CN113506851A - Low-power-consumption porphyrin zinc memristor and preparation method thereof - Google Patents

Low-power-consumption porphyrin zinc memristor and preparation method thereof Download PDF

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CN113506851A
CN113506851A CN202110775166.0A CN202110775166A CN113506851A CN 113506851 A CN113506851 A CN 113506851A CN 202110775166 A CN202110775166 A CN 202110775166A CN 113506851 A CN113506851 A CN 113506851A
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memristor
change layer
resistance
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porphyrin zinc
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CN113506851B (en
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明建宇
陈雨婷
姚鸿巍
解令海
凌海峰
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Nanjing University of Posts and Telecommunications
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Abstract

The invention discloses a low-power-consumption porphyrin zinc memristor and a preparation method thereof, wherein the porphyrin zinc memristor sequentially comprises a bottom electrode, an organic resistance-change layer, an inorganic resistance-change layer and a top electrode from bottom to top, the organic resistance-change layer is micromolecular porphyrin zinc, the bottom electrode is indium tin oxide, and the top electrode is metal aluminum, and the porphyrin zinc memristor is characterized in that the inorganic resistance-change layer is a non-stoichiometric aluminum oxide film with the thickness of 6-10nm, and the oxygen-aluminum ratio, which is the number ratio of oxygen atoms to aluminum atoms in the non-stoichiometric aluminum oxide film, is 1.2-1.3. The inorganic resistance change layer is non-stoichiometric aluminum oxide prepared by adopting a thermal atomic layer deposition film. According to the invention, by introducing a thermal atomic layer deposition process means, the high-quality controllable non-stoichiometric aluminum oxide film is obtained, the switching power consumption and the stability of the organic memristor are improved, and the organic memristor has a synapse weight updating process with good linearity while having biological synapse response.

Description

Low-power-consumption porphyrin zinc memristor and preparation method thereof
Technical Field
The invention belongs to the field of organic photoelectric materials and neuromorphic hardware, and particularly relates to a low-power-consumption zinc porphyrin memristor and a preparation method thereof.
Background
In the current big data era mainly comprising unstructured data such as real-time voice, images and neural signals, a computing system and a computing unit with stronger computing power are urgently needed, so that research and development of neural morphological hardware with brain-like characteristics (high parallelism, low power consumption and high density) become the basis of future computing research. A two-terminal memristor with a reconfigurable operation-history-dependent resistance switching behavior can simulate the synaptic function of a biological synapse, and is one of the most promising technologies for constructing a simulated neural network for neuromorphic computation. Unlike the two-stage resistance states (high resistance state and low resistance state) of conventional electrically-stored digital resistive-like devices, it is often necessary to simulate the multi-stage switching characteristics of memristors in order to simulate synaptic function, since such switching characteristics are proven to achieve multi-stage weights in the same continuous pulses, high linearity enhancement and suppression processes, and lower operating power consumption.
In recent years, organic memristors mainly made of organic materials provide choices of multifunction, flexibility and weight reduction for neuromorphic hardware, and are becoming the most potential technical scheme of artificial neural network core elements. However, compared with the traditional inorganic memristor, the array development of the organic memristor is hindered by operation crosstalk, write noise and short service life. Therefore, the advantages of organic materials and inorganic materials are combined together to form research targets for many groups of subjects, such as synthesis of organic-inorganic hybrid polymer materials (ACS Nano,2011,5,3469-3474), and combination of the advantages of organic materials and inorganic materials by using the structural characteristics of organic materials (Advanced Science2020,7(8):1902864), but these methods have the disadvantages of complex process, long development period, and the like. Although there have been designs that simply stack organic-inorganic interfaces (Advanced Electronic Materials 2016,2(2)), their higher power consumption levels have not met the need for low power consumption operating neuromorphic hardware.
Patent document CN106601909A discloses an organic memristor, wherein an inorganic resistance-change layer is formed by a low vacuum evaporation in-situ method, and is obtained by directly evaporating metal aluminum, although the oxygen-aluminum ratio of the inorganic resistance-change layer can be reduced to a certain extent by this method, the oxygen-aluminum ratio in the inorganic resistance-change layer obtained by this regulation and control method is uncertain, and the aluminum-oxygen ratio in the film of the inorganic resistance-change layer of devices produced in the same batch is different, which causes instability of device performance. The reason that the aluminum oxygen ratio of the inorganic resistance-change layer obtained by the preparation method is too low is that the deposition duration and speed of the deposited aluminum oxide film in the vacuum thermal evaporation mode can be controlled in the deposition process, namely the thickness of the deposited film, the oxygen content and the aluminum content in the aluminum oxide cannot be actively regulated and controlled in other modes, the in-situ grown aluminum oxide film is essentially evaporated with metal aluminum, and when the aluminum thickness is increased to a certain value, the film is changed into a metal aluminum layer, so that the method is difficult to fix the specific components and the proportion of the inorganic resistance-change layer, and the prepared device has poor switching uniformity and high power consumption.
Disclosure of Invention
Aiming at the technical problems of the existing organic memristors, a collocation strategy aiming at organic materials and inorganic materials still needs to be designed so as to realize the analogue synaptic plasticity analogue application of the low-power consumption analogue memristor with the multi-stage switching characteristic; the invention provides a porphyrin zinc organic memristor with stable performance and low power consumption and a corresponding preparation method, and the organic memristor with the organic-inorganic interface regulation and control simulation type is prepared.
In a first aspect, the invention provides a low-power-consumption porphyrin zinc memristor which comprises a four-layer structure, wherein the four-layer structure sequentially comprises a top electrode, an inorganic resistance change layer, an organic resistance change layer and a bottom electrode from top to bottom; the resistance change layer is used for realizing multi-stage switching characteristics.
Wherein, the top electrode material is metallic aluminum and is used for being connected with the ground.
The organic resistance change layer is made of zinc porphyrin and serves as an ion transport layer;
the inorganic resistance change layer is made of a non-stoichiometric aluminum oxide film with the thickness of 6-10nm, and the quantity ratio of oxygen atoms to aluminum atoms in the non-stoichiometric aluminum oxide film, namely the oxygen-aluminum ratio, is 1.2-1.3 and serves as an ion source layer. The non-stoichiometric aluminum oxide film is used as an inorganic resistance change layer coupled with an organic resistance change layer in the zinc porphyrin memristor, the inorganic resistance change layer is used as an oxygen ion/oxygen vacancy providing layer, the organic resistance change layer is provided under an applied electric field to complete a series of ion transportation and electron transmission functions, the oxygen-aluminum ratio of the non-stoichiometric aluminum oxide film is 1.2-1.3, the oxygen-aluminum ratio is lower than that of the oxygen-aluminum ratio, namely lower than 1.2, and the prepared memristor has lower running current, so that the running power consumption is low; and the oxygen to aluminum ratio is close to 1.5 or equal to 1.5, the device is inoperable.
The bottom electrode is indium tin oxide and is used for inputting an external power supply electric signal, the bottom electrode comprises indium tin oxide and a glass substrate, the indium tin oxide is positioned on the glass substrate, and the square resistance value of the indium tin oxide is about 10 ohms.
In a second aspect, the invention provides a preparation method of the porphyrin zinc memristor with low power consumption, which comprises the following steps: firstly, preparing an organic resistance-change layer on a bottom electrode, then preparing an inorganic resistance-change layer on the organic resistance-change layer, and finally preparing a top electrode on the inorganic resistance-change layer. In particular, the inorganic resistance-change layer is formed by adopting a chemical vapor deposition method during preparation of the inorganic resistance-change layer, non-stoichiometric aluminum oxide with the aluminum oxygen content ratio lower than the stoichiometric ratio is obtained in a more controllable mode, and the film quality of the inorganic resistance-change layer is improved.
The preparation method of the low-power-consumption porphyrin zinc memristor further comprises the following steps:
(1) for the bottom electrode indium tin oxide, acetone, ethanol and deionized water are sequentially adopted to be respectively cleaned in an ultrasonic cleaning machine for 5-15 minutes, after the deionized water cleaning is finished, nitrogen is adopted to remove surface moisture, and finally the bottom electrode indium tin oxide is placed in an electrothermal blowing drying oven to be dried;
(2) carrying out ultraviolet ozone treatment on the indium tin oxide bottom electrode in the step (1) for 5 minutes;
(3) filling the indium tin oxide bottom electrode processed in the step (2) into a vacuum evaporation device, and waiting for the vacuum degree in the cavity to be lower than 5 multiplied by 10-4After pa, evaporation is started, and the rate of evaporation of zinc porphyrin is about
Figure BDA0003154526490000041
Controlling the thickness to be 10-25nm by adopting a quartz crystal oscillator, and determining the thickness of the film by using a step profiler;
(4) placing the film obtained in the step (3) in a vacuum degree of less than 5 × 10-4pa to room temperature;
(5) taking the film obtained in the step (4) out of the vacuum evaporation equipment, and putting the film into a film coating chamber of a thermal atomic deposition film preparation system, wherein the temperature of the film coating chamber in the thermal atomic deposition film preparation system is 150-200 ℃;
(6) introducing a trimethylaluminum precursor source in the thermal atomic deposition film preparation system to the surface of the film placed in the step (5) through a trimethylaluminum precursor atomic layer deposition valve (namely, an ALD valve) to obtain a trimethylaluminum precursor;
(7) cleaning the trimethyl aluminum precursor in the step (6) by using inert gas nitrogen;
(8) introducing a deionized water precursor in a deionized water precursor source bottle in the thermal atomic deposition film preparation system onto the trimethylaluminum precursor through a deionized water precursor ALD valve to obtain a preliminarily formed non-stoichiometric aluminum oxide film with a thickness of about 0.1 nm;
(9) flushing the surface of the non-stoichiometric aluminum oxide film preliminarily formed in the step (8) by using inert gas nitrogen, and blowing away residual deionized water;
(10) repeating the steps (6) - (9) until a non-stoichiometric aluminum oxide film with the thickness of 6-10nm is obtained, wherein the thickness of the film is determined by a step meter;
(11) and (4) taking the film in the step (10) out of a coating chamber of the thermal atomic deposition film preparation system, and putting the film into vacuum evaporation equipment. Waiting for the vacuum degree in the cavity to be lower than 5 x 10-4After pa, evaporation of a metallic aluminum top electrode of about 100nm is started. The rate of evaporating the top electrode is
Figure BDA0003154526490000042
Controlling the thickness to be 90-110nm by adopting a quartz crystal oscillator, and determining the thickness of the film by using a step profiler;
(12) after the evaporation is finished, the top electrode in the step (11) is placed in a vacuum degree lower than 5 multiplied by 10-4pa to room temperature. The relevant electrical tests were then performed.
Preferably, the process pressure of the coating chamber and the vacuum pipeline in the thermal atomic deposition equipment is 5mTorr-10 mTorr.
Preferably, the temperature of the trimethylaluminum precursor bottle is 20-30 ℃, the gas carrying amount is 10sccm-100sccm, the temperature of the deionized water precursor bottle is 20-30 ℃, and the gas carrying amount is 10sccm-100 sccm; the temperature of the trimethyl aluminum precursor ALD valve, the deionized water precursor ALD and the gas carrying pipeline in the thermal atomic deposition equipment is 80-120 ℃. On the one hand, the temperature setting can meet the reaction requirement; on the other hand, the temperature and the carrier gas flow can reduce the probability of blockage of each device and loop caused by condensation reflux of the trimethyl aluminum precursor and the deionized water precursor.
Preferably, the opening time of the trimethyl aluminum precursor ALD valve is 15ms-20ms, and the opening time of the deionized water precursor ALD valve is 15ms-20 ms.
According to the preparation method of the low-power-consumption porphyrin zinc memristor, the aluminum oxide film in the organic memristor of the porphyrin zinc is prepared by a thermal atom deposition film preparation method, and the aluminum oxide film deposited by using the chemical vapor deposition is utilized, so that on one hand, the conformal capability of the chemical vapor deposition film in growth is utilized, the defects of the organic resistance-change layer film are filled, and the interface roughness of the whole resistance-change layer in contact with a top electrode is optimized; on the other hand, the oxygen-aluminum ratio in the non-stoichiometric aluminum oxide film can be adjusted within the range of 1.2-1.3 by mainly utilizing the temperature of a coating chamber in the thermal atomic deposition process.
The invention has the following beneficial effects:
on the first hand, the low-power-consumption porphyrin zinc memristor has the characteristics of multi-level conductivity level, high linearity weight updating and low response current level, is a simulation memristor capable of simulating biological synaptic plasticity, and is expected to be applied to the fields of artificial intelligence, novel information technology, Internet of things, computers, bioelectronics and the like.
In a second aspect, according to the preparation method of the porphyrin zinc memristor with low power consumption, the aluminum oxygen content of the inorganic resistance change layer aluminum oxide can be effectively adjusted through parameter adjustment of thermal atom deposition equipment, so that the organic material and the inorganic material can be better coupled, and an interface regulation strategy combining the characteristics of the organic material and the inorganic material is enriched; the preparation method improves the device stability and power consumption of the organic memristor, can obtain a synapse weight updating process with higher linearity, and provides favorable conditions for application to a neuromorphic network.
Drawings
The invention will be further explained with reference to the drawings.
FIG. 1 shows a structure of a low-power-consumption porphyrin zinc memristor device according to the present invention;
FIG. 2 is an AFM photograph of an aluminum oxide film deposited on a zinc porphyrin film in example 1;
FIG. 3 is a continuous current-voltage curve of a low-power porphyrin zinc memristor with an applied voltage of 10V in example 1;
FIG. 4 is a continuous current-voltage curve of the low-power-consumption porphyrin zinc memristor in example 1 with a voltage magnitude of-9V;
FIG. 5 is a continuous current-voltage curve of a low-power porphyrin zinc memristor with an applied voltage of 6V in example 1;
FIG. 6 is a current-voltage curve of the low-power-consumption porphyrin zinc memristor test at different scanning step frequencies (0.01V \0.03V \0.05V) at 9V in example 1;
FIG. 7 is a circuit connection mode of a low-power-consumption porphyrin zinc memristor in an actual test direct current test and a pulse test in embodiment 1;
FIG. 8 shows specific pulse waveform characteristics of a low-power-consumption porphyrin zinc memristor set in a pulse test in example 1;
FIG. 9 shows the long-term excitation and long-term inhibition characteristics of the low-power-consumption porphyrin zinc memristor under continuous pulse stimulation in example 1;
FIG. 10 is an X-ray energy spectrum analysis of a non-stoichiometric aluminum oxide film prepared at a temperature of 150 ℃ in a coating chamber of the system for depositing a thin film by setting a thermal atomic layer in example 1;
FIG. 11 is an X-ray energy spectrum analysis of a non-stoichiometric aluminum oxide film prepared at a temperature of 200 ℃ in a coating chamber of the system for depositing a thin film by setting a thermal atomic layer in example 2.
Detailed Description
The present invention will be further described with reference to specific examples. It should be noted that these embodiments are not intended to limit the present invention.
Example 1
In the embodiment of the present application, when a non-stoichiometric alumina film is prepared, a thermal atomic deposition film preparation system is used which includes: the device comprises a trimethyl aluminum precursor source bottle, a deionized water precursor source bottle, a coating chamber, a carrier gas pipeline, a trimethyl aluminum precursor ALD valve, a deionized water precursor ALD valve and a vacuum pipeline. And the ALD valve of the trimethyl aluminum precursor is respectively connected with the source bottle of the trimethyl aluminum precursor and the carrier gas pipeline, and the ALD valve of the deionized water precursor is respectively connected with the source bottle of the deionized water and the carrier gas pipeline. The carrier gas pipeline is connected with the film coating chamber. The trimethyl aluminum precursor ALD valve is responsible for conveying a trimethyl aluminum precursor in a trimethyl aluminum precursor source bottle into the coating chamber through a carrier gas pipeline; and the deionized water precursor ALD valve is responsible for conveying the deionized water precursor in the deionized water precursor source bottle to the coating chamber through the carrier gas pipeline. The vacuum pipeline is connected with the coating cavity and used for ensuring the vacuum environment of the coating cavity.
During actual preparation, the room temperature of the laboratory is kept at about 25 ℃, and the indoor humidity is kept below 30%.
The device in the embodiment of the application comprises the following preparation steps:
(1) firstly, substrate cleaning is carried out on indium tin oxide of a bottom electrode and a glass substrate, and acetone, ethanol and deionized water are respectively and sequentially adopted to carry out cleaning for 10 minutes in an ultrasonic cleaning machine with 100 Khz. Then, blowing off the moisture on the surface of the substrate by adopting nitrogen, and placing the substrate in an electrothermal blowing dry box preheated to 120 ℃ in advance for high-temperature drying for 20 minutes;
(2) placing the dried substrate in an ultraviolet ozone cleaning machine for ultraviolet ozone treatment for 5 minutes;
(3) placing the processed substrate in vacuum evaporation equipment under vacuum pressure lower than 5 × 10-4After pa, the deposition of the organic resistance change layer is started. The organic resistance change layer is made of zinc porphyrin and has the evaporation rate of
Figure BDA0003154526490000081
The thickness of the zinc porphyrin layer was about 25nm, and the film thickness was measured by a step meter.
(4) And on the premise of keeping the original vacuum pressure, cooling the porphyrin zinc layer film waiting for the completion of the evaporation to room temperature.
(5) And after the evaporation of the organic resistance change layer is finished, taking out the substrate. The method comprises the steps of putting the film into a coating cavity of thermal atomic layer deposition equipment, and simultaneously setting process parameters in a thermal atomic layer deposition film preparation system, wherein the temperature of the coating cavity is 150 ℃, the temperature of a trimethyl aluminum precursor source bottle is 25 ℃ and the flow rate of a carrier gas is 10sccm, the temperature of a deionized water precursor source bottle is 25 ℃ and the flow rate of the carrier gas is 10sccm, and the temperatures of a trimethyl aluminum precursor ALD valve, the deionized water precursor ALD valve and a carrier gas pipeline in the thermal atomic layer deposition film preparation system are 120 ℃.
(6) And (3) allowing a trimethyl aluminum precursor source in the thermal atomic deposition equipment to enter air through a trimethyl aluminum precursor ALD valve for 20ms and depositing the trimethyl aluminum precursor on the surface of the substrate to obtain the trimethyl aluminum precursor. And (3) purging the trimethyl aluminum precursor for 20s by using inert gas nitrogen. And introducing a deionized water precursor in a deionized water precursor source bottle in the thermal atomic deposition equipment onto the trimethylaluminum precursor through 15ms of inlet air of a deionized water precursor ALD valve to obtain a non-stoichiometric aluminum oxide film, and cleaning the deionized water precursor for 20s by using inert gas nitrogen. Repeating the above steps 80 times to obtain a non-stoichiometric film with a thickness of about 10nm, the thickness of which is determined by a step meter.
(7) And putting the device with the indium tin oxide/zinc porphyrin/non-stoichiometric aluminum oxide structure sequentially obtained on the substrate from bottom to top through vacuum evaporation and thermal atomic layer deposition into vacuum evaporation equipment again. Waiting for the vacuum pressure to be lower than 5X 10- 4After pa, vapor deposition of the top electrode is started. The top electrode material is metallic aluminum, and the evaporation rate is
Figure BDA0003154526490000082
The thickness of the metallic aluminum layer is about 100nm, and the film thickness is measured by a step meter.
(8) And on the premise of keeping the original vacuum pressure, taking out the porphyrin zinc layer film after the evaporation is finished and cooling the film to room temperature to obtain the single low-power-consumption porphyrin zinc memristor.
As shown in fig. 1, the low-power-consumption porphyrin zinc memristor prepared in embodiment 1 is an organic-inorganic regulation and control analog memristor 100 based on porphyrin zinc formed on a glass substrate, and fig. 1a is a full view of a device prepared by using a cross-stacked structure. FIG. 1b is a schematic diagram of a cross point, i.e., a single device in FIG. 1a, which has a structure comprising, from bottom to top, an ITO bottom electrode 104, an organic resistance-change layer 103 comprising zinc porphyrin (ZnTPP) with a thickness of 25nm, and non-stoichiometric aluminum oxide (AlO) with a thickness of 10nmx) A top electrode 101 composed of an inorganic resistance change layer 102 and a metal aluminum Al with a thickness of 100 nm; AlO calculated by X-ray energy spectrum testxThe value of x is 1.208.
FIG. 2 is an Atomic Force Microscope (AFM) topography of a nonstoichiometric alumina thin film on a zinc porphyrin layer prepared by a thermal atomic layer deposition thin film preparation system prepared in example 1. It can be seen that due to the conformal growth characteristic of chemical vapor deposition in thermal atomic layer deposition, the nonstoichiometric thin film on the small molecule porphyrin zinc thin film still has the morphological characteristic of the small molecule thin film.
In order to simulate the synaptic function, the memristor usually adopts an external input signal as an excitation, two port electrodes are respectively used as front and rear synapses, and the current level regulated in real time is equivalent to a synaptic weight and plays a role in signal transmission. Therefore, if the current level is regarded as the synaptic weight level regulated in real time in the memristor, the above result shows the similar characteristic with biological synapse. The voltages with different polarities can be adopted to simulate the excitation and inhibition processes of biological synapses.
Fig. 3 is a current-voltage characteristic diagram of the organic-inorganic regulation and control analog memristor based on zinc porphyrin under continuous 50 times of 10V forward voltage scanning, and it can be seen from the diagram that the device does not have abrupt increase or decrease of current level, shows a multi-level switching characteristic that the current level gradually increases gradually as the scanning times increase, and conforms to the characteristics of the analog memristor. Meanwhile, when the device is continuously scanned for 50 times, the response current level is about 150 microamperes, and the current-voltage curve is kept stable, which shows that the device has stable low-power-consumption switching characteristics.
Fig. 4 is a current-voltage characteristic diagram of the organic-inorganic regulation and control analog memristor based on zinc porphyrin under continuous negative voltage scanning of 50 times to 9V, and it can be seen from the diagram that the device does not have abrupt current level increase or decrease, shows multi-stage switching characteristics as the scanning times increase, and conforms to the characteristics of the analog memristor. While the current level gradually decreased under 50 consecutive sweeps.
Fig. 5 is a current-voltage characteristic diagram of the organic-inorganic regulation and control analog memristor based on zinc porphyrin under continuous 10 times of 6V forward voltage scanning, and it can be seen from the diagram that the device does not have abrupt increase or decrease of current level, shows multi-stage switching characteristics as the scanning times increase, and simultaneously, the response current level is about 0.8 microampere, which greatly reduces the energy consumption required by switching. While it shows a tendency of gradually decreasing the current level in the forward direction as the number of scans increases. The device can not only have the inhibition characteristic of biological synapses under negative voltage scanning, but also realize the characteristic in a positive direction.
Fig. 6 shows that the organic-inorganic regulation and control analog memristor based on zinc porphyrin performs forward continuous scanning of 9V at scanning step frequencies of 0.01 volt, 0.03 volt and 0.05 volt. It can be seen that at 0.05 volt step frequency, the current-voltage curve area is small, while the response current level at 9V is only around 20 microamperes; as the step frequency is gradually reduced, at a step frequency of 0.01 volts, the current-voltage curve area is gradually increased and the response current level is up to about 400 microamps. The phenomenon occurs because the organic memristor is based on the working mechanism of the ion-electron transport process, and the inorganic resistive layer can excite more oxygen ions or oxygen vacancies under the smaller stimulation frequency, so that the organic resistive layer can transport more ions and electrons, and the response current and the curve area are increased. The device has the characteristics similar to those of the memristor reported at present.
Fig. 7 shows a circuit connection mode of the organic-inorganic regulation and control analog memristor based on zinc porphyrin in actual test direct current tests and pulse tests, and measurement is performed by adopting a gischii 2636B digital source table and a de 2912A digital source table. Wherein, the digital source meter of Jishili 2636B is mainly responsible for the electrical characteristic test of the direct current part, and is responsible for the pulse electrical test of the digital source meter of De 2912A.
FIG. 8 is a pulse waveform applied in the pulse test, in which the central hatched portion in the FIG. 8 corresponds to the pulse waveform in the enlarged view at the lower left of the figure; the amplitude of the forward pulse is 10V, and the pulse width is 50ms as seen from the detailed pulse diagram in the figure. The time interval from when one pulse ends to when the next pulse starts is 40 ms. The positive going pulse takes 3V as the read voltage to read the conductance level after 10V voltage stimulation and the negative going pulse takes 5V as the read voltage to read the conductance level after-10V voltage stimulation. The total number of pulses applied was 200, with 100 positive voltages and 100 negative voltages.
FIG. 9 is a graph of the change in conductance level read at the read voltage under the pulsed stimulus of FIG. 8. It can be seen from the figure that under the stimulation of forward continuous pulse, the level of conductance is gradually increased, corresponding to the long-time excitation process of biological synapses under the continuous stimulation, and the weight update level with good linearity is possessed. Under the stimulation of negative continuous pulses, the level of the conductance is gradually reduced, and the weight update level with good linearity is the same as the weight update level corresponding to the long-time inhibition process of the biological synapse under the continuous stimulation. The linearity of the weight update reflects the rate of change of conductance with the number of voltage pulses. The low linearity results in complex weight modulation and redundant power consumption and time penalty during the neural morphology network training process.
According to the embodiment, a thermal atomic layer deposition process is applied to the organic memristor based on zinc porphyrin, the non-stoichiometric aluminum oxide film is obtained through the thermal atomic layer deposition film preparation system and serves as an inorganic resistance change layer, the non-stoichiometric aluminum oxide film preparation process is more controllable, the aluminum oxide content can be better controlled, the organic material characteristics and the inorganic material characteristics are better combined, and the overall regulation and control of the memristor are completed. In addition, due to the capability of conformal growth of the non-stoichiometric aluminum oxide film obtained by the thermal atomic layer deposition film preparation system, the organic resistance-change layer can be better attached, the contact area between the resistance-change layer and the top electrode is increased, the contact interface between the whole resistance-change layer and the top electrode has smaller roughness, the switching current and voltage are reduced through electrical test, and the stable multi-stage switching characteristic is possessed. More importantly, the device has a weight updating process with good linearity in the process of simulating the long-time excitation and the long-time inhibition of the biological synapse characteristics, and the weight updating process provides a basis for further application to the field of neuromorphic hardware.
Example 2
In this embodiment 2, the process of preparing an alumina film using a thermal atomic layer deposition film preparation system is the same as that in embodiment 1, except that the temperature of a coating chamber in the thermal atomic layer deposition film preparation system is 200 ℃.
As shown in fig. 11, the X-ray energy spectrum analysis of the alumina prepared after the temperature of the coating chamber of the system for preparing the thermal atomic layer deposited film is set to 200 ℃ in application example 2 shows that compared with the alumina film prepared at 150 ℃ in the coating chamber in fig. 10, the peak area of O1s is increased by about 1000, and the peak area of Al2p changes by only about 160 at the two temperatures, so it is reasonable to believe that when the temperature of the coating chamber is increased, the oxygen content is correspondingly increased, thereby achieving the purpose of controlling the inorganic resistance-change layer. In the embodiment, different coating chamber temperatures are adopted in the thermal atomic deposition film preparation system, the alumina films with different oxygen contents are prepared, and the controllability of the oxygen content of the inorganic resistance change layer is proved.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the claims of the present invention.

Claims (10)

1. The porphyrin zinc memristor sequentially comprises a bottom electrode, an organic resistance-change layer, an inorganic resistance-change layer and a top electrode from bottom to top, wherein the organic resistance-change layer is micromolecular porphyrin zinc, the bottom electrode is indium tin oxide, and the top electrode is metal aluminum, and is characterized in that the inorganic resistance-change layer is a non-stoichiometric aluminum oxide film with the thickness of 6-10nm, and the oxygen-aluminum ratio, which is the number ratio of oxygen atoms to aluminum atoms in the non-stoichiometric aluminum oxide film, is 1.2-1.3.
2. The preparation method of a low-power-consumption porphyrin zinc memristor according to claim 1, which comprises the steps of firstly preparing an organic resistance-change layer on a bottom electrode, then preparing an inorganic resistance-change layer on the organic resistance-change layer, and finally preparing a top electrode on the inorganic resistance-change layer, wherein the preparation method of the organic resistance-change layer specifically comprises the following steps:
step S1: placing a substrate which is evaporated with an organic resistance-change layer in a coating cavity of a thermal atomic deposition film preparation system, wherein the temperature of the coating cavity is set to be 80-200 ℃;
step S2: introducing a trimethylaluminum precursor source in the thermal atomic deposition film preparation system to the surface of the substrate on which the organic resistance-change layer is evaporated in the step S1 through a trimethylaluminum precursor atomic layer deposition valve to obtain a deposition trimethylaluminum precursor;
step S3: cleaning the surface of the trimethyl aluminum precursor deposited in the step S2 by using inert gas nitrogen, wherein the cleaning time is 20-60S;
step S4: introducing a deionized water precursor onto the deposition trimethylaluminum precursor cleaned in the step S3 through a deionized water precursor atomic layer deposition valve to obtain an initially formed non-stoichiometric aluminum oxide film with a thickness of about 0.1 nm;
step S5: cleaning the preliminarily formed non-stoichiometric aluminum oxide film with the thickness of 0.1nm in the step S4 by using inert gas nitrogen for 20-60S;
step S6: and repeating the steps S2-S5 until a non-stoichiometric aluminum oxide film with the thickness of 6-10nm, namely the inorganic resistance change layer, is obtained.
3. The preparation method of the low-power-consumption porphyrin zinc memristor according to claim 2, wherein the organic resistance change layer is formed by a vacuum evaporation film forming method, and the vacuum degree is controlled to be 5 x 10-4pa at a vapor deposition rate of
Figure FDA0003154526480000021
The thickness is controlled to be 15-25nm by adopting a quartz crystal oscillator.
4. The preparation method of the low-power-consumption porphyrin zinc memristor according to claim 2, wherein the preparation method of the top electrode is that the top electrode is prepared by thermal vacuum evaporation, and the vacuum degree is controlled to be 5 x 10-4pa at a vapor deposition rate of
Figure FDA0003154526480000022
The thickness is controlled to be 90-110nm by adopting a quartz crystal oscillator.
5. The preparation method of the low-power-consumption porphyrin zinc memristor according to claim 2, wherein in step S6, the thickness of the 6-10nm non-stoichiometric aluminum oxide film is determined by a step profiler.
6. The method for preparing a porphyrin zinc memristor with low power consumption according to claim 2, wherein the temperature of the coating chamber is set to 150 ℃.
7. The preparation method of the porphyrin zinc memristor with low power consumption according to claim 2, wherein the process pressure of a coating chamber and a vacuum pipeline in the thermal atomic deposition equipment is 5mTorr-10 mTorr.
8. The preparation method of the low-power-consumption porphyrin zinc memristor according to claim 2, wherein the preservation temperature of the trimethylaluminum precursor before introduction is 20-30 ℃, the gas carrying amount is 10sccm-100sccm, and the preservation temperature of the deionized water precursor before introduction is 20-30 ℃, the gas carrying amount is 10sccm-100 sccm.
9. The method for preparing a porphyrin zinc memristor with low power consumption according to claim 2, wherein the temperature of the trimethylaluminum precursor atomic layer deposition valve, the deionized water precursor atomic layer deposition valve and the gas carrying pipeline in the thermal atomic deposition device is 80-120 ℃.
10. The preparation method of the low-power-consumption porphyrin zinc memristor according to claim 2, wherein the opening duration of the trimethylaluminum precursor atomic layer deposition valve is 15ms-20ms, and the opening duration of the deionized water precursor atomic layer deposition valve is 15ms-20 ms.
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