CN105742487B - A kind of preparation method of ambipolar nano-film memristor - Google Patents
A kind of preparation method of ambipolar nano-film memristor Download PDFInfo
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- CN105742487B CN105742487B CN201610040610.3A CN201610040610A CN105742487B CN 105742487 B CN105742487 B CN 105742487B CN 201610040610 A CN201610040610 A CN 201610040610A CN 105742487 B CN105742487 B CN 105742487B
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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
- H10N70/026—Formation of the switching material, e.g. layer deposition by physical vapor deposition, e.g. sputtering
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/47—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on strontium titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
Abstract
The invention discloses a kind of preparation method of ambipolar nano-film memristor, it is carrier that it, which is used in the lower caused hole of bias and ionization oxonium ion, the principle of the change of device resistance is realized by the change of hole and ionized oxygen ion generation amount, on the basis of existing technology, the chemical industry skill that conforms to the principle of simplicity and the aspect of chemical formulation two of resistive film nano ceramic material are set about：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 Mg2+Part substitution Ti4+B position substitutions are carried out, to increase Sr (Ti1‑ xMgx)O3‑xThe asymmetry of molecular structure, the technological means such as inner cavity amount are improved, simplify preparation technology, shorten technological process, reduce energy consumption and manufacturing cost, and 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 ambipolar nano thin-film
The preparation method of 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 ambipolar nano-film memristor that production efficiency is high, cost is cheap, the memristor prepared by it are suitable to one
As Circuit theory research and circuit design, there is general and universality.
The present invention the first technical scheme used to achieve the above object is a kind of ambipolar nano-film memristor
Preparation method, it is characterised in that comprise the following steps：
The first step, Sr (Ti are prepared using hydro-thermal method1-xMgx)O3-xTarget, comprise the following steps that：
(1), raw material mixes：
By Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2, by 1: (1-x): x mixed in molar ratio, wherein, 0.0001≤x
≤0.03；
Said mixture is dissolved in 10%-20% dust technology, is placed on magnetic stirring apparatus, is stirred, makes its complete
Fully dissolved；
(2), prepared by powder
NaOH solution is slowly added dropwise into above-mentioned solution until precipitation is complete, filtering is precipitated and is washed with deionized, and is dripped
Add NaOH solution and adjust pH value, and be fitted into reactor, be put into and reach in advance in the thermostatic drying chamber of 150 DEG C of temperature,
Hydro-thermal reaction 24 hours；
After hydro-thermal reaction, reactor is naturally cooled into room temperature, by reactor gained sample with deionized water repeatedly
Cleaning obtains Sr (Ti until removing all soluble-salts after being dried at 60 DEG C1-xMgx)O3-xPowder；
(3), it is granulated：
In Sr (Ti1-xMgx)O3-xPoly-vinyl alcohol solution is added in powder as binding agent, after uniform mixing, crosses 40 mesh sieves
It is granulated；
Wherein：The mass percent concentration of poly-vinyl alcohol solution is 2-5%；The addition and Sr of poly-vinyl alcohol solution
(Ti1-xMgx)O3-xThe mass ratio of powder is 2-5: 100；
(4), 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 Sr
(Ti1-xMgx)O3-xTarget；
Second step, the preparation of bottom electrode：
Selected bottom electrode is lamination layer structure, includes Pt layers, TiO successively from up to down2Layer, SiO2Layer and Si substrates
Layer；
3rd step, the preparation of individual layer nanometer memristor film：
By obtained Sr (Ti1-xMgx)O3-xTarget, using pulse laser method or magnetically controlled sputter method, by Sr (Ti1- xMgx)O3-xIt is deposited on the surface of bottom electrode；
Then, 10-30 minutes are heat-treated at 700-900 DEG C, it is Sr (Ti to obtain chemical composition1-xMgx)O3-xIndividual layer
Ceramic nano 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 Sr (Ti that Pt, which is deposited on above-mentioned chemical composition,1-xMgx)O3-xSingle-layer ceramic nano thin-film on, be made Top electrode, produce
Finished product；
Or：
By In-Ga electrode solutions, surface print method is used to be plated in above-mentioned chemical composition as Sr (Ti1-xMgx)O3-xList
On layer ceramic nano film, Top electrode is made, gets product.
The technical effect directly brought by the technical proposal is that using pulse laser method or magnetically controlled sputter method, directly
By Sr (Ti1-xMgx)O3-xIt is deposited on the upper surface of bottom electrode；And the heat treatment process at subsequent 700-900 DEG C, it is complete in the lump
Into Sr (Ti1-xMgx)O3-xLTCC sintering, so as on the upper surface of bottom electrode formed there is good resistive
The chemical composition of energy is Sr (Ti1-xMgx)O3-xSingle-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 Sr (Ti in above-mentioned technical proposal of the invention1-xMgx)O3-xIt is deposited on bottom electrode
On surface, then attach the resistive film for completing nano ceramics material during the heat treatment 10-30 minutes through low temperature (700-900 DEG C)
Thermal sintering.This both ensure that the efficiency and quality of film dense sintering, avoid temperature too low again too short with soaking time
Film is not fine and close enough, or temperature is too high and soaking time is long causes the damage of film and electrode to deform；
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 with+divalent cation (Mg2+)+4 valency cation (Ti of part substitution4+) carry out B position substitutions, increase
The asymmetry of molecular structure, the hole amount in molecule is improved, is advantageous to strengthen Sr (Ti1-xMgx)O3-xFilm memristor
Memristor performance.
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 second of technical scheme used to achieve the above object is a kind of ambipolar nano-film memristor
Preparation method, it is characterised in that comprise the following steps：
The first step, Sr (Ti are prepared using hydro-thermal method1-xMgx)O3-xTarget, comprise the following steps that：
(1), raw material mixes：
By Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2, by 1: (1-x): x mixed in molar ratio, wherein, 0.0001≤x
≤0.03；
Said mixture is dissolved in 10%-20% dust technology, is placed on magnetic stirring apparatus, is stirred, makes its complete
Fully dissolved；
(2), prepared by powder
NaOH solution is slowly added dropwise into above-mentioned solution until precipitation is complete, filtering is precipitated and is washed with deionized, and is dripped
Add NaOH solution and adjust pH value, and be fitted into reactor, be put into and reach in advance in the thermostatic drying chamber of 150 DEG C of temperature,
Hydro-thermal reaction 24 hours；
After hydro-thermal reaction, reactor is naturally cooled into room temperature, by reactor gained sample with deionized water repeatedly
Cleaning obtains Sr (Ti until removing all soluble-salts after being dried at 60 DEG C1-xMgx)O3-xPowder；
(3), it is granulated：
In Sr (Ti1-xMgx)O3-xPoly-vinyl alcohol solution is added in powder as binding agent, after uniform mixing, crosses 40 mesh sieves
It is granulated；
Wherein：The mass percent concentration of poly-vinyl alcohol solution is 2-5%；The addition and Sr of poly-vinyl alcohol solution
(Ti1-xMgx)O3-xThe mass ratio of powder is 2-5: 100；
(4), 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 Sr
(Ti1-xMgx)O3-xTarget；
Second step, the preparation of bottom electrode：
Selected bottom electrode is lamination layer structure, includes Pt layers, TiO successively from up to down2Layer, SiO2Layer and Si substrates
Layer；
3rd step, the preparation of individual layer nanometer memristor film：
By obtained Sr (Ti1-xMgx)O3-xTarget, using pulse laser method or magnetically controlled sputter method, by Sr (Ti1- xMgx)O3-xIt 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 Sr (Ti1-xMgx)O3-xSingle-layer ceramic nano thin-film on, be made Top electrode；
Finally, 10-30 minutes are heat-treated at 700-900 DEG C, are got product.
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 Sr (Ti1-xMgx)O3-xThe memristor of nano thin-film, its mathematical modeling are specially：The memristor
By the individual layer Sr (Ti being sandwiched between two electrodes1-xMgx)O3-xNano thin-film is formed.
Its memristor mechanism：When a voltage or electric current are added on the device, because film thickness is nanoscale, very little
Voltage will produce huge electric field, Sr (Ti1-xMgx)O3-xWith the surface of air contact under bias can with air
O occurs for oxygen2+4e-→2O2-Reaction, and make to produce hole in film.Meanwhile function influence is biased against inside film O occurs2-
→e-+O-, hole and ionization oxonium ion (O-) principal carrier displacement under electric field action is used as, with hole and ionization
Oxonium ion (O-) change of yield can cause resistance variations between two electrodes, film is corresponded to therewith, and minimum (R is presentedmin) or
Maximum (Rmax) two kinds of different resistance, this is Sr (Ti1-xMgx)O3-xShow the mechanism of memristor characteristic.
Current O (t) represents a certain moment Sr (Ti1-xMgx)O3-xCaused hole amount, M represent bias under bias
Maximum void amount caused by effect is lower, v represent to produce the speed in hole under bias effect.
Due to hole and ionization oxonium ion (O-) yield and the size of current and its duration (i.e. electric charge by it
Accumulation) it is relevant：I.e.：Therefore, film resistor is its function by electric charge：When
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
Point improvement of aspect is studied (with+divalent cation (Mg2+)+4 valency cation (Ti of part substitution4+) B position substitutions are carried out, increase
The asymmetry of molecular structure, the hole amount in molecule is improved, is advantageous to strengthen Sr (Ti1-xMgx)O3-xFilm memristor
Memristor performance).
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 Sr (Ti1-xMgx)O3-xNano 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 Sr (Ti obtained by the present invention1-xMgx)O3-xAmbipolar single-layer nano-film memristor structural representation
Figure；
Fig. 2 is the Sr (Ti obtained by the present invention1-xMgx)O3-xAmbipolar single-layer nano-film memristor M (q) mathematics
Model.
Embodiment
Below in conjunction with the accompanying drawings, the present invention is briefly described.
Fig. 1 is the Sr (Ti obtained by the present invention1-xMgx)O3-xAmbipolar single-layer nano-film memristor structural representation
Figure.
As shown in figure 1, single-layer nano-film memristor of the present invention includes two electrodes (Top electrode and bottom electrode), and put
Sr (Ti between two electrodes1-xMgx)O3-xNano thin-film structure, Top electrode Au, Ag, In-Ga or Pt, bottom electrode Pt,
With Pt/TiO2/SiO2/ Si is substrate.
Fig. 2 is obtained Sr (Ti1-xMgx)O3-xAmbipolar single-layer nano-film memristor M (q) mathematical modeling.
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. Sr (Ti1-xMgx)O3-xMemristor Mechanism of characters.
With reference to embodiment, the present invention is described in further detail.
Explanation：
1st, example 1 below -9, it is that Sr (Ti are prepared using hydro-thermal method1-xMgx)O3-xTarget；Preparing raw material Sr
(NO3)2、Ti(OC4H9)4With Mg (NO3)2Mol ratio is 1: (1-x): x, wherein, 0<x<1.
Sr (Ti are prepared using hydro-thermal method1-xMgx)O3-xTarget, comprise the following steps：
(1), raw material mixes：
By Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2, by 1: (1-x): x mixed in molar ratio, wherein, 0<x<1；
Said mixture is dissolved in 10%-20% dust technology, is placed on magnetic stirring apparatus, is stirred, makes its complete
Fully dissolved；
(2), prepared by powder
NaOH solution is slowly added dropwise into above-mentioned solution until precipitation is complete, filtering is precipitated and is washed with deionized, and is dripped
Add NaOH solution and adjust pH value, and be fitted into reactor, be put into and reach in advance in the thermostatic drying chamber of 150 DEG C of temperature,
Hydro-thermal reaction 24 hours；
After hydro-thermal reaction, reactor is naturally cooled into room temperature, by reactor gained sample with deionized water repeatedly
Cleaning obtains Sr (Ti until removing all soluble-salts after being dried at 60 DEG C1-xMgx)O3-xPowder；
(3), it is granulated：
In Sr (Ti1-xMgx)O3-xPoly-vinyl alcohol solution is added in powder as binding agent, after uniform mixing, crosses 40 mesh sieves
It is granulated；
Wherein：The mass percent concentration of poly-vinyl alcohol solution is 2-5%；The addition and Sr of poly-vinyl alcohol solution
(Ti1-xMgx)O3-xThe mass ratio of powder is 2-5: 100；
(4), 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 Sr
(Ti1-xMgx)O3-xTarget.
2nd, embodiment 10~12 is using the Sr (Ti with embodiment 11-yXy)O3-yTarget identical composition of raw materials；
And it is the preparation method using identical individual layer nanometer memristor film.That is, be using pulse laser method or
Magnetically controlled sputter method uses Au, Ag, Pt plating Top electrode.
Specific preparation method comprises the following steps：
By obtained Sr (Ti1-xMgx)O3-xTarget, using pulse laser method or magnetically controlled sputter method, by Sr (Ti1- xMgx)O3-xIt is deposited on the surface of bottom electrode；
10-30 minutes are heat-treated at 700-900 DEG C, it is Sr (Ti to obtain chemical composition1-yXy)O3-ySingle-layer ceramic receive
Rice film；
Target using material as Au, Ag or Pt, using pulse laser method or magnetically controlled sputter method, Au, Ag or Pt are sunk
Product is Sr (Ti in above-mentioned chemical composition1-xMgx)O3-xSingle-layer ceramic nano thin-film on, be made Top electrode, get product.
Its thickness of electrode is 10nm-50um.
3rd, embodiment 13 is using the Sr (Ti with embodiment 11-yXy)O3-yTarget identical composition of raw materials；Also, it is to use
Printing process uses In-Ga electrode solutions, plates Top electrode.Specific preparation method, step are with reference to embodiment 8~10.
4th, embodiment 14~16 is using the Sr (Ti with embodiment 11-yXy)O3-yTarget identical composition of raw materials；
And it is the preparation method using identical individual layer nanometer memristor film.That is, it is to be used using heat spraying method
Au, Ag, Pt plating Top electrode.
Specific preparation method comprises the following steps：
Target using material as Au, Ag or Pt, using heat spraying method, by Au, Ag or Pt be deposited on above-mentioned chemistry into
It is divided into Sr (Ti1-xMgx)O3-xSingle-layer ceramic nano thin-film on, be made Top electrode；
Finally, 10-30 minutes are heat-treated at 700-900 DEG C, are got product.Its thickness of electrode is 10nm-50um.
5th, embodiment 10~16 is respectively adopted Au, Ag, In-Ga or Pt and makees upper electrode material, the work in specific preparation process
Skill parameter is as shown in table 1 below.
Embodiment 1
Prepare Sr (Ti1-xMgx)O3-xThe composition of raw materials of target is：Sr(NO3)2：Ti(OC4H9)4：Mg(NO3)2=100:99:
1 (mol ratio).
Embodiment 2
Prepare Sr (Ti1-xMgx)O3-xThe composition of raw materials of target is：Sr(NO3)2：Ti(OC4H9)4：Mg(NO3)2=100:98:
2 (mol ratios).
Embodiment 3
Prepare Sr (Ti1-xMgx)O3-xThe composition of raw materials of target is：Sr(NO3)2：Ti(OC4H9)4：Mg(NO3)2=100:97:
3 (mol ratios).
Embodiment 4
Prepare Sr (Ti1-xMgx)O3-xThe composition of raw materials of target is：Sr(NO3)2：Ti(OC4H9)4：Mg(NO3)2=1000:
999:1 (mol ratio).
Embodiment 5
Prepare Sr (Ti1-xMgx)O3-xThe composition of raw materials of target is：Sr(NO3)2：Ti(OC4H9)4：Mg(NO3)2=1000:
998:2 (mol ratios).
Embodiment 6
Prepare Sr (Ti1-xMgx)O3-xThe composition of raw materials of target is：Sr(NO3)2：Ti(OC4H9)4：Mg(NO3)2=1000:
997:3 (mol ratios).
Embodiment 7
Prepare Sr (Ti1-xMgx)O3-xThe composition of raw materials of target is：Sr(NO3)2：Ti(OC4H9)4：Mg(NO3)2=10000:
9999:1 (mol ratio).
Embodiment 8
Prepare Sr (Ti1-xMgx)O3-xThe composition of raw materials of target is：Sr(NO3)2：Ti(OC4H9)4：Mg(NO3)2=10000:
9998:2 (mol ratios).
Embodiment 9
Prepare Sr (Ti1-xMgx)O3-xThe composition of raw materials of target is：Sr(NO3)2：Ti(OC4H9)4：Mg(NO3)2=10000:
9997:3 (mol ratios).
The technological parameter of embodiment 10- embodiments 16 refers to table 1 below：Embodiment 10-16 technological parameter
The detection and inspection of product：
By above-described embodiment 1-16, each final obtained memristor carries out I-V characteristic test, the results showed that：Each memristor
" 8 " font is presented in the I-V characteristic curve of device；
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).
The embodiment 10-16 of table 1 technological parameter
| Embodiment is numbered | Upper electrode material | Top electrode depositional mode | Heat treatment temperature (DEG C) |
| Embodiment 10 | Au | Pulse laser method or magnetically controlled sputter method | 800 |
| Embodiment 11 | Ag | Pulse laser method or magnetically controlled sputter method | 750 |
| Embodiment 12 | Pt | Pulse laser method or magnetically controlled sputter method | 900 |
| Embodiment 13 | In-Ga | Printing process | 850 |
| Embodiment 14 | Au | Heat spraying method | 700 |
| Embodiment 15 | Ag | Heat spraying method | 700 |
| Embodiment 16 | Pt | Heat spraying method | 800 |
Claims (6)
1. a kind of preparation method of ambipolar nano-film memristor, it is characterised in that comprise the following steps：
The first step, Sr (Ti are prepared using hydro-thermal method1-xMgx)O3-xTarget, comprise the following steps that：
(1), raw material mixes：
By Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2, by 1: (1-x): x mixed in molar ratio, wherein, 0.0001≤x≤
0.03；
Said mixture is dissolved in 10%-20% dust technology, is placed on magnetic stirring apparatus, is stirred, makes it completely molten
Solution；
(2), prepared by powder
NaOH solution is slowly added dropwise into above-mentioned solution until precipitation is complete, filtering is precipitated and is washed with deionized, and is added dropwise
NaOH solution simultaneously adjusts pH value, and is fitted into reactor, is put into and reaches in advance in the thermostatic drying chamber of 150 DEG C of temperature, water
Thermal response 24 hours；
After hydro-thermal reaction, reactor is naturally cooled into room temperature, the sample of gained in reactor is cleaned repeatedly with deionized water
Until removing all soluble-salts, Sr (Ti are obtained after being dried at 60 DEG C1-xMgx)O3-xPowder；
(3), it is granulated：
In Sr (Ti1-xMgx)O3-xPoly-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%；The addition of poly-vinyl alcohol solution and Sr (Ti1-xMgx)
O3-xThe mass ratio of powder is 2-5: 100；
(4), 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 Sr
(Ti1-xMgx)O3-xTarget；
Second step, the preparation of bottom electrode：
Selected bottom electrode is lamination layer structure, includes Pt layers, TiO successively from up to down2Layer, SiO2Layer and Si substrate layers；
3rd step, the preparation of individual layer nanometer memristor film：
By obtained Sr (Ti1-xMgx)O3-xTarget, using pulse laser method or magnetically controlled sputter method, by Sr (Ti1-xMgx)
O3-xIt is deposited on the surface of bottom electrode；
Then, 10-30 minutes are heat-treated at 700-900 DEG C, it is Sr (Ti to obtain chemical composition1-xMgx)O3-xSingle-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 Sr (Ti to be deposited on above-mentioned chemical composition1-xMgx)O3-xSingle-layer ceramic nano thin-film on, be made Top electrode, get product；
Or：
By In-Ga electrode solutions, surface print method is used to be plated in above-mentioned chemical composition as Sr (Ti1-xMgx)O3-xSingle-layer ceramic
On nano thin-film, Top electrode is made, gets product.
2. the preparation method of ambipolar nano-film memristor according to claim 1, it is characterised in that the Top electrode
Thickness be 10nm-50um.
3. the preparation method of ambipolar nano-film memristor according to claim 1 or 2, it is characterised in that the list
The thickness of layer ceramic nano film is 10-990nm.
4. a kind of preparation method of ambipolar nano-film memristor, it is characterised in that comprise the following steps：
The first step, Sr (Ti are prepared using hydro-thermal method1-xMgx)O3-xTarget, comprise the following steps that：
(1), raw material mixes：
By Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2, by 1: (1-x): x mixed in molar ratio, wherein, 0.0001≤x≤
0.03；
Said mixture is dissolved in 10%-20% dust technology, is placed on magnetic stirring apparatus, is stirred, makes it completely molten
Solution；
(2), prepared by powder
NaOH solution is slowly added dropwise into above-mentioned solution until precipitation is complete, filtering is precipitated and is washed with deionized, and is added dropwise
NaOH solution simultaneously adjusts pH value, and is fitted into reactor, is put into and reaches in advance in the thermostatic drying chamber of 150 DEG C of temperature, water
Thermal response 24 hours；
After hydro-thermal reaction, reactor is naturally cooled into room temperature, the sample of gained in reactor is cleaned repeatedly with deionized water
Until removing all soluble-salts, Sr (Ti are obtained after being dried at 60 DEG C1-xMgx)O3-xPowder；
(3), it is granulated：
In Sr (Ti1-xMgx)O3-xPoly-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%；The addition of poly-vinyl alcohol solution and Sr (Ti1-xMgx)
O3-xThe mass ratio of powder is 2-5: 100；
(4), 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 Sr
(Ti1-xMgx)O3-xTarget；
Second step, the preparation of bottom electrode：
Selected bottom electrode is lamination layer structure, includes Pt layers, TiO successively from up to down2Layer, SiO2Layer and Si substrate layers；
3rd step, the preparation of individual layer nanometer memristor film：
By obtained Sr (Ti1-xMgx)O3-xTarget, using pulse laser method or magnetically controlled sputter method, by Sr (Ti1-xMgx)
O3-xIt 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 Sr (Ti1-xMgx)O3-xSingle-layer ceramic nano thin-film on, be made Top electrode；
Finally, 10-30 minutes are heat-treated at 700-900 DEG C, are got product.
5. the preparation method of ambipolar nano-film memristor according to claim 4, it is characterised in that the Top electrode
Thickness be 10nm-50um.
6. the preparation method of the ambipolar nano-film memristor according to claim 4 or 5, it is characterised in that the list
The thickness of layer ceramic nano film is 10-990nm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708990A (en) * | 2009-11-27 | 2010-05-19 | 电子科技大学 | Method for preparing nano-crystalline BST film |
| CN102265397A (en) * | 2008-12-23 | 2011-11-30 | 惠普开发有限公司 | Memristive device and methods of making and using same |
| CN102270738A (en) * | 2010-06-03 | 2011-12-07 | 北京大学 | Manufacturing method of memory unit comprising resistor |
| CN103236499A (en) * | 2013-05-07 | 2013-08-07 | 山东科技大学 | Unipolar memristor and preparation method thereof |
| CN103594620A (en) * | 2013-11-05 | 2014-02-19 | 山东科技大学 | Single-layer nano-film memristor and manufacturing method thereof |
-
2016
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102265397A (en) * | 2008-12-23 | 2011-11-30 | 惠普开发有限公司 | Memristive device and methods of making and using same |
| CN101708990A (en) * | 2009-11-27 | 2010-05-19 | 电子科技大学 | Method for preparing nano-crystalline BST film |
| CN102270738A (en) * | 2010-06-03 | 2011-12-07 | 北京大学 | Manufacturing method of memory unit comprising resistor |
| CN103236499A (en) * | 2013-05-07 | 2013-08-07 | 山东科技大学 | Unipolar memristor and preparation method thereof |
| CN103594620A (en) * | 2013-11-05 | 2014-02-19 | 山东科技大学 | Single-layer nano-film memristor and manufacturing method thereof |
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