In this paper, recent progress of binary metal-oxide resistive switching random access memory (RRAM) is reviewed. The physical mechanism, material properties, and electrical characteristics of a variety of binary metal-oxide RRAM are discussed, with a focus on the use of RRAM for nonvolatile memory application. A review of recent development of large-scale RRAM arrays is given. Issues such as uniformity, endurance, retention, multibit operation, and scaling trends are discussed.

Metal–Oxide RRAM

An object is to provide a semiconductor device of which a manufacturing process is not complicated and by which cost can be suppressed, by forming a thin film transistor using an oxide semiconductor film typified by zinc oxide, and a manufacturing method thereof. For the semiconductor device, a gate electrode is formed over a substrate; a gate insulating film is formed covering the gate electrode; an oxide semiconductor film is formed over the gate insulating film; and a first conductive film and a second conductive film are formed over the oxide semiconductor film. The oxide semiconductor film has at least a crystallized region in a channel region.

Semiconductor device, and manufacturing method thereof

This review article attempts to provide a comprehensive review of the recent progress in the so-called resistive random access memories (RRAMs) First, a brief introduction is presented to describe the construction and development of RRAMs, their potential for broad applications in the fields of nonvolatile memory, unconventional computing and logic devices, and the focus of research concerning RRAMs over the past decade Second, both inorganic and organic materials used in RRAMs are summarized, and their respective advantages and shortcomings are discussed Third, the important switching mechanisms are discussed in depth and are classified into ion migration, charge trapping/de-trapping, thermochemical reaction, exclusive mechanisms in inorganics, and exclusive mechanisms in organics Fourth, attention is given to the application of RRAMs for data storage, including their current performance, methods for performance enhancement, sneak-path issue and possible solutions, and demonstrations of 2-D and 3-D crossbar arrays Fifth, prospective applications of RRAMs in unconventional computing, as well as logic devices and multi-functionalization of RRAMs, are comprehensively summarized and thoroughly discussed The present review article ends with a short discussion concerning the challenges and future prospects of the RRAMs

Recent progress in resistive random access memories: Materials, switching mechanisms, and performance

Optical transparency, tunable conducting properties and easy processability make metal oxides key materials for advanced optoelectronic devices. This Review discusses recent advances in the synthesis of these materials and their use in applications. Metal oxides (MOs) are the most abundant materials in the Earth's crust and are ingredients in traditional ceramics. MO semiconductors are strikingly different from conventional inorganic semiconductors such as silicon and III–V compounds with respect to materials design concepts, electronic structure, charge transport mechanisms, defect states, thin-film processing and optoelectronic properties, thereby enabling both conventional and completely new functions. Recently, remarkable advances in MO semiconductors for electronics have been achieved, including the discovery and characterization of new transparent conducting oxides, realization of p-type along with traditional n-type MO semiconductors for transistors, p–n junctions and complementary circuits, formulations for printing MO electronics and, most importantly, commercialization of amorphous oxide semiconductors for flat panel displays. This Review surveys the uniqueness and universality of MOs versus other unconventional electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and selected applications in thin-film transistors, solar cells, diodes and memories.

Metal oxides for optoelectronic applications

This is the first time we report that simply air plasma treatment can also enhances the optical absorbance and absorption region of titanium oxide (TiO2) films, while keeping them transparent. TiO2 thin films having moderate doping of Fe and Co exhibit significant enhancement in the aforementioned optical properties upon air plasma treatment. The moderate doping could facilitate the formation of charge trap centers or avoid the formation of charge recombination centers. Variation in surface species viz. Ti3+, Ti4+, O2−, oxygen vacancies, OH group and optical properties was studied using X-ray photon spectroscopy (XPS) and UV-Vis spectroscopy. The air plasma treatment caused enhanced optical absorbance and optical absorption region as revealed by the formation of Ti3+ and oxygen vacancies in the band gap of TiO2 films. The samples were treated in plasma with varying treatment time from 0 to 60 seconds. With the increasing treatment time, Ti3+ and oxygen vacancies increased in the Fe and Co doped TiO2 films leading to increased absorbance; however, the increase in optical absorption region/red shift (from 3.22 to 3.00 eV) was observed in Fe doped TiO2 films, on the contrary Co doped TiO2 films exhibited blue shift (from 3.36 to 3.62 eV) due to Burstein Moss shift.

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Formation of oxygen vacancies and Ti 3+ state in TiO 2 thin film and enhanced optical properties by air plasma treatment

The characteristics and mechanism of conduction/set process in TiN∕ZnO∕Pt-based resistance random access memory devices with stable and reproducible nanosecond bipolar switching behavior were studied. The dependencies of memory behavior on cell area, operating temperature, and frequency indicate that the conduction mechanism in low-resistance states is due to electrons hopping through filament paths. We also identify that the set process is essentially equivalent to a soft dielectric breakdown associated with a polarization effect caused by the migration of space charges under a low electric field stress. The generation/recovery of oxygen vacancies and nonlattice oxygen ions play a critical role in resistance switching.

Characteristics and mechanism of conduction/set process in TiN∕ZnO∕Pt resistance switching random-access memories

An implantation doping approach is implemented to fabricate Gd-doped HfO2 resistive random access memory (RRAM) devices. The significantly enhanced performances are achieved in the Gd-doped HfO2 RRAM devices including improved uniformity of switching parameters, enlarged ON/OFF ratio, and increased switching speed without obvious reliability degradation. This performance improvement in the Gd-doped HfO2 RRAM devices is clarified to the suppressed randomicity of oxygen vacancy filaments’ formation and the reduced oxygen ion migration barrier induced by trivalent Gd-doping effect. The achieved results also demonstrate the validity of implantation doping approach for the fabrication of RRAM devices.

Gd-doping effect on performance of HfO2 based resistive switching memory devices using implantation approach

A unified model is proposed to elucidate the resistive switching behavior of metal-oxide-based resistive random access memory devices using the concept of electron hopping transport along filamentary conducting paths in dielectric layer. The transport calculation shows that a low-electron-occupied region along the conductive filament (CF) is formed when a critical electric field is applied. The oxygen vacancies in this region are recombined with oxygen ions, resulting in rupture of the CFs. The proposed mechanism was verified by experiments and theoretical calculations. In this physical model, the observed resistive switching behaviors in the oxide-based systems can be quantified and predicted.

Unified Physical Model of Bipolar Oxide-Based Resistive Switching Memory

Oxygen vacancy (VO) plays the critical role for resistive switching in transition metal oxide resistive random access memory (RRAM). First principles calculation is performed to study the impact of metallic ion (Al, Ti, or La) doping in ZrO2 on the behaviors of VO, including defect energy level and formation energy (Evf). Trivalent dopant (Al or La) significantly reduces Evf. Based on the calculated results, ZrO2-based RRAM devices are designed to control the formation of VO, and improved resistive switching uniformity is demonstrated in experiments.

Ionic doping effect in ZrO2 resistive switching memory

A technical solution is presented to improve the uniformity of HfO 2 -based resistive switching memory by embedding thin Al layers between HfO 2 and electrode layers. Compared with those pure HfO 2 devices, a remarkably improved uniformity of switching parameters such as forming voltages, set voltages, and resistances in high/low states was demonstrated in the HfO 2 devices with embedded Al layers. Al atoms are assumed to diffuse into HfO 2 thin films and are intended to localize oxygen vacancies due to reduced oxygen vacancy formation energy, thus stabilizing the generation of conductive filaments, which helps improve the resistive switching uniformity.

Ruqi Han

Papers

Characteristics and mechanism of conduction/set process in TiN∕ZnO∕Pt resistance switching random-access memories

Gd-doping effect on performance of HfO2 based resistive switching memory devices using implantation approach

Unified Physical Model of Bipolar Oxide-Based Resistive Switching Memory

Ionic doping effect in ZrO2 resistive switching memory

Improved Uniformity of Resistive Switching Behaviors in HfO2 Thin Films with Embedded Al Layers