CN102916129A - Resistance random access memory based on vanadium oxide/zinc oxide laminated structure and preparation method thereof - Google Patents
Resistance random access memory based on vanadium oxide/zinc oxide laminated structure and preparation method thereof Download PDFInfo
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- CN102916129A CN102916129A CN2012104401327A CN201210440132A CN102916129A CN 102916129 A CN102916129 A CN 102916129A CN 2012104401327 A CN2012104401327 A CN 2012104401327A CN 201210440132 A CN201210440132 A CN 201210440132A CN 102916129 A CN102916129 A CN 102916129A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 50
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 16
- 238000004544 sputter deposition Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000010409 thin film Substances 0.000 claims abstract description 3
- 229960001296 zinc oxide Drugs 0.000 claims description 41
- 239000010410 layer Substances 0.000 claims description 39
- 239000010408 film Substances 0.000 claims description 19
- 238000005516 engineering process Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 230000008859 change Effects 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000001659 ion-beam spectroscopy Methods 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 230000000750 progressive effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种基于氧化钒/氧化锌叠层结构的阻变存储器，由下电极、阻变层和上电极构成，阻变层为由氧化钒介质层和氧化锌介质层组成的叠层结构，氧化钒介质层和氧化锌介质层薄膜采用直流溅射或射频溅射法制备。本发明的优点是：该阻变存储器采用氧化钒/氧化锌叠层结构，具有氧化锌双极性和单极性极性可控的优势，提高了器件的一致性和重复性；与单层氧化钒相比，reset电流降到了10mA以下；在双极性测试过程中，具有一个渐进的reset过程，可以通过不同振幅的reset电压而得到不同的高阻态的电阻，至少可以获得3个电阻值，并且每个电阻值之间有10倍以上的阻值比，因而可以将其应用于多值存储。
A resistive variable memory based on a vanadium oxide/zinc oxide laminated structure, consisting of a lower electrode, a resistive layer and an upper electrode, the resistive layer is a laminated structure composed of a vanadium oxide dielectric layer and a zinc oxide dielectric layer, and the vanadium oxide The dielectric layer and the zinc oxide dielectric layer thin film are prepared by direct current sputtering or radio frequency sputtering. The advantages of the present invention are: the resistive variable memory adopts a vanadium oxide/zinc oxide laminated structure, which has the advantages of controllable polarity of zinc oxide bipolar and unipolar, and improves the consistency and repeatability of the device; Compared with vanadium oxide, the reset current drops below 10mA; in the bipolar test process, it has a gradual reset process, and different high-impedance state resistors can be obtained through reset voltages of different amplitudes, and at least 3 resistors can be obtained value, and there is a resistance ratio of more than 10 times between each resistance value, so it can be applied to multi-value storage.
Description
Technical field
The invention belongs to microelectronics technology, be specifically related to a kind of resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure and preparation method thereof.
Technical background
Resistance-variable storing device is owing to having higher integration density, faster erasable speed, long retention time, and the potential of multilevel storage is arranged, and has been subject to researcher's extensive concern recent years.The design of resistive research on mechanism, new structure, the proposition of new material, the researcher is pursuing higher integration density, the faster breakthrough of read or write speed, multilevel storage.
The structure of resistance-variable storing device is simple metal-insulator-metal (MIM) structure, i.e. the sandwich structure of upper/lower electrode and middle change resistance layer, and most of change resistance layers are single layer structure.In recent years, because double-deck advantage, the researcher began to have proposed some lamination resistive structures, and performance of devices is improved.(Reliable resistiveswitching device based on bi-layers of ZrO in the document of Gwangju, Korea Science and Technology research institute in 2009
x/ HfO
xFilms), the people such as J.Lee adopts ZrO
x/ HfO
xLaminated construction, obtained stable bipolarity resistive characteristic, and this device has the characteristic potential of multilevel storage.U.S.'s University of Toledo document (Switching Characteristicsof Ru/HfO in 2012
2/ TiO
2-x/ Ru RRAM Devices for Digital and Analog NonvolatileMemory Applications) in, the people such as B.Long and Y.Li pass through HfO
2/ TiO
2-xLaminated construction has obtained higher conforming bipolar structure.
Novel laminated structure can overcome the deficiency that exists in the single layer structure, in conjunction with the advantage of single layer structure, improve the performance of single layer structure, the exploration of novel laminated structure and research become researcher's a focus.
In a kind of resistance-variable storing device based on vanadium oxide film and preparation method thereof (CN102130295A), this seminar uses vanadium oxide as the dielectric layer of resistance-variable storing device, obtained a kind of resistance-variable storing device of single-stage, the reset electric current is 40mA, the vanadium oxide film of individual layer has larger reset electric current during as the change resistance layer material; In a kind of controlled resistance-variable storing device of polarity of zinc oxide and preparation method thereof (CN102194995A), this seminar can obtain single-stage, bipolarity, non-polar resistance-variable storing device by depositing different upper/lower electrodes, the reset electric current is 10mA, but consistency and repeatability still need to improve.
Summary of the invention
The objective of the invention is the technical problem for above-mentioned existence, a kind of resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure and preparation method thereof is provided, this resistance-variable storing device has zinc oxide bipolarity and the controlled advantage of unipolarity polarity, can improve consistency and the repeatability of device.
Technical scheme of the present invention:
A kind of resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure is made of bottom electrode, change resistance layer and top electrode, and change resistance layer is the laminated construction that is comprised of vanadium oxide dielectric layer and zinc oxide dielectric layer, and the composition of zinc oxide is ZnO
1-x, 0＜x＜0.5 wherein, the thickness of zinc oxide dielectric layer is 1-500nm; The composition of vanadium oxide is VO
y, 0.5＜y＜2.5 wherein, the thickness of vanadium oxide dielectric layer is 1-500nm.
Described upper/lower electrode material is conducting metal, metal alloy and conductive metallic compound, and wherein conducting metal is Ta, Cu, Ag, W, Ni, Al or Pt; Metal alloy is Pt/Ti, Ti/Ta, Cu/Ti, Cu/Au, Cu/Al or Al/Zr; Conductive metallic compound is TiN or ITO.
A kind of preparation method of described resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure, step is as follows, and wherein vanadium oxide dielectric layer and zinc oxide dielectric layer thin film technology do not limit precedence:
1) take the Si sheet as substrate, utilize the method for thermal oxidation to prepare SiO
2Insulating barrier;
2) at SiO
2Utilize the method for ion beam sputtering to prepare the Ti adhesion layer on the insulating barrier;
3) prepare bottom electrode at the Ti adhesion layer;
4) adopt direct current sputtering or radio frequency sputtering method deposition vanadium oxide film at bottom electrode, the sputtering technology condition is: base vacuum is less than 10
-4Pa, underlayer temperature are that room temperature-200 ℃, operating pressure 0.1-2Pa, partial pressure of oxygen are that 5%-30%, sputtering power are 50-250W;
5) adopt direct current sputtering or radio frequency sputtering method depositing zinc oxide film at vanadium oxide film, the sputtering technology condition is: base vacuum is less than 10
-4Pa, underlayer temperature are that room temperature-300 ℃, operating pressure are that 0.1-2Pa, partial pressure of oxygen are that 5%-40%, sputtering power are 50-250W;
6) prepare top electrode at zinc-oxide film;
7) utilize method growth one deck SiO of PECVD at top electrode
2As protective layer.
The described method for preparing upper/lower electrode is ion beam sputtering, magnetron sputtering or electron beam evaporation process.
Technical Analysis of the present invention:
The difference of this resistance-variable storing device and traditional single layer structure is, there are two-layer dielectric layer vanadium oxide, zinc oxide, under the effect of extra electric field, the generation rate in a kind of material oxygen room is greater than another material, in a kind of material, just preferentially form like this conductive channel in oxygen room, then the electric field of another material just reaches the requirement that produces the oxygen room, forms the passage in oxygen room.Just the opposite in the Reset process, preferentially form the rear fracture of oxygen space channels.This vanadium oxide/Zinc oxide laminate structure owing to the process at reset is a progressive process, can obtain by the reset voltage of various amplitude the resistance of different high-impedance states.
Advantage of the present invention and beneficial effect are:
This resistance-variable storing device adopts vanadium oxide/Zinc oxide laminate structure, has zinc oxide bipolarity and the controlled advantage of unipolarity polarity, has improved consistency and the repeatability of device; Compare with mono-layer oxidized vanadium, the reset electric current has dropped to below the 10mA; In the bipolarity test process, have a progressive reset process, can obtain by the reset voltage of various amplitude the resistance of different high-impedance states, can obtain at least 3 resistance values, and the resistance value ratio more than 10 times is arranged between each resistance value.
Description of drawings
Fig. 1 is this resistance variation memory structure schematic diagram.
Among the figure: 1. bottom electrode 2. vanadium oxide dielectric layers 3. zinc oxide dielectric layers 4. top electrodes
Fig. 2 is this resistance-variable storing device unipolarity electrology characteristic curve.
Fig. 3 is that this resistance-variable storing device uses analyzing parameters of semiconductor instrument DC scanning, the ambipolar curve of set process and progressive reset process.
Fig. 4 be this resistance-variable storing device when bipolarity, the reset process adopt amplitude be-0.5V and-the endurance curve of three attitudes of 0.85V acquisition, resistance ratio is greater than 10 times between each attitude.
Embodiment
Embodiment 1:
A kind of resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure as shown in Figure 1, is made of bottom electrode 1, change resistance layer and top electrode 4, and change resistance layer is the laminated construction that is comprised of vanadium oxide dielectric layer 2 and zinc oxide dielectric layer 3, and the composition of zinc oxide is ZnO
1-x, wherein x is 0.1, the thickness of zinc oxide dielectric layer is 30nm; The composition of vanadium oxide is VO
y, wherein y is 0.15, the thickness of vanadium oxide dielectric layer is 30nm; Bottom electrode is that Pt, thickness are 50nm, and powering on very, W, thickness are 50nm.
The preparation method of this resistance-variable storing device, step is as follows:
1) take the Si sheet as substrate, use the oxide-diffused stove, the method by thermal oxidation prepares SiO at silicon substrate
2Insulating barrier;
2) at SiO
2Utilize the method for ion beam sputtering to prepare the thick Ti adhesion layer of one deck 10nm on the insulating barrier;
3) adopt the method for electron beam evaporation at the thick Pt bottom electrode of Ti adhesion layer deposition 50nm;
4) adopting the radio frequency sputtering method deposit thickness at bottom electrode is the 30nm vanadium oxide film, and the sputtering technology condition is: target is φ 60mm vanadium oxide ceramic target, and the target intercept is 6.5cm, and base vacuum is less than 10
-4Pa, underlayer temperature are that 200 ℃, operating pressure 1.0Pa, partial pressure of oxygen are 20%, sputtering power is 100W;
5) adopting the radio frequency sputtering method deposit thickness at vanadium oxide film is the 30nm zinc-oxide film, and the sputtering technology condition is: target is φ 60mm zinc oxide ceramic target, and the target intercept is 6.5cm, and base vacuum is less than 10
-4The Pa underlayer temperature is that 200 ℃, operating pressure are that 0.5Pa, partial pressure of oxygen are 20%, sputtering power is 50W;
6) be 50nm tungsten top electrode by Deposited By Dc Magnetron Sputtering thickness on zinc-oxide film, the process conditions of magnetically controlled DC sputtering are: target is φ 60mm metal tungsten target, and the target intercept is 6.5cm, operating pressure 0.5Pa, and Ar flow 20sccm, sputtering power are 50W;
7) utilize method growth one deck SiO of PECVD at top electrode
2As protective layer.
Electrology characteristic is tested by analyzing parameters of semiconductor, and this device is a kind of non-polar device, can realize the bipolarity operation, as shown in Figure 2; Also can realize the unipolarity operation, as shown in Figure 3; By adjusting the amplitude of reset voltage, when reset voltage was 0.5, high-impedance state was about 600ohm, and when the amplitude of reset voltage was 0.85, high-impedance state was about 60kohm, as shown in Figure 4.
Embodiment 2:
A kind of resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure, structure is substantially the same manner as Example 1, and difference is take W as bottom electrode, thickness is 50nm, and TiN is that top electrode, thickness are 100nm.
The preparation method of this resistance-variable storing device, step is as follows:
1), 2) identical with embodiment 1;
3) be 50nm tungsten bottom electrode by Deposited By Dc Magnetron Sputtering thickness on the Ti adhesion layer, the technological parameter of magnetically controlled DC sputtering: target is φ 60mm metal tungsten target, and the target intercept is 6.5cm, and operating pressure is 0.5Pa, and the Ar flow is 20sccm, and sputtering power is 50W;
4) adopting the radio frequency sputtering method deposit thickness at bottom electrode is the 30nm vanadium oxide film, and the sputtering technology condition is: target is φ 60mm vanadium oxide ceramic target, and the target intercept is 6.5cm, and base vacuum is less than 10
-4Pa, underlayer temperature are that 200 ℃, operating pressure 1.0Pa, partial pressure of oxygen are 20%, sputtering power is 100W;
5) adopting the radio frequency sputtering method deposit thickness at vanadium oxide film is the 30nm zinc-oxide film, and the sputtering technology condition is: target is φ 60mm zinc oxide ceramic target, and the target intercept is 6.5cm, and base vacuum is less than 10
-4The Pa underlayer temperature is that 200 ℃, operating pressure are that 1.0Pa, partial pressure of oxygen are 40%, sputtering power is 100W;
6) on zinc-oxide film, be the 100nmTiN top electrode by Deposited By Dc Magnetron Sputtering thickness, the technological parameter of magnetically controlled DC sputtering: target is φ 60mm metal titanium targets, and the target intercept is 6.5cm, and operating pressure is 0.5Pa, nitrogen partial pressure is 7%, and sputtering power is 100W;
7) utilize method growth one deck SiO of PECVD at top electrode
2As protective layer.
Electrology characteristic is by the test of analyzing parameters of semiconductor instrument, and device shows as the bipolarity characteristic, and device has preferably consistency.
Embodiment 3:
A kind of resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure, structure is substantially the same manner as Example 1, and difference is that take W as bottom electrode, W is top electrode, and thickness is 50nm.
The preparation method of this resistance-variable storing device, the preparation technology of step and W electrode is identical with embodiment 1.
Embodiment 4:
A kind of resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure, structure is substantially the same manner as Example 1, and difference is that take Pt as bottom electrode, Cu is top electrode, and thickness is 50nm.
The preparation method of this resistance-variable storing device, the preparation technology of step and Pt electrode is identical with embodiment 1.
Top electrode Cu is by the method preparation of magnetically controlled DC sputtering, and the concrete technology condition is: target is φ 60mm metallic copper target, and the target intercept is 6.5cm, and operating pressure is 1Pa, and the Ar flow is 20sccm, and sputtering power is 50W.
The testing result summary sheet of embodiment 1-4:
Claims (4)
1. resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure, it is characterized in that: be made of bottom electrode, change resistance layer and top electrode, change resistance layer is the laminated construction that is comprised of vanadium oxide dielectric layer and zinc oxide dielectric layer, and the composition of zinc oxide is ZnO
1-x, 0＜x＜0.5 wherein, the thickness of zinc oxide dielectric layer is 1-500nm; The composition of vanadium oxide is VO
y, 0.5＜y＜2.5 wherein, the thickness of vanadium oxide dielectric layer is 1-500nm.
2. described resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure according to claim 1, it is characterized in that: described upper/lower electrode material is conducting metal, metal alloy and conductive metallic compound, and wherein conducting metal is Ta, Cu, Ag, W, Ni, Al or Pt; Metal alloy is Pt/Ti, Ti/Ta, Cu/Ti, Cu/Au, Cu/Al or Al/Zr; Conductive metallic compound is TiN or ITO.
3. one kind as claimed in claim 1 based on the preparation method of the resistance-variable storing device of vanadium oxide/Zinc oxide laminate structure, it is characterized in that step is as follows, and wherein vanadium oxide dielectric layer and zinc oxide dielectric layer thin film technology do not limit precedence:
1) take the Si sheet as substrate, utilize the method for thermal oxidation to prepare SiO
2Insulating barrier;
2) at SiO
2Utilize the method for ion beam sputtering to prepare the Ti adhesion layer on the insulating barrier;
3) prepare bottom electrode at the Ti adhesion layer;
4) adopt direct current sputtering or radio frequency sputtering method deposition vanadium oxide film at bottom electrode, the sputtering technology condition is: base vacuum is less than 10
-4Pa, underlayer temperature are that room temperature-200 ℃, operating pressure 0.1-2Pa, partial pressure of oxygen are that 5%-30%, sputtering power are 50-250W;
5) adopt direct current sputtering or radio frequency sputtering method depositing zinc oxide film at vanadium oxide film, the sputtering technology condition is: base vacuum is less than 10
-4Pa, underlayer temperature are that room temperature-300 ℃, operating pressure are that 0.1-2Pa, partial pressure of oxygen are that 5%-40%, sputtering power are 50-250W;
6) prepare top electrode at zinc-oxide film;
7) utilize method growth one deck SiO of PECVD at top electrode
2As protective layer.
4. the preparation method of described resistance-variable storing device based on vanadium oxide/Zinc oxide laminate structure according to claim 3, it is characterized in that: the described method for preparing upper/lower electrode is ion beam sputtering, magnetron sputtering or electron beam evaporation process.
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| CN103151459A (en) * | 2013-03-28 | 2013-06-12 | 天津理工大学 | Hafnium-oxynitride-based low-power consumption resistive random access memory and preparation method for same |
| CN103296205A (en) * | 2013-07-01 | 2013-09-11 | 天津理工大学 | Low power consumption resistive random access memory and manufacturing method thereof |
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| CN103311435B (en) * | 2013-07-01 | 2015-09-30 | 天津理工大学 | Based on the resistance-variable storing device and preparation method thereof of vanadium oxide/aluminium oxide laminated construction |
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| CN109994605A (en) * | 2019-04-17 | 2019-07-09 | 河南大学 | Resistive memory with multiplexed electrode structure and preparation method thereof |
| CN109980083B (en) * | 2019-04-17 | 2024-06-07 | 河南大学 | Small-area electrode resistance random access memory with filament mechanism and preparation method thereof |
| CN110739395A (en) * | 2019-10-30 | 2020-01-31 | 上海华力微电子有限公司 | Resistive random access memory and preparation method thereof |
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