molecular simulation. What is more, electrical characterization on the ITO | thin co-PNI active layer | Al sandwich devices witnesses a wide alteration of the memory behaviors from no electrical bistability (NULL, co-PNI-TPA0 and co-PNI-TPA1), to static random access memory (SRAM, co-PNI-TPA2 and co-PNI-TPA5), and then to the write-once read-many times memory (WORM, co-PNI-TPA10), implying the significance of composition control on determining the memory characteristics. Mechanisms associated with the switching effect and the charge transfer in the co-PNIs were analyzed based on the optical, electrochemical results and the B3LYP/6–31G(d) calculations. The conversion of the memory effect from NULL, to volatile SRAM, and then to nonvolatile WORM is suggested to result from the gradually increased ability of the synthesized co-PNIs to form stable charge transfer complexes with the increased electron-donating DATPA species. The fine memory tuning achieved here reveals the particular availability of the copolymerization strategy in designing functional polyimides with controlled performances for practical memory applications.

Chemical linkage functions of poly(ether imide)s on the resistive switching memory effects

A series of aromatic poly(ether imide)s, AZTA-PEIs containing triphenylamine and 1,2,4-triazole moieties are prepared and characterized. All the polymers with inherent viscosity from 0.58 to 1.1dL/g show glass transition temperatures in the range of 250–278°C. Resistive switching memory devices are constructed based on the processable poly(ether imide) (AZTA-PEIa). The device can be switched from the initial OFF state to the ON state under either positive or negative electrical sweep at about ±3.2V. The ON state is nonvolatile and can maintain the high conducting state even turning off the electrical power and applying a reverse bias. The device fulfills the requirements of a write-once read-many times memory (WORM) with a high ON/OFF current ratio up to 105 and a long retention time in both ON and OFF states. The bistable switching effects of the polymer result from the conformation-coupled charge transfer from electron donors (triazole-substituted triphenylamine moieties) to electron acceptors (phthalimide moieties). By comparing with the memory behaviors of analogue polymers, the functions of ether and imide in the chemical polymer structure on the memory behaviors are discussed.

Tuning Resistive Switching Memory Behavior from Non-volatile to Volatile by Phenoxy Linkages in Soluble Polyimides Containing Carbazole-Tethered Triazole Groups

Two soluble functional aromatic polyimides (PIs), 6F-CzTZ PI and 6F-OCzTZ PI, are synthesized for memory device applications. The chemical structures of the 6F-CzTZ PI and 6F-OCzTZ PI are basically identical, with the only difference lying in the incorporation of phenoxy linkages in 6F-OCzTZ PI. However, vastly different memory behaviors are observed. The 6F-CzTZ PI displays a non-volatile write-once read-many times (WORM) memory effect with no polarity, while the 6F-OCzTZ PI exhibits volatile static random access memory (SRAM) characteristics and has polarity. Both the PIs exhibit good long-term operation stability, survive to 108 reading cycles with no current degradation, and show ultrafast switching with a response time less than 20 ns. The charge-transfer mechanisms and the roles of the donor and acceptor components in the PIs associated with the electrical switching effect are elucidated on the basis of the experimental and quantum simulation results.

Oligosiloxane functionalized with pendant (1,3-bis(9-carbazolyl)benzene) (mCP) for solution-processed organic electronics.

A new oligosiloxane derivative (ODCzMSi) functionalized with the well-known 1,3-bis(9-carbazolyl)benzene (mCP) pendant moiety, directly linked to the silicon atom of the oligosiloxane backbone, has been synthesized and characterized. Compared to mCP, the attachment of the oligosiloxane chain significantly improves the thermal and morphological stabilities with a high decomposition temperature (Td =540 °C) and glass transition temperature (Tg =142 °C). The silicon-oxygen linkage of ODCzMSi disrupts the backbone conjugation and maintains a high triplet energy level (ET =3.0 eV). A phosphorescent organic light-emitting diode (PhOLED) using iridium bis(4,6-difluorophenyl)pyridinato-N,C(2) picolinate (FIrpic) as the emitter and ODCzMSi as the host shows a relatively low turn-on voltage of 5.0 V for solution-processed PhOLEDs, maximum external quantum efficiency of 9.2 %, and maximum current efficiency of 17.7 cd A(-1) . The overall performance of this device is competitive with the best reported solution-processed blue PhOLEDs. Memory devices using ODCzMSi as an active layer exhibit non-volatile write-once read-many-times (WORM) characteristics with high stability in retention time up to 10(4) s and a low switch on voltage. This switching behaviour is explained by different stable conformations of ODCzMSi with high or low conductivity states which are obtained under the action of electric field through a π-π stacking alignment of the pendant aromatic groups. These results with both PhOLEDs and memory devices demonstrate that this oligosiloxane-mCP hybrid structure is promising and versatile for high performance solution-processed optoelectronic applications.

Write-once-read-many-times characteristics of Pt/Al2O3/ITO memory devices

Nonvolatile write-once-read-many-times (WORM) Pt/Al2O3/ITO memory devices prepared at room temperature were demonstrated. The WORM memory devices show irreversible transition from the initial low resistance (ON) state to the high resistance (OFF) state, high ON/OFF ratio, long data retention, and good reading endurance in air at room temperature. The high performances are promising for employing the Pt/Al2O3/ITO WORM memory devices in permanent storage of information. The nonvolatile memory behaviors could be attributed to the formation and permanent rupture of conductive filament consisting of positively charged oxygen vacancies.

Semi-conjugated acceptor-based polyimides as electrets for nonvolatile transistor memory devices

We report new polyimides as electrets for pentacene-based organic field-effect transistor (OFET) memory devices, consisting of different electron-accepting dianhydride moieties (PI(BPDA-DAP), PI(PMDA-DAP), and PI(ODPA-DAP)), and varied aliphatic spacer lengths (PI(PMDA-DAH) and PI(PMDA-DAD)). The effects of the molecular structures on the charge mobility and OFET memory characteristics were systematically investigated in terms of the related frontier energy levels and morphologies. All the devices showed bistable nonvolatile memory characteristics but with a distinct charge storage behavior. The OFET memory devices using the PI(BPDA-DAP) electret exhibited a larger memory window of 81 V compared to those of PI(PMDA-DAP) and PI(ODPA-DAP), mainly attributed to its low-lying LUMO energy level that results from its more extended conjugation. Both the high retention time (around 104 s for the ON/OFF states) and steady write-read-erase-read (WRER) cycles suggested good stability and read/write properties of the studied devices. As the aliphatic spacer length increased from PI(PMDA-DAP) to PI(PMDA-DAH) and PI(PMDA-DAD), the memory characteristics changed from flash to WORM (write once read many times) behaviour. Furthermore, the memory window was reduced with the increased aliphatic spacer length, due to the reduced density of the conjugated electron-trapping sites. This study demonstrated that the electrical characteristics and charge mobility of transistor memory devices can be effectively modulated through the extent of conjugation of the electron accepting moiety and spacer length in polymer electrets.

Coating two-dimensional nanomaterials with metal-organic frameworks.

We demonstrate the coating of various 2D nanomaterials including MoS2 nanosheets, graphene oxide (GO), and reduced graphene oxide (rGO) with zeolitic imidazolate frameworks (i.e., ZIF-8) via a facile procedure. Additionally, ternary core-shell structures like Pt-MoS2@ZIF-8, Pt-GO@ZIF-8, and Pt-rGO@ZIF-8 have also been prepared. As a proof-of-concept application, a memory device based on MoS2@ZIF-8 hybrid was fabricated and it exhibited write-once-read-many-times (WORM) memory effect with high ON/OFF ratio and long operating lifetime. It is expected that MOF coated 2D nanomaterials may find wide applications in energy storage and conversion, catalysis, sensing, and information storage devices.

Synthesis of imidazole derivatives and study of the ON-based different memory performances.

We report the synthesis of two imidazole-based small molecules with different planarity of terminal aromatic rings and their application in memory devices with a sandwich configuration. The optical, electric, and the on-based device performances were systematically investigated. Surprisingly, the device based on BT-PMZ exhibited volatile static random access memory (SRAM) behavior, whereas that based on BT-BMZ showed nonvolatile write-once-read-many-times (WORM) behavior. Further studies on the film morphology and the molecular electronic structure were carried out to investigate the underlying mechanism for the large difference in their performance. Moreover, the performance of the device that incorporates a LiF buffer layer (5 nm) embedded at the interface between the BT-BMZ active layer and the Al top electrode as well as that of the device with a cold-deposited top electrode of mercury droplet was further investigated. At that point a dramatic change in memory performance of the devices from the WORM to SRAM type was observed. The intrinsic volatile SRAM performance for the two molecules results from the moderate electron-withdrawing strength of the acceptor moieties and thus weak trapping of the charge carriers.

Temperature dependence of resistive switching behaviors in resistive random access memory based on graphene oxide film

We reported resistive switching behaviors in the resistive random access memory (RRAM) devices based on the different annealing temperatures of graphene oxide (GO) film as active layers. It was found that the resistive switching characteristics of an indium tin oxide (ITO)/GO/Ag structure have a strong dependence on the annealing temperature of GO film. When the annealing temperature of the GO film was 20 °C, the devices showed typical write-once-read-many-times (WORM) type memory behaviors, which have good memory performance with a higher ON/OFF current ratio (∼104), the higher the high resistance state (HRS)/low resistance state (LRS) ratio (∼105) and stable retention characteristics (>103 s) under lower programming voltage (−1 V and −0.5 V). With the increasing annealing temperature of GO film, the resistive switching behavior of RRAM devices gradually weakened and eventually disappeared. This phenomenon could be understood by the different energy level distributions of the charge traps in GO film, and the different charge injection ability from the Ag electrode to GO film, which is caused by the different annealing temperatures of the GO film.

Electrical switching and conduction mechanisms of nonvolatile write-once-read-many-times memory devices with ZnO nanoparticles embedded in polyvinylpyrrolidone

We reported on the influence of zinc oxide nanoparticles (ZnO NPs) on the electrical bistable behavior of nonvolatile write-once-read-many-times (WORM) memory devices based on an indium-tin oxide/polyvinylpyrrolidone (PVP):ZnO NPs/aluminum (ITO/PVP:ZnO/Al) structure. The maximum ON/OFF current ratio of the nonvolatile WORM memory devices was approximately 3×103 and the devices remained in the ON state even after the applied voltage was turned off. In addition, reliability studies for response time and once write/continuous read operations of the optimal ZnO NPs concentration are presented. The response times of both rise-time and fall-time were about 3 and 6μs respectively. The conduction mechanisms of all voltage regions of the device were analyzed by theoretical models and electron trapping in the ZnO NPs of the electron tunneling among a PVP matrix was discussed.

Synthesis of Alternating Copolysiloxane with Terthiophene and Perylenediimide Derivative Pendants for Involatile WORM Memory Device

Alternating copolysiloxane with both electron donor terthiophene and electron acceptor perylenediimide derivative pendants (PTSi‐alt‐PDISi) is synthesized successfully. The polymer exhibits high decomposition and glass transition temperatures, good film‐forming ability, and high morphological stability. The estimated HOMO and LUMO energy levels of PTSi‐alt‐PDISi are –5.77 and –3.90 eV, respectively. The fabricated memory device with the configuration of ITO/PTSi‐alt‐PDISi/Au(Al) shows nonvolatile write‐once‐read‐many‐times (WORM) memory characteristics. Its turn‐on threshold voltage is 1.7 V, while its ON/OFF current density ratio is around 104 in ambient atmosphere. The well‐defined memory property of PTSi‐alt‐PDISi is attributed to the transition of the pendant terthiophene and perylenediimide groups from the disoriented state to the ordered face‐to‐face conformation at the threshold voltage and the charge transfer interaction between pendent terthiophene donor and perylenediimide acceptor moieties, which are confirmed by XRD patterns and fluorescence emission measurement. This suggests that the new donor–acceptor polysiloxanes have potential applications in the field of memory devices.

Realization of write-once-read-many-times memory device with O2 plasma-treated indium gallium zinc oxide thin film

A write-once-read-many-times (WORM) memory devices based on O2 plasma-treated indium gallium zinc oxide (IGZO) thin films has been demonstrated. The device has a simple Al/IGZO/Al structure. The device has a normally OFF state with a very high resistance (e.g., the resistance at 2 V is ∼109 Ω for a device with the radius of 50 μm) as a result of the O2 plasma treatment on the IGZO thin films. The device could be switched to an ON state with a low resistance (e.g., the resistance at 2 V is ∼103 Ω for the radius of 50 μm) by applying a voltage pulse (e.g., 10 V/1 μs). The WORM device has good data-retention and reading-endurance capabilities.

Recombinant protein-based nanoscale biomemory devices.

Biomolecular computing devices that are based on the properties of biomolecular activities offer a unique possibility for constructing new computing structures. A new concept of using various biomolecules has been proposed in order to develop a protein-based memory device that is capable of switching physical properties when electrical input signals are applied to perform memory switching. To clarify the proposed concept, redox protein is immobilized on Au nanoelectrodes to catalyze reversible reactions of redox-active molecules, which is controlled electrochemically and reversibly converted between its ON/OFF states. In this review, we summarize recent research towards developing nanoscale biomemory devices including design, synthesis, fabrication, and functionalization based on the proposed concept. At first we analyze the memory function properties of the proposed device at bulk material level and then explain the WORM (write-once-read-many times) nature of the device, later we extend the analysis to multi-bit and multi-level storage functions, and then we focus the developments in nanoscale biomemory devices based on the electron transport of redox molecules to the underlying Au patterned surface. The developed device operates at very low voltages and has good stability and excellent reversibility, proving to be a promising platform for future memory devices.

Electronic effect of terminal acceptor groups on different organic donor-acceptor small-molecule based memory devices.

In this work, three new organic donor–acceptor small-molecules, in which bicarbazole served as the electron donor, and benzothiazole, nitryl or 1,1′-dicyanovinyl were used as the electron acceptor, were designed and synthesized in order to fabricate sandwiched memory devices. Acceptors with a variable electron-delocalized extent and electron-withdrawing strength were attached to the molecular backbone in order to investigate the effect on the devices switching behavior. The bi-n-butylcarbazole benzothiazole (BCZ-BT) based memory device exhibited volatile static random access memory (SRAM) switching behaviour, while the devices based on bi-n-butylcarbazole nitryl (BCZ-NO2) was found to exhibit stable nonvolatile write-once-read-many-times (WORM) data storage characteristics and the bi-n-butylcarbazole dicyanovinyl (BCZ-CN) device acted as rewritable flash memory with a higher ON/OFF current ratio of about 104. Therefore, tunable data storage devices synthesized by adjusting the terminal acceptor groups offer feasible guidance for the rational design of organic molecules to achieve superior memory performance.

Feasibility study of using a Zener diode as the selection device for bipolar RRAM and WORM memory arrays

Cross-bar arrays are usually used for the high density application of resistive random access memory (RRAM) devices. However, cross-talk interference limits an increase in the integration density. In this paper, the Zener diode is proposed as a selection device to suppress the sneak current in bipolar RRAM arrays. Measurement results show that the Zener diode can act as a good selection device, and the sneak current can be effectively suppressed. The readout margin is sufficiently improved compared to that obtained without the selection device. Due to the improvement for the reading disturbance, the size of the cross-bar array can be enhanced to more than 103 × 103. Furthermore, the possibility of using a write-once-read-many-times (WORM) cross-bar array is also demonstrated by connecting the Zener diode and the bipolar RRAM in series. These results strongly suggest that using a Zener diode as a selection device opens up great opportunities to realize high density bipolar RRAM arrays.

Electronic memory devices based on the chalcone with negative electrostatic potential regions

The molecular electrostatic potential (ESP) properties were used for the explanation of organic electric memory ability. Several chalcone compounds, owning a negative ESP region locates at the oxygen atom, were selected in this paper to validate the selection of compounds for organic memory materials. The synthesis, characterization, fabrication of the organic memory devices and the electrical properties for them were reported, and they were shown as WORM (write once read many times) type memory devices. The molecular geometries were optimized by the addition of a changeable electric field in the x direction inside the molecules using FF-DFT (Finite Field-Density Functionary Theory) method. The relationship between ESP of the molecules under different electric field and the property was discussed, and the mechanisms associated with the memory effect were also elucidated from DFT calculation results.

Tunable Electrical Memory Characteristics Using Polyimide:Polycyclic Aromatic Compound Blends on Flexible Substrates

Resistance switching memory devices with the configuration of poly(ethylene naphthalate)(PEN)/Al/polyimide (PI) blend/Al are reported. The active layers of the PI blend films were prepared from different compositions of poly[4,4'-diamino-4″-methyltriphenylamine-hexafluoroisopropylidenediphthalimide] (PI(AMTPA)) and polycyclic aromatic compounds (coronene or N,N-bis[4-(2-octyldodecyloxy)phenyl]-3,4,9,10-perylenetetracarboxylic diimide (PDI-DO)). The additives of large π-conjugated polycyclic compounds can stabilize the charge transfer complex induced by the applied electric field. Thus, the memory device characteristic changes from the volatile to nonvolatile behavior of flash and write-once-read-many times (WORM) as the additive contents increase in both blend systems. The main differences between these two blend systems are the threshold voltage values and the additive content to change the memory behavior. Due to the stronger accepting ability and higher electron affinity of PDI-DO than those of coronene, the PI(AMTPA):PDI-DO blend based memory devices show a smaller threshold voltage and change the memory behavior in a smaller additive content. Besides, the memory devices fabricated on a flexible PEN substrate exhibit an excellent durability upon the bending conditions. These tunable memory performances of the developed PI/polycyclic aromatic compound blends are advantageous for future advanced memory device applications.

Interfacial dipole in organic p–n junction to realize write-once–read-many-times memory

A new approach is exploited to realize nonvolatile organic write-once–read-many-times (WORM) memory based on copper phthalocyanine (CuPc)/hexadecafluoro-copper-phthalocyanine (F16CuPc) p–n junction. The as-fabricated device is found to be at its ON state and can be programmed irreversibly to the OFF state by applying a negative bias. The WORM device exhibits a high ON/OFF current ratio of up to 2.6×104. An interfacial dipole layer is testified to be formed and destructed at the p–n junction interface for the ON and OFF states, respectively. The ON state at positive voltage region is attributed to the efficient hole and electron injection from the respective electrodes and then recombination at the CuPc/F16CuPc interface, and the transition of the device to the OFF state results from the destruction of the interfacial dipole layer and formation of an insulating layer which restricts charge carrier recombination at the interface.