CN105576121A - Preparation method of flexible single-layer nano-film memristor - Google Patents
Preparation method of flexible single-layer nano-film memristor Download PDFInfo
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- CN105576121A CN105576121A CN201510996704.3A CN201510996704A CN105576121A CN 105576121 A CN105576121 A CN 105576121A CN 201510996704 A CN201510996704 A CN 201510996704A CN 105576121 A CN105576121 A CN 105576121A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 68
- 239000002356 single layer Substances 0.000 title claims abstract description 45
- 239000002120 nanofilm Substances 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 74
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000010408 film Substances 0.000 claims description 38
- 229910052737 gold Inorganic materials 0.000 claims description 32
- 238000005469 granulation Methods 0.000 claims description 32
- 230000003179 granulation Effects 0.000 claims description 32
- 229910052697 platinum Inorganic materials 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 239000010409 thin film Substances 0.000 claims description 30
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 26
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 26
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 26
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 26
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000013077 target material Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000003746 solid phase reaction Methods 0.000 claims description 6
- 238000010671 solid-state reaction Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011858 nanopowder Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000003854 Surface Print Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 18
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 15
- 230000008859 change Effects 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- -1 oxygen ions Chemical class 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000002800 charge carrier Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000009472 formulation Methods 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 90
- 230000000694 effects Effects 0.000 description 9
- 238000000151 deposition Methods 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004549 pulsed laser deposition Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 230000005684 electric field Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000008261 resistance mechanism Effects 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000013528 artificial neural network Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 210000002569 neuron Anatomy 0.000 description 1
- 230000007996 neuronal plasticity Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000000225 synapse Anatomy 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- 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 preparation method of a flexible single-layer nano-film memristor. Holes and ionized oxygen ions generated by the single-layer nano-film memristor under a bias voltage are utilized as charge carriers; and the change principle of the resistance of a device is achieved by change of output of the holes and the ionized oxygen ions, so that a relatively low calcination temperature is combined by omitting a pre-sintering step of a ceramic material of a resistance film and selecting a raw material with a lower nano ceramic sintering temperature from two aspects of simplification of the preapration technology and chemical formulation of the nano ceramic material of the resistance film; B-site substitution is carried out by partially replacing Ti<4+> with X<2+>; the asymmetry of the molecular structure and the hole quantity in the resistance film are increased; by a series of technical means of coating a green tape to form a 'flexible' lower electrode and the like, the preparation technology is simplified; the technological process is shortened; the production efficiency is improved; the production energy consumption and the manufacturing cost are reduced; and the memristive property of the memristor is greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method of single-layer nano-film memristor, particularly relate to a kind of preparation method of flexible single-layer nano-film memristor; Belong to micro-nano electronic device and nonlinear circuit application.
Background technology
Memristor (memory resistor) is 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 the theoretical pioneer of cell neural network, LeonChua (Cai Shaotang), based on Circuit theory integrality in logic, foretold the existence of memristor theoretically.2008, memristor antetype device was constructed first experimentally in HP Lab, confirmed the theory of LeonChua about memristor, caused worldwide strong interest.Memristor has novel non-linear electric character, and has the features such as density is high, size is little, low in energy consumption, non-volatile concurrently, is considered to one of ideal scheme developing novel nonvolatile storage technologies of future generation.Thus the study hotspot in the field such as information, material is become.In addition, the resistive behavior of memristor and organism neural plasticity have the similitude of height, thus in the development bionical device of nerve synapse and neuromorphic computer etc., have potentiality.
To be Hewlett-Packard laboratory researchers in May, 2008 publish " nature " magazine publishes thesis middlely to be clipped in by nano level two-layer titanium dioxide semiconductive thin film between two nano wires being made up of Pt for the structure of existing memristor, sandwich structure.In fact well-known memristor modeling is exactly a nonlinear resistor having memory function.Can change its resistance by the change controlling electric current, if high value is defined as " 1 ", low resistance is defined as " 0 ".Then this resistance just can realize the function storing data.The memristor modeling of generally acknowledging is by pressing from both sides one deck nano level anoxic titanium deoxid film between two Pt nano wires and neutral titanium deoxid film is formed, although structure is simple, switching speed is relatively low.Although memristor research in recent years achieves larger progress, we also will see, as a basic circuit element, memristor research is just at the early-stage, is mainly manifested in the following aspects:
(1) constantly have in recent years and new recall resistance material and recall resistance body system report, but the memristor model of physics realization at present also seldom and relatively single, there is no unified Universal Model and be described memristor behavior.
The memristor in kind reported in recent years is mostly for the application of certain class or simulates certain function, as high-density nonvolatile memory, CrossbarLatch (intersection dot matrix gate) technology, analog neuron cynapse, and propose.It mostly adopts the switch models similar with HP memristor and working mechanism, and complex manufacturing technology, cost are high, for research memristor characteristic, recalls the theoretical and design of electronic circuits of resistance circuit etc. and does not have generality and universality.
(2) not yet realize at present commercially producing.
Most researchers is difficult to the real memristor element of acquisition one, cause Many researchers when studying memristor and recalling resistance circuit, the hardware experiments cannot carried out in real physical meaning in default of memristor element is more rely on emulation or analog circuit to carry out experimental study.But, memristor simulation model and analog circuit from reality memristor different from those very away from, being also simulation memristor Mathematical Modeling of the more considerations of the hardware implementing carried out with analog circuit and have ignored the essential physical characteristic of memristor.
(3) preparation of the memristor in kind reported, raw material select and process of preparing on require high, condition is harsh, the 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, the mode that its physically based deformation realizes prepares the memristor with lamination layer structure form, concrete preparation method: adopt CaCO
3, SrCO
3and TiO
3make raw material, at 900-1300 DEG C, sinter 15-240min, prepare Ca
(1-x)sr
xtiO
3-δceramic material, then with Ca
(1-x)sr
xtiO
3-δmake target (wherein, 0<x<1,0< δ <3), adopt magnetically controlled sputter method at Pt/TiO
2/ SiO
2plated 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)sr
xtiO
3-δnano thin-film plates one deck electrode.
The essence of its technical scheme, is exactly generally: first prepare the Ca as target
(1-x)sr
xtiO
3-δ(wherein, 0<x<1,0< δ <3) ceramic material, after with this Ca
(1-x)sr
xtiO
3-δtarget made by ceramic material, adopts magnetically controlled sputter method at Pt/TiO
2/ SiO
2plated film on/Si substrate, finally again at Ca
(1-x)sr
xtiO
3-δnano thin-film plates one deck electrode.
The preparation method of technique scheme, its major defect and deficiency are:
1, prepared memristor recalls resistance poor-performing.
Reason is, its change resistance layer: Ca
(1-x)sr
xtiO
3-δnano thin-film is with Ca
(1-x)sr
xtiO
3-δtarget (wherein, 0<x<1,0< δ <3) made by ceramic material, adopts magnetically controlled sputter method to be deposited in lower electrode surface.
The individual layer nanometer film of this version is to be sintered into ceramic material Ca through the calcining of higher temperature (900-1300 DEG C)
(1-x)sr
xtiO
3-δfor target, then by magnetron sputtering deposition on bottom electrode base material, its material itself compact structure, lattice defect and number of cavities 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)sr
xtiO
3-δceramic material target; After magnetron sputtering is shaping, also need heat treatment 10-30min at 700-800 DEG C again.
3, obtained memristor material is hard and crisp, easily because collision causes breaking or damaging, is not easy to transport.
In addition, it is relatively harsh also to there are process conditions in it, the problem and shortage that ratio defective product is on the low side.
Summary of the invention
The object of the invention is, there is provided a kind of and be easy to the preparation method that physics realization, preparation technology are simple, control the flexible single-layer nano-film memristor that difficulty is little, steady quality, production efficiency are high, with low cost, memristor prepared by it has certain flexible, be convenient to adopt LTCC technology integrated, and be suitable for general circuit theoretical research and circuit design, there is generality and universality.
The first technical scheme that the present invention is adopted for achieving the above object is, a kind of preparation method of flexible single-layer nano-film memristor, is characterized in that, comprise the following steps:
The first step, adopts sol-gal process to prepare Ba (Ti
1-yx
y) O
3-ymixture target, concrete steps are as follows:
(1), raw material prepares:
By 1: the mol ratio of (1-y): y gets Ba (CH respectively
3cOO)
2, C
16h
36o
4ti and X (CH
3cOO)
2, wherein, X is Mg, Zn, Ca, 0<y<1, for subsequent use;
(2), colloidal sol preparation:
By Ba (CH
3cOO)
2with X (CH
3cOO)
2after mixed in molar ratio by 1: y is even, be dissolved in acetic acid;
Then, add acetylacetone,2,4-pentanedione used as stabilizers, addition is the 5%-20% of quality of acetic acid, stirs and obtains mixed solution in 5-10 minute;
Afterwards, in gained mixed solution, by Ba:Ti=1: the mol ratio of (1-y), adds C
16h
36o
4ti, stirs 5-10 minute, filters and obtains colloidal sol filtrate;
(3), Ba (Ti
1-yx
y) O
3-ythe preparation of powder:
Gained colloidal sol filtrate is placed in thermostatic drying chamber, at 100-150 DEG C, dries 6-24 hour; Take out, after grinding, obtain Ba (Ti
1-yx
y) O
3-ypowder;
(4), granulation:
At Ba (Ti
1-yx
y) O
3-yadd poly-vinyl alcohol solution in powder as binding agent, after uniform mixing, cross 40 mesh sieves and carry out granulation;
Wherein: the mass percent concentration of poly-vinyl alcohol solution is 2-5%; The mass ratio of the powder after the addition of poly-vinyl alcohol solution and above-mentioned oven dry is 2-5 ︰ 100;
(5), target material moulding:
Compound after granulation is placed on tablet press machine and is pressed into bulk;
Then, it is 20-150mm that block for gained compound is cut into diameter, is highly the slice of cylinder of 2-10mm, obtains Ba (Ti
1-yx
y) O
3-ymixture target;
Or:
The first step, adopts solid state reaction to prepare Ba (Ti
1-yx
y) O
3-ymixture target, concrete steps are as follows:
(1), raw material prepares:
In molar ratio 1: (1-y): y, get BaCO respectively
3, TiO
2and XO; Wherein, X is Mg, Zn or Ca, 0<y<1; For subsequent use;
(2), mixing of materials:
By BaCO
3, TiO
2with XO by 1: (1-y): y mixed in molar ratio evenly after, add deionized water or absolute ethyl alcohol, enter ball mill grinding 4-24 little up to particle size at below 0.08mm;
Then, take out, dry, obtain elementary Ba (Ti
1-yx
y) O
3-ymixed powder;
(3), granulation:
At gained Ba (Ti
1-yx
y) O
3-yadd poly-vinyl alcohol solution in mixed powder as binding agent, after uniform mixing, cross 40 mesh sieves and carry out granulation; Wherein:
The mass percent concentration of poly-vinyl alcohol solution is 2-5%;
The addition of poly-vinyl alcohol solution and Ba (Ti
1-yx
y) O
3-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;
After block compound cut into diameter is 20-150mm, thickness is the slice of cylinder of 2-10mm, obtain Ba (Ti
1-yx
y) O
3-ymixture target;
Second step, the preparation of bottom electrode:
Get low temperature co-fired green band substrate, with Pt or Au for target, adopt pulse laser method or magnetically controlled sputter method, be deposited on by Pt or Au on low temperature co-fired green band substrate, forming material is the bottom electrode of Pt or Au;
3rd step, individual layer nanometer recalls the preparation of resistance film:
By obtained Ba (Ti
1-yx
y) O
3-ynano-mixture target, adopts pulse laser method or magnetically controlled sputter method, by nano-mixture Ba (Ti
1-yx
y) O
3-ybe deposited on the surface of bottom electrode;
Then, heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film, be individual layer nanometer and recall resistance film;
4th step take material as the target of Au, Ag or Pt, and adopt pulse laser method or magnetically controlled sputter method, Au, Ag or Pt being deposited on above-mentioned chemical composition is Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film on, obtained top electrode, obtains individual layer nanometer resistive film memristor;
Or:
4th step, by In-Ga electrode solution, adopting surface print method to be plated in above-mentioned chemical composition is Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film on, obtained top electrode, obtains flexible single-layer nano-film memristor.
The technique effect that technique scheme is directly brought is, adopts pulse laser method or magnetically controlled sputter method, is directly Ba (Ti by chemical composition
1-yx
y) O
3-ymixture (target) be deposited on the upper surface of bottom electrode; And at 700-900 subsequently DEG C heat treatment process, complete Ba (Ti in the lump
1-yx
y) O
3-ythe sintering of LTCC, thus on the upper surface of bottom electrode, form the chemical composition with good change resistance performance be Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film.
With prior art first by mixed material high-temperature calcination, be fired into ceramic material, again with this ceramic material for target carries out magnetron sputtering deposition in lower electrode surface, compare with the preparation technology forming 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;
Technique scheme compared with prior art, has not only just dispensed the step that high-temperature calcination is prefabricated into ceramic material simply.What is more important, in technique scheme of the present invention, is by Ba (Ti
1-yx
y) O
3-y(X=Mg, Zn, Ca) mixture target material deposition in lower electrode surface, then to have attached the thermal sintering of the resistive film of nano ceramics material in the heat treatment 10-30 minute process of low temperature (700-900 DEG C).This both ensure that efficiency and the quality of film dense sintering, avoided again the too low and too short film of temperature retention time of temperature fine and close not, or temperature is too high and temperature retention time is long causes the damage of film and electrode to be out of shape;
Further, in the chemical composition of resistive film, with the memristor ratio of above-mentioned immediate prior art, technique scheme of the present invention passes through+divalent cation (X by employing
2+=Mg
2+, Zn
2+, Ca
2+) part replacement+4 valency cation (Ti
4+) carry out the replacement of B position, increase Ba (Ti
1-yx
y) O
3-ythe asymmetry of molecular structure, improves Ba (Ti
1-yx
y) O
3-yin hole amount, be conducive to strengthening Ba (Ti
1-yx
y) O
3-yfilm memristor recall resistive energy.
Further, in technique scheme, because substrate is the LTCC green band being coated with bottom electrode Pt or Au, make Ba (Ti
1-yx
y) O
3-ymemristor product has certain flexible, is not only convenient to transport carrying, and is convenient to adopt LTCC technology integrated.
Be preferably, the thickness of above-mentioned top electrode is 10nm-50um.
The technique effect that this optimal technical scheme is directly brought is, on the basis ensureing memristor performance, carries out the selection of the thickness of top electrode in this wide in range scope of 10nm-50um, is conducive to reducing technique controlling difficulty, improves rate of finished products.
Further preferably, the thickness of above-mentioned single-layer ceramic nano thin-film is 10-990nm.
The technique effect that this optimal technical scheme is directly brought is, our experience shows, the thickness of single-layer ceramic nano thin-film is 10-990nm, has comparatively good change resistance performance on the one hand; On the other hand, technology controlling and process is convenient to.The second technical scheme that the present invention is adopted for achieving the above object is, a kind of preparation method of flexible single-layer nano-film memristor, is characterized in that, comprise the following steps:
The first step, adopts sol-gal process to prepare Ba (Ti
1-yx
y) O
3-ymixture target, concrete steps are as follows:
(1), raw material prepares:
By 1: the mol ratio of (1-y): y gets Ba (CH respectively
3cOO)
2, C
16h
36o
4ti and X (CH
3cOO)
2, wherein, X is Mg, Zn, Ca, 0<y<1, for subsequent use;
(2), colloidal sol preparation:
By Ba (CH
3cOO)
2with X (CH
3cOO)
2after mixed in molar ratio by 1: y is even, be dissolved in acetic acid;
Then, add acetylacetone,2,4-pentanedione used as stabilizers, addition is the 5%-20% of quality of acetic acid, stirs and obtains mixed solution in 5-10 minute;
Afterwards, in gained mixed solution, by Ba:Ti=1: the mol ratio of (1-y), adds C
16h
36o
4ti, stirs 5-10 minute, filters and obtains colloidal sol filtrate;
(3), Ba (Ti
1-yx
y) O
3-ythe preparation of powder:
Gained colloidal sol filtrate is placed in thermostatic drying chamber, at 100-150 DEG C, dries 6-24 hour; Take out, after grinding, obtain Ba (Ti
1-yx
y) O
3-ypowder;
(4), granulation:
At Ba (Ti
1-yx
y) O
3-yadd poly-vinyl alcohol solution in powder as binding agent, after uniform mixing, cross 40 mesh sieves and carry out granulation;
Wherein: the mass percent concentration of poly-vinyl alcohol solution is 2-5%; The mass ratio of the powder after the addition of poly-vinyl alcohol solution and above-mentioned oven dry is 2-5 ︰ 100;
(5), target material moulding:
Compound after granulation is placed on tablet press machine and is pressed into bulk;
Then, it is 20-150mm that block for gained compound is cut into diameter, is highly the slice of cylinder of 2-10mm, obtains Ba (Ti
1-yx
y) O
3-ymixture target;
Or:
The first step, adopts solid state reaction to prepare Ba (Ti
1-yx
y) O
3-ymixture target, concrete steps are as follows:
(1), raw material prepares:
In molar ratio 1: (1-y): y, get BaCO respectively
3, TiO
2and XO; Wherein, X is Mg, Zn or Ca, 0<y<1; For subsequent use;
(2), mixing of materials:
By BaCO
3, TiO
2with XO by 1: (1-y): y mixed in molar ratio evenly after, add deionized water or absolute ethyl alcohol, enter ball mill grinding 4-24 little up to particle size at below 0.08mm;
Then, take out, dry, obtain elementary Ba (Ti
1-yx
y) O
3-ymixed powder;
(3), granulation:
At gained Ba (Ti
1-yx
y) O
3-yadd poly-vinyl alcohol solution in mixed powder as binding agent, after uniform mixing, cross 40 mesh sieves and carry out granulation; Wherein:
The mass percent concentration of poly-vinyl alcohol solution is 2-5%;
The addition of poly-vinyl alcohol solution and Ba (Ti
1-yx
y) O
3-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;
After block compound cut into diameter is 20-150mm, thickness is the slice of cylinder of 2-10mm, obtain Ba (Ti
1-yx
y) O
3-ymixture target;
Second step, the preparation of bottom electrode:
Get low temperature co-fired green band substrate, with Pt or Au for target, adopt pulse laser method or magnetically controlled sputter method, be deposited on by Pt or Au on low temperature co-fired green band substrate, forming material is the bottom electrode of Pt or Au;
3rd step, individual layer nanometer recalls the preparation of resistance film:
By obtained Ba (Ti
1-yx
y) O
3-ynano-mixture target, adopts pulse laser method or magnetically controlled sputter method, by nano-mixture Ba (Ti
1-yx
y) O
3-ybe deposited on the surface of bottom electrode;
4th step take material as the target of Au, Ag or Pt, and adopt heat spraying method, Au, Ag or Pt being deposited on above-mentioned chemical composition is Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film on, obtained top electrode;
Finally, heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film on,
Obtain flexible single-layer nano-film memristor.
The technique effect that technique scheme is directly brought is, is easy to physics realization, preparation technology is simple, control difficulty is little, steady quality, production efficiency are high, with low cost.Concrete reason, with above, repeats no longer one by one.
Be preferably, the thickness of above-mentioned top electrode is 10nm-50um.
The technique effect that this optimal technical scheme is directly brought is, on the basis ensureing memristor performance, carries out the selection of the thickness of top electrode in this wide in range scope of 10nm-50um, is conducive to reducing technique controlling difficulty, improves rate of finished products.
Further preferably, the thickness of above-mentioned single-layer ceramic nano thin-film is 10-990nm.
The technique effect that this optimal technical scheme is directly brought is, our experience shows, the thickness of single-layer ceramic nano thin-film is 10-990nm, has comparatively good change resistance performance on the one hand; On the other hand, technology controlling and process is convenient to.
It should be noted that, the single-layer nano-film memristor prepared by the present invention, it is recalled resistance resistive principle and is, with the hole produced under bias voltage and ionized oxygen ion for charge carrier, under electric field action, rely on the change of this hole and ionized oxygen ion generation amount, to realize the change of device resistance.
Be not difficult to find out, its working mechanism and Mathematical Modeling possess generality and universality.
For understanding technical characterstic of the present invention better, be described in detail from principle below in conjunction with memristor correlation theory.
Of the present invention based on Ba (Ti
1-yx
y) O
3-ythe memristor of (X=Mg, Zn, Ca) nano thin-film, it recalls resistance mechanism and Mathematical Modeling is specially: this memristor is by the individual layer Ba (Ti be sandwiched between two electrodes
1-yx
y) O
3-ynano thin-film is formed.
Due to+divalent cation (X
2+=Mg
2+, Zn
2+, Ca
2+) part replacement+4 valency cation (Ti
4+), increase Ba (Ti
1-yx
y) O
3-ythe asymmetry of molecular structure, improves Ba (Ti
1-yx
y) O
3-yin hole amount.When a voltage or electric current are added on this device, because film thickness is nanoscale, very little voltage will produce huge electric field, Ba (Ti
1-yx
y) O
3-yo can be there is under bias in the surface contacted with air with the oxygen in air
2+ 4e
-→ 2O
2-reaction, and make to produce hole in film.
Meanwhile, generation O is affected in film inside by bias effect
2-→ e
-+ O
-, hole and ionized oxygen ion (O
-) as principal carrier displacement under electric field action, along with hole and ionized oxygen ion (O
-) resistance variations that the change of generation can cause between two electrodes, corresponding film presents minimum (R with it
min) or maximum (R
max) two kinds of different resistance, this is Ba (Ti
1-yx
y) O
3-yrepresent the mechanism recalling resistance characteristic.Now represent a certain moment Ba (Ti with O (t)
1-yx
y) O
3-ythe hole amount produced under bias, the maximum void amount that M produces under representing bias effect, v produces the speed in hole under representing bias effect.Due to hole and ionized oxygen ion (O
-) generation with by its size of current and the duration (i.e. charge accumulated) relevant:
that is:
therefore, film resistor is its function by electric charge: work as R
min<<R
maxtime,
Because bias voltage (electric current) interrupts without driving electric field in rear film, and the motion such as each ion, electronics, hole is at normal temperatures inactive, hole and ionized oxygen ion (O in film
-) measure and cannot return the front state of biasing (electric current passes through), resistance when therefore there is memory effect and keep bias voltage (electric current) to interrupt.
In sum, the present invention is relative to prior art, and the improvement of the core of thought and know-why aspect is two aspects technically:
One is, the ceramic material eliminated as resistive film component fires step in advance; Two are, the improvement (+divalent cation (X of resistive film ceramic material chemical composition aspect
2+=Mg
2+, Zn
2+, Ca
2+) part replacement+4 valency cation (Ti
4+) carry out the replacement of B position, increase Ba (Ti
1-yx
y) O
3-ythe asymmetry of molecular structure, improves Ba (Ti
1-yx
y) O
3-yin hole amount, be conducive to strengthening Ba (Ti
1-yx
y) O
3-yfilm memristor recall resistive energy).
Further, based on the improvement of above-mentioned two aspects, the resistive film making ceramic material structurally, there occurs useful optimum change (significantly adding number of cavities), causes final memristor to recall remarkable improvement and the raising of resistive energy.
Need to further illustrate: in above-mentioned two kinds of technical schemes, respectively according to the difference selecting upper electrode material or plated electrode method separately, different to the order of adopted nano thin-film heat treatment.Its object is to:
Ensure Ba (Ti
1-yx
y) O
3-ynano thin-film and top electrode have high fitness and associativity, with avoid top electrode damage or between electrode and film in conjunction with bad.
Be not difficult to find out, the present invention relative to prior art, have preparation technology simple, control that difficulty is little, steady quality, production efficiency are high, with low cost, recalling of obtained memristor product resistively better can wait beneficial effect.
Accompanying drawing explanation
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 accompanying drawing, brief description is carried out to the present invention.
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 comprises two electrodes (top electrode and bottom electrode), and is placed in the Ba (Ti between two electrodes
1-yx
y) O
3-ynano thin-film structure, power on very Au, Ag, In-Ga or Pt, and bottom electrode is Pt or Au, with LTCC green band for substrate.
Fig. 2 is the Mathematical Modeling of single-layer nano-film memristor M (q) of the present invention.
As can be seen from Figure 2, of the present invention recall resistance mechanism along with hole and ionized oxygen ion (O
-) resistance variations that the change of generation can cause between two electrodes, corresponding film presents minimum (R with it
min) or maximum (R
max) two kinds of different resistance, i.e. Ba (Ti
1-yx
y) O
3-yrecall resistance Mechanism of characters.
Below in conjunction with embodiment, the present invention is described in further detail.
Illustrate:
1, embodiment 1-9 is all adopt sol-gal process to prepare Sr (Ti
1-xmg
x) O
3-xmixture target.
Raw materials and formula consist of mol ratio Ba (CH
3cOO)
2: (1-y) C
16h
36o
4ti: yX (CH
3cOO)
2(X=Mg, Zn, Ca), wherein, 0<y<1;
Sol-gal process is adopted to prepare Ba (Ti
1-yx
y) O
3-ymixture target, comprises the steps:
1st step: by Ba (CH
3cOO)
2with X (CH
3cOO)
2(X=Mg, Zn, Ca), by the mixed in molar ratio of 1: y, is dissolved in acetic acid, adds acetylacetone,2,4-pentanedione used as stabilizers, and addition is the 5%-20% of quality of acetic acid, stirs and obtains mixed solution in 5-10 minute;
2nd step: in final stoicheiometry Ba:Ti=1 in mixed solution: the ratio of (1-y) adds C
16h
36o
4ti, stirs 5-10 minute, filters;
3rd step: the solution (colloidal sol) after filtering is placed in thermostatic drying chamber, and dried through 6-24 hour at 100-150 DEG C, the powder after oven dry is for subsequent use;
4th step: granulation, adopt mass fraction be the poly-vinyl alcohol solution of 2-5% as binding agent, the addition of binding agent is treat the 2-5% of granulation mixture quality mark, cross 40 mesh sieves carry out granulation;
5th step: compacting, the compound after granulation being sieved utilizes tablet press machine to suppress, and to be cut to diameter be 20-150mm, is highly the slice of cylinder of 2-10mm.
2, embodiment 10-18, be all adopt solid state reaction to prepare Ba (Ti
1-yx
y) O
3-ymixture target; Wherein, X=Mg, Zn, Ca.
Ba (Ti
1-yx
y) O
3-yraw materials and the formula of mixture target consist of mol ratio BaCO
3: (1-y) TiO
2: yXO (X=Mg, Zn, Ca), wherein, 0<y<1; Solid state reaction is adopted to prepare described Ba (Ti
1-yx
y) O
3-y, comprise the steps:
1st step: mixing, by BaCO
3, TiO
2with XO (X=Mg, Zn, Ca) by 1: the mixed in molar ratio of (1-y): y, adds deionized water or absolute ethyl alcohol, ball milling, then dry, obtain compound;
2nd step: granulation, adopt mass fraction be the poly-vinyl alcohol solution of 2-5% as binding agent, the addition of binding agent is treat the 2-5% of granulation powder mass fraction, cross 40 mesh sieves carry out granulation;
3rd step: compacting, the compound after granulation being sieved utilizes tablet press machine to suppress, and to be cut to diameter be 20-150mm, is highly the slice of cylinder of 2-10mm.
3, embodiment 19 ~ 21 all adopts the Ba (Ti with embodiment 1
1-yx
y) O
3-ythe composition of raw materials that mixture target is identical;
Further, be the target of Au, Ag or Pt respectively with material, adopt pulse laser method or magnetically controlled sputter method, Au, Ag or Pt are deposited on Ba (Ti
1-yx
y) O
3-yon nano thin-film.
Adopt the preparation method of identical single-layer nano-film memristor, adopt pulsed laser deposition PLD or magnetically controlled sputter method to use Au, Ag, Pt to plate electrode, this preparation method comprises the steps:
1st step, with Ba (Ti
1-yx
y) O
3-y(X=Mg, Zn, Ca) makes target, adopt pulsed laser deposition PLD or magnetically controlled sputter method plated film on the LTCC green band being coated with bottom electrode Pt or Au in advance, form change resistance layer, the thickness of plated film is 10-990nm, then through 700-900 DEG C of heat treatment 10-30 minute;
2nd step take material as the target of Au, Ag or Pt, adopts pulse laser method or magnetically controlled sputter method, at Ba (Ti
1-yx
y) O
3-ynano thin-film plates one deck top electrode.
4, embodiment 22 adopts the Ba (Ti with embodiment 1
1-yx
y) O
3-ythe composition of raw materials that mixture target is identical; Further, be adopt printing process to use In-Ga electrode solution to plate one deck top electrode.
5, embodiment 23 ~ 25 is Ba (Ti
1-yx
y) O
3-ythe top electrode process of (X=Mg, Zn, Ca) nano thin-film, all adopts embodiment 1Ba (Ti
1-yx
y) O
3-ythe composition of raw materials that mixture target is identical, adopts the preparation method of identical single-layer nano-film memristor, and adopt other deposition methods to use Au, Ag, Pt to plate electrode, this preparation method comprises the steps:
1st step, with Ba (Ti
1-yx
y) O
3-ymake target, adopt pulsed laser deposition PLD or magnetically controlled sputter method plated film on the LTCC green band being coated with bottom electrode Pt or Au in advance, form change resistance layer, the thickness of plated film is 10-990nm;
2nd step, at Ba (Ti
1-yx
y) O
3-ynano thin-film plates one deck top electrode, then through 700-900 DEG C of heat treatment 10-30 minute.
The preparation method of above-mentioned nano-film memristor, its thickness of electrode is 10nm-50um, and described upper electrode material is Au, Ag, In-Ga or Pt.
6, embodiment 19-25 adopts Au, Ag, In-Ga or Pt to make upper electrode material respectively, and the technological parameter in concrete preparation process is as shown in table 1 below.
Embodiment 1
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: Ba (CH
3cOO)
2: C
16h
36o
4ti:X (CH
3cOO)
2=100:99:1 (mol ratio).
Embodiment 2
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: Ba (CH
3cOO)
2: C
16h
36o
4ti:X (CH
3cOO)
2=100:98:2 (mol ratio).
Embodiment 3
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: Ba (CH
3cOO)
2: C
16h
36o
4ti:X (CH
3cOO)
2=100:97:3 (mol ratio).
Embodiment 4
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: Ba (CH
3cOO)
2: C
16h
36o
4ti:X (CH
3cOO)
2=1000:999:1 (mol ratio).
Embodiment 5
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: Ba (CH
3cOO)
2: C
16h
36o
4ti:X (CH
3cOO)
2=1000:998:2 (mol ratio).
Embodiment 6
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: Ba (CH
3cOO)
2: C
16h
36o
4ti:X (CH
3cOO)
2=1000:997:3 (mol ratio).
Embodiment 7
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: Ba (CH
3cOO)
2: C
16h
36o
4ti:X (CH
3cOO)
2=10000:9999:1 (mol ratio).
Embodiment 8
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: Ba (CH
3cOO)
2: C
16h
36o
4ti:X (CH
3cOO)
2=10000:9998:2 (mol ratio).
Embodiment 9
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: Ba (CH
3cOO)
2: C
16h
36o
4ti:X (CH
3cOO)
2=10000:9997:3 (mol ratio).
Embodiment 10
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: BaCO
3: TiO
2: XO=100:99:1 (mol ratio).
Embodiment 11
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: BaCO
3: TiO
2: XO=100:98:2 (mol ratio).
Embodiment 12
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: BaCO
3: TiO
2: XO=100:97:3 (mol ratio).
Embodiment 13
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: BaCO
3: TiO
2: XO=1000:999:1 (mol ratio).
Embodiment 14
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: BaCO
3: TiO
2: XO=1000:998:2 (mol ratio).
Embodiment 15
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: BaCO
3: TiO
2: XO=1000:997:3 (mol ratio).
Embodiment 16
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: BaCO
3: TiO
2: XO=10000:9999:1 (mol ratio).
Embodiment 17
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: BaCO
3: TiO
2: XO=10000:9998:2 (mol ratio).
Embodiment 18
Preparation Ba (Ti
1-yx
y) O
3-ythe composition of raw materials of mixture target is: BaCO
3: TiO
2: XO=10000:9997:3 (mol ratio).
The technological parameter of table 1 embodiment 19-25
| 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 of product and inspection:
Final for above-described embodiment 1-25 obtained memristor is carried out I-V characteristic test, and result shows:
The I-V characteristic curve of such 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).
Claims (6)
1. a preparation method for flexible single-layer nano-film memristor, is characterized in that, comprises the following steps:
The first step, adopts sol-gal process to prepare Ba (Ti
1-yx
y) O
3-ymixture target, concrete steps are as follows:
(1), raw material prepares:
By 1: the mol ratio of (1-y): y gets Ba (CH respectively
3cOO)
2, C
16h
36o
4ti and X (CH
3cOO)
2, wherein, X is Mg, Zn, Ca, 0<y<1, for subsequent use;
(2), colloidal sol preparation:
By Ba (CH
3cOO)
2with X (CH
3cOO)
2after mixed in molar ratio by 1: y is even, be dissolved in acetic acid;
Then, add acetylacetone,2,4-pentanedione used as stabilizers, addition is the 5%-20% of quality of acetic acid, stirs and obtains mixed solution in 5-10 minute;
Afterwards, in gained mixed solution, by Ba:Ti=1: the mol ratio of (1-y), adds C
16h
36o
4ti, stirs 5-10 minute, filters and obtains colloidal sol filtrate;
(3), Ba (Ti
1-yx
y) O
3-ythe preparation of powder:
Gained colloidal sol filtrate is placed in thermostatic drying chamber, at 100-150 DEG C, dries 6-24 hour; Take out, after grinding, obtain Ba (Ti
1-yx
y) O
3-ypowder;
(4), granulation:
At Ba (Ti
1-yx
y) O
3-yadd poly-vinyl alcohol solution in powder as binding agent, after uniform mixing, cross 40 mesh sieves and carry out granulation;
Wherein: the mass percent concentration of poly-vinyl alcohol solution is 2-5%; The mass ratio of the powder after the addition of poly-vinyl alcohol solution and above-mentioned oven dry is 2-5 ︰ 100;
(5), target material moulding:
Compound after granulation is placed on tablet press machine and is pressed into bulk;
Then, it is 20-150mm that block for gained compound is cut into diameter, is highly the slice of cylinder of 2-10mm, obtains Ba (Ti
1-yx
y) O
3-ymixture target;
Or:
The first step, adopts solid state reaction to prepare Ba (Ti
1-yx
y) O
3-ymixture target, concrete steps are as follows:
(1), raw material prepares:
In molar ratio 1: (1-y): y, get BaCO respectively
3, TiO
2and XO; Wherein, X is Mg, Zn or Ca, 0<y<1; For subsequent use;
(2), mixing of materials:
By BaCO
3, TiO
2with XO by 1: (1-y): y mixed in molar ratio evenly after, add deionized water or absolute ethyl alcohol, enter ball mill grinding 4-24 little up to particle size at below 0.08mm;
Then, take out, dry, obtain elementary Ba (Ti
1-yx
y) O
3-ymixed powder;
(3), granulation:
At gained Ba (Ti
1-yx
y) O
3-yadd poly-vinyl alcohol solution in mixed powder as binding agent, after uniform mixing, cross 40 mesh sieves and carry out granulation; Wherein:
The mass percent concentration of poly-vinyl alcohol solution is 2-5%;
The addition of poly-vinyl alcohol solution and Ba (Ti
1-yx
y) O
3-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;
After block compound cut into diameter is 20-150mm, thickness is the slice of cylinder of 2-10mm, obtain Ba (Ti
1-yx
y) O
3-ymixture target;
Second step, the preparation of bottom electrode:
Get low temperature co-fired green band substrate, with Pt or Au for target, adopt pulse laser method or magnetically controlled sputter method, be deposited on by Pt or Au on low temperature co-fired green band substrate, forming material is the bottom electrode of Pt or Au;
3rd step, individual layer nanometer recalls the preparation of resistance film:
By obtained Ba (Ti
1-yx
y) O
3-ynano-mixture target, adopts pulse laser method or magnetically controlled sputter method, by nano-mixture Ba (Ti
1-yx
y) O
3-ybe deposited on the surface of bottom electrode;
Then, heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film, be individual layer nanometer and recall resistance film;
4th step take material as the target of Au, Ag or Pt, and adopt pulse laser method or magnetically controlled sputter method, Au, Ag or Pt being deposited on above-mentioned chemical composition is Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film on, obtained top electrode, obtains individual layer nanometer resistive film memristor;
Or:
4th step, by In-Ga electrode solution, adopting surface print method to be plated in above-mentioned chemical composition is Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film on, obtained top electrode, obtains flexible single-layer nano-film memristor.
2. the preparation method of flexible single-layer nano-film memristor according to claim 1, is characterized in that, the thickness of described top electrode is 10nm-50um.
3. the preparation method of flexible single-layer nano-film memristor according to claim 1 and 2, is characterized in that, the thickness of described single-layer ceramic nano thin-film is 10-990nm.
4. a preparation method for flexible single-layer nano-film memristor, is characterized in that, comprises the following steps:
The first step, adopts sol-gal process to prepare Ba (Ti
1-yx
y) O
3-ymixture target, concrete steps are as follows:
(1), raw material prepares:
By 1: the mol ratio of (1-y): y gets Ba (CH respectively
3cOO)
2, C
16h
36o
4ti and X (CH
3cOO)
2, wherein, X is Mg, Zn, Ca, 0<y<1, for subsequent use;
(2), colloidal sol preparation:
By Ba (CH
3cOO)
2with X (CH
3cOO)
2after mixed in molar ratio by 1: y is even, be dissolved in acetic acid;
Then, add acetylacetone,2,4-pentanedione used as stabilizers, addition is the 5%-20% of quality of acetic acid, stirs and obtains mixed solution in 5-10 minute;
Afterwards, in gained mixed solution, by Ba:Ti=1: the mol ratio of (1-y), adds C
16h
36o
4ti, stirs 5-10 minute, filters and obtains colloidal sol filtrate;
(3), Ba (Ti
1-yx
y) O
3-ythe preparation of powder:
Gained colloidal sol filtrate is placed in thermostatic drying chamber, at 100-150 DEG C, dries 6-24 hour; Take out, after grinding, obtain Ba (Ti
1-yx
y) O
3-ypowder;
(4), granulation:
At Ba (Ti
1-yx
y) O
3-yadd poly-vinyl alcohol solution in powder as binding agent, after uniform mixing, cross 40 mesh sieves and carry out granulation;
Wherein: the mass percent concentration of poly-vinyl alcohol solution is 2-5%; The mass ratio of the powder after the addition of poly-vinyl alcohol solution and above-mentioned oven dry is 2-5 ︰ 100;
(5), target material moulding:
Compound after granulation is placed on tablet press machine and is pressed into bulk;
Then, it is 20-150mm that block for gained compound is cut into diameter, is highly the slice of cylinder of 2-10mm, obtains Ba (Ti
1-yx
y) O
3-ymixture target;
Or:
The first step, adopts solid state reaction to prepare Ba (Ti
1-yx
y) O
3-ymixture target, concrete steps are as follows:
(1), raw material prepares:
In molar ratio 1: (1-y): y, get BaCO respectively
3, TiO
2and XO; Wherein, X is Mg, Zn or Ca, 0<y<1; For subsequent use;
(2), mixing of materials:
By BaCO
3, TiO
2with XO by 1: (1-y): y mixed in molar ratio evenly after, add deionized water or absolute ethyl alcohol, enter ball mill grinding 4-24 little up to particle size at below 0.08mm;
Then, take out, dry, obtain elementary Ba (Ti
1-yx
y) O
3-ymixed powder;
(3), granulation:
At gained Ba (Ti
1-yx
y) O
3-yadd poly-vinyl alcohol solution in mixed powder as binding agent, after uniform mixing, cross 40 mesh sieves and carry out granulation; Wherein:
The mass percent concentration of poly-vinyl alcohol solution is 2-5%;
The addition of poly-vinyl alcohol solution and Ba (Ti
1-yx
y) O
3-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;
After block compound cut into diameter is 20-150mm, thickness is the slice of cylinder of 2-10mm, obtain Ba (Ti
1-yx
y) O
3-ymixture target;
Second step, the preparation of bottom electrode:
Get low temperature co-fired green band substrate, with Pt or Au for target, adopt pulse laser method or magnetically controlled sputter method, be deposited on by Pt or Au on low temperature co-fired green band substrate, forming material is the bottom electrode of Pt or Au;
3rd step, individual layer nanometer recalls the preparation of resistance film:
By obtained Ba (Ti
1-yx
y) O
3-ynano-mixture target, adopts pulse laser method or magnetically controlled sputter method, by nano-mixture Ba (Ti
1-yx
y) O
3-ybe deposited on the surface of bottom electrode;
4th step take material as the target of Au, Ag or Pt, and adopt heat spraying method, Au, Ag or Pt being deposited on above-mentioned chemical composition is Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film on, obtained top electrode;
Finally, heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Ba (Ti
1-yx
y) O
3-ysingle-layer ceramic nano thin-film on,
Obtain flexible single-layer nano-film memristor.
5. the preparation method of flexible single-layer nano-film memristor according to claim 4, is characterized in that, the thickness of described top electrode is 10nm-50um.
6. the preparation method of the flexible single-layer nano-film memristor according to claim 4 or 5, is characterized in that, the thickness of described single-layer ceramic nano thin-film is 10-990nm.
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