Bistable electrical switching and nonvolatile memory effect in mixed composite of oxadiazole acceptor and carbazole donor

Bistable electrical switching and nonvolatile memory devices with the configuration of indium tin oxide (ITO)/active layer/aluminum (Al) are reported. The active layer were prepared from the mixed compositions of 2-(4-tert-butylphenyl)-5-(4-biphenylyl)-1,3,4-oxadiazole, (PBD) and poly(N-vinylcarbazole) (PVK). The as-fabricated ITO/PBD:PVK/Al sandwiched devices exhibited rewriteable flash memory property. Due to the strong interaction between oxadiazole acceptor and carbazole donor, the devices demonstrate excellent performance. The memory devices can operate over a small voltage range, the absolute value of switching-on threshold voltage is less than 1 V and the switching-off threshold voltage is less than 3.5 V. The ON/OFF ratio of current switches in the range of 10⁴–10² during the variation of applied voltage and the two different resistance states can be maintained over 4 h.     

Polymer composite of poly(vinyl phenol)-reduced graphene oxide reduced by vitamin C in low energy consuming write-once–read-many times memory devices

We report the application of reduced graphene oxide, using vitamin C as reducing agent, to make a composite with poly(vinyl phenol) as the active layer of write-once–read-many times memory devices. These devices present a high ON/OFF current ratio of 10⁵ when read at 1 V, retain the information for a long time maintaining the ON/OFF current ratio constant, and require low energy for performing at 5 V the memory write (less than 10^?8 J cm^?2 device active area) and read operations.     

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 6 μs 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.     

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 1.1 dL/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 ±3.2 V. 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.     

Unipolar nonvolatile memory devices with composites of poly(9-vinylcarbazole) and titanium dioxide nanoparticles

Organic-based devices with an 8 × 8 array structure using titanium dioxide nanoparticles (TiO₂ NPs) embedded in poly(9-vinylcarbazole) (PVK) film exhibited bistable resistance states and a unipolar nonvolatile memory effect. TiO₂ NPs were a key factor for realizing the bistability and the concentration of TiO₂ NPs influenced ON/OFF ratio. From electrical measurements, switching mechanism of PVK:TiO₂ NPs devices was closely associated with filamentary conduction model and it was found that the OFF state was dominated by thermally activated transport while the ON state followed tunneling transport. PVK:TiO₂ NPs memory devices in 8 × 8 array structure showed a uniform cell-to-cell switching, stable switching endurance, and a high retention time longer than 10⁴ s.     

Twistable nonvolatile organic resistive memory devices

We fabricated an 8 × 8 cross-bar array-type organic nonvolatile memory devices on twistable poly(ethylene terephthalate) (PET) substrate. A composite of polyimide (PI) and 6-phenyl-C61 butyric acid methyl ester (PCBM) was used as the active material for the memory devices. The organic memory devices showed a high ON/OFF current ratio, reproducibility with good endurance cycle, and stability with long retention time over 5 × 10⁴ s on the flat substrate. The device performance remained well under the twisted condition with a twist angle up to ～30°. The twistable organic memory device has a potential to be utilized in more complex flexible organic device configurations.     

A flexible polymer memory device

A flexible polymer memory device is demonstrated in a sandwich structure of polypyrrole/P6FBEu/Au. Conductance switching at a voltage of about 4 V, with an ON/OFF current ratio up to 200, was observed in this flexible memory device. At the low-conductivity state, current density–voltage (J–V) characteristics of the device were dominated by a charge injection current. At the high conductivity state, J–V characteristics were dominated by a space-charge-limited current. Both the ON and OFF states are stable up to 10⁶ read cycles at a read voltage of 1 V. The device can be used as a write-once read-many-times (WORM) memory with good electronic stability.     

Nonvolatile memory and opto-electrical characteristics of organic memory devices with zinc oxide nanoparticles embedded in the tris(8-hydroxyquinolinato)aluminum light-emitting layer

The nonvolatile organic memory devices based on the tris(8-hydroxyquinolinato)aluminum (Alq₃) emitting layer embedded with zinc oxide nanoparticles (ZnO-NPs) are reported. The devices have a typical tri-layer structure consisting of the Alq₃/ZnO-NPs/Alq₃ layers interposed between indium tin oxide (ITO) and aluminum (Al) electrodes. An external bias is used to program the ON and OFF states of the device that are separated by a four-orders-of-magnitude difference in conductivity. No significant degradation of the device is observed in either the ON or OFF state after continuous stress (∼10⁵ s) and multicycle (∼10³ cycles) testings. These nanoparticles behave as the charge trapping units, which enable the nonvolatile electrical bistability when biased to a sufficiently high voltage. Impedance spectroscopy, capacitance–voltage (C–V) and current–voltage (I–V) analysis are used to verify the possible physical mechanism of the switching operation. Moreover, it is found that the location of the ZnO-NPs could affect the memory and opto-electrical characteristics of the devices, such as the ON/OFF ratio, threshold voltage and turn-on voltage, which can be attributed to the influence of the ZnO-NPs and diffused Al atoms in the bulk of the Alq₃ layer.     

In-plane electrical bistability of photochromic diarylethene/Cu composite film

Electrical bistability is an essential property for memory devices. We report here the in-plane electrical bistability of photochromic diarylethene (DAE)/Cu composite film, which is prepared by Cu vapor deposition on the DAE surface with a low glass-transition temperature. The low-current level around 10⁻⁸ A was switched to a high-current level of ca. 10⁻⁴ A at a low threshold voltage (V_th) in the first voltage sweep. Once this switching occurred, the high-current level was kept in the second voltage sweep, and electrical bistability was achieved for the in-plane current. V_th was distributed in a wide range of voltages (0.5–10 V), and the colored sample obtained by the UV irradiation showed a relatively higher V_th than the colorless sample. The highest ON–OFF ratio in current was ca. 10⁶. The origin of the bistability attributed to the electrical breakdown in the insulated lines that was consisted of DAE in Cu film. The in-plane bistability of the DAE/Cu composite film has good retention time (>60 min) and readout-cycle endurance (>10⁶ cycles), indicating that it is suitable for write-once organic semiconductor memory characteristics.     

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.     

Characterization of scaled MANOS nonvolatile semiconductor memory (NVSM) devices

We have modeled and characterized scaled Metal–Al₂O₃–Nitride–Oxide–Silicon (MANOS) nonvolatile semiconductor memory (NVSM) devices. The MANOS NVSM transistors are fabricated with a high-K (K_A = 9) blocking insulator of ALD deposited Al₂O₃ (8 nm), a LPCVD silicon nitride film (8 nm) for charge-storage, and a thermally grown tunneling oxide (2.2 nm). A low voltage program (+8 V, 30 μs) and erase (?8 V, 100 ms) provides an initial memory window of 2.7 V and a 1.4 V window at 10 years for an extracted nitride trap density of 6 × 10¹⁸ traps/cm³ eV. The devices show excellent endurance with no memory window degradation to 10⁶ write/erase cycles. We have developed a pulse response model of write/erase operations for SONOS-type NVSMs. In this model, we consider the major charge transport mechanisms are band-to-band tunneling and/or trap-assisted tunneling. Electron injection from the inversion layer is treated as the dominant carrier injection for the write operation, while hole injection from the substrate and electron injection from the gate electrode are employed in the erase operation. Meanwhile, electron back tunneling is needed to explain the erase slope of the MANOS devices at low erase voltage operation. Using a numerical method, the pulse response of the threshold voltages is simulated in good agreement with experimental data. In addition, we apply this model to advanced commercial TANOS devices.     

Characterization of PI:PCBM organic nonvolatile resistive memory devices under thermal stress

In this study, we fabricated nonvolatile organic memory devices using a mixture of polyimide (PI) and 6-phenyl-C61 butyric acid methyl ester (PCBM) (denoted as PI:PCBM) as an active memory material with Al/PI:PCBM/Al structure. Upon increasing the temperature from room temperature to 470 K, we demonstrated the good nonvolatile memory properties of our devices in terms of the distribution of ON and OFF state currents, the threshold voltage from OFF state to ON state transition, the retention, and the endurance. Our organic memory devices exhibited an excellent ON/OFF ratio (I_ON/I_OFF > 10³) through more than 200 ON/OFF switching cycles and maintained ON/OFF states for longer than 10⁴ s without showing any serious degradation under measurement temperatures up to 470 K. We also confirmed the structural robustness under thermal stress through transmission electron microscopy cross-sectional images of the active layer after a retention test at 470 K for 10⁴ s. This study demonstrates that the operation of PI:PCBM organic memory devices could be controlled at high temperatures and that the structure of our memory devices was maintained during thermal stress. These results may enable the use of nonvolatile organic memory devices in high temperature environments.     

High mobility multibit nonvolatile memory elements based organic field effect transistors with large hysteresis

High mobility multibit nonvolatile memory elements based on organic field effect transistors with a thin layer of polyquinoline (PQ) were reported. The devices show a high mobility of 1.5 cm² V⁻¹ s⁻¹ in the saturation region which is among the best reported for nonvolatile organic memory transistors. The multibit nonvolatile memory elements can be operated at voltage less than 100 V with good stability under continuous operation condition and show long retention time. The different initial scanning positive gate voltages to −100 V result in several ON states, while the scanning gate voltage from −100 V to positive voltage leads to same OFF state. The charge trapping model of electrons into the PQ layer was used to explain the origin of the memory properties.     

Flexible nonvolatile organic ferroelectric memory transistors fabricated on polydimethylsiloxane elastomer

The flexible organic ferroelectric nonvolatile memory thin film transistors (OFMTs) were fabricated on polydimethylsiloxane (PDMS) elastomer substrates, in which an organic ferroelectric poly(vinylidene-trifluoroethylene) and an organic semiconducting poly(9,9-dioctylfluorene-co-bithiophene) layers were used as gate insulator and active channel, respectively. The carrier mobility, on/off ratio, and subthreshold swing of the OFMTs fabricated on PDMS showed 5 × 10⁻² cm² V⁻¹ s⁻¹, 7.5 × 10³, and 2.5 V/decade, respectively. These obtained values did not markedly change when the substrate was bent with a radius of curvature of 0.6 cm. The memory on/off ratio was initially obtained to be 1.5 × 10³ and maintained to be 20 even after a lapse of 2000 s. The fabricated OFMTs exhibited sufficiently encouraging device characteristics even on the PDMS elastomer to realize mechanically stretchable nonvolatile memory devices.     

Polymeric gate dielectric interlayer of cross-linkable poly(styrene-r-methylmethacrylate) copolymer for ferroelectric PVDF-TrFE field effect transistor memory

A new polymeric gate dielectric interlayer of a cross-linkable poly(styrene-random-methylmethacrylate) copolymer is introduced with a good thermal and chemical resistance in bottom gate Ferroelectric Field Effect Transistor (FeFET) memory with pentacene active layer and ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) one. A thin uniform PVDF-TrFE film was successfully formed with well defined ferroelectric microdomains on an interlayer. Thickness of the interlayer turns out to be one of the most important factors for controlling gate leakage current which is supposed to be minimized for high ON/OFF bistability of a FeFET memory. An interlayer inserted between gate electrode and PVDF-TrFE layer significantly reduces gate leakage current, leading to source–drain OFF current of approximately 10^?11 A in particular when its thickness becomes greater than approximately 25 nm. A reliable FeFET device shows a clockwise I-V hysteresis with drain current bistablility of 10³ at ±40 V gate voltage.     

Electrical bistability,negative differential resistance and carrier transport in flexible organic memory device based on polymer bilayer structure

Bistable nonvolatile memory devices containing two different layers of polymers, viz. MEH-PPV (poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenyl vinylene]) and PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)) has been fabricated by a simple spin-coating technique on flexible polyimide (PI) substrates with a structure Al/MEH-PPV/PEDOT:PSS/Ag-Pd/PI. The current–voltage measurements of the as-fabricated devices showed a nonvolatile electrical bistability with electric field induced charge transfer through the polymer layers and negative differential resistance (NDR) which is attributed to the charge trapping in the MEH-PPV layer. The current ON/OFF ratio between the high-conducting state (ON state) and low-conducting state (OFF state) is found to be of the order of 10³ at room temperature which is comparable to organic field effect transistor based memory devices. We propose that such an improvement of rectification ratio (ON/OFF ratio) is caused due to the inclusion of PEDOT:PSS, which serves as a conducting current path for carrier transport; however, NDR is an effect of the trapped charges in the MEH-PPV electron confinement layer. The device shows excellent stability over 10⁴ s without any significant degradation under continuous readout testing in both the ON and OFF states. The carrier transport mechanism of the fabricated organic bistable device has been explained on the basis of different conduction mechanisms such as thermionic emission, space-charge-limited conduction, and Fowler–Nordheim tunneling. A band diagram is proposed to explain the charge transport phenomena. These bilayer structures are free from the drawbacks of the single organic layer based memory devices where the phase separation between the nanoparticles and polymers leads to the degradation of device stability and lifetime.     

Using metal/organic junction engineering to prepare an efficient organic base-modulation triode and its inverter

In this study, we investigated the influence of a buffer layer of molybdic oxide (MoO₃) at the metal/organic junction on the behavior of organic base-modulation triodes. The performance of devices featuring MoO₃/Al as the emitter electrode was enhanced relative to that of corresponding devices with Au and Ag, presumably because of the reduced in the contact barrier and the prevention of metal diffusion into the organic layer. The device exhibited an output current of ?16.1 μA at V_B = ?5 V and a current ON/OFF ratio of 10³. Using this architecture, we constructed resistance–load inverters that exhibited a calculated gain of 6.     

A low voltage SANOS nonvolatile semiconductor memory (NVSM) device

In this paper, we present a new Polysilicon–Aluminum Oxide–Nitride–Oxide–Silicon (SANOS) device structure suitable for future nonvolatile semiconductor memories. Replacing SiO₂ with a high-K material, Al₂O₃ (K_f = 9) as the top blocking layer of the conventional SONOS device increases the electric field across the tunnel oxide, while reducing the electric field across the blocking layer with its dielectric constant during write and erase operations. Therefore, this new device can achieve lower programming voltages and faster programming speed than the conventional SONOS device. We have fabricated SANOS capacitors with 2 nm tunnel oxide, 5 nm silicon nitride and 8 nm aluminum oxide and studied the programming speed and charge retention characteristics of the new devices. These new SANOS devices achieve a 2 V reduction in the programming voltages with 2.1 V initial memory window.     

Characterization of TiOxNy nanoparticles embedded in HfOxNy as charge trapping nodes for nonvolatile memory device applications

Silicon-oxide–nitride-oxide–silicon devices with nanoparticles (NPs) as charge trapping nodes (CTNs) are important to provide enhanced performance for nonvolatile memory devices. To study these topics, the TiO_xN_y metal oxide NPs embedded in the HfO_xN_y high-k dielectric as CTNs of the nonvolatile memory devices were investigated via the thermal synthesis using Ti thin-film oxidized in the mixed O₂/N₂ ambient. Well-isolated TiO_xN_y NPs with a diameter of 5–20 nm, a surface density of ～3 × 10¹¹ cm^?2, and a charge trap density of around 2.33 × 10¹² cm^?2 were demonstrated. The writing characteristic measurements illustrate that the memory effect is mainly due to the hole trapping.     

Highly-reproducible nonvolatile memristive devices based on polyvinylpyrrolidone: Graphene quantum-dot nanocomposites

The properties of nonvolatile memristive devices (NMD) fabricated utilizing organic/inorganic hybrid nanocomposites were investigated due to their superior advantages such as mechanical flexibility, low cost, low-power consumption, simple technological process in fabrication and high reproducibility. The current-voltage (I-V) curves for the Al/polyvinylpyrrolidone (PVP): graphene quantum-dot (GQD)/indium-tin-oxide (ITO) memristive devices showed current bistability characteristics at 300 K. The window margins corresponding to the high-conductivity (ON) state and the low-conductivity (OFF) state of the devices increased with increasing concentration of the GQDs. The ON/OFF ratio of the optimized device was 1 × 10⁴, which was the largest memory margin among the devices fabricated in this research. The endurance number of ON/OFF switching was above 1 × 10² cycles, and the retention time was relatively constant, maintaining a value above 10⁴ s. The devices showed high reproducibility with the writing voltage being distributed between −0.5 and −1.5 V and the erasing voltage being distributed between 2 and 3 V. The ON state currents remained between 0.02 and 0.03 A, and the OFF state currents stayed between 10⁻⁶ and 10⁻⁴ A. The carrier transport mechanisms are illustrated by using both the results obtained by fitting the I-V curves and the energy band diagrams of the devices.