CN110379922B - Flexible Ag/MoS 2 Preparation method of/Cu resistive random access memory - Google Patents
Flexible Ag/MoS 2 Preparation method of/Cu resistive random access memory Download PDFInfo
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Abstract
The invention aims to provide flexible Ag/MoS 2 The preparation method of the/Cu resistive random access memory comprises the following steps of sequentially arranging a substrate, a sacrificial layer, a bottom electrode, a resistive layer and a top electrode from bottom to top; the substrate is a glass sheet, the sacrificial layer is soluble starch, and the resistance change layer is MoS prepared by a hydrothermal method 2 The nanospheres and the top and bottom electrodes are respectively made of silver and copper. The preparation method comprises the steps of spin-coating a layer of soluble starch film between a glass sheet and a bottom electrode, and finally dissolving the starch film in deionized water to ensure that Ag/MoS 2 the/Cu resistive random access memory is separated from the glass sheet, and the device can be transferred to any substrate. The selected sacrificial layer material has low cost, no toxicity and simple transfer process, the transferred device shows the nonvolatile bipolar resistance change storage characteristic, and the transfer process has no influence on the resistance change characteristic of the device and is MoS 2 The preparation method provides possibility in the preparation of the flexible novel two-dimensional material resistive random access memory.
Description
Technical Field
The invention belongs to the technical field of microelectronics, and particularly relates to flexible Ag/MoS 2 A preparation method of a/Cu resistive random access memory.
Background
In recent years, with the development of industries such as communication, electronics, artificial intelligence and the like, the demand of the market for memories is increased dramatically, and the performance requirements for the memories are increased. A typical Flash memory (Flash) of the nonvolatile memory has advantages of high speed, large capacity, and the like, and is a development direction of the nonvolatile memory. However, the development of flash memory has met technical bottlenecks, and therefore, the development of new memories can promote the further development of the whole industry. The resistance variable memory shows a high resistance state and a low resistance state by applying external voltage to the resistance variable memory to realize information storage, has the advantages of non-volatility, high erasing speed, high storage density, low energy consumption, capability of multi-level storage and the like, and becomes a powerful candidate of the next generation storage technology.
In the structure of the resistive random access memory, the resistive layer material has important influence on the basic performance of the device, so that the search for a suitable resistive random access material is particularly important. MoS 2 Is an important transition metal sulfide. It is a layered material with a structure similar to graphene. MoS 2 The micro-nano material has good physical and chemical properties, large specific surface area, high electronic transmission, good mechanical flexibility and good chemical stability, is a novel semiconductor material, becomes a hotspot of material field research in recent years, is widely applied to various fields of micro-electromechanical resonators, supercapacitors, biosensors, lithium ion batteries, photocatalysis, friction mechanics and the like, and has wide application and market prospects.
At present, in MoS 2 The research of preparing the resistance-change memory as the resistance-change layer material mainly uses the traditional plane hard material as the substrate, so that the traditional hard MoS 2 The resistive random access memory cannot be deformed. In addition, moS is prepared directly on any curved surface substrate 2 The resistive random access memory has a complex process and is not easy to realize, so that the resistive random access memory is limited in the application field of flexible electronic equipment.
Disclosure of Invention
The invention provides a flexible Ag/MoS 2 The preparation method of the/Cu resistive random access memory solves the problem of MoS with the traditional plane hard material as the substrate in the prior art 2 Can not deform and can change MoS 2 The resistive random access memory is transferred onto an arbitrary substrate.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
flexible Ag/MoS 2 Preparation method of/Cu resistive random access memory and method thereofThe method comprises the following specific steps:
step 1), preparing a starch solution with the concentration of 0.015 to 0.05 g/ml;
step 2), putting the cleaned glass sheet at the center of a sample holder in a spin coater, dripping the prepared starch solution on the glass sheet, setting the rotation speed and time of the spin coater, and starting the spin coater;
step 3), repeating the step 2) for four times;
step 4), evaporating a metal substrate film with the thickness of 50 to 500nm on a glass sheet of the starch film by adopting a vacuum evaporation coating film;
step 5) preparing MoS prepared by adopting a hydrothermal method 2 Ball milling in isopropanol for 2-6 h to prepare MoS 2 A suspension;
step 6) preparing a layer of MoS on the bottom electrode by adopting a spin-coating method 2 A film;
step 7) adopting vacuum evaporation coating on MoS 2 A top electrode with the diameter of 250 mu m and the thickness of 50 to 500nm is vapor-plated on the film;
step 8), putting the prepared device into deionized water, dissolving the water-soluble starch sacrificial layer, and obtaining Ag/MoS 2 And after the/Cu resistive random access memory and the glass sheet are completely separated, transferring the device to a different substrate, and performing a resistive characteristic test by adopting a Gishily (keithely) 4200-SCS semiconductor characteristic analyzer.
Further, in the step 2), the size of the glass sheet is 20 mm × 20 mm × 2mm, the glass sheet is respectively ultrasonically cleaned in acetone and absolute ethyl alcohol for 10 min, then is washed by deionized water, and the moisture on the surface of the glass sheet is blown away by a nitrogen gun; the parameters of the spin coater are set as follows: the low rotation speed is 500rpm, the time is 20s, the high rotation speed is 1000 to 3000 rpm, and the time is 99 s.
Further, in step 4), the vacuum evaporation conditions are as follows: vapor deposition rate of 1~2A and background vacuum of less than 5 x 10A -4 Pa and the evaporation power is 160-190 w.
Further, in the step 5), ammonium molybdate, thiourea and hydroxylamine hydrochloride are used as raw materials to prepare MoS by a hydrothermal method 2 Preparation of MoS 2 MoS required for suspension 2 The amount of (A) is 1 to 4gThe volume of the propanol is 10 to 40ml.
Further, in step 7), the vacuum deposition conditions are as follows: vapor deposition rate of 1~2A and background vacuum of less than 5 x 10A -4 Pa and the evaporation power is 130-160 w.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, under the dilemma that the traditional silicon-based memory can not meet the development of a flexible electronic device, the water-soluble starch film is taken as a sacrificial layer, and the starch film is dissolved by deionized water, so that Ag/MoS is formed 2 the/Cu resistive random access memory is completely separated from the glass substrate, so that the possibility of transferring the device to any substrate is realized; the method does not use a chemical corrosive agent, only uses deionized water to dissolve the starch film, does not heat in the dissolving process, and is safe, environment-friendly, simple and quick; the invention relates to MoS 2 A new idea is provided for the preparation of the novel flexible two-dimensional material resistive random access memory.
Drawings
FIG. 1 is a schematic diagram of the transfer process of the method of the present invention;
FIG. 2 is a schematic diagram of a test;
FIG. 3 (a) shows the transfer of the device to a plexiglas rod of 10mm diameter; FIG. 3 (b) is an I-V plot of the test;
FIG. 4 (a) shows the transfer of the device to a plexiglas rod 14mm in diameter; FIG. 4 (b) is an I-V plot of a test;
FIG. 5 (a) shows the transfer of the device to a plexiglas rod 18mm in diameter; FIG. 5 (b) is an I-V plot of the test;
fig. 6 is a schematic structural diagram of a memory.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings. Wherein like elements in different embodiments are numbered with like associated elements. In the following description, numerous details are set forth in order to provide a better understanding of the present application. However, those skilled in the art will readily recognize that some of the features may be omitted or replaced with other elements, materials, methods in different instances.
The invention aims to provide flexible Ag/MoS 2 Referring to fig. 6, the memory comprises a substrate, a sacrificial layer, a bottom electrode, a resistive layer and a top electrode which are sequentially arranged from bottom to top; the substrate is a glass sheet, the sacrificial layer is soluble starch which is easy to form a film and is easy to dissolve in water, and the change-resistant layer is MoS prepared by a hydrothermal method 2 The nanospheres and the top and bottom electrodes are respectively made of metal silver (Ag) and copper (Cu). Referring to fig. 1, the preparation method of the present invention is mainly based on the principle that a layer of soluble starch film is spin-coated between a glass sheet and a bottom electrode, and the starch film is dissolved in deionized water after the device is prepared, such that Ag/MoS is formed 2 the/Cu resistive random access memory is separated from the glass sheet, and the device can be transferred to any substrate. The selected sacrificial layer material has low cost and no toxicity, the transfer process is simple and easy to operate, the transferred device shows the nonvolatile bipolar resistance change storage characteristic, and the transfer process has no influence on the resistance change characteristic of the device, see fig. 2, the invention is MoS 2 The preparation method provides possibility in the preparation of the flexible novel two-dimensional material resistive random access memory.
Example 1:
step 1), preparing 0.03g/ml starch solution;
step 2), putting the cleaned glass sheet (20 mm multiplied by 20 mm multiplied by 2 mm) at the center of a sample holder in a spin coater, dripping the prepared solution on the glass sheet, setting the low rotating speed to be 500rpm and the time to be 20s and the high rotating speed to be 1000rpm and the time to be 99s, and starting the spin coater;
step 3), repeating the step 2) for four times;
and 4) evaporating a Cu substrate film with the thickness of 500nm on the glass sheet coated with the starch film by adopting a vacuum coating method, wherein the vacuum evaporation conditions are as follows: the evaporation rate is 1 angs/s, the background vacuum is less than 5 multiplied by 10 < -4 > Pa, and the evaporation power is 180w;
step 5), weighing MoS prepared by hydrothermal method 2 1g, adding 10 ml isopropanol, ball milling at 300 rpm for 3h to prepare MoS 2 A suspension;
step 6), preparing a layer of MoS by adopting a spin coating method 2 Film, conditions were: the rotating speed is 2000 rpm, and the time is 30s;
step 7) adopting a vacuum coating method to coat on MoS 2 A silver top electrode with the thickness of 500nm and the diameter of 250 mu m is vapor-plated on the film; the vacuum evaporation conditions were: the evaporation rate is 1A/s, the background vacuum is less than 5 x 10 -4 Pa, evaporation power of 150w;
step 8), putting the prepared device into deionized water, wherein the starch sacrificial layer can be dissolved, and Ag/MoS 2 After the/Cu resistive random access memory is completely separated from the glass substrate, the device is transferred to a plexiglass rod with the diameter of 10mm, and a Gishili (keithely) 4200-SCS semiconductor characteristic analyzer is adopted to carry out a resistive random characteristic test, for example, as shown in a graph of an I-V curve of the plexiglass rod transferred to the diameter of 10mm and the test, the on-off ratio is about 100.
Example 1 is the best mode.
Example 2:
step 1), preparing 0.03g/ml starch solution;
step 2), putting the cleaned glass sheet (2 cm multiplied by 2 cm) at the center of a sample holder in a spin coater, dripping the prepared solution on the glass sheet, setting the low rotating speed to be 500rpm and the time to be 20s, setting the high rotating speed to be 1250rpm and the time to be 99s, and starting the spin coater;
step 3), repeating the step 2) for four times;
step 4), evaporating a Cu substrate film with the thickness of 500nm on the glass sheet coated with the starch film by adopting a vacuum coating method, wherein the vacuum evaporation conditions are as follows: the evaporation rate is 1A/s, the background vacuum is less than 5 x 10 -4 Pa, the evaporation power is 180w;
step 5), weighing MoS prepared by hydrothermal method 2 1g, adding 10 ml isopropanol, ball milling at 300 rpm for 3h to prepare MoS 2 A suspension;
step 6), preparing a layer of MoS by adopting a spin coating method 2 Film, conditions were: the rotating speed is 2000 rpm, and the time is 30s;
step 7) adopting a vacuum coating method to coat on MoS 2 A silver top electrode with the thickness of 500nm and the diameter of 250 mu m is vapor-plated on the film; the vacuum evaporation conditions were: the evaporation rate is 1A/s,Background vacuum less than 5 x 10 -4 Pa, evaporation power of 150w;
step 8), putting the prepared device into deionized water, wherein the starch sacrificial layer can be dissolved, and Ag/MoS 2 After the/Cu resistive random access memory is completely separated from the glass substrate, the device is transferred to a plexiglass rod with the diameter of 14mm, and a Gishili (keithely) 4200-SCS semiconductor characteristic analyzer is adopted to carry out a resistive random characteristic test, for example, FIG. 4 is an I-V curve diagram of the plexiglass rod transferred to the diameter of 14mm and the test, and the on-off ratio is about 100.
Example 3:
step 1), preparing 0.03g/ml starch solution;
step 2), putting the cleaned glass sheet (2 cm multiplied by 2 cm) at the center of a sample holder in a spin coater, dripping the prepared solution on the glass sheet, setting the low rotating speed to be 500rpm and the time to be 20s and the high rotating speed to be 1500 rpm and the time to be 99s, and starting the spin coater;
step 3), repeating the step 2) for four times;
and 4) evaporating a Cu substrate film with the thickness of 500nm on the glass sheet coated with the starch film by adopting a vacuum coating method, wherein the vacuum evaporation conditions are as follows: the evaporation rate is 1 ang/s, the background vacuum is less than 5 multiplied by 10 < -4 > Pa, and the evaporation power is 180w;
step 5), weighing MoS prepared by hydrothermal method 2 1g, adding 10 ml isopropanol, ball milling at 300 rpm for 3h to prepare MoS 2 A suspension;
step 6), preparing a layer of MoS by adopting a spin coating method 2 Film, conditions were: rotating speed of 2000 rpm and time of 30s;
step 7) adopting a vacuum coating method to coat on MoS 2 A silver top electrode with the thickness of 500nm and the diameter of 250 mu m is vapor-plated on the film; the vacuum evaporation conditions were: the evaporation rate is 1 angstrom/s, the background vacuum is less than 5 multiplied by 10 < -4 > Pa, and the evaporation power is 150w;
step 8), putting the prepared device into deionized water, wherein the starch sacrificial layer can be dissolved, and Ag/MoS 2 Completely separating the Cu resistive random access memory from the glass substrate, transferring the device to an organic glass rod with the diameter of 18mm, and adopting a Keithely (Keithely)4200-SCS semiconductor characteristic Analyzer tests were performed as shown in FIG. 5 for I-V plots transferred to a 18mm diameter plexiglass stick and tested, with an on-off ratio of about 100.
It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (1)
1. Flexible Ag/MoS 2 The preparation method of the/Cu resistive random access memory is characterized by comprising the following specific steps of:
step 1), preparing a starch solution with the concentration of 0.015 to 0.05 g/ml;
step 2), putting the cleaned glass sheet at the center of a sample holder in a spin coater, dripping the prepared starch solution on the glass sheet, setting the rotation speed and time of the spin coater, and starting the spin coater;
step 3), repeating the step 2) for four times;
step 4), evaporating a metal substrate film with the thickness of 50 to 500nm on a glass sheet of the starch film by adopting a vacuum evaporation coating film;
step 5), preparing MoS by adopting a hydrothermal method 2 Ball milling in isopropanol for 2-6 h to prepare MoS 2 A suspension;
step 6), preparing a layer of MoS on the bottom electrode by adopting a spin coating method 2 A film;
step 7) adopting vacuum evaporation coating on MoS 2 A top electrode with the diameter of 250 mu m and the thickness of 50 to 500nm is vapor-plated on the film;
step 8), putting the prepared device into deionized water, dissolving the water-soluble starch sacrificial layer, and obtaining Ag/MoS 2 After the/Cu resistive random access memory and the glass sheet are completely separated, transferring the device to different substrates, and performing resistive random access characteristic test by adopting a Gishili (keithely) 4200-SCS semiconductor characteristic analyzer;
in the step 2), the size of the glass sheet is 20 mm multiplied by 20 mm multiplied by 2mm, the glass sheet is respectively ultrasonically cleaned in acetone and absolute ethyl alcohol for 10 min, then is washed by deionized water, and is blown away by a nitrogen gun to remove the moisture on the surface of the glass sheet; the parameters of the spin coater are set as follows: low rotation speed of 500rpm, time of 20s, high rotation speed of 1000 to 3000 rpm, time of 99 s;
in the step 4), the vacuum evaporation conditions are as follows: vapor deposition rate of 1~2A and background vacuum of less than 5 x 10A -4 Pa, the evaporation power is 160-190 w;
in the step 5), ammonium molybdate, thiourea and hydroxylamine hydrochloride are used as raw materials to prepare MoS by a hydrothermal method 2 Preparation of MoS 2 MoS required for suspension 2 The amount of the isopropanol is 1 to 4g, and the volume of the isopropanol is 10 to 40ml;
in step 7), the vacuum evaporation conditions are as follows: vapor deposition rate of 1~2A and background vacuum of less than 5 x 10A -4 Pa and the evaporation power is 130 to 160 w.
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| CN113594358B (en) * | 2021-04-16 | 2023-01-31 | 西安工业大学 | Ag/MoSe 2 -PMMA/Cu resistive random access memory and preparation method thereof |
| CN113328036B (en) * | 2021-05-21 | 2022-11-08 | 西安工业大学 | Ag/[ SnS 2 /PMMA]/Cu low-power-consumption resistive random access memory and preparation method thereof |
| CN113594362B (en) * | 2021-07-29 | 2023-01-31 | 西安工业大学 | Low-power consumption nanometer SnS 2 Flexible resistive random access memory and preparation method thereof |
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