CN105591028A - Preparation method of single-layer nano-film memristor using LTCC green tape as substrate - Google Patents
Preparation method of single-layer nano-film memristor using LTCC green tape as substrate Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- G—PHYSICS
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- G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
- G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
Abstract
The invention discloses a preparation method of a single-layer nano-film memristor using an LTCC green tape as a substrate. According to the invention, cavities and ionized oxygen ions generated by the single-layer nano-film memristor under a bias voltage are utilized, the change principle of device resistance is realized dependent on the changes of the generation numbers of the cavities and the ionized oxygen ions, and from technology simplification and resistive film raw material formula improvement, the preparation method is characterized in that a pre-sintering step of the resistive film ceramic material is omitted, a ceramic raw material lower in sintering temperature is selected, and a lower sintering temperature is adopted; B site substitution is carried out by replacing Ti4+ with an X2+ part, so that the asymmetry of the molecule structure and the number of internal cavities of the resistive film are increased; in addition, a series of technical means is adopted, for example, film plating is carried out on the LTCC green tape to form a flexible lower electrode, the preparation technology is simplified, the production efficiency is improved, the production energy consumption and the manufacturing cost are lowered, and the memristive performance of the memristor is substantially improved.
Description
Technical field
The present invention relates to a kind of preparation method of individual layer nano thin-film memristor, relate in particular to a kind of preparation method of the individual layer nano thin-film memristor taking LTCC green band as substrate; 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 after main flow electronic applications, is a passive electric circuit element relevant to magnetic flux and electric charge. As far back as 1971, the theoretical pioneer of international nonlinear circuit and cell neural network, LeonChua (Cai Shaotang), based on Circuit theory integrality in logic, has foretold the existence of memristor theoretically. 2008, HP Lab was constructed memristor antetype device first experimentally, had confirmed the theory of LeonChua about memristor, had caused worldwide strong interest. Memristor has novel non-linear electrical properties, 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. Thereby become the study hotspot in the field such as information, material. In addition, the resistive behavior of memristor and organism neural plasticity have the similitude of height, thereby have potentiality at aspects such as the development bionical device of nerve synapse and neuromorphic computers.
To be the laboratory research personnel of Hewlett-Packard publish middle nano level two-layer titanium dioxide semiconductive thin film being clipped between two nano wires being made up of Pt that publish thesis on " nature " magazine, sandwich structure to the structure of existing memristor in May, 2008. In fact well-known memristor modeling is exactly a nonlinear resistor that has memory function. Can change its resistance by the variation of controlling electric current, if high value is defined as to " 1 ", low resistance is defined as " 0 ". This resistance just can be realized the function of storage data. Generally acknowledged memristor modeling is to form by pressing from both sides the nano level anoxic titanium deoxid film of one deck and neutral titanium deoxid film between two Pt nano wires, although simple in structure, switching speed is relatively low. Although memristor research has in recent years obtained larger progress, we also will see, as a basic component, memristor research is just at the early-stage, is mainly manifested in the following aspects:
(1) constantly have in recent years new recalling resistance material and recall resistance body system report, but the memristor model of physics realization is at present also little and relatively single, behavior is described to memristor to there is no unified Universal Model.
The memristor in kind of report is mostly for certain class application or simulates certain function in recent years, as high-density nonvolatile memory, CrossbarLatch (intersection dot matrix gate) technology, analog neuron cynapse, and propose. It mostly adopts switch model and the working mechanism similar with HP memristor, and complex manufacturing technology, cost are high, for research memristor characteristic, recall resistance circuit theory and design of electronic circuits etc. and do not have generality and universality.
(2) not yet realize and commercially producing at present.
Most researchers is difficult to obtain a real memristor element, when causing Many researchers at research memristor and recalling resistance circuit, cannot carry out the hardware experiments in real physical meaning in default of memristor element, be more to rely on emulation or analog circuit to carry out experimental study. But memristor simulation model and analog circuit differ greatly from actual memristor characteristic, simulation memristor Mathematical Modeling that what the hardware that carries out with analog circuit was realized more considerations is also and ignored the essential physical characteristic of memristor.
(3) preparation of the memristor in kind of having 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 memristor element in kind of being correlated with.
In the physics realization of memristor, in prior art, more advanced is, Chinese patent application CN103594620A discloses a kind of individual layer nano thin-film memristor and preparation method thereof, its mode based on physics realization is prepared the memristor with lamination layer structure form, concrete preparation method: adopt CaCO3，SrCO3And TiO3Make raw material, at 900-1300 DEG C, sintering 15-240min, prepares Ca(1-x)SrxTiO3-δCeramic material, then with Ca(1-x)SrxTiO3-δMake target (wherein, 0 < x < 1,0 < δ < 3), adopt 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; Finally at Ca(1-x)SrxTiO3-δOn nano thin-film, plate one deck electrode.
The essence of its technical scheme, is 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-δCeramic material is made target, adopts magnetically controlled sputter method at Pt/TiO2/SiO2Plated film on/Si substrate, finally again at Ca(1-x)SrxTiO3-δOn nano thin-film, plate one deck electrode.
The preparation method of technique scheme, its major defect and deficiency are:
1, prepared memristor is recalled resistance poor-performing.
Reason is, its change resistance layer: Ca(1-x)SrxTiO3-δNano thin-film is with Ca(1-x)SrxTiO3-δCeramic material is made target (wherein, 0 < x < 1,0 < δ < 3), 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)SrxTiO3-δFor target, then by magnetron sputtering deposition on bottom electrode base material, its material internal structure densification own, 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 under the high temperature of 900-1300 DEG C, calcine, and prepares Ca(1-x)SrxTiO3-δCeramic material target; After magnetron sputtering moulding, also need heat treatment 10-30min at 700-800 DEG C again.
3, prepared memristor material is hard and crisp, easily, because collision causes breaking or damaging, is not easy to transport.
In addition, it also exists process conditions relatively harsh, the problem and shortage that ratio defective product is on the low side.
Summary of the invention
The object of the invention is, provide a kind of be easy to physics realization, preparation technology simple, control that difficulty is little, the preparation method of the individual layer nano thin-film memristor taking LTCC green band as substrate that steady quality, production efficiency are high, with low cost, its prepared memristor 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 adopted is for achieving the above object that a kind of preparation method of the individual layer nano thin-film memristor taking LTCC green band as substrate, is characterized in that, comprises the following steps:
The first step, adopts hydro-thermal method to prepare Ba (Ti1-yXy)O3-yTarget, concrete steps are as follows:
(1), raw material mixes:
By Ba (NO3)2、Ti(OC4H9)4And X (NO3)2, by 1: (1-y): the mixed in molar ratio of y, wherein, X is Mg, Zn, Ca, 0 < y < 1, for subsequent use;
Said mixture is dissolved in rare nitric acid of 10%-20%, is placed on magnetic stirring apparatus, stir, it is dissolved completely;
(2), powder preparation
In above-mentioned solution, slowly drip NaOH solution until precipitation is complete, filtering-depositing also washs by deionized water, drips NaOH solution and also regulates pH value, and pack in reactor, put into and reach in advance the thermostatic drying chamber of determining 150 DEG C of temperature, hydro-thermal reaction 24 hours;
After hydro-thermal reaction, reactor is naturally cooled to room temperature, the sample of gained in reactor is cleaned repeatedly by deionized water until remove all soluble-salts, after drying, obtain Ba (Ti at 60 DEG C1-yXy)O3-yPowder;
(3), granulation:
At Ba (Ti1-yXy)O3-yIn powder, add poly-vinyl alcohol solution 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;
(4), target material moulding:
Compound after granulation is placed in and on tablet press machine, is pressed into bulk;
Then, it is 20-150mm that block gained compound is cut into diameter, is highly the slice of cylinder of 2-10mm, obtains Ba (Ti1-yXy)O3-yTarget;
Second step, the preparation of bottom electrode:
Get LTCC green band substrate, taking Pt or Au as target, adopt pulse laser method or magnetically controlled sputter method, Pt or Au are deposited on LTCC green band substrate, forming material is the bottom electrode of Pt or Au;
The 3rd step, individual layer nanometer is recalled the preparation of resistance film:
By prepared Ba (Ti1-yXy)O3-yNano-mixture target, adopts pulse laser method or magnetically controlled sputter method, by Ba (Ti1-yXy)O3-yBe deposited on the surface of bottom electrode;
Then, heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Ba (Ti1-yXy)O3-ySingle-layer ceramic nano thin-film, be individual layer nanometer and recall resistance film;
The 4th step, taking material as Au, the target of Ag or Pt, adopts pulse laser method or magnetically controlled sputter method, and it is Ba (Ti that Au, Ag or Pt are deposited on to above-mentioned chemical composition1-yXy)O3-ySingle-layer ceramic nano thin-film on, make top electrode, get product;
Or:
By In-Ga electrode solution, adopting surface print method to be plated in above-mentioned chemical composition is Ba (Ti1-yXy)O3-ySingle-layer ceramic nano thin-film on, make top electrode, get product.
The technique effect that technique scheme is directly brought is to adopt pulse laser method or magnetically controlled sputter method, directly by Ba (Ti1-yXy)O3-yBe deposited on the upper surface of bottom electrode; And at subsequently 700-900 DEG C heat treatment process, complete in the lump Ba (Ti1-yXy)O3-yThe sintering of LTCC, be Ba (Ti thereby form the chemical composition with good change resistance performance on the upper surface of bottom electrode1-yXy)O3-ySingle-layer ceramic nano thin-film.
With prior art first by mixed material high-temperature calcination, be fired into ceramic material, carry out magnetron sputtering deposition taking this ceramic material as target in lower electrode surface again, to form preparation technology's comparison of resistive film, the topmost improvement of preparation technology of technique scheme is: dispensed preceding ceramic material calcine technology step. This simplified memristor preparation technology, shortened technological process, improved production efficiency, and reduced energy consumption;
Technique scheme compared with prior art, has not only just dispensed high-temperature calcination and has been prefabricated into the step of ceramic material simply. What is more important, in technique scheme of the present invention, is by Ba (Ti1-yXy)O3-y(X=Mg, Zn, Ca) mixture target is deposited in lower electrode surface, then in the heat treatment 10-30 of low temperature (700-900 DEG C) minute process, has attached the thermal sintering of the resistive film of nano ceramics material. This had both ensured efficiency and the quality of film dense sintering, avoided again temperature too low fine and close not with the too short film of temperature retention time, or excess Temperature and the long damage distortion that causes film and electrode of temperature retention time;
And aspect the chemical composition of resistive film, with the memristor ratio of above-mentioned immediate prior art, technique scheme of the present invention is by pass through+divalent of employing cation (X2+＝Mg2+，Zn2+，Ca2+) part replacement+4 valency cation (Ti4+) carry out the replacement of B position, increase Ba (Ti1-yXy)O3-yThe asymmetry of molecular structure, has improved Ba (Ti1-yXy)O3-yIn hole amount, be conducive to strengthen Ba (Ti1-yXy)O3-yFilm memristor recall resistive energy.
Further, in technique scheme, because substrate is the LTCC green band that is coated with bottom electrode Pt or Au, make Ba (Ti1-yXy)O3-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 ensureing, on the basis of memristor performance, to carry out the selection of the thickness of top electrode in this wide in range scope of 10nm-50um, to be conducive to reduce technique controlling difficulty, raising yield rate.
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 on the one hand comparatively good change resistance performance; On the other hand, be convenient to technology controlling and process.
The second technical scheme that the present invention adopted is for achieving the above object that a kind of preparation method of the individual layer nano thin-film memristor taking LTCC green band as substrate, is characterized in that, comprises the following steps:
The first step, adopts hydro-thermal method to prepare Ba (Ti1-yXy)O3-yTarget, concrete steps are as follows:
(1), raw material mixes:
By Ba (NO3)2、Ti(OC4H9)4And X (NO3)2, by 1: (1-y): the mixed in molar ratio of y, wherein, X is Mg, Zn, Ca, 0 < y < 1, for subsequent use;
Said mixture is dissolved in rare nitric acid of 10%-20%, is placed on magnetic stirring apparatus, stir, it is dissolved completely;
(2), powder preparation
In above-mentioned solution, slowly drip NaOH solution until precipitation is complete, filtering-depositing also washs by deionized water, drips NaOH solution and also regulates pH value, and pack in reactor, put into and reach in advance the thermostatic drying chamber of determining 150 DEG C of temperature, hydro-thermal reaction 24 hours;
After hydro-thermal reaction, reactor is naturally cooled to room temperature, the sample of gained in reactor is cleaned repeatedly by deionized water until remove all soluble-salts, after drying, obtain Ba (Ti at 60 DEG C1-yXy)O3-yPowder;
(3), granulation:
At Ba (Ti1-yXy)O3-yIn powder, add poly-vinyl alcohol solution 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;
(4), target material moulding:
Compound after granulation is placed in and on tablet press machine, is pressed into bulk;
Then, it is 20-150mm that block gained compound is cut into diameter, is highly the slice of cylinder of 2-10mm, obtains Ba (Ti1-yXy)O3-yTarget;
Second step, the preparation of bottom electrode:
Get LTCC green band substrate, taking Pt or Au as target, adopt pulse laser method or magnetically controlled sputter method, Pt or Au are deposited on LTCC green band substrate, forming material is the bottom electrode of Pt or Au;
The 3rd step, individual layer nanometer is recalled the preparation of resistance film:
By prepared Ba (Ti1-yXy)O3-yNano-mixture target, adopts pulse laser method or magnetically controlled sputter method, by Ba (Ti1-yXy)O3-yBe deposited on the surface of bottom electrode;
The 4th step, taking material as Au, the target of Ag or Pt, adopts heat spraying method, and it is Ba (Ti that Au, Ag or Pt are deposited on to above-mentioned chemical composition1-yXy)O3-ySingle-layer ceramic nano thin-film on, make top electrode;
Finally, heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Ba (Ti1-yXy)O3-ySingle-layer ceramic nano thin-film on,
Get product.
The technique effect that technique scheme is directly brought is, be easy to physics realization, preparation technology simple, control that difficulty is little, steady quality, production efficiency be 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 ensureing, on the basis of memristor performance, to carry out the selection of the thickness of top electrode in this wide in range scope of 10nm-50um, to be conducive to reduce technique controlling difficulty, raising yield rate.
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 on the one hand comparatively good change resistance performance; On the other hand, be convenient to technology controlling and process.
It should be noted that, the individual layer nano thin-film memristor that the present invention is prepared, it is recalled resistance resistive principle and is, taking the hole that produces under bias voltage and ionized oxygen ion as carrier, under electric field action, rely on the variation of this hole and ionized oxygen ion generation, to realize the variation of device resistance.
Be not difficult to find out, its working mechanism and Mathematical Modeling possess generality and universality.
For understanding better technical characterstic of the present invention, be elaborated from principle below in conjunction with memristor correlation theory.
Of the present invention based on Ba (Ti1-yXy)O3-yThe memristor of (X=Mg, Zn, Ca) nano thin-film, it recalls resistance mechanism and Mathematical Modeling is specially: this memristor is by being sandwiched in two individual layer Ba (Ti between electrode1-yXy)O3-yNano thin-film forms.
Due to+divalent cation (X2+＝Mg2+，Zn2+，Ca2+) part replacement+4 valency cation (Ti4+), increase Ba (Ti1-yXy)O3-yThe asymmetry of molecular structure, has improved Ba (Ti1-yXy)O3-yIn hole amount. In the time that a voltage or electric current are added on this device, because film thickness is nanoscale, very little voltage will produce huge electric field, Ba (Ti1-yXy)O3-yUnder bias effect, can there is O with airborne oxygen in the surface contacting with air2+4e-→2O2-Reaction, and make generation hole in film.
Meanwhile, affected by bias effect O occurs2-→e-+O-, hole and ionized oxygen ion (O-) as main carrier displacement under electric field action, along with hole and ionized oxygen ion (O-) variation of generation can cause the resistance variations between two electrodes, corresponding film presents minimum (R with itmin) or maximum (Rmax) two kinds of different resistance, this is Ba (Ti1-yXy)O3-yRepresent the mechanism of recalling resistance characteristic. Now use O (t) to represent a certain moment Ba (Ti1-yXy)O3-yThe hole amount producing under bias effect, M represents the maximum void amount producing under bias effect, v represents to produce under bias effect the speed in hole. Due to hole and ionized oxygen ion (O-) generation relevant with size of current and duration (being charge accumulated) thereof by it:That is:Therefore, film resistor is it by the function of electric charge: work as Rmin<<RmaxTime,
Because bias voltage (electric current) interrupts in rear film without driving electric field, and the motion such as each ion, electronics, hole is at normal temperatures inactive, hole and ionized oxygen ion (O in film-) amount cannot return the front state of biasing (electric current passes through), therefore there is memory effect and keep bias voltage (electric current) interrupt time resistance.
In sum, the present invention is with respect to prior art, and the improvement of the core of thought and know-why aspect is two aspects technically:
The one,, omit as the ceramic material of resistive film component and fired in advance step; The 2nd,, the improvement (+divalent cation (X of resistive film ceramic material chemical composition aspect2+＝Mg2+，Zn2+，Ca2+) part replacement+4 valency cation (Ti4+) carry out the replacement of B position, increase Ba (Ti1-yXy)O3-yThe asymmetry of molecular structure, has improved Ba (Ti1-yXy)O3-yIn hole amount, be conducive to strengthen Ba (Ti1-yXy)O3-yFilm memristor recall resistive energy).
And, based on the improvement of above-mentioned two aspects, make the resistive film of ceramic material structurally, there is useful optimum variation (significantly having increased number of cavities), cause 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 of selecting separately upper electrode material or plated electrode method, to the order difference of adopted nano thin-film heat treatment. Its object is:
Ensure Ba (Ti1-yXy)O3-yNano thin-film and top electrode have high fitness and associativity, to avoid the combination between top electrode damage or electrode and film bad.
Be not difficult to find out, the present invention is with respect to prior art, have preparation technology simple, control that difficulty is little, steady quality, production efficiency be high, with low cost, recalling of prepared memristor product resistively can better wait beneficial effect.
Brief description of the drawings
Fig. 1 is the individual layer nano thin-film memristor structural representation under one embodiment of the present invention;
Fig. 2 is the Mathematical Modeling of individual layer nano thin-film memristor M of the present invention (q).
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is briefly explained.
Fig. 1 is the individual layer nano thin-film memristor structural representation taking LTCC green band as substrate of the present invention.
As shown in Figure 1, the individual layer nano thin-film memristor of the present invention taking LTCC green band as substrate comprises two electrodes (top electrode and bottom electrode), and is placed in the Ba (Ti between two electrodes1-yXy)O3-yNano thin-film structure, power on very Au, Ag, In-Ga or Pt, bottom electrode is Pt or Au, taking LTCC green band as substrate.
Fig. 2 is the Mathematical Modeling of the individual layer nano thin-film memristor M (q) of the present invention taking LTCC green band as substrate.
As can be seen from Figure 2, the individual layer nano thin-film memristor of the present invention taking LTCC green band as substrate, it recalls resistance mechanism along with hole and ionized oxygen ion (O-) variation of generation can cause the resistance variations between two electrodes, corresponding film presents minimum (R with itmin) or maximum (Rmax) two kinds of different resistance, i.e. Ba (Ti1-yXy)O3-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 to adopt hydro-thermal method to prepare Ba (Ti1-yXy)O3-yTarget; Raw materials and formula consist of mol ratio Ba (NO3)2∶(1-y)Ti(OC4H9)4∶yX(NO3)2(X=Mg, Zn, Ca), wherein, 0 < y < 1;
Adopt hydro-thermal method to prepare Ba (Ti1-yXy)O3-yTarget, includes following step:
The 1st step: by Ba (NO3)2、Ti(OC4H9)4And X (NO3)2, by 1: (1-y): the mixed in molar ratio of y, wherein, X is Mg, Zn, Ca, 0 < y < 1, for subsequent use;
The 2nd step: said mixture is dissolved in rare nitric acid of 10%-20%, is placed on magnetic stirring apparatus, stir, it is dissolved completely;
The 3rd step: slowly drip NaOH solution until precipitation is complete in above-mentioned solution, filtering-depositing also washs by deionized water, drips NaOH solution and also regulates pH value, and pack in reactor, put into and reach in advance the thermostatic drying chamber of determining 150 DEG C of temperature, hydro-thermal reaction 24 hours;
The 4th step: after hydro-thermal reaction, reactor is naturally cooled to room temperature, the sample of gained in reactor is cleaned repeatedly by deionized water until remove all soluble-salts, obtain Ba (Ti after drying at 60 DEG C1-yXy)O3-yPowder;
The 5th step: granulation, the poly-vinyl alcohol solution that employing mass fraction is 2-5% is as binding agent, and the addition of binding agent is to treat the 2-5% of granulation mixture quality mark, crosses 40 mesh sieves and carries out granulation;
The 6th step: compacting, the compound after granulation is sieved utilizes tablet press machine compacting, and to be cut to diameter be 20-150mm, is highly the slice of cylinder of 2-10mm.
2, embodiment 10～12 all adopts and the Ba (Ti of embodiment 11-yXy)O3-yThe composition of raw materials that target is identical;
And, respectively taking material as Au, the target of Ag or Pt, adopt pulse laser method or magnetically controlled sputter method, Au, Ag or Pt are deposited on to Ba (Ti1-yXy)O3-yOn nano thin-film.
Adopt the preparation method of identical individual layer nano thin-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:
The 1st step, with Ba (Ti1-yXy)O3-y(X=Mg, Zn, Ca) makes target, adopt pulsed laser deposition PLD or magnetically controlled sputter method plated film on the LTCC green band that is coated with in advance bottom electrode Pt or Au, form change resistance layer, the thickness of plated film is 10-990nm, then through 700-900 DEG C of heat treatment 10-30 minute;
The 2nd step, taking material as Au, the target of Ag or Pt, adopts pulse laser method or magnetically controlled sputter method, at Ba (Ti1-yXy)O3-yOn nano thin-film, plate one deck top electrode.
3, the Ba (Ti of embodiment 13 employings and embodiment 11-yXy)O3-yThe composition of raw materials that target is identical; And, be to adopt printing process to use In-Ga electrode solution to plate one deck top electrode.
4, embodiment 14～16 is Ba (Ti1-yXy)O3-yThe top electrode processing of (X=Mg, Zn, Ca) nano thin-film, all adopts embodiment 1Ba (Ti1-yXy)O3-yThe composition of raw materials that target is identical, adopts the preparation method of identical individual layer nano thin-film memristor, adopts other heat deposition methods to use Au, Ag, Pt to plate electrode, and this preparation method comprises the steps:
The 1st step, with Ba (Ti1-yXy)O3-yMake target, adopt pulsed laser deposition PLD or magnetically controlled sputter method plated film on the LTCC green band that is coated with in advance bottom electrode Pt or Au, form change resistance layer, the thickness of plated film is 10-990nm;
The 2nd step, at Ba (Ti1-yXy)O3-yOn nano thin-film, plate one deck top electrode, then through 700-900 DEG C of heat treatment 10-30 minute.
The preparation method of above-mentioned nano thin-film memristor, its thickness of electrode is 10nm-50um, described upper electrode material is Au, Ag, In-Ga or Pt.
5, embodiment 10-16 adopts respectively Au, Ag, In-Ga or Pt to make upper electrode material, and the technological parameter in concrete preparation process is as shown in table 1 below.
Embodiment 1
Preparation Ba (Ti1-yXy)O3-yThe composition of raw materials of target is: Ba (NO3)2：Ti(OC4H9)4：X(NO3)2=100:99:1 (mol ratio).
Embodiment 2
Preparation Ba (Ti1-yXy)O3-yThe composition of raw materials of target is: Ba (NO3)2：Ti(OC4H9)4：X(NO3)2=100:98:2 (mol ratio).
Embodiment 3
Preparation Ba (Ti1-yXy)O3-yThe composition of raw materials of target is: Ba (NO3)2：Ti(OC4H9)4：X(NO3)2=100:97:3 (mol ratio). Embodiment 4
Preparation Ba (Ti1-yXy)O3-yThe composition of raw materials of target is: Ba (NO3)2：Ti(OC4H9)4：X(NO3)2=1000:999:1 (mol ratio).
Embodiment 5
Preparation Ba (Ti1-yXy)O3-yThe composition of raw materials of target is: Ba (NO3)2：Ti(OC4H9)4：X(NO3)2=1000:998:2 (mol ratio).
Embodiment 6
Preparation Ba (Ti1-yXy)O3-yThe composition of raw materials of target is: Ba (NO3)2：Ti(OC4H9)4：X(NO3)2=1000:997:3 (mol ratio).
Embodiment 7
Preparation Ba (Ti1-yXy)O3-yThe composition of raw materials of target is: Ba (NO3)2：Ti(OC4H9)4：X(NO3)2=10000:9999:1 (mol ratio).
Embodiment 8
Preparation Ba (Ti1-yXy)O3-yThe composition of raw materials of target is: Ba (NO3)2：Ti(OC4H9)4：X(NO3)2=10000:9998:2 (mol ratio).
Embodiment 9
Preparation Ba (Ti1-yXy)O3-yThe composition of raw materials of target is: Ba (NO3)2：Ti(OC4H9)4：X(NO3)2=10000:9997:3 (mol ratio).
The technological parameter of table 1 embodiment 10-16
| Embodiment numbering | Upper electrode material | Top electrode depositional mode | Heat treatment temperature (DEG C) |
| Embodiment 10 | Au | Pulse laser method or magnetically controlled sputter method | 800 |
| Embodiment 11 | Ag | Pulse laser method or magnetically controlled sputter method | 750 |
| Embodiment 12 | Pt | Pulse laser method or magnetically controlled sputter method | 900 |
| Embodiment 13 | In-Ga | Printing | 850 |
| Embodiment 14 | Au | Heat deposition | 700 |
| Embodiment 15 | Ag | Heat deposition | 700 |
| Embodiment 16 | Pt | Heat deposition | 800 |
The detection of product and inspection:
Final above-described embodiment 1-16 prepared memristor is carried out to I-V characteristic test, and result shows:
The I-V characteristic curve of such memristor all presents " 8 " font;
And pressurize size and pressing time by change, its I-V characteristic can all show memristor peculiar non-volatile (, Memorability).
Claims (6)
1. a preparation method for the individual layer nano thin-film memristor taking LTCC green band as substrate, is characterized in that, comprises the following steps:
The first step, adopts hydro-thermal method to prepare Ba (Ti1-yXy)O3-yTarget, concrete steps are as follows:
(1), raw material mixes:
By Ba (NO3)2、Ti(OC4H9)4And X (NO3)2, by 1: (1-y): the mixed in molar ratio of y, wherein, X is Mg, Zn, Ca, 0 < y < 1, for subsequent use;
Said mixture is dissolved in rare nitric acid of 10%-20%, is placed on magnetic stirring apparatus, stir, it is dissolved completely;
(2), powder preparation
In above-mentioned solution, slowly drip NaOH solution until precipitation is complete, filtering-depositing also washs by deionized water, drips NaOH solution and also regulates pH value, and pack in reactor, put into and reach in advance the thermostatic drying chamber of determining 150 DEG C of temperature, hydro-thermal reaction 24 hours;
After hydro-thermal reaction, reactor is naturally cooled to room temperature, the sample of gained in reactor is cleaned repeatedly by deionized water until remove all soluble-salts, after drying, obtain Ba (Ti at 60 DEG C1-yXy)O3-yPowder;
(3), granulation:
At Ba (Ti1-yXy)O3-yIn powder, add poly-vinyl alcohol solution 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;
(4), target material moulding:
Compound after granulation is placed in and on tablet press machine, is pressed into bulk;
Then, it is 20-150mm that block gained compound is cut into diameter, is highly the slice of cylinder of 2-10mm, obtains Ba (Ti1-yXy)O3-yTarget;
Second step, the preparation of bottom electrode:
Get LTCC green band substrate, taking Pt or Au as target, adopt pulse laser method or magnetically controlled sputter method, Pt or Au are deposited on LTCC green band substrate, forming material is the bottom electrode of Pt or Au;
The 3rd step, individual layer nanometer is recalled the preparation of resistance film:
By prepared Ba (Ti1-yXy)O3-yNano-mixture target, adopts pulse laser method or magnetically controlled sputter method, by Ba (Ti1-yXy)O3-yBe deposited on the surface of bottom electrode;
Then, heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Ba (Ti1-yXy)O3-ySingle-layer ceramic nano thin-film, be individual layer nanometer and recall resistance film;
The 4th step, taking material as Au, the target of Ag or Pt, adopts pulse laser method or magnetically controlled sputter method, and it is Ba (Ti that Au, Ag or Pt are deposited on to above-mentioned chemical composition1-yXy)O3-ySingle-layer ceramic nano thin-film on, make top electrode, get product; Or: by In-Ga electrode solution, adopting surface print method to be plated in above-mentioned chemical composition is Ba (Ti1-yXy)O3-ySingle-layer ceramic nano thin-film on, make top electrode, get product.
2. the preparation method of the individual layer nano thin-film memristor taking LTCC green band as substrate according to claim 1, is characterized in that, the thickness of described top electrode is 10nm-50um.
3. the preparation method of the individual layer nano thin-film memristor taking LTCC green band as substrate 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 the individual layer nano thin-film memristor taking LTCC green band as substrate, is characterized in that, comprises the following steps:
The first step, adopts hydro-thermal method to prepare Ba (Ti1-yXy)O3-yTarget, concrete steps are as follows:
(1), raw material mixes:
By Ba (NO3)2、Ti(OC4H9)4And X (NO3)2, by 1: (1-y): the mixed in molar ratio of y, wherein, X is Mg, Zn, Ca, 0 < y < 1, for subsequent use;
Said mixture is dissolved in rare nitric acid of 10%-20%, is placed on magnetic stirring apparatus, stir, it is dissolved completely;
(2), powder preparation
In above-mentioned solution, slowly drip NaOH solution until precipitation is complete, filtering-depositing also washs by deionized water, drips NaOH solution and also regulates pH value, and pack in reactor, put into and reach in advance the thermostatic drying chamber of determining 150 DEG C of temperature, hydro-thermal reaction 24 hours;
After hydro-thermal reaction, reactor is naturally cooled to room temperature, the sample of gained in reactor is cleaned repeatedly by deionized water until remove all soluble-salts, after drying, obtain Ba (Ti at 60 DEG C1-yXy)O3-yPowder;
(3), granulation:
At Ba (Ti1-yXy)O3-yIn powder, add poly-vinyl alcohol solution 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;
(4), target material moulding:
Compound after granulation is placed in and on tablet press machine, is pressed into bulk;
Then, it is 20-150mm that block gained compound is cut into diameter, is highly the slice of cylinder of 2-10mm, obtains Ba (Ti1-yXy)O3-yTarget;
Second step, the preparation of bottom electrode:
Get LTCC green band substrate, taking Pt or Au as target, adopt pulse laser method or magnetically controlled sputter method, Pt or Au are deposited on LTCC green band substrate, forming material is the bottom electrode of Pt or Au;
The 3rd step, individual layer nanometer is recalled the preparation of resistance film:
By prepared Ba (Ti1-yXy)O3-yNano-mixture target, adopts pulse laser method or magnetically controlled sputter method, by Ba (Ti1-yXy)O3-yBe deposited on the surface of bottom electrode;
The 4th step, taking material as Au, the target of Ag or Pt, adopts heat spraying method, and it is Ba (Ti that Au, Ag or Pt are deposited on to above-mentioned chemical composition1-yXy)O3-ySingle-layer ceramic nano thin-film on, make top electrode;
Finally, heat treatment 10-30 minute at 700-900 DEG C, obtaining chemical composition is Ba (Ti1-yXy)O3-ySingle-layer ceramic nano thin-film on, get product.
5. the preparation method of the individual layer nano thin-film memristor taking LTCC green band as substrate according to claim 4, is characterized in that, the thickness of described top electrode is 10nm-50um.
6. according to the preparation method of the individual layer nano thin-film memristor taking LTCC green band as substrate described in claim 4 or 5, it is characterized in that, the thickness of described single-layer ceramic nano thin-film is 10-990nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560195A (en) * | 2018-11-15 | 2019-04-02 | 南京邮电大学 | A kind of preparation method based on the uniform MXene film of silicon-based semiconductor devices and its in the application of memristor |
| CN112687794A (en) * | 2020-12-28 | 2021-04-20 | 山东科技大学 | Flexible memristor with self-repairing capability and preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708990A (en) * | 2009-11-27 | 2010-05-19 | 电子科技大学 | Method for preparing nano-crystalline BST film |
| CN102265397A (en) * | 2008-12-23 | 2011-11-30 | 惠普开发有限公司 | Memristive device and methods of making and using same |
| CN103236499A (en) * | 2013-05-07 | 2013-08-07 | 山东科技大学 | Unipolar memristor and preparation method thereof |
| CN103594620A (en) * | 2013-11-05 | 2014-02-19 | 山东科技大学 | Single-layer nano-film memristor and manufacturing method thereof |
| CN104795493A (en) * | 2015-04-21 | 2015-07-22 | 东北师范大学 | Nanowire array based memristor and manufacturing method thereof |
-
2016
- 2016-01-21 CN CN201610039902.5A patent/CN105591028B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102265397A (en) * | 2008-12-23 | 2011-11-30 | 惠普开发有限公司 | Memristive device and methods of making and using same |
| CN101708990A (en) * | 2009-11-27 | 2010-05-19 | 电子科技大学 | Method for preparing nano-crystalline BST film |
| CN103236499A (en) * | 2013-05-07 | 2013-08-07 | 山东科技大学 | Unipolar memristor and preparation method thereof |
| CN103594620A (en) * | 2013-11-05 | 2014-02-19 | 山东科技大学 | Single-layer nano-film memristor and manufacturing method thereof |
| CN104795493A (en) * | 2015-04-21 | 2015-07-22 | 东北师范大学 | Nanowire array based memristor and manufacturing method thereof |
Non-Patent Citations (4)
| Title |
|---|
| HECTOR BELTRAN,ET AL: "Enhanced Conductivity and Nonlinear Voltage–Current Characteristics of Nonstoichiometric BaTiO<sub>3</sub> Ceramics", 《J. AM. CERAM. SOC.》 * |
| HECTOR BELTRAN,ET AL: "Voltage-Dependent Low-Field Bulk Resistivity in BaTiO<sub>3</sub>:Zn Ceramics", 《J. AM. CERAM. SOC.》 * |
| KIM H.,ET AL: "Optimization of the semiconductor-metal transition in VO<sub>2</sub> epitaxial thin films as a function of oxygen growth pressure", 《APPLIED PHYSICS LETTERS》 * |
| MARTA PRADES,ET AL: "Field enhanced bulk conductivity of BaTiO<sub>3</sub>:Mg ceramics", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560195A (en) * | 2018-11-15 | 2019-04-02 | 南京邮电大学 | A kind of preparation method based on the uniform MXene film of silicon-based semiconductor devices and its in the application of memristor |
| CN109560195B (en) * | 2018-11-15 | 2022-08-30 | 南京邮电大学 | Preparation method of uniform MXene film based on silicon-based semiconductor device and application of uniform MXene film in memristor |
| CN112687794A (en) * | 2020-12-28 | 2021-04-20 | 山东科技大学 | Flexible memristor with self-repairing capability and preparation method |
| CN112687794B (en) * | 2020-12-28 | 2024-03-19 | 山东科技大学 | Flexible memristor with self-repairing capability and preparation method |
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