Nanoscale Topotactic Phase Transformation in SrFeOx Epitaxial Thin Films for High‐Density Resistive Switching Memory

Resistive switching (RS) memory has stayed at the forefront of next‐generation nonvolatile memory technologies. Recently, a novel class of transition metal oxides (TMOs), which exhibit reversible topotactic phase transformation between insulating brownmillerite (BM) phase and conducting perovskite (PV) phase, has emerged as promising candidate materials for RS memories. Nevertheless, the microscopic mechanism of RS in these TMOs is still unclear. Furthermore, RS devices with simultaneously high density and superior memory performance are yet to be reported. Here, using SrFeO_x as a model system, it is directly observed that PV SrFeO₃ nanofilaments are formed and extend almost through the BM SrFeO_2.5 matrix in the ON state and are ruptured in the OFF state, unambiguously revealing a filamentary RS mechanism. The nanofilaments are ≈10 nm in diameter, enabling to downscale Au/SrFeO_x/SrRuO₃ RS devices to the 100 nm range for the first time. These nanodevices exhibit good performance including ON/OFF ratio as high as ≈10⁴, retention time over 10⁵ s, and endurance up to 10⁷ cycles. This study significantly advances the understanding of the RS mechanism in TMOs exhibiting topotactic phase transformation, and it also demonstrates the potential of these materials for use in high‐density RS memories.     

Topotactic Metal–Insulator Transition in Epitaxial SrFeOx Thin Films

Topotactic phase transformation enables structural transition without losing the crystalline symmetry of the parental phase and provides an effective platform for elucidating the redox reaction and oxygen diffusion within transition metal oxides. In addition, it enables tuning of the emergent physical properties of complex oxides, through strong interaction between the lattice and electronic degrees of freedom. In this communication, the electronic structure evolution of SrFeO_x epitaxial thin films is identified in real‐time, during the progress of reversible topotactic phase transformation. Using real‐time optical spectroscopy, the phase transition between the two structurally distinct phases (i.e., brownmillerite and perovskite) is quantitatively monitored, and a pressure–temperature phase diagram of the topotactic transformation is constructed for the first time. The transformation at relatively low temperatures is attributed to a markedly small difference in Gibbs free energy compared to the known similar class of materials to date. This study highlights the phase stability and reversibility of SrFeO_x thin films, which is highly relevant for energy and environmental applications exploiting the redox reactions.     

Substitutional Carbon‐Modified Anatase TiO2 Decahedral Plates Directly Derived from Titanium Oxalate Crystals via Topotactic Transition

Changing the composition and/or structure of some metal oxides at the atomic level can significantly improve their performance in different applications. Although many strategies have been developed, the introduction of heteroatoms, particularly anions to the internal part of metal oxide particles, is still not adequate. Here, an effective strategy is demonstrated for directly preparing polycrystalline decahedral plates of substitutional carbon‐doped anatase TiO₂ from titanium (IV) oxalate by a thermally induced topotactic transition in an inert atmosphere. Because of the carbon concentration gradient introduced in side of the plates, the carbon‐doped TiO₂ (TiO_2–xC_x) shows an increased visible light absorption and a two orders of magnitude higher electrical conductivity than pure TiO₂. Consequently, it can be used as a photocatalyst and an active material for lithium storage and shows much superior activity in generating hydroxyl radicals under visible light and greatly increased electrical‐specific capacity at high charge–discharge rates. The strategy developed could also be applicable to the atomic‐scale modification of other metal oxides.     

Molybdenum Disulfide Nanosheet/Quantum Dot Dynamic Memristive Structure Driven by Photoinduced Phase Transition

MoS₂ 2D nanosheets (NS) with intercalated 0D quantum dots (QDs) represent promising structures for creating low‐dimensional (LD) resistive memory devices. Nonvolatile memristors based 2D materials demonstrate low power consumption and ultrahigh density. Here, the observation of a photoinduced phase transition in the 2D NS/0D QDs MoS₂ structure providing dynamic resistive memory is reported. The resistive switching of the MoS₂ NS/QD structure is observed in an electric field and can be controlled through local QD excitations. Photoexcitation of the LD structure at different laser power densities leads to a reversible MoS₂ 2H‐1T phase transition and demonstrates the potential of the LD structure for implementing a new dynamic ultrafast photoresistive memory. The dynamic LD photomemristive structure is attractive for real‐time pattern recognition and photoconfiguration of artificial neural networks in a wide spectral range of sensitivity provided by QDs.     

Coupled Ionic and Electronic Transport Model of Thin‐Film Semiconductor Memristive Behavior

The memristor, the fourth passive circuit element, was predicted theoretically nearly 40 years ago, but we just recently demonstrated both an intentional material system and an analytical model that exhibited the properties of such a device. Here we provide a more physical model based on numerical solutions of coupled drift‐diffusion equations for electrons and ions with appropriate boundary conditions. We simulate the dynamics of a two‐terminal memristive device based on a semiconductor thin film with mobile dopants that are partially compensated by a small amount of immobile acceptors. We examine the mobile ion distributions, zero‐bias potentials, and current–voltage characteristics of the model for both steady‐state bias conditions and for dynamical switching to obtain physical insight into the transport processes responsible for memristive behavior in semiconductor films.     

Non-Fermi Behavior of the Itinerant-Electron Ferromagnet near the Quantum Phase Transition Point

We used the Renormalization Group (RG) method in the Hertz–Millis version to study the quantum phase transition of the itinerant-electron ferromagnet. Near the quantum phase transition point the system present a non-Fermi behavior in agreement with the experimental results. The importance of long-range interactions considered by Belitz–Kirkpatrick–Vojta was taken into consideration, showing the importance of the marginal parameters.     

Ultrasensitive Memristive Synapses Based on Lightly Oxidized Sulfide Films

For biological synapses, high sensitivity is crucial for transmitting information quickly and accurately. Compared to biological synapses, memristive ones show a much lower sensitivity to electrical stimuli since much higher voltages are needed to induce synaptic plasticity. Yet, little attention has been paid to enhancing the sensitivity of synaptic devices. Here, electrochemical metallization memory cells based on lightly oxidized ZnS films are found to show highly controllable memristive switching with an ultralow SET voltage of several millivolts, which likely originates from a two‐layer structure of ZnS films, i.e., the lightly oxidized and unoxidized layers, where the filament rupture/rejuvenation is confined to the two‐layer interface region several nanometers in thickness due to different ion transport rates in these two layers. Based on such devices, an ultrasensitive memristive synapse is realized where the synaptic functions of both short‐term plasticity and long‐term potentiation are emulated by applying electrical stimuli several millivolts in amplitude, whose sensitivity greatly surpasses that of biological synapses. The dynamic processes of memorizing and forgetting are mimicked through a 5 × 5 memristive synapse array. In addition, the ultralow operating voltage provides another effective solution to the relatively high energy consumption of synaptic devices besides reducing the operating current and pulse width.     

Non-Fermi Behavior Near a Quantum Phase Transition Driven by Disorder

We showed that in a d-wave two-dimensional superconductor the disorder given by non-magnetic impurities at low temperature leads to a non-Fermi behavior for the normal state. The transition is similar to the superconductor–insulator transition in a model with a dissipative term.     

Oxygen Exchange Processes between Oxide Memristive Devices and Water Molecules

Resistive switching based on transition metal oxide memristive devices is suspected to be caused by the electric‐field‐driven motion and internal redistribution of oxygen vacancies. Deriving the detailed mechanistic picture of the switching process is complicated, however, by the frequently observed influence of the surrounding atmosphere. Specifically, the presence or absence of water vapor in the atmosphere has a strong impact on the switching properties, but the redox reactions between water and the active layer have yet to be clarified. To investigate the role of oxygen and water species during resistive switching in greater detail, isotope labeling experiments in a N₂/H₂¹⁸O tracer gas atmosphere combined with time‐of‐flight secondary‐ion mass spectrometry are used. It is explicitly demonstrated that during the RESET operation in resistive switching SrTiO₃‐based memristive devices, oxygen is incorporated directly from water molecules or oxygen molecules into the active layer. In humid atmospheres, the reaction pathway via water molecules predominates. These findings clearly resolve the role of humidity as both oxidizing agent and source of protonic defects during the RESET operation.     

Photoinduced Phase Transition in Infinite-Layer Nickelates

The quantum phase transition caused by regulating the electronic correlation in strongly correlated quantum materials has been a research hotspot in condensed matter science. Herein, a photon-induced quantum phase transition from the Kondo-Mott insulating state to the low temperature metallic one accompanying with the magnetoresistance changing from negative to positive in the infinite-layer NdNiO₂ films is reported, where the antiferromagnetic coupling among the Ni¹⁺ localized spins and the Kondo effect are effectively suppressed by manipulating the correlation of Ni-3d and Nd-5d electrons under the photoirradiation. Moreover, the critical temperature T_c of the superconducting-like transition exhibits a dome-shaped evolution with the maximum up to ≈42 K, and the electrons dominate the transport process proved by the Hall effect measurements. These findings not only make the photoinduction a promising way to control the quantum phase transition by manipulating the electronic correlation in Mott-like insulators, but also shed some light on the possibility of the superconducting in electron-doped nickelates.     

光声效应在研究铁电陶瓷相变中的应用

本文报导了用光声技术研究铁电陶瓷 Pb(Zr,Ti,Sn)O_3(PSZT),透明 PLZT 以及 Li_(1-x)Na_xNbO_3(LNN)的相变,清楚地揭示了这些陶瓷所呈现的不同相变特性以及相变点随组分的变化,与某些常规研究方法相比较,显示了在相变点附近,光声信号的幅度和相位的变化非常灵敏。并用热力学解释了实验结果。     

板钛矿相对TiO2纳米晶相转变的影响研究

本文以Ti(O BU) 4为前驱体 ,采用溶胶 凝胶工艺制备了TiO2 纳米晶。通过X 射线衍射 (XRD)分析证明了所制备的锐钛矿相TiO2 纳米晶中含有一些板钛矿相 ,发现在较低的热处理温度下 ,TiO2 纳米晶就发生了相转变 ,并且板钛矿 金红石相转变的过程比锐钛矿 金红石相转变过程快 ;同时锐钛矿相的晶胞常数c的变化似乎部分归因于有板钛矿相的存在。差热 热重同步分析 (DTA TGA)表明 ,在 36 0～ 5 0 0°C之间 ,可以观察到板钛矿 锐钛矿相转变的存在。最后对TiO2 纳米晶中含有的板钛矿相对锐钛矿 金红石相转变的作用机制进行了简要的分析。     

Non-Fermi Behavior Near Ferromagnetic Quantum Phase Transition

We propose a model for the explanation of the non-Fermi behavior near the ferromagnetic quantum phase transition. The scaling equations have been used to calculate the specific heat and we showed that the quantum effects are responsible for the T ln T term from the specific heat. The results are in agreement with recent experimental data obtained in the Ni _x Pd_{1 – x} system. The relation with the other approaches was also discussed.