Multi‐Nonvolatile State Resistive Switching Arising from Ferroelectricity and Oxygen Vacancy Migration

Resistive switching phenomena form the basis of competing memory technologies. Among them, resistive switching, originating from oxygen vacancy migration (OVM), and ferroelectric switching offer two promising approaches. OVM in oxide films/heterostructures can exhibit high/low resistive state via conducting filament forming/deforming, while the resistive switching of ferroelectric tunnel junctions (FTJs) arises from barrier height or width variation while ferroelectric polarization reverses between asymmetric electrodes. Here the authors demonstrate a coexistence of OVM and ferroelectric induced resistive switching in a BaTiO₃ FTJ by comparing BaTiO₃ with SrTiO₃ based tunnel junctions. This coexistence results in two distinguishable loops with multi‐nonvolatile resistive states. The primary loop originates from the ferroelectric switching. The second loop emerges at a voltage close to the SrTiO₃ switching voltage, showing OVM being its origin. BaTiO₃ based devices with controlled oxygen vacancies enable us to combine the benefits of both OVM and ferroelectric tunneling to produce multistate nonvolatile memory devices.     

Recent Advances of Flexible Data Storage Devices Based on Organic Nanoscaled Materials

Following the trend of miniaturization as per Moore's law, and facing the strong demand of next‐generation electronic devices that should be highly portable, wearable, transplantable, and lightweight, growing endeavors have been made to develop novel flexible data storage devices possessing nonvolatile ability, high‐density storage, high‐switching speed, and reliable endurance properties. Nonvolatile organic data storage devices including memory devices on the basis of floating‐gate, charge‐trapping, and ferroelectric architectures, as well as organic resistive memory are believed to be favorable candidates for future data storage applications. In this Review, typical information on device structure, memory characteristics, device operation mechanisms, mechanical properties, challenges, and recent progress of the above categories of flexible data storage devices based on organic nanoscaled materials is summarized.     

A Strategy to Design High‐Density Nanoscale Devices utilizing Vapor Deposition of Metal Halide Perovskite Materials

The demand for high memory density has increased due to increasing needs of information storage, such as big data processing and the Internet of Things. Organic–inorganic perovskite materials that show nonvolatile resistive switching memory properties have potential applications as the resistive switching layer for next‐generation memory devices, but, for practical applications, these materials should be utilized in high‐density data‐storage devices. Here, nanoscale memory devices are fabricated by sequential vapor deposition of organolead halide perovskite (OHP) CH₃NH₃PbI₃ layers on wafers perforated with 250 nm via‐holes. These devices have bipolar resistive switching properties, and show low‐voltage operation, fast switching speed (200 ns), good endurance, and data‐retention time >10⁵ s. Moreover, the use of sequential vapor deposition is extended to deposit CH₃NH₃PbI₃ as the memory element in a cross‐point array structure. This method to fabricate high‐density memory devices could be used for memory cells that occupy large areas, and to overcome the scaling limit of existing methods; it also presents a way to use OHPs to increase memory storage capacity.     

Development of ferroelectric oxides based resistive switching materials

Resistive random access memory (RRAM) is one of the most promising candidates that satisfies the requirements of new generation non-volatile memories, as a consequence of its high density, outstanding scalability, and low power consumption. The review is based on a summary of recent studies in ferroelectric oxides based resistive switching (RS) materials and devices. It highlights the various ferroelectric oxide materials with RS behaviour and the underlying mechanisms including filament-type and interface-type mechanism. In the end, the challenge in current RRAM for future high-density data storage applications is addressed.     

Device performance of ferroelectric/correlated oxide heterostructures for non-volatile memory applications

Ferroelectric field effect devices offer the possibility of non-volatile data storage. Attempts to integrate perovskite ferroelectric materials with silicon semiconductors, however, have been largely unsuccessful in creating non-volatile, nondestructive read memory elements because of difficulties in controlling the ferroelectric/semiconductor interface. Correlated oxide systems have been explored as alternative channel materials to form all-perovskite field effect devices. We examine a non-volatile memory using an electric-field-induced metal-insulator transition in PbZr(0.2)Ti(0.8)O(3)/La(1 - x)Sr(x)MnO(3) (PZT/LSMO), PZT/La(1 - x)Ca(x)MnO(3) (PZT/LCMO) and PZT/La(1 - x)Sr(x)CoO(3) (PZT/LSCO) devices. The performance of these devices in the areas of switching time and retention are discussed.     

Multiferroic Heterostructures Integrating Ferroelectric and Magnetic Materials

Multiferroic heterostructures can be synthesized by integrating monolithic ferroelectric and magnetic materials, with interfacial coupling between electric polarization and magnetization, through the exchange of elastic, electric, and magnetic energy. Although the nature of the interfaces remains to be unraveled, such cross coupling can be utilized to manipulate the magnetization (or polarization) with an electric (or magnetic) field, known as a converse (or direct) magnetoelectric effect. It can be exploited to significantly improve the performance of or/and add new functionalities to many existing or emerging devices such as memory devices, tunable microwave devices, sensors, etc. The exciting technological potential, along with the rich physical phenomena at the interface, has sparked intensive research on multiferroic heterostructures for more than a decade. Here, we summarize the most recent progresses in the fundamental principles and potential applications of the interface‐based magnetoelectric effect in multiferroic heterostructures, and present our perspectives on some key issues that require further study in order to realize their practical device applications.     

Towards the Development of Flexible Non‐Volatile Memories

Flexible non‐volatile memories have attracted tremendous attentions for data storage for future electronics application. From device perspective, the advantages of flexible memory devices include thin, lightweight, printable, foldable and stretchable. The flash memories, resistive random access memories (RRAM) and ferroelectric random access memory/ferroelectric field‐effect transistor memories (FeRAM/FeFET) are considered as promising candidates for next generation non‐volatile memory device. Here, we review the general background knowledge on device structure, working principle, materials, challenges and recent progress with the emphasis on the flexibility of above three categories of non‐volatile memories.     

Development of Bismuth Ferrite as a Piezoelectric and Multiferroic Material by Cobalt Substitution

Bismuth ferrite (BiFeO₃) is the most widely studied multiferroic material with robust ferroelectricity and antiferromagnetic ordering at room temperature. One of the possible device applications of this material is one that utilizes the ferroelectric/piezoelectric property itself such as ferroelectric memory components, actuators, and so on. Other applications are more challenging and make full use of its multiferroic property to realize novel spintronics and magnetic memory devices, which can be addressed electrically as well as magnetically. This progress report summarizes the recent attempt to control the piezoelectric and magnetic properties of BiFeO₃ by cobalt substitution.     

PLL jitter reduction by utilizing a ferroelectric capacitor as a VCO timing element

Ferroelectric capacitors have steadily been integrated into semiconductor processes due to their potential as storage elements within memory devices. Polarization reversal within ferroelectric capacitors creates a high nonlinear dielectric constant along with a hysteresis profile. Due to these attributes, a phase-locked loop (PLL), when based on a ferroelectric capacitor, has the advantage of reduced cycle-to-cycle jitter. PLLs based on ferroelectric capacitors represent a new research area for reduction of oscillator jitter.     

Organic multiferroic tunnel junctions with ferroelectric poly(vinylidene fluoride) barriers

Organic materials are promising for applications in spintronics due to their long spin-relaxation times in addition to their chemical flexibility and relatively low production costs. Most studies of organic materials for spintronics focus on nonpolar dielectrics or semiconductors, serving as passive elements in spin transport devices. Here, we demonstrate that employing organic ferroelectrics, such as poly(vinylidene fluoride) (PVDF), as barriers in magnetic tunnel junctions (MTJs) allows new functionality in controlling the tunneling spin polarization via the ferroelectric polarization of the barrier. Using first-principles methods based on density functional theory we investigate the spin-resolved conductance of Co/PVDF/Co and Co/PVDF/Fe/Co MTJs as model systems. We show that these tunnel junctions exhibit multiple resistance states associated with different magnetization configurations of the electrodes and ferroelectric polarization orientations of the barrier. Our results indicate that organic ferroelectrics may open a new and promising route in organic spintronics with implications for low-power electronics and nonvolatile data storage.     

Organic non-volatile memories from ferroelectric phase-separated blends

New non-volatile memories are being investigated to keep up with the organic-electronics road map. Ferroelectric polarization is an attractive physical property as the mechanism for non-volatile switching, because the two polarizations can be used as two binary levels. However, in ferroelectric capacitors the read-out of the polarization charge is destructive. The functionality of the targeted memory should be based on resistive switching. In inorganic ferroelectrics conductivity and ferroelectricity cannot be tuned independently. The challenge is to develop a storage medium in which the favourable properties of ferroelectrics such as bistability and non-volatility can be combined with the beneficial properties provided by semiconductors such as conductivity and rectification. Here we present an integrated solution by blending semiconducting and ferroelectric polymers into phase-separated networks. The polarization field of the ferroelectric modulates the injection barrier at the semiconductor-metal contact. The combination of ferroelectric bistability with (semi)conductivity and rectification allows for solution-processed non-volatile memory arrays with a simple cross-bar architecture that can be read out non-destructively. The concept of an electrically tunable injection barrier as presented here is general and can be applied to other electronic devices such as light-emitting diodes with an integrated on/off switch.     

Interface-induced room-temperature multiferroicity in BaTiO₃

Multiferroic materials possess two or more ferroic orders but have not been exploited in devices owing to the scarcity of room-temperature examples. Those that are ferromagnetic and ferroelectric have potential applications in multi-state data storage if the ferroic orders switch independently, or in electric-field controlled spintronics if the magnetoelectric coupling is strong. Future applications could also exploit toroidal moments and optical effects that arise from the simultaneous breaking of time-reversal and space-inversion symmetries. Here, we use soft X-ray resonant magnetic scattering and piezoresponse force microscopy to reveal that, at the interface with Fe or Co, ultrathin films of the archetypal ferroelectric BaTiO? simultaneously possess a magnetization and a polarization that are both spontaneous and hysteretic at room temperature. Ab initio calculations of realistic interface structures provide insight into the origin of the induced moments and bring support to this new approach for creating room-temperature multiferroics.     

One-dimensional nanostructures of ferroelectric perovskites

Nanorods, nanowires, and nanotubes of ferroelectric perovskites have recently been studied with increasing intensity due to their potential use in non-volatile ferroelectric random access memory, nano-electromechanical systems, energy-harvesting devices, advanced sensors, and in photocatalysis. This Review summarizes the current status of these 1D nanostructures and gives a critical overview of synthesis routes with emphasis on chemical methods. The ferroelectric and piezoelectric properties of the 1D nanostructures are discussed and possible applications are highlighted. Finally, prospects for future research within this field are outlined.     

Individually addressable epitaxial ferroelectric nanocapacitor arrays with near Tb inch-2 density

Ferroelectric materials have emerged in recent years as an alternative to magnetic and dielectric materials for nonvolatile data-storage applications. Lithography is widely used to reduce the size of data-storage elements in ultrahigh-density memory devices. However, ferroelectric materials tend to be oxides with complex structures that are easily damaged by existing lithographic techniques, so an alternative approach is needed to fabricate ultrahigh-density ferroelectric memories. Here we report a high-temperature deposition process that can fabricate arrays of individually addressable metal/ferroelectric/metal nanocapacitors with a density of 176 Gb inch(-2). The use of an ultrathin anodic alumina membrane as a lift-off mask makes it possible to deposit the memory elements at temperatures as high as 650 degrees C, which results in excellent ferroelectric properties.     

Complementary Resistive Switching Using Metal–Ferroelectric–Metal Tunnel Junctions

Complementary resistive switching (CRS) devices are receiving attention because they can potentially solve the current‐sneak and current‐leakage problems of memory arrays based on resistive switching (RS) elements. It is shown here that a simple anti‐serial connection of two ferroelectric tunnel junctions, based on BaTiO₃, with symmetric top metallic electrodes and a common, floating bottom nanometric film electrode, constitute a CRS memory element. It allows nonvolatile storage of binary states (“1” = “HRS+LRS” and “0” = “LRS+HRS”), where HRS (LRS) indicate the high (low) resistance state of each ferroelectric tunnel junction. Remarkably, these states have an identical and large resistance in the remanent state, characteristic of CRS. Here, protocols for writing information are reported and it is shown that non‐destructive or destructive reading schemes can be chosen by selecting the appropriate reading voltage amplitude. Moreover, this dual‐tunnel device has a significantly lower power consumption than a single ferroelectric tunnel junction to perform writing/reading functions, as is experimentally demonstrated. These findings illustrate that the recent impressive development of ferroelectric tunnel junctions can be further exploited to contribute to solving critical bottlenecks in data storage and logic functions implemented using RS elements.     

Non‐Volatile Ferroelectric Memory with Position‐Addressable Polymer Semiconducting Nanowire

One‐dimensional nanowires (NWs) have been extensively examined for numerous potential nano‐electronic device applications such as transistors, sensors, memories, and photodetectors. The ferroelectric‐gate field effect transistors (Fe‐FETs) with semiconducting NWs in particular in combination with ferroelectric polymers as gate insulating layers have attracted great attention because of their potential in high density memory integration. However, most of the devices still suffer from low yield of devices mainly due to the ill‐control of the location of NWs on a substrate. NWs randomly deposited on a substrate from solution‐dispersed droplet made it extremely difficult to fabricate arrays of NW Fe‐FETs. Moreover, rigid inorganic NWs were rarely applicable for flexible non‐volatile memories. Here, we present the NW Fe‐FETs with position‐addressable polymer semiconducting NWs. Polymer NWs precisely controlled in both location and number between source and drain electrode were achieved by direct electrohydrodynamic NW printing. The polymer NW Fe‐FETs with a ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) exhibited non‐volatile ON/OFF current margin at zero gate voltage of approximately 10² with time‐dependent data retention and read/write endurance of more than 10⁴ seconds and 10² cycles, respectively. Furthermore, our device showed characteristic bistable current hysteresis curves when being deformed with various bending radii and multiple bending cycles over 1000 times.     

Fabrication of epitaxial nanostructured ferroelectrics and investigation of their domain structures

Nanostructured ferroelectrics are important objects for studies on ferroelectric size effects as well as for applications to memory devices with ultra-high memory density. In the present article, we introduce several approaches for the synthesis of confined ferroelectrics with sizes in and below the hundreds of nanometer range, including top-down processes like e-beam lithography, self-assembly methods like chemical solution deposition, and growth by pulsed laser deposition using stencil masks. Furthermore, the ferroelectric domain structure of part of these nanostructures is investigated by means of synchrotron X-ray diffraction, and its contribution to the ferroelectric properties is discussed.     

LED switching of spiropyran-doped polymer films

Spiropyrans are a well-known family of photochromic compounds that switch from uncoloured to highly coloured upon exposure to UV light with potential applications such as optical switches and memory storage devices. Typically the light sources used for controlling the state of the spiropyran are high power sources such as mercury lamps and lasers. Here we report the use of low power light emitting diodes (LEDs) to actuate the colour change in spiropyran-doped polymer films. The use of LEDs as an effective means of switching the dye expands the possible applications of these types of photochromic materials.     

Organic Nonvolatile Memory Devices Based on Ferroelectricity

A memory functionality is a prerequisite for many applications of electronic devices. Organic nonvolatile memory devices based on ferroelectricity are a promising approach toward the development of a low‐cost memory technology. In this Review Article we discuss the latest developments in this area with a focus on three of the most important device concepts: ferroelectric capacitors, field‐effect transistors, and diodes. Integration of these devices into larger memory arrays is also discussed.     

PZT铁电薄、厚膜及其制备技术研究进展

铁电薄、厚膜材料具有良好的铁电、压电、热释电、电光及非线性光学特性,在微电子学、光电子学、集成光学和微电子机械系统等领域有许多重要的应用.近年来,随着铁电薄、厚膜制备技术的发展,PZT厚膜材料及厚膜器件成为科学工作者研究的热点.介绍了PZT铁电薄、厚膜材料与器件的研究进展以及PZT铁电薄、厚膜制备技术及几种典型的PZT铁电薄、厚膜材料制备技术的特点,并指出了目前存在的一些问题和未来的发展方向.