We present molecular-dynamic simulations of memory resistors (memristors) including the crystal field effects on mobile ionic species such as oxygen vacancies appearing during operation of the device. Vacancy distributions show different patterns depending on the ratio of a spatial period of the crystal field to a characteristic radius of the vacancy-vacancy interaction. There are signatures of the orientational order and of spatial voids in the vacancy distributions for some crystal field potentials. The crystal field stabilizes the patterns after they are formed, resulting in a non-volatile switching of the simulated devices.
We analyzed micrometer-scale titanium-niobium-oxide prototype memristors, which exhibited low write-power (<3 μW) and energy (<200 fJ/bit/μm2), low read-power (~nW), and high endurance (>millions of cycles). To understand their physico-chemical operating mechanisms, we performed in-operando synchrotron x-ray transmission nanoscale spectromicroscopy using an ultra-sensitive time-multiplexed technique. We observed only spatially uniform material changes during cell operation, in sharp contrast to the frequently detected formation of a localized conduction channel in transition-metal-oxide memris…
While the recent establishment of the role of thermophoresis/diffusion-driven oxygen migration during resistance switching in metal oxide memristors provided critical insights required for memristor modeling, extended investigations of the role of oxygen migration during ageing and failure remain to be detailed. Such detailing will enable failure-tolerant design, which can lead to enhanced performance of memristor-based next-generation storage-class memory. Here we directly observed lateral oxygen migration using in-situ synchrotron x-ray absorption spectromicroscopy of HfOx memristors during …
Transition metal oxide memristors, or resistive random-access memory (RRAM) switches, are under intense development for storage-class memory because of their favorable operating power, endurance, speed, and density. Their commercial deployment critically depends on predictive compact models based on understanding nanoscale physico-chemical forces, which remains elusive and controversial owing to the difficulties in directly observing atomic motions during resistive switching, Here, using scanning transmission synchrotron x-ray spectromicroscopy to study in-situ switching of hafnium oxide memri…
Memristors are receiving keen interest because of their potential varied applications and promising large-scale information storage capabilities. Tantalum oxide is a memristive material that has shown promise for high-performance nonvolatile computer memory. The microphysics has been elusive because of the small scale and subtle physical changes that accompany conductance switching. In this study, we probed the atomic composition, local chemistry and electronic structure of functioning tantalum oxide memristors through spatially mapped O K-edge x-ray absorption. We developed a time-multiplexed…
Oxygen migration in tantalum oxide, a promising next-generation storage material, is studied using in-operando x-ray absorption spectromicroscopy and is used to microphysically describe accelerated evolution of conduction channel and device failure. The resulting ring-like patterns of oxygen concentration are modeled using thermophoretic forces and Fick diffusion, establishing the critical role of temperature-activated oxygen migration that has been under question lately.
Understanding the resistive switching behavior, or the resistance change, of oxide-based memristor devices, is critical to predicting their responses with known electrical inputs. Also, with the known electrical response of a memristor, one can confirm its usefulness in non-volatile memory and/or in artificial neural networks. Although bi- or multi-layered oxides have been reported to improve the switching performance, compared to the single oxide layer, the detailed explanation about why the switching can easily be improved for some oxides combinations is still missing. Herein, we fabricated …
Anomalous Platinum and Oxygen Transport during Electroforming of NbOx Memristors
University of New South Wales (UNSW Sydney)（新南威尔士大学）；The Australian National University（澳大利亚国立大学）；Curtin University（科廷大学）；Jahangirnagar University（贾汉吉尔纳加尔大学）
Progress of silicon based technology is nearing its physical limit, as minimum feature size of components is reaching a mere 10 nm. The resistive switching behaviour of transition metal oxides and the associated memristor device is emerging as a competitive technology for next generation electronics. Significant progress has already been made in the past decade and devices are beginning to hit the market; however, it has been mainly the result of empirical trial and error. Hence, gaining theoretical insight is of essence. In the present work we report the striking result of a connection betwee…
We report a complementary metal oxide semiconductor (CMOS) technology compatible ferroelectric tunnel junction memristor grown directly on top of a Silicon substrate using a scandium doped aluminum nitride as the ferroelectric layer.
Developing materials that can lead to compact versions of artificial neurons (neuristors) and synapses (memristors) is the main aspiration of the nascent neuromorphic materials research field. Oscillating circuits are interesting as neuristors, emulating the firing of action potentials. We present room-temperature self-oscillating devices fabricated from epitaxial thin films of semiconducting TbMnO3. We show that these electrical oscillations induce concomitant mechanical oscillations that produce audible sound waves, offering an additional degree of freedom to interface with other devices. Th…
Electrical switching has been observed in carefully designed metal-insulator-metal devices built at small geometries. These devices are also commonly known as memristors and consist of specific materials such as transition metal oxides, chalcogenides, perovskites, oxides with valence defects, or a combination of an inert and an electrochemically active electrode. No simple physical device has been reported to exhibit electrical switching. We have discovered that a simple point-contact or a granular arrangement formed of metal pieces exhibits bipolar switching. These devices, referred to as coh…
Self-ordered nanotubular titania TiO2-NT with outer tube diameter of 45 nm are synthesized using the anodic oxidation of titanium foil. Four sets of memristors with 100 $μm$ diameter based on Ti/TiO2-NT/Au sandwich structures with an oxide layer thickness of 80, 120, 160 and 200 nm are fabricated. Current-voltage (CV) characteristics for the obtained samples in the static and dynamic operation modes are studied. Resistance in high and low resistance states is estimated. Basing on the analysis of the CV characteristics in dynamic mode (> 14 000 switchings) a prospective of use for synthesized T…
We describe via simulation novel optimization algorithms for a Hopfield neural network constructed using manufacturable three-terminal Silicon-Oxide-Nitride-Oxide-Silicon (SONOS) synaptic devices. We first present a computationally-light, memristor-based, highly accurate compact model for the SONOS. Using the compact model, we describe techniques of simulated annealing in Hopfield networks by exploiting imperfect problem definitions, current leakage, and the continuous tunability of the SONOS to enable transient chaotic group dynamics. We project improvements in energy consumption and latency …
We present a tutorial on the principles of crystal growth of intermetallic and oxide compounds from molten solutions, with an emphasis on the fundamental principles governing the underlying phase equilibria and phase diagrams of multicomponent systems.
Single crystalline thin films of complex oxides show a rich variety of functional properties such as ferroelectricity, piezoelectricity, ferro and antiferromagnetism etc. that have the potential for completely new electronic applications (1-2). Direct synthesis of such oxides on Si remains challenging due to the fundamental crystal chemistry and mechanical incompatibility of dissimilar interfaces (3-16). Here we report integration of thin (down to 1 unit cell) single crystalline, complex oxide films onto Si substrates, by epitaxial transfer at room temperature. In a field effect transistor usi…
2D electron gases (2DEGs) formed at oxide interfaces provide a rich testbed for fundamental physics and device applications. While the discussion of the physical origins of this phenomenon continues, the recent discovery of oxide 2DEGs at non-epitaxial interfaces between amorphous and crystalline oxides provides useful insight onto this debate. Furthermore, using amorphous oxides offers a low-cost route towards realizing 2DEGs for device applications. In this work, the band offsets of a simple model system of amorphous-crystalline oxide interface are investigated. The model system consists of …
The ring opening polymerization of cyclic butylene terephthalate into poly (butylene terephthalate) (pCBT) in the presence of reduced graphene oxide (RGO) is an effective method for the preparation of polymer nanocomposites. The inclusion of RGO nanoflakes dramatically affects the crystallization of pCBT, shifting crystallization peak temperature to higher temperatures and, overall, increasing the crystallization rate. This was due to a super nucleating effect caused by RGO, which is maximized by highly reduced graphene oxide. Furthermore, combined analyses by differential scanning calorimetry…
Structural transitions and the melting behavior of crystalline poly(ethylene oxide),(CH2-CH2-O)n, (PEO) has been investigated using fully atomistic, constant pressure-constant temperature (NPT) molecular dynamics (MD) simulations. Melting of PEO proceeds in two stages; Order parameters reveal the loss of interchain orientational correlations and of chain helicity in the first and second stages of melting respectively. Sliding diffusion and anisotropic reorientational dynamics of the polymer backbone are observed in the solid state, in agreement with 1H NMR experiments.
The work of this thesis comprises extensive Noncontact Atomic Force Microscopy (NC-AFM) characterization of clean metal-oxide (YSZ(100)/(111) and MgO(100)) and graphitic (HOPG) supports as templates for the novel, photochemically induced nucleation of cobalt oxide nanostructures, particularly Cobalt (III) Oxide. The nanostructure-support surfaces were also studied by X-ray Photoelectron Spectroscopy (XPS) to verify the nature of the supported cobalt oxide and to corroborate the surface topographic and phase NC-AFM data. Heteroepitaxial growth of Co2O3 nanostructures proves to exhibit a variety…
For the study of polarization reversal features in the structure of "mixed ionic-electronic conductor - on - ferroelectric" type, the hydrogen bonded molecular ferroelectric crystal triglycine sulphate (TGS) is used. The dynamic currant-voltage (I-V-) loops of thin TGS plates of polar (010) cut with dissimilar electrodes on the opposite surfaces (vacuum deposited Ag and Ag-paste diluted with a water-ethanol mixture) are investigated. After electroforming in the low-voltage vicinity of coercive voltage, during further cycling, a reversible transformation of I-V-loop shape occurs from typical of…
The development of new high dielectric materials is essential for advancement in modern electronics. Oxides are generally regarded as the most promising class of high dielectric materials for industrial applications as they possess both high dielectric constants and large band gaps. Most previous researches on high dielectrics were limited to already known materials. In this study, we conducted an extensive search for high dielectrics over a set of ternary oxides by combining crystal structure prediction and density functional perturbation theory calculations. From this search, we adopted mult…
Delafossite oxide CuAlO2 has engaged great attention as a promising p-type conducting oxide. In this work, high-quality CuAlO2 single crystals with a size of several millimeters (mm) are successfully achieved with a reactive crucible melting method. The crystals are characterized by X-ray diffraction, scanning electron microscopy with energy-dispersive spectroscopy, transport measurement, and magnetic susceptibility measurement. The grown single crystals are free of contamination from a copper oxide flux. This work provides a new approach to growing high-quality delafossite oxide CuAlO2 with a…
During a bioInspired crystallization process, incorporation of amino acids into the crystal structure of ZnO induces lattice strain that leads to linear bandgap shifts.
Cupric oxide single crystal thin films were grown by plasma-assisted molecular beam epitaxy. X-ray diffraction, Raman spectrum and in situ reflection high-energy electron diffraction show that the thin films are 2x2 reconstructed with an in-plane compression and out-of-plane stretching. Thermal stimulated current measurement indicates that the electric polarization response presents in the special 2D cupric oxide single crystal thin film over a wide temperature range from 130 K to near-room temperature. We infer that the abnormal electric response involves the changing of phase transition temp…
Memristors based on a double barrier design have been analysed by various nano spectroscopic methods to unveil details about its microstructure and conduction mechanism. The device consists of an AlOx tunnel barrier and a NbOy/Au Schottky barrier sandwiched between Nb bottom electrode and Au top electrode. As it was anticipated that the local chemical composition of the tunnel barrier, i.e. oxidation state of the metals as well as concentration and distribution of oxygen ions, have a major influence on electronic conduction, these factors were carefully analysed. A combined approach was chosen…
The development prospects of memristive elements for non-volatile memory with use of the metal-dielectric-metal sandwich structures with a thin oxide layer are due to the possibility of reliable forming the sustained functional states with quantized resistance. In the paper we study the properties of fabricated memristors based on the non-stoichiometric $ZrO_2$ nanotubes in different resistive switching modes. Anodic oxidation of the $Zr$ foil has been used to synthesize a zirconia layer of $1.7$ $μ$$m$ thickness, consisting of an ordered array of vertically oriented nanotubes with outer diame…
We report on sexithiophene films, about 150nm thick, grown by thermal evaporation on single crystal oxides and, as comparison, on Si/SiO2. By heating the entire deposition chamber at 100 C we obtain standing-up oriented molecules all over the bulk thickness. Surface morphology shows step-like islands, each step being only one monolayer height. The constant and uniform warming of the molecules obtained by heating the entire deposition chamber allows a stable diffusion-limited growth process. Therefore, the regular growth kinetic is preserved when increasing the thickness of the film. Electrical…
Divalent tin oxides have attracted considerable attention as novel p-type oxide semiconductors, which are essential for realizing future oxide electronic devices. Recently, p-type Sn2Nb2O7 and SnNb2O6 were developed; however, enhanced hole mobility by reducing defect concentrations is required for practical use. In this work, we investigate the correlation between the formation of oxygen vacancy which may reduce the hole-generation efficiency and hole mobility, and the crystal structure in Sn-Nb complex oxides. Extended X-ray absorption fine structure spectroscopy and Rietveld analysis of x-ra…
ABO3 oxides with the perovskite-related structures are attracting significant interest due to their promising physical and chemical properties for many applications requiring tunable chemistry, including fuel cells, catalysis, and electrochemical water splitting. Here we report on the crystal structure of the entire family of perovskite oxides with ABO3 stoichiometry, where A and B are Ba, Sr, Mn, Ce. Given the vast size of this chemically complex material system, exploration for stable perovskite-related structures with respect to its constituent elements and annealing temperature is performe…
Simultaneous differential thermal analysis (DTA) and thermogravimetric (TG) measurements with copper oxide/aluminum oxide mixtures were performed in atmospheres with varying oxygen partial pressures and with crucibles made of different materials. Only sapphire and platinum crucibles proved to be stable under conditions that are useful for the growth of CuAlO$_2$ delafossite single crystals. Then the ternary phase diagram Al$_2$O$_3$-CuO-Cu and its isopleth section Cu$_2$O-Al$_2$O$_3$ were redetermined. Millimeter sized crystals could be obtained from copper oxide melts with 1-2 mol % addition …
The thermal conductivities of beta-Ga2O3 single crystals along four different crystal directions were measured in the temperature range of 80-495K using the time domain thermoreflectance (TDTR) method. A large anisotropy was found. At room temperature, the [010] direction has the highest thermal conductivity of 27.0+/-2.0 W/mK, while that along the [100] direction has the lowest value of 10.9+/-1.0 W/mK. At high temperatures, the thermal conductivity follows a ~1/T relationship characteristic of Umklapp phonon scattering, indicating phonon-dominated heat transport in the \b{eta}-Ga2O3 crystal.…
The epitaxial growth of multifunctional oxides on semiconductors has opened a pathway to introduce new functionalities to semiconductor device technologies. In particular, ferroelectric materials integrated on semiconductors could lead to low-power field-effect devices that can be used for logic and memory. Essential to realizing such field-effect devices is the development of ferroelectric metal-oxide-semiconductor (MOS) capacitors, in which the polarization of a ferroelectric gate is coupled to the surface potential of a semiconducting channel. Here we demonstrate that ferroelectric MOS capa…
The elasticity and piezoelectricity of zinc oxide (ZnO) crystals and single layers are investigated from the first-principles calculations. It is found that a ZnO thin film less than three Zn-O layers prefers a planar graphite-like structure to the wurtzite structure. ZnO single layers are much more flexible than graphite single layers in the elasticity and stronger than boron nitride single layers in the piezoelectricity. Single-walled ZnO nanotubes (SWZONTs) can exist in principle because of their negative binding energy. The piezoelectricity of SWZONTs depends on their chirality. For most Z…
We study the equilibrium arrangements of polarization vortices in (PbTiO$_3$)$_n$/(SrTiO$_3$)$_n$ superlattices by means of second-principles simulations. We find that, at low temperatures, polarization vortices organize in a regular arrangement in which clockwise and counter-clockwise vortices alternate positions, leading to a crystal-like structure with well defined handedness. This chiral crystal melts at a critical temperature $T_\mathrm{M}$ into a chiral liquid, where long-range order is lost but handedness is preserved. At even higher temperatures, $T_\mathrm{C}$, a second phase transiti…
Hydroflux Crystal Growth of Alkali Tellurate Oxide-Hydroxides
Department of Physics, Oregon State University（俄勒冈州立大学物理系）；Department of Chemistry, Johns Hopkins University（约翰斯·霍普金斯大学化学系）；Institute for Quantum Matter, William H. Miller III Department of Physics and Astronomy, Johns Hopkins University（约翰斯·霍普金斯大学量子物质研究所威廉·H·米勒三世物理与天文学系）；Department of Materials Science and Engineering, Johns Hopkins University（约翰斯·霍普金斯大学材料科学与工程系）
The excellent material properties of diamond make it highly desirable for many extreme electronic applications that are out of reach of conventional electronic materials. For commercial diamond devices to become a reality, it is necessary to have an effective surface passivation since the passivation determines the ability of the device to withstand high surface electric fields. In this paper we present data from lateral Time-of-Flight studies on SiO2-passivated intrinsic single-crystalline CVD diamond. The SiO2 films were deposited using three different techniques. The influence of the passiv…
Physics-Informed Neural Network Surrogate for Oxygen Vacancy Dynamics in epitaxial $\mathrm{SrTiO_3}$ on Si memristors via Dynamic Spectral Optimization
Computational searching and screening of new functional materials exploiting earth abundant elements can accelerate developments of their energy applications. Based on a state-of-the-art materials search algorithm and ab initio calculations, we demonstrate a recently suggested stable silicon oxide with a layered structure (Si$_{3}$O) as an ideal photovoltaic material. With many-body first-principles approaches, the monolayer and layered bulk of Si$_{3}$O show direct quasiparticle gaps of 1.85 eV and 1.25 eV, respectively, while an optical gap of about 1.2 eV is nearly independent of the number…
Polar magnetic oxide HoCrWO$_6$ is synthesized and its crystal structure, magnetic structure, and thermodynamic properties are investigated. HoCrWO$_6$ forms the polar crystal structure (space group Pna2$_1$ (#33)) due to the cation ordering of W$^{6+}$ and Cr$^{3+}$. There is an antiferromagnetic transition at TN = 24.5 K along with the magnetic entropy change (~5 J.Kg.$^{-1}$K$^{-1}$ at 70 kOe). Neutron diffraction measurement indicates that both Cr and Ho sublattices are ordered with the moment of 2.32(5)$μ_B$ and 8.7(4)$μ_B$ at 2 K, respectively. While Cr forms A-type collinear antiferroma…
Ferroelectric oxides have attracted much attention due to their wide range of applications, especially in electronic devices such as nonvolatile memories and tunnel junctions. As a result, the monolithic integration of these materials into silicon technology and its nanostructuration to develop alternative cost-effective processes are among the central points in current technology. In this work, we used a chemical route to obtain nanowire thin films of a novel Sr1+δMn8O16 (SMO) hollandite-type manganese oxide on silicon. Scanning transmission electron microscopy combined with crystallographic …
The electronic properties of single- and multi-cation transparent conducting oxides (TCOs) are investigated using first-principles density functional approach. A detailed comparison of the electronic band structure of stoichiometric and oxygen deficient In$_2$O$_3$, $α$- and $β$-Ga$_2$O$_3$, rock salt and wurtzite ZnO, and layered InGaZnO$_4$ reveals the role of the following factors which govern the transport and optical properties of these TCO materials: (i) the crystal symmetry of the oxides, including both the oxygen coordination and the long-range structural anisotropy; (ii) the electroni…
In the present work we use TiO2 nanotube arrays, carrying a Pt coating that is optimally dewetted, as a photocatalyst to generate H2. In order to achieve a maximum H2-generation efficiency, on the one hand an ideal thermal dewetting of the Pt layer into nanoparticles is needed that requires an oxygen free heat treatment, and on the other hand an optimal crystallization of the TiO2 nanotubes into anatase with reduced defect density is achieved only by annealing in O2 containing environment. To overcome this issue, we combine adequate reducing and oxidizing conditions in a multiple annealing tre…
Built-in electric fields across heterojunctions between semiconducting materials underpin the functionality of modern device technologies. Heterojunctions between semiconductors and epitaxially grown crystalline oxides provide a rich setting in which built-in fields can be explored. Here, we present an electrical transport and hard X-ray photoelectron spectroscopy study of epitaxial SrNbxTi1-xO3-δ / Si heterojunctions. A non-monotonic anomaly in the sheet resistance is observed near room temperature, which is accompanied by a crossover in sign of the Hall resistance. The crossover is consisten…
We report calculations indicating that amorphous RAO$_3$ oxides, with R and A trivalent cations, have approximately the same static dielectric constant as their perovskite crystal phase. The effect is due to the disorder-activated polar response of non-polar crystal modes at low frequency, which compensates a moderate but appreciable reduction of the ionic dynamical charges. The dielectric response was studied via density-functional perturbation theory. Amorphous samples were generated by molecular dynamics melt-and-quench simulations.
Continued progress in high speed computing depends on breakthroughs in both materials synthesis and device architectures. The performance of logic and memory can be enhanced significantly by introducing a memristor, a two terminal device with internal resistance that depends on the history of the external bias voltage. State of the art memristors, based on metal insulator metal (MIM) structures with insulating oxides, such as TiO2, are limited by a lack of control over the filament formation and external control of the switching voltage. Here, we report a class of memristors based on grain bou…
We have applied the bond valence method to cerium oxides to determine the oxidation states of the Ce ion at the various site symmetries of the crystals. The crystals studied include cerium dioxide and the two sesquioxides along with some selected intermediate phases which are crystallographically well characterized. Our results indicate that cerium dioxide has a mixed-valence ground state with an f-electron population on the Ce site of 0.27 while both the A- and C-sesquioxides have a nearly pure f^1 configuration. The Ce sites in most of the intermediate oxides have non-integral valences. Furt…
A sizable transverse thermoelectric coefficient N , large to the extent that it potentially serves applications, is predicted to arise, by means of first-principles calculations, in a Skyrmion crystal assumed on EuO monolayer where carrier electrons are introduced upon a quantum anomalous Hall insulating phase of Chern number C = 2. This encourages future experiments to pursue such an effect.
Simulation of 'hybrid' superconductors of 3d-, 4d- and 5d-transition elements consisting of two different superconducting fragments located between positively charged ions planes - B'O2 oxide planes and B2C2 intermetallic layers - has been performed on the basis of the structure of Sr2Mn3As2O2 (A2(B2C2)(B'O2)). The oxide planes are similar to those of CuO2 in high-temperature superconducting cuprates while the intermetallic layers - to those of Ni2B2 in low-temperature superconducting borocarbides RNi2B2C and Fe2As2 layers in high-temperature superconducting oxypnictides RFeAsO1-xFx.
Acoustic Phonon Characteristics of Gallium Oxide Single Crystals Investigated with Brillouin-Mandelstam Light Scattering Spectroscopy
University of California, Los Angeles（加州大学洛杉矶分校）；California NanoSystems Institute, University of California, Los Angeles（加州大学洛杉矶分校加利福尼亚纳米系统研究所）；Auburn University（奥本大学）；University of California, Riverside（加州大学河滨分校）；Arizona State University（亚利桑那州立大学）
