CN110071216A - A kind of dual oxide layer RRAM and preparation method thereof - Google Patents
A kind of dual oxide layer RRAM and preparation method thereof Download PDFInfo
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- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 18
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 18
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
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- 230000008014 freezing Effects 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910009112 xH2O Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 241000588731 Hafnia Species 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
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- 150000004706 metal oxides Chemical class 0.000 abstract description 9
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- 150000004767 nitrides Chemical class 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
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- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Semiconductor Memories (AREA)
Abstract
The invention belongs to technical field of electronic devices, specific to protect the dual oxide nitride layer RRAM and preparation method thereof based on metal oxide.Dual oxide nitride layer RRAM includes the top electrode layer being from top to bottom stacked, resistive oxide layer and substrate；The resistive oxide layer is the In by being stacked under2O3And Al2O3Double-level-metal oxide layer；The top electrode layer includes top electrode of several arrays in resistive oxide layer, and the top electrode is equipped with protective layer on the surface far from resistive oxide layer；The substrate includes bottom electrode layer and insulating layer.The present invention is all made of the preparation of solwution method technique to double layer of metal oxide layer, realizes the preparation of low cost RRAM, and compared to the RRAM device of single metal oxide layer, resistive characteristic is more preferable, and equipment and raw material investment are less, it can be achieved that large-scale industrial application.
Description
Technical field
The present invention relates to microelectronics technology, specifically a kind of dual oxide layer RRAM based on metal oxide
(Resistive random access memory, resistive formula random access memory) and preparation method thereof.
Background technique
With the fast development of computer technology, the mankind enter the digital technology epoch already, as extremely important base
Plinth memory component, memory have not replaceable status.Memory can be divided into three categories: magnetic disk storage, disc memory
And semiconductor memory.Wherein semiconductor memory can be divided into volatile and non-volatile two major classes again.So-called volatile storage
Device, needs electricity consumption during the information exactly stored to maintain, after power-off, the loss of data of write-in, such as static memory
(SRAM), dynamic memory (DRAM) etc..On the contrary, nonvolatile memory can continue to keep information, such as flash memory after a loss of power
(Flash), resistive formula random access memory (RRAM) etc..Requirement with memory to reading speed and access capability is more next
Higher, RRAM shows one's talent in numerous nonvolatile memories by its excellent performance.RRAM is made using metal oxide
For storage medium, by the variation to the voltage being applied on metal oxide layer (Metal Oxide), so that memory is in height
Change back and forth between resistance state, to realize the erasable of data, unlatching or block current channel and storage.Because its low pressure,
At a high speed, the distinguishing features such as low-power consumption, low cost, extensive concern of the RRAM by industry.
The existing research for RRAM is concentrated mainly on Ultrahigh, storage material screening, the optimization of storage material performance
And its raising of stability etc..Wherein, the research for resistive oxide layer preparation process is most important.Traditional resistive oxygen
Change layer film can be realized by the methods of sputtering, chemical vapor deposition (CVD), atomic layer deposition (ALD), but the above method by
It is limited to equipment, high production cost is unable to satisfy the industrial production demand of high-volume low cost.
Summary of the invention
The present invention is insufficient for the research of prior art RRAM, provides a kind of dual oxide layer RRAM based on metal oxide
And preparation method thereof, it is able to satisfy the industrial production demand of high-volume low cost.
The present invention is achieved by the following technical solutions:
The dual oxide layer RRAM of the first aspect of the present invention, including the top electrode layer being from top to bottom stacked, resistive oxygen
Change layer and substrate；The top electrode layer includes top electrode of several arrays in resistive oxide layer, and the top electrode is far from resistance
The surface for becoming oxide layer is equipped with protective layer；The resistive oxide layer is double-level-metal oxide layer；The substrate includes being stacked
Upper layer bottom electrode layer and lower layer insulating layer.
The protective layer is any one in metal aluminum film layer, metallic titanium membrane layer or tungsten film layer.
The top electrode is cylindrical metal nickel film layer or titanium nitride thin film layer, with a thickness of 30~80nm, diameter 0.1
~0.3mm.
The double-level-metal oxide layer of the resistive oxide layer is the hafnium oxide HfO on upper layer2The indium oxide of film layer and lower layer
In2O3Film layer, with a thickness of respectively 5~80nm.
The bottom electrode layer is metal platinum (Pt) film layer or silicon (Si) film layer, with a thickness of 50~150nm.
Preferably, the insulating layer is using the three-decker being stacked, including titanium (Ti) film being from top to bottom arranged
Layer/silica (SiO2) film layer/silicon (Si) film layer.
Second aspect of the present invention provides the preparation method of above-mentioned dual oxide layer RRAM, comprising:
A) substrate is cleaned；
Substrate is successively immersed to deionized water, dehydrated alcohol, in deionized water, is cleaned by ultrasonic respectively；Third time is super
After sound cleaning, substrate is rinsed with deionized water and with being dried with nitrogen；
B) resistive oxide layer is prepared；
Take indium nitrate hydrate InN3O9.xH2O is configured to the In of 0.13~0.21mol/L2O3Precursor solution；It will configuration
Good In2O3Precursor solution is added dropwise on bottom electrode layer, carries out spin coating, after, it carries out being annealed to solution freezing film, make
Obtain In2O3Film layer,
Take eight hydrate HfOCl of oxychlorination hafnium2.8(H2O) it is dissolved in ethylene glycol monomethyl ether (HOCH2CH2OCH3) in be configured to 0.2
The HfO of~0.5mol/L2Precursor solution；By configured HfO2Precursor solution stirs evenly, and is then allowed to stand aging, will be old
HfO after change2In is added dropwise in precursor solution2O3In film layer, spin coating is carried out, after spin coating, carries out being annealed to solution being frozen into
HfO is made in film2Film layer；
C) top electrode layer is prepared；
Particle or powdered upper electrode material are coated in resistive oxide layer by evaporation coating method, form top electrode
Layer；
D) protective layer is prepared；
Granular metal coating layer material is coated on the separate resistance of each top electrode in upper electrode layer by evaporation coating method
Become on the surface of oxide layer, the RRAM based on aluminum oxide is made.
In step a), surface plasma cleaning is carried out to substrate again under vacuum environment after being cleaned by ultrasonic, to increase
The hydrophily of strong bottom electrode layer, improves the filming performance of resistive oxide layer；The surface plasma cleaning process time need to continue
At least 35min completes the interior progress resistive oxide layer preparation of 10min after surface plasma cleaning.
In step b), the In2O3Precursor solution is configured under 20 DEG C to 30 DEG C environment, is at the uniform velocity stirred to clarify,
5~10min need to be stood after stirring under room temperature environment, wherein InN3O9.xH2The purity of O solute is 99.99%.
In step b), the In2O3Precursor solution is added dropwise by the syringe of polyethersulfone resin material filter tip in hearth electrode
On layer, preferably 0.45 μm of aperture.
In step b), In is made2O3Film layer annealing temperature is 150~350 DEG C, and annealing time is no more than 1h.
In step b), by configured HfO2Precursor solution carries out water bath stirring, and bath temperature is 50~80 DEG C,
Mixing time is no more than 2.5h.
In step b), the HfO2 precursor solution stirred evenly is stood and carries out aging, time of repose is no more than 3 days.
In step b), HfO is made2Annealing temperature is 150~350 DEG C when film layer, and annealing time is no more than 1h.
In step c), granular top electrode layer material or metal coating layer material are placed in earthenware by the evaporation coating method
In crucible, the mask plate that aperture is 0.1~0.3mm is covered in resistive oxide layer, is put into electron beam evaporation deposition machine and carries out
Evaporation coating operation.
The process of preparing of dual oxide layer RRAM, comprising:
A) substrate is cleaned；
The substrate of purchase is completely immersed in the beaker for holding deionized water, the beaker is placed in deionized water environment
Carry out first time ultrasonic cleaning；After being cleaned by ultrasonic for the first time, substrate is completely immersed in the beaker for holding dehydrated alcohol, it will be described
Beaker, which is placed in deionized water environment, carries out second of ultrasonic cleaning；After second is cleaned by ultrasonic, substrate is rinsed with deionized water
Remaining impurity is removed, is completely immersed in substrate in the beaker for holding deionized water later, the beaker is placed in deionized water
Third time ultrasonic cleaning is carried out in environment；After third time is cleaned by ultrasonic, substrate is rinsed with deionized water and with being dried with nitrogen；
B) resistive oxide layer is prepared；
Indium nitrate hydrate (InN3O9.xH2O) is taken, before the In2O3 of 0.13~0.21mol/L is configured to deionized water
Drive liquid solution；Configured In2O3 precursor solution is added dropwise on bottom electrode layer, spin coating is carried out, spin-coating time is no more than
60s, revolving speed are 2500~3500rpm；It after spin coating, carries out being annealed to solution freezing film, In2O3 film layer is made, moves back
Fiery temperature is 150~350 DEG C, and annealing time is no more than 1h.Eight hydrate of oxychlorination hafnium (HfOCl2.8 (H2O)) is taken to be dissolved in second two
The HfO2 precursor solution of 0.2~0.5mol/L is configured in alcohol methyl ether (HOCH2CH2OCH3)；By configured HfO2 forerunner
Liquid solution carries out water bath stirring, and bath temperature is 50~80 DEG C, and mixing time is no more than 2.5h；The HfO2 that will be stirred evenly
Precursor solution, which is stood, carries out aging, and time of repose is no more than 3 days；It is thin that In2O3 is added dropwise in HfO2 precursor solution after aging
In film layer, spin coating is carried out, spin-coating time is no more than 40s, and revolving speed is 2500~3500rpm；After spin coating, be annealed to molten
HfO2 film layer is made in liquid freezing film, and annealing temperature is 150~350 DEG C, and annealing time is no more than 1h；
C) top electrode layer is prepared；
Particle or powdered upper electrode material are coated in resistive oxide layer by evaporation coating method, form top electrode
Layer；
D) protective layer is prepared；
Granular metal coating layer material is coated on the separate resistance of each top electrode in upper electrode layer by evaporation coating method
Become on the surface of oxide layer, the RRAM based on aluminum oxide is made.
Technical effect
Compared with prior art, the present invention has the following technical effect that
1) resistive oxide layer is prepared using pure solwution method, it is simple to operate, realize the RRAM preparation of low cost, equipment
The less preparation that can be used for large area RRAM device is invested with raw material, realizes large-scale industrial application；
2) compared to the RRAM device of traditional handicraft production single layer resistive oxide layer, resistive effect is more preferable, for set
(SET) and voltage required for reset (RESET) process is smaller, and between 1~2V, the double-deck resistive oxide layer makes absolute value
The tolerance and stability of device also increase；
3) use elemental metals or elemental metals compound-material as top electrode, instead of on traditional oxide material
Electrode further reduces costs and optimizes preparation process.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of embodiment 1；
Fig. 2 is resistive characteristic variations figure of the embodiment 1 within the scope of 200~300 DEG C；
In figure: coat of metal 100, top electrode 101, the second resistive oxide layer 200, the first resistive oxide layer 201, bottom electricity
Pole layer 300, ti thin film layer 400, silica membrane layer 401, silicon membrane layer 402.
Specific embodiment
The specific embodiment of the invention is described below in conjunction with attached drawing.
Embodiment 1
As shown in Figure 1, the present embodiment is related to a kind of dual oxide layer RRAM based on metal oxide, including layer from top to bottom
The top electrode layer of folded setting, resistive oxide layer and substrate, the upper electrode layer include several arrays in resistive oxide layer 200
Top electrode 101, the top electrode 101 are equipped with coat of metal 100 on the surface far from resistive oxide layer 200；
The coat of metal 100 is tungsten (W) film layer.
Top electrode 101 is cylindrical metal compound titanium nitride (TiN) film layer in the top electrode layer, with a thickness of 30~
80nm, diameter are 0.1~0.3mm, it is preferable that with a thickness of 60nm, diameter 0.1mm.
The second resistive oxide layer 200 is HfO2 film layer, and the first resistive oxide layer 201 is In2O3 film layer.
The substrate includes bottom electrode layer 300 and insulating layer；
The bottom electrode layer is metal platinum (Pt) film layer, with a thickness of 50~150nm, it is preferable that with a thickness of 100nm.
The insulating layer is using the three-decker being stacked, including titanium (Ti) film layer/dioxy being from top to bottom arranged
SiClx (SiO2) film layer/silicon (Si) film layer.
The present embodiment is related to the process of preparing of above-mentioned RRAM, comprising:
A) substrate is cleaned；
Substrate is completely immersed in the beaker for holding deionized water, the beaker is placed in deionized water environment and carries out
15min ultrasonic cleaning；
After being cleaned by ultrasonic for the first time, substrate is completely immersed in the beaker for holding dehydrated alcohol, the beaker is placed in
Second of 15min ultrasonic cleaning is carried out in ion water environment；
After second is cleaned by ultrasonic, substrate is rinsed with deionized water and removes remaining ethanol impurity, it is later that substrate is complete
Immersion is held in the beaker of deionized water, and the beaker is placed in progress third time 15min ultrasonic cleaning in deionized water environment；
After third time is cleaned by ultrasonic, substrate is rinsed with deionized water and with being dried with nitrogen；
The above-mentioned substrate for being cleaned by ultrasonic and being dried is put into the vacuum chamber of surface plasma cleaning machine, table is carried out
Face plasma cleaning is to enhance the hydrophily of bottom electrode layer 300；The surface plasma cleaning process time continues 45min；
B) resistive oxide layer is prepared；
Under the conditions of room temperature (25 DEG C), indium nitrate hydrate (InN3O9.xH2O) is taken, 0.13 is configured to deionized water~
The In of 0.21mol/L2O3Precursor solution；Preferably, 0.9g is taken, the InN that purity is 99.99%3O9.xH2O is placed in a beaker,
And 20ml deionized water is added into beaker, it is configured to the In of 0.15mol/L2O3Precursor solution；It at the uniform velocity stirs clear to solution
Clearly, 25min is stood later；
After completing surface plasma cleaning in 10min, configured In2O3 precursor solution is passed through into 0.45 μm of hole
Diameter, PES material filter tip syringe be added dropwise on bottom electrode layer 300, spin coating 45s, revolving speed be 2500~3500rpm；Spin coating is complete
Bi Hou is placed in 200 DEG C~300 DEG C of heating plate anneal 1h, In2O3Precursor solution freezing film on bottom electrode layer 300,
Resistive oxide layer 201 is made；
Under the conditions of room temperature (25 DEG C), eight hydrate of oxychlorination hafnium (HfOCl2.8 (H is taken2O)) it is dissolved in ethylene glycol monomethyl ether
(HOCH2CH2OCH3) in be configured to the HfO2 precursor solution of 0.2~0.5mol/L；Preferably, the 2.46g, purity is taken to be
99.99% HfOCl2.8 (H2O it) is placed in a beaker, and 20ml ethylene glycol monomethyl ether solvent is added into beaker, be configured to
The HfO2 precursor solution of 0.3mol/L；Configured HfO2 precursor solution is subjected to water bath stirring, bath temperature is
50~80 DEG C, mixing time is no more than 2.5h；Preferably, bath temperature is 70 degree, mixing time 2h；By what is stirred evenly
HfO2 precursor solution, which is stood, carries out aging, and time of repose is no more than 3 days；Preferably, time of repose is 2 days；
Complete HfO2 precursor solution will be configured to hinder by the syringe dropwise addition of 0.22 μm of aperture, PTFE material filter tip
Become in oxide layer 201, spin coating 30s, revolving speed is 2500~3500rpm；After spin coating, it is placed in 200 DEG C~300 DEG C of heating plate
Upper annealing 1h, HfO2Resistive oxide layer 200 is made in precursor solution freezing film in resistive oxide layer 201；
C) top electrode layer is prepared；
Particulate lithium compound material TiN is placed in the crucible of electron beam evaporation deposition machine, is 0.1mm by aperture
Mask plate be covered in resistive oxide layer 200, mask plate is lowered on the suction disc in coating machine cavity, close cavity carry out
Evaporation coating operation, metal compound material TiN is coated in resistive oxide layer 200, formed have the half of top electrode 101 at
Product；
D) protective layer is prepared；
After top electrode 101 completes, granulated metallic material W is placed in the crucible of electron beam evaporation deposition machine,
The mask plate that aperture is 0.1mm is covered on top electrode 101, mask plate is lowered on the suction disc in coating machine cavity, is closed
Closed chamber body carries out double evaporation-cooling coating operation, is coated with to form metal W protective layer 100 on top electrode 101.
The resistive effect for being illustrated in figure 2 the present embodiment RRAM device answers test result, using 0 point of abscissa as line of demarcation, just
Axis be SET (set) process, negative axis be RESET (reset) process, voltage bias absolute value all in 4V hereinafter, and resistive effect answer
It is held in a certain range, occurs the gradual change phenomenon of certain probability during RESET.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel only illustrate the present invention it should be appreciated that the present invention is not limited by examples detailed above described in examples detailed above and specification
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its is equal
Object defines.
Claims (10)
1. a kind of dual oxide layer RRAM, which is characterized in that including the top electrode layer being from top to bottom stacked, resistive oxide layer and
Substrate；
The top electrode layer includes top electrode of several arrays in resistive oxide layer, and the top electrode is far from resistive oxide layer
Surface be equipped with protective layer；The resistive oxide layer is double-level-metal oxide layer；The substrate includes the upper layer being stacked
The insulating layer of bottom electrode layer and lower layer.
2. a kind of dual oxide layer RRAM according to claim 1, which is characterized in that the protective layer is metal aluminium film
Any one in layer, metallic titanium membrane layer or tungsten film layer.
3. a kind of dual oxide layer RRAM according to claim 1, which is characterized in that the top electrode is cylindrical metal nickel
Film layer or titanium nitride thin film layer, with a thickness of 30~80nm.
4. a kind of dual oxide layer RRAM according to claim 3, which is characterized in that the double-level-metal of the resistive oxide layer
Oxide layer is the hafnia film layer on upper layer and the indium oxide film layer of lower layer, with a thickness of respectively 5~80nm.
5. a kind of dual oxide layer RRAM according to claim 1, which is characterized in that the bottom electrode layer is metal platinum film
Layer or silicon membrane layer, with a thickness of 50~150nm.
6. a kind of dual oxide layer RRAM according to claim 1, which is characterized in that the insulating layer use was stacked
Three-decker, including the ti thin film layer/silica membrane layer/silicon membrane layer being from top to bottom arranged.
7. the method for preparing dual oxide layer RRAM as claimed in any one of claims 1 to 6, includes the following steps:
A) substrate is cleaned；
Substrate is successively immersed to deionized water, dehydrated alcohol, in deionized water, is cleaned by ultrasonic respectively；Third time ultrasound is clear
After washing, substrate is rinsed with deionized water and with being dried with nitrogen；
B) resistive oxide layer is prepared；
Take indium nitrate hydrate InN3O9.xH2O is configured to the In of 0.13~0.21mol/L2O3Precursor solution；It will be configured
In2O3Precursor solution is added dropwise on bottom electrode layer, carries out spin coating, after, it carries out being annealed to solution freezing film, be made
In2O3Film layer,
Take eight hydrate HfOCl of oxychlorination hafnium2.8(H2O) it is dissolved in the HfO that 0.2~0.5mol/L is configured in ethylene glycol monomethyl ether2Before
Drive liquid solution；By configured HfO2Precursor solution stirs evenly, and is then allowed to stand aging, by the HfO after aging2Presoma is molten
Drop adds In2O3In film layer, spin coating is carried out, after spin coating, carries out being annealed to solution freezing film, HfO is made2Film layer；
C) top electrode layer is prepared；
Particle or powdered upper electrode material are coated in resistive oxide layer by evaporation coating method, form upper electrode layer；
D) protective layer is prepared；
Granular metal coating layer material is coated in upper electrode layer each top electrode far from resistive oxygen by evaporation coating method
On the surface for changing layer, the RRAM based on aluminum oxide is made.
8. the method according to the description of claim 7 is characterized in that
In step a), surface plasma cleaning, the surface are carried out to substrate again under vacuum environment after being cleaned by ultrasonic
The plasma cleaning process time need to continue at least 35min, complete the interior progress resistive oxide layer system of 10min after surface plasma cleaning
It is standby.
9. the method according to the description of claim 7 is characterized in that in step b), the In2O3Precursor solution passes through polyethers
The syringe of sulphone resin material filter tip is added dropwise on bottom electrode layer；In is made2O3Film layer annealing temperature is 150~350 DEG C, is moved back
The fiery time is no more than 1h.
10. the method according to the description of claim 7 is characterized in that in step b), by configured HfO2Precursor solution into
The stirring of row water bath, bath temperature are 50~80 DEG C, and mixing time is no more than 2.5h, and HfO is made2Annealing temperature when film layer
It is 150~350 DEG C, annealing time is no more than 1h.
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