Use of centrosymmetric Mott insulators in a resistive switched memory for storing data
09837607 · 2017-12-05
Assignee
Inventors
- Laurent Cario (Nantes, FR)
- Etienne Janod (La Chapelle sur Erdre, FR)
- Benoit Corraze (Carquefou, FR)
- Marie-Paule Besland (Orvault, FR)
- Vincent Guiot (Didcot, GB)
Cpc classification
H10N70/882
ELECTRICITY
G11C13/0007
PHYSICS
International classification
Abstract
A material belonging to the family of centrosymmetric Mott insulators is used as an active material in a resistively switched memory for storing data. The material is placed between two electrical electrodes, by virtue of which an electric field of a preset value is applied in order to form, by way of an electron avalanche effect, an elementary information cell that has at least two logic states.
Claims
1. A method comprising: placing a material configured in a centrosymmetric Mott-insulating regime and having an energy band gap at the Fermi level, said material between first and second electrical electrodes to form an active material of a resistive switching memory for storing data, the active material having an electronic avalanche effect such that application of an electrical field of a predetermined value to the first and second electrical electrodes forms, by the electronic avalanche effect in said material, an elementary information cell having at least two logic states; and switching the material between the at least two logic states comprising applying an electrical field to the first and second electrical electrodes using a power supply.
2. A resistive switching memory for storing data, comprising: first and second electrodes; a material configured in a centrosymmetric Mot-insulating regime and having an energy band gap at the Fermi level, said material being positioned between the first and second electrical electrodes to form an active material of a resistive switching memory, the active material having an electronic avalanche effect such that application of an electrical field of a predetermined value to the first and second electrodes forms, by the electronic avalanche effect in said material, an elementary information cell having at least two logic states; and a power supply configured to apply an electrical field to the first and second electrical electrodes to switch the material between the at least two logic states.
3. A method according to claim 1, said material belonging to a sub-family of inorganic compounds.
4. A method according to claim 1, comprising: choosing the chemical composition of the material so as to set an electrical field threshold value beyond which the material switches over from a first state of electrical resistance to one or more different states of electrical resistance to form the elementary information cell having at least two logic states.
5. A resistive switching memory according to claim 2, said material belonging to a sub-family of inorganic compounds.
6. A resistive switching memory according to claim 2, wherein said material is an organic compound in the form of a solid solution κ-(BEDT-TTF).sub.2Cu[N(CN).sub.2]Br.sub.xCl.sub.1-x (0≦x≦1).
7. A resistive switching memory according to claim 2, wherein the chemical composition of the material comprises an electrical field threshold value beyond which the material switches over from a first state of electrical resistance to one or more different states of electrical resistance to form the elementary information cell having at least two logic states.
8. A method according to claim 1, wherein the Fermi level is placed between an upper Hubbard band and a lower Hubbard band of the active material.
9. A resistive switch according to claim 2, wherein the Fermi level is placed between an upper Hubbard band and a lower Hubbard band of the active material.
10. A method according to claim 1, wherein the material comprises a compound meeting the formula NiS.sub.2-xSe.sub.x, with 0.00≦x≦0.59.
11. A method according to claim 1, wherein the material comprises a compound meeting the formula V.sub.2-xM.sub.xO.sub.3, with 0.02≦x≦0.50 and with M comprising at least one of the following elements or a combination of these elements: Ti, Cr, Fe, Al or Ga.
12. A resistive switch according to claim 2, wherein the material comprises a compound meeting the formula NiS.sub.2-xSe, with 0.00≦x≦0.59.
13. A resistive switch according to claim 2, wherein the material comprises a compound meeting the formula V.sub.2-xM.sub.xO.sub.3, with 0.02≦x≦0.50 and with M comprising at least one of the following elements or a combination of these elements: Ti, Cr, Fe, Al or Ga.
14. A method comprising: placing a material configured in a centrosymmetric Mott-insulating regime and having an energy band gap at the Fermi level, said material between first and second electrical electrodes to form an active material of a resistive switching memory for storing data, the active material having an electronic avalanche effect such that application of an electrical field of a predetermined value to the first and second electrical electrodes forms, by the electronic avalanche effect in said material, an elementary information cell having at least two logic states; wherein said material comprises one of: a compound meeting the formula NiS.sub.2-xSe.sub.x, with 0.00≦x≦0.59; and a compound meeting the formula V.sub.2-xM.sub.xO.sub.3, with 0.02≦x≦0.50 and with M comprising at least one of the following elements or a combination of these elements: Ti, Cr, Fe, Al or Ga.
15. A method according to claim 14, comprising choosing the chemical composition of the material so as to set an electrical field threshold value beyond which the material switches over from a first state of electrical resistance to one or more different states of electrical resistance to form the elementary information cell having at least two logic states.
16. A method according to claim 14, wherein the Fermi level is placed between an upper Hubbard band and a lower Hubbard band of the active material.
17. A resistive switching memory for storing data, comprising: first and second electrodes; a material configured in a centrosymmetric Mott-insulating regime and having an energy band gap at the Fermi level, said material being positioned between the first and second electrical electrodes to form an active material of a resistive switching memory, the active material having an electronic avalanche effect such that application of an electrical field of a predetermined value to the first and second electrodes forms, by the electronic avalanche effect in said material, an elementary information cell having at least two logic states; wherein said material comprises one of: a compound meeting the formula NiS.sub.2-xSe.sub.x, with 0.00≦x≦0.59; and a compound meeting the formula V.sub.2-xM.sub.xO.sub.3, with 0.02≦x≦0.50 and with M comprising at least one of the following elements or a combination of these elements: Ti, Cr, Fe, Al or Ga.
18. A resistive switching memory according to claim 17, said material belonging to a sub-family of inorganic compounds.
19. A resistive switching memory according to claim 17, wherein the chemical composition of the material comprises an electrical field threshold value beyond which the material switches over from a first state of electrical resistance to one or more different states of electrical resistance to form the elementary information cell having at least two logic states.
20. A resistive switch according to claim 17, wherein the Fermi level is placed between an upper Hubbard band and a lower Hubbard band of the active material.
Description
5. LIST OF FIGURES
(1) Other features and advantages of the invention shall appear more clearly from the following description, given by way of an indicative and non-exhaustive example and from the appended drawings, of which:
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6. DETAILED DESCRIPTION
(17) In all the figures of the present document, identical elements and steps are designated by a same numerical reference.
(18) As discussed here above, the principle of the invention lies in the astute use of a material belonging to the family of centrosymmetric Mott insulators as an active material in a memory for storing data. The inventors have indeed brought to light the existence, in this family of materials, of a phenomenon of reversible resistive switching induced by electrical pulses. In particular, the inventors have surprisingly discovered that this phenomenon is closely linked to the particular electronic properties of these materials. Indeed, when an electrical field of a predetermined value is applied to one of these materials, the electronic structure of said material is thereby modified: research conducted in recent years shows that resistive switching is initiated by a phenomenon of electronic origin comparable to the electron avalanche phenomenon known in semi-conductors but hitherto unknown in this family of materials. This result is remarkable since it enables a novel use of the family of centrosymmetric Mott insulators as active materials in data storage memories of the RRAM or MEMRISTOR type for example.
(19) Mott insulators constitute a class of materials, the electronic structure of which results from the presence of strong Coulomb repulsion between electrons. The electronic structure of the solids is generally described in the context of band theory which disregards these Coulomb repulsions between electrons situated on the same site (atoms, atom aggregates or molecules). This theory is appropriate for metals and semi-conductors (or band insulators) but does not accurately describe the case of Mott insulators. According to this theory, the creation of crystalline orbitals in a solid forms a succession of energy bands accessible to the electrons.
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(21) As a rule, as illustrated in
(22) This concept of a Mott insulator with only one electron situated on a band can be extended to the case of multiband Mott insulators possessing an integer number of electrons situated on several bands.
(23) More particularly, the family of Mott insulators (with one or more bands) is constituted by two sub-classes, on the one hand Mott-Hubbard insulators (
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(25) The various research studies highlighting the properties of these materials are described in detail here below. By way of an illustrative example, these are works of research done for compounds meeting the formulae NiS.sub.2-xSe.sub.x and V.sub.2-xCr.sub.xO.sub.3. Of course, the invention is not limited to these compounds alone but can be applied to any compound belonging to the family of centrosymmetric type Mott insulators, i.e. insulators having a crystallographic structure that possesses an inversion center. By way of examples, the invention can also be applied to the following compounds: the solid solution κ-(BEDT-TTF).sub.2Cu[N(CN).sub.2]Br.sub.xCl.sub.1-x, the RNiO.sub.3 series where R is a mixture of rare earths, the solid solution V.sub.2-xAl.sub.xO.sub.3.
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(27) The associated experimental electrical assembly diagram is illustrated in
(28) The logic component consists of a Metal-Mott insulator-Metal structure constituted by a piece of crystal 1 and two contact points situated on either side of the piece of crystal 1.
(29) In one alternative application of the invention, it is possible to obtain a Metal-Mott insulator-Metal type structure, for example of the Au/NiS.sub.1.89Se.sub.0.11/Au type, using a method of thin-layer deposition on a substrate, for example a silicon substrate.
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(31) The curves show that the logic component incorporating the compound NiS.sub.2 forms an elementary logic information cell containing at least three resistance states. Several resistive switching cycles were reproduced over time at 100 K and at 300 K without any fatigue effect of the material.
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(34) The tests were made on a Metal-Mott insulator-Metal type structure incorporating the compounds NiS.sub.2, NiS.sub.1.89Se.sub.0.11, NiS.sub.1.79Se.sub.0.21, NiS.sub.1.70Se.sub.0.30, NiS.sub.1.63Se.sub.0.37 series-mounted with the following resistors: R.sub.load (NiS.sub.2)=500Ω, R.sub.load (NiS.sub.1.89Se.sub.0.11)=500Ω, R.sub.load (NiS.sub.1.79Se.sub.0.21)=500Ω, R.sub.load (NiS.sub.1.70Se.sub.0.30)=500Ω, R.sub.load (NiS.sub.1.63Se.sub.0.37)=1.2 kΩ. It is observed on these curves that, for each compound, the state after switching is defined by a voltage threshold value. More specifically, it is seen that the electrical field threshold value (E.sub.thres), is value (E is equal to about 7 kV/cm for the compound NiS.sub.2, 5 kV/cm for the compound NiS.sub.1.89Se.sub.0.11, 4 kV/cm for the compound NiS.sub.1.70Se.sub.0.21, 3 kV/cm for the compound NiS.sub.1.70Se.sub.0.30, 1.7 kV/cm for the compound NiS.sub.1.63Se.sub.0.37. In other words, the resistive switching induced by the electrical pulse is linked to an electrical field effect with the appearance of an electrical field threshold value beyond which the material switches over from a first state of electrical resistance to a lower state of electrical resistance to form an elementary logic information cell.
(35) The inventors have discovered that the threshold value of the electrical field varies according to a relationship of power with the band-gap energy of the Mott compounds as shown by the study of the NiS.sub.2-xSe.sub.x series of compounds. The characteristic shape of the curve I(V), the threshold value of the electrical field (of the order of some kV/cm) and the progress of this threshold value as a function of the band-gap energy of the NiS.sub.2-xSe.sub.x compounds show that the volatile resistive switching of these compounds is related to a dielectric breakdown by electron avalanche effect. This avalanche effect or creation of electron-hole pairs through impact ionization leading to a multiplication of the carriers, well known in classic semi-conductors, was hitherto unknown for Mott insulators. Indeed, as can be seen in the graph of
(36) It must be noted that the volatile and non-volatile character of the resistive transition depends essentially on the amplitude of the electrical field applied to the active material.
(37) It must also be noted that the inventors have discovered that the switching time decreases when the thickness of the active material decreases.
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(39) In one alternative application of the invention, a Metal-Mott insulator-Metal type structure obtained by means of a method of thin-layer deposition advantageously, through the reduction of thickness of the active material, greatly lowers the switching voltage (for example to less than 2 V) and greatly reduces the duration of the pulses needed for the switching (for example to less than 100 ns).
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(42) These curves also show that, for each compound, a volatile resistive transition appears for a given electrical threshold value (E.sub.thres): about 2.2 kV/cm for the compound V.sub.˜1.85Cr.sub.˜0.15O.sub.3, and about 3.8 kV/cm for the compound V.sub.˜1.94Cr.sub.˜0.06O.sub.3 for a distance between electrodes of about 60 to 80 μm.
(43) These electrical field threshold values have been entered in the graph illustrating the progress of the threshold electrical field as a function of the band-gap energy (see
(44) This discovery therefore establishes the fact that this electron avalanche property as well as its consequences are general to all centrosymmetric Mott insulators. The effect of the electrical field on these materials induces a dielectric breakdown by electron avalanche effect. This has the consequence of locally destroying the Mott insulating state and restoring a metallic state, causing the appearance of a resistive transition.
(45) An exemplary embodiment of the invention proposes a material that can be used as an active material of a resistive switching memory for storing data that presents real prospects of industrial-scale exploitation.
(46) An exemplary embodiment of the invention proposes a material that enables switching between at least two states of electrical resistance by application of electrical fields of relatively low amplitude.
(47) An exemplary embodiment of the invention proposes a material that can be used to obtain switching times between at least two states of electrical resistance that are shorter than the switching times for the prior art memories described further above.
(48) An exemplary embodiment of the invention proposes a material of this kind that increases the quantity of data stored per unit of volume.
(49) Although the present disclosure has been described with reference to one or more examples, workers skilled in the art will recognize that changes may be made in form and detail without departing from the scope of the disclosure and/or the appended claims.