CN105576121B - A kind of preparation method of flexible single-layer nano-film memristor - Google Patents
A kind of preparation method of flexible single-layer nano-film memristor Download PDFInfo
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- 229910052737 gold Inorganic materials 0.000 claims description 32
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 30
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- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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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
- H10N70/041—Modification of switching materials after formation, e.g. doping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
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- Manufacturing & Machinery (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of preparation method of flexible single-layer nano-film memristor, with single-layer nano-film memristor, caused hole and ionization oxonium ion under bias are carrier for it, by the change of hole and ionized oxygen ion generation amount, to realize the principle of the change of device resistance, set about in terms of preparation technology simplifies the chemical formulation two with resistive film nano ceramic material, by dispensing the advance sintering step of resistive film ceramic material, from the lower raw material of nano ceramics sintering temperature, with reference to using lower calcining heat；And by with X2+Part substitution Ti4+B position substitutions are carried out, increase the asymmetry and internal hole amount of resistive membrane molecule structure；And use the plated film on green band to form the series technique means such as " flexibility " bottom electrode, preparation technology is simplified, technological process is shortened, improves production efficiency, and energy consumption and manufacturing cost are reduced, greatly improve the memristor performance of memristor.
Description
Technical field
The present invention relates to a kind of preparation method of single-layer nano-film memristor, more particularly to a kind of flexible single-layer nanometer thin
The preparation method of film memristor；Belong to micro-nano electronic device and nonlinear circuit application field.
Background technology
Memristor (memory resistor) is that relay resistance, electric capacity and inductance enter the 4th kind of passive circuit member behind mainstream electronic field
Part, it is a passive electric circuit element related to magnetic flux and electric charge.Early in 1971, international nonlinear circuit and cellular neural
Network theory pioneer, integralities of the Leon Chua (Cai Shaotang) based on Circuit theory in logic, has theoretically foretold memristor
Presence.2008, memristor antetype device was experimentally constructed first by HP Lab, it was confirmed that Leon Chua are relevant
The theory of memristor, cause worldwide strong interest.Memristor has novel non-linear electric property, and has concurrently
The features such as density is high, size is small, low in energy consumption, non-volatile, it is considered to be development new nonvolatile storage technologies of future generation
One of ideal scheme.Thus as the study hotspot in the fields such as information, material.In addition, the resistive behavior of memristor and organism
Neural plasticity has the similitude of height, thus in the bionical device of development nerve synapse and neuromorphic computer etc. tool
It is potential.
The structure of existing memristor is that Hewlett-Packard laboratory researchers publish in May, 2008《It is natural》Magazine
On publish thesis it is middle nano level two-layer titanium dioxide semiconductive thin film is clipped in by between two nano wires made of Pt, Sanming City
Control structure.Well-known memristor modeling is actually a nonlinear resistor for having memory function.Pass through control
The change of electric current processed can change its resistance, if high value is defined as " 1 ", low resistance is defined as " 0 ".Then this resistance can
To realize the function of data storage.Generally acknowledged memristor modeling is nano level scarce by pressing from both sides one layer between two Pt nano wires
Oxygen titanium deoxid film and neutral titanium deoxid film are formed, although simple in construction, switching speed compares relatively low.Although
Memristor research in recent years achieves larger progress, but we will also see, for the circuit element basic as one, recall
Resistance device research just starts to walk, and is mainly manifested in the following aspects：
(1) constantly there are new memristor material and memristor system report, but the memristor model of physics realization at present in recent years
It is also seldom and relatively single, it there is no unified Universal Model that memristor behavior is described.
The memristor in kind reported in recent years is applied both for certain class greatly or simulates certain function, as high density is non-volatile
Property memory, Crossbar Latch (intersect dot matrix gate) technology, analog neuron cynapse, and propose.It is used mostly
The switch models and working mechanism similar with HP memristors, and complex manufacturing technology, cost are high, it is special for research memristor
Property, memristor Circuit theory and design of electronic circuits etc. be without general and universality.
(2) not yet realize and commercially produce at present.
Most researchers be difficult to obtain a real memristor element, cause Many researchers research memristor and
During memristor circuit, the hardware experiments in real physical meaning can not be carried out in default of memristor element, be more to rely on
Emulation or analog circuit carry out experimental study.However, memristor simulation model and analog circuit are from actual memristor characteristic
Differ greatly, the hardware carried out with analog circuit realizes more consider and simulation memristor mathematical modeling and have ignored memristor
The intrinsic physical trait of device.
(3) preparation for the memristor in kind reported, require that height, condition are severe in raw material selection and process of preparing
Quarter, condition in general laboratory or R＆D institution are difficult to the preparation for completing related memristor element in kind.
It is in the prior art, more advanced in the physics realization of memristor, Chinese patent application CN103594620A
A kind of single-layer nano-film memristor and preparation method thereof is disclosed, its mode based on physics realization is prepared with composite bed
The memristor of structure type, specific preparation method：Using CaCO3, SrCO3And TiO3Make raw material, sintered at 900-1300 DEG C
15-240min, prepare Ca(1-x)SrxTiO3-δCeramic material, then with Ca(1-x)SrxTiO3-δMake target (wherein, 0<x<1,0<
δ<3), using magnetically controlled sputter method in Pt/TiO2/SiO2Plated film on/Si substrates, the thickness of plated film is 20-900nm, then through 700-
800 DEG C of heat treatment 10-30min；Finally in Ca(1-x)SrxTiO3-δLast layer electrode is plated on nano thin-film.
The essence of its technical scheme, it is exactly generally：First prepare the Ca as target(1-x)SrxTiO3-δ(wherein, 0<
x<1,0<δ<3) ceramic material, after with the Ca(1-x)SrxTiO3-δCeramic material makees target, using magnetically controlled sputter method in Pt/
TiO2/SiO2Plated film on/Si substrates, finally again in Ca(1-x)SrxTiO3-δLast layer electrode is plated on nano thin-film.
The preparation method of above-mentioned technical proposal, its major defect and deficiency are：
1st, prepared memristor memristor poor-performing.
Reason is, its change resistance layer：Ca(1-x)SrxTiO3-δNano thin-film is with Ca(1-x)SrxTiO3-δCeramic material makees target
Material (wherein, 0<x<1,0<δ<3), it is deposited on using magnetically controlled sputter method in lower electrode surface.
The individual layer nanometer film of this structure type, it is that pottery is sintered into the calcining by higher temperature (900-1300 DEG C)
Ceramic material Ca(1-x)SrxTiO3-δFor target, then by magnetron sputtering deposition on bottom electrode base material, its material itself knot
Structure is fine and close, and lattice defect and number of cavities are on the low side.
2nd, preparation technology is complicated, long preparation period, and energy consumption is higher：
Reason is that its preparation technology needs first to calcine at a high temperature of 900-1300 DEG C, prepares Ca(1-x)SrxTiO3-δ
Ceramic material target；After magnetron sputtering shaping, it is also necessary to be heat-treated 10-30min at 700-800 DEG C again.
3rd, obtained memristor material is hard and crisp, not readily transportable easily because collision causes to rupture or damages.
In addition, also there is the problem of process conditions are relatively harsh, and ratio defective product is relatively low and deficiency in it.
The content of the invention
It is an object of the present invention to provide one kind be easy to physics realization, preparation technology is simple, control difficulty is small, steady quality,
The preparation method for the flexible single-layer nano-film memristor that production efficiency is high, cost is cheap, the memristor prepared by it have
Certain flexible, it is easy to integrate using LTCC technology, and is suitable to general circuit theoretical research and circuit design, there is generality
And universality.
The present invention the first technical scheme used to achieve the above object is a kind of flexible single-layer nano thin-film memristor
The preparation method of device, it is characterised in that comprise the following steps：
The first step, Ba (Ti are prepared using sol-gal process1-yXy)O3-yMixture target, is comprised the following steps that：
(1), raw material prepares：
By 1: (1-y): y mol ratio takes Ba (CH respectively3COO)2、C16H36O4Ti and X (CH3COO)2, wherein, X Mg,
Zn, Ca, 0.0001≤y≤0.03, it is standby；
(2), prepared by colloidal sol：
By Ba (CH3COO)2With X (CH3COO)2By 1: y mixed in molar ratio it is uniform after, be dissolved in acetic acid；
Then, acetylacetone,2,4-pentanedione used as stabilizers is added, addition is the 5%-20% of quality of acetic acid, and stirring 5-10 minutes obtain
Mixed solution；
Afterwards, into gained mixed solution, by Ba:Ti=1: the mol ratio of (1-y), C is added16H36O4Ti, stir 5-10
Minute, it is filtrated to get colloidal sol filtrate；
(3)、Ba(Ti1-yXy)O3-yThe preparation of powder：
Gained colloidal sol filtrate is placed in thermostatic drying chamber, 6-24 hours are dried at 100-150 DEG C；Take out, after grinding
Obtain Ba (Ti1-yXy)O3-yPowder；
(4), it is granulated：
In Ba (Ti1-yXy)O3-yPoly-vinyl alcohol solution is added in powder as binding agent, after uniform mixing, 40 mesh sieves is crossed and enters
Row is granulated；
Wherein：The mass percent concentration of poly-vinyl alcohol solution is 2-5%；The addition of poly-vinyl alcohol solution and above-mentioned baking
The mass ratio of powder after dry is 2-5: 100；
(5), target material moulding：
Compound after granulation is placed on tablet press machine and is pressed into bulk；
Then, gained bulk compound is cut into a diameter of 20-150mm, the highly slice of cylinder for 2-10mm, produces Ba
(Ti1-yXy)O3-yMixture target；
Or：
The first step, Ba (Ti are prepared using solid state reaction1-yXy)O3-yMixture target, is comprised the following steps that：
(1), raw material prepares：
In molar ratio 1: (1-y): y, take BaCO respectively3、TiO2And XO；Wherein, X Mg, Zn or Ca, 0.0001≤y≤
0.03；It is standby；
(2), material mixes：
By BaCO3、TiO2With XO by 1: (1-y): y mixed in molar ratio it is uniform after, add deionized water or absolute ethyl alcohol,
Enter ball mill grinding 4-24 hours to particle size in below 0.08mm；
Then, take out, dry, obtain primary Ba (Ti1-yXy)O3-yMixed powder；
(3), it is granulated：
In gained Ba (Ti1-yXy)O3-yPoly-vinyl alcohol solution is added in mixed powder as binding agent, after uniform mixing, mistake
40 mesh sieves are granulated；Wherein：
The mass percent concentration of poly-vinyl alcohol solution is 2-5%；
The addition of poly-vinyl alcohol solution and Ba (Ti1-yXy)O3-yThe mass ratio of nano-powder is 2-5: 100；
(4), target material moulding：
Compound after granulation is placed on tablet press machine and is pressed into bulk；
Afterwards by the slice of cylinder that block compound cuts into a diameter of 20-150mm, thickness is 2-10mm, Ba (Ti are produced1- yXy)O3-yMixture target；
Second step, the preparation of bottom electrode：
Low temperature co-fired green band substrate is taken,, will using pulse laser method or magnetically controlled sputter method using Pt or Au as target
Pt or Au is deposited on low temperature co-fired green band substrate, forms the bottom electrode that material is Pt or Au；
3rd step, the preparation of individual layer nanometer memristor film：
By obtained Ba (Ti1-yXy)O3-yNano-mixture target, using pulse laser method or magnetically controlled sputter method,
By nano-mixture Ba (Ti1-yXy)O3-yIt is deposited on the surface of bottom electrode；
Then, 10-30 minutes are heat-treated at 700-900 DEG C, it is Ba (Ti to obtain chemical composition1-yXy)O3-yIndividual layer pottery
Porcelain nano thin-film, as individual layer nanometer memristor film；
4th step, the target using material as Au, Ag or Pt, using pulse laser method or magnetically controlled sputter method, by Au, Ag
Or it is Ba (Ti that Pt, which is deposited on above-mentioned chemical composition,1-yXy)O3-ySingle-layer ceramic nano thin-film on, be made Top electrode, produce list
Layer nanometer resistive film memristor；
Or：
4th step, by In-Ga electrode solutions, surface print method is used to be plated in above-mentioned chemical composition as Ba (Ti1-yXy)
O3-ySingle-layer ceramic nano thin-film on, be made Top electrode, produce flexible single-layer nano-film memristor.
The technical effect directly brought by the technical proposal is that using pulse laser method or magnetically controlled sputter method, directly
It is Ba (Ti by chemical composition1-yXy)O3-yMixture (target) be deposited on the upper surface of bottom electrode；And in subsequent 700-
Heat treatment process at 900 DEG C, Ba (Ti are completed in the lump1-yXy)O3-yLTCC sintering, so as in the upper of bottom electrode
It is Ba (Ti that the chemical composition with good change resistance performance is formed on surface1-yXy)O3-ySingle-layer ceramic nano thin-film.
With prior art first by mixed material high-temperature calcination, ceramic material is fired into, again using the ceramic material as target
Magnetron sputtering deposition is carried out in lower electrode surface, is compared with forming the preparation technology of resistive film, the preparation of above-mentioned technical proposal
The most important improvement of technique is：Preceding ceramic material calcine technology step is dispensed.This simplifies the system of memristor
Standby technique, shorten technological process, improve production efficiency, and reducing energy consumption；
Above-mentioned technical proposal is merely not only simply to have dispensed high-temperature calcination to be prefabricated into ceramics compared with prior art
The step of material.What is more important, it is by Ba (Ti in above-mentioned technical proposal of the invention1-yXy)O3-y(X=Mg, Zn, Ca)
Mixture target material deposition has been attached in lower electrode surface, then during the heat treatment 10-30 minutes through low temperature (700-900 DEG C)
Into the thermal sintering of the resistive film of nano ceramics material.This both ensure that the efficiency and quality of film dense sintering, avoid again
Temperature is too low and the too short film of soaking time is not fine and close enough, or temperature is too high and long film and the electrode of causing of soaking time
Damage deformation；
Also, in terms of the chemical composition of resistive film, the memristor ratio with above-mentioned immediate prior art is of the invention
Above-mentioned technical proposal is by using passing through+divalent cation (X2+=Mg2+, Zn2+, Ca2+)+4 valency cation (Ti of part substitution4+)
B position substitutions are carried out, increase Ba (Ti1-yXy)O3-yThe asymmetry of molecular structure, improve Ba (Ti1-yXy)O3-yIn hole
Amount, be advantageous to strengthen Ba (Ti1-yXy)O3-yThe memristor performance of film memristor.
Further, in above-mentioned technical proposal, because substrate is the LTCC green bands that are coated with bottom electrode Pt or Au so that Ba
(Ti1-yXy)O3-yMemristor product has certain flexible, is not only convenient for transport and carries, and is easy to use LTCC technology collection
Into.
Preferably, the thickness of above-mentioned Top electrode is 10nm-50um.
What the optimal technical scheme was directly brought has the technical effect that, on the basis of memristor performance is ensured, in 10nm-
The selection of the thickness of Top electrode is carried out in this wide in range scope of 50um, advantageously reduces technique controlling difficulty, improves yield rate.
Further preferably, the thickness of above-mentioned single-layer ceramic nano thin-film is 10-990nm.
What the optimal technical scheme was directly brought has the technical effect that, ours experience have shown that, single-layer ceramic nano thin-film
Thickness is 10-990nm, on the one hand has more good change resistance performance；On the other hand, it is easy to technology controlling and process.The present invention is real
Second of technical scheme is a kind of preparation method of flexible single-layer nano-film memristor used by existing above-mentioned purpose, and it is special
Sign is, comprises the following steps：
The first step, Ba (Ti are prepared using sol-gal process1-yXy)O3-yMixture target, is comprised the following steps that：
(1), raw material prepares：
By 1: (1-y): y mol ratio takes Ba (CH respectively3COO)2、C16H36O4Ti and X (CH3COO)2, wherein, X Mg,
Zn, Ca, 0.0001≤y≤0.03, it is standby；
(2), prepared by colloidal sol：
By Ba (CH3COO)2With X (CH3COO)2By 1: y mixed in molar ratio it is uniform after, be dissolved in acetic acid；
Then, acetylacetone,2,4-pentanedione used as stabilizers is added, addition is the 5%-20% of quality of acetic acid, and stirring 5-10 minutes obtain
Mixed solution；
Afterwards, into gained mixed solution, by Ba:Ti=1: the mol ratio of (1-y), C is added16H36O4Ti, stir 5-10
Minute, it is filtrated to get colloidal sol filtrate；
(3)、Ba(Ti1-yXy)O3-yThe preparation of powder：
Gained colloidal sol filtrate is placed in thermostatic drying chamber, 6-24 hours are dried at 100-150 DEG C；Take out, after grinding
Obtain Ba (Ti1-yXy)O3-yPowder；
(4), it is granulated：
In Ba (Ti1-yXy)O3-yPoly-vinyl alcohol solution is added in powder as binding agent, after uniform mixing, 40 mesh sieves is crossed and enters
Row is granulated；
Wherein：The mass percent concentration of poly-vinyl alcohol solution is 2-5%；The addition of poly-vinyl alcohol solution and above-mentioned baking
The mass ratio of powder after dry is 2-5: 100；
(5), target material moulding：
Compound after granulation is placed on tablet press machine and is pressed into bulk；
Then, gained bulk compound is cut into a diameter of 20-150mm, the highly slice of cylinder for 2-10mm, produces Ba
(Ti1-yXy)O3-yMixture target；
Or：
The first step, Ba (Ti are prepared using solid state reaction1-yXy)O3-yMixture target, is comprised the following steps that：
(1), raw material prepares：
In molar ratio 1: (1-y): y, take BaCO respectively3、TiO2And XO；Wherein, X Mg, Zn or Ca, 0.0001≤y≤
0.03；It is standby；
(2), material mixes：
By BaCO3、TiO2With XO by 1: (1-y): y mixed in molar ratio it is uniform after, add deionized water or absolute ethyl alcohol,
Enter ball mill grinding 4-24 hours to particle size in below 0.08mm；
Then, take out, dry, obtain primary Ba (Ti1-yXy)O3-yMixed powder；
(3), it is granulated：
In gained Ba (Ti1-yXy)O3-yPoly-vinyl alcohol solution is added in mixed powder as binding agent, after uniform mixing, mistake
40 mesh sieves are granulated；Wherein：
The mass percent concentration of poly-vinyl alcohol solution is 2-5%；
The addition of poly-vinyl alcohol solution and Ba (Ti1-yXy)O3-yThe mass ratio of nano-powder is 2-5: 100；
(4), target material moulding：
Compound after granulation is placed on tablet press machine and is pressed into bulk；
Afterwards by the slice of cylinder that block compound cuts into a diameter of 20-150mm, thickness is 2-10mm, Ba (Ti are produced1- yXy)O3-yMixture target；
Second step, the preparation of bottom electrode：
Low temperature co-fired green band substrate is taken,, will using pulse laser method or magnetically controlled sputter method using Pt or Au as target
Pt or Au is deposited on low temperature co-fired green band substrate, forms the bottom electrode that material is Pt or Au；
3rd step, the preparation of individual layer nanometer memristor film：
By obtained Ba (Ti1-yXy)O3-yNano-mixture target, using pulse laser method or magnetically controlled sputter method,
By nano-mixture Ba (Ti1-yXy)O3-yIt is deposited on the surface of bottom electrode；
4th step, the target using material as Au, Ag or Pt, using heat spraying method, Au, Ag or Pt are deposited on above-mentioned
Chemical composition is Ba (Ti1-yXy)O3-ySingle-layer ceramic nano thin-film on, be made Top electrode；
Finally, 10-30 minutes are heat-treated at 700-900 DEG C, it is Ba (Ti to obtain chemical composition1-yXy)O3-yIndividual layer pottery
On porcelain nano thin-film,
Produce flexible single-layer nano-film memristor.
The technical effect directly brought by the technical proposal is that it is easy to physics realization, preparation technology is simple, controls difficulty
Small, steady quality, production efficiency are high, cost is cheap.Specific reason no longer repeats with above one by one.
Preferably, the thickness of above-mentioned Top electrode is 10nm-50um.
What the optimal technical scheme was directly brought has the technical effect that, on the basis of memristor performance is ensured, in 10nm-
The selection of the thickness of Top electrode is carried out in this wide in range scope of 50um, advantageously reduces technique controlling difficulty, improves yield rate.
Further preferably, the thickness of above-mentioned single-layer ceramic nano thin-film is 10-990nm.
What the optimal technical scheme was directly brought has the technical effect that, ours experience have shown that, single-layer ceramic nano thin-film
Thickness is 10-990nm, on the one hand has more good change resistance performance；On the other hand, it is easy to technology controlling and process.
It should be noted that the single-layer nano-film memristor prepared by the present invention, its memristor resistive principle are, with
Hole and ionization oxonium ion are carrier caused by bias is lower, under electric field action, are produced by the hole and ionization oxonium ion
The change of amount, to realize the change of device resistance.
It is not difficult to find out, its working mechanism and mathematical modeling possess general and universality.
To more fully understand the technical characterstic of the present invention, carried out specifically from principle with reference to memristor correlation theory
It is bright.
The present invention based on Ba (Ti1-yXy)O3-yThe memristor of (X=Mg, Zn, Ca) nano thin-film, its memristor mechanism sum
Learning model is specially：The memristor is by the individual layer Ba (Ti between being sandwiched in two electrodes1-yXy)O3-yNano thin-film is formed.
Due to+divalent cation (X2+=Mg2+, Zn2+, Ca2+)+4 valency cation (Ti of part substitution4+), increase Ba
(Ti1-yXy)O3-yThe asymmetry of molecular structure, improve Ba (Ti1-yXy)O3-yIn hole amount.When a voltage or electric current add
When on to the device, because film thickness is nanoscale, the voltage of very little will produce huge electric field, Ba (Ti1-yXy)O3-y
O can occur with the oxygen in air under bias with the surface of air contact2+4e-→2O2-Reaction, and make to produce in film
Hole.
Meanwhile function influence is biased against inside film O occurs2-→e-+O-, hole and ionization oxonium ion (O-) as master
Carrier displacement under electric field action is wanted, with hole and ionization oxonium ion (O-) change of yield can cause two electrodes
Between resistance variations, correspond to film therewith and minimum (R be presentedmin) or maximum (Rmax) two kinds of different resistance, this is Ba
(Ti1-yXy)O3-yShow the mechanism of memristor characteristic.Current O (t) represents a certain moment Ba (Ti1-yXy)O3-yProduce under bias
Raw hole amount, M represent caused maximum void amount under bias effect, and v represents to produce the speed in hole under bias effect.Due to
Hole and ionization oxonium ion (O-) yield it is relevant with the size of current by it and its duration (i.e. charge accumulated)：I.e.：Therefore, film resistor is its function by electric charge：Work as Rmin<<RmaxWhen,
Because bias (electric current) to interrupt in rear film without driving electric field, and each ion, electronics, hole etc. are moved at normal temperatures
It is inactive, hole and ionization oxonium ion (O in film-) amount can not retract the state before biasing (electric current passes through), therefore have
Memory effect and keep bias (electric current) interrupt when resistance.
In summary, the present invention is relative to prior art, technically the improvement of the core in terms of thought and technical principle
Point is two aspects：
First, eliminate the ceramic material as resistive film component fires step in advance；Second, resistive film ceramic material
Study a point improvement (+divalent cation (X for aspect2+=Mg2+, Zn2+, Ca2+)+4 valency cation (Ti of part substitution4+) carry out B positions
Substitution, increases Ba (Ti1-yXy)O3-yThe asymmetry of molecular structure, improve Ba (Ti1-yXy)O3-yIn hole amount, favorably
In enhancing Ba (Ti1-yXy)O3-yThe memristor performance of film memristor).
Also, improved based on above-mentioned both sides so that for the resistive film of ceramic material in structure, there occurs beneficial good
Property change (being added significantly to number of cavities), cause significantly improving and improving for final memristor memristor performance.
It should be further stated that：In above two technical scheme, basis each selects upper electrode material or plating respectively
The difference of electrode method is different to the order of used nano thin-film heat treatment.Its object is to：
Ensure Ba (Ti1-yXy)O3-yNano thin-film has high fitness and associativity with Top electrode, to avoid Top electrode
Damage or combination between electrode and film are bad.
Be not difficult to find out, the present invention relative to prior art, have preparation technology is simple, control difficulty is small, steady quality, life
Produce that efficiency high, cost are cheap, the beneficial effects such as the memristor performance of obtained memristor product is more preferable.
Brief description of the drawings
Fig. 1 is the single-layer nano-film memristor structural representation under one embodiment of the present invention；
Fig. 2 is the mathematical modeling of single-layer nano-film memristor M (q) of the present invention.
Embodiment
Below in conjunction with the accompanying drawings, the present invention is briefly described.
Fig. 1 is the single-layer nano-film memristor structural representation under one embodiment of the present invention.
As shown in figure 1, single-layer nano-film memristor of the present invention includes two electrodes (Top electrode and bottom electrode), and put
Ba (Ti between two electrodes1-yXy)O3-yNano thin-film structure, Top electrode Au, Ag, In-Ga or Pt, bottom electrode be Pt or
Au, using LTCC greens band as substrate.
Fig. 2 is the mathematical modeling of single-layer nano-film memristor M (q) of the present invention.
From figure 2 it can be seen that the memristor mechanism of the present invention is with hole and ionization oxonium ion (O-) yield change
The resistance variations between two electrodes can be caused, film is corresponded to therewith and minimum (R is presentedmin) or maximum (Rmax) two kinds of different electricity
Resistance, i.e. Ba (Ti1-yXy)O3-yMemristor Mechanism of characters.
With reference to embodiment, the present invention is described in further detail.
Explanation：
1st, embodiment 1-9, it is that Sr (Ti are prepared using sol-gal process1-xMgx)O3-xMixture target.
Preparing raw material and formula composition are mol ratio Ba (CH3COO)2∶(1-y)C16H36O4Ti∶y X(CH3COO)2(X=
Mg, Zn, Ca), wherein, 0<y<1；
Ba (Ti are prepared using sol-gal process1-yXy)O3-yMixture target, comprises the steps：
1st step：By Ba (CH3COO)2With X (CH3COO)2(X=Mg, Zn, Ca) presses 1: y mixed in molar ratio, is dissolved in second
Acid, acetylacetone,2,4-pentanedione used as stabilizers is added, addition is the 5%-20% of quality of acetic acid, and stirring 5-10 minutes obtain mixed solution；
2nd step：Final stoicheiometry Ba is pressed into mixed solution:The ratio of Ti=1: (1-y) adds C16H36O4Ti, stirring
5-10 minutes, filtering；
3rd step：Solution (colloidal sol) after filtering is placed in thermostatic drying chamber, dried at 100-150 DEG C through 6-24 hours
Dry, the powder after drying is standby；
4th step：It is granulated, it is 2-5% poly-vinyl alcohol solution as binding agent, the addition of binding agent to use mass fraction
For the 2-5% of mixture quality fraction to be granulated, cross 40 mesh sieves and be granulated；
5th step：Compacting, the compound being granulated after sieving is suppressed using tablet press machine, and be cut to a diameter of 20-
150mm, the highly slice of cylinder for 2-10mm.
2nd, embodiment 10-18, it is that Ba (Ti are prepared using solid state reaction1-yXy)O3-yMixture target；Wherein, X
=Mg, Zn, Ca.
Ba(Ti1-yXy)O3-yThe preparing raw material and formula composition of mixture target are mol ratio BaCO3∶(1-y)TiO2∶y
XO (X=Mg, Zn, Ca), wherein, 0<y<1；Ba (the Ti are prepared using solid state reaction1-yXy)O3-y, comprise the steps：
1st step：Mixing, by BaCO3, TiO21 is pressed with XO (X=Mg, Zn, Ca): (1-y): y mixed in molar ratio, addition are gone
Ionized water or absolute ethyl alcohol, ball milling, are then dried, and obtain compound；
2nd step：It is granulated, it is 2-5% poly-vinyl alcohol solution as binding agent, the addition of binding agent to use mass fraction
For the 2-5% of powder mass fraction to be granulated, cross 40 mesh sieves and be granulated；
3rd step：Compacting, the compound being granulated after sieving is suppressed using tablet press machine, and be cut to a diameter of 20-
150mm, the highly slice of cylinder for 2-10mm.
3rd, embodiment 19~21 is using the Ba (Ti with embodiment 11-yXy)O3-yMixture target identical composition of raw materials；
Also, the respectively target using material as Au, Ag or Pt, will using pulse laser method or magnetically controlled sputter method
Au, Ag or Pt are deposited on Ba (Ti1-yXy)O3-yOn nano thin-film.
Using the preparation method of identical single-layer nano-film memristor, using pulsed laser deposition PLD or magnetron sputtering
Method is comprised the following steps using Au, Ag, Pt plating Top electrode, the preparation method：
1st step, with Ba (Ti1-yXy)O3-y(X=Mg, Zn, Ca) makees target, is splashed using pulsed laser deposition PLD or magnetic control
Shooting method plated film on the LTCC green bands for be coated with advance bottom electrode Pt or Au, change resistance layer is formed, the thickness of plated film is 10-
990nm, then through 700-900 DEG C of heat treatment 10-30 minute；
2nd step, the target using material as Au, Ag or Pt, using pulse laser method or magnetically controlled sputter method, in Ba
(Ti1-yXy)O3-yLast layer Top electrode is plated on nano thin-film.
4th, embodiment 22 is using the Ba (Ti with embodiment 11-yXy)O3-yMixture target identical composition of raw materials；Also,
It is that In-Ga electrode solutions plating last layer Top electrode is used using printing process.
5th, embodiment 23~25 is Ba (Ti1-yXy)O3-yThe Top electrode processing of (X=Mg, Zn, Ca) nano thin-film, is used
Embodiment 1Ba (Ti1-yXy)O3-yMixture target identical composition of raw materials, using the system of identical single-layer nano-film memristor
Preparation Method, comprised the following steps using other deposition methods using Au, Ag, Pt plating Top electrode, the preparation method：
1st step, with Ba (Ti1-yXy)O3-yMake target, plated using pulsed laser deposition PLD or magnetically controlled sputter method in advance
There is plated film on bottom electrode Pt or Au LTCC green bands, form change resistance layer, the thickness of plated film is 10-990nm；
2nd step, in Ba (Ti1-yXy)O3-yLast layer Top electrode is plated on nano thin-film, then through 700-900 DEG C of heat treatment 10-
30 minutes.
The preparation method of above-mentioned nano-film memristor, its thickness of electrode are 10nm-50um, and the upper electrode material is
Au, Ag, In-Ga or Pt.
6th, embodiment 19-25 is respectively adopted Au, Ag, In-Ga or Pt and makees upper electrode material, the technique in specific preparation process
Parameter is as shown in table 1 below.
Embodiment 1
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：Ba(CH3COO)2：C16H36O4Ti：X
(CH3COO)2=100:99:1 (mol ratio).
Embodiment 2
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：Ba(CH3COO)2：C16H36O4Ti：X
(CH3COO)2=100:98:2 (mol ratios).
Embodiment 3
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：Ba(CH3COO)2：C16H36O4Ti：X
(CH3COO)2=100:97:3 (mol ratios).
Embodiment 4
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：Ba(CH3COO)2：C16H36O4Ti：X
(CH3COO)2=1000:999:1 (mol ratio).
Embodiment 5
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：Ba(CH3COO)2：C16H36O4Ti：X
(CH3COO)2=1000:998:2 (mol ratios).
Embodiment 6
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：Ba(CH3COO)2：C16H36O4Ti：X
(CH3COO)2=1000:997:3 (mol ratios).
Embodiment 7
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：Ba(CH3COO)2：C16H36O4Ti：X
(CH3COO)2=10000:9999:1 (mol ratio).
Embodiment 8
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：Ba(CH3COO)2：C16H36O4Ti：X
(CH3COO)2=10000:9998:2 (mol ratios).
Embodiment 9
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：Ba(CH3COO)2：C16H36O4Ti：X
(CH3COO)2=10000:9997:3 (mol ratios).
Embodiment 10
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：BaCO3：TiO2：XO=100:99:1 (mole
Than).
Embodiment 11
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：BaCO3：TiO2：XO=100:98:2 (mole
Than).
Embodiment 12
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：BaCO3：TiO2：XO=100:97:3 (mole
Than).
Embodiment 13
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：BaCO3：TiO2：XO=1000:999:1 (mole
Than).
Embodiment 14
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：BaCO3：TiO2：XO=1000:998:2 (mole
Than).
Embodiment 15
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：BaCO3：TiO2：XO=1000:997:3 (mole
Than).
Embodiment 16
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：BaCO3：TiO2：XO=10000:9999:1 (rubs
That ratio).
Embodiment 17
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：BaCO3：TiO2：XO=10000:9998:2 (rub
That ratio).
Embodiment 18
Prepare Ba (Ti1-yXy)O3-yThe composition of raw materials of mixture target is：BaCO3：TiO2：XO=10000:9997:3 (rub
That ratio).
The embodiment 19-25 of table 1 technological parameter
| Embodiment is numbered | Upper electrode material | Top electrode depositional mode | Heat treatment temperature (DEG C) |
| Embodiment 19 | Au | Pulse laser method or magnetically controlled sputter method | 800 |
| Embodiment 20 | Ag | Pulse laser method or magnetically controlled sputter method | 750 |
| Embodiment 21 | Pt | Pulse laser method or magnetically controlled sputter method | 900 |
| Embodiment 22 | In-Ga | Printing | 850 |
| Embodiment 23 | Au | Heat deposition | 700 |
| Embodiment 24 | Ag | Heat deposition | 700 |
| Embodiment 25 | Pt | Heat deposition | 800 |
The detection and inspection of product：
The final obtained memristors of above-described embodiment 1-25 are subjected to I-V characteristic test, the results showed that:
" 8 " font is presented in the I-V characteristic curve of such memristor；
And by changing pressurization size and pressing time, its I-V characteristic can show non-easy specific to memristor
The property lost (that is, Memorability).
Claims (6)
1. a kind of preparation method of flexible single-layer nano-film memristor, it is characterised in that comprise the following steps：
The first step, Ba (Ti are prepared using sol-gal process1-yXy)O3-yMixture target, is comprised the following steps that：
(1), raw material prepares：
By 1: (1-y): y mol ratio takes Ba (CH respectively3COO)2、C16H36O4Ti and X (CH3COO)2, wherein, X Mg, Zn,
Ca, 0.0001≤y≤0.03 are standby；
(2), prepared by colloidal sol：
By Ba (CH3COO)2With X (CH3COO)2By 1: y mixed in molar ratio it is uniform after, be dissolved in acetic acid；
Then, acetylacetone,2,4-pentanedione used as stabilizers is added, addition is the 5%-20% of quality of acetic acid, and stirring 5-10 minutes are mixed
Solution；
Afterwards, into gained mixed solution, by Ba:Ti=1: the mol ratio of (1-y), C is added16H36O4Ti, 5-10 minutes are stirred,
It is filtrated to get colloidal sol filtrate；
(3)、Ba(Ti1-yXy)O3-yThe preparation of powder：
Gained colloidal sol filtrate is placed in thermostatic drying chamber, 6-24 hours are dried at 100-150 DEG C；Take out, obtained after grinding
Ba(Ti1-yXy)O3-yPowder；
(4), it is granulated：
In Ba (Ti1-yXy)O3-yPoly-vinyl alcohol solution is added in powder as binding agent, after uniform mixing, 40 mesh sieves is crossed and is made
Grain；
Wherein：The mass percent concentration of poly-vinyl alcohol solution is 2-5%；After the addition of poly-vinyl alcohol solution and above-mentioned drying
Powder mass ratio be 2-5: 100；
(5), target material moulding：
Compound after granulation is placed on tablet press machine and is pressed into bulk；
Then, gained bulk compound is cut into a diameter of 20-150mm, the highly slice of cylinder for 2-10mm, produces Ba
(Ti1-yXy)O3-yMixture target；
Or：
The first step, Ba (Ti are prepared using solid state reaction1-yXy)O3-yMixture target, is comprised the following steps that：
(1), raw material prepares：
In molar ratio 1: (1-y): y, take BaCO respectively3、TiO2And XO；Wherein, X Mg, Zn or Ca, 0.0001≤y≤0.03；
It is standby；
(2), material mixes：
By BaCO3、TiO2With XO by 1: (1-y): y mixed in molar ratio it is uniform after, add deionized water or absolute ethyl alcohol, goal
Grinding machine grinding 4-24 hours are to particle size in below 0.08mm；
Then, take out, dry, obtain primary Ba (Ti1-yXy)O3-yMixed powder；
(3), it is granulated：
In gained Ba (Ti1-yXy)O3-yPoly-vinyl alcohol solution is added in mixed powder as binding agent, after uniform mixing, crosses 40 mesh
Sieve is granulated；Wherein：
The mass percent concentration of poly-vinyl alcohol solution is 2-5%；
The addition of poly-vinyl alcohol solution and Ba (Ti1-yXy)O3-yThe mass ratio of nano-powder is 2-5: 100；
(4), target material moulding：
Compound after granulation is placed on tablet press machine and is pressed into bulk；
Afterwards by the slice of cylinder that block compound cuts into a diameter of 20-150mm, thickness is 2-10mm, Ba (Ti are produced1-yXy)O3-y
Mixture target；
Second step, the preparation of bottom electrode：
Take low temperature co-fired green band substrate, using Pt or Au as target, using pulse laser method or magnetically controlled sputter method, by Pt or
Au is deposited on low temperature co-fired green band substrate, forms the bottom electrode that material is Pt or Au；
3rd step, the preparation of individual layer nanometer memristor film：
By obtained Ba (Ti1-yXy)O3-yNano-mixture target, using pulse laser method or magnetically controlled sputter method, it will receive
Rice mixture Ba (Ti1-yXy)O3-yIt is deposited on the surface of bottom electrode；
Then, 10-30 minutes are heat-treated at 700-900 DEG C, it is Ba (Ti to obtain chemical composition1-yXy)O3-ySingle-layer ceramic receive
Rice film, as individual layer nanometer memristor film；
4th step, the target using material as Au, Ag or Pt, using pulse laser method or magnetically controlled sputter method, by Au, Ag or Pt
It is Ba (Ti to be deposited on above-mentioned chemical composition1-yXy)O3-ySingle-layer ceramic nano thin-film on, be made Top electrode, produce individual layer and receive
Rice resistive film memristor；
Or：
4th step, by In-Ga electrode solutions, surface print method is used to be plated in above-mentioned chemical composition as Ba (Ti1-yXy)O3-yList
On layer ceramic nano film, Top electrode is made, produces flexible single-layer nano-film memristor.
2. the preparation method of flexible single-layer nano-film memristor according to claim 1, it is characterised in that the upper electricity
The thickness of pole is 10nm-50um.
3. the preparation method of flexible single-layer nano-film memristor according to claim 1 or 2, it is characterised in that described
The thickness of single-layer ceramic nano thin-film is 10-990nm.
4. a kind of preparation method of flexible single-layer nano-film memristor, it is characterised in that comprise the following steps：
The first step, Ba (Ti are prepared using sol-gal process1-yXy)O3-yMixture target, is comprised the following steps that：
(1), raw material prepares：
By 1: (1-y): y mol ratio takes Ba (CH respectively3COO)2、C16H36O4Ti and X (CH3COO)2, wherein, X Mg, Zn,
Ca, 0.0001≤y≤0.03 are standby；
(2), prepared by colloidal sol：
By Ba (CH3COO)2With X (CH3COO)2By 1: y mixed in molar ratio it is uniform after, be dissolved in acetic acid；
Then, acetylacetone,2,4-pentanedione used as stabilizers is added, addition is the 5%-20% of quality of acetic acid, and stirring 5-10 minutes are mixed
Solution；
Afterwards, into gained mixed solution, by Ba:Ti=1: the mol ratio of (1-y), C is added16H36O4Ti, 5-10 minutes are stirred,
It is filtrated to get colloidal sol filtrate；
(3)、Ba(Ti1-yXy)O3-yThe preparation of powder：
Gained colloidal sol filtrate is placed in thermostatic drying chamber, 6-24 hours are dried at 100-150 DEG C；Take out, obtained after grinding
Ba(Ti1-yXy)O3-yPowder；
(4), it is granulated：
In Ba (Ti1-yXy)O3-yPoly-vinyl alcohol solution is added in powder as binding agent, after uniform mixing, 40 mesh sieves is crossed and is made
Grain；
Wherein：The mass percent concentration of poly-vinyl alcohol solution is 2-5%；After the addition of poly-vinyl alcohol solution and above-mentioned drying
Powder mass ratio be 2-5: 100；
(5), target material moulding：
Compound after granulation is placed on tablet press machine and is pressed into bulk；
Then, gained bulk compound is cut into a diameter of 20-150mm, the highly slice of cylinder for 2-10mm, produces Ba
(Ti1-yXy)O3-yMixture target；
Or：
The first step, Ba (Ti are prepared using solid state reaction1-yXy)O3-yMixture target, is comprised the following steps that：
(1), raw material prepares：
In molar ratio 1: (1-y): y, take BaCO respectively3、TiO2And XO；Wherein, X Mg, Zn or Ca, 0.0001≤y≤0.03；
It is standby；
(2), material mixes：
By BaCO3、TiO2With XO by 1: (1-y): y mixed in molar ratio it is uniform after, add deionized water or absolute ethyl alcohol, goal
Grinding machine grinding 4-24 hours are to particle size in below 0.08mm；
Then, take out, dry, obtain primary Ba (Ti1-yXy)O3-yMixed powder；
(3), it is granulated：
In gained Ba (Ti1-yXy)O3-yPoly-vinyl alcohol solution is added in mixed powder as binding agent, after uniform mixing, crosses 40 mesh
Sieve is granulated；Wherein：
The mass percent concentration of poly-vinyl alcohol solution is 2-5%；
The addition of poly-vinyl alcohol solution and Ba (Ti1-yXy)O3-yThe mass ratio of nano-powder is 2-5: 100；
(4), target material moulding：
Compound after granulation is placed on tablet press machine and is pressed into bulk；
Afterwards by the slice of cylinder that block compound cuts into a diameter of 20-150mm, thickness is 2-10mm, Ba (Ti are produced1-yXy)O3-y
Mixture target；
Second step, the preparation of bottom electrode：
Take low temperature co-fired green band substrate, using Pt or Au as target, using pulse laser method or magnetically controlled sputter method, by Pt or
Au is deposited on low temperature co-fired green band substrate, forms the bottom electrode that material is Pt or Au；
3rd step, the preparation of individual layer nanometer memristor film：
By obtained Ba (Ti1-yXy)O3-yNano-mixture target, using pulse laser method or magnetically controlled sputter method, it will receive
Rice mixture Ba (Ti1-yXy)O3-yIt is deposited on the surface of bottom electrode；
4th step, the target using material as Au, Ag or Pt, using heat spraying method, Au, Ag or Pt are deposited on to above-mentioned chemistry
Composition is Ba (Ti1-yXy)O3-ySingle-layer ceramic nano thin-film on, be made Top electrode；
Finally, 10-30 minutes are heat-treated at 700-900 DEG C, it is Ba (Ti to obtain chemical composition1-yXy)O3-ySingle-layer ceramic receive
On rice film,
Produce flexible single-layer nano-film memristor.
5. the preparation method of flexible single-layer nano-film memristor according to claim 4, it is characterised in that the upper electricity
The thickness of pole is 10nm-50um.
6. the preparation method of the flexible single-layer nano-film memristor according to claim 4 or 5, it is characterised in that described
The thickness of single-layer ceramic nano thin-film is 10-990nm.
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| CN112687794B (en) * | 2020-12-28 | 2024-03-19 | 山东科技大学 | Flexible memristor with self-repairing capability and preparation method |
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