CN118055689A - Memristor based on ferrite ceramic and preparation method thereof - Google Patents
Memristor based on ferrite ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 21
- 229910001053 Nickel-zinc ferrite Inorganic materials 0.000 claims abstract description 63
- 150000002500 ions Chemical class 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 238000000151 deposition Methods 0.000 claims abstract description 37
- 230000008859 change Effects 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000002120 nanofilm Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000001354 calcination Methods 0.000 claims description 33
- 239000012153 distilled water Substances 0.000 claims description 33
- 239000002244 precipitate Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 4
- -1 iron ions Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 23
- 230000007547 defect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 29
- 238000001755 magnetron sputter deposition Methods 0.000 description 28
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/883—Oxides or nitrides
- H10N70/8836—Complex metal oxides, e.g. perovskites, spinels
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Abstract
The invention relates to the technical field of memristor preparation, in particular to a memristor based on ferrite ceramic and a preparation method thereof, comprising the following steps: s1, depositing a metal conductive film on a non-conductive substrate to serve as a lower electrode; s2, depositing a nano film on the lower electrode prepared in the S1 by using Gd ion doped nickel zinc ferrite ceramic as a resistance change layer; and S3, depositing a metal conductive film serving as an upper electrode on the resistive layer prepared in the step S2 to obtain the nickel-zinc ferrite. According to the technical scheme, a proper amount of Gd ions are used for doping nickel zinc ferrite and used as a resistance change layer material for preparing the memristor, so that lattice defects and holes in the resistance change layer are increased, and the memristor performance is obviously improved and improved.
Description
Technical Field
The invention relates to the technical field of memristor preparation, in particular to a memristor based on ferrite ceramic and a preparation method thereof.
Background
The memristor is a nonlinear resistance element with a memory function, mainly utilizes the transition phenomenon of different resistance states (high and low resistance states) of certain film materials under the action of electric excitation to store data, has the advantages of non-volatile memory characteristics, high speed, low power consumption, integration of memory, easy high integration and the like, and has great application prospects in the fields of modern information storage, brain-like artificial intelligence, implantable bioelectronic devices and the like.
In general, a basic unit of a memristor is a "sandwich" structure constructed by upper and lower electrodes and a resistive layer material with a memristive function in the middle. Among them, the development of resistive layer materials is one of the keys to obtain high performance memristors. At present, the variety of resistive layer materials capable of realizing memristors is wide. The binary or multi-element metal oxide is a common resistive layer selection material for preparing the memristor, and compared with other sulfide, organic matters and other material systems, the application of the metal oxide as a resistive active layer material is earliest, and the metal oxide is relatively more mature, but how to further improve the performance of the metal oxide is a key for expanding the application of the material.
In order to improve the performance of memristors, researchers explore a plurality of memristor materials, wherein ferrite materials are the focus of current researches, and nickel zinc ferrite is widely focused due to the advantages of high resistivity, low electromagnetic loss, high mechanical hardness, excellent broadband characteristics and the like, but reports of applying nickel zinc ferrite to memristors in the prior art are few, so that the invention provides the memristor using metal doped nickel zinc ferrite as a resistance change layer material, and the performance of the memristor is improved by regulating and controlling a preparation method of the memristor.
Disclosure of Invention
The invention aims to provide a memristor based on ferrite ceramic and a preparation method thereof, which uses a proper amount of Gd ions doped with nickel zinc ferrite and uses the Gd ions as a resistance change layer material to prepare the memristor, so that lattice defects and holes in the resistance change layer are increased, and the memristor performance is obviously improved and enhanced.
In order to achieve the above purpose, the invention provides a preparation method of a memristor based on ferrite ceramics, which comprises the following steps:
s1, depositing a metal conductive film on a non-conductive substrate to serve as a lower electrode;
S2, depositing a nano film on the lower electrode prepared in the S1 by using Gd ion doped nickel zinc ferrite ceramic as a resistance change layer;
And S3, depositing a metal conductive film serving as an upper electrode on the resistive layer prepared in the step S2 to obtain the nickel-zinc ferrite.
Preferably, the non-conductive substrate in the step S1 is a Si substrate, and the lower electrode is made of Pt or Au.
Preferably, the doping concentration of Gd ions in the Gd ion doped nickel zinc ferrite ceramic in the S2 is 1-10% of that of iron ions. According to the invention, the doping concentration of Gd ions is controlled in the above range, and the oxygen vacancy content in the resistive layer is controlled in a proper range, so that the stability of the memristor can be improved.
Preferably, the preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
S2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating and uniformly mixing to obtain a metal salt solution, dissolving GdCl 3 in distilled water to obtain a doped solution, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
S2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 9-11 to obtain a precipitate, washing and drying the precipitate, and grinding the precipitate into particles;
S2.3, after preliminary calcination is carried out on the particles, dividing the particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension, pouring the mixture into cold sintering equipment, heating and pressurizing, maintaining for 20-40 min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
Preferably, the temperature of the heating and mixing in S2.1 is 70-80 ℃.
Preferably, the washing in S2.2 is performed until the filtrate is neutral, and the drying is performed at a temperature of 75-85 ℃.
Preferably, the solid-liquid ratio of the other part of particles in S2.3 to the suspension is 0.5-1:5. The invention controls the solid-liquid ratio in the above range, and can reduce the density of the ceramic, thereby improving the cavity content in the ceramic, and facilitating the cavity change after the voltage is applied.
Preferably, the temperature of the preliminary calcination in S2.3 is 400-550 ℃, the calcination time is 2.8-3.8 h, the temperature of the cold sintering equipment is 180-220 ℃, and the pressurizing pressure is 280-320 Mpa.
Preferably, the upper electrode in S3 is made of one of Au, ag or Pt.
Preferably, the deposition in S1, S2 and S3 is a pulse laser method or a magnetron sputtering method.
The memristor manufactured by the manufacturing method of the memristor based on ferrite ceramic.
The invention has the beneficial effects that:
(1) The memristor resistance change principle is that holes and ionized oxygen ions generated under bias are taken as carriers, and the change of the generated amounts of the holes and the ionized oxygen ions is relied on under the action of an electric field so as to realize the change of the resistance of the device. According to the invention, the Gd ion doped nickel zinc ferrite is used as a material of the resistance change layer, and the Gd ion doping reduces the formation energy in the crystal grains and near the crystal boundary, so that more oxygen vacancies are formed at the crystal boundary around the doping site, the number of holes in the resistance change layer is increased, and the improvement of the resistance change performance of the resistance change layer is facilitated.
(2) In the prior art, the mixed raw materials are calcined at high temperature (1000-1250 ℃) to prepare the ceramic material, and then the ceramic material is deposited on the surface of the lower electrode to form the resistive layer.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a schematic diagram of a ferrite ceramic based memristor of the present disclosure.
Detailed Description
The invention will be further described with reference to the drawings and examples. Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The above-mentioned features of the invention or the features mentioned in the specific examples can be combined in any desired manner, and these specific examples are only intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
FIG. 1 is a schematic diagram of a memristor based on ferrite ceramics, and as shown in the figure, the invention provides a preparation method of the memristor based on ferrite ceramics, which comprises the following steps:
S1, selecting SiO 2/Si as a substrate, and depositing a Pt metal conductive film on the substrate by a magnetron sputtering method to serve as a lower electrode;
S2, selecting Gd ion doped nickel zinc ferrite ceramic as a material of a resistance variable layer, and depositing a Gd ion doped nickel zinc ferrite ceramic film on a lower electrode by a magnetron sputtering method to serve as the resistance variable layer;
And S3, depositing a Pt metal conductive film serving as an upper electrode on the resistance change layer by adopting a magnetron sputtering method to obtain the nickel-zinc ferrite.
The preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
S2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating to 70 ℃ for mixing, obtaining a metal salt solution after uniform mixing, dissolving GdCl 3 in distilled water to obtain a doped solution, wherein the concentration of GdCl 3 is 1% of that of FeCl 3, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
S2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 9 to obtain a precipitate, washing the precipitate to be neutral, drying at the temperature of 75 ℃, and grinding the precipitate into particles;
S2.3, pouring the particles into a crucible, and placing the crucible into a box-type furnace for preliminary calcination, wherein the temperature of the preliminary calcination is 400 ℃ and the time is 2.8h. After the preliminary calcination is completed, dividing the calcined particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension according to the solid-to-liquid ratio of 0.5:5, pouring the mixture into cold sintering equipment, controlling the temperature to 180 ℃, controlling the pressure to 280Mpa, maintaining for 20min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
Example 2
A preparation method of a memristor based on ferrite ceramic comprises the following steps:
S1, selecting SiO 2/Si as a substrate, and depositing a Pt metal conductive film on the substrate by a magnetron sputtering method to serve as a lower electrode;
S2, selecting Gd ion doped nickel zinc ferrite ceramic as a material of a resistance variable layer, and depositing a Gd ion doped nickel zinc ferrite ceramic film on a lower electrode by a magnetron sputtering method to serve as the resistance variable layer;
And S3, depositing a Pt metal conductive film serving as an upper electrode on the resistance change layer by adopting a magnetron sputtering method to obtain the nickel-zinc ferrite.
The preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
s2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating to 75 ℃ for mixing, obtaining a metal salt solution after uniform mixing, dissolving GdCl 3 in distilled water to obtain a doped solution, wherein the concentration of GdCl 3 is 5% of that of FeCl 3, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
s2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 10 to obtain a precipitate, washing the precipitate to be neutral, drying at the temperature of 80 ℃, and grinding the precipitate into particles;
S2.3, pouring the particles into a crucible, and placing the crucible into a box-type furnace for preliminary calcination, wherein the temperature of the preliminary calcination is 480 ℃ and the time is 3.0h. After the preliminary calcination is completed, dividing the calcined particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension according to the solid-to-liquid ratio of 0.6:5, pouring the mixture into cold sintering equipment, controlling the temperature to be 200 ℃, controlling the pressure to be 300Mpa, maintaining for 25min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
Example 3
A preparation method of a memristor based on ferrite ceramic comprises the following steps:
S1, selecting SiO 2/Si as a substrate, and depositing a Pt metal conductive film on the substrate by a magnetron sputtering method to serve as a lower electrode;
S2, selecting Gd ion doped nickel zinc ferrite ceramic as a material of a resistance variable layer, and depositing a Gd ion doped nickel zinc ferrite ceramic film on a lower electrode by a magnetron sputtering method to serve as the resistance variable layer;
And S3, depositing a Pt metal conductive film serving as an upper electrode on the resistance change layer by adopting a magnetron sputtering method to obtain the nickel-zinc ferrite.
The preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
S2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating to 80 ℃ for mixing, obtaining a metal salt solution after uniform mixing, dissolving GdCl 3 in distilled water to obtain a doped solution, wherein the concentration of GdCl 3 is 10% of that of FeCl 3, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
S2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 11 to obtain a precipitate, washing the precipitate to be neutral, drying at the temperature of 85 ℃, and grinding the precipitate into particles;
S2.3, pouring the particles into a crucible, and placing the crucible into a box-type furnace for preliminary calcination, wherein the temperature of the preliminary calcination is 550 ℃ and the time is 3.8h. After the preliminary calcination is completed, dividing the calcined particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension according to a solid-to-liquid ratio of 1:5, pouring the mixture into cold sintering equipment, controlling the temperature to 220 ℃, controlling the pressure to 320Mpa, maintaining for 40min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
Example 4
A preparation method of a memristor based on ferrite ceramic comprises the following steps:
S1, selecting SiO 2/Si as a substrate, and depositing a Pt metal conductive film on the substrate by a magnetron sputtering method to serve as a lower electrode;
S2, selecting Gd ion doped nickel zinc ferrite ceramic as a material of a resistance variable layer, and depositing a Gd ion doped nickel zinc ferrite ceramic film on a lower electrode by a magnetron sputtering method to serve as the resistance variable layer;
And S3, depositing a Pt metal conductive film serving as an upper electrode on the resistance change layer by adopting a magnetron sputtering method to obtain the nickel-zinc ferrite.
The preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
s2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating to 75 ℃ for mixing, obtaining a metal salt solution after uniform mixing, dissolving GdCl 3 in distilled water to obtain a doped solution, wherein the concentration of GdCl 3 is 5% of that of FeCl 3, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
s2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 10 to obtain a precipitate, washing the precipitate to be neutral, drying at the temperature of 75 ℃, and grinding the precipitate into particles;
S2.3, pouring the particles into a crucible, and placing the crucible into a box-type furnace for preliminary calcination, wherein the temperature of the preliminary calcination is 500 ℃ and the time is 3.5h. After the preliminary calcination is completed, dividing the calcined particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension according to the solid-to-liquid ratio of 0.5:5, pouring the mixture into cold sintering equipment, controlling the temperature to be 200 ℃, controlling the pressure to be 300Mpa, maintaining for 30min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
Example 5
A preparation method of a memristor based on ferrite ceramic comprises the following steps:
S1, selecting SiO 2/Si as a substrate, and depositing a Pt metal conductive film on the substrate by a magnetron sputtering method to serve as a lower electrode;
S2, selecting Gd ion doped nickel zinc ferrite ceramic as a material of a resistance variable layer, and depositing a Gd ion doped nickel zinc ferrite ceramic film on a lower electrode by a magnetron sputtering method to serve as the resistance variable layer;
And S3, depositing a Pt metal conductive film serving as an upper electrode on the resistance change layer by adopting a magnetron sputtering method to obtain the nickel-zinc ferrite.
The preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
s2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating to 75 ℃ for mixing, obtaining a metal salt solution after uniform mixing, dissolving GdCl 3 in distilled water to obtain a doped solution, wherein the concentration of GdCl 3 is 5% of that of FeCl 3, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
s2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 10 to obtain a precipitate, washing the precipitate to be neutral, drying at the temperature of 75 ℃, and grinding the precipitate into particles;
S2.3, pouring the particles into a crucible, and placing the crucible into a box-type furnace for preliminary calcination, wherein the temperature of the preliminary calcination is 500 ℃ and the time is 3.5h. After the preliminary calcination is completed, dividing the calcined particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension according to the solid-to-liquid ratio of 0.6:5, pouring the mixture into cold sintering equipment, controlling the temperature to be 200 ℃, controlling the pressure to be 300Mpa, maintaining for 30min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
Example 6
A preparation method of a memristor based on ferrite ceramic comprises the following steps:
S1, selecting SiO 2/Si as a substrate, and depositing a Pt metal conductive film on the substrate by a magnetron sputtering method to serve as a lower electrode;
S2, selecting Gd ion doped nickel zinc ferrite ceramic as a material of a resistance variable layer, and depositing a Gd ion doped nickel zinc ferrite ceramic film on a lower electrode by a magnetron sputtering method to serve as the resistance variable layer;
And S3, depositing a Pt metal conductive film serving as an upper electrode on the resistance change layer by adopting a magnetron sputtering method to obtain the nickel-zinc ferrite.
The preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
s2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating to 75 ℃ for mixing, obtaining a metal salt solution after uniform mixing, dissolving GdCl 3 in distilled water to obtain a doped solution, wherein the concentration of GdCl 3 is 5% of that of FeCl 3, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
s2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 10 to obtain a precipitate, washing the precipitate to be neutral, drying at the temperature of 75 ℃, and grinding the precipitate into particles;
S2.3, pouring the particles into a crucible, and placing the crucible into a box-type furnace for preliminary calcination, wherein the temperature of the preliminary calcination is 500 ℃ and the time is 3.5h. After the preliminary calcination is completed, dividing the calcined particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension according to the solid-to-liquid ratio of 0.7:5, pouring the mixture into cold sintering equipment, controlling the temperature to be 200 ℃, controlling the pressure to be 300Mpa, maintaining for 30min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
Example 7
A preparation method of a memristor based on ferrite ceramic comprises the following steps:
S1, selecting SiO 2/Si as a substrate, and depositing a Pt metal conductive film on the substrate by a magnetron sputtering method to serve as a lower electrode;
S2, selecting Gd ion doped nickel zinc ferrite ceramic as a material of a resistance variable layer, and depositing a Gd ion doped nickel zinc ferrite ceramic film on a lower electrode by a magnetron sputtering method to serve as the resistance variable layer;
And S3, depositing a Pt metal conductive film serving as an upper electrode on the resistance change layer by adopting a magnetron sputtering method to obtain the nickel-zinc ferrite.
The preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
s2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating to 75 ℃ for mixing, obtaining a metal salt solution after uniform mixing, dissolving GdCl 3 in distilled water to obtain a doped solution, wherein the concentration of GdCl 3 is 5% of that of FeCl 3, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
s2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 10 to obtain a precipitate, washing the precipitate to be neutral, drying at the temperature of 75 ℃, and grinding the precipitate into particles;
S2.3, pouring the particles into a crucible, and placing the crucible into a box-type furnace for preliminary calcination, wherein the temperature of the preliminary calcination is 500 ℃ and the time is 3.5h. After the preliminary calcination is completed, dividing the calcined particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension according to the solid-to-liquid ratio of 0.8:5, pouring the mixture into cold sintering equipment, controlling the temperature to be 200 ℃, controlling the pressure to be 300Mpa, maintaining for 30min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
Example 8
A preparation method of a memristor based on ferrite ceramic comprises the following steps:
S1, selecting SiO 2/Si as a substrate, and depositing a Pt metal conductive film on the substrate by a magnetron sputtering method to serve as a lower electrode;
S2, selecting Gd ion doped nickel zinc ferrite ceramic as a material of a resistance variable layer, and depositing a Gd ion doped nickel zinc ferrite ceramic film on a lower electrode by a magnetron sputtering method to serve as the resistance variable layer;
And S3, depositing a Pt metal conductive film serving as an upper electrode on the resistance change layer by adopting a magnetron sputtering method to obtain the nickel-zinc ferrite.
The preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
s2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating to 75 ℃ for mixing, obtaining a metal salt solution after uniform mixing, dissolving GdCl 3 in distilled water to obtain a doped solution, wherein the concentration of GdCl 3 is 5% of that of FeCl 3, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
s2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 10 to obtain a precipitate, washing the precipitate to be neutral, drying at the temperature of 75 ℃, and grinding the precipitate into particles;
S2.3, pouring the particles into a crucible, and placing the crucible into a box-type furnace for preliminary calcination, wherein the temperature of the preliminary calcination is 500 ℃ and the time is 3.5h. After the preliminary calcination is completed, dividing the calcined particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension according to the solid-to-liquid ratio of 0.9:5, pouring the mixture into cold sintering equipment, controlling the temperature to be 200 ℃, controlling the pressure to be 300Mpa, maintaining for 30min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
Example 9
A preparation method of a memristor based on ferrite ceramic comprises the following steps:
S1, selecting SiO 2/Si as a substrate, and depositing a Pt metal conductive film on the substrate by a magnetron sputtering method to serve as a lower electrode;
S2, selecting Gd ion doped nickel zinc ferrite ceramic as a material of a resistance variable layer, and depositing a Gd ion doped nickel zinc ferrite ceramic film on a lower electrode by a magnetron sputtering method to serve as the resistance variable layer;
And S3, depositing a Pt metal conductive film serving as an upper electrode on the resistance change layer by adopting a magnetron sputtering method to obtain the nickel-zinc ferrite.
The preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
s2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating to 75 ℃ for mixing, obtaining a metal salt solution after uniform mixing, dissolving GdCl 3 in distilled water to obtain a doped solution, wherein the concentration of GdCl 3 is 5% of that of FeCl 3, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
s2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 10 to obtain a precipitate, washing the precipitate to be neutral, drying at the temperature of 75 ℃, and grinding the precipitate into particles;
S2.3, pouring the particles into a crucible, and placing the crucible into a box-type furnace for preliminary calcination, wherein the temperature of the preliminary calcination is 500 ℃ and the time is 3.5h. After the preliminary calcination is completed, dividing the calcined particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension according to a solid-to-liquid ratio of 1:5, pouring the mixture into cold sintering equipment, controlling the temperature to be 200 ℃, controlling the pressure to be 300Mpa, maintaining for 30min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
I-V characteristic tests are carried out on the memristors finally prepared in the embodiments 1-9, and the results show that I-V characteristic curves of the memristors are all 8-shaped; and by varying the magnitude of the pressurization and the pressurization time, both of its I-V characteristics can exhibit non-volatility (i.e., memory) that is characteristic of memristors.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (10)
1. The preparation method of the memristor based on ferrite ceramic is characterized by comprising the following steps of:
s1, depositing a metal conductive film on a non-conductive substrate to serve as a lower electrode;
S2, depositing a nano film on the lower electrode prepared in the S1 by using Gd ion doped nickel zinc ferrite ceramic as a resistance change layer;
And S3, depositing a metal conductive film serving as an upper electrode on the resistive layer prepared in the step S2 to obtain the nickel-zinc ferrite.
2. The method for manufacturing the ferrite-ceramic-based memristor according to claim 1, wherein: in S1, the non-conductive substrate is a Si substrate, and the lower electrode is made of Pt or Au.
3. The method for manufacturing the ferrite-ceramic-based memristor according to claim 1, wherein: the doping concentration of Gd ions in the Gd ion doped nickel zinc ferrite ceramic in the S2 is 1-10% of that of iron ions.
4. The method for preparing the memristor based on ferrite ceramic according to claim 1, wherein the preparation of the Gd ion doped nickel zinc ferrite ceramic in S2 comprises the following steps:
S2.1, weighing raw materials FeCl 3、NiCl2 and ZnCl 2 according to a molar ratio of 4:1:1, dissolving in distilled water, heating and uniformly mixing to obtain a metal salt solution, dissolving GdCl 3 in distilled water to obtain a doped solution, adding the doped solution into the metal salt solution, and uniformly mixing to obtain a solution to be treated;
S2.2, adding NaOH into the solution to be treated under the condition of stirring, controlling the pH value to be 9-11 to obtain a precipitate, washing and drying the precipitate, and grinding the precipitate into particles;
S2.3, after preliminary calcination is carried out on the particles, dividing the particles into two parts, adding one part of the particles into distilled water to obtain suspension, mixing the other part of the particles with the suspension, pouring the mixture into cold sintering equipment, heating and pressurizing, maintaining for 20-40 min, and demoulding and drying to obtain the Gd ion doped nickel-zinc ferrite ceramic.
5. The method for manufacturing the ferrite-ceramic-based memristor, as set forth in claim 4, is characterized in that: the temperature of heating and mixing in S2.1 is 70-80 ℃.
6. The method for manufacturing the ferrite-ceramic-based memristor, as set forth in claim 4, is characterized in that: and S2.2, washing until the filtrate is neutral, and drying at 75-85 ℃.
7. The method for manufacturing the ferrite-ceramic-based memristor, as set forth in claim 4, is characterized in that: and the solid-liquid ratio of the other part of particles in the S2.3 to the suspension is 0.5-1:5.
8. The method for manufacturing the ferrite-ceramic-based memristor, as set forth in claim 4, is characterized in that: the temperature of the preliminary calcination in S2.3 is 400-550 ℃, the calcination time is 2.8-3.8 h, the heating temperature of the cold sintering equipment is 180-220 ℃, and the pressurizing pressure is 280-320 Mpa.
9. The method for manufacturing the ferrite-ceramic-based memristor according to claim 1, wherein: and S3, the upper electrode is made of one of Au, ag or Pt.
10. A memristor made by the method of manufacturing a ferrite-ceramic-based memristor of any one of claims 1-9.
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