CN112820825A - Preparation method of artificial synapse device based on lead-free perovskite - Google Patents
Preparation method of artificial synapse device based on lead-free perovskite Download PDFInfo
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- 210000000225 synapse Anatomy 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 83
- 239000011521 glass Substances 0.000 claims abstract description 80
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000004528 spin coating Methods 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000010409 thin film Substances 0.000 claims abstract description 23
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 239000010931 gold Substances 0.000 claims abstract description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 7
- 230000001133 acceleration Effects 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 2
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000059 patterning Methods 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
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- 238000004506 ultrasonic cleaning Methods 0.000 description 17
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 9
- 239000012498 ultrapure water Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
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- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 229910001385 heavy metal Inorganic materials 0.000 description 2
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- 239000012780 transparent 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
- H10N70/20—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
- H10N70/011—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
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/021—Formation of switching materials, e.g. deposition of layers
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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
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Abstract
The invention belongs to the technical field of semiconductor device preparation, and particularly relates to a preparation method of an artificial synapse device based on lead-free perovskite. The method comprises the steps of firstly cleaning a glass substrate and carrying out plasma treatment, then dropwise adding a lead-free perovskite precursor solution on the substrate, and dropwise adding toluene in the spin coating process to form a lead-free perovskite thin film; and finally, evaporating a gold electrode on the lead-free perovskite thin film to prepare the lead-free perovskite artificial synapse device. The method is simple and easy to operate, and the prepared perovskite film is compact and uniform and has good coverage; the film forming effect is regulated and controlled by adjusting the time point of dripping the toluene, a compact and uniform lead-free perovskite film is obtained at the optimal time point, and the green and environment-friendly lead-free perovskite artificial synapse device with good performance is prepared.
Description
Technical Field
The invention belongs to the technical field of semiconductor device preparation, and relates to a preparation method of a full-solution lead-free perovskite artificial synapse device.
Background
An artificial synapse device is an electronic device that mimics the behavior of biological synapses. The advent of artificial synapse devices is considered as a strong candidate for the next generation of computationally-integrated computing systems, in the context of the increasing proximity of moore's law to the limits and the increasing restrictions on data processing by the memory walls of von neumann computer systems. The computing system based on the artificial synapse device has the advantages of high reading and writing speed, low power consumption, simple structure, simple manufacture, low cost, capability of realizing storage and computation at the same time and the like.
Perovskites have been widely studied in the field of electronic materials due to their advantages of high carrier mobility, large light absorption coefficient, and the like. The perovskite can be dissolved in an organic solvent, the electronic device can be prepared by a solution method, and the method has the characteristics of simple process and low cost, and is also applied to the preparation of the artificial synapse device. Most of the perovskite materials selected at present are lead-containing perovskite systems with high toxicity and do not meet the production requirement of green environmental protection, so that an artificial synapse device prepared based on the lead-free perovskite is necessary.
The invention provides a preparation method of an artificial synapse device based on lead-free perovskite, which adopts low-toxicity antimony to replace high-toxicity lead to synthesize the methylamine-antimony-Chloride (CH) while ensuring the advantages of simplicity and low cost of a full-solution preparation method3NH3)3Sb2Cl9Perovskite is used as a resistance change layer, so that an artificial synapse device is prepared, (CH)3NH3)3Sb2Cl9Compared with lead-containing perovskites, perovskites have great pollution to human bodies and the environmentGreatly reduced, and meets the requirements of green and environment-friendly production.
Disclosure of Invention
The invention aims to provide a method for an organic-inorganic perovskite artificial synapse device without toxic heavy metals, so as to overcome the pollution of the conventional lead-containing perovskite artificial synapse device to the environment. Dropwise adding lead-free perovskite precursor liquid on a glass substrate, dropwise adding methylbenzene in the spin coating process to form a lead-free perovskite thin film, adjusting the time point of dropwise adding methylbenzene to regulate and control the film forming effect, and obtaining a compact and uniform lead-free perovskite thin film at the optimal time point.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a method based on (CH)3NH3)3Sb2Cl9The scheme of the artificial synapse device with perovskite as the resistance-change layer is that metal antimony (chemical symbol: Sb) is used for replacing common toxic heavy metal lead (chemical symbol: Pb) to prepare the perovskite resistance-change layer, and the regulation and control of the resistance-change layer are realized after voltage is applied to an upper electrode and a lower electrode, so that the simulation of biological synapse behavior is realized.
Furthermore, the artificial synapse device has a vertical structure, the lower electrode is made of Indium Tin Oxide (ITO) transparent material, and the middle layer is made of (CH)3NH3)3Sb2Cl9The perovskite thin film, the upper electrode is metal gold (chemical symbol: Au).
and 5, grounding the lower electrode of the artificial synapse device manufactured in the step 4, connecting the upper electrode to the anode, and applying voltage to regulate and control synapse behavior.
Preferably, in the step 1, the glass substrate is sequentially cleaned in an ultrasonic cleaning machine for 10-30 minutes by using a glass cleaning agent, ultrapure water, ethanol and acetone, dried in an oven at 60-100 ℃ for 6-12 hours, and then etched for 5-30 minutes by using a plasma etching machine.
Preferably, in step 1, the (CH)3NH3)3Sb2Cl9The precursor solution is prepared from methylamine chloride (chemical formula is CH)3NH3Cl) and antimony trichloride (SbCl)3) The two solid materials are mixed according to a molar ratio of 3: 2.
Preferably, in step 1, the (CH)3NH3)3Sb2Cl9Preferably, the concentration of the precursor solution is 1 mmol/m, in step 1, the spin coating procedure is set to two steps, the first step speed is 500 rpm for 2s, the second step speed is 4000rpm for 200s, and the angular acceleration is 4000 rpm/s2。
Preferably, in the step 2, the spin coating speed is 2000-4000 rpm.
Preferably, in step 2, toluene is added dropwise 10-500 s after the start of spin coating, and preferably added dropwise at 180s after the start of spin coating at 4000rpm in step 1.
Preferably, in the step 3, the annealing temperature is 60-150 ℃, preferably 70-120 ℃, and the time is 10-60 minutes, preferably 30 minutes.
Preferably, in step 4, the vacuum degree of the evaporation is 3 × 10-3Pa ~ 9×10-3Pa, the evaporation rate is 0.1-10 nm/s, and the thickness of the upper electrode is 50-200 nm.
Preferably, the voltage added in the step 5 is-10 to 10V, and preferably 0.5 to 5V.
The invention has the following remarkable advantages:
(1) the preparation method is simple, and the crystallization time of the perovskite precursor is accurately grasped to carry out recrystallization through the preparation method of the all-solution process, namely toluene is dripped in 180s in the step 2, so that the lead-free perovskite thin film with uniform film formation, high crystallinity and compact film layer is obtained.
(2) The invention simulates biological synapse behavior in the artificial synapse device by regulating and controlling the mode of applied voltage, including incremental forward or reverse voltage, positive pulse, negative pulse and alternate pulse, thereby realizing the preparation of the bionic artificial synapse device.
Drawings
FIG. 1 is an optical microscope photograph of example 1 of the present invention;
FIG. 2 is an optical microscope photograph of example 2 of the present invention;
FIG. 3 is an optical microscope photograph showing a 3 rd embodiment of the present invention;
FIG. 4 is a sectional view of the embodiment 1, 2, 3 of the present invention;
FIG. 5 is a graph showing a performance test of example 1 of the present invention;
FIG. 6 is a graph showing the performance test of example 2 of the present invention;
FIG. 7 is a graph showing a performance test of example 3 of the present invention;
FIG. 8 is a graph showing the performance test of the artificial synapse of the lead-containing perovskite in comparative example 1.
[ label description ]: in fig. 4, 1 is glass, 2 is Indium Tin Oxide (ITO) etched on the glass, 3 is a perovskite thin film, and 4 is top electrode gold.
Detailed Description
The technical scheme of the invention is specifically explained below with reference to the accompanying drawings.
As shown in fig. 4, a lead-free perovskite artificial synapse device comprising a combination of ITO glass substrates 1 and 2, wherein patterning of indium tin oxide should not be considered limited to a specific pattern. The lead-free perovskite thin film 3 is controlled to crystallize by changing the time of dropping and coating toluene. The upper electrode 4 is formed by vacuum deposition.
In order to further understand the proposed method of the present invention, those skilled in the art will now be described with reference to specific examples. The present invention is further described in the preferred embodiments, which should not be construed as limited to the embodiments set forth herein, nor should it be construed as limited to the scope of the invention which is to be protected by the claims.
Example 1:
1) a glass substrate with patterned Indium Tin Oxide (ITO) was used, with dimensions of 2.5cm by 1.1 mm. Using a glass cleaner at a ratio of 1: dissolving the glass substrate in ultrapure water according to the volume ratio of 20 to obtain a cleaning solution, completely immersing the glass substrate in the cleaning solution, and then putting the glass substrate into an ultrasonic cleaning machine to clean for 20 minutes to remove organic or inorganic matters on the surface; then, completely immersing the glass substrate in ultrapure water, and cleaning the glass substrate in an ultrasonic cleaning machine for 20 minutes to remove most of the cleaning liquid; then, completely immersing the substrate in an ethanol solution with the purity of 95%, and then putting the substrate in an ultrasonic cleaning machine for cleaning for 20 minutes to further remove organic matters; and finally, completely immersing the glass substrate in an acetone solution with the purity of 95%, and then placing the glass substrate in an ultrasonic cleaning machine for cleaning for 20 minutes to further remove organic matters. And taking out the glass substrate after cleaning, and drying in an oven at 70 ℃ for 6 hours. And after drying, etching the surface of the glass substrate covered with the indium tin oxide in an oxygen plasma surface treatment machine for 10 minutes. The glass substrate with patterned Indium Tin Oxide (ITO) is referred to as glass substrate for short.
2) Preparation of (CH) 1mol/L3NH3)3Sb2Cl9And (3) placing the precursor solution into a magnetic stirrer at the temperature of 80 ℃ for heating and stirring for 2 hours. And filtering the solution by using a filter with the pore diameter of 0.22 mu m, wherein the obtained solution is called precursor solution for short.
3) And (3) placing the glass substrate treated in the step (1) on a spin coater, taking 90 mu L of precursor solution by using a liquid-transferring gun, uniformly dripping the precursor solution on the glass substrate, and starting spin coating after the precursor solution is stably spread. The spin coating procedure was set to two steps, a first step speed of 500 rpm for 2s, a second step speed of 4000rpm for 200s, and angular accelerations of 4000 rpm/s2。
4) At the 180 th s after the start of spin coating at 4000rpm, 90. mu.L of a toluene solution was quickly dropped onto the film by using a pipette gun, and spin coating was continued for 20 seconds.
5) And after the spin coating is finished, the substrate covered with the perovskite thin film is placed on a heating table at 90 ℃ for annealing for 30 minutes to form a compact perovskite thin film.
6) Under vacuum degree of 3X 10-3Pa~9×10-3And (3) evaporating and plating an upper electrode in a Pa vacuum environment, wherein the electrode material is gold (chemical symbol: Au) with the purity of 99.999 percent, the evaporation rate is 0.1nm/s, and the thickness of the upper electrode is 60 nm.
7) The film formation was observed using a fluorescence microscope. FIG. 1 is a dark-field optical morphology diagram of the lead-free perovskite thin film prepared in example 1, wherein the perovskite is granular, the particles are small, the formed film is dense, and gaps are not basically observed.
8) The lower electrode of the artificial synapse device is grounded, and the upper electrode is applied with a voltage which is increased by 0.02V and is from 0 to 2V to regulate and control the synapse behavior, and the experimental result is shown in FIG. 5. The results show that the current exhibits a large hysteresis curve under the application of voltage, and the current increases significantly with the increase of the number of voltage sweeps, the trend of change is smooth, indicating that the resistance gradually increases with the accumulation of current, exhibiting good resistance-controlling characteristics, meaning that example 1 has good resistance-changing characteristics.
Example 2:
1) a glass substrate with patterned Indium Tin Oxide (ITO) was used, with dimensions of 2.5cm by 1.1 mm. Using a glass cleaner at a ratio of 1: dissolving the glass substrate in ultrapure water according to the volume ratio of 20 to obtain a cleaning solution, completely immersing the glass substrate in the cleaning solution, and then putting the glass substrate into an ultrasonic cleaning machine to clean for 20 minutes to remove organic or inorganic matters on the surface; then, completely immersing the glass substrate in ultrapure water, and cleaning the glass substrate in an ultrasonic cleaning machine for 20 minutes to remove most of the cleaning liquid; then, completely immersing the substrate in an ethanol solution with the purity of 95%, and then putting the substrate in an ultrasonic cleaning machine for cleaning for 20 minutes to further remove organic matters; and finally, completely immersing the glass substrate in an acetone solution with the purity of 95%, and then placing the glass substrate in an ultrasonic cleaning machine for cleaning for 20 minutes to further remove organic matters. And taking out the glass substrate after cleaning, and drying in an oven at 70 ℃ for 6 hours. And after drying, etching the surface of the glass substrate covered with the indium tin oxide in an oxygen plasma surface treatment machine for 10 minutes. The glass substrate with patterned Indium Tin Oxide (ITO) is referred to as glass substrate for short.
2) Preparation of (CH) 1mol/L3NH3)3Sb2Cl9And (3) placing the precursor solution into a magnetic stirrer at the temperature of 80 ℃ for heating and stirring for 2 hours. And filtering the solution by using a filter with the pore diameter of 0.22 mu m, wherein the obtained solution is called precursor solution for short.
3) And (3) placing the glass substrate treated in the step (1) on a spin coater, taking 90 mu L of precursor solution by using a liquid-transferring gun, uniformly dripping the precursor solution on the glass substrate, and starting spin coating after the precursor solution is stably spread. The spin coating procedure was set to two steps, a first step speed of 500 rpm for 2s, a second step speed of 4000rpm for 220s, and angular accelerations of 4000 rpm/s2。
4) At the 200 th s after the start of spin coating at 4000rpm, 90. mu.L of a toluene solution was quickly dropped onto the film by using a pipette gun, and the spin coating was continued for 20 seconds.
5) And after the spin coating is finished, the substrate covered with the perovskite thin film is placed on a heating table at 90 ℃ for annealing for 30 minutes to form a compact perovskite thin film.
6) Under vacuum degree of 3X 10-3Pa~9×10-3And (3) evaporating and plating an upper electrode in a Pa vacuum environment, wherein the electrode material is gold with the purity of 99.999 percent, the evaporation rate is 0.1nm/s, and the thickness of the upper electrode is 60 nm.
7) The film formation was observed using a fluorescence microscope. FIG. 2 is a dark-field optical morphology diagram of the lead-free perovskite thin film prepared in example 2, wherein the perovskite is in a strip shape, the crystal is large, and the formed film has many holes.
8) The lower electrode of the artificial synapse device is grounded, and the upper electrode is applied with a voltage which is increased by 0.02V and is from 0 to 2V to regulate and control the synapse behavior, and the experimental result is shown in FIG. 6. The results show that the current exhibits a distinct hysteresis window under the application of voltage, illustrating that the resistance is controlled by the current in example 2. However, the magnitude of the current does not change significantly after multiple voltage scanning, and the current is relatively large, which indicates that the current directly conducted between the electrodes is dominant due to the direct contact between the upper and lower electrodes of the device under the film layer with low density, so the resistance change effect of embodiment 2 is poor.
Example 3:
1) a glass substrate with patterned Indium Tin Oxide (ITO) was used, with dimensions of 2.5cm by 1.1 mm. Using a glass cleaner at a ratio of 1: dissolving the glass substrate in ultrapure water according to the volume ratio of 20 to obtain a cleaning solution, completely immersing the glass substrate in the cleaning solution, and then putting the glass substrate into an ultrasonic cleaning machine to clean for 20 minutes to remove organic or inorganic matters on the surface; then, completely immersing the glass substrate in ultrapure water, and cleaning the glass substrate in an ultrasonic cleaning machine for 20 minutes to remove most of the cleaning liquid; then, completely immersing the substrate in an ethanol solution with the purity of 95%, and then putting the substrate in an ultrasonic cleaning machine for cleaning for 20 minutes to further remove organic matters; and finally, completely immersing the glass substrate in an acetone solution with the purity of 95%, and then placing the glass substrate in an ultrasonic cleaning machine for cleaning for 20 minutes to further remove organic matters. And taking out the glass substrate after cleaning, and drying in an oven at 70 ℃ for 6 hours. And after drying, etching the surface of the glass substrate covered with the indium tin oxide in an oxygen plasma surface treatment machine for 10 minutes. The glass substrate with patterned Indium Tin Oxide (ITO) is referred to as glass substrate for short.
2) Preparation of (CH) 1mol/L3NH3)3Sb2Cl9And (3) placing the precursor solution into a magnetic stirrer at the temperature of 80 ℃ for heating and stirring for 2 hours. And filtering the solution by using a filter with the pore diameter of 0.22 mu m, wherein the obtained solution is called precursor solution for short.
3) And (3) placing the glass substrate treated in the step (1) on a spin coater, taking 90 mu L of precursor solution by using a liquid-transferring gun, uniformly dripping the precursor solution on the glass substrate, and starting spin coating after the precursor solution is stably spread. The spin coating procedure was set to two steps, a first step speed of 500 rpm for 2s, a second step speed of 4000rpm for 290s, and angular accelerations of 4000 rpm/s2。
4) At 270 th s after the start of spin coating at 4000rpm, 90. mu.L of a toluene solution was quickly dropped onto the film by using a pipette gun, and spin coating was continued for 20 s.
5) And after the spin coating is finished, the substrate covered with the perovskite thin film is placed on a heating table at 90 ℃ for annealing for 30 minutes to form a compact perovskite thin film.
6) In trueThe degree of hollowness is 3 x 10-3Pa~9×10-3And (3) evaporating and plating an upper electrode in a Pa vacuum environment, wherein the electrode material is gold with the purity of 99.999 percent, the evaporation rate is 0.1nm/s, and the thickness of the upper electrode is 60 nm.
7) The film formation was observed using a fluorescence microscope. FIG. 3 is a dark-field optical morphology diagram of the lead-free perovskite thin film prepared in example 3, wherein the perovskite is in a short rod shape, the crystal size is medium, and the formed film is sparse.
8) The lower electrode of the artificial synapse device is grounded, and the upper electrode is applied with a voltage which is increased by 0.02V and is from 0 to 2V to regulate and control the synapse behavior, and the experimental result is shown in FIG. 7. The results show that a significant hysteresis window appears in the current at the first voltage sweep, indicating that the memristive effect exists in example 3. However, the current hysteresis window is not obvious in the subsequent voltage scanning, the current is large, the curve is unchanged, and the resistance value of the resistor is not changed. Therefore, the film layer with low density can be deduced to conduct the upper electrode and the lower electrode, the current of the film layer is dominant, and the resistance change effect is poor.
Comparative example 1
The preparation method of the lead-containing perovskite artificial synapse comprises the following steps:
1) a glass substrate with patterned Indium Tin Oxide (ITO) was used, with dimensions of 2.5cm by 1.1 mm. Using a glass cleaner at a ratio of 1: dissolving the glass substrate in ultrapure water according to the volume ratio of 20 to obtain a cleaning solution, completely immersing the glass substrate in the cleaning solution, and then putting the glass substrate into an ultrasonic cleaning machine to clean for 20 minutes to remove organic or inorganic matters on the surface; then, completely immersing the glass substrate in ultrapure water, and cleaning the glass substrate in an ultrasonic cleaning machine for 20 minutes to remove most of the cleaning liquid; then, completely immersing the substrate in an ethanol solution with the purity of 95%, and then putting the substrate in an ultrasonic cleaning machine for cleaning for 20 minutes to further remove organic matters; and finally, completely immersing the glass substrate in an acetone solution with the purity of 95%, and then placing the glass substrate in an ultrasonic cleaning machine for cleaning for 20 minutes to further remove organic matters. And taking out the glass substrate after cleaning, and drying in an oven at 70 ℃ for 6 hours. And after drying, etching the surface of the glass substrate covered with the indium tin oxide in an oxygen plasma surface treatment machine for 10 minutes. The glass substrate with patterned Indium Tin Oxide (ITO) is referred to as glass substrate for short.
2) 0.2 mol/L CsPbBr is prepared3Precursor solution (CsBr: PbBr)2=1:1, the solvent is DMSO), and placing the mixture in a magnetic stirrer at 80 ℃ to heat and stir for 2 hours. And filtering the solution by using a filter with the pore diameter of 0.22 mu m, wherein the obtained solution is called precursor solution for short.
3) And (3) placing the glass substrate treated in the step (1) on a spin coater, taking 90 mu L of precursor solution by using a liquid-transferring gun, uniformly dripping the precursor solution on the glass substrate, and starting spin coating after the precursor solution is stably spread. The spin coating procedure was set to two steps, a first step speed of 500 rpm for 2s, a second step speed of 4000rpm for 100s, and angular accelerations of 4000 rpm/s2。
4) At the 60 th second after the start of spin coating at 4000rpm, 90. mu.L of a toluene solution was quickly dropped onto the film by using a pipette gun, and the spin coating was continued for 40 seconds.
5) And after the spin coating is finished, the substrate covered with the perovskite thin film is placed on a heating table at 90 ℃ for annealing for 30 minutes to form a compact perovskite thin film.
6) Under vacuum degree of 3X 10-3Pa~9×10-3And (3) evaporating and plating an upper electrode in a Pa vacuum environment, wherein the electrode material is gold with the purity of 99.999 percent, the evaporation rate is 0.1nm/s, and the thickness of the upper electrode is 60 nm.
7) The lower electrode of the artificial synapse device is grounded, and the upper electrode is applied with a voltage which is increased by 0.02V and is from 0 to 2V to regulate and control the synapse behavior, and the experimental result is shown in FIG. 8. The result shows that the current curve window is very small and is close to a straight line; and the front and back scanning current is basically unchanged, which shows that the resistance value is not obviously changed and the memristive effect is poor.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A preparation method of an artificial synapse device based on lead-free perovskite is characterized by comprising the following steps:
step 1, placing the ITO glass substrate subjected to graphical etching on a spin coater, and placing (CH)3NH3)3Sb2Cl9 Dropwise adding the precursor solution on the surface of the glass, and starting spin coating after the solution is uniformly dispersed on the surface of the glass;
step 2, quickly dripping toluene on the glass substrate in the step 1 after the spin coating is started, and continuing the spin coating for 20-40 seconds;
step 3, placing the glass substrate in the step 2 on a heating platform for annealing to form a lead-free perovskite thin film;
step 4, evaporating and plating a layer of gold on the thin film in the step 3, wherein the thickness of the gold is 50 nm-200 nm, and obtaining a lead-free perovskite artificial synapse device;
and 5, grounding the lower electrode of the artificial synapse device manufactured in the step 4, connecting the upper electrode to the anode, and applying a voltage of 0.5-5V to regulate and control the synapse behavior.
2. The method according to claim 1, wherein in step 1, the glass substrate is etched by an oxygen plasma etcher after being sequentially cleaned and dried.
3. The method according to claim 1, wherein in step 1, the (CH) is3NH3)3Sb2Cl9The precursor solution is prepared by mixing two solid materials of methylamine chloride and antimony trichloride, and is dissolved in dimethyl sulfoxide, and the concentration is 0.1-5 mmol/mL.
4. The method according to claim 1, wherein in step 1, the glass substrate is a glass substrate patterned by etching using ITO, and the patterning of ITO should not be specified to a specific pattern.
5. The method according to claim 1, wherein in the step 1, the spin coating process is set to two steps, the first step speed is 500 rpm for 2s, the second step speed is 4000rpm for 200s, and the angular acceleration is 4000 rpm/s2。
6. The production method according to claim 5, wherein toluene is added dropwise at 180s after the start of spin coating at 4000 rpm.
7. The method according to claim 1, wherein the annealing temperature in step 3 is 60 to 150 ℃ for 10 to 60 minutes.
8. The method according to claim 1, wherein in the step 4, the degree of vacuum of evaporation is 3X 10-3Pa~9×10-3Pa, and the evaporation rate is 0.1-10 nm/s.
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