A composite multilayer memristor and its preparation method

Abstract

The present invention provides a composite multilayer memristor and a method for fabricating the same. The composite multilayer memristor of the present invention features an active electrode modulation layer with arrayed through-holes. This allows atoms in the active electrode layer to undergo array optimization of the active electrode before passing through the functional layer. This enables arrayed regulation of the formation sites of conductive filaments, significantly improving the uniformity and stability of the memristor. Unlike specialized active electrode array fabrication processes, this method directly and continuously fabricates the functional layer and active electrode modulation layer by regulating the fabrication process of the functional layer. This method eliminates the need for complex fabrication processes, is cost-effective, and can be fabricated on a large scale.

Description

Technical Field

[0001] The present invention belongs to the technical field of microelectronic devices, and in particular relates to a composite multilayer memristor and a preparation method thereof. Background Art

[0002] With the rapid development of modern information technology, the performance of electronic devices plays a critical and fundamental role in driving progress in numerous fields. Since its discovery, memristors, as an emerging electronic component, have demonstrated enormous potential for application in a wide range of fields, including information storage, logic circuit design, and neuromorphic computing. For example, traditional storage technologies such as magnetic disks and optical disks have gradually encountered bottlenecks in data storage density, read / write speeds, and power consumption. Memristors, with their unique resistance tunability, enable high-density storage at the nanoscale while offering advantages such as low power consumption. They are poised to revolutionize existing technologies and become a core component of next-generation storage technologies. However, in practical applications, memristors still face numerous performance limitations, such as resistance conversion stability, switching speed uniformity, and durability.

[0003] With the increasing demand for high-performance, low-power, and highly integrated electronic systems, overcoming and optimizing the existing performance limitations of memristors has become a research hotspot in the field of electronic technology. For example, Reference 1 (AThreshold Switching Selector Based on Highly Ordered Ag Nanodots for X-Point Memory Applications. Adv. Sci. 2019, 6, 1900024) and Reference 2 (High-Uniformity Threshold Switching HfO2-Based Selectors with Patterned Ag Nanodots. Adv. Sci. 2020, 7, 2002251) achieved the fabrication of highly uniform and stable memristors by arraying active electrodes. However, the demanding fabrication conditions and high cost of these memristors have limited their large-scale application.

[0004] For another example, the patent application with publication number US20220123208A1 discloses a memristor, comprising an active electrode, an inert electrode, and a resistive switching layer, wherein the resistive switching layer comprises a porous insulating layer and a conductive filament, wherein the porous insulating layer is disposed between the active electrode and the inert electrode, and the porous insulating layer has a through-channel hole; the conductive filament is formed in the through-channel hole. By utilizing the porous insulating layer structure, this patent also preliminarily realizes the memristive characteristic. However, since the porous insulating layer is a through-hole structure, its dark current is large, so the switch is relatively small and the stability is poor. At the same time, the preparation of the through-hole structure requires an etching process, which is complicated and time-consuming. Summary of the Invention

[0005] In order to solve the above technical problems existing in the prior art, the present invention provides a composite multilayer memristor and a preparation method thereof, which improves the uniformity and stability of the memristor while reducing the operating voltage, and the preparation process is simple.

[0006] The present invention provides a composite multilayer memristor, comprising a base layer and an inert electrode layer, a functional layer, an active electrode modulation layer, and an active electrode layer sequentially formed on the base layer, wherein the functional layer and the active electrode modulation layer are both made of oxide materials, the active electrode modulation layer has arrayed through holes, and the active electrode layer has connection points extending along the through holes to the functional layer, and the connection points are used as arrayed active electrodes.

[0007] Preferably, the oxide materials used in the functional layer and the active electrode modulation layer are each one or more of aluminum oxide, hafnium oxide, silicon dioxide, and zinc oxide. Aluminum oxide, hafnium oxide, silicon dioxide, and zinc oxide have high dielectric constants and large resistance values, enabling memristive properties with a high on / off ratio. Further preferably, the oxide materials used in both the functional layer and the active electrode modulation layer are aluminum oxide.

[0008] Preferably, the thickness of the functional layer is 8~12 nm. Within this range, the memristor has a large switching ratio while the operating voltage is relatively small, resulting in a low operating current and thus high operating stability. The thickness of the functional layer is further preferably 10 nm; the thickness of the active electrode modulation layer is 3~8 nm. Within this range, the active electrode modulation layer can form stable arrayed through holes, thereby realizing arrayed regulation of the conductive filament formation sites. The thickness of the active electrode modulation layer is further preferably 5 nm.

[0009] Preferably, the substrate layer is a PET substrate, a silicon substrate or a quartz substrate with a thickness of 100-300 μm; the inert electrode layer is Au or Pt with a thickness of 20-40 nm; and the active electrode layer is Cu or Ag with a thickness of 20-40 nm.

[0010] Preferably, an adhesion layer is provided between the base layer and the inert electrode layer; and an electrode protection layer is provided on the surface of the active electrode layer.

[0011] Preferably, the adhesion layer is Cr, Ni or Ti, with a thickness of 3-5 nm; the electrode protection layer is Au, with a thickness of 20-40 nm.

[0012] The present invention also provides a method for preparing the composite multilayer memristor, comprising the following steps:

[0013] (2) Depositing an adhesion layer on the surface of the substrate;

[0014] (3) depositing an inert electrode layer on the surface of the adhesion layer;

[0015] (4) growing a functional layer on the surface of the inert electrode layer;

[0016] (5) growing an active electrode modulation layer on the surface of the functional layer;

[0017] (6) depositing an active electrode layer on the surface of the active electrode modulation layer;

[0018] (7) Depositing an electrode protection layer on the surface of the active electrode layer;

[0019] Wherein, in step (4), the precursor and the oxygen source reaction gas for forming the functional layer are circulated in sequence to realize the layer-by-layer growth of the oxide material of the functional layer; in step (5), the precursor and the reaction gas for forming the active electrode modulation layer are circulated in sequence to realize the layer-by-layer growth of the oxide material of the active electrode modulation layer; the molar ratio of the precursor and the oxygen source reaction gas for forming the active electrode modulation layer is not higher than the molar ratio of the precursor and the oxygen source reaction gas for forming the functional layer, and the temperature when growing the active electrode modulation layer is lower than the temperature when growing the functional layer, so that the active electrode modulation layer formed by growth has arrayed through holes, and the active electrode layer formed by deposition has connection points extending along the through holes to the functional layer.

[0020] Preferably, the molar ratio of the precursor to the oxygen source reaction gas used to form the functional layer is 1:1-4; the molar ratio of the precursor to the oxygen source reaction gas used to form the active electrode modulation layer is 1:1-6; the growth temperature when growing the functional layer in step (4) is 200-300°C; and the growth temperature when growing the active electrode modulation layer in step (5) is 50-100°C. The relatively high growth temperature and relatively precise raw material ratio give the functional layer a high insulating property, thereby providing a large switching ratio and a low dark current; the relatively low growth temperature and the molar ratio of the precursor to the oxygen source reaction gas enable the active electrode modulation layer to form a non-continuous array of through holes, preferably with diameters of the formed through holes and connection points within the range of 50-500 nm.

[0021] Preferably, in step (4), for different functional layer materials, the process selection is as follows:

[0022] ZnO: The raw materials are diethylzinc (precursor) and water vapor (oxygen source), the raw material molar ratio is 1:1, and the growth temperature is 200-250 °C;

[0023] Al2O3: The raw materials are trimethylaluminum (precursor) and water vapor (oxygen source), the raw material molar ratio is 2:3, and the growth temperature is 250~300℃;

[0024] HfO2: The raw materials are tetrakis(dimethylamino)hafnium (precursor, CAS: 19782-68-4) and ozone (oxygen source), with a molar ratio of 1:4, and the growth temperature is 200-300°C;

[0025] SiO2: The raw materials are dichlorosilane (precursor) and water vapor (oxygen source), the molar ratio of the raw materials is 1:2, and the growth temperature is 200~250 ℃.

[0026] Preferably, in step (5), for different active electrode modulation layer materials, the process selection is as follows:

[0027] ZnO: The raw materials are diethylzinc (precursor) and water vapor (oxygen source), the raw material molar ratio is 1:1-2, and the growth temperature is 50-100 °C;

[0028] Al2O3: The raw materials are trimethylaluminum (precursor) and water vapor (oxygen source), the raw material molar ratio is 1:1.5~3, and the growth temperature is 50~75℃;

[0029] HfO2: The raw materials are tetrakis(dimethylamino)hafnium (precursor) and ozone (oxygen source), the raw material molar ratio is 1:4-6, and the growth temperature is 50-75 ℃;

[0030] SiO2: The raw materials are dichlorosilane (precursor) and water vapor (oxygen source), the molar ratio of the raw materials is 1:2~3, and the growth temperature is 50~100 ℃.

[0031] Further preferably, in step (4), the raw materials are trimethylaluminum and water vapor, the raw materials have a molar ratio of 2:3, and the growth temperature is 250°C; in step (5), the raw materials are trimethylaluminum and water vapor, the raw materials have a molar ratio of 1:3, and the growth temperature is 50°C. The surface of the functional layer obtained in this way is more uniform and dense, the active electrode modulation layer obtained has more arrayed and more evenly distributed through-holes, and the obtained memristor has better uniformity and stability.

[0032] Preferably, in step (2), the adhesion layer is deposited by high vacuum magnetron sputtering technology; in step (3), the inert electrode layer is deposited by high vacuum magnetron sputtering technology; in step (4), the functional layer is grown by atomic layer growth technology; in step (5), the active electrode modulation layer is grown by atomic layer growth technology; in step (6), the active electrode layer is deposited by thermal evaporation technology; and in step (7), the electrode protection layer is deposited by thermal evaporation technology.

[0033] The working principle of the composite multilayer memristor of the present invention is as follows:

[0034] a. The main function of the base layer is to provide support and provide a base for the entire device;

[0035] b. The adhesion layer acts as a transition layer to improve the adhesion between the inert electrode and the substrate, thereby achieving stable adhesion of the inert electrode to the substrate;

[0036] c. The inert electrode layer acts as a conductive end, possessing excellent electrical conductivity and enabling the memristor to be connected to an electric field. The inert electrode layer material is chemically stable, does not ionize under an electric field, and does not react with the active electrode material, acting as a cutoff material to prevent the active electrode material from migrating along the electric field lines.

[0037] d. The active electrode layer material is chemically active and can be ionized under the action of an electric field. The ionized ions migrate toward the inert electrode layer under the action of the electric field. The migrating active electrode material can form a conductive path, i.e., a conductive filament, in the insulating functional layer.

[0038] e. The functional layer, as an insulating layer, is the core of the resistive switching properties. Before active electrode material passes through the functional layer to form conductive filaments, the functional layer provides a high resistance. When conductive filaments form, the functional layer's resistance decreases. After the electric field driving the conductive filaments is removed, the functional layer uses its own lattice repulsion to cut the conductive filaments, restoring the device's high resistance, thereby achieving high-low resistance conversion.

[0039] f. The active electrode modulation layer has an array of through holes, forming a connection point where the active electrode extends to the functional layer, thereby achieving array modulation of the active electrode;

[0040] g. The active electrode protective layer is used to isolate the air and prevent the active electrode from being oxidized.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] The composite multilayer memristor of the present invention is provided with an active electrode modulation layer having arrayed through-holes, so that the atoms of the active electrode layer are pre-optimized by the active electrode array through the active electrode modulation layer before passing through the functional layer, thereby achieving arrayed regulation of the conductive filament formation sites, thereby significantly improving the uniformity and stability of the memristor. Unlike a dedicated active electrode array preparation process, the present invention can directly achieve continuous preparation of the functional layer and the active electrode modulation layer by regulating the preparation process of the functional layer, without the need for a complex preparation process, with low cost and large-scale preparation. At the same time, compared with the direct introduction of through-holes, the present invention still retains a highly dense functional layer, has a lower dark current, and consumes less power, and therefore has greater application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 Schematic diagram of the structure of the composite multilayer memristor of the present invention.

[0044] Figure 2 This is a scanning electron microscope image of the functional layer of the composite multilayer memristor in Example 1 of the present invention.

[0045] Figure 3 This is a scanning electron microscope image of the active electrode modulation layer of the composite multilayer memristor in Example 1 of the present invention.

[0046] Figure 4 1 is a diagram illustrating the statistical distribution of the pore sizes of the active electrode modulation layer of the composite multilayer memristor in Example 1 of the present invention.

[0047] Figure 5 This is a current-voltage response diagram of the composite multilayer memristor in Example 1 of the present invention after 100 cycles. The ordinate 1E-6 represents 1×10 -6 , the same below.

[0048] Figure 6 3 is a graph showing the relationship between the threshold turn-on voltage and the number of cycles of the composite multilayer memristor under 100 cycles in Example 1 of the present invention.

[0049] Figure 7 3 is a statistical distribution characteristic diagram of the threshold conversion voltage of the composite multilayer memristor under 100 cycles in Example 1 of the present invention.

[0050] Figure 8 This is a current-voltage response diagram of the memristor in comparative example 1 after 100 cycles.

[0051] Figure 9 This is a current-voltage response diagram of the composite multilayer memristor in Example 2 of the present invention after 100 cycles.

[0052] Figure 10 This is a current-voltage response diagram of the memristor in comparative example 2 after 100 cycles.

[0053] Figure 11 This is a current-voltage response diagram of the composite multilayer memristor in Example 3 of the present invention after 100 cycles.

[0054] Figure 12 This is a current-voltage response diagram of the memristor in comparative example 3 after 100 cycles.

[0055] Reference numerals:

[0056] S110: base layer, S1101: adhesion layer, S1102: inert electrode layer, S1103: functional layer, S1104: active electrode modulation layer, S1105: active electrode layer, S1106: electrode protection layer. DETAILED DESCRIPTION

[0057] Example 1

[0058] A composite multilayer memristor and a method for preparing the same are as follows:

[0059] 1) Ultrasonic cleaning of a silicon substrate (100 μm) was performed using acetone, isopropanol, ethanol, and distilled water for 5 minutes in sequence to obtain a clean silicon substrate surface.

[0060] 2) A 3 nm thick Cr adhesion layer was deposited on a clean silicon substrate using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1 and a vacuum degree of 8 Torr. The target material was 99.99% pure Cr.

[0061] 3) A 40 nm thick Pt inert electrode layer was deposited on the surface of the Cr adhesion layer by magnetron sputtering. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1 and a vacuum degree of 8 Torr. The target material was Pt with a purity of 99.99%.

[0062] 4) A 10 nm thick Al2O3 functional layer is grown on the surface of the inert electrode layer using an atomic layer deposition system. The specific process is as follows:

[0063] The raw materials are trimethylaluminum and water in a molar ratio of 2:3, and the growth temperature is 250°C. First, trimethylaluminum gas is introduced into a reaction chamber at a substrate temperature of 250°C, forming a trimethylaluminum molecular film on the surface of an inert electrode. Water vapor is then introduced into the chamber to react with the adsorbed trimethylaluminum molecular film to produce a continuous and dense aluminum oxide material. The preparation process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0064] like Figure 2 As shown, the surface of the prepared functional layer is uniform and dense. The functional layer serves as the core of resistance conversion and provides a larger switching ratio for the memristor.

[0065] 5) Grow an Al2O3 active electrode modulation layer with a thickness of 5 nm on the surface of the functional layer using atomic layer growth technology. The specific process is as follows:

[0066] The raw materials are trimethylaluminum and water in a molar ratio of 1:3, and the growth temperature is 50°C. First, trimethylaluminum gas is introduced into a reaction chamber at a substrate temperature of 50°C, forming a trimethylaluminum molecular film on the surface of the functional layer. Water vapor is then introduced into the chamber to react with the adsorbed trimethylaluminum molecular film to produce a porous alumina material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0067] like Figure 3 As shown, arrayed through holes are formed in the prepared active electrode modulation layer, and the pore size statistics are as follows Figure 4 As shown, array modulation of active electrodes can be achieved, which promotes the formation of uniform conductive filaments and is a key step in the preparation of composite multilayer memristors.

[0068] 6) A 20 nm thick Ag active electrode layer was deposited on the surface of the active electrode modulation layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1.5×10 -4 Pa, the steaming material is Ag with a purity of 99.99%.

[0069] 7) A 40 nm thick Au electrode protective layer was deposited on the surface of the active electrode layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1.5×10 -4 Pa, the steaming material is 99.99% pure Au.

[0070] Thus, the composite multilayer memristor is prepared. The structure of the prepared composite multilayer memristor is as follows: Figure 1 shown.

[0071] Example 2

[0072] 1) Ultrasonic cleaning of a silicon substrate (300 μm) was performed using acetone, isopropanol, ethanol, and distilled water for 5 minutes in sequence to obtain a clean silicon substrate surface.

[0073] 2) A 5 nm thick Ti adhesion layer was deposited on a clean silicon substrate using magnetron sputtering. The magnetron cavity contained a mixture of nitrogen and argon with a gas volume ratio of 1:1 and a vacuum degree of 8 Torr. The target material was 99.99% pure Ti.

[0074] 3) A 30 nm thick Pt inert electrode layer was deposited on the surface of the Ti adhesion layer using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was Pt with a purity of 99.99%.

[0075] 4) Grow an 8 nm thick Al2O3 functional layer on the surface of the inert electrode layer using atomic layer growth technology. The specific process is as follows:

[0076] The raw materials are trimethylaluminum and water in a molar ratio of 2:3, and the growth temperature is 300°C. First, trimethylaluminum gas is introduced into a reaction chamber at a substrate temperature of 300°C, forming a trimethylaluminum molecular film on the surface of an inert electrode. Water vapor is then introduced into the chamber to react with the adsorbed trimethylaluminum molecular film to produce a continuous and dense aluminum oxide material. The preparation process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0077] 5) Grow an Al2O3 active electrode modulation layer with a thickness of 3 nm on the surface of the functional layer using atomic layer growth technology. The specific process is as follows:

[0078] The raw materials are trimethylaluminum and water in a molar ratio of 1:1.5, and the growth temperature is 75°C. First, trimethylaluminum gas is introduced into a reaction chamber at a substrate temperature of 75°C, forming a trimethylaluminum molecular film on the surface of the functional layer. Water vapor is then introduced into the chamber to react with the adsorbed trimethylaluminum molecular film to produce a porous alumina material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0079] 6) A Cu active electrode layer with a thickness of 30 nm was deposited on the surface of the active electrode modulation layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1.5×10 -4 Pa, the steaming material is Cu with a purity of 99.99%.

[0080] 7) A 20 nm thick Au electrode protective layer was deposited on the surface of the active electrode layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1.5×10 -4 Pa, the steaming material is 99.99% pure Au.

[0081] Example 3

[0082] 1) Ultrasonic cleaning of PET substrate (150 μm) was performed with acetone, isopropyl alcohol, ethanol, and distilled water for 5 minutes in sequence to obtain a clean PET substrate surface.

[0083] 2) A 5 nm thick Ni adhesion layer was deposited on the surface of a clean PET substrate using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was 99.99% pure Ni.

[0084] 3) A 40 nm thick Au inert electrode layer was deposited on the surface of the Ni adhesion layer using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was 99.99% pure Au.

[0085] 4) Grow an 8 nm thick HfO2 functional layer on the surface of the inert electrode layer using atomic layer growth technology. The specific process is as follows:

[0086] The raw materials are tetrakis(dimethylamino)hafnium and ozone, with a molar ratio of 1:4, and the growth temperature is 300°C. First, tetrakis(dimethylamino)hafnium gas is introduced into a reaction chamber at a substrate temperature of 300°C, forming a layer of tetrakis(dimethylamino)hafnium molecules on the surface of an inert electrode. Ozone gas is then introduced into the chamber to react with the adsorbed tetrakis(dimethylamino)hafnium molecules to produce a continuous and dense hafnium oxide material. The preparation process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0087] 5) Grow an 8 nm thick HfO2 active electrode modulation layer on the surface of the functional layer using atomic layer growth technology. The specific process is as follows:

[0088] The raw materials are tetrakis(dimethylamino)hafnium and ozone, with a molar ratio of 1:4, and the growth temperature is 50°C. First, tetrakis(dimethylamino)hafnium gas is introduced into a reaction chamber at a substrate temperature of 50°C to form a tetrakis(dimethylamino)hafnium molecular film on the surface of the functional layer. Ozone gas is then introduced into the chamber to react with the adsorbed tetrakis(dimethylamino)hafnium molecular film to produce a porous hafnium oxide material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0089] 6) A 40 nm thick Cu active electrode layer was deposited on the surface of the active electrode modulation layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1×10 -4 Pa, the steaming material is Cu with a purity of 99.99%.

[0090] 7) A 30 nm thick Au electrode protective layer was deposited on the surface of the active electrode layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1×10 -4 Pa, the steaming material is 99.99% pure Au.

[0091] Example 4

[0092] 1) Ultrasonic cleaning of a silicon substrate (100 μm) was performed using acetone, isopropanol, ethanol, and distilled water for 5 minutes in sequence to obtain a clean silicon substrate surface.

[0093] 2) A 5 nm thick Ti adhesion layer was deposited on a clean silicon substrate using magnetron sputtering. The magnetron cavity contained a mixture of nitrogen and argon with a gas volume ratio of 1:1 and a vacuum degree of 8 Torr. The target material was 99.99% pure Ti.

[0094] 3) A 20 nm thick Au inert electrode layer was deposited on the surface of the Ti adhesion layer using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was 99.99% pure Au.

[0095] 4) Grow a 10 nm thick HfO2 functional layer on the surface of the inert electrode layer using atomic layer growth technology. The specific process is as follows:

[0096] The raw materials are tetrakis(dimethylamino)hafnium and ozone, with a molar ratio of 1:4, and the growth temperature is 200°C. First, tetrakis(dimethylamino)hafnium gas is introduced into a reaction chamber at a substrate temperature of 200°C, forming a layer of tetrakis(dimethylamino)hafnium molecules on the surface of an inert electrode. Ozone gas is then introduced into the chamber to react with the adsorbed tetrakis(dimethylamino)hafnium molecules to produce a continuous and dense hafnium oxide material. The preparation process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0097] 5) A 3 nm thick HfO2 active electrode modulation layer is grown on the surface of the functional layer using atomic layer growth technology. The specific process is as follows:

[0098] The raw materials are tetrakis(dimethylamino)hafnium and ozone, with a molar ratio of 1:6, and the growth temperature is 75°C. First, tetrakis(dimethylamino)hafnium gas is introduced into a reaction chamber at a substrate temperature of 75°C to form a tetrakis(dimethylamino)hafnium molecular film on the surface of the functional layer. Ozone gas is then introduced into the chamber to react with the adsorbed tetrakis(dimethylamino)hafnium molecular film to produce a porous hafnium oxide material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0099] 6) A 25 nm thick Ag active electrode layer was deposited on the surface of the active electrode modulation layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1×10 -4 Pa, the steaming material is Ag with a purity of 99.99%.

[0100] 7) A 20 nm thick Au electrode protective layer was deposited on the surface of the active electrode layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1×10 -4 Pa, the steaming material is 99.99% pure Au.

[0101] Example 5

[0102] 1) Ultrasonic cleaning of a quartz substrate (100 μm) was performed using acetone, isopropyl alcohol, ethanol, and distilled water for 5 minutes in sequence to obtain a clean quartz substrate surface.

[0103] 2) A Ti adhesion layer with a thickness of 5 nm was deposited on the surface of a clean quartz substrate using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was Ti with a purity of 99.99%.

[0104] 3) A 40 nm thick Pt inert electrode layer was deposited on the surface of the Ti adhesion layer by magnetron sputtering. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1 and a vacuum degree of 8 Torr. The target material was 99.99% pure Pt.

[0105] 4) A ZnO functional layer with a thickness of 12 nm is grown on the surface of the inert electrode layer using atomic layer growth technology. The specific process is as follows:

[0106] The raw materials are diethylzinc and water in a 1:1 molar ratio, and the growth temperature is 200°C. First, diethylzinc gas is introduced into a reaction chamber at a substrate temperature of 200°C, forming a layer of diethylzinc molecules on the surface of an inert electrode. Water vapor is then introduced into the reaction chamber to react with the adsorbed diethylzinc molecules to produce a continuous, dense zinc oxide material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0107] 5) A 3 nm thick ZnO active electrode modulation layer is grown on the surface of the functional layer using atomic layer growth technology. The specific process is as follows:

[0108] The raw materials are diethylzinc and water in a molar ratio of 1:2, and the growth temperature is 100°C. First, diethylzinc gas is introduced into a reaction chamber at a substrate temperature of 100°C to form a diethylzinc molecular film on the surface of the functional layer. Water vapor is then introduced into the reaction chamber to react with the adsorbed diethylzinc molecular film to produce a porous zinc oxide material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0109] 6) A 20 nm thick Ag active electrode layer was deposited on the surface of the active electrode modulation layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1.5×10 -4 Pa, the steaming material is Ag with a purity of 99.99%.

[0110] 7) A 30 nm thick Au electrode protective layer was deposited on the surface of the active electrode layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1.5×10 -4 Pa, the steaming material is 99.99% pure Au.

[0111] Example 6

[0112] 1) Ultrasonic cleaning of a silicon substrate (150 μm) was performed using acetone, isopropanol, ethanol, and distilled water for 5 minutes in sequence to obtain a clean silicon substrate surface.

[0113] 2) A 5 nm thick Ti adhesion layer was deposited on a clean silicon substrate using magnetron sputtering. The magnetron cavity contained a mixture of nitrogen and argon with a gas volume ratio of 1:1 and a vacuum degree of 8 Torr. The target material was 99.99% pure Ti.

[0114] 3) A 30 nm thick Pt inert electrode layer was deposited on the surface of the Ti adhesion layer using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was Pt with a purity of 99.99%.

[0115] 4) A ZnO functional layer with a thickness of 10 nm is grown on the surface of the inert electrode layer using atomic layer growth technology. The specific process is as follows:

[0116] The raw materials are diethylzinc and water in a 1:1 molar ratio, and the growth temperature is 250°C. First, diethylzinc gas is introduced into a reaction chamber at a substrate temperature of 250°C, forming a layer of diethylzinc molecules on the surface of an inert electrode. Water vapor is then introduced into the reaction chamber to react with the adsorbed diethylzinc molecules to produce a continuous and dense zinc oxide material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0117] 5) A 5 nm thick ZnO active electrode modulation layer is grown on the surface of the functional layer using atomic layer growth technology. The specific process is as follows:

[0118] The raw materials are diethylzinc and water in a 1:1 molar ratio, and the growth temperature is 50°C. First, diethylzinc gas is introduced into a reaction chamber at a substrate temperature of 50°C, forming a diethylzinc molecular film on the surface of the functional layer. Water vapor is then introduced into the reaction chamber to react with the adsorbed diethylzinc molecular film to produce a porous zinc oxide material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0119] 6) A 30 nm thick Cu active electrode layer was deposited on the surface of the active electrode modulation layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1.5×10 -4 Pa, the steaming material is Cu with a purity of 99.99%.

[0120] 7) A 20 nm thick Au electrode protective layer was deposited on the surface of the active electrode layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1.5×10 -4Pa, the steaming material is 99.99% pure Au.

[0121] Example 7

[0122] 1) Ultrasonic cleaning of a silicon substrate (200 μm) was performed using acetone, isopropanol, ethanol, and distilled water for 5 minutes in sequence to obtain a clean silicon substrate surface.

[0123] 2) A Ti adhesion layer with a thickness of 3 nm was deposited on the surface of a clean silicon substrate using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was Ti with a purity of 99.99%.

[0124] 3) A 30 nm thick Pt inert electrode layer was deposited on the surface of the Ti adhesion layer using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was Pt with a purity of 99.99%.

[0125] 4) Grow an 8 nm thick SiO2 functional layer on the surface of the inert electrode layer using atomic layer growth technology. The specific process is as follows:

[0126] The raw materials are dichlorosilane and water in a molar ratio of 1:2, and the growth temperature is 250°C. First, dichlorosilane gas is introduced into a reaction chamber with a substrate temperature of 250°C, forming a layer of dichlorosilane molecules on the surface of an inert electrode. Water vapor is then introduced into the chamber to react with the adsorbed dichlorosilane molecules to produce a continuous and dense silicon dioxide material. This process is repeated repeatedly until the target thickness is reached, completing the preparation process.

[0127] 5) A 5 nm thick SiO2 active electrode modulation layer is grown on the surface of the functional layer using atomic layer growth technology. The specific process is as follows:

[0128] The raw materials are dichlorosilane and water in a molar ratio of 1:3, and the growth temperature is 100°C. First, dichlorosilane gas is introduced into a reaction chamber at a substrate temperature of 100°C to form a dichlorosilane molecular film on the surface of the functional layer. Water vapor is then introduced into the chamber to react with the adsorbed dichlorosilane molecular film to produce a porous silica material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0129] 6) A 25 nm thick Cu active electrode layer was deposited on the surface of the active electrode modulation layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1×10 -4 Pa, the steaming material is Cu with a purity of 99.99%.

[0130] 7) A 25 nm thick Au electrode protective layer was deposited on the surface of the active electrode layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1×10 -4 Pa, the steaming material is 99.99% pure Au.

[0131] Example 8

[0132] 1) Ultrasonic cleaning of a quartz substrate (300 μm) was performed using acetone, isopropyl alcohol, ethanol, and distilled water for 5 minutes in sequence to obtain a clean quartz substrate surface.

[0133] 2) A 5 nm thick Cr adhesion layer was deposited on the surface of a clean quartz substrate using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1 and a vacuum degree of 8 Torr. The target material was Cr with a purity of 99.99%.

[0134] 3) A 40 nm thick Au inert electrode layer was deposited on the surface of the Cr adhesion layer using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was 99.99% pure Au.

[0135] 4) A 10 nm thick SiO2 functional layer is grown on the surface of the inert electrode layer using atomic layer growth technology. The specific process is as follows:

[0136] The raw materials are dichlorosilane and water in a molar ratio of 1:2, and the growth temperature is 200°C. Dichlorosilane gas is first introduced into a reaction chamber at a substrate temperature of 200°C, forming a layer of dichlorosilane molecules on the surface of an inert electrode. Water vapor is then introduced into the chamber to react with the adsorbed dichlorosilane molecules to produce a continuous and dense silicon dioxide material. This process is repeated multiple times until the target thickness is reached.

[0137] 5) A 3 nm thick SiO2 active electrode modulation layer is grown on the surface of the functional layer using atomic layer growth technology. The specific process is as follows:

[0138] The raw materials are dichlorosilane and water in a molar ratio of 1:2, and the growth temperature is 50°C. First, dichlorosilane gas is introduced into a reaction chamber at a substrate temperature of 50°C, forming a dichlorosilane molecular film on the surface of the functional layer. Water vapor is then introduced into the chamber to react with the adsorbed dichlorosilane molecular film to produce a porous silica material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0139] 6) A 30 nm thick Ag active electrode layer was deposited on the surface of the active electrode modulation layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1×10 -4Pa, the steaming material is Ag with a purity of 99.99%.

[0140] 7) A 30 nm thick Au electrode protective layer was deposited on the surface of the active electrode layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1×10 -4 Pa, the steaming material is 99.99% pure Au.

[0141] Example 9

[0142] 1) Ultrasonic cleaning of PET substrate (150 μm) was performed with acetone, isopropyl alcohol, ethanol, and distilled water for 5 minutes in sequence to obtain a clean PET substrate surface.

[0143] 2) A 3 nm thick Cr adhesion layer was deposited on the surface of a clean PET substrate using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was 99.99% pure Cr.

[0144] 3) A 30 nm thick Au inert electrode layer was deposited on the surface of the Cr adhesion layer using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was 99.99% pure Au.

[0145] 4) Grow an 8 nm thick HfO2 functional layer on the surface of the inert electrode layer using atomic layer growth technology. The specific process is as follows:

[0146] The raw materials are tetrakis(dimethylamino)hafnium and ozone, with a molar ratio of 1:2, and the growth temperature is 300°C. First, tetrakis(dimethylamino)hafnium gas is introduced into a reaction chamber at a substrate temperature of 300°C, forming a layer of tetrakis(dimethylamino)hafnium molecules on the surface of an inert electrode. Ozone gas is then introduced into the chamber to react with the adsorbed tetrakis(dimethylamino)hafnium molecules to produce a continuous and dense hafnium oxide material. The preparation process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0147] 5) Grow an Al2O3 active electrode modulation layer with a thickness of 5 nm on the surface of the functional layer using atomic layer growth technology. The specific process is as follows:

[0148] The raw materials are trimethylaluminum and water in a molar ratio of 1:3, and the growth temperature is 50°C. First, trimethylaluminum gas is introduced into a reaction chamber at a substrate temperature of 50°C, forming a trimethylaluminum molecular film on the surface of the functional layer. Water vapor is then introduced into the chamber to react with the adsorbed trimethylaluminum molecular film to produce a porous alumina material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0149] 6) A 20 nm thick Cu active electrode layer was deposited on the surface of the active electrode modulation layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1.5×10 -4 Pa, the steaming material is Cu with a purity of 99.99%.

[0150] 7) A 30 nm thick Au electrode protective layer was deposited on the surface of the active electrode layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1.5×10 -4 Pa, the steaming material is 99.99% pure Au.

[0151] Example 10

[0152] 1) Ultrasonic clean the silica quartz substrate (250 μm) with acetone, isopropyl alcohol, ethanol, and distilled water for 5 minutes in sequence to obtain a clean quartz substrate surface.

[0153] 2) A Ti adhesion layer with a thickness of 5 nm was deposited on the surface of a clean quartz substrate using magnetron sputtering technology. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1, the vacuum degree was 8 Torr, and the target material was Ti with a purity of 99.99%.

[0154] 3) A 35 nm thick Pt inert electrode layer was deposited on the surface of the Ti adhesion layer by magnetron sputtering. The magnetron cavity was filled with a mixture of nitrogen and argon with a gas volume ratio of 1:1 and a vacuum degree of 8 Torr. The target material was Pt with a purity of 99.99%.

[0155] 4) A 10 nm thick SiO2 functional layer is grown on the surface of the inert electrode layer using atomic layer growth technology. The specific process is as follows:

[0156] The raw materials are dichlorosilane and water in a molar ratio of 1:2, and the growth temperature is 250°C. First, dichlorosilane gas is introduced into a reaction chamber with a substrate temperature of 250°C, forming a layer of dichlorosilane molecules on the surface of an inert electrode. Water vapor is then introduced into the chamber to react with the adsorbed dichlorosilane molecules to produce a continuous and dense silicon dioxide material. This process is repeated repeatedly until the target thickness is reached, completing the preparation process.

[0157] 5) Grow an Al2O3 active electrode modulation layer with a thickness of 5 nm on the surface of the functional layer using atomic layer growth technology. The specific process is as follows:

[0158] The raw materials are trimethylaluminum and water in a molar ratio of 1:3, and the growth temperature is 50°C. First, trimethylaluminum gas is introduced into a reaction chamber at a substrate temperature of 50°C, forming a trimethylaluminum molecular film on the surface of the functional layer. Water vapor is then introduced into the chamber to react with the adsorbed trimethylaluminum molecular film to produce a porous alumina material. This process is repeated multiple times until the target thickness is reached, completing the preparation process.

[0159] 6) A 20 nm thick Cu active electrode layer was deposited on the surface of the active electrode modulation layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1×10 -4 Pa, the steaming material is Cu with a purity of 99.99%.

[0160] 7) A 40 nm thick Au electrode protective layer was deposited on the surface of the active electrode layer by thermal evaporation technology. The vacuum degree of the thermal evaporation chamber was 1×10 -4 Pa, the steaming material is 99.99% pure Au.

[0161] Comparative Example 1

[0162] Different from Example 1, the prepared memristor has no active electrode modulation layer.

[0163] Comparative Example 2

[0164] Different from Example 2, the prepared memristor has no active electrode modulation layer.

[0165] Comparative Example 3

[0166] Different from Example 3, the prepared memristor has no active electrode modulation layer.

[0167] Test Example 1

[0168] The active electrode layer and the inert electrode layer of the composite multilayer memristor prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3 were connected to the positive and negative electrodes of the electrical testing equipment 2612 in sequence through tungsten probes to perform a memristor performance test. During the test, the current limit was 10 -7 A, the voltage step size was 0.03 V, and the applied voltage was scanned in a 0-1-0 V cycle.

[0169] For the test results of Example 1, Figure 5 The voltage-current curve relationship obtained after 100 cycles is shown. In each cycle scan, the switching ratio of the memristor is large and the voltage is small, indicating that its memristor performance is excellent and the power consumption is low. The cycle stability results can be obtained by using the memristor resistance conversion voltage as the vertical axis and the scan sequence as the horizontal axis, as shown in the figure. Figure 6As shown in Figure 2, it can be seen that the turn-on voltage fluctuation of the memristor is small, so it is more stable. At the same time, the distribution of the memristor resistance conversion voltage is statistically analyzed, as shown in Figure 2. Figure 7 As shown in Figure 1, the turn-on voltage of the memristor is mainly concentrated in the range of 0.08~0.11V, the turn-on voltage distribution is concentrated, and the performance is stable. In summary, the prepared memristor has a large switching ratio, low power consumption, excellent uniformity and stability, and has great application potential. However, the memristor without an active electrode modulation layer in Comparative Example 1 has a large operating voltage and significant fluctuations, and its uniformity and stability are poor. Figure 8 shown.

[0170] For the test results of Example 2, Figure 9 The voltage-current curve relationship obtained after 100 cycles is shown. In each cycle scan, the on-off ratio of the memristor is large and the voltage is small, indicating that its memristor performance is excellent and the power consumption is low. At the same time, the turn-on voltage of the memristor is relatively concentrated, indicating that the uniformity and stability of the memristor resistance conversion voltage are good. In contrast, the memristor without an active electrode modulation layer in Comparative Example 2 has poor uniformity and stability, such as Figure 10 shown.

[0171] For the test results of Example 3, Figure 11 The voltage-current curve relationship obtained after 100 cycles is shown. In each cycle scan, the on-off ratio of the memristor is large and the voltage is small, indicating that its memristor performance is excellent and the power consumption is low. At the same time, the turn-on voltage of the memristor is relatively concentrated, indicating that the uniformity and stability of the memristor resistance conversion voltage are good. In contrast, the memristor without an active electrode modulation layer in Comparative Example 3 has poor uniformity and stability, such as Figure 12 shown.

Claims

1. A composite multilayer memristor, characterized in that: It includes a base layer and an inert electrode layer, a functional layer, an active electrode modulation layer, and an active electrode layer sequentially formed on the base layer. The functional layer and the active electrode modulation layer are both made of oxide materials, the active electrode modulation layer has arrayed through holes, and the active electrode layer has connection points extending along the through holes to the functional layer; The thickness of the functional layer is 8-12 nm; the thickness of the active electrode modulation layer is 3-8 nm; The method for preparing the composite multilayer memristor comprises the following steps: (1) Cleaning the base material; (2) Depositing an adhesion layer on the surface of the substrate; (3) depositing an inert electrode layer on the surface of the adhesion layer; (4) growing a functional layer on the surface of the inert electrode layer; (5) growing an active electrode modulation layer on the surface of the functional layer; (6) depositing an active electrode layer on the surface of the active electrode modulation layer; (7) Depositing an electrode protection layer on the surface of the active electrode layer; Wherein, in step (4), the precursor and oxygen source reaction gas for forming the functional layer are circulated in sequence to achieve layer-by-layer growth of the oxide material of the functional layer; in step (5), the precursor and oxygen source reaction gas for forming the active electrode modulation layer are circulated in sequence to achieve layer-by-layer growth of the oxide material of the active electrode modulation layer; the molar ratio of the precursor and oxygen source reaction gas for forming the active electrode modulation layer is not higher than the molar ratio of the precursor and oxygen source reaction gas for forming the functional layer, and the temperature when growing the active electrode modulation layer is lower than the temperature when growing the functional layer, so that the grown active electrode modulation layer has arrayed through holes, and the deposited active electrode layer has connection points extending along the through holes to the functional layer.

2. The composite multilayer memristor according to claim 1, characterized in that The oxide materials used in the functional layer and the active electrode modulation layer are each one or more of aluminum oxide, hafnium oxide, silicon dioxide and zinc oxide.

3. The composite multilayer memristor according to claim 1, characterized in that The substrate layer is a PET substrate, a silicon substrate or a quartz substrate, and has a thickness of 100-300 μm; The inert electrode layer is Au or Pt, with a thickness of 20-40 nm; The active electrode layer is Cu or Ag, and has a thickness of 20-40 nm.

4. The composite multilayer memristor according to claim 1, characterized in that An adhesion layer is further provided between the base layer and the inert electrode layer; An electrode protection layer is also provided on the surface of the active electrode layer.

5. The composite multilayer memristor according to claim 4, characterized in that: The adhesion layer is Cr, Ni or Ti, and has a thickness of 3 to 5 nm; The electrode protection layer is Au with a thickness of 20-40 nm.

6. The composite multilayer memristor according to claim 1, characterized in that: The molar ratio of the precursor and the oxygen source reaction gas used to form the functional layer is 1:1-4; The molar ratio of the precursor and the oxygen source reaction gas used to form the active electrode modulation layer is 1:1-6; The growth temperature of the functional layer in step (4) is 200-300°C; The growth temperature of the active electrode modulation layer in step (5) is 50~100℃.

7. The composite multilayer memristor according to claim 6, characterized in that: In step (4), for different functional layer materials, the process selection is as follows: ZnO: The raw materials are diethyl zinc and water vapor, the raw material molar ratio is 1:1, and the growth temperature is 200~250℃; Al2O3: The raw materials are trimethylaluminum and water vapor, the raw material molar ratio is 2:3, and the growth temperature is 250~300℃; HfO2: The raw materials are tetrakis(dimethylamino)hafnium and ozone, the raw material molar ratio is 1:4, and the growth temperature is 200~300℃; SiO2: The raw materials are dichlorosilane and water vapor, the raw material molar ratio is 1:2, and the growth temperature is 200~250℃; In step (5), for different active electrode modulation layer materials, the process selection is as follows: ZnO: The raw materials are diethyl zinc and water vapor, the raw material molar ratio is 1:1~2, and the growth temperature is 50~100℃; Al2O3: The raw materials are trimethylaluminum and water vapor, the raw material molar ratio is 1:1.5~3, and the growth temperature is 50~75℃; HfO2: The raw materials are tetrakis(dimethylamino)hafnium and ozone, the raw material molar ratio is 1:4~6, and the growth temperature is 50~75℃; SiO2: The raw materials are dichlorosilane and water vapor, the molar ratio of the raw materials is 1:2~3, and the growth temperature is 50~100 ℃.

8. The composite multilayer memristor according to claim 1, characterized in that: In step (2), the adhesion layer is deposited by high vacuum magnetron sputtering technology; In step (3), an inert electrode layer is deposited using a high vacuum magnetron sputtering technique; In step (4), the functional layer is grown using atomic layer growth technology; In step (5), an active electrode modulation layer is grown using atomic layer growth technology; In step (6), the active electrode layer is deposited by thermal evaporation technology; In step (7), the electrode protection layer is deposited by thermal evaporation technology.

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