CN112820824A - Perovskite memristor and preparation method thereof - Google Patents
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- 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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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
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- 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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- 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
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Abstract
The invention discloses a perovskite memristor and a preparation method thereof, wherein the perovskite memristor comprises a bottom electrode, a lead-free perovskite layer, a polymer protective layer and a top electrode layer which are arranged from bottom to top; the lead-free perovskite layer is a lead-free metal halide perovskite which is in a compact polygonal nanoparticle structure. The method comprises the following steps: spin-coating a lead-free metal halide perovskite precursor solution on the bottom electrode by adopting a thermal dynamic spin-coating method, and annealing to form a lead-free perovskite layer on the bottom electrode; spin-coating a polymer solution on the lead-free perovskite layer, annealing, and forming a polymer protective layer on the lead-free perovskite layer; and preparing a top electrode on the polymer protective layer through thermal evaporation, and forming a top electrode layer on the polymer protective layer to obtain the perovskite memristor. The invention avoids the use of toxic lead, and the lead-free perovskite is compact polygonal nano particles, has high coverage rate and prevents short circuit.
Description
Technical Field
The invention belongs to the technical field of memories, and particularly relates to a perovskite memristor and a preparation method thereof.
Background
The resistive random access memory has received more and more attention in the fields of memory devices, artificial synapses and the like because of the advantages of high conversion speed, high inheritance density and low power consumption. Furthermore, the scaling limitations of current silicon-based flash memory technologies are even overcome due to the potential of the simple metal-insulator-metal structure of ReRAM to achieve high integration density. Flexible electronics are of interest because of their flexible, foldable, stretchable, or wearable nature, and in these applications, flexible memory devices are highly desirable. To date, although many materials with resistive switching characteristics have been extensively studied, there are still few reports on flexible memristors. Of those materials used in ReRAM, inorganic oxide materials have gained attention over the last few years, particularly inorganic perovskite materials, such as PrxCa1–xMnO3(PCMO),SrTiO3(STO), and BaTiO3. However, perovskite oxide thin films still require high temperature processing processes, which limits their application in flexible electronics.
Organic-inorganic lead-halogen perovskites prepared by solution processes exhibit unparalleled performance in a variety of applications, such as solar cells, light emitting diodes, thin film transistors, and memristors. The outstanding performance of perovskites is attributed to the excellent material properties (strong light absorption, tunable band gap, bipolar charge transport and long carrier diffusion distance). Unfortunately, the toxicity of lead has hindered further large-scale commercial applications. Into perovskiteThe replacement of lead element by nontoxic element is imminent. Replacement of toxic lead by the group IVA elements tin (Sn) or germanium (Ge) is an effective approach. However tin or germanium based perovskites are less stable because Sn2+ is readily oxidized to Sn4+ and Ge2+ to Ge when exposed to air4+. However, Sn2+The inherent instability cannot be completely solved.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a perovskite memristor and a preparation method thereof, and aims to adopt lead-free perovskite to avoid the use of toxic lead, and the lead-free perovskite is compact polygonal nano-particles, so that the coverage rate of a lead-free perovskite layer is high, and short circuit is prevented.
To achieve the above objects, according to one aspect of the present invention, there is provided a perovskite memristor including a bottom electrode, a lead-free perovskite layer, a polymer protective layer, and a top electrode layer arranged from bottom to top;
the lead-free perovskite layer is a lead-free metal halide perovskite which is in a compact polygonal nanoparticle structure.
Preferably, the compound is AgBiI4Perovskite, AgBiCl4Perovskite, AgBiBr4One of perovskites.
Preferably, the lead-free perovskite layer is coated on the bottom electrode by a thermal dynamic spin coating method.
Preferably, the thickness of the lead-free perovskite layer is 400-500 nm.
Preferably, the polymer protective layer is one of PMMA, PET and PC, and the thickness of the polymer protective layer is 20-30 nm.
Preferably, the bottom electrode is glass plated with indium tin oxide; the top electrode layer is a silver electrode layer or a copper electrode layer, and the thickness of the top electrode layer is 40-60 nm.
According to another aspect of the present invention, there is provided a method of preparing the perovskite memristor described above, including the steps of:
(1) spin-coating a lead-free metal halide perovskite precursor solution on the bottom electrode by adopting a thermal dynamic spin coating method, and then carrying out annealing treatment at 100-200 ℃ to form a lead-free perovskite layer on the bottom electrode;
(2) spin-coating a polymer solution on the lead-free perovskite layer, and then annealing at 80-100 ℃ to form a polymer protective layer on the lead-free perovskite layer;
(3) and preparing a top electrode on the polymer protective layer through thermal evaporation, wherein the evaporation rate is 0.1-0.3nm/s, and forming a top electrode layer on the polymer protective layer to obtain the perovskite memristor.
Preferably, the thermal dynamic spin coating method is specifically: preheating and preserving heat of a bottom electrode at 50-80 ℃, then placing the bottom electrode on a spin coater for 3000 revolutions per second for spin coating, and dynamically injecting a lead-free metal halide perovskite precursor solution onto the rotating bottom electrode for 40 seconds.
Preferably, the lead-free metal halide perovskite precursor solution is prepared by mixing and dissolving silver iodide and bismuth halide in a DMSO solution according to a mass ratio of 1:1 to obtain the precursor solution, wherein the concentration of the precursor solution is 1-1.5 mol/L.
Preferably, the bottom electrode is further subjected to a pretreatment, specifically: and ultrasonically cleaning the glass substrate for 15 to 20 minutes by using acetone and ethanol respectively, cleaning the glass substrate by using deionized water, and finally putting the glass substrate into an ultraviolet ozone cleaning machine for treatment for 30 to 40 minutes.
In general, at least the following advantages can be obtained by the above technical solution contemplated by the present invention compared to the prior art.
(1) According to the invention, the lead-free metal halide perovskite is adopted, so that the use of toxic lead is avoided, the lead-free perovskite is compact polygonal nano particles, the polygonal nano particles are favorable for the growth of a film, the polygonal nano particles are closely arranged, and the water chestnuts of the particles fill gaps among the particles, so that the coverage rate of a lead-free perovskite layer is high, and the short circuit is prevented.
(2) The lead-free metal halide perovskite adopted in the invention is Ag, so that the perovskite memristor has the advantages of low operating voltage and large window, and the operating voltage is about 0.1-0.2V. The operation voltage of the memristor prepared by the traditional perovskite is lower than that of the memristor prepared by the traditional perovskite.
(3) The lead-free metal halide perovskite adopted in the invention has no organic component, and the stability of the device is greatly improved.
(4) According to the preparation method, the lead-free perovskite layer is prepared by the thermal dynamic spin coating method, the thermal dynamic spin coating can better promote the rapid volatilization of the solvent, so that the crystallization process is accelerated, the coverage rate of the formed film can be greatly increased compared with that of the common spin coating method, and the problems of short circuit and the like are effectively avoided.
(5) The temperature in the thermal dynamic spin coating method is strictly controlled to be 50-80 ℃, the highest film forming coverage rate can be realized, if the temperature is too low, the solvent volatilization rate can not be reached, and if the temperature is too high, the solvent volatilization is too fast, even the vaporization phenomenon occurs, and the film forming is not facilitated. And the annealing treatment temperature after the lead-free metal halide perovskite precursor solution is coated by the thermal dynamic spin coating method is strictly controlled to be 100-200 ℃, so that the sufficient crystallization of the film layer can be ensured. If the temperature is too low, the perovskite layer cannot be crystallized, and if the temperature is too high, the perovskite layer undergoes pyrolysis.
Drawings
FIG. 1 is a schematic diagram of a perovskite memristor structure provided by an embodiment of the present disclosure;
FIG. 2 is a scanning electron microscope image of a lead-free perovskite layer prepared in the perovskite memristor preparation method provided in embodiment 1 of the present disclosure;
FIG. 3 is a scanning electron microscope image of a lead-free perovskite layer prepared in the perovskite memristor preparation method provided by comparative example 1 of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
One embodiment of the invention provides a perovskite memristor, which comprises a bottom electrode, a lead-free perovskite layer, a polymer protection layer and a top electrode layer which are arranged from bottom to top; the lead-free perovskite layer is a lead-free metal halide perovskite which is in a compact polygonal nanoparticle structure.
Preferably, the compound is AgBiI4Perovskite, AgBiCl4Perovskite, AgBiBr4One of perovskites.
Preferably, the lead-free perovskite layer is coated on the bottom electrode by a thermal dynamic spin coating method.
Preferably, the thickness of the lead-free perovskite layer is 400-500 nm.
Preferably, the polymer protective layer is one of PMMA, PET and PC, and the thickness of the polymer protective layer is 20-30 nm.
Preferably, the bottom electrode is glass plated with indium tin oxide; the top electrode layer is a silver electrode layer or a copper electrode, and the thickness of the top electrode layer is 40-60 nm.
Another embodiment of the present invention provides a method for preparing the above perovskite memristor, including the following steps:
(1) spin-coating a lead-free metal halide perovskite precursor solution on the bottom electrode by adopting a thermal dynamic spin coating method, and then carrying out annealing treatment at 100-200 ℃ to form a lead-free perovskite layer on the bottom electrode;
(2) spin-coating a polymer solution on the lead-free perovskite layer, and then annealing at 80-100 ℃ to form a polymer protective layer on the lead-free perovskite layer;
(3) and preparing a top electrode on the polymer protective layer through thermal evaporation, wherein the evaporation rate is 0.1-0.3nm/s, and forming a top electrode layer on the polymer protective layer to obtain the perovskite memristor.
Preferably, the thermal dynamic spin coating method is specifically: preheating and preserving heat of a bottom electrode at 50-80 ℃, then placing the bottom electrode on a spin coater for 3000 revolutions per second for spin coating, and dynamically injecting a lead-free metal halide perovskite precursor solution onto the rotating bottom electrode for 40 seconds.
Preferably, the lead-free metal halide perovskite precursor solution is prepared by mixing and dissolving silver iodide and bismuth halide in a DMSO solution according to a mass ratio of 1:1 to obtain the precursor solution, wherein the concentration of the precursor solution is 1-1.5 mol/L.
Preferably, the bottom electrode is further subjected to a pretreatment, specifically: and ultrasonically cleaning the glass substrate for 15 to 20 minutes by using acetone and ethanol respectively, cleaning the glass substrate by using deionized water, and finally putting the glass substrate into an ultraviolet ozone cleaning machine for treatment for 30 to 40 minutes.
The technical solution of the present invention is further illustrated in detail by the following specific examples and comparative examples:
example 1
The embodiment provides a preparation method of a perovskite memristor, which comprises the following steps:
(1) pretreatment of the bottom electrode: and ultrasonically cleaning Indium Tin Oxide (ITO) coated glass (ITO) by using acetone and ethanol for 20 minutes respectively, removing organic matters on the surface of the ITO, cleaning the ITO by using deionized water, and finally, treating the ITO in an ultraviolet ozone cleaning machine for 40 minutes to perform surface modification.
(2)AgBiI4Preparing a precursor solution: silver iodide and bismuth iodide were mixed and dissolved in a DMSO solution at a concentration of 1M in a mass ratio of 1: 1.
(3) Preparation of lead-free perovskite layer: AgBiI is spin-coated on the pretreated bottom electrode by adopting a thermal dynamic spin coating method4Precursor solution, then annealing treatment is carried out at 100 ℃, and AgBiI is formed on the bottom electrode4A perovskite layer. Preheating a bottom electrode at 60 ℃, then placing the bottom electrode on a spin coater for 3000 revolutions per second for spin coating, and dynamically injecting a precursor solution onto the rotating bottom electrode after the spin coating is started, wherein the spin coating time is 40 seconds. The pretreatment specifically comprises the following steps: and ultrasonically cleaning the glass substrate for 15 to 20 minutes by using acetone and ethanol respectively, cleaning the glass substrate by using deionized water, and finally putting the glass substrate into an ultraviolet ozone cleaning machine for treatment for 30 to 40 minutes.
(4) Preparation of polymer protective layer: in the AgBiI4Spin coating PMMA in chlorobenzene solution on the perovskite layer, then annealing at 88 ℃ and coating AgBiI4A PMMA protective layer is formed on the perovskite layer.
(5) Preparing a top electrode layer: and preparing a silver electrode on the PMMA protective layer through thermal evaporation, wherein the evaporation rate is 0.1nm/s, and forming a silver top electrode layer on the polymer protective layer to obtain the perovskite memristor.
Product characterization:
1. scanning electron microscopy testing
For AgBiI prepared in the step (3)4The perovskite layer was subjected to scanning electron microscopy testing. Referring to fig. 2, it can be seen that: the obtained AgBiI4 perovskite layer is formed by densely arranging polygonal single crystal particles, the size of the particles is about 400 nanometers, the film coverage rate is high, the formed film is smooth, the preparation of the subsequent film is facilitated, and the problem of short circuit can be effectively avoided.
Examples 2 to 5
In this example, the perovskite memristor was prepared by the same preparation method as in example 1, the process parameters of the steps in examples 2-5 are different, and the differences between examples 2-5 and example 1 are shown in table 1.
TABLE 1 perovskite memristor preparation method step technological parameters
AgBiI in the perovskite memristors prepared by examples 2-54The perovskite layer is of a compact polygonal nanoparticle structure.
Comparative example 1
The comparative example was prepared in the same manner as in example 1, except that AgBiI was not applied by the thermal spin coating method in step (3)4Precursor solution, and coating AgBiI by using a common spin coating method4And (3) precursor solution. Referring to fig. 3, it can be seen from the electron microscopic characterization that the perovskite layer prepared by the conventional spin coating method has a low coverage and considerable pores, which directly causes short-circuiting of the device.
Comparative examples 2 to 15
Comparative example 2 provides memristor of Au and CH arranged from top to bottom3NH3PbI3ITO, PET, the memristor provided by the comparative example 3 is Au, Cs arranged from top to bottom3Bi3I9ITO, PET, comparative example 4 as the memristor from top to bottom3NH3PbI3、Pt、Ti、SiO2Si, comparative example 5 provides memristors of Au and CH arranged from top to bottom3NH3PbClxI3-x、TiO2Ti, comparative example 6 provides memristors of Ag and CH arranged from top to bottom3NH3PbBr2.54Cl0.46FTO, glass, memristor provided in comparative example 7 is Ag and CH arranged from top to bottom3NH3PbBr3FTO, glass, memristor provided by comparative example 8 is Ag and CH arranged from top to bottom3NH3PbI3-xClxFTO, glass, memristor provided in comparative example 9 is Au in top-down arrangement, (amino polymer/oleic acid stabilized barium titanate)n、Pt、Ti、SiO2Si, memristor supplied in comparative example 10 is Ag, BiMnO arranged from top to bottom3Ti, comparative example 11 provides memristors of Au and CH arranged from top to bottom3NH3PbI3-x ClxFTO, glass, the memristor provided by the comparative example 12 is Au, Ti, ZnO and niobium doped strontium titanate, Al and Au which are arranged from top to bottom, and the memristor provided by the comparative example 13 is Al, CsPbBr which are arranged from top to bottom3PEDOT PSS, ITO, PET, comparative example 14 provides memristors with Cu, CH arranged from top to bottom3NH3PbI3PEDOT PSS, ITO, glass, comparative example 15 provides memristors with Au and BaTi arranged from top to bottom0.95Co0.05O3、SrRuO3Mica.
The perovskite memristor prepared by the method provided by the embodiment of the invention is subjected to on-off ratio and operating voltage tests with other traditional memristors. The test results are shown in Table 2.
Table 2 memristor performance test results provided in examples and comparative examples
From the results of table 2, it can be seen that the AgBiI4 perovskite memristor provided by the embodiment of the present invention has the minimum operating voltage (set voltage and reset voltage) relative to other types of perovskite memristors (organic perovskite memristors, inorganic perovskite memristors, etc.), the power consumption of the device can be greatly reduced, and the on-off ratio of the AgBiI4 perovskite memristor provided by the embodiment of the present invention is at an upstream level in the perovskite-type memristors.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A perovskite memristor is characterized by comprising a bottom electrode, a lead-free perovskite layer, a polymer protective layer and a top electrode layer which are arranged from bottom to top;
the lead-free perovskite layer is a lead-free metal halide perovskite which is in a compact polygonal nanoparticle structure.
2. The perovskite memristor of claim 1, wherein the lead-free metal halide perovskite is AgBiI4Perovskite, AgBiCl4Perovskite, AgBiBr4One of perovskites.
3. The perovskite memristor of claim 1, wherein the lead-free perovskite layer is obtained by coating on the bottom electrode by a thermal dynamic spin coating method.
4. The perovskite memristor of claim 3, wherein the thickness of the lead-free perovskite layer is 400-500 nm.
5. The perovskite memristor of claim 3, wherein the polymer protective layer is one of PMMA, PET, PC, the thickness of the polymer protective layer being 20-30 nm.
6. The perovskite memristor of any of claims 1-3, wherein the bottom electrode is indium tin oxide coated glass; the top electrode layer is a silver electrode layer or a copper electrode layer, and the thickness of the top electrode layer is 40-60 nm.
7. A method of making the perovskite memristor of any of claims 1-6, comprising the steps of:
(1) spin-coating a lead-free metal halide perovskite precursor solution on the bottom electrode by adopting a thermal dynamic spin coating method, and then carrying out annealing treatment at 100-200 ℃ to form a lead-free perovskite layer on the bottom electrode;
(2) spin-coating a polymer solution on the lead-free perovskite layer, and then annealing at 80-100 ℃ to form a polymer protective layer on the lead-free perovskite layer;
(3) and preparing a top electrode on the polymer protective layer through thermal evaporation, wherein the evaporation rate is 0.1-0.3nm/s, and forming a top electrode layer on the polymer protective layer to obtain the perovskite memristor.
8. The method according to claim 7, wherein the thermal dynamic spin coating method is specifically: preheating and insulating the bottom electrode at 50-80 ℃, then placing the bottom electrode on a spin coater for 3000 revolutions per second for spin coating, and dynamically injecting the lead-free metal halide perovskite precursor solution onto the rotating bottom electrode.
9. The production method according to claim 8, wherein the lead-free metal halide perovskite precursor solution is produced by mixing and dissolving silver iodide and bismuth halide in a DMSO solution at a mass ratio of 1:1 to obtain the precursor solution, and the concentration of the precursor solution is 1 to 1.5 mol/L.
10. The method according to claim 8, wherein the bottom electrode is further subjected to a pretreatment, specifically: and ultrasonically cleaning the glass substrate for 15 to 20 minutes by using acetone and ethanol respectively, cleaning the glass substrate by using deionized water, and finally putting the glass substrate into an ultraviolet ozone cleaning machine for treatment for 30 to 40 minutes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113540346A (en) * | 2021-07-20 | 2021-10-22 | 泉州师范学院 | Organic/inorganic composite perovskite memristor with planar structure and preparation method thereof |
| CN113725357A (en) * | 2021-08-17 | 2021-11-30 | 南京邮电大学 | Memristor and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058049A (en) * | 2016-06-17 | 2016-10-26 | 南京理工大学 | Preparation method of large-grain perovskite film memristor memory cell |
| CN109088002A (en) * | 2018-07-11 | 2018-12-25 | 深圳大学 | A kind of flash memory and preparation method thereof based on halogen perovskite material |
| CN109346601A (en) * | 2018-11-26 | 2019-02-15 | 南京理工大学 | The preparation method of the multiple resistive memristor of full-inorganic perovskite |
-
2021
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058049A (en) * | 2016-06-17 | 2016-10-26 | 南京理工大学 | Preparation method of large-grain perovskite film memristor memory cell |
| CN109088002A (en) * | 2018-07-11 | 2018-12-25 | 深圳大学 | A kind of flash memory and preparation method thereof based on halogen perovskite material |
| CN109346601A (en) * | 2018-11-26 | 2019-02-15 | 南京理工大学 | The preparation method of the multiple resistive memristor of full-inorganic perovskite |
Non-Patent Citations (1)
| Title |
|---|
| HAIBO YE: "High performance flexible memristors based on a lead free AgBiI4 perovskite with an ultralow operating voltage", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113540346A (en) * | 2021-07-20 | 2021-10-22 | 泉州师范学院 | Organic/inorganic composite perovskite memristor with planar structure and preparation method thereof |
| CN113540346B (en) * | 2021-07-20 | 2024-02-02 | 泉州师范学院 | Organic/inorganic composite perovskite memristor with planar structure and preparation method thereof |
| CN113725357A (en) * | 2021-08-17 | 2021-11-30 | 南京邮电大学 | Memristor and preparation method thereof |
| CN113725357B (en) * | 2021-08-17 | 2023-11-14 | 南京邮电大学 | Memristor and preparation method thereof |
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