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WO2011071009A1 - Élément à résistance variable utilisant une réaction électrochimique et son procédé de fabrication - Google Patents

Élément à résistance variable utilisant une réaction électrochimique et son procédé de fabrication Download PDF

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WO2011071009A1
WO2011071009A1 PCT/JP2010/071811 JP2010071811W WO2011071009A1 WO 2011071009 A1 WO2011071009 A1 WO 2011071009A1 JP 2010071811 W JP2010071811 W JP 2010071811W WO 2011071009 A1 WO2011071009 A1 WO 2011071009A1
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electrode
conductive layer
ion conductive
metal
ion
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Japanese (ja)
Inventor
幸秀 辻
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NEC Corp
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NEC Corp
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Priority to JP2011545199A priority Critical patent/JP5621784B2/ja
Priority to US13/514,385 priority patent/US8878153B2/en
Publication of WO2011071009A1 publication Critical patent/WO2011071009A1/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/021—Formation of switching materials, e.g. deposition of layers
    • H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B63/00—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/041—Modification of switching materials after formation, e.g. doping
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H10N70/24—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies
    • H10N70/245—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies the species being metal cations, e.g. programmable metallization cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/821—Device geometry
    • H10N70/826—Device geometry adapted for essentially vertical current flow, e.g. sandwich or pillar type devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/841—Electrodes
    • H10N70/8416—Electrodes adapted for supplying ionic species
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/883—Oxides or nitrides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/883—Oxides or nitrides
    • H10N70/8833—Binary metal oxides, e.g. TaOx

Definitions

  • the present invention relates to a variable resistance element used for programmable logic and memory and a method for manufacturing the variable resistance element, and more particularly to a variable resistance element using an electrochemical reaction and a method for manufacturing the variable resistance element.
  • Non-patent Document 1 Metal ion migration and electrochemistry in ionic conductors (solids in which ions can move freely inside) as nonvolatile switching elements for programmable logic that can change the circuit configuration of memory devices or semiconductor devices
  • a resistance change element using reaction is disclosed (Non-patent Document 1).
  • Such a resistance change element has a first electrode 11 capable of supplying metal ions, an ion conductive layer 20 capable of conducting metal ions, and less ionized than the first electrode 11 as schematically shown in FIG.
  • a three-layer structure with the second electrode 12 is formed.
  • the resistance change element described in Patent Document 1 copper ions are used as metal ions, the first electrode 11 serving as the supply source is copper, a metal oxide layer such as tantalum oxide as the ion conductive layer 20, and further ionization. Platinum is used as the difficult second electrode 12.
  • a variable resistance element using such an electrochemical reaction is characterized by a small size and a large resistance ratio between on and off.
  • FIG. 2 shows an operation schematic diagram (a) and a voltage-current graph (b) of the variable resistance element.
  • the variable resistance element is in an off state with high resistance immediately after fabrication.
  • the first electrode 11 is grounded and a negative voltage is applied to the second electrode 12 as shown in FIGS. 2 (a) and 2 (b).
  • Metal ions 13 are generated from the metal of one electrode 11 by an electrochemical reaction and dissolved in the ion conductive layer 20. Then, metal ions 13 in the ion conductive layer 20 are deposited as metal on the surface of the second electrode 12. As shown in FIG.
  • the deposited metal forms a metal bridge between the first electrode 11 and the second electrode 12 to electrically connect the first electrode 11 and the second electrode 12 (ON state). ).
  • the first electrode 11 is grounded and a positive voltage is applied to the second electrode 12 as shown in FIG. Thereby, as shown to (d) of FIG. 2, a part of metal bridge
  • two ion conductive layers 21 having different ion conductivities (or ion diffusion coefficients) between the first electrode 11 and the second electrode 12, 22 is arranged on the first electrode 11 side by disposing the ion conduction layer 21 having a large diffusion coefficient of metal ions on the first electrode 11 side, so that the metal bridge 14 is cut at a position close to the first electrode 11 side, so There is a method to improve (Non-Patent Document 2).
  • Non-Patent Document 2 there remains an uncertainty that the position at which the crosslink breaks is unknown in the ion conductive layer 21 (film thickness T) in contact with the first electrode 11. This is because the position where the diffusion coefficient D is maximized is spatially widened.
  • the present invention relates to a variable resistance element using an electrochemical reaction, wherein the position at which the metal bridge is cut is limited to the closest part to the first electrode in the ion conductive layer, which is most desirable as the cut position. And a manufacturing method thereof.
  • the variable resistance element includes a first electrode serving as a supply source of metal ions, a second electrode that is less likely to be ionized (that is, having a higher oxidation-reduction potential) than the first electrode, An resistance change element including an ion conductive layer interposed between the first electrode and the second electrode and capable of conducting the metal ions, wherein the variable resistance element diffuses into the ion conductive layer until it contacts the first electrode.
  • a first region whose coefficient increases continuously toward the first electrode is disposed adjacent to the first electrode.
  • a method of manufacturing a resistance change element includes a first electrode serving as a metal ion supply source, and a second electrode that is less likely to be ionized (that is, has a higher redox potential) than the first electrode.
  • a variable resistance element manufacturing method comprising: an electrode; and an ion conductive layer interposed between the first electrode and the second electrode and capable of conducting the metal ions, wherein the metal oxide or the metal oxynitride And a plasma treatment process for the ion conductive layer for changing the oxygen concentration or nitrogen concentration of the ion conductive layer along the direction perpendicular to the layer, that is, the direction between the electrodes.
  • the method of manufacturing a resistance change element includes a first electrode serving as a metal ion supply source, a second electrode that is less ionizable than the first electrode, the first electrode, And a metal oxide or metal oxynitride comprising a metal oxide or metal oxynitride that is interposed between the second electrodes and is capable of conducting the metal ions.
  • Co-sputtering so as to change the component supply ratio from the target of the product and the target of the silicon compound to form an ion conductive layer in which the silicon-containing concentration is changed along the layer vertical direction, that is, the direction between the electrodes; It is characterized by including.
  • variable resistance element manufacturing method includes a first electrode serving as a metal ion supply source, a second electrode that is less ionizable than the first electrode, the first electrode, An oxygen concentration in an apparatus for sputtering a metal oxide target, comprising: an ion conducting layer comprising a metal oxide that is interposed between second electrodes and capable of conducting the metal ions; And forming an ion conductive layer in which the oxygen-containing concentration of the metal oxide of the ion conductive layer is changed along the direction perpendicular to the layer, that is, the direction between the electrodes.
  • variable resistance element manufacturing method includes a first electrode serving as a supply source of metal ions, a second electrode that is less likely to be ionized than the first electrode, the first electrode, An ion conductive layer made of a metal oxynitride that is interposed between second electrodes and is capable of conducting the metal ions, and a method of manufacturing a resistance change element, wherein the metal oxynitride target is sputtered Sputtering while changing the oxygen / nitrogen concentration ratio of the metal to form an ion conductive layer in which the oxygen / nitrogen content concentration ratio of the metal oxynitride of the ion conductive layer is changed along the direction perpendicular to the layer, that is, between the electrodes. And a step of performing.
  • variable resistance element operating method is such that the temperature dependence of the diffusion coefficient inside the ion conductive layer on the side in contact with the first electrode is the temperature of the diffusion coefficient on the side in contact with the second electrode.
  • the gradient of the diffusion coefficient inside the ion conductive layer on the side in contact with the first electrode is an operation of transitioning from the high resistance state to the low resistance state. It is characterized by being performed in a temperature range larger than the gradient of the diffusion coefficient on the side in contact with the two electrodes.
  • the present invention it is possible to achieve a resistance change element that limits the position at which the crosslink breaks to the closest portion to the first electrode in the ion conductive layer, which is most desirable as the breakable position.
  • the maximum point of the diffusion coefficient in the ion conductive layer is uniquely determined in the film thickness direction in the ion conductive layer, and the position coincides with the place where the ion conductive layer and the first electrode are in contact (FIG. 6). .
  • the position at which the bridging metal is cut when transitioning from the on-state to the off-state is limited to the closest portion to the first electrode in the ion conductive layer, which is most desirable as the position to be cut off. It is possible to suppress variations in the off state and a decrease in insulation resistance rather than the structure.
  • FIG. 4 is an operation schematic diagram (a) and a voltage-current graph (b) of the variable resistance element. It is a schematic diagram which shows the subject of the resistance change element of a prior art. It is another schematic diagram which shows the subject of the resistance change element of a prior art. It is a schematic diagram which shows the subject of the resistance change element of a prior art. It is a schematic diagram of the structure of the resistance change element which concerns on one Embodiment of this invention. It is a graph which shows the relationship between an impurity concentration and a diffusion coefficient. It is a graph which shows the relationship between oxygen concentration and a diffusion coefficient. It is a graph which shows the relationship between a forming voltage and a set voltage. It is a graph which shows the relationship between oxygen-nitrogen concentration ratio and a diffusion coefficient. It is a graph which shows the temperature dependence of a diffusion coefficient.
  • the ion conductive layer further includes a second region having a constant diffusion coefficient, and the second region is formed between the first region and the second electrode. It is preferable that the diffusion coefficient of the area 2 is equal to or less than the minimum diffusion coefficient in the first area. That is, at the junction between the first region and the second region, the diffusion coefficient changes continuously, or in a discrete case, increases from the second region to the first region in steps.
  • the ion conductive layer is a compound containing two or more elements, and the diffusion coefficient is given a gradient by changing the composition ratio of the two or more elements along the layer vertical direction, that is, the direction between the electrodes.
  • the first region is formed.
  • the compound containing two or more elements is preferably a compound of a metal and nitrogen and / or a chalcogen element which is a group 16 element of the periodic table.
  • the ion conductive layer is preferably a metal oxide or a metal oxynitride.
  • the ion conductive layer is preferably tantalum oxide or tantalum oxynitride.
  • the first region having a gradient in the diffusion coefficient is formed by containing impurities in the ion conductive layer and changing the amount of the impurities along the layer vertical direction, that is, the direction between the electrodes. Is preferred.
  • the ion conductive layer is preferably tantalum oxide or tantalum oxynitride containing silicon as the impurity.
  • the temperature dependence of the diffusion coefficient inside the ion conductive layer on the side in contact with the first electrode is larger than the temperature dependence of the diffusion coefficient on the side in contact with the second electrode.
  • the step of forming the ion conductive layer is a step of forming the ion conductive layer in contact with the first electrode.
  • the metal oxide or metal oxynitride is preferably tantalum oxide or tantalum oxynitride.
  • variable resistance element Accordingly, an embodiment of a variable resistance element according to the present invention will be described.
  • FIG. 6 is a schematic cross-sectional view of a variable resistance element according to an embodiment of the present invention, and illustrates a change in diffusion coefficient (D) in the film thickness direction (that is, the direction connecting two electrodes) X of the ion conductive layer. It is.
  • the resistance change element includes a first electrode 11 serving as a supply source of metal ions, a second electrode 12 that is less ionized than the first electrode 11, and the first electrode 11 and the second electrode 12.
  • An ion conductive layer 23 that is interposed therebetween and can conduct metal ions is provided.
  • the diffusion coefficient of the first region R adjacent to the first electrode 11 continuously increases toward the first electrode 11 as it approaches the first electrode 11.
  • the position where the diffusion coefficient D is maximized is only determined at the closest point to the first electrode 11.
  • the diffusion coefficient only needs to change in the film thickness direction at a certain temperature, and the temperature at which the difference in diffusion coefficient appears may be a high temperature or a low temperature other than the actual use temperature ( ⁇ 40 ° C. to 85 ° C.).
  • the region R in which the diffusion coefficient changes is a part of the ion conductive layer 23 in FIG. 6, but it goes without saying that the entire ion conductive layer 23 may be a region in which the diffusion coefficient changes.
  • the first electrode 11 is preferably made of a metal or alloy whose main material is at least one of Cu, Ag and Pb in order to supply ions to the ion conductive layer 23.
  • the main material is desirably Cu.
  • these metals or alloys may be present on at least part of the surface of the first electrode 11 that is in contact with the ion conductive layer 23. Therefore, in addition to the method of configuring the entire first electrode 11 as a single layer film, it is possible to configure the layer in contact with the ion conductive layer 23 as a laminated structure with Cu or the like. Moreover, you may comprise so that a contact surface with the ion conductive layer 23 may become a composite surface of the metal which can supply ions, such as Cu, and the metal which other ion supply does not produce.
  • the second electrode 12 is made of a conductor that hardly receives metal ions from the ion conductive layer 23.
  • a refractory metal such as platinum, aluminum, gold, titanium, tungsten, vanadium, niobium, tantalum, chromium, or molybdenum, a nitride of at least one of these metals, or at least of these metals Any silicide or an alloy in which a plurality of these metals are combined is preferable.
  • the second electrode 12 it is only necessary that at least the surface of the second electrode 12 in contact with the ion conductive layer 23 is made of the above material. Therefore, in addition to the method of configuring the entire second electrode 12 as a single layer film, it is possible to configure a layer in contact with the ion conductive layer 23 as a laminated structure with the above material.
  • the material of the ion conductive layer 23 is preferably a compound of a metal and a chalcogen element containing nitrogen, oxygen, sulfur, selenium, tellurium, or the like.
  • a metal and a chalcogen element containing nitrogen, oxygen, sulfur, selenium, tellurium, or the like.
  • sulfides and oxides containing at least one of copper, tungsten, tantalum, molybdenum, chromium, titanium and cobalt metals in the periodic table of elements and oxysulfides having an arbitrary sulfur-oxygen ratio, etc. Is preferred.
  • metal oxynitrides having an arbitrary oxygen-nitrogen ratio are also preferable.
  • a metal added with impurities such as silicon may be used.
  • a metal oxide particularly tantalum oxide (Ta 2 O 5 ) or titanium oxide (TiO 2 ) is preferable.
  • Ta 2 O 5 tantalum oxide
  • TiO 2 titanium oxide
  • an element (impurity) different from the element constituting the ion conductive layer 23 serving as a base may be added.
  • Si is used as an additive impurity of tantalum oxide (Ta 2 O 5 )
  • the diffusion coefficient can be increased by reducing the Si concentration in the ion conductive layer 23 closer to the first electrode 11.
  • the ion conductive layer is a compound composed of two or more elements, the diffusion coefficient can be changed by changing the composition ratio of the elements.
  • the oxygen concentration (composition ratio of metal and oxygen) can be changed in the film direction.
  • the ion conductive layer is a metal oxynitride
  • the composition ratio of oxygen and nitrogen may be changed in the film direction.
  • the film thickness of the ion conductive layer can be set within a range of about 5 to 200 nm, but is particularly preferably within a range of 10 to 100 nm. If the film thickness is 10 nm or less, a leakage current is likely to occur at the time of OFF due to a tunnel current or a Schottky current. On the other hand, if the film thickness is 100 nm or more, the switching voltage becomes 10 V or more and the semiconductor device This is because it is difficult to put it to practical use.
  • the region where the diffusion coefficient is changed may not be the entire ion conduction layer, and the diffusion coefficient may be constant in a part of the ion conduction layer 23 in contact with the second electrode 12 as shown in FIG.
  • An ion conductive layer having a different composition ratio of constituent elements in the film thickness direction or an ion conductive layer having a different impurity addition amount may be formed at the time of forming the ion conductive layer or a uniform ion conductive layer. You may perform by the processing after doing.
  • a source source for each element is separately installed in the film forming apparatus, and the supply amount to each deposition surface is adjusted to the deposition. Adjust it.
  • the film formation method is not particularly limited, and MBE (Molecular Beam Epitaxy), CVD (Chemical Vapor Deposition), co-sputtering, reactive sputtering, or the like may be used.
  • the operating temperature of the resistance change element is not particularly limited, but when the temperature acceleration coefficient of the diffusion coefficient differs in the film thickness direction, it is desirable to rewrite the temperature at a temperature at which the gradient of the diffusion coefficient increases in the film thickness direction.
  • the maximum point of the diffusion coefficient in the ion conductive layer 23 is uniquely determined in the film thickness direction in the ion conductive layer, and the position thereof is a place where the ion conductive layer 23 and the first electrode 11 are in contact with each other. Match (FIG. 6). For this reason, the position at which the bridging metal is cut when transitioning from the on-state to the off-state is limited to the closest portion to the first electrode 11 in the ion conductive layer 23, which is most desirable as the position to be cut, as shown in FIG. It is possible to suppress variations in the off state and a decrease in insulation resistance as compared with the conventional structure.
  • Example 1 of the resistance change element according to the present invention includes a first electrode 11 serving as a metal ion supply source, a second electrode 12 that is less likely to be ionized than the first electrode 11, It consists of an ion conductive layer 23 that is interposed between the electrode 11 and the second electrode 12 and can conduct metal ions, and the diffusion coefficient in the region of the ion conductive layer 23 is changed.
  • the material of the first electrode 11 is copper
  • the material of the second electrode 12 is platinum
  • the material of the ion conductive layer 23 is tantalum oxide (Ta 2 O 5 ).
  • FIG. 7 shows the relationship between the Si / Ta ratio and the electric field strength for transition from the off state to the on state.
  • the diffusion coefficient in the ion conductive layer 23 is increased by decreasing the amount of silicon added in the tantalum oxide that is the ion conductive layer 23 from the second electrode side toward the first electrode side.
  • a co-sputtering method was used to form tantalum oxide to which silicon was added.
  • Two sputtering targets of silicon oxide (SiO 2 ) and tantalum oxide (Ta 2 O 5 ) are installed in the chamber, and the supply rate from the two sputtering sources to the deposition layer is input to each sputtering source, and the inside of the chamber.
  • the amount of silicon contained in tantalum oxide can be adjusted by adjusting the gas pressure, the distance from the target, or the opening time of the selective shutter.
  • the maximum point of the diffusion coefficient of copper in tantalum oxide, the amount of silicon addition being reduced from the second electrode side toward the first electrode, is the contact between the tantalum oxide (ion conductive layer 23) and the copper electrode as the first electrode 11. It coincides with the place (FIG. 6). For this reason, the position at which the bridging metal is cut when transitioning from the on state to the off state is limited to the closest portion to the copper electrode 11 in tantalum oxide, which is the ion conductive layer 23, which is most desirable as the position to be cut. It is possible to suppress the variation in the OFF state and the decrease in the insulation resistance as compared with the simple two-layer structure as shown in FIG.
  • Example 2 Next, Example 2 will be described.
  • the first electrode 11 serving as a metal ion supply source
  • the second electrode 12 that is less likely to be ionized than the first electrode 11, and the first electrode 11 and the second electrode 12. It consists of an ion conductive layer 23 that is interposed between and can conduct metal ions.
  • the material of the first electrode 11 was copper
  • the material of the second electrode 12 was platinum
  • the material of the ion conductive layer 23 was tantalum oxide (Ta 2 O 5 ).
  • Example 2 the composition ratio of tantalum and oxygen in tantalum oxide was adjusted in order to give a gradient to the diffusion coefficient of copper ions in tantalum oxide.
  • the relationship between the composition ratio and the ease of copper ion diffusion has been investigated in advance by forming a resistance change element of tantalum oxide having a certain composition ratio.
  • FIG. 8 shows the relationship between the O / Ta ratio and the electric field strength for transition from the off state to the on state. It shows that a diffusion coefficient is so high that the positive applied voltage (electric field strength) to the 1st electrode 11 required in order to diffuse copper and to change from an OFF state to an ON state is low.
  • the diffusion coefficient in the ion conductive layer was increased by reducing the amount of oxygen in tantalum oxide, which is the ion conductive layer 23, from the second electrode side toward the first electrode.
  • the variable resistance element according to Example 2 Reactive sputtering was used to form tantalum oxide films having different composition ratios.
  • the composition ratio of the formed tantalum oxide was changed by changing the ratio of argon and oxygen in the chamber when sputtering the tantalum oxide (Ta 2 O 5 ) target.
  • the oxygen concentration of tantalum oxide may be changed by performing plasma treatment after tantalum oxide is deposited. In this case, the oxygen concentration increases as it is closer to the surface when exposed to plasma in an oxidizing atmosphere with a high amount of active oxygen, and the oxygen concentration increases as it is closer to the surface when exposed to plasma in a reducing atmosphere such as active hydrogen. Get smaller.
  • the maximum point of the diffusion coefficient of copper in tantalum oxide in which the amount of oxygen is reduced from the second electrode side toward the first electrode is the place where the tantalum oxide (ion conductive layer 23) and the copper electrode as the first electrode 11 are in contact with each other. (FIG. 6).
  • the position at which the bridging metal is cut when transitioning from the on state to the off state is limited to the closest portion to the copper electrode 11 in tantalum oxide, which is the ion conductive layer 23, which is most desirable as the position to be cut.
  • a forming voltage Vf an effect of lowering a voltage required for the first switch immediately after manufacture (this is particularly called a forming voltage Vf) can be obtained.
  • the initial operating voltage Vf is sufficiently higher than the voltage Vs when turning on the second time from the off state.
  • a voltage is applied between the layers, so that the same effect as applying a voltage (forming) after forming the element can be obtained during the process.
  • the forming voltage Vf becomes substantially the same as the set voltage Vs by the plasma processing, two power sources for forming and setting are unnecessary, and the peripheral circuit can be made small.
  • Example 3 As shown in FIG. 6, Example 3 according to the variable resistance element of the present invention also includes a first electrode 11 serving as a metal ion supply source, a second electrode 12 that is less likely to be ionized than the first electrode 11, and the first electrode 11. It consists of an ion conductive layer 23 that is interposed between the electrode 11 and the second electrode 12 and is capable of conducting metal ions.
  • the material of the first electrode 11 was copper
  • the material of the second electrode 12 was platinum
  • the material of the ion conductive layer 23 was tantalum oxynitride (TaON).
  • FIG. 10 shows the relationship between the N / O ratio and the electric field strength for transitioning from the off state to the on state. It shows that a diffusion coefficient is so high that the positive applied voltage (electric field strength) to the 1st electrode 11 required in order to diffuse copper and to change from an OFF state to an ON state is low. As shown in FIG.
  • Reactive sputtering is used to form tantalum oxynitride films having different concentration ratios of oxygen and nitrogen.
  • the ratio of oxygen and nitrogen in the formed tantalum oxynitride was changed by changing the ratio of oxygen and nitrogen in the chamber when sputtering the tantalum target.
  • nitrogen plasma treatment may be performed after deposition of tantalum oxide to replace oxygen in tantalum oxide with nitrogen. When exposed to nitrogen plasma, the closer to the tantalum oxide surface, the greater the nitrogen concentration.
  • oxygen in the tantalum nitride may be replaced with oxygen by performing oxygen plasma treatment after the deposition of tantalum nitride.
  • the temperature dependence (or the temperature dependence of the diffusion coefficient) of the voltage (electric field strength) necessary for transitioning from the off state to the on state varies depending on the ratio of oxygen and nitrogen as shown in FIG. A difference occurs in the diffusion coefficient. Therefore, the device may be operated with the diffusion coefficient gradient increased by increasing the temperature of the element.
  • the maximum point of the diffusion coefficient of copper in tantalum oxynitride, in which the amount of nitrogen is reduced from the second electrode side toward the first electrode, is the place where the tantalum oxynitride and the copper electrode as the first electrode 11 are in contact (FIG. 6). ). For this reason, the position at which the bridging metal is cut when transitioning from the on-state to the off-state is limited to the closest portion to the copper electrode 11 in tantalum oxynitride, which is the ion conductive layer 23, which is most desirable as the position to be cut. As compared with the simple two-layer structure shown in FIG.
  • First electrode 12 Second electrode 13
  • Metal ion 14 Metal bridge 15
  • Recoverable part 20 (of metal bridge)
  • Ion conduction layer 21 First ion conduction layer 22
  • Second ion conduction layer 23 Ion conduction with gradient in diffusion coefficient layer

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Abstract

L'invention porte sur une structure pour un élément à résistance variable qui utilise une réaction électrochimique. Ladite structure limite la position dans laquelle une liaison transversale métallique rompt à la position dans laquelle il est préférable que ladite liaison transversale se rompe : à savoir, la partie d'une couche conductrice d'ions la plus proche d'une première électrode. L'invention porte également sur un procédé de fabrication de l'élément à résistance variable. L'élément à résistance variable présente une première électrode (11) qui sert de source d'ions métalliques, une seconde électrode (12) qui est moins ionisable (c'est-à-dire, qui présente un potentiel redox plus élevé) que la première électrode, et une couche conductrice d'ions (23) qui est intercalée entre les première et seconde électrodes et qui peut conduire les ions métalliques. Il existe une première région dans la couche conductrice d'ions, adjacente à la première électrode, qui possède un coefficient de diffusion qui croît de façon continue vers la première électrode jusqu'à la première électrode. (fig. 6).
PCT/JP2010/071811 2009-12-08 2010-12-06 Élément à résistance variable utilisant une réaction électrochimique et son procédé de fabrication Ceased WO2011071009A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2011545199A JP5621784B2 (ja) 2009-12-08 2010-12-06 電気化学反応を利用した抵抗変化素子の製造方法
US13/514,385 US8878153B2 (en) 2009-12-08 2010-12-06 Variable resistance element having gradient of diffusion coefficient of ion conducting layer

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Application Number Priority Date Filing Date Title
JP2009278446 2009-12-08
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US8878153B2 (en) 2014-11-04
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JPWO2011071009A1 (ja) 2013-04-22
JP2014199959A (ja) 2014-10-23

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