CN106206944A - A kind of nano-film memristor and preparation method thereof - Google Patents
A kind of nano-film memristor and preparation method thereof Download PDFInfo
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- 239000002120 nanofilm Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000010408 film Substances 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011787 zinc oxide Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000005055 memory storage Effects 0.000 claims abstract description 14
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 12
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 10
- 239000010409 thin film Substances 0.000 claims abstract description 9
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004544 sputter deposition Methods 0.000 claims abstract description 8
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 238000001259 photo etching Methods 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910001020 Au alloy Inorganic materials 0.000 claims description 2
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910000765 intermetallic 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
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 238000009825 accumulation Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 11
- 210000000225 synapse Anatomy 0.000 abstract description 11
- 210000002569 neuron Anatomy 0.000 abstract description 9
- 230000006870 function Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000006386 memory function Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 22
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 19
- 229910052593 corundum Inorganic materials 0.000 description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 241000588731 Hafnia Species 0.000 description 6
- 229960001296 zinc oxide Drugs 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910003074 TiCl4 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000008141 laxative Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 210000005036 nerve Anatomy 0.000 description 3
- 230000001543 purgative effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- -1 bottom electrode Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000018992 Prunus glandulosa Nutrition 0.000 description 1
- 240000001619 Prunus glandulosa Species 0.000 description 1
- 235000013999 Prunus japonica Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000003977 synaptic function Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- H10N70/20—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C23C16/303—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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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
- H10N70/023—Formation of switching materials, e.g. deposition of layers by chemical vapor deposition, e.g. MOCVD, ALD
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of nano-film memristor, including substrate, described substrate is followed successively by bottom electrode, memory storage layer, upper electrode；Memory storage layer sequentially consists of aluminum oxide film, hafnium oxide/zinc oxide or hafnium oxide/aluminium oxide coupled double-layer thin film；The invention also discloses the preparation method of memristor, utilize plasma enhanced atomic first to prepare bottom electrode titanium nitride；Use technique for atomic layer deposition, bottom electrode titanium nitride layer is sequentially depositing growth memory storage layer；The method using d.c. sputtering, physical vapour deposition (PVD) or photoetching forms the upper electrode of memristor；The memristor structure of the present invention, under pulse voltage effect, shows the Learning and Memory function of the analog neuron synapse of excellence；Being provided simultaneously with multiple-state storage function and the ability of analog neuron synapse, manufacturing process is simple, reliable, and can realize the step coverage of high-aspect-ratio, it is simple to large-scale industrial production manufacture.
Description
Technical field
The invention belongs to microelectronics technology, particularly a kind of nano-film memristor and preparation method thereof.
Background technology
Memristor, also known as memory resistor, is that the 4th kind behind relay resistance, electric capacity and inductance entrance mainstream electronic field is basic
Passive electric circuit element, owing to it is as variable resistance, it is possible to " remembeing " both end voltage, changes by changing both end voltage
The size of current passed through.Therefore, memristor is actually a kind of nonlinear resistance having memory function, can serve as storage unit
Part.
As far back as 1971, the scientist Cai Shaotang of Chinese origin professor of Univ California-Berkeley was at research electric charge, electricity
When stream, relation between voltage and magnetic flux, from Circuit theory, disclose the existence of memristor.This concept of memristor proposes
After nearly 40 years, on the basis of widely studied to resistance-variable storing device, real memory resistor just in 2008 by Hewlett-Packard
Finding, work is published on Nature periodical, causes the sensation of academia and industrial quarters.To existing memory resistor and system
Research shows, the material system that memristor system relates to is the abundantest, also contains the Physiochemical mechanism of complexity.The few Chinese bush cherry of Cai recently
Redefine again to memristor system, it is believed that every resistive system being capable of similar Lissajous curve all should belong to
Memristor.One typical feature of memristor is, under electric field action, system can reflect outfield by the change of resistance state
The history loaded, therefore has " memory " function, and using this feature as memory resistor or a basic criterion of system,
Making " memory resistor resistance state is with the response in outfield " to become the status of equal importance with the relation of " electricity and magnetic flux ", this becomes
One important criterion of memory resistor.
Memristor as a kind of brand-new storage concept, relevant research be in flourish in, lack high-quality recall
Resistance device material system and the extensive memristor manufacturing technology compatible with microelectronic technique, become one of restriction memristor development
Bottleneck.
Ald (ALD) is substantially a kind of special chemical vapor deposition (CVD) method, is by vaporous precursors
Pulse is alternately passed through reative cell, and chemical absorption of surface reaction occurs on depositing base, thus the method forming thin film.Before
Drive the body chemisorbed on surface and have from restricted and self-saturation feature, therefore can be controlled by the cycle-index of reaction
The thickness of made membrane.For conventional deposition processes, ald, is lower temperature growth process, can tune accurate to thickness
Control in nanometer, sub-nanometer scale, and there is three-dimensional conformability and large-area uniformity, the international semiconductor TIA of excellence
(ITRS) using ALD and metal organic chemical vapor deposition, plasma enhanced chemical vapor deposition side by side as with microelectronics work
The growing technology that skill is compatible, has been used to the preparation of gate medium titanium dioxide hafnio ultrathin membrane in cmos device.
Due to the memristor time memory characteristic to resistance so that it is at sunykatuib analysis, IC design, multi-state memory
Have broad application prospects etc. various fields.Therefore, the artificial intelligence fields such as the calculating of class brain, neutral net are had become as new
Study hotspot.Exploitation high-quality memristor material system and preparation technology are the key points of the art.
Summary of the invention
The present invention provides a kind of nano-film memristor and preparation method thereof, memristor structure under pulse voltage effect,
Also show the Learning and Memory function of the analog neuron synapse of excellence；Simultaneously by ALD technique, can conveniently regulating and controlling coupled double-layer
The content of Lacking oxygen in oxide.
The technical solution adopted in the present invention is: a kind of nano-film memristor, including substrate, described substrate depends on
Secondary for bottom electrode, memory storage layer, upper electrode；Described memory storage layer the most successively by by alumina layer, zinc oxide/
The coupled double-layer thin film that hafnium oxide or hafnium oxide/aluminium oxide are constituted.
Further, described nano-film memristor, it is characterised in that described substrate is SiO2/ Si substrate.
Further, described bottom electrode is titanium nitride.
Further, the thickness of described bottom electrode is 30-200nm.
Further, described power on extremely conducting metal, metal alloy or conductive metallic compound.
Further, the thickness of described upper electrode is 50-200nm.
Further, described conducting metal is Al, Ti, Ni, Ru, Cu, Ag, W, Au or Pt；Described metal alloy is Pt/Ti
Alloy, Cu/Ti alloy, Cu/Au alloy or Cu/Al alloy.
Further, in described memory storage layer, the aluminum oxide film film thickness of neighbouring TiN electrode is fixed as 3nm；Oxygen on it
Changing hafnium/zinc oxide bilayer film thickness is 4-8nm/4-8nm, and described hafnium oxide/aluminium oxide bilayer film thickness is 4-
8nm/4-8nm。
The invention also discloses the preparation method of a kind of nano-film memristor, specifically comprise the following steps that
(1) with silicon chip as substrate, plasma enhanced atomic is utilized first to prepare bottom electrode titanium nitride；
(2) use technique for atomic layer deposition, bottom electrode titanium nitride layer is sequentially depositing growth aluminum oxide film, zinc-oxide film
The memory storage layer constituted with hafnia film；
(3) method using d.c. sputtering, physical vapour deposition (PVD) or photoetching forms the upper electrode of memristor.
The present invention is relative to the beneficial effect of prior art:
(1) by ALD technique, can the content of Lacking oxygen in conveniently regulating and controlling oxide memory storage layer.Thus, by changing device
Upper applying voltage direction and size, can obtain the high low resistance state of difference of device, and then realize multiple-state storage.
(2) the memristor structure of the present invention is under pulse voltage effect, shows the study of the analog neuron synapse of excellence
With memory function；It is provided simultaneously with multiple-state storage function and the ability of analog neuron synapse of excellence；
(3) preparation technology of the present invention, make use of the technique for atomic layer deposition that traditional CMOS technology compatibility is novel, technique letter
Single, reliable, the Al of growth2O3Thin film and HfO2And ZnO film uniformity, compactness and conformability are excellent, can accuracy controlling three
The thickness of layer nano thin-film, and the step coverage of high-aspect-ratio can be realized, it is simple to large-scale industrial production manufacture.
Accompanying drawing explanation
Fig. 1 is Pt/HfO of the present invention2/ZnO/Al2O3/ TiN memristor organigram；
Fig. 2 is Pt/HfO in the embodiment of the present invention 12/ZnO/Al2O3/ TiN memristor device is swept at direct current when being in original state
Retouch the current-voltage characteristic curve test figure under voltage.
Fig. 3 is Pt/HfO in the embodiment of the present invention 12/ZnO/Al2O3Reset continuously under/TiN memristor DC voltage sweep-
Current-voltage characteristic curve test figure under continuous reset state.
Fig. 4 is Pt/HfO in the embodiment of the present invention 12/ZnO/Al2O3Electric current-electricity under/TiN memristor pulse voltage effect
Pressure characteristic curve test figure.
Fig. 5 is Pt/HfO in the embodiment of the present invention 12/ZnO/Al2O3Electricity when/TiN memristor structure electric current changes over
The increasing or decreasing change test figure of stream.
Fig. 6 is Pt/HfO in the embodiment of the present invention 12/ZnO/Al2O3In/TiN memristor structure, higher pulse voltage or
The pulse voltage of person's last longer all can make the column test figure that current changing rate increases.
Fig. 7 is Pt/HfO in the embodiment of the present invention 12/ZnO/Al2O3In/TiN memristor structure, current value is with increasing continuously
Or the pulse voltage number of times that reduces continuously and the test figure that changes.
Fig. 8 is Pt/Al in the embodiment of the present invention 32O3/HfO2/Al2O3Electric current under/TiN memristor pulse voltage effect-
Voltage response test figure.
Fig. 9 is Pt/Al in the embodiment of the present invention 32O3/HfO2/Al2O3In/TiN memristor structure, higher pulse voltage
Or the pulse voltage of last longer all can make the column test figure that current changing rate increases.
Figure 10 is Pt/Al in the embodiment of the present invention 32O3/HfO2/Al2O3In/TiN memristor structure, current value is with increasing continuously
The pulse voltage number of times added or reduce continuously and the test figure changed.
Figure 11 is Au/Al in the embodiment of the present invention 52O3/HfO2/Al2O3/ TiN memristor continuous impulse scanning voltage effect
Under current-voltage characteristic curve test figure.
Figure 12 is Ru/Al in the embodiment of the present invention 62O3/ZnO/HfO2Under/TiN memristor continuous impulse scanning voltage effect
Current-voltage characteristic curve test figure.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiment of the present invention is described further.
Embodiment 1
(1) to clean SiO2/ Si silicon chip is substrate, utilizes plasma enhanced atomic first to prepare bottom electrode TiN, specifically
Step is as follows:
TiN growth temperature is 400 DEG C, with TiCl4、NH3Plasma respectively as Ti and N source, wherein TiCl4Pulse time
Between be 0.1 second, carrier gas is High Purity Nitrogen (99.999%) and simultaneously as purgative gas, and its scavenging period is 4 seconds；NH3Plasma
Carrier gas be high-purity argon (99.999%), its burst length is 24 seconds, and High Purity Nitrogen is 6 seconds as the scavenging period of purgative gas,
TiCl4Source temperature be room temperature, in this enforcement, TiN thickness is 30nm.
(2) technique for atomic layer deposition is used to grow lower floor's aluminum oxide film, zinc-oxide film successively in bottom electrode TiN layer
The memory storage layer constituted with hafnia film, atom layer deposition process condition is: functional membrane growth temperature is 250 DEG C, with three
Aluminium methyl, diethyl zinc, four-dimethylamino ethylamine base hafnium and secondary deionized water are respectively as the source of Al, Zn, Hf and O, source, each road
Burst length be 0.1 second, carrier gas is High Purity Nitrogen (99.999%) and simultaneously as purgative gas, and its scavenging period is 4 seconds.
Four-dimethylamino ethylamine base hafnium source temperature is 155 DEG C, trimethyl aluminium, diethyl zinc and H2O source temperature is all room temperature.
Lower floor aluminium oxide (Al in (bottom electrode) TiN layer in the present embodiment2O3) film thickness is 3nm；Zinc oxide (ZnO)
Film thickness is 5nm；Hafnium oxide (HfO2) film thickness is 5nm.
In actual mechanical process, lower floor's aluminium oxide thickness keeps 3nm constant, and its performance during the two thickness correspondent equal
Optimum, when ZnO value is 5nm, HfO2Also it is 5nm,Total memory layer thickness is 13nm.
(3) with the method for d.c. sputtering, Pt being formed upper electrode, its thickness is 100nm, i.e. obtains complete memristor knot
Structure, as it is shown in figure 1, be followed successively by from top to bottom, upper electrode, hafnia film, zinc-oxide film, aluminum oxide film, bottom electrode, silicon
Substrate.
In actual operating process, it is possible to use the conductive metallic materials such as Au or Ru, sink with d.c. sputtering, physical vapor
The techniques such as long-pending or photoetching form electrode on resistance-variable storing device.
By Semiconductor Parameter Analyzer, the electrology characteristic of the memristor that the present embodiment obtains is tested, test result
As shown in Fig. 2,3,4,5,6,7.
Wherein Fig. 2 is that embodiment memristor current-voltage when being in original state under dc sweeps voltage effect is special
Linearity curve test figure, device shows typical ambipolar resistive switching behaviour, is more than through investigating its on-off ratio (HRS/LRS)
10。
Fig. 3 is that under the present embodiment memristor DC voltage sweep, the current-voltage under replacement-continuous reset state is special continuously
Linearity curve test figure.General resistance-variable storing device can only be at two different voltages, it is achieved the storage of two different resistances.This reality
Execute example, from the beginning of 1.15V, often increase 0.05V and resistance just can be made to improve a step, until resistance value reaches saturated shape during 1.7V
State, resistance value no longer changes, and obtains 11 different resistance values altogether.Stopping in any resistance, state does not changes, until next
Individual scanning voltage is come.Meanwhile, resistance can load reverse restriction electric current and is allowed to gradually restore.The most same device can
Realize the storage of different stage.This setting continuously limits electric current or arranges resetting voltage continuously so that device is from high-impedance state
Vary continuously to low resistance state or to be varied continuously to high-impedance state for realizing the multistage storage of device by low resistance state be extremely important
's.
Current-voltage characteristic curve test under Fig. 4 the present embodiment memristor pulse voltage effect.Fig. 4 is at continuous arteries and veins
(forward is 0 to 1.4V, and pulse width is 100 milliseconds to rush voltage；Being reversed 0 to-0.6V, pulse width is 100 milliseconds) scanning
Under, in device, current value continuously reduces respectively or increases continuously.In addition to multiple-state storage step by step, memristor storage numerical digit letter
Cease the most extremely important.General resistance-variable storing device can only realize the binary storage between " 0 " and " 1 ", and in this example
Memristor, device has only to just to allow with the pulse of 1.4V resistance improve a step, then can improve again with a 1.4V pulse again
One step.Just making device enter saturation with 6 such pulses, resistance no longer changes.Stopping in any resistance, state does not changes
Become, until next pulse is come.Reverse six pulse can also be loaded be allowed to restore.That is each storage in this example
Unit has 6 different conditions, which achieves multi-system storage, and this example can realize at least senary storage, so that storage
Density is greatly increased.Meanwhile, this is also very similar to the multiple case of neuron memory, for realizing (emulation) similar biological neural
The function of synapse is laid a good foundation.
According to the concept of memristor, the memory resistor that this example is mentioned is can to distinguish with continually varying character based on resistance
In resistive formula memorizer, and the quantity of electric charge that flows through is depended in this change, and its change simultaneously can keep after power is turned off.This
The nonlinear transmission characteristic (transfer rate of nerve synapse stimulates with outer signals and changes) of one characteristic and nerve synapse
Similar.In order to clearly demonstrate the trend of such a change, depict Fig. 5 electric current and voltage versus time curve figure.
As it is shown in figure 5, be Pt/HfO in the embodiment of the present invention2/ZnO/Al2O3/ TiN memristor structure electric current changes over (pulse time
Number increase) time electric current increasing or decreasing change test figure, its numerical value is corresponding with Fig. 4.It is obvious that along with pulse (voltage) is secondary
The increase (minimizing) of number, pulse current reduces (increasing) accordingly, and corresponding resistance value is just to increase (minimizing).This feature
Simulating the function of nerve synapse completely, device creates memory to its charge number flowed through.
The electric conductivity size of this device can also be by adjusting the persistent period of the potential pulse applied and the big of amplitude
Little carry out.Higher amplitude and long-term pulse can make electric conductivity (current values) be increased or decreased faster,
As shown in Figure 6.If we are using the electric conductivity of memory resistor as a synapse weight, above-mentioned phenomenon is then dashed forward with biological neuron
Touch the nonlinear transmission characteristic shown and there is close similarity.Fig. 6 is in embodiment memristor structure, higher pulse
The pulse voltage of voltage or last longer all can make the column test figure that current changing rate increases.
Fig. 7 is in embodiment memristor structure, and current value becomes with the pulse voltage number of times increased continuously or reduce continuously
The test figure changed.
Knowable to result illustrated above, the electrology characteristic that the memory resistor in the present embodiment is had, i.e. resistance can connect
Continue and change and resistance value state can be kept, be that typical case's memristor is exclusive.
Memory resistor in the present embodiment is expected in terms of realizing multistage multiple-state storage and analog neuron synapse realize dashing forward
Broken.
Embodiment 2
Except the lower floor aluminium oxide (Al in bottom electrode TiN layer in the present embodiment2O3) film thickness is 3nm；Zinc oxide (ZnO) is thin
Film thickness is 4nm；Hafnium oxide (HfO2) film thickness is 4nm, other detailed description of the invention are identical with above-described embodiment 1.
Embodiment 3
(1) to clean SiO2/ Si silicon chip is substrate, utilizes plasma to strengthen ald growth 30nm thickness hearth electrode TiN；
(2) utilize ald grow successively on hearth electrode TiN the aluminum oxide film of 3nm, 5nm, 5nm, hafnia film,
Aluminum oxide film, total memory layer thickness is 13nm；
(3) utilize the Pt of Q150T S (Quorum Technologies) sputter coating instrument deposition metal 200nm as powering on
Pole, i.e. obtains this memory resistor structure, as it is shown in figure 1, be followed successively by from top to bottom, upper electrode, aluminum oxide film, and hafnium oxide is thin
Film, aluminum oxide film, bottom electrode, silicon chip.
Utilize Semiconductor Parameter Analyzer to combine Cascade probe station and this memory resistor is carried out electrical performance testing, survey
Test result as shown in Figure 8,9, 10, its result and above-mentioned HfO2/ZnO/Al2O3Performance be similar to, have equally multiple-state storage effect and
Analog neuron synaptic function.
Embodiment 4
Except the lower floor Al in bottom electrode TiN layer in the present embodiment2O3Film thickness is 3nm, HfO2Film thickness is 8nm, upper strata
Al2O3Film thickness is 8nm, and total memory layer thickness is 19nm, and other detailed description of the invention are identical with above-described embodiment 3..
Embodiment 5
The present embodiment uses Au conductive metallic material, is lithographically formed the upper electrode of memory resistor after using d.c. sputtering.
(1) to clean SiO2/ Si silicon chip is substrate, utilizes plasma enhanced atomic first to prepare bottom electrode TiN,
In this enforcement, TiN thickness is 60nm.
(2) technique for atomic layer deposition is used to grow lower floor's aluminum oxide film, hafnia film successively in bottom electrode TiN layer
The memory storage layer constituted with aluminum oxide film, the lower floor Al in hearth electrode TiN layer in the present embodiment2O3Film thickness is 3nm,
HfO2Film thickness is 4nm, upper strata Al2O3Film thickness is 4nm, and total memory layer thickness is 11nm.
(3) with the method for d.c. sputtering then photoetching, Au being formed upper electrode, its thickness is 200nm, i.e. obtains complete
Memristor structure.
Figure 11 is the current-voltage characteristic curve test figure under the present embodiment memristor continuous impulse scanning voltage effect.
At continuous impulse voltage, (forward is 0 to 1.2V, and pulse width is 100 milliseconds；Being reversed 0 to-0.6V, pulse width is 100 millis
Second) scanning under, in device, current value continuously reduces respectively or increases continuously.
Embodiment 6
The present embodiment uses Ru conductive metallic material, uses the technique of physical vapour deposition (PVD) to form the upper electrode of memory resistor.
(1) to clean SiO2/ Si silicon chip is substrate, utilizes plasma enhanced atomic first to prepare bottom electrode TiN,
In this enforcement, TiN thickness is 200nm.
(2) technique for atomic layer deposition is used to grow lower floor's aluminum oxide film, hafnia film successively in bottom electrode TiN layer
The memory storage layer constituted with aluminum oxide film, the lower floor Al in hearth electrode TiN layer in the present embodiment2O3Film thickness is 3nm；
ZnO film thickness is 8nm；Upper strata HfO2Film thickness is 8nm, and total memory layer thickness is 19nm.
(3) with the method for physical vapour deposition (PVD), Ru being formed upper electrode, its thickness is 50nm, i.e. obtains complete memristor
Structure.
Figure 12 is the current-voltage characteristic curve test figure under the present embodiment memristor continuous impulse scanning voltage effect.
At continuous impulse voltage, (forward is 0 to 1.6V, and pulse width is 100 milliseconds；Being reversed 0 to-0.4V, pulse width is 100 millis
Second) scanning under, in device, current value continuously reduces respectively or increases continuously.
Claims (9)
1. a nano-film memristor, including substrate, it is characterised in that described substrate is followed successively by bottom electrode, memory
Accumulation layer, upper electrode；Described memory storage layer the most successively by alumina layer, zinc oxide/hafnium oxide or hafnium oxide/
The coupled double-layer thin film that aluminium oxide is constituted.
Nano-film memristor the most according to claim 1, it is characterised in that described substrate is SiO2/ Si substrate.
Nano-film memristor the most according to claim 1, it is characterised in that described bottom electrode is titanium nitride.
Nano-film memristor the most according to claim 3, it is characterised in that the thickness of described bottom electrode is 30-
200nm。
Nano-film memristor the most according to claim 1, it is characterised in that described power on extremely conducting metal, gold
Belong to alloy or conductive metallic compound.
Nano-film memristor the most according to claim 5, it is characterised in that the thickness of described upper electrode is 50-
200nm。
Nano-film memristor the most according to claim 5, it is characterised in that described conducting metal is Al, Ti, Ni,
Ru, Cu, Ag, W, Au or Pt；Described metal alloy is Pt/Ti alloy, Cu/Ti alloy, Cu/Au alloy or Cu/Al alloy.
Nano-film memristor the most according to claim 1, it is characterised in that neighbouring TiN in described memory storage layer
The aluminum oxide film film thickness of electrode is fixed as 3nm；Described hafnium oxide/zinc oxide bilayer film thickness is 4-8nm/4-8nm；
Described hafnium oxide/aluminium oxide bilayer film thickness is 4-8nm/4-8nm.
9. the preparation method of a nano-film memristor, it is characterised in that specifically comprise the following steps that
(1) with silicon chip as substrate, plasma enhanced atomic is utilized first to prepare bottom electrode titanium nitride；
(2) use technique for atomic layer deposition, bottom electrode titanium nitride layer is sequentially depositing growth aluminum oxide film, zinc oxide/oxygen
Change hafnium thin film or the memory storage layer of hafnium oxide/aluminium oxide composition；
(3) method using d.c. sputtering, physical vapour deposition (PVD) or photoetching forms the upper electrode of memristor.
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