CN119496466B - A composite memristor and liquid pool electrochemical reaction large frequency modulation oscillator device - Google Patents
A composite memristor and liquid pool electrochemical reaction large frequency modulation oscillator deviceInfo
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Abstract
本发明公开了一种复合忆阻器和液池电化学反应的大幅调频振荡器件，涉及电子元器件技术、神经形态器件、电子信息处理等多个领域；该大幅调频振荡器件包括直流电源、第一电极、氧化还原液池、第二电极与忆阻器，通过阈值开关效应实现导电态转变，并借助氧化还原液池与忆阻器工作电路的串联，构建了固‑液界面的工作环境，在不同幅值的直流电压驱动下，器件能在零点几赫兹至几千赫兹宽频范围内实现稳定的振荡，适用于模拟人工神经元行为、宽频脉冲序列生成及数字信号处理等多种应用场景。
The present invention discloses a high-frequency modulation oscillator device for composite memristor and liquid pool electrochemical reaction, which relates to multiple fields such as electronic component technology, neuromorphic devices, and electronic information processing. The high-frequency modulation oscillator device comprises a DC power supply, a first electrode, a redox liquid pool, a second electrode, and a memristor. The conductive state transition is achieved through a threshold switching effect. By virtue of the series connection of the redox liquid pool and the memristor working circuit, a solid-liquid interface working environment is constructed. Driven by DC voltages of different amplitudes, the device can achieve stable oscillation in a wide frequency range from a few tenths of a hertz to several kilohertz. The device is suitable for multiple application scenarios such as simulating artificial neuron behavior, generating broadband pulse trains, and processing digital signals.
Description
Technical Field
The invention relates to the field of wideband signal generation and neuromorphic devices, in particular to a frequency modulation oscillation device for electrochemical reaction of a composite memristor and a liquid pool, which has a wide frequency modulation range and can cover a frequency range from a few tenths of hertz to a few kilohertz.
Background
In the field of signal generation, a traditional all-solid-state electronic frequency modulation mode, such as a frequency modulation circuit based on an amplifier, realizes frequency modulation of signals by adjusting gain, a feedback network or adopting structures such as a voltage-controlled oscillator (VCO). However, such circuits often have problems such as high power consumption, limited frequency adjustment range, and complex circuit structure, and the limitation thereof is particularly prominent in a scene where wideband modulation is required.
In the field of neuromorphic devices, novel oscillating devices have appeared in recent years, which combine memristors, solid-state capacitors and solid-state resistors, and such devices utilize the threshold switching effect of the memristors, that is, when an applied voltage reaches or exceeds the threshold voltage of the memristors, the conductivity of the devices can be reversibly and significantly changed in a nonlinear manner between non-conduction and conduction, so as to realize a switching function. The change mechanism is caused by the formation and destruction of the conductive wire under the action of an electric field. The memristor-based neuromorphic device can directly simulate information transmission and processing processes among neurons, and has the remarkable advantage of extremely low power consumption. In addition, the resistance tunability and memory properties of memristors are similar to the long-term plasticity of neurons, enabling such devices to mimic certain key properties of biological neural networks, such as learning, memory, and decision making. However, such memristor-based neuromorphic devices also suffer from the disadvantage of a narrow operating frequency range. As shown in FIG. 2, when different voltages are applied to a device of a typical niobium oxide memristor composite solid-state resistor and solid-state capacitor, the oscillation of the device is unstable at low frequency, so that the oscillation frequency error is extremely large, and at high frequency (the frequency is more than hundreds of hertz), the device can stably oscillate, but the frequency range of the stable oscillation of the device is limited, and the cross-magnitude regulation and control are difficult to realize. This problem is prevalent in various types of oscillating devices of the typical memristor-capacitance-resistance architecture, which typically oscillate stably only in the high frequency range, while the stable oscillation in the low frequency range is left blank, as described in documents "Biological plausibility and stochasticity in scalable VO2 active memristor neurons[J].Nature communications,2018,9(1):4661" and "An artificial spiking afferent nerve based on Mott memristors for neurorobotics[J].Nature communications,2020,11(1):51". In view of the regularity and stability of the pulse of biological neurons, and the pulse frequency thereof covers a wide range (from a few tenths of hertz to kilohertz), such composite memristors and solid state resistive, solid state capacitive devices cannot meet the requirements of broadband signal processing and increasingly complex artificial neurons, in particular the requirements of biocompatibility (biological neurons mostly operate in liquid environments).
Another neuromorphic device faces the difficulty of being deeply fused with a liquid environment, and is currently connected directly to a solution environment, mainly through all-solid-state electronics. In the research of aluminum ion electronic devices, although liquid is introduced as a capacitance medium, the charge storage capacity is enhanced by utilizing the high dielectric constant of the liquid, the design is more focused on the improvement of the physical characteristics of the electronic devices, the electrochemical reaction advantages of electrodes and a liquid pool are not fully fused, and the capability of the devices in simulating the dynamic change and learning process in a biological neural network is limited. In addition, some devices that sense glucose through interfacial oxidation reactions, while capable of sensing chemical changes in the environment to some extent, such designs often rely on additional artificial neuron pulse generation circuitry or amplifier oscillation circuitry to amplify weak electrochemical signals so that they can be identified and processed. Such a configuration not only increases the complexity and cost of the system, but may introduce additional noise and delay that affects the overall performance and real-time performance of the neuromorphic system.
Therefore, developing a large-scale frequency modulation oscillation device for electrochemical reaction of a composite memristor and a liquid pool becomes a technical problem to be solved in the field.
Disclosure of Invention
In order to solve the problems, the invention designs an artificial neuron working model based on the working principles of biological neurons and synapses, and the model is also a working model of the large-scale frequency modulation oscillation device disclosed by the invention, and as shown in fig. 3, the model shows a typical biological neuron and a working model of synapses thereof, and the biological neurons realize information transmission and activation through neurotransmitter transmission between chemical synapses. In the biomimetic model of the present invention, the memristor acts as a neuron, the two electrodes simulate synapses, and the ions in the redox couple pool between the two electrodes act as neurotransmitters in the synaptic cleft. The obtained oscillation device for electrochemical reaction of the composite memristor and the liquid pool has wide spectrum coverage range, and covers the frequency range from a few tenths of hertz to a few kilohertz.
Specifically, the invention is realized by the following technical scheme:
Firstly, the invention provides a large-scale frequency modulation oscillation device for electrochemical reaction of a composite memristor and a liquid pool, which comprises a direct current power supply, a first electrode, a redox couple liquid pool, a second electrode and a threshold switch type memristor, wherein the positive electrode of the direct current power supply is connected with the first electrode, the negative electrode of the direct current power supply is sequentially connected with the threshold switch type memristor and the second electrode in series, a gap for accommodating the redox couple liquid pool is formed between the first electrode and the second electrode to form a closed loop together, the redox couple liquid pool is an ionic solution containing the redox couple, and the equivalent circuit diagram of the device is shown in fig. 4.
The materials of the first electrode and the second electrode can be preferably selected from platinum, gold, carbon or ITO according to the specific conditions of the experiment, and the conducting wire is made of conventional copper wires and the like.
The above-mentioned threshold-switching memristor refers to a memristor having a threshold switching effect, and the term "threshold switching effect" refers to a sudden abrupt decrease in resistance from a high-resistance (HR) state to a low-resistance (LR) state when an applied voltage exceeds a threshold voltage, and a sudden abrupt increase in resistance from the low-resistance (LR) state to the high-resistance (HR) state when the applied voltage is lower than a holding voltage.
The threshold-switching memristor is a conventional memristor in the art. The memristor structure prepared in the embodiment is designed as disclosed in literature "Effect of electrode materials on resistive switching behaviour of NbOx-based memristive devices[J].Scientific Reports,2023,13(1):17003", and is composed of a bottom electrode, a resistance changing layer and a top electrode, as shown in fig. 5, wherein the materials of the top electrode and the bottom electrode can be selected from materials such as platinum, gold, tungsten or titanium nitride according to the manufacturing process of the memristor. The material of the resistive layer can be metal oxide (such as niobium oxide) or binary compound of non-metal and chalcogen element (such as silicon telluride). Before the memristor is prepared to complete the access circuit, a scanning voltage lower than 3V and exceeding the threshold voltage of the memristor is required to be applied to the memristor, so that the memristor has a threshold switching effect, and the threshold switching type memristor is obtained.
In the large-amplitude frequency modulation oscillation device, the direct-current power supply voltage needs to be higher than the threshold voltage of the memristor, meanwhile, the highest partial voltage at two ends of the memristor in the working process of the device is not lower than the threshold voltage, and the lowest partial voltage is not higher than the holding voltage. Preferably, the DC power supply voltage is lower than 3V and higher than the threshold voltage of the memristor, the term "threshold voltage" refers to the voltage value at which the device starts to switch states (rapidly switches from a high-resistance state to a low-resistance state) when the applied voltage exceeds a certain threshold, and the term "holding voltage" refers to the minimum voltage required by the memristor to be able to hold the states after switching to the low-resistance state.
The term "redox couple" refers to a reducing species and its corresponding oxidized form that loses electrons at the anode (oxidation) upon application of a voltage, while the oxidizing species gains electrons at the cathode (reduction), thereby effecting a reversible redox electrochemical reaction. The ionic solution containing the redox couple may be any one of an iron-based electrolyte and an iodine-based electrolyte. In the embodiment of the invention, ferric redox pair ion solutions with the ion concentration of Fe 3+ and Fe 2+ of 1mol/L are prepared by using ferric chloride and ferrous chloride, and a commercial iodine I 3 -/I- redox pair electrolyte is adopted.
In the large-amplitude frequency modulation oscillation device disclosed by the invention, an oxidation-reduction pair in a liquid pool is subjected to electrochemical reaction under the action of an externally applied electric field, electrons flow out from a negative electrode of a power supply and flow into a cathode (a second electrode) through a lead, oxidizing ions are reduced and consumed at the cathode, so that the concentration of the oxidizing ions near the surface of the cathode is reduced, the high-concentration oxidizing ions in a bulk liquid pool diffuse and transfer mass to a low-concentration area on the surface of the cathode, and the anode (a first electrode) is subjected to the opposite process, as shown in fig. 5. The process realizes ion diffusion in the solution and exchange of electrons at the solid-liquid interface, thereby realizing circuit conduction of the solid-liquid interface.
The invention further provides a preparation method of the large-amplitude frequency modulation oscillation device, which comprises the following specific steps:
1) Electroforming memristors electroforming is performed using an active ammeter (e.g., keithley 2450) to apply a sweep voltage to the memristor below 3V but above its threshold voltage. The memristor is initially in a High Resistance (HR) state, but can rapidly transition to a Low Resistance (LR) state when the scan voltage increases up to a threshold voltage of the memristor, and then can rapidly transition to a High Resistance (HR) state when the scan voltage gradually decreases up to less than a holding voltage of the memristor. This marks the completion of the electroforming process, successfully obtaining a memristor with threshold switching characteristics, the memristor threshold switching characteristics diagram being shown in FIG. 6.
2) The device is assembled by connecting one end of the electroformed memristor to the negative electrode of a direct current power supply, and connecting the other end of the electroformed memristor to a second electrode, wherein the positive electrode of the direct current power supply is connected to the first electrode, then about 50 microliters of redox couple ionic liquid is dripped on the first electrode, and the second electrode is covered on the solution and keeps a gap with the first electrode, so that the redox couple liquid clamped between the two electrodes can flow and completely cover the first electrode and the second electrode area (the surface contacted with the solution). Thus, the preparation of the large-scale frequency modulation oscillation device is completed.
Further, the memristor is prepared by the following steps:
S01, exposing the pattern model on a substrate (substrate material is optional silicon oxide, quartz plate, etc.) with photoresist coated, and developing.
The photolithography step is conventional in the art, such as a photolithography machine manufactured by He Zhi technology (Suzhou) under the model UV Litho-ACA PRO. The photolithography parameters can be adjusted according to practical conditions, such as photolithography time of 500ms, illumination intensity of 0.5, etc., and pattern models are subjected to photolithography on a substrate with the AZ-5214 photoresist spin-coated, and then development is performed. Reference is made to this step "Dropout neuronal unit with tunable probability based on NbOx stochastic memristor for efficient suppression of overfitting[J].
Microelectronic Engineering,2022,259:111778 ".
S02, performing photoetching and sputtering target materials on the substrate subjected to photoetching in the step S01 by utilizing a magnetron sputtering technology in sequence to form a bottom electrode, a resistance change layer and a top electrode, and then stripping to obtain the memristor;
The sputtering is a conventional technology in the field, and a Q150TES high-precision multifunctional vacuum metal sputtering instrument manufactured by Quorum Technologies company is used in the example, and a bottom electrode, a resistance changing layer and a top electrode are respectively sputtered to target materials according to the manufacturing process of the memristor;
the above-mentioned peeling step includes immersing the sample of sputtered target material in an acetone solution for 5 minutes, and then performing ultrasonic treatment with an ultrasonic cleaner at a power of 3W for 10 seconds to wash off the other portions, leaving the target portion. Then placing the sample into isopropanol solution, carrying out ultrasonic treatment for 10s at a power of 3W, washing off acetone, fishing out the sample, and drying with nitrogen to obtain the memristor;
The memristor fabrication process is a conventional method in the art, and the fabrication method is disclosed in reference "Total ionizing dose effects of gamma-ray radiation on NbOx-based selector devices for crossbar array memory[J].IEEE Transactions on Nuclear Science,2017,64(6):1535-1539".
The invention further provides a testing and using method of the large-amplitude frequency modulation oscillation device, which comprises the following specific steps:
And a direct current power supply (such as a Tektronix AFG31000 or Keithley 2450 generator) is used for applying voltage in a working circuit, current in the circuit is measured through a current amplifier to change in real time, a liquid pool and memristor voltage division waveform curve is recorded through an oscilloscope (such as RIGOL DHO 4204), and the electrical response of the composite memristor and the liquid pool electrochemical reaction device under different direct currents is obtained.
For example, in example 1, a device using a composite niobium oxide and an iron-based electrolyte bath was used, and stable oscillation of current in a line was observed by applying a direct-current voltage stimulus, as shown in fig. 7, by changing the direct-current power supply voltage, and the oscillation frequency was adjusted from a few tenths of hertz to a few khz. During the period, as the voltage rises, the resistance state and the partial pressure at two ends of the memristor change, and meanwhile, the impedance and the partial pressure of the liquid pool are changed. The voltage across the bath varies as shown in figure 8. The output voltage of the direct current power supply changes, and line oscillation and solution partial pressure oscillation can be affected. At different dc voltages, the solution partial pressure decreases as the dc voltage decreases. Unlike all-solid-state resistance-capacitance, the impedance response of a solution changes significantly with partial pressure. Particularly, when the partial pressure between the first electrode and the second electrode is reduced, the equivalent capacitance of the solid-liquid interface is increased, so that stable oscillation under low frequency is realized.
The device has excellent frequency modulation characteristics, can generate frequency signals crossing multiple orders of magnitude, and has the performance which is obviously superior to that of the oscillating devices of other current composite memristors, fills up the blank of the field of complex signal generation, and effectively makes up the defect of the artificial neuron in the aspect of simulating the low-frequency pulse of the biological neuron. By introducing a liquid environment, the device further improves the similarity between the artificial neuron and the biological neuron, and greatly simplifies the structure of the oscillating circuit. The device has the advantages of extremely simple structure, stable oscillation signals, integration of the advantages of electrochemical reaction of the liquid pool and the electrode and the like, can realize stable oscillation within a wide frequency range from a few tenths of hertz to a few kilohertz, and is suitable for simulating various application scenes such as artificial neuron behaviors, broadband pulse sequence generation, digital signal processing and the like. In conclusion, the device not only realizes breakthrough in performance, but also shows unique value and potential in application fields.
Drawings
FIG. 1 is a schematic diagram of a largely frequency modulated oscillation device for the electrochemical reaction of a composite memristor and a liquid pool;
Wherein, the device comprises a 1-direct current power supply, a 2-memristor, a 3-redox solution, a 4-first electrode, a 5-second electrode and an A-ammeter. The redox solution 3, the first electrode 4 and the second electrode 5 form a liquid pool for electrochemical reaction.
FIG. 2 is an equivalent circuit diagram and an electrical performance diagram of an oscillating device of a composite memristor and solid state circuit element;
and b is an error diagram of the oscillation frequency of the device under different voltages, and the instability of the device at low frequency and the stability at high frequency are intuitively shown.
FIG. 3 is a diagram of a biological neuron transfer information and synaptic biological working model and an artificial neuron working model according to the invention.
FIG. 4 is an equivalent circuit diagram of a largely frequency modulated oscillation device for the electrochemical reaction of a composite memristor and a liquid pool.
FIG. 5 is a schematic diagram of a structure of a largely frequency modulated oscillation device that combines memristor and liquid pool electrochemical reactions.
FIG. 6 is a threshold switching characteristic diagram of a memristor;
The memristor is initially in a High Resistance (HR) state, but can rapidly transition to a Low Resistance (LR) state when the scan voltage increases up to a threshold voltage of the memristor, and then can rapidly transition to a High Resistance (HR) state when the scan voltage gradually decreases up to less than a holding voltage of the memristor.
FIG. 7 is a graph of the large scale frequency modulation characteristics of an oscillating device of a composite niobium oxide memristor and Fe 2+/Fe3+ liquid bath electrochemical reaction;
The frequency of the device is greatly modulated under different voltages, the frequency spans multiple orders, so that different time scales are selected, and the frequency modulation capability of the device is displayed by respectively 10s, 1s, 0.1s, 10ms, 1ms and 0.1m from bottom to top, and the oscillating frequency diagram of the device under different voltages intuitively displays the stable frequency modulation capability of the device.
FIG. 8 is a graph of voltage waveforms and statistics of the two ends of the liquid pool under different DC power supply output voltages;
The graph b is a statistical curve of the maximum value and the minimum value of the partial pressure of the two ends of the liquid pool under the output voltage of the direct current power supply, so that the partial pressure of the two ends of the liquid pool can be reduced along with the reduction of the direct current voltage, and the impedance response of the solution can be obviously changed along with the change of the partial pressure, so that the equivalent capacitance of a solid-liquid interface can be increased when the partial pressure between the first electrode and the second electrode is reduced, and stable oscillation under low frequency is realized.
FIG. 9 is a voltage-frequency plot of a composite silicon telluride memristor and an iodine-based electrolyte bath at different voltages;
The visible device shows the characteristic of increasing with the rising frequency of the voltage, and the frequency rises from a few tenths of hertz to a few kilohertz, thereby proving the excellent frequency modulation range and wide application potential.
Fig. 2, 7 and 9 above are all based on the test method disclosed in literature "Microscopic Modeling and Optimization of NbOx Mott Memristor for Artificial Neuron Applications[J].IEEE Transactions on Electron Devices,2022,69(12):6686-6692", by gradually increasing the voltage to test the oscillation frequency of the oscillating device of the composite memristor at different voltages.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and detailed description for the purpose of better understanding of the technical solution of the present invention to those skilled in the art. Embodiments of the present invention will hereinafter be described in detail, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary only for explaining the present invention and are not to be construed as limiting the present invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The photo-etching machine manufacturer used in the embodiment is Hezhi technology (Suzhou) Co., ltd, the photo-etching machine model is UV Litho-ACA PRO, and the light source is ultraviolet light.
The metal sputtering instrument is a Q150TES high-precision multifunctional vacuum metal sputtering instrument produced by Quorum Technologies company.
The positive photoresist developer is purchased from Jiangyin river microelectronic materials Co., ltd, model ZX-238;
high purity indium pellets were purchased from ala Ding Gongsi.
Example 1 preparation of a Large frequency modulated Oscillating device with niobium oxide memristor composite Fe 3+/Fe2+ electrochemical cell
1) The single-sided polished P-type silicon wafer produced by Chinese electric department 46 is selected, the diameter of the silicon wafer is 100+/-0.3 mm, the thickness is 400+/-15 mu m, the crystal orientation is <100> +/-0.5 degrees, and the thickness of the surface oxide layer is 300nm.
The silicon dioxide surface of the silicon wafer doped with boron is used as an insulating surface substrate, the resistivity of the silicon dioxide surface is 0.05-0.2 omega cm, AZ5214 photoresist is used, and the silicon dioxide surface is spin-coated for 1 minute and 30 seconds at the rotating speed of 3500 revolutions per minute by a spin coater.
2) The silicon wafer spin-coated in 1) was placed on a hot stage and heated at 100 ℃ for 5 minutes to cure the photoresist.
3) And (3) placing the silicon wafer in the step (2) on a sample stage of a photoetching machine for photoetching, and setting the photoetching parameters to be 500ms of illumination time and 0.5 of illumination intensity.
4) And 3) placing the silicon wafer subjected to the photoetching in the step 3) into positive photoresist developer for developing for 1 minute, and removing photoresist of the exposed part to form a target pattern.
5) The silicon wafer in 4) was placed in a metal sputter to sputter platinum (30 nm thick, 200s with 20mA current in a high purity argon environment) as the bottom electrode of the target memristor.
6) Soaking the silicon wafer sputtered in the step 5) into acetone, using an ultrasonic cleaner after 5 minutes, and performing ultrasonic treatment for 10 seconds under the power of 3W to remove residual photoresist and other impurities.
7) Repeating the steps 1) to 4) to prepare for sputtering the resistive layer and the top electrode.
8) The silicon wafer in 7) is put into a metal sputtering instrument to be sputtered with niobium oxide (the thickness of 20nm, 80mA current is used for sputtering 600s under the mixed gas with the argon-oxygen ratio of 3:1) and platinum (the thickness of 30nm, and 20mA current is used for sputtering 200s under the high-purity argon environment) in sequence, and the niobium oxide is respectively used as a resistive layer and a top electrode of the target memristor.
9) And (5) repeating the step (6) to obtain the niobium oxide memristor.
10 The silicon wafer (niobium oxide memristor) in 9) is quickly taken out, put into isopropanol, then cleaned for 10 seconds with ultrasonic waves under the power of 3W, and finally dried with nitrogen. The niobium oxide memristor of this example was prepared by the method disclosed in reference "Total ionizing dose effects of gamma-ray radiation on NbOx-based selector devices for crossbar array memory[J].IEEE Transactions on Nuclear Science,2017,64(6):1535-1539".
11 Electroforming the niobium oxide memristor of 10), applying a 2V scan voltage (exceeding the memristor threshold voltage) using Keithley 2450 ammeter, and connecting a 1kΩ resistor in series to protect the memristor. And observing current change, and when the memristor is reversibly changed into a low-resistance state along with the scanning voltage from a high-resistance state, indicating that electroforming is completed, and obtaining the threshold switch-type memristor for later use.
12 13.5G FeCl 3·6H2 O and 9.9g FeCl 2·4H2 O reagent are weighed by an electronic balance, and are sequentially put into a beaker, 50mL deionized water or ultrapure water is added to prepare a mixed ion solution of Fe 3+ and Fe 2+, the molar ratio of Fe 3+ to Fe 2+ in the mixed ion solution is 1:1, the concentration is 1mol/L, and in specific implementation, other Fe 3 + to Fe 2+ ratios and ion concentrations can be used to realize the aim of the invention.
13 Copper wires are respectively connected with the two electrodes by indium particles, the mixed solution is dripped on the first electrode, and then the second electrode is covered, so that the solution is diffused and covers the surfaces of the two electrodes.
In this embodiment, the first electrode and the second electrode are made of ITO, and have a rectangular shape with a length of 2mm and a width of 2mm, and in a specific implementation, other conventional electrode materials such as gold, platinum, carbon, etc. may be used.
14 One end of the threshold switch type memristor prepared in the step 11) is connected to the negative electrode of a direct current power supply (Tektronix AFG 31000) through a copper wire, and the other end of the threshold switch type memristor is connected with a second electrode. And connecting the first electrode with the positive electrode of the direct current power supply in series to form a closed loop, thereby obtaining the large-amplitude frequency modulation oscillation device.
The composition diagram of the large-scale frequency modulation oscillation device of the electrochemical reaction of the composite memristor and the iron electrolyte liquid pool prepared by the embodiment is shown in fig. 1, the equivalent circuit diagram is shown in fig. 4, and the structural schematic diagram is shown in fig. 5.
The large-amplitude frequency modulation oscillation device prepared in the embodiment is tested, voltage is applied through a direct current power supply, current in a line is measured through a current amplifier to change in real time, a liquid pool and memristor voltage division waveform curve is recorded through an oscilloscope (such as RIGOL DHO 4204), and electrical responses of the composite memristor and the liquid pool electrochemical reaction device under different direct currents are obtained. As shown in fig. 7, as the output voltage of the dc power supply increases, the pulse oscillation of the device becomes denser and increases in the order of magnitude, and by adjusting the applied voltage, the oscillation frequency can be stably and continuously adjusted in a wide range from a few tenths of hertz to a few kilohertz, and excellent frequency adjustment capability is exhibited.
Example 2 preparation of a Large amplitude frequency modulated Oscillating device with silicon telluride memristor composite I -/I3 - electrolyte
1) The single-sided polished P-type silicon wafer manufactured by the Chinese electric department 46 is selected, the diameter of the silicon wafer is 100+/-0.3 mm, the thickness of the silicon wafer is 400+/-15 mu m, the crystal orientation is <100> +/-0.5 degrees, and the thickness of an oxide layer on the surface of the silicon wafer is 300nm.
The silicon dioxide surface of the silicon chip doped with boron is used as an insulating surface substrate, and the resistivity of the silicon chip is 0.05-0.2 omega cm. AZ5214 photoresist was used and spin coated by a spin coater at 3500 rpm for 1 minute 30 seconds.
2) The silicon wafer spin-coated in 1) was placed on a hot stage and heated at 100 ℃ for 5 minutes to cure the photoresist.
3) And (3) placing the silicon wafer in the step (2) on a sample stage of a photoetching machine for photoetching, and setting the photoetching parameters to be 500ms of illumination time and 0.5 of illumination intensity.
4) And 3) placing the silicon wafer subjected to the photoetching in the step 3) into positive photoresist developer for developing for 1 minute, and removing photoresist of the exposed part to form a target pattern.
5) The silicon wafer in 4) was placed in a metal sputter to sputter tungsten (60 nm thick, sputtered with 80mA current for 300s in a high purity argon environment) as the bottom electrode of the target memristor.
6) Soaking the silicon wafer sputtered in the step 5) into acetone, using an ultrasonic cleaner after 5 minutes, and performing ultrasonic treatment for 10 seconds under the power of 3W to remove residual photoresist and other impurities.
7) Repeating the steps 1) to 4) to prepare for sputtering the resistive layer and the top electrode.
8) And (3) placing the silicon wafer in the step 7) into a metal sputtering instrument, and sequentially sputtering silicon telluride (with the thickness of 20nm, sputtering for 200s with 40mA current in a high-purity argon environment) and tungsten (with the thickness of 60nm, sputtering for 300s with 80mA current in a high-purity argon environment) to respectively serve as a resistive layer and a top electrode of the target memristor.
9) Soaking the silicon wafer sputtered in the step 8) into acetone, using an ultrasonic cleaner after 5 minutes, and performing ultrasonic treatment for 10 seconds under the power of 3W to remove residual photoresist and other impurities, thereby obtaining the silicon telluride memristor. Silicon telluride memristor reference "The ovonic threshold switching characteristics in SixTe1-x based selector devices.Applied Physics A 124.11(2018):734" in this example discloses a method preparation
10 And (3) rapidly taking out the silicon wafer (silicon telluride memristor) in the step 9), putting the silicon wafer into isopropanol, carrying out ultrasonic treatment for 10s under the power of a ultrasonic cleaner 3W, and finally taking out and drying with nitrogen.
11 Electroforming the silicon telluride memristor in 10), applying a scan voltage of 1.5V (above the memristor threshold voltage) using Keithley 2450 ammeter. And (3) observing current change, and when the memristor is reversibly changed from a high-resistance state to a low-resistance state along with the change of the scanning voltage, indicating that electroforming is completed, and obtaining the threshold switch-type memristor for later use.
12 Copper wires were connected to the two electrodes with indium particles, respectively, and then AN iodine-based electrolyte (available from epivitte technologies, inc., model OPV-AN-I, electrolyte composition including iodine, anhydrous lithium iodide, PMI, guanidine isothiocyanate, TBP acetonitrile, concentration of I -: 0.07mol/L, concentration of I 3 -: 0.07mol/L was used. In a specific application, other commercially available iodine based electrolytes can be used) drop 50 microliters onto the first electrode, and then cover the second electrode, allowing the electrolyte to diffuse and cover both electrode surfaces, forming an electrochemical pool.
In this embodiment, the first electrode and the second electrode are made of platinum, and each of the first electrode and the second electrode is rectangular with a length of 3cm and a width of 3cm, so as to increase the contact area of the solid solution and reduce the interface impedance.
13 And (3) connecting one end of the threshold switch type memristor in the 11) to the negative electrode of the direct current power supply through a copper wire, and connecting the other end of the threshold switch type memristor with the second electrode. And connecting the first electrode with the positive electrode of the direct current power supply in series to form a closed loop, thereby obtaining the large-amplitude frequency modulation oscillation device.
The device constitution diagram is shown in fig. 1, the equivalent circuit diagram is shown in fig. 4, and the structural schematic diagram is shown in fig. 5.
The large-scale frequency modulation oscillation device of the silicon telluride memristor composite iodine electrolyte prepared in the embodiment is detected by applying voltage to a direct-current power supply, current change is implemented in a measuring circuit, and experimental results are shown in fig. 9 (the iodine electrolyte, solvent acetonitrile, and the concentrations of I - and I 3 - are all 0.07 mol/L), and as the voltage rises, the frequency of the device ranges from a few tenths of hertz to a few kilohertz, so that excellent frequency tuning capability is shown.
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| CN116723760A (en) * | 2022-02-28 | 2023-09-08 | 清华大学 | Memristor structure capable of simulating synaptic plasticity and action potential and preparation method thereof |
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| US8212621B2 (en) * | 2010-10-29 | 2012-07-03 | Hewlett-Packard Development Company, L.P. | Memristive programmable frequency source and method |
| US8324976B2 (en) * | 2011-04-01 | 2012-12-04 | Hewlett-Packard Development Company, L.P. | Oscillator circuitry having negative differential resistance |
| KR20130125613A (en) * | 2012-05-09 | 2013-11-19 | 삼성전자주식회사 | Frequency tunable device, operating method of the same and radio frequency circuit including frequency tunable device |
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| CN115275002B (en) * | 2022-07-18 | 2024-04-30 | 北京大学 | Liquid-liquid interface type memristor and inhibition type nerve synapse device |
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| US10135015B1 (en) * | 2017-11-02 | 2018-11-20 | Palo Alto Research Center Incorporated | Electrochemical clock and oscillator devices |
| CN116723760A (en) * | 2022-02-28 | 2023-09-08 | 清华大学 | Memristor structure capable of simulating synaptic plasticity and action potential and preparation method thereof |
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