Candidate For Nonvolatile Memory Devices Research Articles

Phase Transformation Driven by Oxygen Vacancy Redistribution as the Mechanism of Ferroelectric Hf0.5Zr0.5O2 Fatigue

AbstractAs a promising candidate for nonvolatile memory devices, the hafnia‐based ferroelectric system has recently been a hot research topic. Although significant progress has been made over the past decade, the endurance problem is still an obstacle to its final application. In perovskite‐based ferroelectrics, such as the well‐studied Pb[ZrxTi1−x]O3 (PZT) family, polarization fatigue has been discussed within the framework of the interaction of charged defects (such as oxygen vacancies) with the moving domains during the switching process, particularly at the electrode‐ferroelectric interface. Armed with this background, a hypothesis is set out to test that a similar mechanism can be in play with the hafnia‐based ferroelectrics. The conducting perovskite La‐Sr‐Mn‐O is used as the contact electrode to create La0.67Sr0.33MnO3 / Hf0.5Zr0.5O2 (HZO)/ La0.67Sr0.33MnO3 capacitor structures deposited on SrTiO3‐Si substrates. Nanoscale X‐ray diffraction is performed on single capacitors, and a structural phase transition from polar o‐phase toward non‐polar m‐phase is demonstrated during the bipolar switching process. The energy landscape of multiphase HZO has been calculated at varying oxygen vacancy concentrations. Based on both theoretical and experimental results, it is found that a polar to non‐polar phase transformation caused by oxygen vacancy redistribution during electric cycling is a likely explanation for fatigue in HZO.

Giant Tunneling Electroresistance Induced by Interfacial Doping in Pt/BaTiO3/Pt Ferroelectric Tunnel Junctions

Ferroelectric tunnel junctions (FTJs) are very promising candidates for nonvolatile memory devices and a large tunneling electroresistance (TER) ratio is essential for their high performance. This work intends to achieve large TER ratio by interfacial doping in FTJs by taking ${\mathrm{Pt}/\mathrm{Ba}\mathrm{Ti}\mathrm{O}}_{3}/\mathrm{Pt}$ tunnel junctions as an example. By introducing Na (or $\mathrm{Li}$) substitutions for $\mathrm{Ti}$ atoms at the right interface, the resultant strong Coulomb repulsion from the negatively charged ${\mathrm{Na}\mathrm{O}}_{2}$ interface pushes the electrons to higher energy in an increasing manner from left to right in the whole ${\mathrm{Ba}\mathrm{Ti}\mathrm{O}}_{3}$ barrier, which leads to rapidly increasing potential energy profile and partial metallization close to the right interface in the left polarization state. However, in the right polarization state, since the right ferroelectric polarization produces a decreasing potential energy profile from left to right, although the ${\mathrm{Na}\mathrm{O}}_{2}$ interface also pushes the electrons to much higher energy and the slope of the potential energy profile changes from negative to positive, the final slope of the potential energy profile is much less steeper and the Fermi level is always inside the band gap, leading to a completely insulating state. The substantially different distributions of the electrostatic potential energy profile in the two polarization states lead to great differences in the transport properties. Based on density-functional-theory calculations, a TER ratio up to ${10}^{5}$% is achieved. The results indicate that a negatively charged interface based on interfacial substitution is a promising method for obtaining a large TER ratio in FTJs, and thus will have implications for the further understanding and design of high-performance FTJs.

Direct Observation of Interface-Dependent Multidomain State in the BaTiO3 Tunnel Barrier of a Multiferroic Tunnel Junction Memristor.

Multiferroic tunnel junctions (MFTJs), normally consisting of a four-state resistance, have been studied extensively as a potential candidate for nonvolatile memory devices. More interestingly, the MFTJs whose resistance can be tuned continuously with applied voltage were also reported recently. Since the performance of MFTJs is closely related to their interfacial structures, it is necessary to investigate MFTJs at the atomic scale. In this work, atomic-resolution HAADF, ABF, and EELS of the La0.7Sr0.3MnO3/BaTiO3/La0.7Sr0.3MnO3 MFTJ memristor have been obtained with aberration-corrected scanning transmission electron microscopy (STEM). These results demonstrate varied degree of interfacial cation intermixing at the bottom BTO/LSMO interface, which has a direct influence on the polarization of the ferroelectric barrier BTO and the electronic structure of Mn near the interfaces. We also took advantage of a simplified model to explain the relation between the interfacial behavior and polarization states, which could be a contributing factor to the transport properties of this MFTJ.

Regulating crystal structure and ferroelectricity in Sr doped HfO2 thin films fabricated by metallo-organic decomposition

HfO2 based binary ferroelectric oxides are promising candidate for nonvolatile memory devices due to their compatibility with the current Si-based technology. In this work, Sr doped HfO2 (Sr:HfO2) ferroelectric thin films with Sr concentration from 0% to 10 mol% were prepared on the platinum electrodes by metallo-organic decomposition (MOD). It was demonstrated that uniform Sr:HfO2 thin films with extremely low roughness can be achieved and crystallized by MOD under a 700 °C annealing process. A wake-up stage was believed more essential for the ferroelectricity of the MOD derived Sr:HfO2 thin film, since the remnant polarization of 13.3 µC/cm2 and high dielectric constant of 30 were obtained after 105 cycling tests. The transformation from monoclinic phase to cubic phase was observed with increasing the Sr concentration and the thickness of the films. X-ray photoelectron spectroscopy analysis confirmed the bonding type of O-Hf-O and O-Sr-O bonds in the film. The microscopic crystal structure of ferroelectric orthorhombic phase was observed by high resolution transmission electronic microscope. The intrinsic ferroelectricity of Sr:HfO2 film was demonstrated by the hysteresis polarization-voltage loops and distinct current peaks in the current-voltage curve. Stable domain structure and its switching dynamics were monitored by piezoresponse force microscopy, indicating the native polarization of Sr:HfO2. This work will provide a controllable routine to fabricate ferroelectric HfO2 based thin films using MOD method.

Ferroelectricity in Lu doped HfO2 layers

Doped HfO2 has become a promising candidate for non-volatile memory devices since it can be easily integrated into existing CMOS technology. Many dopants like Y, Gd, and Sr have been investigated for the stabilization of ferroelectric HfO2. Here, we report the fabrication of capacitors comprising ferroelectric HfO2 metal-insulator-metal structures with TiN bottom and top electrodes using the dopant Lu. Amorphous 5% Lu doped HfO2 was deposited by pulsed laser deposition and afterwards annealed to achieve the ferroelectric, orthorhombic phase (space group Pbc21). The polarization of the layers was confirmed by capacitance-voltage, polarization-voltage, and current-voltage measurements. Depending on the anneal temperature, the remanent polarization changes and the initial state of the oxide varies. The layer exhibits initially a pinched hysteresis up to an annealing temperature of 600 °C and an unpinched hysteresis at 700 °C. The maximum polarization is about 11 μC/cm2 which is measured after 104 cycles and stable up to 106 cycles. The influence of the layer thickness on the oxide properties is investigated for 10–40 nm thick HfLuO; however, a thickness dependence of the ferroelectric properties is not observed.

Carbon nanowalls: A new material for resistive switching memory devices

In this work, we report for the first time the resistive switching behavior of a new type of device made of carbon nanowalls (CNWs) deposited on fluorine-doped tin oxide (FTO) substrate. This new device shows a forming-free bipolar resistive switching behavior, with a low operating voltage of 2 V and long retention time (5 × 10ˆ4 s). The CNWs are synthesized by electrophoretic deposition of a solution of polyynes obtained by arc discharge. We show that the environmentally-friendly and time-saving fabrication process we developed could overcome the current complex fabrication process of carbon-based memory devices which impede their large-scale development. The obtained results demonstrate the good reproducibility of the device's production process, and that the device's electrical performances can be engineered with a control of the fabrication parameters. The study presented suggests that CNWs are promising candidates for non-volatile memory devices and in carbon-based electronics.

High-resolution characterization of multiferroic heterojunction using aberration-corrected scanning transmission electron microscopy

Multiferroic tunnel junctions have been considered as potential candidates for nonvolatile memory devices. Understanding the atomic structure at the interface is crucial for optimizing the performances in such oxide electronics. Spatially resolved electron energy loss spectroscopy (EELS) combined with aberration-corrected scanning transmission electron microscopy is employed to measure the compositional profiles across the interfaces of different layers with atomic resolution. Two-dimensional elemental imaging with atomic resolution is demonstrated, and the influences of the interface sharpness, the terminal layer, and cation intermixing are investigated. An asymmetric sublattice intermixing at the Pr0.8Ca0.2MnO3/BaTiO3/La0.7Sr0.3MnO3 interface is observed, which can affect the local Mn valence and coupling. The reduction in the Mn valence at the interface is further studied using EELS near-edge fine structures.

Reversible photo-chem-electrotriggered three-state luminescence switching based on core–shell nanostructures

Reversible three-state fluorescence switches triggered by light, electricity and chemical inputs based on "sponges" of Pyronin Y-doped silica nanoparticles (PYDS) and polyoxometalate K14[Na(H2O)P5W30O110] (Na-POMs) core-shell nanostructures were realized. Under one or two signal inputs, the system exhibited distinct three-state interconvertible automaton, achieving reversible "on" and "off" luminescence switches via the related luminescence quenching effect. The features of the system correspond to the equivalent circuitry of an IMPLICATION logic gate performing the Boolean operation by using potential and chemical as inputs. Such a multi-chromic device with novel structure possesses several advantages, such as relative low operation voltage, large reproducibility and reversibility, apparent fluorescence contrast, and long-time stability, which make it a suitable candidate for nonvolatile memory devices. In addition, the current protocol for the hybrid film fabrication can be easily extended from the polyoxometalate and organic dyes to other novel nanostructures matched multifunctional stimulus-responsive species and fluorescence materials in the future.

Electrochemical Addressing of the Optical Properties of a Monolayer on a Transparent Conducting Substrate

Don't forget to write! Electrochemical charge storage in a ruthenium-based monolayer on a hydrophilic substrate (for example, indium tin oxide coated glass) produces redox switching of the optical properties of the system (see picture). This read/write process can be carried out at low voltage in air and monitored by UV/Vis spectrophotometry. This makes the monolayer system a suitable candidate for nonvolatile memory devices.

Growth mechanism of YMnO3 film as a new candidate for nonvolatile memory devices

We have proposed ReMnO3 (Re: rare earth) thin films for nonvolatile memory devices. We examine the growth mechanism of YMnO3 films on (0001)ZnO:Al/(0001) sapphire substrate using rf magnetron sputtering and pulsed laser deposition methods with oxide compound target. We have succeeded in obtaining (0001) epitaxial YMnO3 films on (111) MgO and (0001)ZnO:Al/(0001) sapphire substrate, and polycrystalline films on (111)Pt/(111)MgO. For an optimal structure, the film needed much less oxygen from the gas phase compared to other oxide films. The composition (Y/Mn ratio) of the YMnO3 films changed drastically by varying the partial oxygen pressure in the sputtering gas. In addition the Y/Mn ratio slinfled with sputter time due to target surface modification, probably caused by Y segregation. An extremely small amount of oxygen is required to form the YMnO3 crystal. This was confirmed by pulsed laser deposition experiments.

Epitaxially grown YMnO3 film: New candidate for nonvolatile memory devices

We have proposed ReMnO3 (Re:rare earth) thin films as a new candidate for nonvolatile memory devices. In this letter, we report on fabrication of (0001) YMnO3 films on (111)MgO, (0001)ZnO:Al/(0001) sapphire, and (111)Pt/(111)MgO using rf magnetron sputtering. We succeeded in obtaining (0001) epitaxial YMnO3 films on (111) MgO and (0001)ZnO:Al/(0001) sapphire substrate, and polycrystalline films on (111)Pt/(111)MgO. The dielectric properties of the epitaxial and polycrystalline YMnO3 films are almost the same. The dielectric permittivities of both films are smaller than those reported for YMnO3 single crystal.

Fabrication of YMnO3 Films: New Candidate for Non-Volatile Memory Devices

AbstractWe have proposed ReMnO3 (Re:rare earth) thin films, as a new candidate for nonvolatile memory devices. In this paper, we try to fabricate (0001) oriented YMnO3 films on (111)MgO, (0001)ZnO:Al/(0001) sapphire and (111)Pt/(111)MgO using rf magnetron sputtering. We succeed in obtaining (0001) epitaxial YMnO3 films on (111) MgO and (0001)ZnO:Al/(0001)sapphire substrate, and polycrystalline films on (111)Pt/(1 11)MgO for the first time. Electrical property of the bottom electrode (ZnO:Al) changes with varying the deposition condition of YMnO3 films. However, we find an optimum deposition condition of ZnO:Al film such that it functions as a bottom electrode even after YMnO3 film deposition. The dielectric properties of the epitaxial and polycrystalline YMnO3 films are almost the same. The YMnO3 films show leaky electrical properties. This may be caused by a change in the valence electron of Mn from 3+.