CN105742487A - Method for preparing bipolar nano-film memristor - Google Patents
Method for preparing bipolar nano-film memristor Download PDFInfo
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- 238000005520 cutting process Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
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- 239000001301 oxygen Substances 0.000 abstract description 10
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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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- C—CHEMISTRY; METALLURGY
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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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- 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
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- Semiconductor Memories (AREA)
Abstract
The invention discloses a method for preparing a bipolar nano-film memristor. The method adopts the principle that holes and ionized oxygen ions generated under bias voltage are taken as carriers, and the change in device resistance is realized by changing the number of holes and ionized oxygen ions generated. On the basis of the prior art, the process and the chemical formula of the variable-resistance film nano-ceramic material are simplified. The step of variable-resistance film ceramic material pre-sintering is omitted, nano-ceramic raw materials with lower sintering temperature are chosen, and a lower calcination temperature is adopted. Mg<2+> partially replaces Ti<4+> in B-substitution to increase the asymmetry of the molecular structure of Sr(Ti(1-x)Mgx)O(3-x) and increase the number of holes inside. Therefore, the preparation process is simplified, the process flow is shortened, the energy consumption of production and the manufacturing cost are lowered, and the memristive performance of the memristor is improved greatly.
Description
Technical field
The present invention relates to the preparation method of a kind of single-layer nano-film memristor, particularly relate to the preparation method of a kind of ambipolar nano-film memristor；Belong to micro-nano electronic device and nonlinear circuit application.
Background technology
Memristor (memory resistor) is that relay resistance, electric capacity and inductance enter the 4th kind of passive electric circuit element behind mainstream electronic field, is a passive electric circuit element relevant to magnetic flux and electric charge.As far back as 1971, international nonlinear circuit and cell neural network theory pioneer, Leon Chua (Cai Shaotang), based on Circuit theory integrity in logic, foretold the existence of memristor theoretically.2008, HP Lab has constructed memristor antetype device the most experimentally it was confirmed Leon Chua is about the theory of memristor, causes worldwide strong interest.Memristor has the non-linear electric character of novelty, and has the features such as density is high, size is little, low in energy consumption, non-volatile concurrently it is considered to be develop one of ideal scheme of novel nonvolatile storage technologies of future generation.Thus become the study hotspot in the field such as information, material.Additionally, the resistive behavior of memristor and organism neural plasticity have the similarity of height, thus at the development aspect such as the bionical device of nerve synapse and neuromorphic computer, there are potentiality.
The structure of existing memristor is Hewlett-Packard laboratory researchers in May, 2008 to be published to publish thesis on " naturally " magazine and middle is clipped between two nano wires being made up of Pt by nano level two-layer titanium dioxide semiconductive thin film, sandwich structure.Actually one nonlinear resistor having memory function of well-known memristor modeling.Can change its resistance by controlling the change of electric current, if high value is defined as " 1 ", low resistance is defined as " 0 ".The most this resistance just can realize storing the function of data.The memristor modeling generally acknowledged is to be made up of one layer of nano level anoxia titanium deoxid film of folder between two Pt nano wires and neutral titanium deoxid film, although simple in construction, but switching speed compares relatively low.Although memristor research in recent years achieves bigger progress, but we also to see, for a basic component, memristor research is the most at the early-stage, is mainly manifested in the following aspects:
(1) the most constantly there are new memristor material and memristor system report, but the memristor model of physics realization at present is the most little and the most single, there is no unified Universal Model and is described memristor behavior.
The memristor in kind reported in recent years is both for greatly the application of certain class or simulates certain function, such as high-density nonvolatile memory, Crossbar Latch (intersect dot matrix gate) technology, analog neuron synapse, and proposes.It uses the switch models similar with HP memristor and working mechanism mostly, and complex manufacturing technology, cost are high, does not have generality and universality for research memristor characteristic, memristor Circuit theory and design of electronic circuits etc..
(2) the most not yet realize commercially producing.
Most researchers is difficult to obtain a real memristor element, cause Many researchers when studying memristor and memristor circuit, the hardware experiments in real physical meaning cannot be carried out in default of memristor element, be more dependent on emulation or analog circuit to carry out experimentation.But, memristor simulation model and analog circuit are very remote from actual memristor different from those, and what the hardware carried out with analog circuit realized more consideration is also to simulate memristor mathematical model and have ignored the intrinsic physical trait of memristor.
(3) preparation of the memristor in kind reported, raw material select and require on process of preparing high, condition harsh, laboratory that condition is general or R&D institution have been difficult to the preparation of relevant memristor element in kind.
In the physics realization of memristor, in prior art, more advanced is, Chinese patent application CN103594620A discloses a kind of single-layer nano-film memristor and preparation method thereof, its mode based on physics realization prepares the memristor with lamination layer structure form, concrete preparation method: use CaCO3, SrCO3And TiO3Make raw material, at 900-1300 DEG C, sinter 15-240min, prepare Ca(1-x)SrxTiO3- δCeramic material, then with Ca(1-x)SrxTiO3- δMake target (wherein, 0 < x < 1,0 < δ < 3), use magnetically controlled sputter method at Pt/TiO2/SiO2Plated film on/Si substrate, the thickness of plated film is 20-900nm, then through 700-800 DEG C of heat treatment 10-30min；Last at Ca(1-x)SrxTiO3- δLast layer electrode is plated on nano thin-film.
The essence of its technical scheme, be exactly generally: first prepare the Ca as target(1-x)SrxTiO3- δ(wherein, 0 < x < 1,0 < δ < 3) ceramic material, after with this Ca(1-x)SrxTiO3- δTarget made by ceramic material, uses magnetically controlled sputter method at Pt/TiO2/SiO2Plated film on/Si substrate, the most again at Ca(1-x)SrxTiO3- δLast layer electrode is plated on nano thin-film.
The preparation method of technique scheme, its major defect and deficiency be:
1, prepared memristor memristor poor-performing.
Reason is, its change resistance layer: Ca(1-x)SrxTiO3- δNano thin-film is with Ca(1-x)SrxTiO3- δTarget (wherein, 0 < x < 1,0 < δ < 3) made by ceramic material, uses magnetically controlled sputter method to be deposited in lower electrode surface.
The monolayer nanometer film of this version, is to be sintered into ceramic material Ca with the calcining through higher temperature (900-1300 DEG C)(1-x)SrxTiO3- δFor target, then by magnetron sputtering deposition on bottom electrode base material, its material itself compact structure, lattice defect and number of cavities are on the low side.
2, complicated process of preparation, manufacturing cycle is long, and energy consumption is higher:
Reason is, its preparation technology needs first to calcine under the high temperature of 900-1300 DEG C, prepares Ca(1-x)SrxTiO3- δCeramic material target；After magnetron sputtering molding, in addition it is also necessary to heat treatment 10-30min at 700-800 DEG C again.
3, obtained memristor material is hard and crisp, easily causes rupturing or damaging because of collision, not readily transportable.
Additionally, its to there is also process conditions relatively harsh, the problem and shortage that ratio defective product is on the low side.
Summary of the invention
It is an object of the invention to, there is provided a kind of be prone to physics realization, preparation technology is simple, control the preparation method of the ambipolar nano-film memristor that difficulty is little, steady quality, production efficiency are high, with low cost, its prepared memristor is suitable to general circuit theoretical research and circuit design, has generality and universality.
The first technical scheme that the present invention is used for achieving the above object is, the preparation method of a kind of ambipolar nano-film memristor, it is characterised in that comprise the following steps:
The first step, uses hydro-thermal method to prepare Sr (Ti1-xMgx)O3-xTarget, specifically comprises the following steps that
(1), raw material mixing:
By Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2, by 1: the mixed in molar ratio of (1-x): x, wherein, 0 < x < 1；
Said mixture is dissolved in the dust technology of 10%-20%, is placed on magnetic stirring apparatus, is stirred so that it is be completely dissolved；
(2), prepared by powder body
Being slowly added dropwise NaOH solution in above-mentioned solution until precipitation completely, filters precipitation and is washed with deionized, dropping NaOH solution also regulates pH value, and load in reactor, puts into the thermostatic drying chamber reaching to determine temperature 150 DEG C in advance, hydro-thermal reaction 24 hours；
After hydro-thermal reaction, reactor is naturally cooled to room temperature, the sample deionized water of gained in reactor being cleaned repeatedly until removing all soluble-salts, after drying at 60 DEG C, obtaining Sr (Ti1-xMgx)O3-xPowder body；
(3), pelletize:
At Sr (Ti1-xMgx)O3-xIn powder body, addition poly-vinyl alcohol solution is as binding agent, after uniform mixing, crosses 40 mesh sieves and carries out pelletize；
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 body is 2-5 100；
(4), target material moulding:
Compound after pelletize is placed on tablet machine and is pressed into bulk；
Then, gained bulk compound cutting into a diameter of 20-150mm, height is the slice of cylinder of 2-10mm, obtains Sr (Ti1-xMgx)O3-xTarget；
Second step, the preparation of bottom electrode:
Selected bottom electrode is lamination layer structure, includes Pt layer, TiO the most successively2Layer, SiO2Layer and Si substrate layer；
3rd step, the preparation of monolayer nanometer memristor film:
By obtained Sr (Ti1-xMgx)O3-xTarget, uses pulse laser method or magnetically controlled sputter method, by Sr (Ti1-xMgx)O3-xIt is deposited on the surface of bottom electrode；
Then, heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Sr (Ti1-xMgx)O3-xSingle-layer ceramic nano thin-film, be monolayer nanometer memristor film；
4th step, with material as Au, the target of Ag or Pt, uses pulse laser method or magnetically controlled sputter method, and it is Sr (Ti that Au, Ag or Pt are deposited on above-mentioned chemical composition1-xMgx)O3-xSingle-layer ceramic nano thin-film on, prepare upper electrode, get product；
Or:
By In-Ga electrode solution, using surface print method to be plated in above-mentioned chemical composition is Sr (Ti1-xMgx)O3-xSingle-layer ceramic nano thin-film on, prepare upper electrode, get product.
What technique scheme was directly brought has the technical effect that, uses 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 at 700-900 DEG C subsequently heat treatment process, complete Sr (Ti in the lump1-xMgx)O3-xThe sintering of LTCC, thus on the upper surface of bottom electrode, form that to have the chemical composition of good change resistance performance be Sr (Ti1-xMgx)O3-xSingle-layer ceramic nano thin-film.
With prior art first will mix raw material high-temperature calcination, it is fired into ceramic material, carries out magnetron sputtering deposition with this ceramic material in lower electrode surface for target again, comparing with the preparation technology of formation resistive film, the topmost improvement of preparation technology of technique scheme is: dispensed preceding ceramic material calcine technology step.This simplify the preparation technology of memristor, shorten technological process, improve production efficiency, and reduce energy consumption；
Compared with prior art, not only simply dispensed high-temperature calcination simply is prefabricated into the step of ceramic material to technique scheme.What is more important, in the technique scheme of the present invention, is by Sr (Ti1-xMgx)O3-xIt is deposited in lower electrode surface, then attached the thermal sintering of the resistive film of nano ceramics material during 10-30 minute through the heat treatment of low temperature (700-900 DEG C).This efficiency that both ensure that thin film dense sintering and quality, avoid again temperature too low and the too short thin film of temperature retention time is the finest and close, or temperature is too high and the long damage causing thin film and electrode of temperature retention time deforms；
Further, in terms of the chemical composition of resistive film, with the memristor ratio of above-mentioned immediate prior art, the technique scheme of the present invention is by using with+divalent cation (Mg2+) part replacement+4 valency cation (Ti4+) carry out the replacement of B position, increase the unsymmetry of molecular structure, improve the hole amount in molecule, be conducive to strengthening Sr (Ti1-xMgx)O3-xThe memristor performance of thin film memristor.
Being preferably, the thickness of above-mentioned upper electrode is 10nm-50um.
What this optimal technical scheme was directly brought has the technical effect that, the selection of the thickness of electrode on ensureing on the basis of memristor performance, carrying out in this wide in range scope of 10nm-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 this optimal technical scheme was directly brought has the technical effect that, we experience have shown that, the thickness of single-layer ceramic nano thin-film is 10-990nm, on the one hand has the best change resistance performance；On the other hand, it is simple to technology controlling and process.
The second technical scheme that the present invention is used for achieving the above object is, the preparation method of a kind of ambipolar nano-film memristor, it is characterised in that comprise the following steps:
The first step, uses hydro-thermal method to prepare Sr (Ti1-xMgx)O3-xTarget, specifically comprises the following steps that
(1), raw material mixing:
By Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2, by 1: the mixed in molar ratio of (1-x): x, wherein, 0 < x < 1；
Said mixture is dissolved in the dust technology of 10%-20%, is placed on magnetic stirring apparatus, is stirred so that it is be completely dissolved；
(2), prepared by powder body
Being slowly added dropwise NaOH solution in above-mentioned solution until precipitation completely, filters precipitation and is washed with deionized, dropping NaOH solution also regulates pH value, and load in reactor, puts into the thermostatic drying chamber reaching to determine temperature 150 DEG C in advance, hydro-thermal reaction 24 hours；
After hydro-thermal reaction, reactor is naturally cooled to room temperature, the sample deionized water of gained in reactor being cleaned repeatedly until removing all soluble-salts, after drying at 60 DEG C, obtaining Sr (Ti1-xMgx)O3-xPowder body；
(3), pelletize:
At Sr (Ti1-xMgx)O3-xIn powder body, addition poly-vinyl alcohol solution is as binding agent, after uniform mixing, crosses 40 mesh sieves and carries out pelletize；
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 body is 2-5 100；
(4), target material moulding:
Compound after pelletize is placed on tablet machine and is pressed into bulk；
Then, gained bulk compound cutting into a diameter of 20-150mm, height is the slice of cylinder of 2-10mm, obtains Sr (Ti1-xMgx)O3-xTarget；
Second step, the preparation of bottom electrode:
Selected bottom electrode is lamination layer structure, includes Pt layer, TiO the most successively2Layer, SiO2Layer and Si substrate layer；
3rd step, the preparation of monolayer nanometer memristor film:
By obtained Sr (Ti1-xMgx)O3-xTarget, uses pulse laser method or magnetically controlled sputter method, by Sr (Ti1-xMgx)O3-xIt is deposited on the surface of bottom electrode；
4th step, with material as Au, the target of Ag or Pt, uses heat spraying method, and it is Sr (Ti that Au, Ag or Pt are deposited on above-mentioned chemical composition1-xMgx)O3-xSingle-layer ceramic nano thin-film on, prepare upper electrode；
Finally, at 700-900 DEG C, heat treatment 10-30 minute, gets product.
What technique scheme was directly brought has the technical effect that, it is easy to physics realization, preparation technology are simply, difficulty is little, steady quality, production efficiency are high, with low cost in control.Concrete reason, with above, repeats the most one by one.
Being preferably, the thickness of above-mentioned upper electrode is 10nm-50um.
What this optimal technical scheme was directly brought has the technical effect that, the selection of the thickness of electrode on ensureing on the basis of memristor performance, carrying out in this wide in range scope of 10nm-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 this optimal technical scheme was directly brought has the technical effect that, we experience have shown that, the thickness of single-layer ceramic nano thin-film is 10-990nm, on the one hand has the best change resistance performance；On the other hand, it is simple 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 is, with bias under produce hole and ionized oxygen ion as carrier, under electric field action, rely on this hole and the change of ionized oxygen ion generation amount, to realize the change of device resistance.
Being not difficult to find out, its working mechanism and mathematical model possess generality and universality.
For being more fully understood that the technical characterstic of the present invention, it is described in detail from principle below in conjunction with memristor correlation theory.
The present invention based on Sr (Ti1-xMgx)O3-xThe memristor of nano thin-film, its mathematical model is particularly as follows: this memristor is by the monolayer Sr (Ti being sandwiched between two electrodes1-xMgx)O3-xNano thin-film is constituted.
Its memristor mechanism: when a voltage or electric current are added on this device, owing to film thickness is nanoscale, the least voltage will produce huge electric field, Sr (Ti1-xMgx)O3-xWith the oxygen in air, O can occur under bias with the surface of air contact2+4e-→2O2-Reaction, and produce hole in making thin film.Meanwhile, inside thin film, it is biased against function influence O occurs2-→e-+O-, hole and ionized oxygen ion (O-) as principal carrier displacement under electric field action, along with hole and ionized oxygen ion (O-) change of generation amount can cause the resistance variations between two electrodes, corresponding thin film presents minimum (R therewithmin) or maximum (Rmax) two kinds of different resistance, this is Sr (Ti1-xMgx)O3-xRepresent the mechanism of memristor characteristic.
Now represent a certain moment Sr (Ti with O (t)1-xMgx)O3-xThe hole amount produced under bias, M represents the maximum void amount produced under bias effect, and v represents the speed producing hole under bias effect.
Due to hole and ionized oxygen ion (O-) generation amount relevant with by its size of current and persistent period (i.e. charge accumulated) thereof:That is:Therefore, film resistor is its function by electric charge: work as Rmin<<RmaxTime,
Because without driving electric field in bias (electric current) interruption rear film, and the most each ion, electronics, hole etc. are moved inactive, hole and ionized oxygen ion (O in thin film-) measure and cannot return the state that biasing (electric current passes through) is front, therefore there is memory effect and keep biasing resistance when (electric current) interrupts.
In sum, the present invention is relative to prior art, and the improvement of the core in terms of thought and know-why is two aspects technically:
One is, eliminates the ceramic material as resistive film component and fires step in advance；Two are, the improvement in terms of resistive film ceramic material chemical composition is (with+divalent cation (Mg2+) part replacement+4 valency cation (Ti4+) carry out the replacement of B position, increase the unsymmetry of molecular structure, improve the hole amount in molecule, be conducive to strengthening Sr (Ti1-xMgx)O3-xThe memristor performance of thin film memristor).
Further, improve based on above-mentioned both sides so that the resistive film of ceramic material structurally, there occurs useful optimum change (being added significantly to number of cavities), causes significantly improving and improving of final memristor memristor performance.
Need to further illustrate: in above two technical scheme, respectively according to each selecting upper electrode material or the difference of plated electrode method, different to the order of the nano thin-film heat treatment used.Its object is to:
Ensure Sr (Ti1-xMgx)O3-xNano thin-film and upper electrode have high fitness and associativity, to avoid the combination between upper electrode damage or electrode and thin film bad.
Being not difficult to find out, the present invention, relative to prior art, has that preparation technology is simple, controls that difficulty is little, steady quality, production efficiency are high, with low cost, and the memristor performance of obtained memristor product more preferably waits beneficial effect.
Accompanying drawing explanation
Fig. 1 is the Sr (Ti obtained by the present invention1-xMgx)O3-xAmbipolar single-layer nano-film memristor structural representation；
Fig. 2 is the Sr (Ti obtained by the present invention1-xMgx)O3-xThe mathematical model of ambipolar single-layer nano-film memristor M (q).
Detailed description of the invention
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.
As it is shown in figure 1, single-layer nano-film memristor of the present invention includes two electrodes (upper electrode and bottom electrode), and the Sr (Ti being placed between two electrodes1-xMgx)O3-xNano thin-film structure, power on extremely Au, Ag, In-Ga or Pt, and bottom electrode is Pt, with Pt/TiO2/SiO2/ Si is substrate.
Fig. 2 is obtained Sr (Ti1-xMgx)O3-xThe mathematical model of ambipolar single-layer nano-film memristor M (q).
From figure 2 it can be seen that the memristor mechanism of the present invention is along with hole and ionized oxygen ion (O-) change of generation amount can cause the resistance variations between two electrodes, corresponding thin film presents minimum (R therewithmin) or maximum (Rmax) two kinds of different resistance, i.e. Sr (Ti1-xMgx)O3-xMemristor Mechanism of characters.
Below in conjunction with embodiment, the present invention is described in further detail.
Illustrate:
1, example 1 below-9, are all to use hydro-thermal method to prepare Sr (Ti1-xMgx)O3-xTarget；Prepare raw material Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2Mol ratio is 1: (1-x): x, wherein, 0 < x < 1.
Hydro-thermal method is used to prepare Sr (Ti1-xMgx)O3-xTarget, comprises the following steps:
(1), raw material mixing:
By Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2, by 1: the mixed in molar ratio of (1-x): x, wherein, 0 < x < 1；
Said mixture is dissolved in the dust technology of 10%-20%, is placed on magnetic stirring apparatus, is stirred so that it is be completely dissolved；
(2), prepared by powder body
Being slowly added dropwise NaOH solution in above-mentioned solution until precipitation completely, filters precipitation and is washed with deionized, dropping NaOH solution also regulates pH value, and load in reactor, puts into the thermostatic drying chamber reaching to determine temperature 150 DEG C in advance, hydro-thermal reaction 24 hours；
After hydro-thermal reaction, reactor is naturally cooled to room temperature, the sample deionized water of gained in reactor being cleaned repeatedly until removing all soluble-salts, after drying at 60 DEG C, obtaining Sr (Ti1-xMgx)O3-xPowder body；
(3), pelletize:
At Sr (Ti1-xMgx)O3-xIn powder body, addition poly-vinyl alcohol solution is as binding agent, after uniform mixing, crosses 40 mesh sieves and carries out pelletize；
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 body is 2-5 100；
(4), target material moulding:
Compound after pelletize is placed on tablet machine and is pressed into bulk；
Then, gained bulk compound cutting into a diameter of 20-150mm, height is the slice of cylinder of 2-10mm, obtains Sr (Ti1-xMgx)O3-xTarget.
2, embodiment 10～12 all uses the Sr (Ti with embodiment 11-yXy)O3-yThe composition of raw materials that target is identical；
And it is all the preparation method using identical monolayer nanometer memristor film.It is i.e., all to use pulse laser method or magnetically controlled sputter method to use Au, Ag, Pt to plate electrode.
Concrete preparation method comprises the steps:
By obtained Sr (Ti1-xMgx)O3-xTarget, uses pulse laser method or magnetically controlled sputter method, by Sr (Ti1-xMgx)O3-xIt is deposited on the surface of bottom electrode；
Heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Sr (Ti1-yXy)O3-ySingle-layer ceramic nano thin-film；
With material as Au, the target of Ag or Pt, use pulse laser method or magnetically controlled sputter method, it is Sr (Ti that Au, Ag or Pt are deposited on above-mentioned chemical composition1-xMgx)O3-xSingle-layer ceramic nano thin-film on, prepare upper electrode, get product.Its thickness of electrode is 10nm-50um.
3, embodiment 13 uses the Sr (Ti with embodiment 11-yXy)O3-yThe composition of raw materials that target is identical；Further, it is to use printing process to use In-Ga electrode solution, plates electrode.Concrete preparation method, step are with reference to embodiment 8～10.
4, embodiment 14～16 all uses the Sr (Ti with embodiment 11-yXy)O3-yThe composition of raw materials that target is identical；
And it is all the preparation method using identical monolayer nanometer memristor film.It is i.e., all to use heat spraying method to use Au, Ag, Pt to plate electrode.
Concrete preparation method comprises the steps:
With material as Au, the target of Ag or Pt, use heat spraying method, it is Sr (Ti that Au, Ag or Pt are deposited on above-mentioned chemical composition1-xMgx)O3-xSingle-layer ceramic nano thin-film on, prepare upper electrode；
Finally, at 700-900 DEG C, heat treatment 10-30 minute, gets product.Its thickness of electrode is 10nm-50um.
5, embodiment 10～16 is respectively adopted Au, Ag, In-Ga or Pt and makees upper electrode material, and the technological parameter in concrete preparation process is as shown in table 1 below.
Embodiment 1
Preparation 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
Preparation 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 ratio).
Embodiment 3
Preparation 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 ratio).
Embodiment 4
Preparation 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
Preparation 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 ratio).
Embodiment 6
Preparation 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 ratio).
Embodiment 7
Preparation 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
Preparation 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 ratio).
Embodiment 9
Preparation 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 ratio).
The technological parameter of embodiment 10-embodiment 16 refers to table 1 below: the technological parameter of embodiment 10-16
The detection of product and inspection:
Above-described embodiment 1-16 each final obtained memristor is carried out I-V characteristic test, and result shows: the I-V characteristic curve of each memristor all presents " 8 " font；
And by changing pressurization size and pressing time, its I-V characteristic can all show non-volatile specific to memristor (that is, Memorability).
The technological parameter of table 1 embodiment 10-16
| Embodiment is numbered | Upper electrode material | Upper 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. the preparation method of an ambipolar nano-film memristor, it is characterised in that comprise the following steps:
The first step, uses hydro-thermal method to prepare Sr (Ti1-xMgx)O3-xTarget, specifically comprises the following steps that
(1), raw material mixing:
By Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2, by 1: the mixed in molar ratio of (1-x): x, wherein, 0 < x < 1；
Said mixture is dissolved in the dust technology of 10%-20%, is placed on magnetic stirring apparatus, is stirred so that it is be completely dissolved；
(2), prepared by powder body
Being slowly added dropwise NaOH solution in above-mentioned solution until precipitation completely, filters precipitation and is washed with deionized, dropping NaOH solution also regulates pH value, and load in reactor, puts into the thermostatic drying chamber reaching to determine temperature 150 DEG C in advance, hydro-thermal reaction 24 hours；
After hydro-thermal reaction, reactor is naturally cooled to room temperature, the sample deionized water of gained in reactor being cleaned repeatedly until removing all soluble-salts, after drying at 60 DEG C, obtaining Sr (Ti1-xMgx)O3-xPowder body；
(3), pelletize:
At Sr (Ti1-xMgx)O3-xIn powder body, addition poly-vinyl alcohol solution is as binding agent, after uniform mixing, crosses 40 mesh sieves and carries out pelletize；
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 body is 2-5 100；
(4), target material moulding:
Compound after pelletize is placed on tablet machine and is pressed into bulk；
Then, gained bulk compound cutting into a diameter of 20-150mm, height is the slice of cylinder of 2-10mm, obtains Sr (Ti1-xMgx)O3-xTarget；
Second step, the preparation of bottom electrode:
Selected bottom electrode is lamination layer structure, includes Pt layer, TiO the most successively2Layer, SiO2Layer and Si substrate layer；
3rd step, the preparation of monolayer nanometer memristor film:
By obtained Sr (Ti1-xMgx)O3-xTarget, uses pulse laser method or magnetically controlled sputter method, by Sr (Ti1-xMgx)O3-xIt is deposited on the surface of bottom electrode；
Then, heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Sr (Ti1-xMgx)O3-xSingle-layer ceramic nano thin-film, be monolayer nanometer memristor film；
4th step, with material as Au, the target of Ag or Pt, uses pulse laser method or magnetically controlled sputter method, and it is Sr (Ti that Au, Ag or Pt are deposited on above-mentioned chemical composition1-xMgx)O3-xSingle-layer ceramic nano thin-film on, prepare upper electrode, get product；Or: by In-Ga electrode solution, using surface print method to be plated in above-mentioned chemical composition is Sr (Ti1-xMgx)O3-xSingle-layer ceramic nano thin-film on, prepare upper electrode, get product.
The preparation method of ambipolar nano-film memristor the most according to claim 1, it is characterised in that the thickness of described upper electrode is 10nm-50um.
The preparation method of ambipolar nano-film memristor the most according to claim 1 and 2, it is characterised in that the thickness of described single-layer ceramic nano thin-film is 10-990nm.
4. the preparation method of an ambipolar nano-film memristor, it is characterised in that comprise the following steps:
The first step, uses hydro-thermal method to prepare Sr (Ti1-xMgx)O3-xTarget, specifically comprises the following steps that
(1), raw material mixing:
By Sr (NO3)2、Ti(OC4H9)4With Mg (NO3)2, by 1: the mixed in molar ratio of (1-x): x, wherein, 0 < x < 1；
Said mixture is dissolved in the dust technology of 10%-20%, is placed on magnetic stirring apparatus, is stirred so that it is be completely dissolved；
(2), prepared by powder body
Being slowly added dropwise NaOH solution in above-mentioned solution until precipitation completely, filters precipitation and is washed with deionized, dropping NaOH solution also regulates pH value, and load in reactor, puts into the thermostatic drying chamber reaching to determine temperature 150 DEG C in advance, hydro-thermal reaction 24 hours；
After hydro-thermal reaction, reactor is naturally cooled to room temperature, the sample deionized water of gained in reactor being cleaned repeatedly until removing all soluble-salts, after drying at 60 DEG C, obtaining Sr (Ti1-xMgx)O3-xPowder body；
(3), pelletize:
At Sr (Ti1-xMgx)O3-xIn powder body, addition poly-vinyl alcohol solution is as binding agent, after uniform mixing, crosses 40 mesh sieves and carries out pelletize；
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 body is 2-5 100；
(4), target material moulding:
Compound after pelletize is placed on tablet machine and is pressed into bulk；
Then, gained bulk compound cutting into a diameter of 20-150mm, height is the slice of cylinder of 2-10mm, obtains Sr (Ti1-xMgx)O3-xTarget；
Second step, the preparation of bottom electrode:
Selected bottom electrode is lamination layer structure, includes Pt layer, TiO the most successively2Layer, SiO2Layer and Si substrate layer；
3rd step, the preparation of monolayer nanometer memristor film:
By obtained Sr (Ti1-xMgx)O3-xTarget, uses pulse laser method or magnetically controlled sputter method, by Sr (Ti1-xMgx)O3-xIt is deposited on the surface of bottom electrode；
4th step, with material as Au, the target of Ag or Pt, uses heat spraying method, and it is Sr (Ti that Au, Ag or Pt are deposited on above-mentioned chemical composition1-xMgx)O3-xSingle-layer ceramic nano thin-film on, prepare upper electrode；
Finally, at 700-900 DEG C, heat treatment 10-30 minute, gets product.
The preparation method of ambipolar nano-film memristor the most according to claim 4, it is characterised in that the thickness of described upper electrode is 10nm-50um.
6. according to the preparation method of the ambipolar nano-film memristor described in claim 4 or 5, it is characterised in that the thickness of described single-layer ceramic nano thin-film is 10-990nm.
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| 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 |
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