Understanding of multi-level resistive switching mechanism in GeOx through redox reaction in H2O2/sarcosine prostate cancer biomarker detection.

Formation-free multi-level resistive switching characteristics by using 10 nm-thick polycrystalline GeOx film in a simple W/GeOx/W structure and understanding of switching mechanism through redox reaction in H2O2/sarcosine sensing (or changing Ge°/Ge4+ oxidation states under external bias) have been reported for the first time. Oxidation states of Ge0/Ge4+ are confirmed by both XPS and H2O2 sensing of GeOx membrane in electrolyte-insulator-semiconductor structure. Highly repeatable 1000 dc cycles and stable program/erase (P/E) endurance of >106 cycles at a small pulse width of 100 ns are achieved at a low operation current of 0.1 µA. The thickness of GeOx layer is found to be increased to 12.5 nm with the reduction of polycrystalline grain size of <7 nm after P/E of 106 cycles, which is observed by high-resolution TEM. The switching mechanism is explored through redox reaction in GeOx membrane by sensing 1 nM H2O2, which is owing to the change of oxidation states from Ge0 to Ge4+ because of the enhanced O2- ions migration in memory device under external bias. In addition, sarcosine as a prostate cancer biomarker with low concentration of 50 pM to 10 µM is also detected.

Temperature-Dependent Non-linear Resistive Switching Characteristics and Mechanism Using a New W/WO3/WOx/W Structure.

Post-metal annealing temperature-dependent forming-free resistive switching memory characteristics, Fowler-Nordheim (F-N) tunneling at low resistance state, and after reset using a new W/WO3/WOx/W structure have been investigated for the first time. Transmission electron microscope image shows a polycrystalline WO3/WOx layer in a device with a size of 150 × 150 nm(2). The composition of WO3/WOx is confirmed by X-ray photo-electron spectroscopy. Non-linear bipolar resistive switching characteristics have been simulated using space-charge limited current (SCLC) conduction at low voltage, F-N tunneling at higher voltage regions, and hopping conduction during reset, which is well fitted with experimental current-voltage characteristics. The barrier height at the WOx/W interface for the devices annealed at 500 °C is lower than those of the as-deposited and annealed at 400 °C (0.63 vs. 1.03 eV). An oxygen-vacant conducting filament with a diameter of ~34 nm is formed/ruptured into the WO3/WOx bilayer owing to oxygen ion migration under external bias as well as barrier height changes for high-resistance to low-resistance states. In addition, the switching mechanism including the easy method has been explored through the current-voltage simulation. The devices annealed at 500 °C have a lower operation voltage, lower barrier height, and higher non-linearity factor, which are beneficial for selector-less crossbar memory arrays.

Resistive and New Optical Switching Memory Characteristics Using Thermally Grown Ge0.2Se0.8 Film in Cu/GeSex/W Structure.

It is known that conductive-bridge resistive-random-access-memory (CBRAM) device is very important for future high-density nonvolatile memory as well as logic application. Even though the CBRAM devices using different materials, structures, and switching performance have been reported in Nanoscale Res. Lett., 2015, however, optical switching characteristics by using thermally grown Ge0.2Se0.8 film in Cu/GeSex/W structure are reported for the first time in this study. The Cu/GeSex/W memory devices have low current compliances (CCs) ranging from 1 nA to 500 µA with low voltage of ±1.2 V, high resistance ratio of approximately 10(3), stable endurance of >200 cycles, and good data retention of >7 × 10(3) s at 85 °C. Multi-steps of RESET phenomena and evolution of Cu filaments' shape under CCs ranging from 1 nA to 500 µA have been discussed. Under external white-light illumination with an intensity of 2.68 mW/cm(2) (wavelength ranges from 390 to 700 nm), memory device shows optical switching with long read pulse endurance of >10(5) cycles. This CBRAM device has optically programmed and electrically erased, which can open up a new area of research field for future application.

Conductive-bridging random access memory: challenges and opportunity for 3D architecture.

The performances of conductive-bridging random access memory (CBRAM) have been reviewed for different switching materials such as chalcogenides, oxides, and bilayers in different structures. The structure consists of an inert electrode and one oxidized electrode of copper (Cu) or silver (Ag). The switching mechanism is the formation/dissolution of a metallic filament in the switching materials under external bias. However, the growth dynamics of the metallic filament in different switching materials are still debated. All CBRAM devices are switching under an operation current of 0.1 µA to 1 mA, and an operation voltage of ±2 V is also needed. The device can reach a low current of 5 pA; however, current compliance-dependent reliability is a challenging issue. Although a chalcogenide-based material has opportunity to have better endurance as compared to an oxide-based material, data retention and integration with the complementary metal-oxide-semiconductor (CMOS) process are also issues. Devices with bilayer switching materials show better resistive switching characteristics as compared to those with a single switching layer, especially a program/erase endurance of >10(5) cycles with a high speed of few nanoseconds. Multi-level cell operation is possible, but the stability of the high resistance state is also an important reliability concern. These devices show a good data retention of >10(5) s at >85°C. However, more study is needed to achieve a 10-year guarantee of data retention for non-volatile memory application. The crossbar memory is benefited for high density with low power operation. Some CBRAM devices as a chip have been reported for proto-typical production. This review shows that operation current should be optimized for few microamperes with a maintaining speed of few nanoseconds, which will have challenges and also opportunities for three-dimensional (3D) architecture.

Comparison of resistive switching characteristics using copper and aluminum electrodes on GeOx/W cross-point memories.

Comparison of resistive switching memory characteristics using copper (Cu) and aluminum (Al) electrodes on GeOx/W cross-points has been reported under low current compliances (CCs) of 1 nA to 50 µA. The cross-point memory devices are observed by high-resolution transmission electron microscopy (HRTEM). Improved memory characteristics are observed for the Cu/GeOx/W structures as compared to the Al/GeOx/W cross-points owing to AlOx formation at the Al/GeOx interface. The RESET current increases with the increase of the CCs varying from 1 nA to 50 µA for the Cu electrode devices, while the RESET current is high (>1 mA) and independent of CCs varying from 1 nA to 500 µA for the Al electrode devices. An extra formation voltage is needed for the Al/GeOx/W devices, while a low operation voltage of ±2 V is needed for the Cu/GeOx/W cross-point devices. Repeatable bipolar resistive switching characteristics of the Cu/GeOx/W cross-point memory devices are observed with CC varying from 1 nA to 50 µA, and unipolar resistive switching is observed with CC >100 µA. High resistance ratios of 102 to 104 for the bipolar mode (CCs of 1 nA to 50 µA) and approximately 108 for the unipolar mode are obtained for the Cu/GeOx/W cross-points. In addition, repeatable switching cycles and data retention of 103 s are observed under a low current of 1 nA for future low-power, high-density, nonvolatile, nanoscale memory applications.

Resistive switching memory characteristics of Ge/GeOx nanowires and evidence of oxygen ion migration.

The resistive switching memory of Ge nanowires (NWs) in an IrOx/Al2O3/Ge NWs/SiO2/p-Si structure is investigated. Ge NWs with an average diameter of approximately 100 nm are grown by the vapor-liquid-solid technique. The core-shell structure of the Ge/GeOx NWs is confirmed by both scanning electron microscopy and high-resolution transmission electron microscopy. Defects in the Ge/GeOx NWs are observed by X-ray photoelectron spectroscopy. Broad photoluminescence spectra from 10 to 300 K are observed because of defects in the Ge/GeOx NWs, which are also useful for nanoscale resistive switching memory. The resistive switching mechanism in an IrOx/GeOx/W structure involves migration of oxygen ions under external bias, which is also confirmed by real-time observation of the surface of the device. The porous IrOx top electrode readily allows the evolved O2 gas to escape from the device. The annealed device has a low operating voltage (<4 V), low RESET current (approximately 22 µA), large resistance ratio (>103), long pulse read endurance of >105 cycles, and good data retention of >104 s. Its performance is better than that of the as-deposited device because the GeOx film in the annealed device contains more oxygen vacancies. Under SET operation, Ge/GeOx nanofilaments (or NWs) form in the GeOx film. The diameter of the conducting nanofilament is approximately 40 nm, which is calculated using a new method.

Enhanced nanoscale resistive switching memory characteristics and switching mechanism using high-Ge-content Ge0.5Se0.5 solid electrolyte.

We demonstrate enhanced repeatable nanoscale bipolar resistive switching memory characteristics in Al/Cu/Ge0.5Se0.5/W, as compared with Al/Cu/Ge0.2Se0.8/W structures, including stable AC endurance (>105 cycles), larger average SET voltage (approximately 0.6 V), excellent data retention (>105 s) at 85°C, and a high resistance ratio (>104) with a current compliance of 8 µA and a small operation voltage of ±1.5 V. A small device size of 150 × 150 nm2 and a Cu nanofilament with a small diameter of 30 nm are both observed by high-resolution transmission electron microscope in the SET state. The GexSe1 - x solid electrolyte compositions are confirmed by both energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The switching mechanism relies on the smaller barrier heights for holes rather than for electrons; the positively charged Cuz+ ions (i.e., holes) migrate through the defects in the GexSe1 - x solid electrolytes during SET/RESET operations. Hence, the Cu nanofilament starts to grow at the Ge0.5Se0.5/W interface, and starts to dissolve at the Cu/Ge0.5Se0.5 interface, as illustrated in the energy band diagrams. Owing to both the higher barrier for hole injection at the Cu/Ge0.5Se0.5 interface than at the Cu/Ge0.2Se0.8 interface and greater thermal stability, the resistive switching memory characteristics of the Al/Cu/Ge0.5Se0.5/W are improved relative to the Al/Cu/Ge0.2Se0.8/W devices. The Al/Cu/Ge0.5Se0.5/W memory device can also be operated with a low current compliance of 1 nA, and hence, a low SET/RESET power of 0.61 nW/6.4 pW is achieved. In addition, a large memory size of 1,300 Pbit/in2 is achieved with a small nanofilament diameter of 0.25 Å for a small current compliance of 1 nA.

Excellent resistive memory characteristics and switching mechanism using a Ti nanolayer at the Cu/TaOx interface.

Excellent resistive switching memory characteristics were demonstrated for an Al/Cu/Ti/TaOx/W structure with a Ti nanolayer at the Cu/TaOx interface under low voltage operation of ± 1.5 V and a range of current compliances (CCs) from 0.1 to 500 µA. Oxygen accumulation at the Ti nanolayer and formation of a defective high-κ TaOx film were confirmed by high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photo-electron spectroscopy. The resistive switching memory characteristics of the Al/Cu/Ti/TaOx/W structure, such as HRS/LRS (approximately 104), stable switching cycle stability (>106) and multi-level operation, were improved compared with those of Al/Cu/TaOx/W devices. These results were attributed to the control of Cu migration/dissolution by the insertion of a Ti nanolayer at the Cu/TaOx interface. In contrast, CuOx formation at the Cu/TaOx interface was observed in an Al/Cu/TaOx/W structure, which hindered dissolution of the Cu filament and resulted in a small resistance ratio of approximately 10 at a CC of 500 µA. A high charge-trapping density of 6.9 × 1016 /cm2 was observed in the Al/Cu/Ti/TaOx/W structure from capacitance-voltage hysteresis characteristics, indicating the migration of Cu ions through defect sites. The switching mechanism was successfully explained for structures with and without the Ti nanolayer. By using a new approach, the nanoscale diameter of Cu filament decreased from 10.4 to 0.17 nm as the CC decreased from 500 to 0.1 µA, resulting in a large memory size of 7.6 T to 28 Pbit/sq in. Extrapolated 10-year data retention of the Ti nanolayer device was also obtained. The findings of this study will not only improve resistive switching memory performance but also aid future design of nanoscale nonvolatile memory.