CN108365089A - Prepared by a kind of solution combustion method has analog- and digital- multi-functional NiO bases memory resistor and preparation method - Google Patents
Prepared by a kind of solution combustion method has analog- and digital- multi-functional NiO bases memory resistor and preparation method Download PDFInfo
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- CN108365089A CN108365089A CN201810011585.5A CN201810011585A CN108365089A CN 108365089 A CN108365089 A CN 108365089A CN 201810011585 A CN201810011585 A CN 201810011585A CN 108365089 A CN108365089 A CN 108365089A
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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 without a potential-jump barrier or surface barrier, 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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- 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 without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/021—Formation of the switching material, e.g. layer deposition
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Abstract
The present invention relates to the technical fields of microelectronics, have analog- and digital- multi-functional NiO bases memory resistor and preparation method more particularly, to prepared by a kind of solution combustion method.Prepared by a kind of solution combustion method has analog- and digital- multi-functional NiO bases memory resistor, wherein from the bottom to top, including substrate, metallic bottom electrode, NiO base resistives dielectric layer, metallic top electrode.The preparation of the NiO base memory resistors, it is characterized in that NiO base dielectric layers utilize solution combustion method, it is prepared using coating process, advantage is that can print technique using solution combustion method prepares resistive medium layer film, the technique that film is prepared with traditional vacuum deposition is compared, and film-forming temperature is low, equipment is simply not necessarily to vacuum, prepared by low cost, suitable large area.
Description
Technical field
The present invention relates to the technical fields of microelectronics, have simulation more particularly, to prepared by a kind of solution combustion method
With the multi-functional NiO bases memory resistor of number and preparation method.
Background technology
Memristor is the both ends nonvolatile semiconductor memory member based on electric resistance changing, it can be divided into two types：Analogue type
Memristor and numeric type memristor.Numeric type memristor has simple in structure, density height, low in energy consumption, non-volatile as a new generation
Property memory is widely studied.Analogue type memristor has the characteristics that resistance is continuously adjustable, can be used as analogue type non-volatile memory
Device is applied on programmable analog circuit, is applied in the novel calculating such as neural network and artificial intelligence especially as artificial synapse
The fields such as energy.
Memory resistor is simple in structure, usually medium/metal layer
The sandwich structure of/metal, transition metal oxide（ZnO, NiO, TiO, TaO, NbO etc.）Medium as memory resistor
Layer, is widely used and reports, preparation method is usually the vacuum methodes such as sputtering, thermal oxide, of high cost.In recent years, due to molten
Liquid method prepare film have many advantages, such as it is at low cost, simple for process and with flexible electronic good compatibility, attract wide attention.Resistive
Mechanism be commonly referred to be the formation and fracture of conductive filament in resistive dielectric layer.Memristor based on filament conductive mechanism is general
Unexpected SET/RESET transformations, i.e. numeric type memristor is presented.In contrast, the resistive mechanism of analogue type memory resistor is not still
It is clear.In particular, having the individual devices of analog- and digital- resistive characteristic to be seldom reported simultaneously.
Invention content
The present invention is at least one defect overcome described in the above-mentioned prior art, provides a kind of tool prepared by solution combustion method
There are analog- and digital- multi-functional NiO bases memory resistor and preparation method, the memory resistor of the invention low, work with manufacturing cost
Skill simple advantage has analog- and digital- multi-functional resistive characteristic in characteristic, can substantially reduce digital-to-analog mixing memristor
The process complexity of circuit.
The technical scheme is that：A kind of solution combustion method preparation is recalled with analog- and digital- multi-functional NiO bases
Hinder device, wherein from the bottom to top, including substrate, metallic bottom electrode, NiO base resistives dielectric layer, metallic top electrode.
The present invention uses solwution method, and the dielectric layer of memory resistor is prepared using coating process.
We are prepared for the memristor based on NiO by solution combustion method coating process in the present invention.Recall in single NiO
The multi-functional characteristics such as analog- and digital- bipolarity resistive are obtained in resistance unit simultaneously.This work is expected to reduce by simulation/number
The manufacture complexity of the hydrid integrated circuit of word memristor composition, hardware support is provided for the development of neural computer.
Further, the resistive dielectric layer is the NiO base films prepared using solution combustion method coating process, is
The polycrystalline state film of cubic phase.
Further, the thickness of the NiO base medium layer films is 30nm-100nm, and preparation temperature 300 to 400 is spent.
Further, metallic bottom electrode is the big inert metal of work function, such as Au, Pt, is easy and p-type NiO dielectric layers
Form Ohmic contact；Metallic top electrode is the small metal of work function, such as Ag, Cu, is easy to form Xiao Te with p-type NiO dielectric layers
Base contacts.
A kind of preparation method with analog- and digital- multi-functional NiO bases memory resistor prepared by solution combustion method,
In, include the following steps：
S1. solvent is done with alcohols, incendiary agent is done with acetylacetone,2,4-pentanedione etc., stabilizer is done with ammonium hydroxide, oxidant is done with metal nitrate nickel
And metal ion source, stable presoma is formed by techniques such as stirring, filtering, agings；
S2. the substrate for being coated with metallic bottom electrode is subjected to surface treatment and forms water-wetted surface；
S3. solution combustion method coating process spin coating NiO bases resistive dielectric layer on substrate is then used；
S4. it according to the requirement of thickness of dielectric layers, can be repeatedly coated with；
S5. subsequent heat treatment mode is used, the reaction of presoma is promoted, forms NiO films.
Specific technical solution：
（1）Utilize electron beam evaporation plating system evaporation metal hearth electrode；Wherein, metallic bottom electrode is using the big metal of work function, with p
Type NiO dielectric layers form Ohmic contact；
（2）Solution combustion method coating prepares NiO resistive medium layer films, wherein：
A, using alcohols as solvent, acetylacetone,2,4-pentanedione is incendiary agent, and ammonium hydroxide is stabilizer, and nickel nitrate is oxidant and the sources Ni；By stirring
It mixes, filter, the techniques such as aging, forming solution presoma.
B, the substrate for being coated with metallic bottom electrode is handled by way of plasma or UV, forms water-wetted surface；
C, using coating method, NiO presomas are coated on hearth electrode, substrate, which is then transferred to baking in heating plate, is handled；
According to the requirement of film thickness, repeats the above process and be repeatedly coated with；Every time before coating, to the film that toasted carry out table again
Face hydrophily processing；
D, in order to keep film reaction more abundant, increase the compactness of film, film is finally spent at 300 degree -400 in range and is carried out
The annealing of air atmosphere；
（3）Top electrode is prepared, and graphical；Wherein, top electrode is using the small metal of work function, the shape between p-type NiO dielectric layers
At Schottky contacts；
In the present invention, before carrying out Forming using high voltage, which shows resistance and continuously enlarges or reduce non-
Linear change characteristic.Analysis on Mechanism thinks to form Schottky between the NiO of p-type semiconductor and the metallic top electrode of low work function
Contact, the migration of oxygen defect changes the Schottky barrier at interface, so as to cause the nonlinear change of resistance.On the other hand, it adopts
After carrying out Forming operations to device with high voltage, device shows the digital resistive characteristic of sudden change of resistivity, mechanism composite guide
Electric filament mechanism.Multi-functional memristor characteristic provides hardware supported for the development of the technologies such as neural computing, is expected to reduce mould
The manufacture complexity of the hybrid circuit of quasi-/digital memristor composition.
Compared with prior art, advantageous effect is：1）The preparation of NiO dielectric layers uses solwution method, utilizes coating process system
It is standby, it is simple for process, at low cost and good with flexible circuit processing compatibility；2）The NiO bases memory resistor of preparation is in the same resistive
There are analog- and digital- two kinds multi-functional resistive characteristics simultaneously in unit, be expected to reduce the integrated electricity of analog/digital hybrid memristor
The manufacture complexity on road simulates development of the non-linear resistive characteristic also for neural computing system and provides hardware support.
Description of the drawings
Fig. 1 is Si/SiO in the embodiment of the present invention2The structural schematic diagram of/Ti/Pt/NiO/Ag memristors.
Fig. 2 is Si/SiO in the embodiment of the present invention2The current value of/Ti/Pt/NiO/Ag memristors is with continuously just（It is negative）It sweeps
Voltage is retouched to be gradually reduced（Increase）Trend chart.
Fig. 3 is Si/SiO in the embodiment of the present invention2/ Ti/Pt/NiO/Ag memristors, electric Forming processes, first time and
Current-voltage characteristic curve figure under 100th DC voltage sweep.
Specific implementation mode
The attached figures are only used for illustrative purposes and cannot be understood as limitating the patent；It is attached in order to more preferably illustrate the present embodiment
Scheme certain components to have omission, zoom in or out, does not represent the size of actual product；To those skilled in the art,
The omitting of some known structures and their instructions in the attached drawings are understandable.Being given for example only property of position relationship described in attached drawing
Illustrate, should not be understood as the limitation to this patent.
Fig. 1 is Si/SiO in the embodiment of the present invention2The structural schematic diagram of/Ti/Pt/NiO/Ag memristors.Including substrate Si/
SiO2, hearth electrode Ti/Pt, resistive dielectric layer NiO, top electrode Ag.Si/SiO in the embodiment of the present invention2/ Ti/Pt/NiO/Ag memristors
The specific preparation process flow of device is as follows：
1. substrate Si/SiO that couple present invention uses2Organic washing is carried out, organic contaminations are removed；
2. hearth electrode Ti/Pt, thickness 50nm/20nm is deposited using electron beam evaporation plating system；
3. preparing resistive dielectric layer NiO using solution combustion coating process on hearth electrode, specific technique is as follows：
1）Using dimethoxy-ethanol as solvent, acetylacetone,2,4-pentanedione is fuel, and ammonium hydroxide is stabilizer, and nickel nitrate is nickel source and oxidant,
Above-mentioned mixed solution is stirred 20 hours in air, and is filtered by 0.2 μm of syringe, aging 24 hours is formed stable
Solution presoma；
2）The substrate for being coated with metallic bottom electrode is subjected to oxygen gas plasma processing, forms water-wetted surface；
3）It is coated with precursor solution on the hearth electrode surface by hydrophilic modifying by spin coating proceeding, spin coating rotating speed is 4300rpm,
Time is 30s, then transfers substrates on hot plate and is toasted 30 minutes under 300 degree；Thickness is about 10nm；
4）In order to obtain the NiO films that thickness is 50nm, by step 3）It is repeated 5 times；In order to increase the adhesiveness of film, in spin coating
Film surface is handled with oxygen gas plasma to improve the hydrophily on surface again before lower thin film；
5）In order to increase the compactness of film, finally film is annealed 0.5 hour in tube furnace, temperature is 350 DEG C, and atmosphere is
Air.
4. utilizing mask plate, top electrode Ag, thickness 160nm are crossed using electron beam evaporation system steaming；
The test of electric property is carried out to the memory resistor obtained in the present embodiment by Agilent B1500A semiconductor parameters instrument,
The result of test is as shown in Figures 2 and 3.
Fig. 2 is Si/SiO in the embodiment of the present invention2/ Ti/Pt/NiO/Ag memristors are scanned in continuous back bias voltage and positive bias
Under current-voltage（I-V）Curve.During the test, Ag top electrodes are biased and hearth electrode Pt is kept to be grounded.Even
Under the scanning of continuous positive bias voltage（0→1V→0V）Electric current is gradually reduced.On the contrary, being scanned in continuous back bias voltage（0 V→-1
V→0 V）Under, electric current gradually increases.Device shows as nonlinear resistance conversion characteristic, i.e. artifical resistance conversion characteristic.
Fig. 3 is Si/SiO in the embodiment of the present invention2The high voltage electricity Forming characteristics of/Ti/Pt/NiO/Ag memristors, with
And after device Forming, for the first time with the current-voltage characteristic curve under the 100th DC voltage sweep.The device passes through
After high voltage electricity Forming processes, typical mutation formula resistance variations, i.e. numeric type resistance transformation characteristic are showed.Limitation electricity
Stream is 1mA, and when scanning voltage is 0 to -1.5V, resistance is at the voltage of about -0.7V from low resistance state（LRS）It is converted to high-impedance state
（HRS）, Set processes occur at 0.5V, resistance is changed into LRS by HRS.Memory window device after 100 scan cycles is special
Property remain unchanged, illustrate the digital resistance variations have repeatability.
The device is before electric Forming, and current characteristics shows Schottky barrier rectification characteristic, and with scanning times
Variation, continuity variation is occurring for the Schottky barrier of NiO and the interfaces Ag, therefore speculates that its nonlinear resistance changes（Mould
Quasi- resistance variations）Mechanism be, oxygen related defects interface aggregates or diffusion cause schottky barrier height change caused by；
And device, after electric Forming, low resistance state shows ohms current characteristic, meets conductive filament model；
In conclusion Si/SiO in the embodiment of the present invention2/ Ti/Pt/NiO/Ag memristors are prepared based on solwution method coating process,
With advantage simple for process, at low cost.It is artifical resistance conversion characteristic before high voltage Forming；Through too high voltages
After Forming, device shows to be mutated the i.e. digital resistance transformation characteristic of formula resistance variation characteristic.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
All any modification, equivalent and improvement etc., should be included in the claims in the present invention made by within the spirit and principle of invention
Protection domain within.
Claims (5)
1. prepared by a kind of solution combustion method has analog- and digital- multi-functional NiO bases memory resistor, which is characterized in that under
It is supreme, including substrate, metallic bottom electrode, NiO base resistives dielectric layer, metallic top electrode.
2. prepared by a kind of solution combustion method according to claim 1 has analog- and digital- multi-functional NiO bases memristor
Device, it is characterised in that：The resistive dielectric layer is the NiO base films prepared using solution combustion method coating process, is
The polycrystalline state film of cubic phase.
3. prepared by a kind of solution combustion method according to claim 1 has analog- and digital- multi-functional NiO bases memristor
Device, it is characterised in that：The thickness of the NiO base medium layer films is 30nm-100nm, and preparation temperature 300 to 400 is spent.
4. prepared by a kind of solution combustion method according to claim 1 has analog- and digital- multi-functional NiO bases memristor
Device, it is characterised in that：The metallic bottom electrode is the big inert metal of work function, is easy and p-type NiO dielectric layers form Europe
Nurse contacts；Metallic top electrode is the small metal of work function, is easy to form Schottky contacts with p-type NiO dielectric layers.
5. prepared by a kind of solution combustion method described in claim 1 has analog- and digital- multi-functional NiO bases memory resistor
Preparation method, which is characterized in that prepare NiO dielectric layers and be as follows：
S1. solvent is done with alcohols, incendiary agent is done with acetylacetone,2,4-pentanedione etc., stabilizer is done with ammonium hydroxide, oxidant is done with metal nitrate nickel
And metal ion source, stable presoma is formed by techniques such as stirring, filtering, agings；
S2. the substrate for being coated with metallic bottom electrode is subjected to surface treatment and forms water-wetted surface；
S3. solution combustion method coating process spin coating NiO bases resistive dielectric layer on substrate is then used；
S4. it according to the requirement of thickness of dielectric layers, can be repeatedly coated with；
S5. subsequent heat treatment mode is used, the reaction of presoma is promoted, forms NiO films.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585647A (en) * | 2018-10-22 | 2019-04-05 | 西安理工大学 | Nickel oxide/titanium oxide/nickel oxide multi-heterostructure-layers memristor preparation method |
| CN109860390A (en) * | 2019-02-28 | 2019-06-07 | 西交利物浦大学 | RRAM device and preparation method thereof based on graphene oxide |
| CN109978019A (en) * | 2019-03-07 | 2019-07-05 | 东北师范大学 | Image steganalysis simulation mixes memristor equipment and preparation with number, realizes STDP learning rules and image steganalysis method |
| CN110571328A (en) * | 2019-08-14 | 2019-12-13 | 天津大学 | Bipolar resistance switch memory based on nickel oxide film and preparation method |
| CN111613662A (en) * | 2020-05-27 | 2020-09-01 | 东北大学 | Bias-induced collinear antiferromagnetic material generated spin-polarized current and regulation and control method thereof |
| US11456418B2 (en) | 2020-09-10 | 2022-09-27 | Rockwell Collins, Inc. | System and device including memristor materials in parallel |
| US11462267B2 (en) | 2020-12-07 | 2022-10-04 | Rockwell Collins, Inc. | System and device including memristor material |
| US11469373B2 (en) | 2020-09-10 | 2022-10-11 | Rockwell Collins, Inc. | System and device including memristor material |
| US11631808B2 (en) | 2020-12-07 | 2023-04-18 | Rockwell Collins, Inc. | System and device including memristor material |
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| US8283649B2 (en) * | 2009-07-28 | 2012-10-09 | Hewlett-Packard Development Company, L.P. | Memristor with a non-planar substrate |
| CN102931346A (en) * | 2011-08-12 | 2013-02-13 | 中国科学院微电子研究所 | Memristor device and manufacturing method thereof |
| CN104815983A (en) * | 2015-04-20 | 2015-08-05 | 齐鲁工业大学 | Carbon-coated nickel oxide/metallic nickel and simple synthesis method thereof |
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| US8283649B2 (en) * | 2009-07-28 | 2012-10-09 | Hewlett-Packard Development Company, L.P. | Memristor with a non-planar substrate |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585647A (en) * | 2018-10-22 | 2019-04-05 | 西安理工大学 | Nickel oxide/titanium oxide/nickel oxide multi-heterostructure-layers memristor preparation method |
| CN109585647B (en) * | 2018-10-22 | 2022-10-14 | 西安理工大学 | Preparation method of nickel oxide/titanium oxide/nickel oxide multilayer heterojunction memristor |
| CN109860390A (en) * | 2019-02-28 | 2019-06-07 | 西交利物浦大学 | RRAM device and preparation method thereof based on graphene oxide |
| CN109978019A (en) * | 2019-03-07 | 2019-07-05 | 东北师范大学 | Image steganalysis simulation mixes memristor equipment and preparation with number, realizes STDP learning rules and image steganalysis method |
| CN110571328A (en) * | 2019-08-14 | 2019-12-13 | 天津大学 | Bipolar resistance switch memory based on nickel oxide film and preparation method |
| CN111613662A (en) * | 2020-05-27 | 2020-09-01 | 东北大学 | Bias-induced collinear antiferromagnetic material generated spin-polarized current and regulation and control method thereof |
| CN111613662B (en) * | 2020-05-27 | 2021-06-11 | 东北大学 | Method for regulating and controlling spin polarization current generated by bias-induced collinear antiferromagnetic material |
| US11456418B2 (en) | 2020-09-10 | 2022-09-27 | Rockwell Collins, Inc. | System and device including memristor materials in parallel |
| US11469373B2 (en) | 2020-09-10 | 2022-10-11 | Rockwell Collins, Inc. | System and device including memristor material |
| US11462267B2 (en) | 2020-12-07 | 2022-10-04 | Rockwell Collins, Inc. | System and device including memristor material |
| US11631808B2 (en) | 2020-12-07 | 2023-04-18 | Rockwell Collins, Inc. | System and device including memristor material |
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Application publication date: 20180803 |