CN110190185B - Flexible device with memristor characteristic and diode behavior and preparation method thereof - Google Patents
Flexible device with memristor characteristic and diode behavior and preparation method thereof Download PDFInfo
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- CN110190185B CN110190185B CN201910500434.0A CN201910500434A CN110190185B CN 110190185 B CN110190185 B CN 110190185B CN 201910500434 A CN201910500434 A CN 201910500434A CN 110190185 B CN110190185 B CN 110190185B
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- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 230000006399 behavior Effects 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910012820 LiCoO Inorganic materials 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000004544 sputter deposition Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 18
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 9
- 239000002390 adhesive tape Substances 0.000 claims description 3
- 230000015654 memory Effects 0.000 abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000000873 masking effect Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910002902 BiFeO3 Inorganic materials 0.000 description 1
- 230000005689 Fowler Nordheim tunneling Effects 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 239000002699 waste material Substances 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
- H10N70/021—Formation of switching materials, e.g. deposition of layers
- H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
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- 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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- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Semiconductor Memories (AREA)
Abstract
The invention provides a flexible device with memristive characteristics and diode behaviors and a preparation method thereof. The manufacturing method comprises the following steps: s1, selecting a flexible materialAs a substrate; s2, sequentially cleaning the substrate by deionized water, ethanol, acetone, ethanol and deionized water; s3, depositing metal titanium on the substrate in the transverse 10% -90% area as the lower electrode; s4, shielding a region of the lower electrode, which is 0-30% of the longitudinal direction, by using a mold; s5, depositing LiCoO on the uncovered lower electrode surface by radio frequency sputtering2As a dielectric layer; s6, masking the dielectric layer with a mask having a mesh, and depositing silver, titanium or copper metal on the dielectric layer through the mesh. The flexible device is prepared by the magnetron sputtering method, the memristor characteristic and the diode behavior can be realized, and the flexible device can be used for replacing a diode and a memory with the same power to be applied to a circuit board so as to realize the coexistence effect of the diode and the memory.
Description
Technical Field
The invention belongs to the technical field of thin film devices, and particularly relates to a flexible device with memristive characteristics and diode behaviors and a preparation method thereof.
Background
Compared with the existing electronic device, the flexible electronic device has the unique advantages of simple device structure, convenient processing, low manufacturing cost, high mechanical flexibility, strong universality, good material controllability and the like, the flexible electronic technology provides opportunities for realizing new equipment such as foldable equipment, bendable equipment, telescopic equipment, wearable equipment and the like, and has attracted extensive attention in the field of electronic devices in recent years. Memory devices are one of the major components of most electronic devices, and thus, research into fabricating memory devices on flexible substrates having reliable electrical properties and stability has been widely focused.
Currently used memories can be divided into two categories, namely volatile random access memories and non-volatile memories. The main products of the former are a dynamic random access memory and a static random access memory, the data storage speed is high, but after power supply is finished, the stored information can disappear quickly, so that the information stored in the volatile memory needs to be refreshed continuously. The latter is mainly ROM (read only memory), PROM (programmable memory), EEPROM (electrically erasable memory), Flash (Flash memory) and the like, which have relatively slow storage speed but still can keep storing data after power off, and are widely used in many small electronic devices, wherein Flash is the most mature non-volatile memory at present.
Since the concept of the memristive memory is proposed, the memristive random access memory has become a research hotspot in the fields of electronic technology, physics, materials science, physical chemistry and information technology. The memristor should have a structure of two electrodes and a dielectric material. The conducting mechanism in the dielectric layer film mainly comprises models of Schottky emission, space charge limited conduction, ohmic conduction, Poole-Freekele emission, thermal field emission, Fowler-Nordheim tunneling, direct tunneling, hopping conduction, ion conduction and the like. The conduction models have good theoretical basis for the charge conduction in the memristor, so that the research of the people has a solid foundation. The dielectric layer materials for preparing the memristor are mainly semiconductors such as ZnO, TiO2, ZrO2, NiO, BiFeO3, SrTiO3, Fe2O3 and the like, and organic semiconductor materials, and because the semiconductor materials are difficult to obtain and high in price, the semiconductor materials are difficult to recover and low in sustainable utilization rate, and part of the semiconductor materials are toxic and have negative effects on the environment and human bodies. Dielectric layer materials have been extensively studied and explored in the fields of insulators, transition metal oxides, polymer materials, semiconductor materials, biological materials, and the like. In this invention we tried to use LiCoO2 to make memristors because of its good electrochemical performance, Co and Li in LiCoO2 can be recovered by chemical precipitation. Therefore, the memristive device prepared by using LiCoO2 has practical application prospect and will be very significant in the long term. In the application of multifunctional electronic devices, electronic devices that simultaneously display a variety of physical properties are of great significance. In this work, flexible devices of Ag/LiCoO2/Ti/PET construction were fabricated by magnetron sputtering and exhibited different properties under different test conditions. Both the memristive properties of the materials and the diode behavior are very interesting physical phenomena. The diode behavior that occurs for the flexible devices of our fabricated Ag/LiCoO2/Ti/PET structure is mainly metal-semiconductor (contact), which is a hot carrier diode.
The research on the memristive characteristics and the diode behavior device has great significance, and is expected to provide a new way for developing novel multifunctional electronic devices and realizing electronic devices with more excellent performance in the future.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a flexible device with memristance and diode behaviors and a preparation method thereof, wherein the flexible device is prepared by a magnetron sputtering method, can realize the memristance and the diode behaviors, can be used for replacing diodes and memories with the same power to be applied to a circuit board so as to realize the coexistence effect of the diodes and the memories, and further improve the integration level of the circuit board.
The purpose of the invention is realized by the following technical scheme: a flexible device with memristive characteristics and diode behaviors sequentially comprises a substrate made of flexible materials, a lower electrode, a dielectric layer and an upper electrode.
Further, the substrate is made of flexible PET, PVA, PI or PEN; the lower electrode is made of metal titanium and is positioned on 10-90% of the transverse area of the substrate; the dielectric layer adopts LiCoO2And (4) preparing.
Furthermore, the upper electrodes are arranged in an array, and the upper electrodes are made of metal silver, titanium or copper.
The invention also provides a preparation method of the flexible device with the memristor characteristic and the diode behavior, which comprises the following steps:
s1, selecting a flexible material as a substrate;
s2, sequentially cleaning the substrate selected in the step S1 by deionized water, ethanol, acetone, ethanol and deionized water for later use;
s3, depositing metal titanium on the cleaned substrate in a transverse 10% -90% area to serve as a lower electrode;
s4, shielding an area of the lower electrode, which is 0-30% of the longitudinal direction of the lower electrode, by using a mold, and fixing the sample by using a high-temperature adhesive tape;
s5, depositing LiCoO on the uncovered lower electrode surface by radio frequency sputtering2As a dielectric layer;
and S6, covering the dielectric layer by using a mask plate with grids, and depositing metal silver, titanium or copper on the dielectric layer through the grids to be used as an upper electrode of the device.
The invention has the beneficial effects that:
1. the flexible device is prepared by the magnetron sputtering method, so that the memory resistance characteristic and the diode behavior can be realized, the flexible device can be used for replacing a diode and a memory with the same power to be applied to a circuit board so as to realize the coexistence effect of the diode and the memory, and the integration level of the circuit board is further improved;
2. LiCoO, a dielectric material used in the present invention2Because of good electrochemical performance, Co and Li in the electrolyte can be recovered by a chemical precipitation method, so that the utilization of waste products is increased, and the pollution of electronic products to the environment is reduced;
3. the memristor prepared by utilizing LiCoO2 has a practical application prospect, and is expected to provide a new way for developing novel multifunctional electronic devices in the future and realizing electronic devices with more excellent performance.
Drawings
FIG. 1 is a block diagram of a flexible device of the present invention;
FIG. 2 is a flow chart of a method of fabricating a flexible device with memristive properties and diode behavior in accordance with the present disclosure;
FIG. 3 shows LiCoO as a dielectric layer material2The crystal structure of (a);
fig. 4 is a current-voltage curve (I-V curve) of the fabricated flexible device.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
As shown in fig. 1, a flexible device with memristive characteristics and diode behavior sequentially comprises a substrate 1 made of flexible materials, a lower electrode 2, a dielectric layer 3 and an upper electrode 4.
Further, the substrate is made of flexible PET, PVA, PI or PEN;the lower electrode 2 is made of metal titanium, and the lower electrode 2 is positioned on 10-90% of the transverse area of the substrate 1; the dielectric layer 3 adopts LiCoO2And (4) preparing.
Further, the upper electrodes 4 are arranged in an array, and the upper electrodes are made of metal silver, titanium or copper.
As shown in fig. 2, the method for manufacturing a flexible device with memristive characteristics and diode behavior provided by the invention comprises the following steps:
s1, selecting a flexible material as a substrate;
s2, sequentially cleaning the substrate selected in the step S1 by deionized water, ethanol, acetone, ethanol and deionized water for later use;
s3, depositing metal titanium on the cleaned substrate in a transverse 10% -90% area to serve as a lower electrode;
s4, shielding an area of the lower electrode, which is 0-30% of the longitudinal direction of the lower electrode, by using a mold, and fixing the sample by using a high-temperature adhesive tape; the lateral and longitudinal directions of the device are not strictly distinguished, and if either direction is selected as the lateral direction, the other direction perpendicular to the lateral direction is automatically the longitudinal direction.
S5, depositing LiCoO on the uncovered lower electrode surface by radio frequency sputtering2As a dielectric layer;
and S6, covering the dielectric layer by using a mask plate with grids, and depositing metal silver, titanium or copper on the dielectric layer through the grids to be used as an upper electrode of the device.
FIG. 3 shows LiCoO as a dielectric layer material2Crystal structure of (2), Li+And Co3 +Each located in alternating octahedral positions in a cubic close-packed.
Fig. 4 is a current-voltage curve (I-V curve) of the fabricated flexible device. When the upper electrode is positively charged and the electrode is grounded, and the voltage scanning range of the test circuit is-2.0V to 2.0V, and the maximum limiting current is 10.0mA, the prepared memristor device has good memristive characteristics; when the upper electrode is grounded, and the voltage sweep range of the test circuit is-4.0V to 4.0V, the (I-V) plot with the maximum current limit of 10.0mA, the device exhibits significant diode behavior.The experiment proves that the structure of the Ag/LiCoO prepared by the invention2The flexible device of/Ti/PET can realize the memristive characteristic and the diode behavior.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (4)
1. A flexible device with memristive characteristics and diode behaviors is characterized by sequentially comprising a substrate (1), a lower electrode (2), a dielectric layer (3) and an upper electrode (4) which are made of flexible materials;
the lower electrode (2) is made of metal titanium, and the lower electrode (2) is positioned on 10-90% of the transverse area of the substrate (1);
the dielectric layer (3) adopts LiCoO2Preparing;
the upper electrode adopts metallic silver.
2. A flexible device with memristive properties and diode behavior according to claim 1, wherein the substrate is flexible PET, PVA, PI or PEN.
3. A flexible device with memristive properties and diode behavior according to claim 1, wherein the upper electrodes (4) are arranged in an array.
4. A method for preparing a flexible device with memristive characteristics and diode behavior according to any one of claims 1 to 3, comprising the following steps:
s1, selecting a flexible material as a substrate;
s2, sequentially cleaning the substrate selected in the step S1 by deionized water, ethanol, acetone, ethanol and deionized water for later use;
s3, depositing metal titanium on the cleaned substrate in a transverse 10% -90% area to serve as a lower electrode;
s4, shielding an area of the lower electrode, which is 0-30% of the longitudinal direction of the lower electrode, by using a mold, and fixing the sample by using a high-temperature adhesive tape;
s5, depositing LiCoO on the uncovered lower electrode surface by radio frequency sputtering2As a dielectric layer;
and S6, covering the dielectric layer by using a mask plate with a grid, and depositing metal silver on the dielectric layer through the grid to be used as an upper electrode of the device.
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FR2969382B1 (en) * | 2010-12-17 | 2022-11-18 | Centre Nat Rech Scient | MEMRISTIVE ELEMENT AND ELECTRONIC MEMORY BASED ON SUCH ELEMENTS |
US9224461B2 (en) * | 2012-11-27 | 2015-12-29 | Intel Corporation | Low voltage embedded memory having cationic-based conductive oxide element |
CN106992249B (en) * | 2017-02-22 | 2019-05-03 | 北京航空航天大学 | A kind of ionic memristor with quantum conductance effect |
US11003981B2 (en) * | 2017-05-25 | 2021-05-11 | International Business Machines Corporation | Two-terminal metastable mixed-conductor memristive devices |
US10229736B2 (en) * | 2017-06-22 | 2019-03-12 | International Business Machines Corporation | Memristive device based on reversible intercalated ion transfer between two meta-stable phases |
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