There exist implementations of memristors with a hysteretic current-voltage curve or with both hysteretic current-voltage curve and hysteretic flux-charge curve. Memristors with hysteretic current-voltage curve use a resistance dependent on the history of the current and voltage and bode well for the future of memory technology due to their simple structure, high energy efficiency, and high integration.
Titanium dioxide memristor Interest in the memristor revived when an experimental solid-state version was reported by
R. Stanley Williams of
Hewlett Packard in 2007. The article was the first to demonstrate that a solid-state device could have the characteristics of a memristor based on the behavior of
nanoscale thin films. The device neither uses magnetic flux as the theoretical memristor suggested, nor stores charge as a capacitor does, but instead achieves a resistance dependent on the history of current. Although not cited in HP's initial reports on their
TiO2 memristor, the resistance switching characteristics of titanium dioxide were originally described in the 1960s. The HP device is composed of a thin (50
nm)
titanium dioxide film between two 5 nm thick
electrodes, one
titanium, the other
platinum. Initially, there are two layers to the titanium dioxide film, one of which has a slight depletion of
oxygen atoms. The oxygen vacancies act as
charge carriers, meaning that the depleted layer has a much lower resistance than the non-depleted layer. When an electric field is applied, the oxygen vacancies drift (see
Fast-ion conductor), changing the boundary between the high-resistance and low-resistance layers. Thus the resistance of the film as a whole is dependent on how much charge has been passed through it in a particular direction, which is reversible by changing the direction of current. Memristance is displayed only when both the doped layer and depleted layer contribute to resistance. When enough charge has passed through the memristor that the ions can no longer move, the device enters
hysteresis. It ceases to integrate
q=∫
I d
t, but rather keeps
q at an upper bound and
M fixed, thus acting as a constant resistor until current is reversed. Memory applications of thin-film oxides had been an area of active investigation for some time.
IBM published an article in 2000 regarding structures similar to that described by Williams. which bodes well for the future of the technology. At these densities it could easily rival the current sub-25 nm
flash memory technology.
Silicon dioxide memristor It seems that memristance has been reported in
nanoscale thin films of silicon dioxide as early as the 1960s . More recently, beginning in 2012, Tony Kenyon, Adnan Mehonic and their group clearly demonstrated that the resistive switching in silicon oxide thin films is due to the formation of oxygen vacancy filaments in defect-engineered silicon dioxide, having probed directly the movement of oxygen under electrical bias, and imaged the resultant conductive filaments using conductive atomic force microscopy.
Polymeric memristor In 2004, Krieger and Spitzer described dynamic doping of polymer and inorganic dielectric-like materials that improved the switching characteristics and retention required to create functioning nonvolatile memory cells. They used a passive layer between electrode and active thin films, which enhanced the extraction of ions from the electrode. It is possible to use
fast-ion conductor as this passive layer, which allows a significant reduction of the ionic extraction field. In July 2008, Erokhin and Fontana claimed to have developed a polymeric memristor before the more recently announced titanium dioxide memristor. In 2010, Alibart, Gamrat, Vuillaume et al. introduced a new hybrid organic/
nanoparticle device (the
NOMFET : Nanoparticle Organic Memory Field Effect Transistor), which behaves as a memristor and which exhibits the main behavior of a biological spiking synapse. This device, also called a synapstor (synapse transistor), was used to demonstrate a neuro-inspired circuit (associative memory showing a pavlovian learning). In 2012, Crupi, Pradhan and Tozer described a proof of concept design to create neural synaptic memory circuits using organic ion-based memristors. The synapse circuit demonstrated
long-term potentiation for learning as well as inactivity based forgetting. Using a grid of circuits, a pattern of light was stored and later recalled. This mimics the behavior of the V1 neurons in the
primary visual cortex that act as spatiotemporal filters that process visual signals such as edges and moving lines. In 2012, Erokhin and co-authors have demonstrated a stochastic three-dimensional matrix with capabilities for learning and adapting based on polymeric memristor.
Layered memristor In 2014, Bessonov et al. reported a flexible memristive device comprising a
MoOx/
MoS2 heterostructure sandwiched between silver electrodes on a plastic foil. The fabrication method is entirely based on printing and solution-processing technologies using two-dimensional layered
transition metal dichalcogenides (TMDs). The memristors are mechanically flexible,
optically transparent and produced at low cost. The memristive behaviour of switches was found to be accompanied by a prominent memcapacitive effect. High switching performance, demonstrated synaptic plasticity and sustainability to mechanical deformations promise to emulate the appealing characteristics of biological neural systems in novel computing technologies.
Atomristor Atomristor is defined as the electrical devices showing memristive behavior in atomically thin
nanomaterials or atomic sheets. In 2018, Ge and Wu et al. in the
Akinwande group at the University of Texas, first reported a universal memristive effect in single-layer
TMD (MX2, M = Mo, W; and X = S, Se) atomic sheets based on vertical
metal-insulator-metal (MIM) device structure. The work was later extended to monolayer
hexagonal boron nitride, which is the thinnest memory material of around 0.33 nm. These atomristors offer forming-free switching and both unipolar and bipolar operation. The switching behavior is found in single-crystalline and poly-crystalline films, with various conducting electrodes (gold, silver and graphene). Atomically thin TMD sheets are prepared via
CVD/
MOCVD, enabling low-cost fabrication. Afterwards, taking advantage of the low
on resistance and large on/off ratio, a high-performance zero-power
RF switch is proved based on MoS2 or h-BN atomristors, indicating a new application of memristors for
5G,
6G and THz communication and connectivity systems. In 2020, atomistic understanding of the conductive virtual point mechanism was elucidated in an article in nature nanotechnology.
Ferroelectric memristor The
ferroelectric memristor reported observing memristor effect in structure based on vertically aligned carbon nanotubes studying bundles of CNT by
scanning tunneling microscope. Later it was found that CNT memristive switching is observed when a nanotube has a non-uniform elastic strain Δ
L0. It was shown that the memristive switching mechanism of strained CNT is based on the formation and subsequent redistribution of non-uniform elastic strain and piezoelectric field
Edef in the nanotube under the influence of an external electric field
E(
x,
t).
Biomolecular memristor Biomaterials have been evaluated for use in artificial synapses and have shown potential for application in neuromorphic systems. In particular, the feasibility of using a collagen‐based biomemristor as an artificial synaptic device has been investigated, whereas a synaptic device based on lignin demonstrated rising or lowering current with consecutive voltage sweeps depending on the sign of the voltage furthermore a natural silk fibroin demonstrated memristive properties; spin-memristive systems based on biomolecules are also being studied. In 2012,
Sandro Carrara and co-authors have proposed the first biomolecular memristor with aims to realize highly sensitive biosensors. Since then, several memristive
sensors have been demonstrated.
Spin memristive systems Spintronic memristor Chen and Wang, researchers at disk-drive manufacturer
Seagate Technology described three examples of possible magnetic memristors. In one device resistance occurs when the spin of electrons in one section of the device points in a different direction from those in another section, creating a
domain wall, a boundary between the two sections. Electrons flowing into the device have a certain spin, which alters the device's magnetization state. Changing the magnetization, in turn, moves the domain wall and changes the resistance. The work's significance led to an interview by
IEEE Spectrum. A first experimental proof of the
spintronic memristor based on domain wall motion by spin currents in a magnetic tunnel junction was given in 2011.
Memristance in a magnetic tunnel junction The
magnetic tunnel junction has been proposed to act as a memristor through several potentially complementary mechanisms, both extrinsic (redox reactions, charge trapping/detrapping and electromigration within the barrier) and intrinsic (
spin-transfer torque).
Extrinsic mechanism Based on research performed between 1999 and 2003, Bowen et al. published experiments in 2006 on a
magnetic tunnel junction (MTJ) endowed with bi-stable spin-dependent states(
resistive switching). The MTJ consists in a SrTiO3 (STO) tunnel barrier that separates
half-metallic oxide LSMO and ferromagnetic metal CoCr electrodes. The MTJ's usual two device resistance states, characterized by a parallel or antiparallel alignment of electrode magnetization, are altered by applying an electric field. When the electric field is applied from the CoCr to the LSMO electrode, the
tunnel magnetoresistance (TMR) ratio is positive. When the direction of electric field is reversed, the TMR is negative. In both cases, large amplitudes of TMR on the order of 30% are found. Since a fully spin-polarized current flows from the
half-metallic LSMO electrode, within the
Julliere model, this sign change suggests a sign change in the effective spin polarization of the STO/CoCr interface. The origin to this multistate effect lies with the observed migration of Cr into the barrier and its state of oxidation. The sign change of TMR can originate from modifications to the STO/CoCr interface density of states, as well as from changes to the tunneling landscape at the STO/CoCr interface induced by CrOx redox reactions. Reports on MgO-based memristive switching within MgO-based MTJs appeared starting in 2008 While the drift of oxygen vacancies within the insulating MgO layer has been proposed to describe the observed memristive effects, on spintronics. This highlights the importance of understanding what role oxygen vacancies play in the memristive operation of devices that deploy complex oxides with an intrinsic property such as ferroelectricity or multiferroicity.
Intrinsic mechanism The magnetization state of a MTJ can be controlled by
Spin-transfer torque, and can thus, through this intrinsic physical mechanism, exhibit memristive behavior. This spin torque is induced by current flowing through the junction, and leads to an efficient means of achieving a
MRAM. However, the length of time the current flows through the junction determines the amount of current needed, i.e., charge is the key variable. The combination of intrinsic (spin-transfer torque) and extrinsic (resistive switching) mechanisms naturally leads to a second-order memristive system described by the state vector
x = (
x1,
x2), where
x1 describes the magnetic state of the electrodes and
x2 denotes the resistive state of the MgO barrier. In this case the change of
x1 is current-controlled (spin torque is due to a high current density) whereas the change of
x2 is voltage-controlled (the drift of oxygen vacancies is due to high electric fields). The presence of both effects in a memristive magnetic tunnel junction led to the idea of a nanoscopic synapse-neuron system.
Spin memristive system A fundamentally different mechanism for memristive behavior has been proposed by Pershin and
Di Ventra. The authors show that certain types of semiconductor spintronic structures belong to a broad class of memristive systems as defined by Chua and Kang. but was not described in terms of memristive behavior. On a short time scale, these structures behave almost as an ideal memristor. The SDC device is the first memristive device available commercially to researchers, students and electronics enthusiast worldwide. The SDC device is operational immediately after fabrication. In the Ge2Se3 active layer, Ge-Ge homopolar bonds are found and switching occurs. The three layers consisting of Ge2Se3/Ag/Ge2Se3, directly below the top tungsten electrode, mix together during deposition and jointly form the silver-source layer. A layer of SnSe is between these two layers ensuring that the silver-source layer is not in direct contact with the active layer. Since silver does not migrate into the active layer at high temperatures, and the active layer maintains a high glass transition temperature of about , the device has significantly higher processing and operating temperatures at and at least , respectively. These processing and operating temperatures are higher than most ion-conducting chalcogenide device types, including the S-based glasses (e.g. GeS) that need to be photodoped or thermally annealed. These factors allow the SDC device to operate over a wide range of temperatures, including long-term continuous operation at . == Implementation of hysteretic flux-charge memristors ==