CN103594620A - Single-layer nano-film memristor and manufacturing method thereof - Google Patents
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Abstract
The invention discloses a single-layer nano-film memristor and a manufacturing method thereof. The single-layer nano-film memristor comprises two electrodes and a Ca(1-x)SrxTiO3-delta nano-film which is arranged between the two electrodes and rich in oxygen vacancies, wherein 0<x<1, 0<delta<3, the nano-film is a single-layer film, and the thickness of the nano-film is 20-900 nanometers. The single-layer nano-film memristor is particularly suitable for ordinary circuit theory studying and circuit design and has generality and university. The invention further discloses a manufacturing method of the single-layer nano-film memristor. According to the manufacturing method of the single-layer nano-film memristor, Ca(1-x)SrxTiO3-delta serves as a target material, a Pt/TiO2/SiO2/Si substrate is plated with a film by means of the magnetron sputtering method, the thickness of the film is 20-900nm, and heat treatment is conducted on the plated film for 10-30min at the temperature of 700-800 DEG C; the Ca(1-x)SrxTiO3-delta nano-film is further plated with a layer of electrode; the thickness of each electrode is 50nm-50um, and the electrodes is made of Au, or Ag, or In-Ga or Pt. The manufacturing method of the single-layer nano-film memristor has the advantages that the technique is simple, the temperature for sintering the target material is low, materials for manufacturing the single-layer nano-film memristor are easy to obtain, and cost is low.
Description
Technical field
The present invention relates to a kind of memristor and preparation method thereof, relate in particular to a kind of individual layer nano thin-film memristor and preparation method thereof, belong to nonlinear circuit application.
Background technology
As far back as 1971, the theoretical pioneer of international nonlinear circuit and cell neural network, the Leon Chua (Cai Shaotang) of Univ California-Berkeley, based on Circuit theory integrality in logic, foretells the existence of the 4th primary element-memristor except resistance, electric capacity, inductance in circuit theoretically.In May, 2008, the researcher of HP Lab has successfully realized first workable memristor prototype in the world, thereby has confirmed the theory of the relevant memristor of Leon Chua, has caused worldwide strong interest.
Because memristor has non-volatile, synaptic function and nano-scale structures, at high-density nonvolatile memory, artificial neural net, large scale integrated circuit, reconfigurable logic and FPGA (Field Programmable Gate Array), bioengineering, pattern recognition, the fields such as signal processing have huge application prospect, will be unlimited for manufacturing storage precision, the non-volatile memory device of superelevation storage density, have and can regulate the artificial neural net of synapse power and similar human brain mode to process with the development of the analog computer of contact details etc. to pave the way, bring revolutionary change to manufacture and the operational mode of computer.As a kind of new basic circuit elements, the appearance of memristor has increased the variation of circuit element, for Circuit theory research and circuit design provide a kind of brand-new development space.
Along with the discovery of HP memristor, the scientific research institution that is engaged in more in the world resistive storage research has also carried out the research of relevant memristor in kind aspect in succession with scholar, constantly has new recalling resistance material and recall resistance body system report.Current research is recalled the mechanism of resistive energy from realizing, and can be divided into based on boundary migration model, based on electron spin blocking model, based on Transformation Mechanism, based on silk conductive mechanism etc.At present domestic also fewer to the research of memristor, in existing research, mostly lay particular emphasis on and recall resistance circuit and systematic research.Although memristor research has in recent years obtained 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, behavior is described to memristor to there is no unified Universal Model.
The memristor in kind of report is mostly for the application of certain class or simulates certain function in recent years, as high-density nonvolatile memory, Crossbar Latch(intersect 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, in default of memristor element, cannot carry out the hardware experiments in real physical meaning, be more to rely on emulation or analog circuit to carry out experimental study.Yet memristor simulation model and analog circuit differ greatly from actual memristor characteristic, the hardware that carries out with analog circuit is realized more considerations is also simulation memristor Mathematical Modeling and ignored the essential physical characteristic of memristor.
Summary of the invention
The object of the invention is, provide a kind of and be specially adapted to general circuit theoretical research and circuit design, have generality and universality, cheap and be easy to the monofilm memristor of physics realization.
The present invention is that the technical scheme that solves the problems of the technologies described above employing is, a kind of individual layer nano thin-film memristor comprises two electrodes and is placed in the Ca between the two
(1-x)sr
xtiO
3-δnano thin-film, wherein, 0<x<1,0< δ <3.Illustrate: in formula, δ represents that oxygen defect is the content in oxygen room.
The technique effect that technique scheme produces is, based on Ca
(1-x)sr
xtiO
3-δthe memristor of material, its working mechanism and Mathematical Modeling are novel, and have more generality and universality.
As preferably, above-mentioned film is single thin film structure, and thickness is 20-900 nanometer.
The technique effect that above-mentioned optimal technical scheme directly produces is, monofilm memristor based on new model, the morphological stability of its nano thin-film is good, and with respect to the memristor of duplicature and even multilayer film, its structure and manufacture craft are simple, cost is low, be convenient to industrialization produces.
Further preferably, above-mentioned Ca (1-x) Sr
xtiO
3-δraw materials and formula consist of mol ratio (1-x) CaCO
3: xSrCO
3: TiO
3, wherein, 0<x<1; Described Ca (1-x) Sr
xtiO
3-δpreparation method, comprise the steps:
The 1st step, by CaCO
3, SrCO
3and TiO
3mix, add deionized water or absolute ethyl alcohol, ball milling, then dries, and obtains compound;
The 2nd step, the poly-vinyl alcohol solution that employing mass fraction is 5～20% is as binding agent, and the addition of binding agent is to treat 5～15% of granulation mixture quality mark, and 40 mesh sieves are crossed in granulation;
The 3rd step, it is 20～150mm that the compound after granulation is sieved utilizes tablet press machine to be pressed into diameter, is highly the disk of 2～50mm;
The 4th step, by the sintering 15～240min at 900～1300 ℃ of the sample after compressing tablet, cools to room temperature with the furnace.
The technique effect that above-mentioned optimal technical scheme directly produces is, Ca (1-x) Sr of one of critical component as memristor target of preparing
xtiO
3-δceramic material, its preparation technology is simple, sintering temperature is low, raw materials is easy to obtain and cost is low.Correspondingly, adopt above-mentioned optimal technical scheme, can effectively reduce the manufacturing cost of end product individual layer nano thin-film memristor.
Further preferably, above-mentioned individual layer nano thin-film memristor, is characterized in that, hole and the ionized oxygen ion producing under bias voltage of take is charge carrier, relies on the variation of described hole and described ionized oxygen ion generation to realize the variation of device resistance under electric field action.
The technique effect that above-mentioned optimal technical scheme directly produces is, hole and the ionized oxygen ion producing under bias voltage of take is charge carrier, under electric field action, rely on the variation of described hole and described ionized oxygen ion generation to realize the individual layer nano thin-film memristor of the variation of device resistance, its performance is more stable.
In sum, individual layer nano thin-film memristor of the present invention has following beneficial effect:
Its working mechanism and Mathematical Modeling are novel, and have more generality and universality;
Its structure and manufacture craft are simple, cost is low, be convenient to industrialization produces;
Hole and the ionized oxygen ion producing under bias voltage of take is charge carrier, relies on the variation of described hole and described ionized oxygen ion generation to realize the individual layer nano thin-film memristor of the variation of device resistance under electric field action, and its performance is more stable.
Two of object of the present invention is that a kind of preparation method of nano thin-film memristor is provided.
The technical scheme that the present invention adopts is for achieving the above object that a kind of preparation method of nano thin-film memristor, comprises the steps:
The first step, with Ca (1-x) Sr
xtiO
3-δmake target, 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 ℃ of heat treatment 10-30min;
Second step, at Ca (1-x) Sr
xtiO
3-δon nano thin-film, plate one deck electrode.
The beneficial effect that technique scheme is brought is, the Ca preparing
(1-x)sr
xtiO
3-δnano thin-film is after 700-800 ℃ of heat treatment 10-30min, both efficiency and the quality of gel mould dense sintering had been guaranteed, avoid 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, selected Pt/TiO
2/ SiO
2the commercially available prod of/Si substrate for having commercially produced, its acquiring way is easy.
As preferably, above-mentioned thickness of electrode is 50nm-50um, and described electrode material is Au, Ag, In-Ga or Pt.
For understanding better the present invention, below in conjunction with memristor correlation theory, from principle, be elaborated.
Of the present invention based on Ca
(1-x)sr
xtiO
3-δthe memristor of nano thin-film, it recalls resistance mechanism and Mathematical Modeling is specially:
This memristor is by being sandwiched in two individual layer Ca between electrode
(1-x)sr
xtiO
3-δnano thin-film forms.When a voltage or electric current are added on this device, because film thickness is nanoscale, very little voltage will produce huge electric field, Ca
(1-x)sr
xtiO
3-δunder bias effect, can there is O with airborne oxygen in the surface contacting with air
2+ 4e
-→ 2O
2-reaction, and make generation hole in film.Meanwhile, affected by bias effect O occurs
2-→ e
-+ O
-, hole and ionized oxygen ion (O
-) as main charge 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 it
min) or maximum (R
max) two kinds of different resistance, this is Ca
(1-x)sr
xtiO
3-δrepresent the mechanism of recalling resistance characteristic.Now use O (t) to represent a certain moment Ca
(1-x)sr
xtiO
3-δthe 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 R
min<<R
maxtime,
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 by), therefore has memory effect and resistance while keeping bias voltage (electric current) to interrupt.
Individual layer nano thin-film memristor of the present invention and preparation method thereof difference from prior art is, the present invention propose and physics realization one class manufacture craft simple, cost is low, be easy to realize and have more the novel passive memristor element of generality and universality, adopt based on Ca
(1-x)sr
xtiO
3-δthe single-layer membrane structure of material, recalls resistance mechanism and Mathematical Modeling unique novel;
The present invention has simplified the manufacture craft of nanometer memristor element, reduces manufacturing cost, is specially adapted to general circuit theoretical research and circuit design, specifically has the following advantages:
Based on Ca
(1-x)sr
xtiO
3-δthe memristor of material, its working mechanism and Mathematical Modeling are novel, and have more generality and universality.
Ca of the present invention
(1-x)sr
xtiO
3-δmemristor be a class based under bias effect with hole and ionized oxygen ion (O
-) the solid electrolyte memristor that conducts electricity for charge carrier.Such memristor is is not researched and developed for computer memory system or human mind system, without special purpose or application background, is a kind ofly with the sub-generation of bias voltage download stream, to change, and the passive electric circuit element that causes its resistance to change.As a kind of basic passive electric circuit element, this memristor for research memristor characteristic, recall resistance circuit theory and design of electronic circuits etc. and have more generality and universality.
Ca of the present invention
(1-x)sr
xtiO
3-δmemristor manufacture craft is simple, cost is low, is easy to carry out physics realization, and described memristor belongs to single-layer membrane structure, adopts magnetron sputtering method to realize Ca
(1-x)sr
xtiO
3-δthe making of nano thin-film.Meanwhile, prepare the required raw material of film and be common chemical agent, cheap.Therefore, the Ca of invention
(1-x)sr
xtiO
3-δit is simple that memristor and the memristor of having reported are at present compared manufacture craft, and manufacturing cost is greatly diminished, and is easy to physics realization.
Accompanying drawing explanation
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).
Embodiment
Below in conjunction with accompanying drawing to Ca of the present invention
(1-x)sr
xtiO
3-δmemristor is described further.
Fig. 1 is the individual layer nano thin-film memristor structural representation under one embodiment of the present invention.As shown in Figure 1, individual layer nano thin-film memristor of the present invention comprises two electrodes 1 and 2, and is placed in the Ca between electrode 1 and 2
(1-x)sr
xtiO
3-δnano thin-film structure, wherein 2 is Pt, 3 is TiO
2, 4 is SiO
2, 5 is Si, 6 is the Pt/TiO having commercially produced
2/ SiO
2/ Si substrate.
Fig. 2 is the Mathematical Modeling of individual layer nano thin-film memristor M of the present invention (q).
Below in conjunction with embodiment, individual layer nano thin-film memristor of the present invention and preparation method thereof is described in detail.
Embodiment 1-9, wherein, Ca (1-x) Sr
xtiO
3-δraw materials and formula consist of mol ratio (1-x) CaCO
3: xSrCO
3: TiO
3, wherein, 0<x<1; Its preparation method, comprises the steps:
The 1st step: by CaCO
3, SrCO
3and TiO
3mix, add deionized water or absolute ethyl alcohol, ball milling, then dries, and obtains compound;
The 2nd step: the poly-vinyl alcohol solution that employing mass fraction is 5～20% is as binding agent, and the addition of binding agent is to treat 5～15% of granulation mixture quality mark, 40 mesh sieves are crossed in granulation;
The 3rd step: it is 20～150mm that the compound after granulation is sieved utilizes tablet press machine to be pressed into diameter, is highly the disk of 2～50mm;
The 4th step: by the sintering 15～240min at 900～1300 ℃ of the sample after compressing tablet, cool to room temperature with the furnace.
Preparation Ca
(1-x)sr
xtiO
3-δthe composition of raw materials of target is, CaCO
3: SrCO
3: TiO
3=9:1:10(mol ratio).
Preparation Ca
(1-x)sr
xtiO
3-δthe composition of raw materials of target is, CaCO
3: SrCO
3: TiO
3=8:2:10(mol ratio).
Embodiment 3
Preparation Ca
(1-x)sr
xtiO
3-δthe composition of raw materials of target is, CaCO
3: SrCO
3: TiO
3=7:3:10(mol ratio).
Embodiment 4
Preparation Ca
(1-x)sr
xtiO
3-δthe composition of raw materials of target is, CaCO
3: SrCO
3: TiO
3=6:4:10(mol ratio).
Embodiment 5
Preparation Ca
(1-x)sr
xtiO
3-δthe composition of raw materials of target is, CaCO
3: SrCO
3: TiO
3=5:5:10(mol ratio).
Embodiment 6
Preparation Ca
(1-x)sr
xtiO
3-δthe composition of raw materials of target is, CaCO
3: SrCO
3: TiO
3=4:6:10(mol ratio).
Embodiment 7
Preparation Ca
(1-x)sr
xtiO
3-δthe composition of raw materials of target is, CaCO
3: SrCO
3: TiO
3=3:7:10(mol ratio).
Embodiment 8
Preparation Ca
(1-x)sr
xtiO
3-δthe composition of raw materials of target is, CaCO
3: SrCO
3: TiO
3=2:8:10(mol ratio).
Embodiment 9
Preparation Ca
(1-x)sr
xtiO
3-δthe composition of raw materials of target is, CaCO
3: SrCO
3: TiO
3=1:9:10(mol ratio).
Embodiment 10～15 is Ca
(1-x)sr
xtiO
3-δthe top electrode of nano thin-film is processed, and all adopts the formula that embodiment 1 is identical, adopts the preparation method of identical individual layer nano thin-film memristor, and this preparation method comprises the steps:
The first step, with Ca (1-x) Sr
xtiO
3-δmake target, 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 ℃ of heat treatment 10-30min;
Second step, at Ca (1-x) Sr
xtiO
3-δon nano thin-film, plate one deck electrode.
The preparation method of above-mentioned nano thin-film memristor, its thickness of electrode is 50nm-50um.
Example 10～15 adopts respectively Au, Ag, In-Ga or Pt to make electrode material, and the technological parameter in concrete preparation process is as shown in table 1.
The technological parameter of table 1 embodiment 10～15
| embodiment numbering | electrode material | top electrode ten thousand formulas | heat treatment temperature (.C) |
| ? | au | printing | 800 |
| ? | au | deposition | room temperature |
| ? | ag | printing | 600 |
| ? | in-Ca | printing | room temperature |
| ? | pt | printing | 900 |
| embodiment 15 | pt | deposition | room temperature |
Claims (6)
1. an individual layer nano thin-film memristor, is characterized in that, comprises two electrodes and is placed in Ca (1-x) Sr of two rich oxygen-containing vacancies between electrode
xtiO
3-δnano thin-film, wherein, 0<x<1,0< δ <3.
2. individual layer nano thin-film memristor according to claim 1, is characterized in that, described Ca (1-x) Sr
xtiO
3-δnano thin-film is single thin film structure, and thickness is 20-900 nanometer.
3. individual layer nano thin-film memristor according to claim 1 and 2, it is characterized in that, hole and the ionized oxygen ion producing under bias voltage of take is charge carrier, relies on the variation of described hole and described ionized oxygen ion generation to realize the variation of device resistance under electric field action.
4. according to the individual layer nano thin-film memristor described in claim 1,2 or 3, it is characterized in that described Ca (1-x) Sr
xtiO
3-δraw materials and formula consist of mol ratio (1-x) CaCO
3: x SrCO
3: TiO
3, wherein, 0<x<1; Described Ca (1-x) Sr
xtiO
3-δpreparation method, comprise the steps:
The 1st step: by CaCO
3, SrCO
3and TiO
3mix, add deionized water or absolute ethyl alcohol, ball milling, then dries, and obtains compound;
The 2nd step: the poly-vinyl alcohol solution that employing mass fraction is 5～20% is as binding agent, and the addition of binding agent is to treat 5～15% of granulation mixture quality mark, 40 mesh sieves are crossed in granulation;
The 3rd step: it is 20～150mm that the compound after granulation is sieved utilizes tablet press machine to be pressed into diameter, is highly the disk of 2～50mm;
The 4th step: by the sintering 15～240min at 900～1300 ℃ of the sample after compressing tablet, cool to room temperature with the furnace.
5. the preparation method of nano thin-film memristor as claimed in claim 1, is characterized in that, comprises the steps:
The first step, with Ca (1-x) Sr
xtiO
3-δmake target, 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 ℃ of heat treatment 10-30min;
Second step, at Ca (1-x) Sr
xtiO
3-δon nano thin-film, plate one deck electrode.
6. the preparation method of nano thin-film memristor according to claim 5, is characterized in that, described thickness of electrode is 50nm-50um, and described electrode material is Au, Ag, In-Ga or Pt.
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| CN105742487B (en) * | 2016-01-21 | 2018-02-06 | 山东科技大学 | A kind of preparation method of ambipolar nano-film memristor |
| CN105742487A (en) * | 2016-01-21 | 2016-07-06 | 山东科技大学 | Method for preparing bipolar nano-film memristor |
| CN105591028B (en) * | 2016-01-21 | 2018-02-06 | 山东科技大学 | A kind of preparation method using LTCC greens band as the single-layer nano-film memristor of substrate |
| CN105552224B (en) * | 2016-01-21 | 2018-02-06 | 山东科技大学 | One kind is based on nanoscale individual layer Bi(1‑x)CaxFeO3‑x/2The preparation method of resistive film memristor |
| CN105591028A (en) * | 2016-01-21 | 2016-05-18 | 山东科技大学 | Preparation method of single-layer nano-film memristor using LTCC green tape as substrate |
| CN105552224A (en) * | 2016-01-21 | 2016-05-04 | 山东科技大学 | Method for preparing memristor based on nanoscale single layer Bi (1-x) CaxFeO3-x/2 resistance variable film |
| CN108950507A (en) * | 2018-08-15 | 2018-12-07 | 电子科技大学 | A kind of memristor switching device and preparation method thereof based on a-TSC:O ceramic membrane |
| CN108950507B (en) * | 2018-08-15 | 2020-03-17 | 电子科技大学 | Memristive switching device based on a-TSC-O ceramic film and preparation method thereof |
| CN110736575A (en) * | 2019-10-23 | 2020-01-31 | 中国科学院半导体研究所 | artificial synapse sensors and preparation method thereof |
| CN112687794A (en) * | 2020-12-28 | 2021-04-20 | 山东科技大学 | Flexible memristor with self-repairing capability and preparation method |
| CN112750951A (en) * | 2020-12-28 | 2021-05-04 | 山东科技大学 | Flexible memristor based on organic solution and preparation method |
| CN112750951B (en) * | 2020-12-28 | 2023-01-10 | 山东科技大学 | Flexible memristor based on organic solution 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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