Memristive devices for computing.

Memristive devices are electrical resistance switches that can retain a state of internal resistance based on the history of applied voltage and current. These devices can store and process information, and offer several key performance characteristics that exceed conventional integrated circuit technology. An important class of memristive devices are two-terminal resistance switches based on ionic motion, which are built from a simple conductor/insulator/conductor thin-film stack. These devices were originally conceived in the late 1960s and recent progress has led to fast, low-energy, high-endurance devices that can be scaled down to less than 10 nm and stacked in three dimensions. However, the underlying device mechanisms remain unclear, which is a significant barrier to their widespread application. Here, we review recent progress in the development and understanding of memristive devices. We also examine the performance requirements for computing with memristive devices and detail how the outstanding challenges could be met.

A phylogeny of Cenozoic macroperforate planktonic foraminifera from fossil data.

We present a complete phylogeny of macroperforate planktonic foraminifer species of the Cenozoic Era (∼65 million years ago to present). The phylogeny is developed from a large body of palaeontological work that details the evolutionary relationships and stratigraphic (time) distributions of species-level taxa identified from morphology ('morphospecies'). Morphospecies are assigned to morphogroups and ecogroups depending on test morphology and inferred habitat, respectively. Because gradual evolution is well documented in this clade, we have identified many instances of morphospecies intergrading over time, allowing us to eliminate 'pseudospeciation' and 'pseudoextinction' from the record and thereby permit the construction of a more natural phylogeny based on inferred biological lineages. Each cladogenetic event is determined as either budding or bifurcating depending on the pattern of morphological change at the time of branching. This lineage phylogeny provides palaeontologically calibrated ages for each divergence that are entirely independent of molecular data. The tree provides a model system for macroevolutionary studies in the fossil record addressing questions of speciation, extinction, and rates and patterns of evolution.

'Memristive' switches enable 'stateful' logic operations via material implication.

The authors of the International Technology Roadmap for Semiconductors-the industry consensus set of goals established for advancing silicon integrated circuit technology-have challenged the computing research community to find new physical state variables (other than charge or voltage), new devices, and new architectures that offer memory and logic functions beyond those available with standard transistors. Recently, ultra-dense resistive memory arrays built from various two-terminal semiconductor or insulator thin film devices have been demonstrated. Among these, bipolar voltage-actuated switches have been identified as physical realizations of 'memristors' or memristive devices, combining the electrical properties of a memory element and a resistor. Such devices were first hypothesized by Chua in 1971 (ref. 15), and are characterized by one or more state variables that define the resistance of the switch depending upon its voltage history. Here we show that this family of nonlinear dynamical memory devices can also be used for logic operations: we demonstrate that they can execute material implication (IMP), which is a fundamental Boolean logic operation on two variables p and q such that pIMPq is equivalent to (NOTp)ORq. Incorporated within an appropriate circuit, memristive switches can thus perform 'stateful' logic operations for which the same devices serve simultaneously as gates (logic) and latches (memory) that use resistance instead of voltage or charge as the physical state variable.

Structural and chemical characterization of TiO2 memristive devices by spatially-resolved NEXAFS.

We used spatially-resolved NEXAFS (near-edge x-ray absorption fine structure) spectroscopy coupled with microscopy to characterize the electronic, structural and chemical properties of bipolar resistive switching devices. Metal/TiO2/metal devices were electroformed with both bias polarities and then physically opened to study the resulting material changes within the device. Soft x-ray absorption techniques allowed isolated study of the different materials present in the device with 100 nm spatial resolution. The resulting morphology and structural changes reveal a picture of localized polarity-independent heating occurring within these devices initiated by and subsequently accelerating polarity-dependent electrochemical reduction/oxidation processes.

Writing to and reading from a nano-scale crossbar memory based on memristors.

We present a design study for a nano-scale crossbar memory system that uses memristors with symmetrical but highly nonlinear current-voltage characteristics as memory elements. The memory is non-volatile since the memristors retain their state when un-powered. In order to address the nano-wires that make up this nano-scale crossbar, we use two coded demultiplexers implemented using mixed-scale crossbars (in which CMOS-wires cross nano-wires and in which the crosspoint junctions have one-time configurable memristors). This memory system does not utilize the kind of devices (diodes or transistors) that are normally used to isolate the memory cell being written to and read from in conventional memories. Instead, special techniques are introduced to perform the writing and the reading operation reliably by taking advantage of the nonlinearity of the type of memristors used. After discussing both writing and reading strategies for our memory system in general, we focus on a 64 x 64 memory array and present simulation results that show the feasibility of these writing and reading procedures. Besides simulating the case where all device parameters assume exactly their nominal value, we also simulate the much more realistic case where the device parameters stray around their nominal value: we observe a degradation in margins, but writing and reading is still feasible. These simulation results are based on a device model for memristors derived from measurements of fabricated devices in nano-scale crossbars using Pt and Ti nano-wires and using oxygen-depleted TiO(2) as the switching material.

The mechanism of electroforming of metal oxide memristive switches.

Metal and semiconductor oxides are ubiquitous electronic materials. Normally insulating, oxides can change behavior under high electric fields--through 'electroforming' or 'breakdown'--critically affecting CMOS (complementary metal-oxide-semiconductor) logic, DRAM (dynamic random access memory) and flash memory, and tunnel barrier oxides. An initial irreversible electroforming process has been invariably required for obtaining metal oxide resistance switches, which may open urgently needed new avenues for advanced computer memory and logic circuits including ultra-dense non-volatile random access memory (NVRAM) and adaptive neuromorphic logic circuits. This electrical switching arises from the coupled motion of electrons and ions within the oxide material, as one of the first recognized examples of a memristor (memory-resistor) device, the fourth fundamental passive circuit element originally predicted in 1971 by Chua. A lack of device repeatability has limited technological implementation of oxide switches, however. Here we explain the nature of the oxide electroforming as an electro-reduction and vacancy creation process caused by high electric fields and enhanced by electrical Joule heating with direct experimental evidence. Oxygen vacancies are created and drift towards the cathode, forming localized conducting channels in the oxide. Simultaneously, O(2-) ions drift towards the anode where they evolve O(2) gas, causing physical deformation of the junction. The problematic gas eruption and physical deformation are mitigated by shrinking to the nanoscale and controlling the electroforming voltage polarity. Better yet, electroforming problems can be largely eliminated by engineering the device structure to remove 'bulk' oxide effects in favor of interface-controlled electronic switching.

Study of SERS chemical enhancement factors using buffer layer assisted growth of metal nanoparticles on self-assembled monolayers.

Highly controlled morphology Au nanoparticle films can be formed on the surfaces of self-assembled monolayers (SAMs) by vapor deposition at cryogenic temperatures (approximately 10 K) with intervening condensed Xe layers on the SAMs serving as a buffer to reduce the kinetic energy of the Au atoms impinging on the surface (buffer layer assisted growth or BLAG). Under these conditions pristine Au nanoparticles (AuNp) of a uniform shape and size were deposited onto two SAMs differing only by their terminal groups, 4-benzenedithiol (BDT) and 4-methylbenzenethiol (MBT), to form -S/Au and -CH(3)/Au interfaces with essentially identical AuNp overlayer morphologies. A surface enhanced Raman (SERS) enhancement factor ratio EF(BDT)/EF(MBT) of approximately 130 was observed uniformly across the surfaces (approximately <10% variation). Since equal electromagnetic contributions to the SERS enhancements are expected from the two identically structured Au overlayer films, the observed SERS intensity ratio accordingly reflects a pure chemical enhancement (CE) contribution arising from the -S/Au relative to the -CH(3)/Au interface and thereby provides the first quantitative experimental data for the magnitude of the SERS CE for well-defined Au-molecule contacts.

A hybrid nanomemristor/transistor logic circuit capable of self-programming.

Memristor crossbars were fabricated at 40 nm half-pitch, using nanoimprint lithography on the same substrate with Si metal-oxide-semiconductor field effect transistor (MOS FET) arrays to form fully integrated hybrid memory resistor (memristor)/transistor circuits. The digitally configured memristor crossbars were used to perform logic functions, to serve as a routing fabric for interconnecting the FETs and as the target for storing information. As an illustrative demonstration, the compound Boolean logic operation (A AND B) OR (C AND D) was performed with kilohertz frequency inputs, using resistor-based logic in a memristor crossbar with FET inverter/amplifier outputs. By routing the output signal of a logic operation back onto a target memristor inside the array, the crossbar was conditionally configured by setting the state of a nonvolatile switch. Such conditional programming illuminates the way for a variety of self-programmed logic arrays, and for electronic synaptic computing.

Quantum conductance oscillations in metal/molecule/metal switches at room temperature.

We apply pressure-modulated conductance microscopy to metal/molecule/metal switches. Apart from pressure-induced conductance peaks that indicate nanoscale conducting pathways, we also observe dips and oscillations for devices with conductance between 1 and 2 conductance quantum. The conductance oscillations arise from interfering electron waves along one or two quantum conductance channels between two partially transmitting electrode surfaces at room temperature, underscoring these devices' potential as coherent, atomic-scale switches.

Memristive switching mechanism for metal/oxide/metal nanodevices.

Nanoscale metal/oxide/metal switches have the potential to transform the market for nonvolatile memory and could lead to novel forms of computing. However, progress has been delayed by difficulties in understanding and controlling the coupled electronic and ionic phenomena that dominate the behaviour of nanoscale oxide devices. An analytic theory of the 'memristor' (memory-resistor) was first developed from fundamental symmetry arguments in 1971, and we recently showed that memristor behaviour can naturally explain such coupled electron-ion dynamics. Here we provide experimental evidence to support this general model of memristive electrical switching in oxide systems. We have built micro- and nanoscale TiO2 junction devices with platinum electrodes that exhibit fast bipolar nonvolatile switching. We demonstrate that switching involves changes to the electronic barrier at the Pt/TiO2 interface due to the drift of positively charged oxygen vacancies under an applied electric field. Vacancy drift towards the interface creates conducting channels that shunt, or short-circuit, the electronic barrier to switch ON. The drift of vacancies away from the interface annilihilates such channels, recovering the electronic barrier to switch OFF. Using this model we have built TiO2 crosspoints with engineered oxygen vacancy profiles that predictively control the switching polarity and conductance.

Scanning tunneling microscopy of template-stripped Au surfaces and highly ordered self-assembled monolayers.

Template stripping of Au films in ultrahigh vacuum (UHV) produces atomically flat and pristine surfaces that serve as substrates for highly ordered self-assembled monolayer (SAM) formation. Atomic resolution scanning tunneling microscopy of template-stripped (TS) Au stripped in UHV confirms that the stripping process produces a flat, predominantly 111 textured, atomically clean surface. Octanethiol SAMs vapor deposited in situ onto UHV TS Au show a c(4 x 2) superlattice with (square root 3 x square root 3) R30 degrees basic molecular structure having an ordered domain size up to 100 nm wide. These UHV results validate the TS Au surface as a simple, clean and high-quality surface preparation method for SAMs deposited from both vapor phase and solution phase.

The missing memristor found.

Anyone who ever took an electronics laboratory class will be familiar with the fundamental passive circuit elements: the resistor, the capacitor and the inductor. However, in 1971 Leon Chua reasoned from symmetry arguments that there should be a fourth fundamental element, which he called a memristor (short for memory resistor). Although he showed that such an element has many interesting and valuable circuit properties, until now no one has presented either a useful physical model or an example of a memristor. Here we show, using a simple analytical example, that memristance arises naturally in nanoscale systems in which solid-state electronic and ionic transport are coupled under an external bias voltage. These results serve as the foundation for understanding a wide range of hysteretic current-voltage behaviour observed in many nanoscale electronic devices that involve the motion of charged atomic or molecular species, in particular certain titanium dioxide cross-point switches.

Oxide and carbide formation at titanium/organic monolayer interfaces.

X-ray photoelectron spectra (XPS) are reported from a series of buried titanium/organic monolayer interfaces accessed through sample delamination in ultrahigh vacuum (UHV). Conventional characterization of such buried interfaces requires ion-mill depth profiling, an energetic process that frequently destroys bonding information by chemically reducing the milled material. In contrast, we show that delaminating the samples at the metal/organic interface in vacuum yields sharp, nonreduced spectra that allow quantitative analysis of the buried interface chemistry. Using this UHV delamination XPS, we examine titanium vapor deposited onto a C18 cadmium stearate Langmuir-Blodgett monolayer supported on Au, SiO2, or PtO2 substrates. Titanium is widely used as an adhesion layer in organic thick film metallization as well as a top metal contact for molecular monolayer junctions, where it has been assumed to form a few-atoms-thick Ti carbide overlayer. We establish here that under many conditions the titanium instead forms a few-nanometers-thick Ti oxide overlayer. Both TiO2 and reduced TiOx species exist, with the relative proportion depending on oxygen availability. Oxygen is gettered during deposition from the ambient, from the organic film, and remarkably, from the substrate itself, producing substrate-dependent amounts of Ti oxide and Ti carbide "damage". On Au substrates, up to 20% of the molecular-monolayer carbon formed titanium carbide, SiO2 substrates approximately 15%, and PtO2 substrates <5%. Titanium oxide formation is also strongly dependent on the deposition rate and chamber pressure.

Metallic nanocrystals near ultrasmooth metallic films for surface-enhanced Raman scattering application.

We studied the effect of the substrate on the surface-enhanced Raman scattering (SERS) signals of metallic nanocrystal films by making a direct comparison between cases with metallic and semiconducting substrate surfaces. Ag nanoparticles smaller than 10 nm were synthesized and uniform arrays were formed on both ultrasmooth metallic and Si surfaces. These substrates provide reproducible SERS signals with high enhancement factors over large areas. Moreover, a SERS signal about one order of magnitude higher was obtained in the metallic surface case as compared with the Si substrate case, which is attributed to stronger plasmon coupling between the nanoparticles and their charge-conjugate images in the underlying metallic surface. The interpretation of our experimental results was confirmed by our finite difference time domain calculations. The dependence of the interaction between the nanoparticles and the substrate surface on the direction of the incident electromagnetic field is also discussed.

Tracing electronic pathways in molecules by using inelastic tunneling spectroscopy.

Using inelastic electron tunneling spectroscopy (IETS) to measure the vibronic structure of nonequilibrium molecular transport, aided by a quantitative interpretation scheme based on Green's function-density functional theory methods, we are able to characterize the actual pathways that the electrons traverse when moving through a molecule in a molecular transport junction. We show that the IETS observations directly index electron tunneling pathways along the given normal coordinates of the molecule. One can then interpret the maxima in the IETS spectrum in terms of the specific paths that the electrons follow as they traverse the molecular junction. Therefore, IETS measurements not only prove (by the appearance of molecular vibrational frequencies in the spectrum) that the tunneling charges, in fact, pass through the molecule, but also can be used to determine the transport pathways and how they change with the geometry and placement of molecules in junctions.

In-situ infrared spectroscopy of buried organic monolayers: influence of the substrate on titanium reactivity with a Langmuir-Blodgett film.

The reactivity of metals vapor deposited onto organic monolayers has historically been correlated to the metal/terminal organic group chemistry. Here we demonstrate that the chemical composition of the substrate unexpectedly plays a significant role as well. In particular, the reactivity of evaporated titanium toward a cadmium stearate Langmuir-Blodgett (LB) film was found to depend on the substrate upon which the LB film was deposited. Infrared spectra taken in a modified ATR (Kretschmann) geometry with a thin Au substrate showed large changes in peak shape, peak position, and peak width in the C-H stretching region, indicating titanium penetration into the LB film and decomposition of the original well-packed monolayer structure. LB monolayers formed on a platinum oxide (PtO(x)) surface showed remarkably small changes after Ti deposition, indicating only a slight increase in disorder and no significant metal penetration into the film. Films on SiO2 substrates showed reactivity between that of Au and PtO(x). These differences in reactivity can be correlated primarily with the amount of available oxygen associated with each substrate, including surface oxide layers and water incorporated within the LB film.

Molecular transport junctions: asymmetry in inelastic tunneling processes.

Inelastic electron tunneling spectroscopy (IETS) measurements are usually carried out in the low-voltage ("Ohmic", i.e., linear) regime where the elastic conduction/voltage characteristic is symmetric to voltage inversion. Inelastic features, normally observed in the second derivative d(2)I/dV(2) are also symmetric (in fact antisymmetric) in many cases, but asymmetry is sometimes observed. We show that such asymmetry can occur because of different energy dependences of the two contact self-energies. This may be attributed to differences in contact density of states (different contact material) or different energy dependence of the coupling (STM-like geometry or asymmetric positioning of molecular vibrational modes in the junction). The asymmetry scales with the difference between the energy dependence of these self-energies and disappears when this dependence is the same for the two contacts. Our nonequilibrium Green function approach goes beyond proposed WKB scattering theory in properly accounting for Pauli exclusion, as well as providing a path to generalizations, including consideration of phonon dynamics and higher-order perturbation theory.