CN101577308A - Variable-resistance memory doped with ZrO2 and preparation method thereof - Google Patents
Variable-resistance memory doped with ZrO2 and preparation method thereof Download PDFInfo
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- CN101577308A CN101577308A CNA2009100865513A CN200910086551A CN101577308A CN 101577308 A CN101577308 A CN 101577308A CN A2009100865513 A CNA2009100865513 A CN A2009100865513A CN 200910086551 A CN200910086551 A CN 200910086551A CN 101577308 A CN101577308 A CN 101577308A
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Abstract
The invention relates to a variable-resistance memory doped with ZrO2 and a preparation method thereof, belonging to the technical field of information memory. The memory comprises an upper electrode, a lower electrode and a resistance conversion memory layer that is arranged between the upper electrode and the lower electrode; the lower electrode is made of Al; and the resistance conversion memory layer is made of Cu doped with ZrO2. The variable-resistance memory doped with ZrO2 has simple structure, takes the Al with strong metal activity as the lower electrode, can absorb the oxygen ions in the ZrO2 in the resistance conversion memory layer and can form a large amount of oxygen vacancies in the ZrO2; when the device is firstly converted from high-resistance state to low-resistance state, the device needs not to be activated by a high operation voltage, thus eliminating the Forming process required when the variable-resistance memory is firstly converted from the high-resistance state to the low-resistance state.
Description
Technical field
The present invention relates to a kind of memory and preparation method thereof, relate in particular to a kind of doping ZrO
2Resistance-variable storing device and preparation method thereof belongs to technical field of information storage.
Background technology
Resistance-variable storing device (RRAM) technology is can realize the reversible basic functional principle that is converted to the resistance of thin-film material between high-impedance state and low resistance state.Just begun the electric resistance changing The Characteristic Study as far back as the sixties in 20th century, but because the restriction of material technology and device manufacturing technology fails to cause concern.In recent years along with the develop rapidly of material preparation technology and device manufacturing technology, resistance-variable storing device is compared with the Flash storage component part of main flow in the market, have density height, low in energy consumption, advantage such as endurance good, but long contractility of retention time is good, therefore cause vast company and researcher's concern once more.
Fig. 1 is the basic structure schematic diagram of prior art resistance-variable storing device.As shown in Figure 1, between top electrode 101 and bottom electrode 103, be provided with electric resistance converting storage layer 102.The resistance value of electric resistance converting storage layer 102 can have two kinds of different states under the applied voltage effect, i.e. high-impedance state and low resistance state, and it can be used for characterizing " 0 " and " 1 " two states respectively.Under the effect of different applied voltages, the resistance value of electric resistance transition type memory at high-impedance state (HRS) and low resistance state (LRS) but between can realize inverse conversion, realize the function of information stores with this.
The material system that constitutes resistance-variable storing device is varied, mainly comprises PrxCa1-xMnO
3(PCMO), LaxCa1-xMnO
3(LCMO), La1-xSrxMO
3Complex oxide such as (LSMO), strontium zirconate (SrZrO
3), strontium titanates (SrTiO
3) etc. the ternary perovskite oxide, macromolecule organic material and binary metal oxide such as Al
2O
3, TiO
2, ZnO, NiO, ZrO
2Deng.Compare with other complex oxide, binary metal oxide is owing to have simple in structurely, and cost of manufacture is low, and and the advantage of existing CMOS process compatible be subjected to more concern.Recently, people improve the performance of device by introducing to mix in the sull with resistive characteristic, and obtain certain effect, the method for this introducing doping not only can increase the retention time of device, improve the endurance of device and make the rate of finished products of device be greatly improved.
In the binary metal oxide material that constitutes resistance-variable storing device, ZrO
2Especially paid close attention in recent years as the high-k dielectric material.With ZrO
2Resistance-variable storing device as storage medium, its main electric resistance changing mechanism is conductive filament, wherein the composition of conductive filament mainly comprises defective that material itself exists, diffuses into electrode metal ion and oxygen room in the accumulation layer, and the oxygen room is more remarkable in these compositions.In the traditional handicraft condition, generally, for ZrO
2As the resistance-variable storing device of storage medium for the first time by high-impedance state when low resistance state changes, need a voltage that is higher than the memory normal operating voltage come activating appts, just can enter into normal store status then, promptly so-called Forming process.Because Forming voltage is bigger, can be higher than the voltage of device operate as normal, the big electric current that produces in the Forming process will produce certain destruction to electric resistance converting storage layer, causes the decreased performance of device.In addition, big Forming voltage means that the initial power consumption of device is higher, thereby is unfavorable for device application in practice.
Summary of the invention
The present invention is directed to existing with ZrO
2The voltage that is higher than the device operate as normal as the resistance-variable storing device of storage medium owing to Forming voltage in the Forming process, and generation has the big electric current of certain destruction to electric resistance converting storage layer, the decreased performance that causes device, and Forming voltage is bigger, also can make the higher deficiency of the initial power consumption of device, a kind of doping ZrO is provided
2Resistance-variable storing device and preparation method thereof.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of doping ZrO
2Resistance-variable storing device comprises top electrode, bottom electrode and the electric resistance converting storage layer between described top electrode and bottom electrode, and described bottom electrode is made by Al, and described electric resistance converting storage layer is by the Cu ZrO that mixes
2Make.
Described electric resistance converting storage layer comprises first metal-oxide film, metallic film and second metal-oxide film, described metallic film is arranged between described first metal-oxide film and second metal-oxide film, and described first metal-oxide film and second metal-oxide film are all for by ZrO
2The film of making, the film of described metallic film for making by Cu.
Further, the thickness of described metallic film is 1 nanometer～10 nanometers.
Further, described top electrode is made by in metal material, metal alloy compositions and the conductive metallic compound one or several.
Further, described metal material is Cu, Au, Ag or Pt.
Further, described metal alloy compositions is Pt/Ti, Cu/Au, Au/Cr or Cu/Al.
Further, described conductive metallic compound is TiN, TaN, ITO or IZO.
Further, the thickness of described electric resistance converting storage layer is 20 nanometers～200 nanometers.
The present invention also provides a kind of technical scheme that solves the problems of the technologies described above as follows: a kind of doping ZrO
2The manufacture method of resistance-variable storing device may further comprise the steps:
Step 1: on substrate, form the Al electrode as bottom electrode;
Step 2: on described bottom electrode, form with Cu doping ZrO
2The film of making is as electric resistance converting storage layer;
Step 3: on described electric resistance converting storage layer, form top electrode.
Described step 2 may further comprise the steps: form first metal-oxide film on described bottom electrode; On described first metal-oxide film, form metallic film; Form second metal-oxide film on described metallic film, wherein, described first metal-oxide film and second metal-oxide film are all for by ZrO
2The film of making, the film of described metallic film for making by Cu.
The invention has the beneficial effects as follows: doping ZrO of the present invention
2Resistance-variable storing device simple in structure adopts the stronger Al of metal active as bottom electrode, can change ZrO in the accumulation layer by absorption resistance
2In oxonium ion, at ZrO
2In form a large amount of oxygen rooms, when device for the first time by high-impedance state when low resistance state changes, no longer need a high operating voltage to come activating appts, thereby eliminate resistance-variable storing device for the first time by high-impedance state needed Forming process when low resistance state changes.The present invention ZrO that mixes
2The manufacture method of resistance-variable storing device is simple, cost is low and good with the traditional cmos process compatibility.
Description of drawings
Fig. 1 is the basic structure schematic diagram of prior art resistance-variable storing device;
Fig. 2 is the embodiment of the invention 1 doping ZrO
2The basic structure schematic diagram of resistance-variable storing device;
Fig. 3 is the embodiment of the invention 2 doping ZrO
2Resistance-variable storing device manufacture method flow chart;
Fig. 4 be the embodiment of the invention respectively with Pt and Al as bottom electrode, Au is as the current-voltage characteristic curve schematic diagram of the resistance-variable storing device of top electrode.
Embodiment
Below in conjunction with accompanying drawing principle of the present invention and feature are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment 1
Fig. 2 is embodiment of the invention doping ZrO
2The basic structure schematic diagram of resistance-variable storing device.As shown in Figure 2, described doping ZrO
2Resistance-variable storing device comprises substrate 201, is arranged at the bottom electrode 202 on the substrate 201, is arranged at the electric resistance converting storage layer on the bottom electrode 202, and is arranged at the top electrode 206 on the electric resistance converting storage layer.Described electric resistance converting storage layer is made up of first metal-oxide film 203, metallic film 204 and second metal-oxide film 205.Described metallic film 204 is arranged between described first metal-oxide film 203 and second metal-oxide film 205, and described first metal-oxide film 203 and second metal-oxide film 205 are all for by ZrO
2The film of making, the film of described metallic film 204 for making by Cu.
Described substrate 201 is generally made by silicon dioxide, doping silicon dioxide or other insulating material.
Described bottom electrode 202 is made by Al.Described top electrode 206 can be the single-layer metal electrode that metals such as Cu, Au, Ag or Pt form, also can be the double-level-metal electrode of metal alloys such as Pt/Ti, Cu/Au, Au/Cr or Cu/Al formation, also can make simultaneously by conductive metallic compounds such as TiN, TaN, ITO or IZO.Described top electrode 206 can also be any two or three alloy that forms in metal, metal alloy and the conductive metallic compound.The thickness of described bottom electrode 202 and top electrode 206 respectively is 10 nanometers～300 nanometers.The thickness that is appreciated that described bottom electrode 202 and top electrode 206 can be identical, also can be different, as long as between 10 nanometers～300 nanometers.
The thickness of described electric resistance converting storage layer is 20 nanometers～200 nanometers.The thickness of described metallic film 204 is 1 nanometer～10 nanometers.The thickness range of described first metal-oxide film 203 and second metal-oxide film 205 is respectively 10 nanometers～100 nanometers, and the thickness of described first metal-oxide film 203 and second metal-oxide film 205 can be identical, also can be inequality.
Doping ZrO of the present invention
2Resistance-variable storing device simple in structure adopts the stronger Al of metal active as bottom electrode, can change ZrO in the accumulation layer by absorption resistance
2In oxonium ion, at ZrO
2In form a large amount of oxygen rooms, when device for the first time by high-impedance state when low resistance state changes, no longer need a high operating voltage to come activating appts, thereby eliminate resistance-variable storing device for the first time by high-impedance state needed Forming process when low resistance state changes.
Fig. 3 is embodiment of the invention doping ZrO
2Resistance-variable storing device manufacture method flow chart.As shown in Figure 3, described manufacture method may further comprise the steps:
Step 301: on substrate, form the Al electrode as bottom electrode.
Described bottom electrode can adopt physical vapor deposition or the formation of chemical vapor deposited method such as electron beam evaporation, sputter.
Step 302: on described bottom electrode, form with Cu doping ZrO
2The film of making is as electric resistance converting storage layer.
In concrete production practices, at first, on described bottom electrode, form first metal-oxide film; Then, on described first metal-oxide film, form metallic film; At last, form second metal-oxide film on described metallic film, wherein, described first metal-oxide film and second metal-oxide film are all for by ZrO
2The film of making, the film of described metallic film for making by Cu.
Described first metal-oxide film, second metal-oxide film and metallic film all can adopt electron beam evaporation, plasma reinforced chemical vapor deposition (PECVD) or atomic layer deposition methods such as (ALD) to form.
Step 303: on described electric resistance converting storage layer, form top electrode.
Described top electrode can adopt physical vapor deposition or the formation of chemical vapor deposited method such as electron beam evaporation, sputter.
By electron beam evaporation process, construct the resistance-variable storing device device with Pt and Al as bottom electrode respectively.At first at dielectric substrate SiO
2Active different Pt of last plated metal respectively and Al are as bottom electrode, on bottom electrode, deposit the zirconia layer of one deck 20nm again, deposit the metal Cu thin layer of one deck 3nm then, deposit the zirconia layer of one deck 20nm afterwards again, deposit the basic structure that the Au top electrode is finished entire device at last.Fig. 4 be the embodiment of the invention respectively with Pt and Al as bottom electrode, Au is as the current-voltage characteristic curve schematic diagram of the resistance-variable storing device of top electrode.As shown in Figure 4, adopting respectively under the stronger situation of Al of stable Pt of metal active and metal active as the bottom electrode of resistive-switching memory, compare with the Pt bottom electrode device that metal active is stable, adopt the stronger Al of metal active, can absorb ZrO as bottom electrode
2In oxonium ion, at ZrO
2The a large amount of oxygen room of middle formation no longer needs a high operating voltage to come activating appts, and lower operating voltage just can be realized the transformation of resistance, thereby eliminates resistance-variable storing device for the first time by high-impedance state needed Forming process when low resistance state changes.
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. doping ZrO
2Resistance-variable storing device comprises top electrode, bottom electrode and the electric resistance converting storage layer between described top electrode and bottom electrode, it is characterized in that described bottom electrode is made by Al, and described electric resistance converting storage layer is by the Cu ZrO that mixes
2Make.
2. doping ZrO according to claim 1
2Resistance-variable storing device, it is characterized in that, described electric resistance converting storage layer comprises first metal-oxide film, metallic film and second metal-oxide film, described metallic film is arranged between described first metal-oxide film and second metal-oxide film, and described first metal-oxide film and second metal-oxide film are all for by ZrO
2The film of making, the film of described metallic film for making by Cu.
3. doping ZrO according to claim 2
2Resistance-variable storing device is characterized in that, the thickness of described metallic film is 1 nanometer～10 nanometers.
4. doping ZrO according to claim 1
2Resistance-variable storing device is characterized in that, described top electrode is made by in metal material, metal alloy compositions and the conductive metallic compound one or several.
5. doping ZrO according to claim 4
2Resistance-variable storing device is characterized in that, described metal material is Cu, Au, Ag or Pt.
6. doping ZrO according to claim 4
2Resistance-variable storing device is characterized in that, described metal alloy compositions is Pt/Ti, Cu/Au, Au/Cr or Cu/Al.
7. doping ZrO according to claim 4
2Resistance-variable storing device is characterized in that, described conductive metallic compound is TiN, TaN, ITO or IZO.
8. according to the arbitrary described doping ZrO of claim 1 to 7
2Resistance-variable storing device is characterized in that, the thickness of described electric resistance converting storage layer is 20 nanometers～200 nanometers.
9. doping ZrO
2The manufacture method of resistance-variable storing device is characterized in that, this manufacture method may further comprise the steps:
Step 1: on substrate, form the Al electrode as bottom electrode;
Step 2: on described bottom electrode, form with Cu doping ZrO
2The film of making is as electric resistance converting storage layer;
Step 3: on described electric resistance converting storage layer, form top electrode.
10. doping ZrO according to claim 9
2The manufacture method of resistance-variable storing device is characterized in that, described step 2 may further comprise the steps: form first metal-oxide film on described bottom electrode; On described first metal-oxide film, form metallic film; Form second metal-oxide film on described metallic film, wherein, described first metal-oxide film and second metal-oxide film are all for by ZrO
2The film of making, the film of described metallic film for making by Cu.
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| CN101853922A (en) * | 2010-04-28 | 2010-10-06 | 北京大学 | Low-voltage resistive random access memory and preparation method thereof |
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| CN102487123B (en) * | 2010-12-06 | 2013-11-06 | 中国科学院微电子研究所 | Nanoscale non-volatile resistive random access memory unit and preparation method thereof |
| CN102487123A (en) * | 2010-12-06 | 2012-06-06 | 中国科学院微电子研究所 | Nanoscale non-volatile resistive random access memory unit and preparation method thereof |
| CN102130296A (en) * | 2010-12-17 | 2011-07-20 | 天津理工大学 | Resistive random access memory based on doped vanadium oxide film and preparation method thereof |
| CN102130297B (en) * | 2010-12-17 | 2013-07-10 | 天津理工大学 | Resistive random access memory based on P/N type oxide laminated structure and preparation method thereof |
| CN102130297A (en) * | 2010-12-17 | 2011-07-20 | 天津理工大学 | Resistive random access memory based on P/N type oxide laminated structure and preparation method thereof |
| CN102130295A (en) * | 2010-12-17 | 2011-07-20 | 天津理工大学 | Resistive random access memory based on vanadium oxide film and preparation method thereof |
| CN102208418A (en) * | 2011-04-08 | 2011-10-05 | 中山大学 | Chip and preparation method thereof |
| CN102931347A (en) * | 2011-08-12 | 2013-02-13 | 中国科学院微电子研究所 | Resistive random access memory and preparation method thereof |
| CN102306705A (en) * | 2011-09-16 | 2012-01-04 | 北京大学 | Multi-valued resistance random access memory with high capacity |
| US8633465B2 (en) | 2011-09-16 | 2014-01-21 | Peking University | Multilevel resistive memory having large storage capacity |
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| CN105098065A (en) * | 2014-05-14 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method for memory cell of resistive random access memory and product thereof |
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