Layered (C6H5CH2NH3)2CuBr4 Perovskite for Multilevel Storage Resistive Switching Memory

Although there have been attempts to use non‐lead based halide perovskite materials as insulating layers for resistive switching memory, the ratio of low resistance state (LRS) to high resistance state (HRS) ( = ON/OFF ratio) and/or endurance is reported to be mostly lower than 10³. Resistive switching memory characteristics of layered (BzA)₂CuBr₄ (BzA = C₆H₅CH₂NH₃) perovskite with high ON/OFF ratio and long endurance are reported here. The X‐ray diffraction (XRD) pattern of the deposited (BzA)₂CuBr₄ layer shows highly oriented (00l) planes perpendicular to a Pt substrate. An Ag/PMMA/(BzA)₂CuBr₄/Pt device shows bipolar switching behavior. A forming step at around +0.5 V is observed before the repeated bipolar switching at the SET voltage of +0.2 V and RESET voltage of ‐0.3 V. The ON/OFF ratio as high as =10⁸ is monitored along with an endurance of ≈2000 cycles and retention time over 1000 s. The high ON/OFF ratio enables multilevel storage characteristics as confirmed by changing the compliance currents. Ohmic conduction at the LRS and Schottky emission at HRS are involved in electrochemical metallization process. The bipolar resistive switching property is retained after storing the device at ambient condition under relative humidity of about 50% for 2 weeks, which indicates that (BzA)₂CuBr₄ is stable memory material.     

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.     

Novel Digital Nonvolatile Memory Devices Based on Semiconducting Polymer Thin Films

Recent increases in the demand for mobile devices have stimulated the development of nonvolatile memory devices with high performance. In this Communication, we describe the fabrication of low‐cost, high‐performance, digital nonvolatile memory devices based on semiconducting polymers, poly(o‐anthranilic acid) and poly(o‐anthranilic acid‐co‐aniline). These memory devices have ground‐breaking and novel current–voltage switching characteristics. The devices are switchable in a very low voltage range (which is much less than those of all other devices reported so far) with a very high ON/OFF current ratio (which is on the order of 10⁵). The low critical voltages have the advantage for nonvolatile memory device applications of low operation voltages and hence low power consumption. With this very low power consumption, the devices demonstrate in air ambient to have very stable ON‐ and OFF‐states without any degradation for a very long time (which has been confirmed up to one year so far) and to be repeatedly written, read and erased. Our study proposes that the ON/OFF switching of the devices is mainly governed by a filament mechanism. The high ON/OFF switching ratio and stability of these devices, as well as their repeatable writing, reading and erasing capability with low power consumption, opens up the possibility of the mass production of high performance digital nonvolatile polymer memory devices with low cost. Further, these devices promise to revolutionize microelectronics by providing extremely inexpensive, lightweight, and versatile components that can be printed onto plastics, glasses or metal foils.     

Interface Modifications of InAs Quantum‐Dots Solids and their Effects on FET Performance

InAs nanocrystals field‐effect transistors with an ON/OFF ratio of 10⁵ are reported. By tailoring the interface regions in the active layer step‐by‐step, the evolution of the ON/OFF ratio can be followed from approximately 5 all the way to around 10⁵. The formation of a semiconducting solid from colloidal nanocrystals is achieved through targeted design of the nanocrystal–nanocrystal interaction. The manipulation characteristics of the nanocrystal interfaces include the matrix surrounding the inorganic core, the interparticle distance, and the order of nanocrystals in the 3D array. Through careful analysis of device characteristics following each treatment, the effect of each on the physical properties of the films are able to be verified. The enhanced performance is related to interparticle spacing, reduction in sub‐gap states, and better electronic order (lower σ parameter). Films with enhanced charge transport qualities retain their quantum‐confined characteristics throughout the procedure, thus making them useful for optoelectronic applications.     

Calamitic Blatter Radicals for Large-Area Solution-Coated Resistive Memories

Radical molecules exhibit fast redox kinetics, are widely explored for data processing and energy storage. However, the insulating aliphatic matrix isolates the radical units, thus resulting in a weak charge transporting ability. Herein, calamitic Blatter radicals (CBR) with highly conductive [1]benzothieno[3,2-b]benzothiophene (BTBT) as the conjugated backbone are designed and synthesized. It is found that bistable redox character associated with large conjugated backbone allows these Blatter radical derivatives to be switched with ON/OFF ratio reaching 10⁶ and retention time exceeding 10⁴ s in solution processed devices. In addition, these radicals are unveiled to perform tunable, multi-mode field-responsive resistance behaviors, including write-once-read-many (WORM), FLASH, and dynamic random access memory (DRAM), by molecular engineering strategy. This finding provides fundamental understanding for charge transferring dynamics and redox-switching mechanism of radical molecules with respect to electronic applications.     

Transition Metal Dichalcogenide‐Based Transistor Circuits for Gray Scale Organic Light‐Emitting Displays

Two types of transition metal dichalcogenide (TMD) transistors are applied to demonstrate their possibility as switching/driving elements for the pixel of organic light‐emitting diode (OLED) display. Such TMD materials are 6 nm thin WSe₂ and MoS₂ as a p‐type and n‐type channel, respectively, and the pixel is thus composed of external green OLED and nanoscale thin channel field effect transistors (FETs) for switching and driving. The maximum mobility of WSe₂‐FETs either as switch or as driver is ≈30 cm² V^?1 s^?1, in linear regime of the gate voltage sweep range. Digital (ON/OFF‐switching) and gray‐scale analogue operations of OLED pixel are nicely demonstrated. MoS₂ nanosheet FET‐based pixel is also demonstrated, although limited to alternating gray scale operation of OLED. Device stability issue is still remaining for future study but TMD channel FETs are very promising and novel for their applications to OLED pixel because of their high mobility and I _D ON/OFF ratio.     

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.     

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.     

Ternary flash memory device based on polycarbazole with ZrO2 composite materials

The poly[2,7-9-(9-heptadecanyl)-9H-carbazole-co-benzo[4,5] imidazole[2,1-a]isoindol-11-one] (PCz-O) was synthesized by Suzuki coupling reaction, which structure was verified by FT-IR, ¹H NMR and ¹³C NMR. The spin coating method was used to prepare RRAM devices based on PCz-O: ZrO₂ nanoparticle active layer, and the devices exhibited ternary switching. Through a series of performance tests, both pure polymer device and composited with ZrO₂ NPs devices had ternary storage characteristics. Among them, the content of composited with 8 wt% ZrO₂ showed the most excellent ternary storage characteristics. The ON/OFF current ratio was 2.60 × 10⁴, and the threshold voltage V_th1/V_th2 was −0.60 V/-1.00 V. The current is stable for 10000 s in both ON/OFF states. After 3300 times of reading, the switch state current of the devices had slight variation. In addition, the switching mechanism of the device was also discussed. Through carefully testing and analyzing, the devices had good stability and durability, and had potential application value in terms of data storage.     

A low-leakage-current CdSe thin film transistor

This paper reports the design, fabrication, and performance of a very low-leakage-current thin film transistor (TFT). The TFT had a double-gate structure and used a 80–100 Å thick CdSe thin film as the semiconductor. The free charge carrier concentration in the semiconductor film was calculated to be 5×10¹⁴/cm³. These factors contributed to achieving a zero-gate-bias current less than 10^?10 A in the TFT. The ON/OFF current ratio of the TFT was measured to be greater than 10⁶. The TFT had acceptable stability in the ON condition and excellent stability in the OFF condition. A life test was performed on a TFT under a zero-gate-bias condition. After 1100 hr of testing, the zero-gate-bias current of the TFT increased from 5.8×10^?10 A to 9×10^?10 A. With extrapolation, the TFT had more than 10,000 hr lifetime.     

Memory stabilities and mechanisms of organic bistable devices with a phase-separated poly(methylmethacrylate)/poly(3-hexylthiophene) hybrid layer

Organic bistable devices (OBDs) with a poly(methylmethacrylate) (PMMA)/poly(3-hexylthiophene) (P3HT) hybrid layer, acting as a charge storage region, formed by using a vertical phase self-separation method were fabricated. The current–voltage curves of the Al/P3HT/PMMA/indium-tin-oxide devices exhibited current bistabilities with a maximum ON/OFF ratio of 1 × 10⁴. The write-read-erase-read sequence results demonstrated the switching characteristics of the OBDs. The cycling endurance number of the ON/OFF switching for the OBD was above 1 × 10⁵. The memory characteristics of the OBDs were attributed to trapping and detrapping processes of electrons into and out of the P3HT/PMMA heterointerfaces.     

Novel Rewritable,Non‐volatile Memory Devices Based on Thermally and Dimensionally Stable Polyimide Thin Films

Novel digital memory devices were fabricated with a thermally and dimensionally stable polyimide containing carbazole moieties in its side groups by using a simple and conventional solution coating process. The devices exhibit excellent unipolar ON and OFF switching behavior. With very low power consumption, the devices can be repeatedly written, read, and erased in air. The ON/OFF current ratio of the devices is high up to 10¹¹. The high ON/OFF switching ratio and stability of the devices, as well as their repeatable writing, reading, and erasing capability with low power consumption, open up the possibility of the mass production of high performance non‐volatile memory devices at low cost.     

Color switching behaviors of organic bistable light-emitting devices fabricated utilizing an aluminum-nanoparticle-embedded tris(8-hydroxyquinoline)aluminum layer and double emitting layers

Organic bistable light-emitting devices (OBLEDs) with an aluminum (Al)-nanoparticle-embedded tris(8-hydroxyquinoline)aluminum (Alq₃) layer and double emitting layers (EMLs) were fabricated to investigate their color switching behaviors. Scanning electron microscopy images showed that Al nanoparticles were formed on the Alq₃ layer. The Al nanoparticles in the Alq₃ layer improved the storage margin of the organic bistable devices (OBDs), and the double EMLs changed the emission color of the organic light-emitting devices (OLEDs) according to the variations of the ON and the OFF states of the OBDs. The variations of the ON and the OFF states of the OBDs could be clearly distinguished by the color switching of the OLED. The luminances of the OBLEDs with double EMLs in the ON and the OFF states were 641.80 and 22.25 cd/m², respectively, and their CIE coordinates at 20 V were (0.42, 0.46) and (0.51, 0.47), respectively, which corresponded to the ON and the OFF states of the OBLEDs.     

Solution processable quinoxaline based molecular materials for organic field effect transistors

Three new solution processable quinoxaline based donor–acceptor–donor (D–A–D) type molecules have been synthesized for application in field effect transistors. These molecules were characterized by UV–visible spectroscopy, thermal gravimetric analysis, differential scanning calorimetry and cyclic voltammetry. DFT calculation gives deeper insight into the electronic structure of these molecules. The crystallinity and morphology features of thin film were investigated using X-ray diffraction. These molecules show liquid crystalline phase confirmed by DSC and optical polarizing microscopy. Investigation of their field effect transistor performance indicated that these molecules exhibited p-type mobility up to 9.7 × 10^?4 cm² V^?1 s^?1 and on/off ratio of 10⁴.     

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.     

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.     

Molecular beam epitaxial growth of P-ZnSe:N using a novel plasma source

We have studied the p-type doping in ZnSe molecular beam epitaxial growth using a novel high-power (5 kW) radio frequency (rf) plasma source. The effect of growth conditions such as the rf power, the Se/Zn flux ratio and the growth temperature on p-ZnSe:N was investigated. The net acceptor concentration (N_A—N_D) of around 1 × 10¹⁸ cm⁻³ was reproducibly achieved. The activation ratio ((N_A—N_D)/[N]) of p-ZnSe:N with N_A—N_D of 1.2 × 10¹⁸ cm⁻³ was found to be as high as 60%, which is the highest value so far obtained for N_A—N_D ∼ 10¹⁸ cm⁻³. The 4.2K photoluminescence spectra of p-ZnSe:N grown under the optimized growth condition showed well-resolved deep donor-acceptor pair emissions even with high N_A—N_D. On leave from Sumitomo Electric Industry Ltd. On leave from Sony Corp.     

A Graphene‐Based Vacuum Transistor with a High ON/OFF Current Ratio

A graphene‐based vacuum transistor (GVT) with a high ON/OFF current ratio is proposed and experimentally realized by employing electrically biased graphene as the electron emitter. The states of a GVT are switched by tuning the bias voltage applied to the graphene emitter with an ON/OFF current ratio up to 10⁶, a subthreshold slope of 120 mV dec^?1 and low working voltages of <10 V, exhibiting switching performances superior to those of previously reported graphene‐based solid‐state transistors. GVTs are fabricated and integrated using silicon microfabrication technology. A perfectly symmetric ambipolar device is achieved by integrating two GVTs, implying the potential of realizing vacuum integrated circuits based on GVTs. GVTs are expected to find applications in extreme environments such as high temperature and intense irradiation.     

Indium-tin-oxide,free, flexible,nonvolatile memory devices based on graphene quantum dots sandwiched between polymethylsilsesquioxane layers

Indium-tin-oxide (ITO) free, nonvolatile memory (NVM) devices based on graphene quantum dots (GQDs) sandwiched between polymethylsilsesquioxane (PMSSQ) layers were fabricated directly on polyethylene terephthalate (PET) substrates by using a solution process technique. Current-voltage (I-V) curves for the silver nanowire/PMSSQ/GQD/PMSSQ/poly(3,4-ethylenethiophene):poly(styrene sulfonate)/PET devices at 300 K showed a current bistability. The ON/OFF ratio of the current bistability for the NVM devices was as large as 1 × 10⁴, and the cycling endurance time of the ON/OFF switching for the NVM devices was above 1 × 10⁴ s. The Schottky emission, Poole-Frenkel emission, trapped-charge limited-current, and space-charge-limited current were dominantly attributed to the conduction mechanisms for the fabricated NVM devices based on the obtained I-V characteristics, and energy band diagrams illustrating the “writing” and the “erasing” processes of the devices.     

Uniform bipolar organic memory using vapor phase polymerized poly (3,4-ethylenedioxythiophene)

Organic memory device has emerged as an excellent candidate for the next generation storage devices due to its high performance and low production cost. In this paper, we report the fabrication and electrical characterization of an organic memory device made of vapor-phase polymerized PEDOT thin films that are highly uniform and free of PSS and free of unreacted reactants. The PEDOT memory device exhibited a typical bipolar resistive switching with a high ON/OFF current ratio of at least 10³, which was maintained for more than 10³ dc sweeping cycles. The device performance was stable for more than 10⁵ s. Moreover, the device containing 64 cells has very high cell to cell uniformity as demonstrated by (1) at least 93% of the cells displaying the ON/OFF current ratio of at least 10³ and (2) the deviation of the set and reset voltages from the average values being less than 0.5 V and 0.4 V, respectively. The maximum current before switching in the reset process was found to increase linearly with increase in the compliance current applied during the set process.